WO2007109260A2 - Silicone elastomer gels - Google Patents

Silicone elastomer gels Download PDF

Info

Publication number
WO2007109260A2
WO2007109260A2 PCT/US2007/006894 US2007006894W WO2007109260A2 WO 2007109260 A2 WO2007109260 A2 WO 2007109260A2 US 2007006894 W US2007006894 W US 2007006894W WO 2007109260 A2 WO2007109260 A2 WO 2007109260A2
Authority
WO
WIPO (PCT)
Prior art keywords
sio
sih
silicone elastomer
composition
extract
Prior art date
Application number
PCT/US2007/006894
Other languages
French (fr)
Other versions
WO2007109260A3 (en
Inventor
Shaow Lin
James Mc Vie
Paul Vandort
Original Assignee
Dow Corning Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Corporation filed Critical Dow Corning Corporation
Priority to CN200780007575.4A priority Critical patent/CN101395206B/en
Priority to US12/293,571 priority patent/US8110630B2/en
Priority to EP07753516.9A priority patent/EP1996644B9/en
Priority to JP2009501505A priority patent/JP5172821B2/en
Priority to KR1020087022919A priority patent/KR101364818B1/en
Publication of WO2007109260A2 publication Critical patent/WO2007109260A2/en
Publication of WO2007109260A3 publication Critical patent/WO2007109260A3/en

Links

Classifications

    • 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
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/042Gels
    • 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
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00Drugs for dermatological disorders
    • 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
    • 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
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
    • 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
    • C08L83/04Polysiloxanes
    • 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
    • C08L83/04Polysiloxanes
    • C08L83/06Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • 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
    • C08G77/04Polysiloxanes
    • C08G77/045Polysiloxanes containing less than 25 silicon atoms
    • 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
    • C08G77/04Polysiloxanes
    • C08G77/12Polysiloxanes containing silicon bound to hydrogen
    • 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
    • C08G77/04Polysiloxanes
    • C08G77/20Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/56Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond

Definitions

  • This invention relates to gel compositions containing a silicone elastomer from the reaction of an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, a compound, or mixture of compounds having at least two aliphatic unsaturated hydrocarbon groups in its molecule, and a hydrosilylation catalyst.
  • the silicone elastomer reaction product may itself be a gelled composition, or optionally may be contained in a carrier fluid to form a gel.
  • the gel compositions may further contain a personal or healthcare active. The actives may be incorporated into the gel via either a pre or post load method.
  • Silicone elastomers have been used extensively in personal care applications for their unique silky and powdery sensory profile. Most of these elastomers can gel volatile silicones fluids as well as low polarity organic solvents such as isododecane. Representative examples of such silicone elastomers are taught in US Patent 5,880,210, and US 5,760,116. To improve compatibilities of silicone elastomers with various personal care ingredients, alkyls, polyether, amines or other organofunctional groups have been grafted onto the silicone elastomer backbone.
  • organofunctional silicone elastomers are taught in US 5,811,487 , US 5,880,210 , US 6,200,581, US 5,236,986, US 6,331,604, US 6,262,170, US 6,531,540, and US 6,365,670. Many of these silicone elastomers have limited compatibilities with various personal care ingredients, personal care actives and healthcare actives. These elastomers loose thickening and gelling efficiency, and even sensory benefits in the presence of personal care ingredients, personal care actives and healthcare actives. There is a need to further improve compatibilities of silicone elastomers with various personal care ingredients and actives.
  • silicone elastomers derived from cyclic organohydrogensiloxanes provide gelled compositions efficiently.
  • the resulting gelled compositions also possess additional benefits, such as improved aesthetics and improved compatibilities with personal care ingredients and actives.
  • This disclosure relates to a gel composition
  • a silicone elastomer from the reaction of; A) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule
  • This disclosure further relates to a process for preparing a silicone elastomer gel containing an active comprising: I) reacting; a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring,
  • A an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated groups of component B) ranges from 2/1 to 8/1, II) further reacting;
  • a personal care or healthcare active may be incorporated into the silicone organic elastomer gel by having it be present during the formation of the silicone organic elastomer gel (pre-load method) or admixing it with a formed silicone organic elastomer gel (post-load method).
  • Component (A) in the present invention is an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule.
  • Organohydrogensiloxanes suitable as component A) in the present invention are any organopolysiloxanes having in its molecule at least two cyclosiloxane rings with at least one silicon bonded hydrogen (SiH) unit on each siloxane ring.
  • Organopolysiloxanes are well known in the art and are often designated as comprising any number of (RaSiOcs), (R 2 SiO), (RSiOu), or (SiQ2) siloxy units where R is independently any organic group.
  • R is methyl in the siloxy unit formulas of an organopolysiloxane, the respective siloxy units are often designated as M, D, T or Q siloxy units.
  • Cyclosiloxane rings contain at least three siloxy units (that is the minimum needed in order to form a siloxane ring), and may be any combination Of(RaSiOoS), (R 2 SiO), (RSiO 1.5), or (S1O 2 ) siloxy units that forms a cyclic structure, providing at least one of the cyclic siloxy units on each siloxane ring contains one SiH unit, that is there is at least one (R 2 HSiOo.s ), (RHSiO), or a (HSiOi. s) siloxy unit present in the ring.
  • These siloxy units can be represented as M H , D H , and T H siloxy units respectively when R is methyl.
  • the cyclosiloxane rings of A) the organohydrogensiloxane are linked together by a divalent organic or siloxane group, or combination thereof.
  • the divalent linking group may be designated as Y and the cyclosiloxane as G.
  • the organohydrogensiloxane of the present invention may be represented by the general formula G-[Y-G] ⁇ , where G is a cyclosiloxane as described above and Y is a divalent organic, a siloxane, a polyoxyalkylene group, or combination thereof, and the subscript a is greater than zero.
  • Y is a divalent organic
  • it may be a divalent hydrocarbon containing 1 to 30 carbons, either as aliphatic or aromatic structures, and may be branched or un-branched.
  • Y can be an alkylene group containing 2 to 20 carbons, or alternatively containing 4 to 12 carbons.
  • Y is a divalent organic, it may also be selected from an organic polymer, such as a polyoxyalkylene group.
  • Y is a siloxane group it may be selected from any organopolysiloxane containing at least two divalent hydrocarbon groups, designated as R 1 .
  • the siloxane linking group can be any organopolysiloxane comprising at least two siloxane units represented by the average formula R 1 wherein
  • R is an organic group
  • R 1 is a divalent hydrocarbon
  • m is zero to 3
  • the R 1 group may be present on any mono, di, or tri-siloxy unit in an organopolysiloxane molecule, for example; (R 1 R 2 SiOo ⁇ ), (R 1 RSiO), or (R 1 SiOi -S ), as well as in combination with other siloxy units not containing an R 1 substituent, such as (R3S1O 0 .5 ), (R 2 SiO), (RSiO 1 . 5 ), or (Si ⁇ 2 ) siloxy units where R is independently any organic group providing there are at least two R 1 substituents in the organopolysiloxane.
  • Representative R 1 groups include; ethylene, propylene, butylene, isobutylene, hexylene, and similar homologs. Alternatively, R 1 is ethylene.
  • siloxane based structures suitable as siloxane linking groups include; (R 2 R 1 SiOoS)(R 2 SiO) x (R 2 R 1 SiOo 5 )
  • Organohydrogensiloxane having at least two SiH containing cyclosiloxane rings may be prepared via a hydrosilylation reaction of a) an organohydrogencyclosiloxane having at least two SiH units on the siloxane ring and,
  • the organohydrogencyclosiloxane (a) having at least two SiH units on the siloxane ring may contain any number of siloxy units (as defined above) provided there are at least two SiH units on the cyclosiloxane ring.
  • the cyclic siloxane can comprise any number of M, M H , D, D H , or T H siloxy units.
  • Representative, non-limiting examples of such organohydrogencyclosiloxanes useful to prepare component (A) have the average formula D H a D b where a is > 1 and b is > 0, and a + b >3.
  • the organohydrogencyclosiloxane may be selected from those having the formula [(CH 3 )HSiO] g where g is 3 — 8, such as D H 4 , D H 51 D H 6 , or mixtures thereof.
  • Suitable compounds containing at least two aliphatic unsaturated hydrocarbon groups in its molecule are described below as component B).
  • hydrosilylation reactions involving organohydrogensiloxanes and unsaturated compounds are well known. Any suitable hydrosilylation catalysts know in the art may be used, or alternatively may be selected from those described below as component C). Any of the known hydrosilylation techniques and reactions may be employed to prepare component A) from i) organohydrogencyclosiloxane having at least two SiH units on the siloxane ring and, B) a compound or mixture of compounds having at least two aliphatic unsaturated groups in its molecule. However, the reaction is conducted in such a manner to provide an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule.
  • component A of the present invention contains at least two silicon-bonded hydrogen atom per molecule, alternatively at least 4 silicon-bonded hydrogen atoms per molecule, or alternatively at least 6 silicon-bonded hydrogen atoms per molecule.
  • This can be accomplished by using in the hydrosilylation reaction a molar excess of the a) the organohydrogencyclosiloxane having at least two SiH units on the siloxane ring vs. the compound containing at least two aliphatic unsaturated groups in its molecule.
  • the molar excess may be expressed as the molar ratio of SiH units to unsaturated group, such ratio may range from 2/1 to 8/1, alternatively from 2/1 to 6/1, or alternatively from 3/1 to 4/1.
  • the organohydrogensiloxane useful as component A) may be selected from any of the organohydrogensiloxanes taught in WO03/093349, which is herein incorporated by reference for its teaching of suitable organohydrogensiloxanes.
  • the organohydrogensiloxane useful as component A) in the present invention typically have a viscosity from 5 to 50,000 mPa-s, alternatively from 10 to 10,000 mPa-s, or alternatively from 25 to 2,000 mPa-s.
  • Representative, non-limiting examples of component A) include;
  • Additives known as inhibitors or stabilizers may be added to component A).
  • Inhibitors such as those described in WO 03/093369 may be added for the purpose of stabilizing component A) during storage, or prior to the addition of component B) to prepare the silicone elastomer gel.
  • the inhibitor may be selected from any compound known to have inhibiting effects of platinum based hydrosilylation reactions. Examples of known inhibitors include triphenyl phosphate, tocopherol (vitamin E), and butylated hydroxy toluene.
  • a particularly preferred inhibitor is vitamin A palmitate, or VAP. When VAP is used, it is typically added at 0.05 to 2.0 parts per 100 parts of component A).
  • VAP When VAP is used, it is typically added at 0.05 to 2.0 parts per 100 parts of component A).
  • Component (B) is a compound, or any mixture of compounds, containing at least two aliphatic unsaturated groups in its molecule.
  • the compound may be any diene, diyne or ene- yne compound.
  • Diene, diyne or ene-yne compounds are those compounds (including polymeric compounds) wherein there are at least two aliphatic unsaturated groups with some separation between the groups within the molecule.
  • the unsaturation groups are at the termini of the compound, or pendant if part of a polymeric compound.
  • R 2 - Y-R 2 where R 2 is a monovalent unsaturated aliphatic hydrocarbon group containing 2 to 12 carbon atoms, and Y is a divalent organic or siloxane group or a combination of these.
  • the compound having the formula R 2 - Y-R 2 as component B) may be considered as being a "organic”, “hydrocarbon”, “organic polymer”, “polyether” or “siloxane”, or combinations thereof, depending on the selection of Y.
  • Y may be a divalent hydrocarbon, a siloxane, a polyoxyalkylene, a polyalkylene, a polyisoalkylene, a hydrocarbon-silicone copolymer, or mixtures thereof.
  • the component (B) is selected from an organic compound, herein denoted as (B 1 ), having the formula R 2 - Y 1 - R 2 where R 2 is a monovalent unsaturated aliphatic group containing 2 to 12 carbon atoms and Y 1 is a divalent hydrocarbon,.
  • the divalent hydrocarbon Y 1 may contain 1 to 30 carbons, either as aliphatic or aromatic structures, and may be branched or un-branched.
  • the linking group Y 1 in B 1 may be an alkylene group containing 1 to 12 carbons.
  • Component (B 1 ) may be selected from ⁇ , ⁇ - unsaturated alkenes or alkynes containing 1 to 30 carbons, and mixtures thereof.
  • Component (B 1 ) may be exemplified by, but not limited to 1,4-pentadiene, 1 ,5-hexadiene; 1,6-heptadiene; 1 ,7-octadiene, 1 ,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13- tetradecadiene, and 1,19-eicosadiene, 1,3-butadiyne, 1, 5-hexadiyne (dipropargyl), and 1- hexene-5-yne.
  • the component (B) is selected from a R 2 - Y 2 - R 2 compound where Y 2 is a siloxane, herein denoted as (B 2 ).
  • the Y 2 siloxane group may be selected from any organopolysiloxane bonded to at least two organic groups having aliphatic unsaturation, designated as R 2 , to form R 2 - Y 2 - R 2 structures.
  • component (B 2 ) can be any organopolysiloxane, and mixtures thereof, comprising at least two siloxane units represented by the average formula R 2 RmSiO(4-mV2 wherein
  • R is an organic group
  • R 2 is a monovalent unsaturated aliphatic group as defined above, and m is zero to 3
  • the R 2 group may be present on any mono, di, or tri siloxy unit in an organopolysiloxane molecule, for example; (R 2 R 2 SiO 05 ), (R 2 RSiO), or (R 2 SiOi. 5 ); as well as in combination with other siloxy units not containing an R 2 substituent, such as (R 3 S1O 0 .
  • R is independently any organic group, alternatively a hydrocarbon containing 1 to 30 carbons, alternatively an alkyl group containing 1 to 30 carbons, or alternatively methyl; providing there are at least two R 2 substituents in the organopolysiloxane.
  • siloxane based R 2 - Y 2 - R 2 structures suitable as component (B 2 ) include; (R 2 R 2 SiOc 5 XSiO 2 Xv(R 2 R 2 SiOa 5 )
  • B 2 may be selected from vinyl functional polydimethylsiloxanes (vinyl siloxanes) or hexenyl functional polydimethylsiloxanes (hexenyl siloxanes), such as those having the average formula;
  • component (B) is selected from a polyether compound, herein denoted as (B 3 ), having the formula R 2 - Y 3 - R 2 compound where R 2 is as defined above and Y 3 is a polyoxyalkylene group having the formula (C n H 2n O) b wherein n is from 2 to 4 inclusive, b is greater than 2, alternatively b can range from 2 to 200, or alternatively b can range from 2 to 100.
  • a polyether compound herein denoted as (B 3 )
  • R 2 is as defined above
  • Y 3 is a polyoxyalkylene group having the formula (C n H 2n O) b wherein n is from 2 to 4 inclusive, b is greater than 2, alternatively b can range from 2 to 200, or alternatively b can range from 2 to 100.
  • the polyoxyalkylene group typically can comprise oxyethylene units (C 2 H4O), oxypropylene units (C 3 H 6 O), oxybutylene or oxytetramethylene units (C 4 H 8 O), or mixtures thereof.
  • the R 2 - Y 3 - R 2 compound may be selected from a polyoxyalkylene group having the formula R 2 -[(C 2 H_jO) c (C 3 H 6 OX 1 (C 4 H 8 O) 6 ]-R 2 where c, d, and e may each independently range from 0 to 200, providing the sum of c + d + e is greater than 2, alternatively the sum of c + d + e ranges from 2 to 200, or alternatively the sum of c + d + e ranges from 2 to 100. [0031] Alternatively, the polyoxyalkylene group comprises only oxypropylene units (C 3 H 6 ⁇ ) d . Representative, non-limiting examples of poly oxypropylene containing R 2
  • H 2 C CH[C 4 H 8 O] C
  • CH 2 C(CH 3 ) CH 2 HC ⁇ CCH 2 [C4H 8 O]eCH2C ⁇ CH HC ⁇ CC(CH 3 ) 2 [C4H 8 ⁇ ] e C(CH 3 ) 2 C ⁇ CH
  • Component B) may also be a mixture of various polyethers, i.e. a mixture of B 3 components.
  • component (B) is selected from a R 2 - Y 4 - R 2 compound, herein denoted as (B 4 ), where R 2 is as defined above and Y 4 is a polyalkylene group, selected from C2 to C6 alkylene units or their isomers.
  • R 2 is as defined above
  • Y 4 is a polyalkylene group, selected from C2 to C6 alkylene units or their isomers.
  • polyisobutylene group which is a polymer containing isobutylene unit. The molecular weight of the polyisobutylene group may vary, but typically ranges from 100 to 10,000 g/mole.
  • R 2 - Y- R 2 compounds containing a polyisobutylene group includes those obtained from BASF under the tradename of OPPONOL BV, such as OPPONOL B V 5K, a diallyl terminated polyisobutylene having an average molecular weight of 5000 g/mole.
  • component (B) is selected from a R 2 - Y 5 - R 2 compound, herein denoted as (B ), where R is as defined above and Y is a hydrocarbon-silicone copolymer group.
  • the hydrocarbon-silicone copolymer group may have the formula
  • R 1 and R are as defined above; u and v are independently > 1, alternatively u ranges from 1 to 20, alternatively v ranges from 2 to 500, or from 2 to 200, q is >1, alternatively q ranges from 2 to 500, alternatively q ranges from 2 to 100.
  • R 2 - Y 5 - R 2 compounds having a hydrocarbon-silicone copolymer group may be prepared via a hydrosilylation reaction between an ⁇ - ⁇ unsaturated hydrocarbon, such as those described above as B 1 , and an organohydrogensiloxane.
  • a hydrosilylation reaction between an ⁇ - ⁇ unsaturated hydrocarbon, such as those described above as B 1 , and an organohydrogensiloxane.
  • Component (B) may also be a mixture of any diene, diyne or ene-yne compound, such as any combinations of B 1 , B 2 , B 3 , B 4 , and B 5 .
  • component (A) and component (B) used to prepare the present composition will depend on the individual components and the desired SiH to aliphatic unsaturation ratio.
  • the ratio of SiH in component (A) to aliphatic unsaturation from component (B) useful to prepare the compositions of the present invention can be from 10:1 to 1 :10, alternatively 5:1 to 1:5, or alternatively 4:1 to 1:4.
  • components (A) and (B) are not the only materials containing aliphatic unsaturated groups and SiH-containing groups in the present composition, then the above ratios relate to the total amount of such groups present in the composition rather than only those components.
  • Component (C) comprises any catalyst typically employed for hydrosilylation reactions. It is preferred to use platinum group metal-containing catalysts. By platinum group it is meant ruthenium, rhodium, palladium, osmium, indium and platinum and complexes thereof. Platinum group metal-containing catalysts useful in preparing the compositions of the present invention are the platinum complexes prepared as described by Willing, U. S. Pat.
  • the platinum-containing catalyst can be platinum metal, platinum metal deposited on a carrier such as silica gel or powdered charcoal, or a compound or complex of a platinum group metal.
  • Preferred platinum-containing catalysts include chloroplatinic acid, either in hexahydrate form or anhydrous form, and or a platinum-containing catalyst which is obtained by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound such as divinyltetramethyldisiloxane, or alkene-platinum-silyl complexes as described in U.S. Patent Application No. 10/017229, filed December 7, 2001, such as (COD)Pt(SiMeCl2)2 > where COD is 1 ,5-cyclooctadiene and Me is methyl.
  • alkene- platinum-silyl complexes may be prepared, for example by mixing 0.015 mole (COD)PtC_2 with 0.045 mole COD and 0.0612 moles HMeSiC ⁇ .
  • the appropriate amount of the catalyst will depend upon the particular catalyst used.
  • the platinum catalyst should be present in an amount sufficient to provide at least 2 parts per million (ppm), preferably 4 to 200 ppm of platinum based on total weight percent solids (all non-solvent ingredients) in the composition. It is highly preferred that the platinum is present in an amount sufficient to provide 4 to 150 weight ppm of platinum on the same basis.
  • the catalyst may be added as a single species or as a mixture of two or more different species.
  • the silicone elastomers may be contained in an optional carrier fluid (D).
  • the carrier fluid may be the same as the solvent used for conducting the hydrosilylation reaction as described above.
  • Suitable carrier fluids include silicones, both linear and cyclic, organic oils, organic solvents and mixtures of these. Specific examples of solvents may be found in U.S. Patent No. 6,200,581, which is hereby incorporated by reference for this purpose.
  • the carrier fluid is a low viscosity silicone or a volatile methyl siloxane or a volatile ethyl siloxane or a volatile methyl ethyl siloxane having a viscosity at 25°C in the range of 1 to 1,000 mm 2 /sec such as hexamethylcyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadeamethylheptasiloxane, heptamethyl-3- ⁇ (trimethylsilyl)oxy) ⁇ trisiloxane, hexamethyl-
  • Organic solvents may be exemplified by, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides and aromatic halides.
  • Hydrocarbons including isododecane, isohexadecane, Isopar L ( CI l-C 13 ), Isopar H ( C11- C12 ), hydrogentated polydecen.
  • Ethers and esters including isodecyl neopentanoate, neopentylglycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n butyl ether, ethyl- 3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methylether acetate (PGMEA), propylene glycol methylether (PGME).
  • octyldodecyl neopentanoate diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, and octyl palmitate.
  • Additional organic carrier fluids suitable as a stand alone compound or as an ingredient to the carrier fluid include fats, oils, fatty acids, and fatty alcohols.
  • the amount of carrier fluid is such that there is 0 to 98 weight percent, alternatively 0.5 to 90 weight percent, alternatively 5 to 80 weight percent, of carrier fluid in composition containing (A) and (B) and (D), where the sum of (A), (B), and (D) is 100 weight percent.
  • Component E) is active selected from any personal or health care active.
  • a personal care active means any compound or mixtures of compounds that are known in the art as additives in the personal care formulations that are typically added for the purpose of treating hair or skin to provide a cosmetic and/or aesthetic benefit.
  • a “healthcare active” means any compound or mixtures of compounds that are known in the art to provide a pharmaceutical or medical benefit.
  • “healthcare active” include materials consider as an active ingredient or active drug ingredient as generally used and defined by the United States Department of Health & Human Services Food and Drug Administration, contained in Title 21, Chapter I, of the Code of Federal Regulations, Parts 200-299 and Parts 300-499.
  • active ingredient can include any component that is intended to furnish pharmacological activity or other direct effect in the diagnosis, cure, mitigation, treatment, or prevention of disease, or to affect the structure or any function of the body of a human or other animals.
  • the phrase can include those components that may undergo chemical change in the manufacture of drug products and be present in drug products in a modified form intended to furnish the specified activity or effect.
  • active ingredients include; drugs, vitamins, minerals; hormones; topical antimicrobial agents such as antibiotic active ingredients, antifungal active ingredients for the treatment of athlete's foot, jock itch, or ringworm, and acne active ingredients; astringent active ingredients; deodorant active ingredients; wart remover active ingredients; corn and callus remover active ingredients; pediculicide active ingredients for the treatment of head, pubic (crab), and body lice; active ingredients for the control of dandruff, seborrheic dermatitis, or psoriasis; and sunburn prevention and treatment agents.
  • topical antimicrobial agents such as antibiotic active ingredients, antifungal active ingredients for the treatment of athlete's foot, jock itch, or ringworm, and acne active ingredients
  • astringent active ingredients deodorant active ingredients
  • wart remover active ingredients corn and callus remover active ingredients
  • pediculicide active ingredients for the treatment of head, pubic (crab), and body lice
  • Vitamins useful herein include, but are not limited to, Vitamin Aj, retinol, C2-C18 esters of retinol, vitamin E, tocopherol, esters of vitamin E, and mixtures thereof.
  • Retinol includes trans-retinol, 1, 3-cis-retinol, 11-cis-retinol, 9-cis-retinol, and 3,4-didehydro-retinol, Vitamin C and its derivatives, Vitamin Bj, Vitamin
  • Vitamin B2 Pro Vitamin B5, panthenol, Vitamin Bg, Vitamin Bj2, niacin, folic acid, biotin, and pantothenic acid.
  • Other suitable vitamins and the INCI names for the vitamins considered included herein are ascorbyl dipalmitate, ascorbyl methylsilanol pectinate, ascorbyl palmitate, ascorbyl stearate, ascorbyl glucocide, sodium ascorbyl phosphate, sodium ascorbate, disodium ascorbyl sulfate, potassium (ascorbyl / tocopherol) phosphate.
  • RETINOL is an International Nomenclature Cosmetic Ingredient Name (INCI) designated by The Cosmetic, Toiletry, and Fragrance Association (CTFA), Washington DC, for vitamin A.
  • CTFA Cosmetic, Toiletry, and Fragrance Association
  • Other suitable vitamins and the INCI names for the vitamins considered included herein are RETINYL ACETATE, RETINYL PALMITATE, RETINYL PROPIONATE, ⁇ -TOCOPHEROL, TOCOPHERSOLAN, TOCOPHERYL ACETATE, TOCOPHERYL LINOLEATE, TOCOPHERYL NICOTINATE, and TOCOPHERYL SUCCINATE.
  • Some examples of commercially available products suitable for use herein are
  • Vitamin A Acetate and Vitamin C both products of Fluka Chemie AG, Buchs, Switzerland; COVI-OX T-50, a vitamin E product of Henkel Corporation, La Grange, Illinois; COVI-OX T-70, another vitamin E product of Henkel Corporation, La Grange, Illinois; and vitamin E Acetate, a product of Roche Vitamins & Fine Chemicals, Nutley, New Jersey.
  • the active ingredient used in processes according to the invention can be an active drug ingredient.
  • active drug ingredients which can be used are hydrocortisone, ketoprofen, timolol, pilocarpine, adriamycin, mitomycin C, morphine, hydromorphone, diltiazem, theophylline, doxorubicin, daunorubicin, heparin, penicillin G, carbenicillin, cephalothin, cefoxitin, cefotaxime, 5-fluorouracil, cytarabine, 6- azauridine, 6-thioguanine, vinblastine, vincristine, bleomycin sulfate, aurothioglucose, suramin, mebendazole, clonidine, scopolamine, propranolol, phenylpropanolamine hydrochloride, ouabain, atropine, haloperidol, isosorbide, nitroglycerin, ibuprofen, ubiquinones, indometh
  • antiacne agents such as benzoyl peroxide and tretinoin
  • antibacterial agents such as chlorohexadiene gluconate
  • antifungal agents such as miconazole nitrate
  • antiinflammatory agents corticosteroidal drugs
  • non-steroidal anti-inflammatory agents such as diclofenac
  • antipsoriasis agents such as clobetasol propionate
  • anesthetic agents such as lidocaine
  • antipruritic agents antidermatitis agents
  • agents generally considered barrier films are examples of active drug ingredients for purposes of the present invention.
  • the active component E) of the present invention can be a protein, such as an ' enzyme.
  • the internal inclusion of enzymes in the silicone elastomer gel have advantages to prevent enzymes from deactivating and maintain bioactive effects of enzymes for longer time.
  • Enzymes include, but are not limited to, commercially available types, improved types, recombinant types, wild types, variants not found in nature, and mixtures thereof.
  • suitable enzymes include hydrolases, cutinases, oxidases, transferases, reductases, hemicellulases, esterases, isomerases, pectinases, lactases, peroxidases, laccases, catalases, and mixtures thereof.
  • Hydrolases include, but are not limited to, proteases (bacterial, fungal, acid, neutral or alkaline), amylases (alpha or beta), lipases, mannanases, cellulases, collagenases, lisozymes, superoxide dismutase, catalase, and mixtures thereof.
  • Said protease include, but are not limited to, trypsin, chymotrypsin, pepsin, pancreatin and other mammalian enzymes; papain, bromelain and other botanical enzymes; subtilisin, epidermin, nisin, naringinase(L-rhammnosidase) urokinase and other bacterial enzymes.
  • Said lipase include, but are not limited to, triacyl-glycerol lipases, monoacyl-glycerol lipases, lipoprotein lipases, e.g. steapsin, erepsin, pepsin, other mammalian, botanical, bacterial lipases and purified ones. Natural papain is preferred as said enzyme. Further, stimulating hormones, e.g. insulin, can be used together with these enzymes to boost the effectiveness of them.
  • Component E) may also be a sunscreen agent.
  • the sunscreen agent can be selected from any sunscreen agent known in the art to protect skin from the harmful effects of exposure to sunlight.
  • the sunscreen compound is typically chosen from an organic compound, an inorganic compound, or mixtures thereof that absorbs ultraviolet (UV) light.
  • sunscreen agent examples include; Aminobenzoic Acid, Cinoxate, Diethanolamine Methoxycinnamate, Digalloyl Trioleate, Dioxybenzone, Ethyl 4-[bis(Hydroxypropyl)] Aminobenzoate, Glyceryl Aminobenzoate, Homosalate, Lawsone with Dihydroxyacetone, Menthyl Anthranilate, Octocrylene, Octyl Methoxycinnamate, Octyl Salicylate, Oxybenzone, Padimate O, Phenylbenzimidazole
  • the sunscreen agent can be a single one or combination of more than one.
  • the sunscreen agent is a cinnamate based organic compound, or alternatively, the sunscreen agent is octyl methoxycinnamate, such as Uvinul® MC 80 an ester of para- methoxycinnamic acid and 2-ethylhexanol.
  • Component E) may also be a fragrance or perfume.
  • the perfume can be any perfume or fragrance active ingredient commonly used in the perfume industry. These compositions typically belong to a variety of chemical classes, as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitrites, terpenic hydrocarbons, heterocyclic nitrogen or sulfur containing compounds, as well as essential oils of natural or synthetic origin. Many of these perfume ingredients are described in detail in standard textbook references such as Perfume and Flavour Chemicals, 1969, S. Arctander, Montclair, New Jersey. [0055] Fragrances may be exemplified by, but not limited to, perfume ketones and perfume aldehydes.
  • perfume ketones are buccoxime; iso jasmone; methyl beta naphthyl ketone; musk indanone; tonalid/musk plus; Alpha-Damascone, Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose, Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone, Alpha-lonone, Beta-lonone, Gamma-Methyl so- called lonone, Fleuramone, Dihydrojasmone, Cis-Jasmone, Iso-E-Super, Methyl-Cedrenyl- ketone or Methyl- Cedrylone, Acetophenone, Methyl-Acetophenone, Para-Methoxy- Acetophenone, Methyl-Beta-Naphtyl-Ketone
  • the perfume ketones are selected for its odor character from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-lonone, Iso-E-
  • the perfume aldehyde is selected for its odor character from adoxal; anisic aldehyde; cymal; ethyl vanillin; florhydral; helional; heliotropin; hydroxycitronellal; koavone; lauric aldehyde; lyral; methyl nonyl acetaldehyde; P. T.
  • More preferred aldehydes are selected for their odor character from 1 -decanal, benzaldehyde, florhydral, 2,4-dimethyl-3-cyclohexen-l -carboxaldehyde; cis/trans-3,7- dimethyl-2,6-octadien-l -al; heliotropin; 2,4,6-trimethyl-3-cyclohexene-l -carboxaldehyde; 2,6-nonadienal; alpha-n-ainyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal, trans-2-hexenal, and mixture thereof.
  • Component E may also be one or more plant extract.
  • Ashitaba extract avocado extract, hydrangea extract, Althea extract, Arnica extract, aloe extract, apricot extract, apricot kernel extract, Ginkgo Biloba extract, fennel extract, turmeric [Curcuma] extract, oolong tea extract, rose fruit extract, Echinacea extract, Scutellaria root extract, Phellodendro bark extract, Japanese Coptis extract, Barley extract, Hyperium extract, White Nettle extract, Watercress extract, Orange extract, Dehydrated saltwater, seaweed extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, Chamomile extract, Carrot extract, Artemisia extract, Glycyrrhiza extract, hibiscustea extract, Pyracantha Fortuneana Fruit extract, Kiwi extract, Cinchona extract, cucumber extract, guanocine, Gardenia extract, Sasa Albo-marginata extract, Sophora root extract, Walnut extract, Grapefruit extract, Clemati
  • the amount of component E) present in the silicone gel composition may vary, but typically range as follows;
  • the active, component E may be added to the silicone gel composition either during the making of the silicone elastomer (pre-load method), or added after the formation of the silicone elastomer gel (post load method).
  • the pre-load method involves; I) reacting; a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring, B) a compound or mixture of compounds having at least two aliphatic unsaturated hydrocarbon groups in its molecules,
  • A an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated hydrocarbon groups of component B) ranges from 2/1 to 8/1, II) reacting;
  • A an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated groups of component B) ranges from 2/1 to 8/1,
  • the silicone elastomers of the present invention are obtainable as hydrosilylation reaction products of components A), B), and C).
  • hydrosilylation means the addition of an organosilicon compound containing silicon-bonded hydrogen, (such as component A) to a compound containing aliphatic unsaturation (such as component B), in the presence of a catalyst (such as component C). Hydrosilylation reactions are known in the art, and any such known methods or techniques may be used to effect the hydrosilylation reaction of components A), B), and C) to prepare the silicone elastomers of the present invention.
  • the hydrosilylation reaction may be conducted in the presence of a solvent, and the solvent subsequently removed by known techniques.
  • the hydrosilylation may be conducted in a solvent, where the solvent is the same as the carrier fluid described as optional component D).
  • the silicone elastomers may be prepared by a process comprising: I) reacting; a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring,
  • Components a, A), B), C) are the same as those described above. Also, the reaction may be conducted under similar conditions as described above. In aforementioned step II) the molar ratio of the SiH units of component A) to the aliphatic unsaturated groups of component B) ranges from 10/1 to 1/10, alternatively from 5/1 to 1/5, or alternatively from 4/1 to 1/4.
  • the silicone elastomers can be added to a carrier fluid (as described above as component D) to form gelled compositions, or alternatively be prepared first in a separate reaction and then added to the carrier fluid to obtain a gel.
  • the gelled compositions of the present invention may be characterized by their hardness or firmness. Useful tests to characterize the gels are those recommended by the Gelatin Manufacturers Institute of America such as the use of a "Texture Analyzer" (model TA.XT2, Stable Micro Systems, Inc., Godalming, England).
  • the gel sample is subject to a compression test with the Texture Analyzer having a probe with a 5.0 kg load cell.
  • the probe approaches the surface of the gel at a speed of 0.5 mm/sec and continues compression into the gel to a distance of 5.0 mm, then holds for 1 second before retreating.
  • the Texture Analyzer detects the resistance force the probe experiences during the compression test. The force exhibited by the load cell is plotted as a function of time.
  • the hardness of the silicone elastomers, gels and elastomer blends (SEBs) for purposes of this invention is defined as the resistance force detected by the probe of the "Texture Analyzer" during the compression test.
  • Two data may be used to characterize hardness: Force 1, the force at the maximum compression point (i.e. the 5.0 mm compression point into the gel surface), and Area F-T: the area-force integration during the 1 second hold at the maximum compression point. The average of a total of 5 tests are typically performed for each gel.
  • the value obtained for Force 1 is converted into Newton (N), by dividing the gram force value by 101.97. (i.e. 1 Newton equals 101.97 g force based on the size of the probe used in this instrument).
  • the second property reported by Texture Analyzer measurement is Area F-T 1 :2, in g force-sec. This is the area integration of the force vs. test time cure. This property is indicative of a gel network since it indicates ability to sustain resistance to the compression force, which is relevant to elastomers and gels.
  • the value is reported in g force-sec, and is converted to Newton-sec in SI unit by dividing the value in g force-sec by
  • the silicone gels of the present invention has a compression hardness of at least
  • the gelled compositions of the present invention can be used to prepare gel paste or gel blend compositions containing actives by; I) shearing the silicone elastomer gel, as described above,
  • the silicone elastomer gel compositions of the present invention blends may be considered as discrete crosslinked silicone elastomer gel particles dispersed in carrier fluids.
  • the silicone elastomer compositions are effective rheological thickeners for lower molecular weight silicone fluids. As such they can be used to prepare useful gel blend compositions, such as "paste" compositions.
  • the aforementioned silicone elastomer gels of known initial elastomer content (IEC) are sheared to obtain small particle size and further diluted to a final elastomer content (FEC).
  • Shearing refers to any shear mixing process, such as obtained from homogenizing, sonalating, or any other mixing processes known in the art as shear mixing.
  • the shear mixing of the silicone elastomer gel composition results in a composition having reduced particle size.
  • the subsequent composition having reduced particle size is then further combined with D) the carrier fluid.
  • the carrier fluid may be any carrier fluid as described above, but typically is a volatile methyl siloxane, such as D5.
  • the technique for combining the D) the carrier fluid with the silicone elastomer composition having reduced particle size is not critical, and typically involves simple stirring or mixing.
  • the resulting compositions may be considered as a paste, having a viscosity greater than 100,000 cP (mPa-s).
  • MeH CYCLICS methylhydrogen cyclosiloxanes (MeH cyclics) having the formula
  • MeH LINEAR an organohydrogenpolysiloxane have the average formula MT ⁇ wD' ⁇ M
  • VINYL SILOXANE #2 a dimethylvinylsiloxy-terminated dimethylpolysiloxane of the general formula
  • PT CATALYST SLY-OFF 4000 (Dow Corning Corporation, Midland MI) Pt catalyst used as provided containing 0.52 weight % Pt.
  • D5 decamethylcyclopentasiloxane or D5 cyclics, DC245 (Dow Corning Corporation, Midland MI) used as provided.
  • IDNP isodecyl neopentanoate obtained from ISP (International Specialty Products Co) under the trade name of CERAPHYL SLK.
  • IDD isododecane
  • Stabilizer Vitamin A palmitate (VAP) and butylated hydroxytoluene (BHT) Methods of Measuring Viscosity of Silicone Elastomer Blends (SEBsI
  • Brookfield HelipathTM Stand when used with a suitable Brookfield Viscometer fitted with a special T-bar type spindle, will permit viscosity/consistency measurements in centipoise values for materials having characteristics similar to paste, putty, cream, gelatin, or wax.
  • a sample size of lOOg in a 4 oz. round jar was required. The following preparation procedure was used before measurement: the sample was de-aired first via centrifuge, then vacuum de-aired for two hours. After de-airing, the sample was conditioned for a minimum of 4 hours @ 25° C. The sample was positioned with T-bar spindle at center. The reading was taken according to the typical procedure for Helipath spindle.
  • spindle 93 (T-bar spindle C) is used for the less viscous sample
  • spindle 95 (T-bar spindle E) for the more viscous samples.
  • the standard setting for rpm was 2.5.
  • the spindle speed is maintained at constant 2.5 rpm and spindle was varied to handle samples with significant viscosities.
  • the hardness (or firmness) of silicone elastomer gels was characterized using a Texture analyzer (model TA.XT2, Stable Micro Systems, Inc., Godalming, England). The Gelatin Manufacturers Institute of America recommends such test methods as a standard procedure.
  • a Vi inch (1.27 cm) diameter cylindrical probe made of DELRIN acetal resin (Dupont) was used for the measurement.
  • the gel sample is subject to the compression test using the probe with the following test cycle: the probe approaches the surface of the gel at a speed of 0.5 mm/sec and continues compression into the gel to a distance of 5.0 mm, then holds for 1 second before retreating.
  • the Texture Analyzer has a 5.0 Kg load cell to detect the resistance force the probe experiences during the compression test. The force exhibited by the load cell is plotted as a function of time.
  • the hardness of the silicone elastomers, gels and elastomer blends is defined as the resistance force detected by the probe during the compression test.
  • Two data are used for the hardness value: Force 1 : the force at the maximum compression point (i.e. the 5.0 mm compression point into the gel surface), and Area F-T: the area-force integration during the 1 second hold at the maximum compression point. A total of 5 tests were performed for each gel and the average of the five tests is reported.
  • Texture Analyzer used for gel hardness measurement is force in gram, as detected by the transducer. Two values are reported for gel hardness: Force 1, the force in gram registered when the probe reached its pre-programmed full indentation (or compression) in gel sample. The unit for Force 1 reading is gram force.
  • the value obtained for Force 1 is converted into Newton (N), by dividing the gram force value by 101.97. (i.e. 1 Newton equals 101.97 g force based on the size of the probe used in this instrument). For instance, a value of 6327 g force converts to 62.0 N.
  • the second property reported by Texture Analyzer measurement is Area F-T 1 :2, in g force-sec. This is the area integration of the force vs. test time cure. This is an indicative property of a gel network as it indicates it ability to sustain resistance to the compression force, which is relevant to elastomers and gels.
  • the value is reported in g force-sec, and is converted to Newton-sec in SI unit by dividing the value in g force-sec by 101.97. For instance, a value of 33,947 g force-sec is 332.9 N s in SI units.
  • the specific [SiH] / [Vi] ratio was kept at 3.0, 3.42, and 4.0 for the three examples and the reaction was conducted at 40 0 C.
  • the finished polymers were clear liquids having the general structures shown in
  • the [SiH] / [Vi] ratios were 3.0, 3.42, and 4.0 for the three examples and the reaction was conducted at 40 0 C.
  • the finished SiH siloxanes were clear liquids having the target structures shown in the Table 2.
  • the SiH content were found to be 0.020%, 0.0240%, and 0.0296% respectively.
  • the [SiH] / [Vi] ratios were kept at 3.42 and 4.0 for the three examples and the reaction was conducted at 40 0 C.
  • a component A) was made using VINYL SILOXANE #4.
  • the SiH siloxanes were clear liquids having the structures summarized in Table 3. The SiH contents were 0.241 %, 0.290%, and 0.376% respectively.
  • Organohydrogensiloxanes illustrative as component A) were prepared by mixing MeH CYCLICS, VINYL SILOXANES (as listed in Table 4) or 1, 5 hexadiene, and (if used) D5 as a carrier fluid in a reaction flask. Then, the mixture was catalyzed by the addition of 3-5 ppm of Pt (Pt catalyst solution containing 0.52 wt% Pt). The mixture was heated to 50 0 C, causing an exothermic hydrosilylation reaction to occur, the temperature was then maintained between 50 and 70 0 C for 3 hours.
  • Pt Pt catalyst solution containing 0.52 wt% Pt
  • Silicone elastomer gels were prepared by reacting the organohydrogensiloxane having at least two SiH containing cyclosiloxane rings as component (A) and aliphatic unsaturated compound as component (B) at a low [SiH] / [Alkeny] ratio of 0.36.
  • Cyclic SiH siloxane of Example 5F a 40% solids in D5 fluid where the cyclic SiH-containing siloxane made from MeH-CYCLICS and VINYL SILOXANE #1 at a SiH/alkenyl ratio of 3.42, was reacted with VINYL SILOXANE #2 in D5 fluid and in isodecyl neopentanoate (IDNP) hydrocarbon ester solvent.
  • IDNP isodecyl neopentanoate
  • Silicone elastomer gels were made with a low elastomer contents (EC), as illustrated in this example. Silicone elastomer gels (Example 7A and 7C) were made at 3.0 % elastomer composition (the total of components (A) and (B)), and 97 % D5 fluid (component (D)). The siloxane spacer had an average DP (degree of polymerization) of 100 in these examples,
  • Silicone elastomer gels were prepared with low amounts of elastomer content using cyclic SiH-containing siloxanes of relatively short spacer (i.e. low dp). Illustrated below are the silicone elastomer gels made from the SiH siloxane of Example 4C (8 dp spacer) and Example 4D (27dp spacer). All gels in this example had 5 wt% elastomer content (i.e. total of components (A) and (B)), and 95% D5 fluid (component (C)).
  • Silicone elastomer blends are discrete crosslinked silicone elastomer gel particles dispersed in carrier fluids. SEBs can function effectively as a rheological thickener for silicone fluids such as D5 fluid as demonstrated in this example.
  • silicone fluids such as D5 fluid as demonstrated in this example.
  • IEC initial elastomer content
  • FEC desirable final elastomer content
  • sample 9A SEB was made by mechanically shearing an elastomer gel to reduce particle size and then diluted further with D5 fluid to yield a final elastomer content (% FEC) of 10% by weight.
  • the final SEB was a clear thick gel paste with a viscosity of about 676,000 cps. Additional SEBs are shown in Table 9. As illustrated by these examples, extremely high viscosities were observed for these compositions of SEBs in cyclic siloxanes.
  • Silicone elastomer gels can be prepared without a carrier fluid present, as illustrated in this example.
  • the total of components (A) and (B) represents the elastomer amount and is equal to 100% in these examples.
  • Silicone elastomer gels were made from the hydrosilylation of the representative cyclic SiH-containing siloxane as component (A) with an alkenyl functional compound in component (B) in the presence of Pt catalyst.
  • the two cyclic SiH siloxanes used for the preparation of 100% silicone elastomer gels were those described above as Example 4J, and example 4K.
  • the molar ratio of silicon-bonded hydrogen [SiH] to [alkenyl] was 0.90.
  • the hardness of these silicone elastomer gels, as measured by Texture Analyzer, is shown in the Tables 1OA and 1OB.
  • the silicone elastomer blends were made from the silicone elastomer gels of 100% elastomer content, by grinding/ shearing the gels, followed by diluting with the selected carrier fluid, either silicone fluids or organic solvents.
  • silicone elastomer gels were prepared following the procedures described above. These silicone elastomer gels were made from the selected cyclic SiH- containing siloxane as component (A), the alkenyl functional compound in component (B), and the balance quantity of D5 fluid. A trace amount of Pt catalyst at a quantity about 4-10 ppm Pt was used to catalyzed the reaction. The molar ratio of silicon-bonded hydrogen [SiH] to [alkenyl] was varied, as shown in the following table. The hydrosilylation reaction was carried out at 50 0 C for 4 hours. Gels formed from 15 minutes to 2 hours after placing in 50 0 C water bath, depending on the composition.
  • the hardness of the silicone elastomer gels derived was characterized using the Texture Analyzer.
  • the "Force 1" is the force reading at the maximum point of the force vs. probe penetration time cure, illustrated in the above figure. This force reading represents the firmness or hardness of the gels in resisting probe penetration.
  • the second property included is the "Force-Time 1 :2 Area” reading. This is the area integration between the maximum force reading and the time it elapsed (1 second in this case). This value represents the elastic nature of the silicone elastomer gels. The higher the value, in both properties, the harder the gels is. As illustrated, silicone elastomer gels with a wide range of hardness are produced.
  • Elastomer gels with very low hardness (soft gels) and with very high hardness readings (not shown yet) can be conveniently prepared by controlling the % elastomer content.
  • the total of components (A) and (B) represents the elastomer content and can be as high as 100%. In the case of neat elastomers, the hardness of such gels is very high and can be processed into powdery type products to give a powdery feel.
  • Gels were prepared from various component (A) and alkenyl-functional compound in component (B) to 10 and 20% elastomer content. Dow Corning 245 fluid was used as component (D). Very soft gels with a force of 4 g were produced. On the other hand, gels with very high force readings may be produced from these components by raising the wt. % elastomer content.
  • Elastomers and gels may be formed over a wide range of SiH / vinyl ratios and at relatively low SiH/vinyl ratios. To illustrate this, the following examples were prepared.
  • Component (A) in this example was an organohydrogensiloxane similar to Example 5F with a 27dp siloxane spacer, made from MeH cyclics and VINYL SILOXANE #5 using a SiH/vinyl ratio of 3.4.
  • Preparation prescribed amounts of components (A) and (B) are charged to a reaction container and mixed to homogeneous, then about 3.5ppm of Pt catalyst (i.e. 0.05 g of Dow Corning Syl-Off Pt solution @ 0.52 % Pt by weight) was introduced while under stirring.
  • Pt catalyst i.e. 0.05 g of Dow Corning Syl-Off Pt solution @ 0.52 % Pt by weight
  • the hydrosilylation reaction was carried out at 70 0 C for 3 hrs. All mixtures except Example 13F gelled within 30 minutes of heating. The gel hardness was characterized using a Texture Analyzer.
  • Example 8B No gel or elastomer was formed in the Example 8B composition, at 5.0 % elastomer content.
  • This example demonstrates the improved thickening and gel-forming capacity of the cyclic SiH- containing siloxane based composition of the present invention vs conventional linear siloxane based silicone elastomers of the art.
  • Silicone Elastomer gels were prepared from cyclic SiH-containing siloxane having various chain architectures (component A), as well as aliphatic unsaturated compounds of various structure and type in component (B). The amounts and components (A) and (B) were calculated to yield a predetermined [SiH] / [Alkeny] molar ratio and a pre-determined % elastomer content in the cured gel. Examples 15B and 15D were charged with 7.15 wt% VAP during the formation of the silicone elastomer gel, and is representative of the "pre-load method".
  • silicone elastomer gels in these examples were prepared according to the following procedures:
  • Silicone elastomer gels with and without a vitamin active were also derived from organohydrogencyclosiloxanes of varying molecular structure as shown in the examples summarized in Table 16.
  • the hardness of the VAP active containing silicone elastomer gels was characterized by the Texture Analyzer, as described above. The gels were prepared according to the procedure described in Example 15.
  • Silicone elastomer gels with and without a vitamin active were also derived from organohydrogencyclosiloxanes having an organic spacer as shown in the examples summarized in Table 17. The gels were prepared according to the procedure described in Example 15.
  • Silicone elastomer blends were prepared from several of the silicone elastomer gels by mechanically shearing a silicone elastomer gel composition characterized as having an initial elastomer content (IEC) to reduce particle size, and subsequently diluting the mixture with additional carrier fluid to a desired final elastomer content (FEC).
  • IEC initial elastomer content
  • FEC final elastomer content
  • Various silicone elastomer blends as summarized in Table 19, were made by mechanically shearing silicone gel compositions using a Hauschild mixer to reduced particle size and then diluted further with Dow Corning 245 fluid to yield silicone elastomer blends having a final elastomer content (FEC) of 10% by weight.
  • the silicone blend compositions of these examples contained VAP, which can be included using the pre-load method (Example 19B and 19D), or from post- loading the VAP by its addition to a silicone gel composition (Example 19A and 19C).
  • HPLC High-performance liquid chromatography
  • Standards were prepared by creating a stock solution of 1000 ug/ml VAP in hexane. This was done by measuring 107.2 mg VAP into a 100 ml volumetric flask. The flask was then filled to the 100 ml level with hexane. The stock solution was then diluted into solutions with concentration of 4, 40, 100, 300, and 500 ug/ml. A calibration curve was constructed using all standards from 4 to 1000 ug/ml. SEB Sample Extraction
  • the assays of VAP in this invention were performed on one of the two HPLC systems: a Waters 600E HPLC equipped with a Waters 991 PDA detector or Waters 2695 Separations unit equipped with a Waters 2996 PDA detector.
  • the column and column guard were Novapak Cl 8 from Waters.
  • the column was heated to a constant temperature of 35° C.
  • the mobile phase was 45% methanol, 20% acrylnitrile, and 35% isopropanol set at a flow rate of 1 ml/min. 10 ul of each sample were injected and allowed to run for 12 minutes.
  • the PDA detector was set to 325 nm wavelength.
  • HPLC High-performance liquid chromatography
  • Silicone elastomer gels were prepared without adding any carrier fluid (component C) from various organohydrogencyclosiloxanes using Example IS procedures. The formulations and resulting gel properties are summarized Table 23.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dispersion Chemistry (AREA)
  • Dermatology (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medicinal Preparation (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Silicon Polymers (AREA)

Abstract

Gel compositions containing a silicone elastomer from the reaction of an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, a compound having at least two aliphatic unsaturated hydrocarbon groups in its molecule, and a hydrosilylation catalyst. The silicone elastomer reaction product may itself be a gelled composition, or optionally may be contained in a carrier fluid to form a gel. The gel compositions may further contain a personal or healthcare active. The actives may be incorporated into the gel via either a pre or post load method.

Description

SILICONE ELASTOMER GELS
Cross Reference to Related Applications
[0001] This application claims the benefit of U.S. Patent Application Serial No. 60/784,340 filed on 21 March 2006, and U.S. Patent Application Serial No. 60/838,803, filed on 18 August 2006, under 35 U.S.C. § 119(e).
Technical Field
[0002] This invention relates to gel compositions containing a silicone elastomer from the reaction of an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, a compound, or mixture of compounds having at least two aliphatic unsaturated hydrocarbon groups in its molecule, and a hydrosilylation catalyst. The silicone elastomer reaction product may itself be a gelled composition, or optionally may be contained in a carrier fluid to form a gel. The gel compositions may further contain a personal or healthcare active. The actives may be incorporated into the gel via either a pre or post load method.
Background
[0003] Silicone elastomers have been used extensively in personal care applications for their unique silky and powdery sensory profile. Most of these elastomers can gel volatile silicones fluids as well as low polarity organic solvents such as isododecane. Representative examples of such silicone elastomers are taught in US Patent 5,880,210, and US 5,760,116. To improve compatibilities of silicone elastomers with various personal care ingredients, alkyls, polyether, amines or other organofunctional groups have been grafted onto the silicone elastomer backbone. Representative of such organofunctional silicone elastomers are taught in US 5,811,487 , US 5,880,210 , US 6,200,581, US 5,236,986, US 6,331,604, US 6,262,170, US 6,531,540, and US 6,365,670. Many of these silicone elastomers have limited compatibilities with various personal care ingredients, personal care actives and healthcare actives. These elastomers loose thickening and gelling efficiency, and even sensory benefits in the presence of personal care ingredients, personal care actives and healthcare actives. There is a need to further improve compatibilities of silicone elastomers with various personal care ingredients and actives. [0004] However, there is still a need to further improve the efficiency of gelling volatile cosmetic fluids such as volatile silicones by silicone elastomers, and in particular to improve the rheological thickening effects by the addition of silicone elastomers to volatile cosmetic fluids. Furthermore, additional benefits are also sought for gelled compositions, such as improving the clarity of gelled silicone compositions and/or improved aesthetics upon application on skin.
[0005] The present inventors have discovered that silicone elastomers derived from cyclic organohydrogensiloxanes provide gelled compositions efficiently. The resulting gelled compositions also possess additional benefits, such as improved aesthetics and improved compatibilities with personal care ingredients and actives.
Summary
[0006] This disclosure relates to a gel composition comprising a silicone elastomer from the reaction of; A) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule
B) a compound or mixture of compounds having at least two aliphatic unsaturated hydrocarbon groups in its molecule,
C) a hydrosilylation catalyst, and;
D) an optional carrier fluid.
[0007] This disclosure further relates to a process for preparing a silicone elastomer gel containing an active comprising: I) reacting; a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring,
B) a compound or mixture of compounds having at least two aliphatic unsaturated hydrocarbon groups in its molecule,
C) a hydrosilylation catalyst, to form
A ) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated groups of component B) ranges from 2/1 to 8/1, II) further reacting;
A ) the organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, with additional quantities of
B) the compound or mixture of compounds containing at least two aliphatic unsaturated groups in its molecules,
C) the hydrosilylation catalyst, in the presence of D) an optional carrier fluid, and
E) a personal care or healthcare active, to form the silicone elastomer gel.
[0008] A personal care or healthcare active may be incorporated into the silicone organic elastomer gel by having it be present during the formation of the silicone organic elastomer gel (pre-load method) or admixing it with a formed silicone organic elastomer gel (post-load method).
Detailed Description
C4) The organohydrosensiloxane having at least two SiH containing cvclosiloxane rings [0009] Component (A) in the present invention is an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule. Organohydrogensiloxanes suitable as component A) in the present invention are any organopolysiloxanes having in its molecule at least two cyclosiloxane rings with at least one silicon bonded hydrogen (SiH) unit on each siloxane ring. Organopolysiloxanes are well known in the art and are often designated as comprising any number of (RaSiOcs), (R2SiO), (RSiOu), or (SiQ2) siloxy units where R is independently any organic group. When R is methyl in the siloxy unit formulas of an organopolysiloxane, the respective siloxy units are often designated as M, D, T or Q siloxy units. Cyclosiloxane rings contain at least three siloxy units (that is the minimum needed in order to form a siloxane ring), and may be any combination Of(RaSiOoS), (R2SiO), (RSiO 1.5), or (S1O2) siloxy units that forms a cyclic structure, providing at least one of the cyclic siloxy units on each siloxane ring contains one SiH unit, that is there is at least one (R2HSiOo.s ), (RHSiO), or a (HSiOi. s) siloxy unit present in the ring. These siloxy units can be represented as MH, DH, and TH siloxy units respectively when R is methyl.
[0010] The cyclosiloxane rings of A) the organohydrogensiloxane are linked together by a divalent organic or siloxane group, or combination thereof. The divalent linking group may be designated as Y and the cyclosiloxane as G. Thus, the organohydrogensiloxane of the present invention may be represented by the general formula G-[Y-G]α , where G is a cyclosiloxane as described above and Y is a divalent organic, a siloxane, a polyoxyalkylene group, or combination thereof, and the subscript a is greater than zero. [0011] When Y is a divalent organic, it may be a divalent hydrocarbon containing 1 to 30 carbons, either as aliphatic or aromatic structures, and may be branched or un-branched. Alternatively, Y can be an alkylene group containing 2 to 20 carbons, or alternatively containing 4 to 12 carbons. [0012] When Y is a divalent organic, it may also be selected from an organic polymer, such as a polyoxyalkylene group.
[0013] When Y is a siloxane group it may be selected from any organopolysiloxane containing at least two divalent hydrocarbon groups, designated as R1. Thus, the siloxane linking group can be any organopolysiloxane comprising at least two siloxane units represented by the average formula R1
Figure imgf000005_0001
wherein
R is an organic group, R1 is a divalent hydrocarbon, and m is zero to 3 The R1 group may be present on any mono, di, or tri-siloxy unit in an organopolysiloxane molecule, for example; (R1R2SiOo^), (R1RSiO), or (R1SiOi-S), as well as in combination with other siloxy units not containing an R1 substituent, such as (R3S1O0.5 ), (R2SiO), (RSiO 1.5), or (Siθ2) siloxy units where R is independently any organic group providing there are at least two R1 substituents in the organopolysiloxane. Representative R1 groups include; ethylene, propylene, butylene, isobutylene, hexylene, and similar homologs. Alternatively, R1 is ethylene.
[0014] Representative, non-limiting, examples of such siloxane based structures suitable as siloxane linking groups include; (R2R1SiOoS)(R2SiO)x(R2R1SiOo5 )
(R3SiO05)(R2SiO)x(R1RSiO)x(R3SiOo5 )
(R3SiOo5)(R2SiO)x(R1RSiO)J(RSiO1 5)Z(RaSiOo5)
where x > 0, y > 2, and z is > 0
[0015] Organohydrogensiloxane having at least two SiH containing cyclosiloxane rings (component A) may be prepared via a hydrosilylation reaction of a) an organohydrogencyclosiloxane having at least two SiH units on the siloxane ring and,
B) a compound or mixture of compounds having at least two aliphatic unsaturated groups in its molecule.
The organohydrogencyclosiloxane (a) having at least two SiH units on the siloxane ring may contain any number of siloxy units (as defined above) provided there are at least two SiH units on the cyclosiloxane ring. For example, the cyclic siloxane can comprise any number of M, MH, D, DH, or TH siloxy units. Representative, non-limiting examples of such organohydrogencyclosiloxanes useful to prepare component (A) have the average formula DH aDb where a is > 1 and b is > 0, and a + b >3. Alternatively, the organohydrogencyclosiloxane may be selected from those having the formula [(CH3)HSiO]g where g is 3 — 8, such as DH4 , DH 51 DH 6 , or mixtures thereof. [0016] Suitable compounds containing at least two aliphatic unsaturated hydrocarbon groups in its molecule are described below as component B).
[0017] Hydrosilylation reactions involving organohydrogensiloxanes and unsaturated compounds are well known. Any suitable hydrosilylation catalysts know in the art may be used, or alternatively may be selected from those described below as component C). Any of the known hydrosilylation techniques and reactions may be employed to prepare component A) from i) organohydrogencyclosiloxane having at least two SiH units on the siloxane ring and, B) a compound or mixture of compounds having at least two aliphatic unsaturated groups in its molecule. However, the reaction is conducted in such a manner to provide an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule.
[0018] Thus, component A of the present invention contains at least two silicon-bonded hydrogen atom per molecule, alternatively at least 4 silicon-bonded hydrogen atoms per molecule, or alternatively at least 6 silicon-bonded hydrogen atoms per molecule. This can be accomplished by using in the hydrosilylation reaction a molar excess of the a) the organohydrogencyclosiloxane having at least two SiH units on the siloxane ring vs. the compound containing at least two aliphatic unsaturated groups in its molecule. The molar excess may be expressed as the molar ratio of SiH units to unsaturated group, such ratio may range from 2/1 to 8/1, alternatively from 2/1 to 6/1, or alternatively from 3/1 to 4/1.
[0019] Alternatively, the organohydrogensiloxane useful as component A) may be selected from any of the organohydrogensiloxanes taught in WO03/093349, which is herein incorporated by reference for its teaching of suitable organohydrogensiloxanes. [0020] The organohydrogensiloxane useful as component A) in the present invention typically have a viscosity from 5 to 50,000 mPa-s, alternatively from 10 to 10,000 mPa-s, or alternatively from 25 to 2,000 mPa-s. [0021] Representative, non-limiting examples of component A) include;
Figure imgf000008_0001
Figure imgf000008_0002
[0022] Additives known as inhibitors or stabilizers may be added to component A). Inhibitors such as those described in WO 03/093369 may be added for the purpose of stabilizing component A) during storage, or prior to the addition of component B) to prepare the silicone elastomer gel. The inhibitor may be selected from any compound known to have inhibiting effects of platinum based hydrosilylation reactions. Examples of known inhibitors include triphenyl phosphate, tocopherol (vitamin E), and butylated hydroxy toluene. A particularly preferred inhibitor is vitamin A palmitate, or VAP. When VAP is used, it is typically added at 0.05 to 2.0 parts per 100 parts of component A). (B) The Compound or mixture of compounds having at least two aliphatic unsaturated hydrocarbon STOUΌS in its molecule
[0023] Component (B) is a compound, or any mixture of compounds, containing at least two aliphatic unsaturated groups in its molecule. The compound may be any diene, diyne or ene- yne compound. Diene, diyne or ene-yne compounds are those compounds (including polymeric compounds) wherein there are at least two aliphatic unsaturated groups with some separation between the groups within the molecule. Typically, the unsaturation groups are at the termini of the compound, or pendant if part of a polymeric compound. Compounds containing terminal or pendant unsaturated groups can be represented by the formula R2- Y-R2 where R2 is a monovalent unsaturated aliphatic hydrocarbon group containing 2 to 12 carbon atoms, and Y is a divalent organic or siloxane group or a combination of these. Typically R2 is CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=C(CH3)CH2- or CHsC-, and similar substituted unsaturated groups such as H2C=C(CH3) -, and HC≡C(CH3)-.
[0024] The compound having the formula R2- Y-R2 as component B) may be considered as being a "organic", "hydrocarbon", "organic polymer", "polyether" or "siloxane", or combinations thereof, depending on the selection of Y. Y may be a divalent hydrocarbon, a siloxane, a polyoxyalkylene, a polyalkylene, a polyisoalkylene, a hydrocarbon-silicone copolymer, or mixtures thereof.
[0025] In one embodiment, the component (B) is selected from an organic compound, herein denoted as (B1), having the formula R2- Y1- R2 where R2 is a monovalent unsaturated aliphatic group containing 2 to 12 carbon atoms and Y1 is a divalent hydrocarbon,. The divalent hydrocarbon Y1 may contain 1 to 30 carbons, either as aliphatic or aromatic structures, and may be branched or un-branched. Alternatively, the linking group Y1 in B1 may be an alkylene group containing 1 to 12 carbons. Component (B1) may be selected from α, ω - unsaturated alkenes or alkynes containing 1 to 30 carbons, and mixtures thereof. Component (B1) may be exemplified by, but not limited to 1,4-pentadiene, 1 ,5-hexadiene; 1,6-heptadiene; 1 ,7-octadiene, 1 ,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13- tetradecadiene, and 1,19-eicosadiene, 1,3-butadiyne, 1, 5-hexadiyne (dipropargyl), and 1- hexene-5-yne. [0026] In another embodiment, the component (B) is selected from a R2- Y2- R2 compound where Y2 is a siloxane, herein denoted as (B2). The Y2 siloxane group may be selected from any organopolysiloxane bonded to at least two organic groups having aliphatic unsaturation, designated as R2, to form R2- Y2- R2 structures. Thus, component (B2) can be any organopolysiloxane, and mixtures thereof, comprising at least two siloxane units represented by the average formula R2 RmSiO(4-mV2 wherein
R is an organic group,
R2 is a monovalent unsaturated aliphatic group as defined above, and m is zero to 3
[0027] The R2 group may be present on any mono, di, or tri siloxy unit in an organopolysiloxane molecule, for example; (R2R2SiO05 ), (R2RSiO), or (R2SiOi.5); as well as in combination with other siloxy units not containing an R2 substituent, such as (R3S1O0.5 ), (R2SiO), (RSiOi 5), or (Siθ2) siloxy units where R is independently any organic group, alternatively a hydrocarbon containing 1 to 30 carbons, alternatively an alkyl group containing 1 to 30 carbons, or alternatively methyl; providing there are at least two R2 substituents in the organopolysiloxane.
[0028] Representative, non-limiting, examples of such siloxane based R2- Y2- R2 structures suitable as component (B2) include; (R2R2SiOc5 XSiO2Xv(R2R2SiOa5 )
(R2R2SiO05 ) (SiO2)W(R2SiO)x(R2R2SiOo5 ) (R2R2SiO05 )(R2SiO)χ(R2R2SiOo.5 ) (R3SiO05 )(R2SiO)x(R2RSiO)y(R3SiO0.5 ) (R3SiO05 )(R2SiO)x(R2RSiO)y(RSiOi sMRsSiOos ) (R3SiO05 )(R2SiO)x(R2RSiO)y(Siθ2)w(R3SiOo.5 ) where w > 0, x > 0, y > 2, and z is > 0, R is an organic group, and R2 is a monovalent unsaturated aliphatic hydrocarbon group.
[0029] B2 may be selected from vinyl functional polydimethylsiloxanes (vinyl siloxanes) or hexenyl functional polydimethylsiloxanes (hexenyl siloxanes), such as those having the average formula;
CH2=CH(Me)2SiO[Me 3SiO]xSi(Me)2CH=CH2 CH2=CH-(CH2)4-(Me)2SiO[Me2SiO]χSi(Me)2-(CH2)4-CH=CH2 Me 3SiO[(Me)2SiO]x[CH2=CH(Me)SiO]y SiMe 3 wherein Me is methyl, x > 0, alternatively x is 0 to 200, alternatively x is 10 to 150, y > 2, alternatively y is 2 to 50, alternatively y is 2 to 10. Vinyl functional polydimethylsiloxanes are known, and there are many commercially available. [0030] In another embodiment, component (B) is selected from a polyether compound, herein denoted as (B3), having the formula R2- Y3- R2 compound where R2 is as defined above and Y3 is a polyoxyalkylene group having the formula (CnH2nO)b wherein n is from 2 to 4 inclusive, b is greater than 2, alternatively b can range from 2 to 200, or alternatively b can range from 2 to 100.
The polyoxyalkylene group typically can comprise oxyethylene units (C2H4O), oxypropylene units (C3H6O), oxybutylene or oxytetramethylene units (C4H8O), or mixtures thereof. Thus, the R2- Y3- R2 compound may be selected from a polyoxyalkylene group having the formula R2-[(C2H_jO)c (C3H6OX1 (C4H8O)6 ]-R2 where c, d, and e may each independently range from 0 to 200, providing the sum of c + d + e is greater than 2, alternatively the sum of c + d + e ranges from 2 to 200, or alternatively the sum of c + d + e ranges from 2 to 100. [0031] Alternatively, the polyoxyalkylene group comprises only oxypropylene units (C3H6θ)d. Representative, non-limiting examples of poly oxypropylene containing R2- Y3- R2 compounds include;
H2C=CHCH2[C3H6O]dCH2CH=CH2 H2C=CH[C3H6θ]dCH=CH2 H2C=C(CH3)CH2[C3H6O]dCH2C(CH3)=CH2 HC≡CCH2[C3H6O]dCH2C≡CH
HC≡CC(CH3)2[C3H6O]dC(CH3)2C≡CH where d is as defined above.
Representative, non-limiting examples of polyoxybutylene or poly(oxytetramethylene) containing R2- Y3- R2 compounds include; H2C=CHCH2[C4H8O]CCH2CH=CH2
H2C=CH[C4H8O]CCH=CH2 H2C=C(CH3)CH2[C4H8O]eCH2C(CH3)=CH2 HC≡CCH2[C4H8O]eCH2C≡CH HC≡CC(CH3)2[C4H8θ]eC(CH3)2C≡CH
Component B) may also be a mixture of various polyethers, i.e. a mixture of B3 components. [0032] In another embodiment, component (B) is selected from a R2- Y4- R2 compound, herein denoted as (B4), where R2 is as defined above and Y4 is a polyalkylene group, selected from C2 to C6 alkylene units or their isomers. One example is polyisobutylene group which is a polymer containing isobutylene unit. The molecular weight of the polyisobutylene group may vary, but typically ranges from 100 to 10,000 g/mole. Representative, non-limiting examples of R2- Y- R2 compounds containing a polyisobutylene group includes those obtained from BASF under the tradename of OPPONOL BV, such as OPPONOL B V 5K, a diallyl terminated polyisobutylene having an average molecular weight of 5000 g/mole. [0033] In yet another embodiment, component (B) is selected from a R2- Y5- R2 compound, herein denoted as (B ), where R is as defined above and Y is a hydrocarbon-silicone copolymer group. The hydrocarbon-silicone copolymer group may have the formula
Figure imgf000012_0001
-
where R1 and R are as defined above; u and v are independently > 1, alternatively u ranges from 1 to 20, alternatively v ranges from 2 to 500, or from 2 to 200, q is >1, alternatively q ranges from 2 to 500, alternatively q ranges from 2 to 100.
R2- Y5- R2 compounds having a hydrocarbon-silicone copolymer group may be prepared via a hydrosilylation reaction between an α-ω unsaturated hydrocarbon, such as those described above as B1, and an organohydrogensiloxane. A representative, non-limiting example of such a reaction is shown below.
Figure imgf000012_0002
1,5-Hexadiene Tetramethyldisiloxane (TMDS)
Figure imgf000013_0001
[0034] Component (B) may also be a mixture of any diene, diyne or ene-yne compound, such as any combinations of B1, B2 , B3 , B4 , and B5.
[0035] The amounts of component (A) and component (B) used to prepare the present composition will depend on the individual components and the desired SiH to aliphatic unsaturation ratio. The ratio of SiH in component (A) to aliphatic unsaturation from component (B) useful to prepare the compositions of the present invention can be from 10:1 to 1 :10, alternatively 5:1 to 1:5, or alternatively 4:1 to 1:4.
[0036] If components (A) and (B) are not the only materials containing aliphatic unsaturated groups and SiH-containing groups in the present composition, then the above ratios relate to the total amount of such groups present in the composition rather than only those components.
(C) The Hvdrosilylation Catalyst
[0037] Component (C) comprises any catalyst typically employed for hydrosilylation reactions. It is preferred to use platinum group metal-containing catalysts. By platinum group it is meant ruthenium, rhodium, palladium, osmium, indium and platinum and complexes thereof. Platinum group metal-containing catalysts useful in preparing the compositions of the present invention are the platinum complexes prepared as described by Willing, U. S. Pat.
No. 3,419,593, and Brown et al, U. S. Pat. No. 5,175,325, each of which is hereby incorporated by reference to show such complexes and their preparation. Other examples of useful platinum group metal-containing catalysts can be found in Lee et al., U. S. Pat. No.
3,989,668; Chang et al., U. S. Pat. No. 5,036,117; Ashby, U. S. Pat. No. 3,159,601;
Lamoreaux, U. S. Pat. No. 3,220,972; Chalk et al., U. S. Pat. No. 3,296,291; Modic, U. S.
Pat. No. 3,516,946; Karstedt, U. S. Pat. No. 3,814,730; and Chandra et al., U. S. Pat. No. 3,928,629 all of which are hereby incorporated by reference to show useful platinum group metal-containing catalysts and methods for their preparation. The platinum-containing catalyst can be platinum metal, platinum metal deposited on a carrier such as silica gel or powdered charcoal, or a compound or complex of a platinum group metal. Preferred platinum-containing catalysts include chloroplatinic acid, either in hexahydrate form or anhydrous form, and or a platinum-containing catalyst which is obtained by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound such as divinyltetramethyldisiloxane, or alkene-platinum-silyl complexes as described in U.S. Patent Application No. 10/017229, filed December 7, 2001, such as (COD)Pt(SiMeCl2)2> where COD is 1 ,5-cyclooctadiene and Me is methyl. These alkene- platinum-silyl complexes may be prepared, for example by mixing 0.015 mole (COD)PtC_2 with 0.045 mole COD and 0.0612 moles HMeSiC^.
[0038] The appropriate amount of the catalyst will depend upon the particular catalyst used. The platinum catalyst should be present in an amount sufficient to provide at least 2 parts per million (ppm), preferably 4 to 200 ppm of platinum based on total weight percent solids (all non-solvent ingredients) in the composition. It is highly preferred that the platinum is present in an amount sufficient to provide 4 to 150 weight ppm of platinum on the same basis. The catalyst may be added as a single species or as a mixture of two or more different species.
(D) The Carrier Fluid
[0039] The silicone elastomers may be contained in an optional carrier fluid (D). Although it is not required, typically the carrier fluid may be the same as the solvent used for conducting the hydrosilylation reaction as described above. Suitable carrier fluids include silicones, both linear and cyclic, organic oils, organic solvents and mixtures of these. Specific examples of solvents may be found in U.S. Patent No. 6,200,581, which is hereby incorporated by reference for this purpose.
[0040] Typically, the carrier fluid is a low viscosity silicone or a volatile methyl siloxane or a volatile ethyl siloxane or a volatile methyl ethyl siloxane having a viscosity at 25°C in the range of 1 to 1,000 mm2/sec such as hexamethylcyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadeamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-
S^.bislCtrimethylsilyOoxyltrisiloxane pentamethyll^methylsilyl^xylcyclotrisiloxane as well as polydimethylsiloxanes, polyethylsiloxanes, polymethylethylsiloxanes, polymethylphenylsiloxanes, polydiphenylsiloxanes. [0041] Organic solvents may be exemplified by, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides and aromatic halides. Hydrocarbons including isododecane, isohexadecane, Isopar L ( CI l-C 13 ), Isopar H ( C11- C12 ), hydrogentated polydecen. Ethers and esters including isodecyl neopentanoate, neopentylglycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n butyl ether, ethyl- 3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methylether acetate (PGMEA), propylene glycol methylether (PGME). octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, and octyl palmitate. Additional organic carrier fluids suitable as a stand alone compound or as an ingredient to the carrier fluid include fats, oils, fatty acids, and fatty alcohols.
[0042] The amount of carrier fluid is such that there is 0 to 98 weight percent, alternatively 0.5 to 90 weight percent, alternatively 5 to 80 weight percent, of carrier fluid in composition containing (A) and (B) and (D), where the sum of (A), (B), and (D) is 100 weight percent.
E) Personal or Healthcare Active
[0043] Component E) is active selected from any personal or health care active. As used herein, a "personal care active" means any compound or mixtures of compounds that are known in the art as additives in the personal care formulations that are typically added for the purpose of treating hair or skin to provide a cosmetic and/or aesthetic benefit. A "healthcare active" means any compound or mixtures of compounds that are known in the art to provide a pharmaceutical or medical benefit. Thus, "healthcare active" include materials consider as an active ingredient or active drug ingredient as generally used and defined by the United States Department of Health & Human Services Food and Drug Administration, contained in Title 21, Chapter I, of the Code of Federal Regulations, Parts 200-299 and Parts 300-499. [0044] Thus, active ingredient can include any component that is intended to furnish pharmacological activity or other direct effect in the diagnosis, cure, mitigation, treatment, or prevention of disease, or to affect the structure or any function of the body of a human or other animals. The phrase can include those components that may undergo chemical change in the manufacture of drug products and be present in drug products in a modified form intended to furnish the specified activity or effect. [0045] Some representative examples of active ingredients include; drugs, vitamins, minerals; hormones; topical antimicrobial agents such as antibiotic active ingredients, antifungal active ingredients for the treatment of athlete's foot, jock itch, or ringworm, and acne active ingredients; astringent active ingredients; deodorant active ingredients; wart remover active ingredients; corn and callus remover active ingredients; pediculicide active ingredients for the treatment of head, pubic (crab), and body lice; active ingredients for the control of dandruff, seborrheic dermatitis, or psoriasis; and sunburn prevention and treatment agents.
[0046] Useful active ingredients for use in processes according to the invention include vitamins and its derivatives, including "pro-vitamins". Vitamins useful herein include, but are not limited to, Vitamin Aj, retinol, C2-C18 esters of retinol, vitamin E, tocopherol, esters of vitamin E, and mixtures thereof. Retinol includes trans-retinol, 1, 3-cis-retinol, 11-cis-retinol, 9-cis-retinol, and 3,4-didehydro-retinol, Vitamin C and its derivatives, Vitamin Bj, Vitamin
B2, Pro Vitamin B5, panthenol, Vitamin Bg, Vitamin Bj2, niacin, folic acid, biotin, and pantothenic acid. Other suitable vitamins and the INCI names for the vitamins considered included herein are ascorbyl dipalmitate, ascorbyl methylsilanol pectinate, ascorbyl palmitate, ascorbyl stearate, ascorbyl glucocide, sodium ascorbyl phosphate, sodium ascorbate, disodium ascorbyl sulfate, potassium (ascorbyl / tocopherol) phosphate. [0047] RETINOL, it should be noted, is an International Nomenclature Cosmetic Ingredient Name (INCI) designated by The Cosmetic, Toiletry, and Fragrance Association (CTFA), Washington DC, for vitamin A. Other suitable vitamins and the INCI names for the vitamins considered included herein are RETINYL ACETATE, RETINYL PALMITATE, RETINYL PROPIONATE, α-TOCOPHEROL, TOCOPHERSOLAN, TOCOPHERYL ACETATE, TOCOPHERYL LINOLEATE, TOCOPHERYL NICOTINATE, and TOCOPHERYL SUCCINATE. [0048] Some examples of commercially available products suitable for use herein are
Vitamin A Acetate and Vitamin C, both products of Fluka Chemie AG, Buchs, Switzerland; COVI-OX T-50, a vitamin E product of Henkel Corporation, La Grange, Illinois; COVI-OX T-70, another vitamin E product of Henkel Corporation, La Grange, Illinois; and vitamin E Acetate, a product of Roche Vitamins & Fine Chemicals, Nutley, New Jersey. [0049] The active ingredient used in processes according to the invention can be an active drug ingredient. Representative examples of some suitable active drug ingredients which can be used are hydrocortisone, ketoprofen, timolol, pilocarpine, adriamycin, mitomycin C, morphine, hydromorphone, diltiazem, theophylline, doxorubicin, daunorubicin, heparin, penicillin G, carbenicillin, cephalothin, cefoxitin, cefotaxime, 5-fluorouracil, cytarabine, 6- azauridine, 6-thioguanine, vinblastine, vincristine, bleomycin sulfate, aurothioglucose, suramin, mebendazole, clonidine, scopolamine, propranolol, phenylpropanolamine hydrochloride, ouabain, atropine, haloperidol, isosorbide, nitroglycerin, ibuprofen, ubiquinones, indomethacin, prostaglandins, naproxen, salbutamol, guanabenz, labetalol, pheniramine, metrifonate, and steroids. [0050] Considered to be included herein as active drug ingredients for purposes of the present invention are antiacne agents such as benzoyl peroxide and tretinoin; antibacterial agents such as chlorohexadiene gluconate; antifungal agents such as miconazole nitrate; antiinflammatory agents; corticosteroidal drugs; non-steroidal anti-inflammatory agents such as diclofenac; antipsoriasis agents such as clobetasol propionate; anesthetic agents such as lidocaine; antipruritic agents; antidermatitis agents; and agents generally considered barrier films.
[0051] The active component E) of the present invention can be a protein, such as an ' enzyme. The internal inclusion of enzymes in the silicone elastomer gel have advantages to prevent enzymes from deactivating and maintain bioactive effects of enzymes for longer time. Enzymes include, but are not limited to, commercially available types, improved types, recombinant types, wild types, variants not found in nature, and mixtures thereof. For example, suitable enzymes include hydrolases, cutinases, oxidases, transferases, reductases, hemicellulases, esterases, isomerases, pectinases, lactases, peroxidases, laccases, catalases, and mixtures thereof. Hydrolases include, but are not limited to, proteases (bacterial, fungal, acid, neutral or alkaline), amylases (alpha or beta), lipases, mannanases, cellulases, collagenases, lisozymes, superoxide dismutase, catalase, and mixtures thereof.
Said protease include, but are not limited to, trypsin, chymotrypsin, pepsin, pancreatin and other mammalian enzymes; papain, bromelain and other botanical enzymes; subtilisin, epidermin, nisin, naringinase(L-rhammnosidase) urokinase and other bacterial enzymes. Said lipase include, but are not limited to, triacyl-glycerol lipases, monoacyl-glycerol lipases, lipoprotein lipases, e.g. steapsin, erepsin, pepsin, other mammalian, botanical, bacterial lipases and purified ones. Natural papain is preferred as said enzyme. Further, stimulating hormones, e.g. insulin, can be used together with these enzymes to boost the effectiveness of them.
[0052] Component E) may also be a sunscreen agent. The sunscreen agent can be selected from any sunscreen agent known in the art to protect skin from the harmful effects of exposure to sunlight. The sunscreen compound is typically chosen from an organic compound, an inorganic compound, or mixtures thereof that absorbs ultraviolet (UV) light. Thus, representative non limiting examples that can be used as the sunscreen agent include; Aminobenzoic Acid, Cinoxate, Diethanolamine Methoxycinnamate, Digalloyl Trioleate, Dioxybenzone, Ethyl 4-[bis(Hydroxypropyl)] Aminobenzoate, Glyceryl Aminobenzoate, Homosalate, Lawsone with Dihydroxyacetone, Menthyl Anthranilate, Octocrylene, Octyl Methoxycinnamate, Octyl Salicylate, Oxybenzone, Padimate O, Phenylbenzimidazole
Sulfonic Acid, Red Petrolatum, Sulisobenzone, Titanium Dioxide, and Trolamine Salicylate, cetaminosalol, Allatoin PABA, Benzalphthalide, Benzophenone, Benzophenone 1-12, 3- Benzylidene Camphor, Benzylidenecamphor Hydrolyzed Collagen Sulfonamide, Benzylidene Camphor Sulfonic Acid, Benzyl Salicylate, Bornelone, Bumetriozole, Butyl Methoxydibenzoylmethane, Butyl PABA, Ceria/Silica, Ceria/Silica Talc, Cinoxate, DEA- Methoxycinnamate, Dibenzoxazol Naphthalene, Di-t-Butyl Hydroxybenzylidene Camphor, Digalloyl Trioleate, Diisopropyl Methyl Cinnamate, Dimethyl PABA Ethyl Cetearyldimonium Tosylate, Dioctyl Butamido Triazone, Diphenyl Carbomethoxy Acetoxy Naphthopyran, Disodium Bisethylphenyl Tiamminotriazine Stilbenedisulfonate, Disodium Distyrylbiphenyl Triaminotriazine Stilbenedisulfonate, Disodium Distyrylbiphenyl
Disulfonate, Drometrizole, Drometrizole Trisiloxane, Ethyl Dihydroxypropyl PABA, Ethyl Diisopropylcinnamate, Ethyl Methoxycinnamate, Ethyl PABA, Ethyl Urocanate, Etrocrylene Ferulic Acid, Glyceryl Octanoate Dimethoxycinnamate, Glyceryl PABA, Glycol Salicylate, Homosalate, Isoamyl p-Methoxycinnamate, Isopropylbenzyl Salicylate, Isopropyl Dibenzolylmethane, Isopropyl Methoxycinnamate, Menthyl Anthranilate, Menthyl Salicylate, 4-Methylbenzylidene, Camphor, Octocrylene, Octrizole, Octyl Dimethyl PABA, Octyl Methoxycinnamate, Octyl Salicylate, Octyl Triazone, PABA, PEG-25 PABA, Pentyl Dimethyl PABA, Phenylbenzimidazole Sulfonic Acid, Polyacrylamidomethyl Benzylidene Camphor, Potassium Methoxycinnamate, Potassium Phenylbenzimidazole Sulfonate, Red Petrolatum, Sodium Phenylbenzimidazole Sulfonate, Sodium Urocanate, TEA- Phenylbenzimidazole Sulfonate, TEA-Salicylate, Terephthalylidene Dicamphor Sulfonic Acid, Titanium Dioxide, Zinc Dioxide, Serium Dioxide, TriPABA Panthenol, Urocanic Acid, and VA/Crotonates/Methacryloxybenzophenone-1 Copolymer. [0053] The sunscreen agent can be a single one or combination of more than one. Alternatively, the sunscreen agent is a cinnamate based organic compound, or alternatively, the sunscreen agent is octyl methoxycinnamate, such as Uvinul® MC 80 an ester of para- methoxycinnamic acid and 2-ethylhexanol.
[0054] Component E) may also be a fragrance or perfume. The perfume can be any perfume or fragrance active ingredient commonly used in the perfume industry. These compositions typically belong to a variety of chemical classes, as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitrites, terpenic hydrocarbons, heterocyclic nitrogen or sulfur containing compounds, as well as essential oils of natural or synthetic origin. Many of these perfume ingredients are described in detail in standard textbook references such as Perfume and Flavour Chemicals, 1969, S. Arctander, Montclair, New Jersey. [0055] Fragrances may be exemplified by, but not limited to, perfume ketones and perfume aldehydes. Illustrative of the perfume ketones are buccoxime; iso jasmone; methyl beta naphthyl ketone; musk indanone; tonalid/musk plus; Alpha-Damascone, Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose, Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone, Alpha-lonone, Beta-lonone, Gamma-Methyl so- called lonone, Fleuramone, Dihydrojasmone, Cis-Jasmone, Iso-E-Super, Methyl-Cedrenyl- ketone or Methyl- Cedrylone, Acetophenone, Methyl-Acetophenone, Para-Methoxy- Acetophenone, Methyl-Beta-Naphtyl-Ketone, Benzyl-Acetone, Benzophenone, Para- Hydroxy-Phenyl-Butanone, Celery Ketone or Livescone, 6-Isopropyldecahydro-2-naphtone, Dimethyl-Octenone, Freskomenthe, 4-( 1 -Ethoxyvinyl)-3,3,5,5,-tetramethyl-Cyclohexanone, Methyl-Heptenone, 2-(2-(4-Methyl-3-cyclohexen-l-yl)propyl)-cyclopentanone, l-(p- Menthen-6(2)-yl)- 1 -propanone, 4-(4-Hydroxy-3 -methoxyphenyl)-2-butanone, 2-Acetyl-3,3- Dimethyl-Norbomane, 6,7-Dihydro-l,l,2,3,3-Pentamethyl-4(5H)-Indanone, 4-Damascol, Dulcinyl or Cassione, Gelsone, Hexalon, Isocyclemone E, Methyl Cyclocitrone, Methyl- Lavender-Ketone, Orivon, Para-tertiary-Butyl-Cyclohexanone, Verdone, Delphone, Muscone, Neobutenone, Plicatone, Veloutone, 2,4,4,7-Tetramethyl-oct-6-en-3-one, and Tetrameran.
[0056] More preferably, the perfume ketones are selected for its odor character from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-lonone, Iso-E-
Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate, methyl cedrylone, and mixtures thereof. [0057] Preferably, the perfume aldehyde is selected for its odor character from adoxal; anisic aldehyde; cymal; ethyl vanillin; florhydral; helional; heliotropin; hydroxycitronellal; koavone; lauric aldehyde; lyral; methyl nonyl acetaldehyde; P. T. bucinal; phenyl acetaldehyde; undecylenic aldehyde; vanillin; 2,6,10-trimethyl-9-undecenal, 3-dodecen-l-al, alpha-n-amyl cinnamic aldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3-(4-tert butylphenyl)-propanal, 2-methyl-3-(para-methoxyphenyl propanal, 2-methyl-4-(2,6,6- trimethyl-2(l)-cyclohexen-l-yl) butanal, 3-phenyl-2-propenal, cis-/trans-3,7-dimethyl-2,6- octadien-1-al, 3,7-dimethyl-6-octen-l-al, [(3,7-dimethyl-6-octenyl)oxy] acetaldehyde, 4- isopropylbenzyaldehyde, l,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde , 2,4- dimethyl-3-cyclohexen-l-carboxaldehyde, 2-methyl-3-(isopropylphenyl)propanal, 1-decanal; decyl aldehyde, 2,6-dimethyl-5-heptenal, 4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal, octahydro-4,7-methano-lH- indenecarboxaldehyde, 3-ethoxy-4-hydroxy benzaldehyde, para- ethyl-alpha, alpha-dimethyl hydrocinnamaldehyde, alpha-methyl-3,4-(methylenedioxy)- hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic aldehyde, m-cymene-7-carboxaldehyde, alpha-methyl phenyl acetaldehyde, 7-hydroxy-3,7-dimethyl octanal, Undecenal, 2,4,6-trimethyl-3-cyclohexene-l-carboxaldehyde, 4-(3)(4-methyl-3- pentenyl)-3-cyclohexen-carboxaldehyde, 1-dodecanal, 2,4-dimethyl cyclohexene-3- carboxaldehyde, 4-(4-hydroxy-4-methyl pentyl)-3 -cylohexene- 1 -carboxaldehyde, 7-methoxy- 3,7-dimethyloctan-l-al, 2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal, 2,6,10- trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl)propanal, dihydrocinnamic aldehyde, 1- methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-l-carbox aldehyde, 5 or 6 methoxyl 0 hexahydro-4,7-methanoindan-l or 2- carboxaldehyde, 3,7-dimethyloctan-l-al, 1 -undecanal, 10-undecen-l-al, 4-hydroxy-3-methoxy benzaldehyde, l-methyl-3-(4-methylpentyl)-3- cyclhexenecarboxaldehyde, 7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, paratolylacetaldehyde; 4-methylphenylacetaldehyde, 2-methyl-4-(2,6,6-trimethyl-l- cyclohexen-l-yl)-2-butena 1, ortho-methoxycinnamic aldehyde, 3,5,6-trimethyl-3- cyclohexene carboxaldehyde, S.T-dimethyl^-methylene-ό-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, peony aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-l-al), hexahydro-4,7-methanoindan- 1 -carboxaldehyde, 2-methyl octanal, alpha-methyl-4-(l -methyl ethyl) benzene acetaldehyde, 6,6-dimethyl-2-norpinene-2- propionaldehyde, para methyl phenoxy acetaldehyde, 2-methyl-3-phenyl-2-propen-l-al, 3,5,5-trimethyl hexanal, Hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo[2.2.1]- hept-5-ene-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-l-pentanal, methylnonyl acetaldehyde, hexanal, trans-2-hexenal, 1-p-menthene-q-carboxaldehyde and mixtures thereof.
[0058] More preferred aldehydes are selected for their odor character from 1 -decanal, benzaldehyde, florhydral, 2,4-dimethyl-3-cyclohexen-l -carboxaldehyde; cis/trans-3,7- dimethyl-2,6-octadien-l -al; heliotropin; 2,4,6-trimethyl-3-cyclohexene-l -carboxaldehyde; 2,6-nonadienal; alpha-n-ainyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal, trans-2-hexenal, and mixture thereof.
[0059] In the above list of perfume ingredients, some are commercial names conventionally known to one skilled in the art, and also includes isomers. Such isomers are also suitable for use in the present invention. [0060] Component E) may also be one or more plant extract. Examples of these components are as follows: Ashitaba extract, avocado extract, hydrangea extract, Althea extract, Arnica extract, aloe extract, apricot extract, apricot kernel extract, Ginkgo Biloba extract, fennel extract, turmeric [Curcuma] extract, oolong tea extract, rose fruit extract, Echinacea extract, Scutellaria root extract, Phellodendro bark extract, Japanese Coptis extract, Barley extract, Hyperium extract, White Nettle extract, Watercress extract, Orange extract, Dehydrated saltwater, seaweed extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, Chamomile extract, Carrot extract, Artemisia extract, Glycyrrhiza extract, hibiscustea extract, Pyracantha Fortuneana Fruit extract, Kiwi extract, Cinchona extract, cucumber extract, guanocine, Gardenia extract, Sasa Albo-marginata extract, Sophora root extract, Walnut extract, Grapefruit extract, Clematis extract, Chlorella extract, mulberry extract, Gentiana extract, black tea extract, yeast extract, burdock extract, rice bran ferment extract, rice germ oil, comfrey extract, collagen, cowberry extract, Gardenia extract, Asiasarum Root extract, Family of Bupleunim extract, umbilical cord extract, Salvia extract, Saponaria extract, Bamboo extract, Crataegus fruit extract, Zanthoxylum fruit extract, shiitake extract, Rehmannia root extract, gromwell extract, Perilla extract, linden extract, Filipendula extract, peony extract, Calamus Root extract, white birch extract, Horsetail extract,Hedera Helix(Ivy) extract, hawthorn extract, Sambucus nigra extract, Achillea millefolium extract, Mentha piperita extract, sage extract, mallow extract, Cnidium officinale Root extract, Japanese green gentian extract, soybean extract, jujube extract, thyme extract, tea extract, clove extract, Gramineae imperata cyrillo extract, Citrus unshiu peel extract Japanese Angellica Root extract, Calendula extract, Peach Kernel extract, Bitter orange peel extract, Houttuyna cordata extract, tomato extract, natto extract, Ginseng extract, Green tea extract (camelliea sinesis), garlic extract, wild rose extract, hibiscus extract, Ophiopogon tuber extarct, Nelumbo nucifera extract, parsley extract, honey, hamamelis extract, Parietaria extract, Isodonis herba extract, bisabolol extract, Loquat extract, coltsfoot extract, butterbur extract, Porid cocos wolf extract, extract of butcher's broom, grape extract, propolis extract, luffa extract, safflower extract, peppermintextract, linden tree extract, Paeonia extract, hop extract, pine tree extract, horse chestnut extract, Mizu-bashou [ Lysichiton camtschatcesejextract, Mukurossi peel extract, Melissa extract, peach extract, cornflower extract, eucalyptus extract, saxifrage extract, citron extract, coix extract, mugwort extract, lavender extract, apple extract, lettuce extract, lemon extract, Chinese milk vetch extract, rose extract, rosemary extract, Roman Chamomile extract, and royal jelly extract.
[0061] The amount of component E) present in the silicone gel composition may vary, but typically range as follows;
.05 to 50 wt%, alternatively 1 to 25 wt %, or alternatively 1 to 10 wt%, based on the amount by weight of silicone elastomer gel present in the composition, that is total weight of components A), B), C) and D) in the silicone gel composition.
[0062] The active, component E), may be added to the silicone gel composition either during the making of the silicone elastomer (pre-load method), or added after the formation of the silicone elastomer gel (post load method). [0063] The pre-load method involves; I) reacting; a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring, B) a compound or mixture of compounds having at least two aliphatic unsaturated hydrocarbon groups in its molecules,
C) a hydrosilylation catalyst, to form
A ) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated hydrocarbon groups of component B) ranges from 2/1 to 8/1, II) reacting;
A ) the organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, with additional quantities of
B) the compound containing at least two aliphatic unsaturated hydrocarbon groups in its molecules, C) the hydrosilylation catalyst, in the presence of
D) an optional carrier fluid, and
E) a personal care or healthcare active, to form the silicone elastomer gel. [0064] The post-load method involves;
I) reacting; a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring, B) a compound or mixture of compounds having at least two aliphatic unsaturated groups in its molecules, C) a hydrosilylation catalyst to form
A ) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated groups of component B) ranges from 2/1 to 8/1,
II) further reacting;
A ) the organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, with additional quantities of
B) the compound containing at least two aliphatic unsaturated groups in its molecules,
C) the hydrosilylation catalyst, in the presence of D) an optional carrier fluid to form a silicone elastomer gel, III) admixing
E) a personal care or healthcare active with the silicone elastomer gel to form the silicone elastomer gel containing active.
The Silicone Elastomer
[0065] The silicone elastomers of the present invention are obtainable as hydrosilylation reaction products of components A), B), and C). The term "hydrosilylation" means the addition of an organosilicon compound containing silicon-bonded hydrogen, (such as component A) to a compound containing aliphatic unsaturation (such as component B), in the presence of a catalyst (such as component C). Hydrosilylation reactions are known in the art, and any such known methods or techniques may be used to effect the hydrosilylation reaction of components A), B), and C) to prepare the silicone elastomers of the present invention.
[0066] The hydrosilylation reaction may be conducted in the presence of a solvent, and the solvent subsequently removed by known techniques. Alternatively, the hydrosilylation may be conducted in a solvent, where the solvent is the same as the carrier fluid described as optional component D).
[0067] Alternatively, the silicone elastomers may be prepared by a process comprising: I) reacting; a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring,
B) a compound or mixture of compounds having at least two aliphatic unsaturated hydrocarbon groups in its molecules,
C) a hydrosilylation catalyst to form A ) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated groups of component B) ranges from 2/1 to 8/1, alternatively from 2/1 to 6/1, or alternatively from 3/1 to 4/1, II) further reacting;
A ) the organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, with additional quantities of B) the compound containing at least two aliphatic unsaturated groups in its molecules,
C) the hydrosilylation catalyst, to form a silicone elastomer.
[0068] Components a, A), B), C) are the same as those described above. Also, the reaction may be conducted under similar conditions as described above. In aforementioned step II) the molar ratio of the SiH units of component A) to the aliphatic unsaturated groups of component B) ranges from 10/1 to 1/10, alternatively from 5/1 to 1/5, or alternatively from 4/1 to 1/4.
Gelled compositions containing the Silicone Elastomer
[0069] The silicone elastomers can be added to a carrier fluid (as described above as component D) to form gelled compositions, or alternatively be prepared first in a separate reaction and then added to the carrier fluid to obtain a gel. The gelled compositions of the present invention may be characterized by their hardness or firmness. Useful tests to characterize the gels are those recommended by the Gelatin Manufacturers Institute of America such as the use of a "Texture Analyzer" (model TA.XT2, Stable Micro Systems, Inc., Godalming, England). The gel sample is subject to a compression test with the Texture Analyzer having a probe with a 5.0 kg load cell. The probe approaches the surface of the gel at a speed of 0.5 mm/sec and continues compression into the gel to a distance of 5.0 mm, then holds for 1 second before retreating. The Texture Analyzer detects the resistance force the probe experiences during the compression test. The force exhibited by the load cell is plotted as a function of time.
[0070] The hardness of the silicone elastomers, gels and elastomer blends (SEBs) for purposes of this invention is defined as the resistance force detected by the probe of the "Texture Analyzer" during the compression test. Two data may used to characterize hardness: Force 1, the force at the maximum compression point (i.e. the 5.0 mm compression point into the gel surface), and Area F-T: the area-force integration during the 1 second hold at the maximum compression point. The average of a total of 5 tests are typically performed for each gel. [0071] The value obtained for Force 1 is converted into Newton (N), by dividing the gram force value by 101.97. (i.e. 1 Newton equals 101.97 g force based on the size of the probe used in this instrument). The second property reported by Texture Analyzer measurement is Area F-T 1 :2, in g force-sec. This is the area integration of the force vs. test time cure. This property is indicative of a gel network since it indicates ability to sustain resistance to the compression force, which is relevant to elastomers and gels. The value is reported in g force-sec, and is converted to Newton-sec in SI unit by dividing the value in g force-sec by
101.97.
[0072] The silicone gels of the present invention has a compression hardness of at least
200 Newton / m , alternatively 400 Newton / m _, or alternatively 600 Newton / m .
Gel Paste compositions containing the Silicone Elastomer
[0073] The gelled compositions of the present invention can be used to prepare gel paste or gel blend compositions containing actives by; I) shearing the silicone elastomer gel, as described above,
II) combining the sheared silicone elastomer gel with additional quantities of
D) the carrier fluid, as described above, and optionally
E) a personal or health care active to form a gel paste or blend composition. [0074] The silicone elastomer gel compositions of the present invention blends may be considered as discrete crosslinked silicone elastomer gel particles dispersed in carrier fluids. Thus, the silicone elastomer compositions are effective rheological thickeners for lower molecular weight silicone fluids. As such they can be used to prepare useful gel blend compositions, such as "paste" compositions.
[0075] To make such silicone elastomer blends, the aforementioned silicone elastomer gels of known initial elastomer content (IEC) are sheared to obtain small particle size and further diluted to a final elastomer content (FEC). "Shearing", as used herein refers to any shear mixing process, such as obtained from homogenizing, sonalating, or any other mixing processes known in the art as shear mixing. The shear mixing of the silicone elastomer gel composition results in a composition having reduced particle size. The subsequent composition having reduced particle size is then further combined with D) the carrier fluid. The carrier fluid may be any carrier fluid as described above, but typically is a volatile methyl siloxane, such as D5. The technique for combining the D) the carrier fluid with the silicone elastomer composition having reduced particle size is not critical, and typically involves simple stirring or mixing. The resulting compositions may be considered as a paste, having a viscosity greater than 100,000 cP (mPa-s).
Examples
[0076] These examples are intended to illustrate the invention to one of ordinary skill in the art and are should not be interpreted as limiting the scope of the invention set forth in the claims.
Materials description
The following materials were used in these examples.
Organohydrogensiloxanes
MeH CYCLICS = methylhydrogen cyclosiloxanes (MeH cyclics) having the formula
[(CH3)HSiO]x where the average value of x is 4.4.
MeH LINEAR = an organohydrogenpolysiloxane have the average formula MTλwD'βM
Siloxane polymers containing unsaturated groups
VINYL SILOXANE #1 = a dimethylvinylsiloxy-terminated dimethylpolysiloxane of the general formula (CH2=CH)(CH3)2SiO[(CH3)2SiO]dpSi(CH3)2(CH=CH2), where the average degree of polymerization (dp) was 8 and having a viscosity of 4 mm2/s at 25°C. VINYL SILOXANE #2 = a dimethylvinylsiloxy-terminated dimethylpolysiloxane of the general formula
(CH2=CH)(CH3)2SiO[(CH3)2SiO]dpSi(CH3)2(CH=CH2), where the average degree of polymerization (dp) was 130 and having a viscosity of 325 mm2/s at 25°C. VINYL SILOXANE #3 = [(CH2=CH)(CH3)2SiO[(CH3)2SiO]3o ]4Si
VINYL SILOXANE #4 = tetramethyltetravinylcyclotetrasiloxane [(CH2=CH)(CH3)SiO]4
VINYL SILOXANE #5 — a dimethylvinylsiloxy-terminated dimethylpolysiloxane of the general formula (CH2=CH)(CH3)2SiO[(CH3)2SiO]dpSi(CH3)2(CH=CH2), where the average degree of polymerization (dp) was 27 and having a viscosity of 25 mm2/s at 25°C.
VINYL SILOXANE #6 = a dimethylhexenylsiloxy-terminated dimethylpolysiloxane of the general formula (CH2=CH(CH2)4)(CH3)2SiO[(CH3)2SiO]dpSi(CH3)2((CH2)4(CH2=CH))> where the average degree of polymerization (dp) was 37 and a viscosity of 40 mm2/s at 25°C. VINYL SILOXANE #7 = a dimethylhexenylsiloxy-terminated dimethylpolysiloxane of the general formula (CH2=CH(CH2)4)(CH3)2SiO[(CH3)2SiO]dpSi(CH3)2((CH2)4(CH2=Cm), where the average degree of polymerization (dp) was 100 and a viscosity of 170 mm /s at 25°C.
VINYL SILOXANE #8 = a dimethylhexenylsiloxy-terminated dimethylpolysiloxane of the general formula (CH2=CH(CH2)4)(CH3)2SiO[(CH3)2SiO]dpSi(CH3)2((CH2)4(CH2=CH)), where the average degree of polymerization (dp) was 200 and a viscosity of 730 mm /s at 25°C.
VINYL SILOXANE #9 = a dimethylvinylsiloxy-terminated dimethylpolysiloxane of the general formula (CH2=CH)(CH3)2SiO[(CH3)2SiO]dPSi(CH3)2(CH=CH2), where the average degree of polymerization (dp) was 27. VINYL SILOXANE #10 = a dimethylvinylsiloxy-terminated dimethylpolysiloxane of the general formula (CH2=CH)(CH3)2SiO[(CH3)2SiO]dpSi(CH3>2(CH=CH2), where the average degree of polymerization (dp) was 430.
Hydrosilylation catalyst
PT CATALYST = SLY-OFF 4000 (Dow Corning Corporation, Midland MI) Pt catalyst used as provided containing 0.52 weight % Pt.
Carrier Fluids
D5 = decamethylcyclopentasiloxane or D5 cyclics, DC245 (Dow Corning Corporation, Midland MI) used as provided.
IDNP = isodecyl neopentanoate obtained from ISP (International Specialty Products Co) under the trade name of CERAPHYL SLK. IDD = isododecane
Stabilizer = Vitamin A palmitate (VAP) and butylated hydroxytoluene (BHT) Methods of Measuring Viscosity of Silicone Elastomer Blends (SEBsI
[0077] The Brookfield Helipath™ Stand, when used with a suitable Brookfield Viscometer fitted with a special T-bar type spindle, will permit viscosity/consistency measurements in centipoise values for materials having characteristics similar to paste, putty, cream, gelatin, or wax.
[0078] The viscosity of silicone elastomer blends was determined using a Brookfield Model RVD-II+ Viscometer with Helipath stand (Brookfield Model D) and T-Bar spindles (Brookfield Helipath Spindle Set). All were purchased from Brookfield Engineering Laboratories, Inc. (11 Commerce Boulevard Middleboro, Massachusetts, USA).
[0079] A sample size of lOOg in a 4 oz. round jar was required. The following preparation procedure was used before measurement: the sample was de-aired first via centrifuge, then vacuum de-aired for two hours. After de-airing, the sample was conditioned for a minimum of 4 hours @ 25° C. The sample was positioned with T-bar spindle at center. The reading was taken according to the typical procedure for Helipath spindle.
[0080] In general, spindle 93 (T-bar spindle C) is used for the less viscous sample, spindle 95 (T-bar spindle E) for the more viscous samples. The standard setting for rpm was 2.5. The spindle speed is maintained at constant 2.5 rpm and spindle was varied to handle samples with significant viscosities.
Measurement of Silicone Elastomer Gel Hardness
The hardness (or firmness) of silicone elastomer gels was characterized using a Texture analyzer (model TA.XT2, Stable Micro Systems, Inc., Godalming, England). The Gelatin Manufacturers Institute of America recommends such test methods as a standard procedure.
For silicone gels and elastomer blends, a Vi inch (1.27 cm) diameter cylindrical probe made of DELRIN acetal resin (Dupont) was used for the measurement. The gel sample is subject to the compression test using the probe with the following test cycle: the probe approaches the surface of the gel at a speed of 0.5 mm/sec and continues compression into the gel to a distance of 5.0 mm, then holds for 1 second before retreating. The Texture Analyzer has a 5.0 Kg load cell to detect the resistance force the probe experiences during the compression test. The force exhibited by the load cell is plotted as a function of time. The hardness of the silicone elastomers, gels and elastomer blends (SEBs) is defined as the resistance force detected by the probe during the compression test. Two data are used for the hardness value: Force 1 : the force at the maximum compression point (i.e. the 5.0 mm compression point into the gel surface), and Area F-T: the area-force integration during the 1 second hold at the maximum compression point. A total of 5 tests were performed for each gel and the average of the five tests is reported.
Texture Analyzer used for gel hardness measurement is force in gram, as detected by the transducer. Two values are reported for gel hardness: Force 1, the force in gram registered when the probe reached its pre-programmed full indentation (or compression) in gel sample. The unit for Force 1 reading is gram force.
The value obtained for Force 1 is converted into Newton (N), by dividing the gram force value by 101.97. (i.e. 1 Newton equals 101.97 g force based on the size of the probe used in this instrument). For instance, a value of 6327 g force converts to 62.0 N. The second property reported by Texture Analyzer measurement is Area F-T 1 :2, in g force-sec. This is the area integration of the force vs. test time cure. This is an indicative property of a gel network as it indicates it ability to sustain resistance to the compression force, which is relevant to elastomers and gels. The value is reported in g force-sec, and is converted to Newton-sec in SI unit by dividing the value in g force-sec by 101.97. For instance, a value of 33,947 g force-sec is 332.9 N s in SI units. Example 1 (reference')
Preparation of an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings with a Short
Spacer between the rings
[0081] Cyclic SiH-containing siloxanes, that is a representative Component A)' s, were made by reacting MeH cyclics with VINYL SILOXANE #1, a dimethyvinyl-ended silicone having on average 8 dimethylsiloxane units (DP = 8), in the presence of Pt catalyst. The specific [SiH] / [Vi] ratio was kept at 3.0, 3.42, and 4.0 for the three examples and the reaction was conducted at 400C. The finished polymers were clear liquids having the general structures shown in
Table 1. The SiH contents of these siloxanes were found to be 0.374%, 0.432%, and 0.505% respectively.
Table 1
Figure imgf000032_0002
Figure imgf000032_0001
Figure imgf000032_0003
Example 2 ("reference)
Preparation of an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings with a Long Spacer
[0082] Cyclic SiH-containing siloxanes (representative component A)) having a linear structure with longer spacer were made by reacting MeH-cyclics with VINYL SILOXANE #2 (DP* = 130) in the presence of a Pt catalyst. The [SiH] / [Vi] ratios were 3.0, 3.42, and 4.0 for the three examples and the reaction was conducted at 400C. The finished SiH siloxanes were clear liquids having the target structures shown in the Table 2. The SiH content were found to be 0.020%, 0.0240%, and 0.0296% respectively. These siloxanes were made in a silicone carrier fluid to reduce the final viscosity.
Table 2
Figure imgf000033_0001
Example 3 (reference)
Preparation of an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings
[0083] Cyclic SiH-containing siloxanes having branched structures were made by reacting MeH cyclics with dimethyvinyl-ended branched silicones or methyvinyl cyclics. Illustrated in the Table 3 are the examples derived from VINYL SILOXANE #3 having about 30 dimethylsiloxane repeat on each of the four branches, yielding a total of about 120 dimethylsiloxane units (DP = 120) in the presence of the Pt catalyst. The [SiH] / [Vi] ratios were kept at 3.42 and 4.0 for the three examples and the reaction was conducted at 400C. Separately, a component A) was made using VINYL SILOXANE #4. The SiH siloxanes were clear liquids having the structures summarized in Table 3. The SiH contents were 0.241 %, 0.290%, and 0.376% respectively.
Table 3. Cyclic SiH siloxane capped, branched organohydrogensiloxanes
Figure imgf000034_0001
Example 4 (reference)
Preparation of an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings
Organohydrogensiloxanes illustrative as component A) were prepared by mixing MeH CYCLICS, VINYL SILOXANES (as listed in Table 4) or 1, 5 hexadiene, and (if used) D5 as a carrier fluid in a reaction flask. Then, the mixture was catalyzed by the addition of 3-5 ppm of Pt (Pt catalyst solution containing 0.52 wt% Pt). The mixture was heated to 500C, causing an exothermic hydrosilylation reaction to occur, the temperature was then maintained between 50 and 700C for 3 hours. The amounts of MeH CYCLICS and the alkenyl compound were calculated to yield a specific [SiH] / [Vi] ratio of 3.42. The resulting organohydrogensiloxanes were clear liquids having the average structures and properties summarized in Table 4.
Table 4
Figure imgf000035_0001
Example 5 (reference)
Preparation of A) organohydrogensiloxanes having at least two SiH containing cyclosiloxane rings
[0084] Additional examples of the cyclic SiH-bearing siloxanes were made as shown below using component B as listed and MeH CYCLICS as component a).
Table 5. Cyclic SiH siloxanes
Figure imgf000036_0001
Example 6
Preparation of Silicone Elastomer Gels from Cyclic SiH Siloxane at Low [SiH] / [Alkenyl] Ratio
[0085] Silicone elastomer gels were prepared by reacting the organohydrogensiloxane having at least two SiH containing cyclosiloxane rings as component (A) and aliphatic unsaturated compound as component (B) at a low [SiH] / [Alkeny] ratio of 0.36. Cyclic SiH siloxane of Example 5F a 40% solids in D5 fluid where the cyclic SiH-containing siloxane made from MeH-CYCLICS and VINYL SILOXANE #1 at a SiH/alkenyl ratio of 3.42, was reacted with VINYL SILOXANE #2 in D5 fluid and in isodecyl neopentanoate (IDNP) hydrocarbon ester solvent. Table 6 summarizes the reactions and subsequent gels produced.
Figure imgf000038_0001
Example 7
Preparation of Silicone Elastomer Gels
[0086] Silicone elastomer gels were made with a low elastomer contents (EC), as illustrated in this example. Silicone elastomer gels (Example 7A and 7C) were made at 3.0 % elastomer composition (the total of components (A) and (B)), and 97 % D5 fluid (component (D)). The siloxane spacer had an average DP (degree of polymerization) of 100 in these examples,
Table 7: Silicone elastomer gels made at low and moderate elastomer contents
#8
Figure imgf000039_0001
Example 8
Silicone Elastomer Gels Made at Low Elastomer Content
[0087] Silicone elastomer gels were prepared with low amounts of elastomer content using cyclic SiH-containing siloxanes of relatively short spacer (i.e. low dp). Illustrated below are the silicone elastomer gels made from the SiH siloxane of Example 4C (8 dp spacer) and Example 4D (27dp spacer). All gels in this example had 5 wt% elastomer content (i.e. total of components (A) and (B)), and 95% D5 fluid (component (C)).
Table 8: Silicone elastomer els made to low elastomer content
Figure imgf000040_0001
Rvffϊϊskl»iϊϋ7ϊiιnf9 iI9wPfnfif!flnϊnϊϊnfl ■KVcπiallfiϊnδiTnM
Figure imgf000040_0002
Example 9
Preparation of Silicone Elastomer Blends from Cyclic SiH Siloxanes:
[0088] Silicone elastomer blends (SEBs) are discrete crosslinked silicone elastomer gel particles dispersed in carrier fluids. SEBs can function effectively as a rheological thickener for silicone fluids such as D5 fluid as demonstrated in this example. To make silicone elastomer blends, the elastomer gels of known initial elastomer content (IEC) from several of the above examples were mechanically sheared to obtain small particle size and further diluted to desirable final elastomer content (FEC). For example, sample 9A SEB was made by mechanically shearing an elastomer gel to reduce particle size and then diluted further with D5 fluid to yield a final elastomer content (% FEC) of 10% by weight. The final SEB was a clear thick gel paste with a viscosity of about 676,000 cps. Additional SEBs are shown in Table 9. As illustrated by these examples, extremely high viscosities were observed for these compositions of SEBs in cyclic siloxanes.
Table 9: Silicone elastomer blends derived from elastomer gels of cyclic SiH-bearing siloxane
Figure imgf000042_0001
Example 10
Examples of Silicone Elastomer Gels prepared neat
[0089] Silicone elastomer gels can be prepared without a carrier fluid present, as illustrated in this example. The total of components (A) and (B) represents the elastomer amount and is equal to 100% in these examples.
[0090] Silicone elastomer gels were made from the hydrosilylation of the representative cyclic SiH-containing siloxane as component (A) with an alkenyl functional compound in component (B) in the presence of Pt catalyst. The two cyclic SiH siloxanes used for the preparation of 100% silicone elastomer gels were those described above as Example 4J, and example 4K. The molar ratio of silicon-bonded hydrogen [SiH] to [alkenyl] was 0.90. The hardness of these silicone elastomer gels, as measured by Texture Analyzer, is shown in the Tables 1OA and 1OB.
Figure imgf000044_0001
Figure imgf000045_0001
The silicone elastomer blends were made from the silicone elastomer gels of 100% elastomer content, by grinding/ shearing the gels, followed by diluting with the selected carrier fluid, either silicone fluids or organic solvents. Example 11
Hardness Property of Selected Silicone Elastomers/ Gels:
[0091] A number of silicone elastomer gels were prepared following the procedures described above. These silicone elastomer gels were made from the selected cyclic SiH- containing siloxane as component (A), the alkenyl functional compound in component (B), and the balance quantity of D5 fluid. A trace amount of Pt catalyst at a quantity about 4-10 ppm Pt was used to catalyzed the reaction. The molar ratio of silicon-bonded hydrogen [SiH] to [alkenyl] was varied, as shown in the following table. The hydrosilylation reaction was carried out at 500C for 4 hours. Gels formed from 15 minutes to 2 hours after placing in 50 0C water bath, depending on the composition.
[0092] The hardness of the silicone elastomer gels derived was characterized using the Texture Analyzer. The "Force 1" is the force reading at the maximum point of the force vs. probe penetration time cure, illustrated in the above figure. This force reading represents the firmness or hardness of the gels in resisting probe penetration. The second property included is the "Force-Time 1 :2 Area" reading. This is the area integration between the maximum force reading and the time it elapsed (1 second in this case). This value represents the elastic nature of the silicone elastomer gels. The higher the value, in both properties, the harder the gels is. As illustrated, silicone elastomer gels with a wide range of hardness are produced.
Figure imgf000047_0001
Example 12
Silicone Gels Hardness Measured by the Texture Analyzer [0093] Elastomer gels with very low hardness (soft gels) and with very high hardness readings (not shown yet) can be conveniently prepared by controlling the % elastomer content. The total of components (A) and (B) represents the elastomer content and can be as high as 100%. In the case of neat elastomers, the hardness of such gels is very high and can be processed into powdery type products to give a powdery feel. [0094] Illustrated in the Table 12, gels were prepared from various component (A) and alkenyl-functional compound in component (B) to 10 and 20% elastomer content. Dow Corning 245 fluid was used as component (D). Very soft gels with a force of 4 g were produced. On the other hand, gels with very high force readings may be produced from these components by raising the wt. % elastomer content.
Figure imgf000049_0001
The actual force vs. probe penetration time cures obtained from Texture Analyzer for a selected group of gels from Table 12 are shown in Figure 1. Example 13
Additional examples of SEBs made at low SiH /vinyl ratios
[0095] Elastomers and gels may be formed over a wide range of SiH / vinyl ratios and at relatively low SiH/vinyl ratios. To illustrate this, the following examples were prepared.
Component (A) in this example was an organohydrogensiloxane similar to Example 5F with a 27dp siloxane spacer, made from MeH cyclics and VINYL SILOXANE #5 using a SiH/vinyl ratio of 3.4.
Figure imgf000050_0002
Figure imgf000050_0001
Figure imgf000050_0003
Preparation: prescribed amounts of components (A) and (B) are charged to a reaction container and mixed to homogeneous, then about 3.5ppm of Pt catalyst (i.e. 0.05 g of Dow Corning Syl-Off Pt solution @ 0.52 % Pt by weight) was introduced while under stirring. The hydrosilylation reaction was carried out at 700C for 3 hrs. All mixtures except Example 13F gelled within 30 minutes of heating. The gel hardness was characterized using a Texture Analyzer.
Example 14 (Comparative Example")
Comparison Examples: Silicone elastomer gels from linear MeH siloxane / hexadiene chemistry
[0096] The thickening or gelling capabilities of representative SEBs of the present invention were evaluated vs thickening capabilities of known silicone elastomers known in the art for thickening such as those described in US 5,811,487 and US 5,880,210. Two silicone elastomer blend compositions were prepared using MD94D'βM SiH polymer (MeH Linear) and 1,5-hexadiene as chain extender, and amount of D5 fluid as the carrier fluid to provide elastomer content of 10.0 and 5.0 % by weight. A water-white, weak and soft gel was obtained for Example 8A, but was not as firm as Example 6A as described above. No gel or elastomer was formed in the Example 8B composition, at 5.0 % elastomer content. This example demonstrates the improved thickening and gel-forming capacity of the cyclic SiH- containing siloxane based composition of the present invention vs conventional linear siloxane based silicone elastomers of the art.
Table 8: Com arison silicone elastomer els
Figure imgf000052_0001
Example 15
Preparation of Silicone Elastomer Gels containing actives
Silicone Elastomer gels were prepared from cyclic SiH-containing siloxane having various chain architectures (component A), as well as aliphatic unsaturated compounds of various structure and type in component (B). The amounts and components (A) and (B) were calculated to yield a predetermined [SiH] / [Alkeny] molar ratio and a pre-determined % elastomer content in the cured gel. Examples 15B and 15D were charged with 7.15 wt% VAP during the formation of the silicone elastomer gel, and is representative of the "pre-load method".
Table 15
Figure imgf000053_0001
The silicone elastomer gels in these examples were prepared according to the following procedures:
1) charge all components except catalyst to a glass container (or a reactor) and stir to homogeneous;
2) catalyze the reaction mixture (with 3 — 5 ppm Pt) and quickly place the mixture in a 7O0C water bath and continue the stirring until the mixture gelled, record the time it takes to reach the gel state;
3) leave the reaction mixture container in the 700C water bath for a total of 4 hrs. Example 16
Preparation of Silicone Elastomer Gels containing actives
Silicone elastomer gels with and without a vitamin active were also derived from organohydrogencyclosiloxanes of varying molecular structure as shown in the examples summarized in Table 16. The hardness of the VAP active containing silicone elastomer gels was characterized by the Texture Analyzer, as described above. The gels were prepared according to the procedure described in Example 15.
Table 16
Figure imgf000054_0001
Example 17
Preparation of Silicone Elastomer Gels
Silicone elastomer gels with and without a vitamin active were also derived from organohydrogencyclosiloxanes having an organic spacer as shown in the examples summarized in Table 17. The gels were prepared according to the procedure described in Example 15.
Table 17
Figure imgf000055_0001
Example 18
Preparation of Silicone Elastomer Gels containing actives
Additional examples of silicone elastomer gels prepared from various organohydrogencyclosiloxanes using the Example 3 procedures are summarized Table 18.
Table 18
Figure imgf000056_0001
Example 19
Preparation of Silicone Elastomer Blends containing actives
Silicone elastomer blends were prepared from several of the silicone elastomer gels by mechanically shearing a silicone elastomer gel composition characterized as having an initial elastomer content (IEC) to reduce particle size, and subsequently diluting the mixture with additional carrier fluid to a desired final elastomer content (FEC). Various silicone elastomer blends, as summarized in Table 19, were made by mechanically shearing silicone gel compositions using a Hauschild mixer to reduced particle size and then diluted further with Dow Corning 245 fluid to yield silicone elastomer blends having a final elastomer content (FEC) of 10% by weight. The silicone blend compositions of these examples contained VAP, which can be included using the pre-load method (Example 19B and 19D), or from post- loading the VAP by its addition to a silicone gel composition (Example 19A and 19C).
Table 19
Figure imgf000057_0001
Example 20
Preparation of Silicone Elastomer Blends containing actives
Additional examples of silicone elastomer blends, prepared from various silicone elastomer gels using the Example 7 procedures, are summarized Table 20.
Table 20
Figure imgf000058_0001
Example 21
Preparation of Silicone Elastomer Blends containing actives
Additional examples of silicone elastomer blends, prepared from various silicone elastomer gels using the Example 19 procedures, are summarized Table 21.
High-performance liquid chromatography (HPLC) was used to verify the presence and integrity of VAP active in SEBs. The details of the HPLC analysis techniques are summarized below.
HPLC Assays for Vitamin A Palmitate in SEB
Standard Preparation
Standards were prepared by creating a stock solution of 1000 ug/ml VAP in hexane. This was done by measuring 107.2 mg VAP into a 100 ml volumetric flask. The flask was then filled to the 100 ml level with hexane. The stock solution was then diluted into solutions with concentration of 4, 40, 100, 300, and 500 ug/ml. A calibration curve was constructed using all standards from 4 to 1000 ug/ml. SEB Sample Extraction
There were two methods of sample extraction used in this study. PXL SEB samples were extracted using hexane only. This was done by adding 0.5 g SEB to 20 g hexane in a vial. The formulation samples (Sepigel and body lotions) were extracted by adding 1 g of formulation sample with 1O g THF : IPA (1:1). The samples were then put on a wrist action shaker for 2 hours of mixing. After mixing was complete the samples were filtered into HPLC vials using 0.45 micron PTFE filters.
HPLC Conditions
The assays of VAP in this invention were performed on one of the two HPLC systems: a Waters 600E HPLC equipped with a Waters 991 PDA detector or Waters 2695 Separations unit equipped with a Waters 2996 PDA detector. The column and column guard were Novapak Cl 8 from Waters. The column was heated to a constant temperature of 35° C. The mobile phase was 45% methanol, 20% acrylnitrile, and 35% isopropanol set at a flow rate of 1 ml/min. 10 ul of each sample were injected and allowed to run for 12 minutes. The PDA detector was set to 325 nm wavelength.
Table 21
Figure imgf000060_0001
Example 22
Preparation of Silicone Elastomer Blends containing actives
Additional examples of silicone elastomer blends, prepared from various silicone elastomer gels using the Example 19 procedures, are summarized Table 22.
High-performance liquid chromatography (HPLC) was used to verify the presence and integrity of VAP active in SEBs using the procedures as summarized in Example 21.
Table 22
Figure imgf000061_0001
Example 23
Preparation of Silicone Elastomer Gels containing actives without carrier fluids
Silicone elastomer gels were prepared without adding any carrier fluid (component C) from various organohydrogencyclosiloxanes using Example IS procedures. The formulations and resulting gel properties are summarized Table 23.
Table HA
Figure imgf000062_0001
Table 23B
Figure imgf000063_0001

Claims

1. A gel composition comprising a silicone elastomer from the reaction of; A) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule
B) a compound or mixture of compounds having at least two aliphatic unsaturated groups in its molecule,
C) a hydrosilylation catalyst, and;
D) an optional carrier fluid.
2. The composition of claim 1 further comprising
E) a personal care or healthcare active.
3. The composition of claim 1 or 2 wherein the organohydrogensiloxane has the formula G-[Y-G]0 where G is a cyclosiloxane containing at least one SiH unit and Y is a divalent organic group, a divalent siloxane group, a divalent polyoxyalkylene group, or combination thereof, and a is greater than zero.
4. The composition of claim 1 or 2 wherein the organohydrogensiloxane is prepared by a hydrosilylation reaction of a) an organohydrogencyclosiloxane having at least two SiH units on the siloxane ring and, B) a compound or mixture of compounds containing at least two aliphatic unsaturated groups in its molecule, wherein the molar ratio of SiH units to unsaturated group ranges from 2/1 to 8/1.
5. The composition of claim 4 wherein the organohydrogencyclosiloxane has the formula [(CH3)HSiO]8 where g is 3 - 8.
6. The composition of claim 1 , 2, or 4 wherein B) the compound containing at least two aliphatic unsaturated groups in its molecule is selected from a compound having the formula R2- Y- R2 where R2 is a monovalent unsaturated aliphatic group and Y is a divalent hydrocarbon, a siloxane, a polyoxyalkylene or mixtures thereof.
7. The composition of claim 1, 2 or 4 wherein the compound containing at least two aliphatic unsaturated groups is selected from an organopolysiloxane comprising at least two siloxane units having a formula R2 RmSiO(4-m)/2 wherein
R is an organic group,
R2 is a monovalent unsaturated aliphatic group, and m is zero to 3.
8. The composition of claim 7 wherein the organopolysiloxane has the formula
(R2R2SiOc5 XSiO2)^(R2R2SiOa5 )
(R2R2SiO05) (SiO2)W(R2SiO)x(R2R2SiOoJ ),
(R2R2SiO05 ^2SiO)x(R2R2SiO05 ),
(R3SiO05 )(R2SiO)x(R2RSiO)y(R3SiO0^ ), (R3SiOa5 )(R2SiO)x(R2RSiO)y(RSiOi.5)z(R3SiO0.5 ), or
(R3SiOo.5 )(R2SiO)x(R2RSiO)y(Si02)w(R3SiOo3 ), where w > O, x > O, y > 2, and z is > O, and R is an organic group, R2 is a monovalent unsaturated aliphatic group.
9. The composition of claim 8 wherein R is methyl and R2 is CH2=CH- or CH2=CH-(CH2)4--
10. The composition of claim 9 wherein the organopolysiloxane is a vinyl functional or hexenyl functional polydimethylsiloxane having the average formula;
CH2=CH(Me)2SiO[Me2SiO]xSi(Me)2CH=CH2 , CH2=CH-(CH2)4-(Me)2SiO[Me SiOJxSi^eMCH^-CH^^ , or
Me 3SiO[(Me)2SiO]x[CH2=CH(Me)SiO]y SiMe 3 wherein Me is methyl, x > 0, and y > 2.
11. The composition of claim 1 wherein C) the hydrosilylation catalyst is a platinum group containing catalyst.
12. The composition of claim 1 wherein the molar ratio of A)/B) is from 10/1 to 1/10.
13. The composition of claim 1 wherein the carrier fluid is a silicone or organic fluid having a viscosity at 25°C in the range of 1 to 1 ,000 mm2/sec.
14. The composition of claim 1 wherein the carrier fluid is decamethylcyclopentasiloxane, isododecane, or isodecyl neopentanoate.
15. The composition of claim 2 wherein E) is a personal care active selected from a vitamin, sunscreen, plant extract, or fragrance.
16. The composition of claim 2 wherein E) is a health care active selected from a topical drug active, protein, enzyme, antifugual, or antimicrobial agent.
17. The composition of claim 2 wherein component E) is vitamin A palmitate.
18. The composition of claim 2 wherein component E) is octyl methoxycinnamate.
19. A process for preparing a silicone elastomer gel comprising: I) reacting; a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring, B) a compound or mixture of compounds containing at least two aliphatic unsaturated groups in its molecules, C) a hydrosilylation catalyst to form
A ) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated groups of component B) ranges from 2/1 to 8/1, II) further reacting;
A ) the organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, with additional quantities of
B) the compound or mixture of compounds containing at least two aliphatic unsaturated groups in its molecules,
C) the hydrosilylation catalyst, in the presence of
D) an optional carrier fluid, to form the silicone elastomer gel.
20. A process for preparing a silicone elastomer gel containing an active comprising: I) reacting; a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring, B) a compound containing at least two aliphatic unsaturated groups in its molecules, C) a hydrosilylation catalyst to form
A ) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated groups of component B) ranges from 2/1 to 8/1,
II) further reacting;
A ) the organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, with additional quantities of
B) the compound containing at least two aliphatic unsaturated groups in its molecules, C) the hydrosilylation catalyst, in the presence of
D) an optional carrier fluid to form a silicone elastomer gel,
III) admixing E) a personal care or healthcare active with the silicone elastomer gel to form the silicone elastomer gel containing active.
21. A process for preparing a silicone elastomer gel containing an active comprising:
I) reacting; a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring, B) a compound containing at least two aliphatic unsaturated groups in its molecules, C) a hydrosilylation catalyst to form
A ) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated groups of component B) ranges from 2/1 to 8/1,
II) further reacting;
A ) the organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, with additional quantities of
B) the compound containing at least two aliphatic unsaturated groups in its molecules, C) the hydrosilylation catalyst, in the presence of
D) an optional carrier fluid,
E) a personal care or healthcare active to form the silicone elastomer gel containing active.
22. The silicone elastomer gel prepared according to claims 19 20, or 21.
23. A process for preparing a gel paste composition comprising;
I) shearing the silicone elastomer gel of claims 1 or 22, II) combining the sheared silicone elastomer gel with additional quantities of
D) the carrier fluid to form a gel paste composition.
24. The gel paste composition prepared according to the process of claim 23.
PCT/US2007/006894 2006-03-21 2007-03-20 Silicone elastomer gels WO2007109260A2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN200780007575.4A CN101395206B (en) 2006-03-21 2007-03-20 Silicone elastomer gels
US12/293,571 US8110630B2 (en) 2006-03-21 2007-03-20 Silicone elastomer gels
EP07753516.9A EP1996644B9 (en) 2006-03-21 2007-03-20 Silicone elastomer gels
JP2009501505A JP5172821B2 (en) 2006-03-21 2007-03-20 Silicone elastomer gel
KR1020087022919A KR101364818B1 (en) 2006-03-21 2007-03-20 Silicone elastomer gels

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US78434006P 2006-03-21 2006-03-21
US60/784,340 2006-03-21
US83880306P 2006-08-18 2006-08-18
US60/838,803 2006-08-18

Publications (2)

Publication Number Publication Date
WO2007109260A2 true WO2007109260A2 (en) 2007-09-27
WO2007109260A3 WO2007109260A3 (en) 2008-07-17

Family

ID=38523048

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2007/006894 WO2007109260A2 (en) 2006-03-21 2007-03-20 Silicone elastomer gels

Country Status (5)

Country Link
US (1) US8110630B2 (en)
EP (1) EP1996644B9 (en)
JP (1) JP5172821B2 (en)
KR (1) KR101364818B1 (en)
WO (1) WO2007109260A2 (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008085360A2 (en) * 2006-12-29 2008-07-17 Dow Corning Corporation Personal care compositions containing silicone elastomer gels
WO2009133765A2 (en) 2008-04-30 2009-11-05 Dow Corning Toray Co., Ltd. Silicon-containing particles, method for manufacturing thereof, oil composition, ceramic material, and method for manufacturing thereof
EP2179721A1 (en) 2008-10-22 2010-04-28 Beiersdorf AG Cosmetic formula with new siloxane elastomers
DE102008053788A1 (en) 2008-10-22 2010-04-29 Beiersdorf Ag Cosmetic formulation with siloxane elastomers to improve microbiological stability
DE102009049721A1 (en) 2008-10-22 2010-04-29 Beiersdorf Ag Cosmetic formulation, useful e.g. for permanent browning of skin, comprises e.g. siloxane elastomers, obtained from reaction of organohydrogen siloxane with substances or mixtures containing e.g. aliphatic unsaturated groups
WO2010046096A2 (en) * 2008-10-22 2010-04-29 Beiersdorf Ag Hair care preparations comprising novel siloxane elastomers
DE102008053791A1 (en) 2008-10-22 2010-04-29 Beiersdorf Ag Cosmetic formulation with siloxane elastomers and particulate matter
DE102008053782A1 (en) 2008-10-22 2010-06-10 Beiersdorf Ag Use of ABC siloxane elastomers obtained from reacting organohydrogen siloxane with substance containing e.g. hydrocarbon, and hydrosilylation catalyst, in cosmetic shaving preparations to improve sliding and cutting capacity while shaving
WO2012027143A1 (en) 2010-08-23 2012-03-01 Dow Corning Corporation Saccharide siloxane copolymers and methods for their preparation and use
WO2012027145A1 (en) 2010-08-23 2012-03-01 Dow Corning Corporation Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use
WO2012027144A1 (en) 2010-08-23 2012-03-01 Dow Corning Corporation Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use
US20120156148A1 (en) * 2009-09-03 2012-06-21 Naoki Shikano Pituitous Silicone Fluids
US8222363B2 (en) 2007-09-26 2012-07-17 Dow Corning Corporation Silicone organic elastomer gels from organopolysiloxane resins
US8236890B2 (en) 2007-09-25 2012-08-07 Dow Corning Corporation Emulsions of silicone elastomer and silicone organic elastomer gels
US8273840B2 (en) 2006-03-21 2012-09-25 Dow Corning Corporation Silicone polyether elastomer gels
US8668916B2 (en) 2010-09-24 2014-03-11 Conopco, Inc. HIPE-gelation process for making highly concentrated, spherical biopolymer gel particle suspensions
US8920783B2 (en) 2006-03-21 2014-12-30 Dow Corning Corporation Silicone-organic elastomer gels
WO2015167963A1 (en) 2014-04-28 2015-11-05 Dow Corning Corporation Cross-linked composition and cosmetic composition comprising the same
WO2016164289A1 (en) * 2015-04-08 2016-10-13 Dow Corning Corporation Pituitous silicone fluid composition
WO2018165434A1 (en) 2017-03-08 2018-09-13 Dow Silicones Corporation Long lasting cosmetic composition comprising silicone elastomer
US10933011B2 (en) 2016-03-14 2021-03-02 Dow Silicones Corporation Composition and method of preparation
CN115926464A (en) * 2022-11-15 2023-04-07 清远高能结加改性材料科技有限公司 Preparation method of silicon rubber reinforced particles and reinforced rubber powder

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8110630B2 (en) 2006-03-21 2012-02-07 Dow Corning Corporation Silicone elastomer gels
US20100303743A1 (en) * 2007-09-26 2010-12-02 John Joseph Kennan Personal Care Compositions Containing Hydrophobic Silicone-Organic Gel Blends
CN102378620A (en) * 2009-03-20 2012-03-14 宝洁公司 Personal-care composition comprising a hydrocarbon wax and a polar oil
EP2408421A2 (en) * 2009-03-20 2012-01-25 The Procter & Gamble Company Personal-care composition comprising oil-soluble solid sunscreens
WO2010111267A2 (en) * 2009-03-23 2010-09-30 The Procter & Gamble Company Personal-care composition comprising a cationic active
US20100305168A1 (en) * 2009-03-23 2010-12-02 Larry Rich Robinson Personal-care composition comprising a cationic active
CN102639606B (en) * 2009-09-03 2014-12-10 道康宁公司 Pituitous silicone fluids
US9593209B2 (en) 2009-10-22 2017-03-14 Dow Corning Corporation Process for preparing clustered functional polyorganosiloxanes, and methods for their use
KR20120101015A (en) 2009-10-23 2012-09-12 다우 코닝 코포레이션 Hydrophilically-modified silicone compositions
EP2617774B1 (en) 2010-09-17 2015-03-04 Terumo Kabushiki Kaisha Silicone rubber composition
WO2013130948A2 (en) 2012-03-01 2013-09-06 The Procter & Gamble Company Sunscreen composition comprising uv composite
US9549891B2 (en) 2012-03-19 2017-01-24 The Procter & Gamble Company Superabsorbent polymers and sunscreen actives for use in skin care compositions
US20140178314A1 (en) 2012-12-19 2014-06-26 The Procter & Gamble Company Compositions and/or articles with improved solubility of a solid active
KR102206708B1 (en) 2013-02-11 2021-01-25 다우 실리콘즈 코포레이션 Stable thermal radical curable silicone adhesive compositions
CN105189685B (en) 2013-02-11 2017-08-08 道康宁公司 Method for forming heat conduction hot radical curing silicone compositions
WO2014124388A1 (en) 2013-02-11 2014-08-14 Dow Corning Corporation Alkoxy-functional organopolysiloxane resin and polymer and related methods for forming same
US10370572B2 (en) 2013-02-11 2019-08-06 Dow Silicones Corporation Moisture-curable hot melt silicone adhesive compositions including an alkoxy-functional siloxane reactive resin
JP6426628B2 (en) 2013-02-11 2018-11-21 ダウ シリコーンズ コーポレーション Curable Silicone Composition Comprising Functionally Concentrated Polyorganosiloxane and Silicone Reactive Diluent
JP6370812B2 (en) 2013-02-11 2018-08-08 ダウ シリコーンズ コーポレーション Clustered functional polyorganosiloxane, process for producing the same, and method of using the same
KR102313564B1 (en) 2013-10-31 2021-10-19 다우 실리콘즈 코포레이션 Cosmetic composition comprising a carboxy-functional elastomers
JP6607861B2 (en) 2013-10-31 2019-11-20 ダウ シリコーンズ コーポレーション Cross-linked composition and method for forming the same
EP3063227B1 (en) 2013-10-31 2020-09-02 Dow Silicones Corporation Cross-linked composition and method of forming the same
KR102273099B1 (en) * 2014-12-17 2021-07-06 주식회사 케이씨씨실리콘 Silicone elastomer composite, silicone elastomer and silicone paste using the same
EP3280771A1 (en) 2015-04-08 2018-02-14 Dow Corning Corporation Pituitous silicone emulsions
US10285926B2 (en) 2015-06-29 2019-05-14 The Procter & Gamble Company Superabsorbent polymers and starch powders for use in skin care compositions
EP3196229B1 (en) 2015-11-05 2018-09-26 Dow Silicones Corporation Branched polyorganosiloxanes and related curable compositions, methods, uses and devices
JP6949831B2 (en) * 2016-05-02 2021-10-13 ダウ・東レ株式会社 Silicone particles, cosmetics and paints containing them, and resins
CN111757917B (en) * 2018-03-27 2022-06-03 陶氏东丽株式会社 Oil-containing silicone elastomer particles and use of cosmetic composition
KR102170712B1 (en) * 2019-01-09 2020-10-27 주식회사 케이씨씨 Silicone elastomers composition and preparation method thereof
KR102478528B1 (en) * 2021-05-25 2022-12-19 김두곤 Environment-friendly elastomer hydrogel using starch, method for manufacturing the same and method for coloring bio-elastomer
CN117700754A (en) * 2023-12-14 2024-03-15 湖南斯洛柯有机硅有限公司 Organosilicon elastomer gel with wiredrawing effect, and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003093369A1 (en) * 2002-05-01 2003-11-13 Dow Corning Corporation Compositions having improved bath life
US20040092655A1 (en) * 2001-04-02 2004-05-13 Takayoshi Otomo Mouldable silicone gel compositions

Family Cites Families (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296291A (en) 1962-07-02 1967-01-03 Gen Electric Reaction of silanes with unsaturated olefinic compounds
US3159601A (en) 1962-07-02 1964-12-01 Gen Electric Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes
US3220972A (en) 1962-07-02 1965-11-30 Gen Electric Organosilicon process using a chloroplatinic acid reaction product as the catalyst
NL131800C (en) 1965-05-17
US3516946A (en) 1967-09-29 1970-06-23 Gen Electric Platinum catalyst composition for hydrosilation reactions
US3814730A (en) 1970-08-06 1974-06-04 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
GB1476314A (en) 1973-06-23 1977-06-10 Dow Corning Ltd Coating process
US3989668A (en) 1975-07-14 1976-11-02 Dow Corning Corporation Method of making a silicone elastomer and the elastomer prepared thereby
US4122029A (en) 1977-07-27 1978-10-24 Dow Corning Corporation Emulsion compositions comprising a siloxane-oxyalkylene copolymer and an organic surfactant
JPH0655897B2 (en) 1988-04-22 1994-07-27 信越化学工業株式会社 Method for producing silicone composition
US5036117A (en) 1989-11-03 1991-07-30 Dow Corning Corporation Heat-curable silicone compositions having improved bath life
GB9103191D0 (en) 1991-02-14 1991-04-03 Dow Corning Platinum complexes and use thereof
JP2631772B2 (en) 1991-02-27 1997-07-16 信越化学工業株式会社 Novel silicone polymer and paste-like silicone composition having water dispersibility using the same
US5387417A (en) 1991-08-22 1995-02-07 Dow Corning Corporation Non-greasy petrolatum emulsion
US5380527A (en) 1991-08-26 1995-01-10 Dow Corning Corporation Alkylmethylsiloxane mixtures for skin care
EP0545002A1 (en) 1991-11-21 1993-06-09 Kose Corporation Silicone polymer, paste-like composition and water-in-oil type cosmetic composition comprising the same
US5493041A (en) 1995-07-21 1996-02-20 Dow Corning Corporation Lightly crosslinked poly(n-alkylmethylsiloxanes) and methods of producing same
US5654362A (en) 1996-03-20 1997-08-05 Dow Corning Corporation Silicone oils and solvents thickened by silicone elastomers
US5919441A (en) 1996-04-01 1999-07-06 Colgate-Palmolive Company Cosmetic composition containing thickening agent of siloxane polymer with hydrogen-bonding groups
US6271295B1 (en) 1996-09-05 2001-08-07 General Electric Company Emulsions of silicones with non-aqueous hydroxylic solvents
US5760116A (en) 1996-09-05 1998-06-02 General Electric Company Elastomer gels containing volatile, low molecular weight silicones
ATE370979T1 (en) 1996-10-29 2007-09-15 Grant Ind Inc GRAFTED RUBBER-LIKE SILICONE GEL WITH INCREASED OIL COMPATIBILITY AND ITS SYNTHESIS
US5811487A (en) 1996-12-16 1998-09-22 Dow Corning Corporation Thickening silicones with elastomeric silicone polyethers
US5880210A (en) 1997-04-01 1999-03-09 Dow Corning Corporation Silicone fluids and solvents thickened with silicone elastomers
GB9708182D0 (en) 1997-04-23 1997-06-11 Dow Corning Sa A method of making silicone in water emulsions
US5889108A (en) 1997-06-02 1999-03-30 Dow Corning Corporation Thickening solvents with elastomeric silicone polyethers
US6051216A (en) 1997-08-01 2000-04-18 Colgate-Palmolive Company Cosmetic composition containing siloxane based polyamides as thickening agents
US5869727A (en) 1997-08-08 1999-02-09 Osi Specialties, Inc. Vacuum process for the manufacture of siloxane-oxyalkylene copolymers
US5929164A (en) 1997-11-05 1999-07-27 Dow Corning Corporation Quenching post cure
US5929162A (en) 1997-12-12 1999-07-27 General Electric Company Elastomer dispersion having a unique particle size distribution
US5998542A (en) 1997-12-12 1999-12-07 General Electric Company Processing of an elastomer dispersion
US5981680A (en) 1998-07-13 1999-11-09 Dow Corning Corporation Method of making siloxane-based polyamides
US6262170B1 (en) 1998-12-15 2001-07-17 General Electric Company Silicone elastomer
US6207717B1 (en) 1999-01-12 2001-03-27 Dow Corning Corporation Entrapment of vitamins with an elastomeric silicone polyether
US6200581B1 (en) 1999-04-28 2001-03-13 Dow Corning Corporation Elastomeric silicone terpolymer
US6365670B1 (en) 2000-03-10 2002-04-02 Wacker Silicones Corporation Organopolysiloxane gels for use in cosmetics
JP4783491B2 (en) 2000-04-17 2011-09-28 東レ・ダウコーニング株式会社 Organopolysiloxane composition and method for producing the same
US6531540B1 (en) 2001-05-16 2003-03-11 General Electric Company Polyether siloxane copolymer network compositions
FR2825914B1 (en) 2001-06-14 2003-09-19 Oreal COMPOSITION BASED ON SILICONE OIL STRUCTURED IN RIGID FORM, IN PARTICULAR FOR COSMETIC USE
FR2825915B1 (en) 2001-06-14 2006-02-03 Oreal COMPOSITION BASED ON STRUCTURED SILICONE OIL IN RIGID FORM, IN PARTICULAR FOR COSMETIC USE
FR2825916B1 (en) 2001-06-14 2004-07-23 Oreal COMPOSITION BASED ON SILICONE OIL STRUCTURED IN RIGID FORM, PARTICULARLY FOR COSMETIC USE
US6605734B2 (en) 2001-12-07 2003-08-12 Dow Corning Corporation Alkene-platinum-silyl complexes
CN100334134C (en) 2002-05-01 2007-08-29 陶氏康宁公司 Organohydrogensilicon compounds
US20030235553A1 (en) 2002-06-12 2003-12-25 L'oreal Cosmetic compositions containing at least one silicone-polyamide polymer, at least one oil and at least one film-forming agent and methods of using the same
US6887934B2 (en) * 2002-08-26 2005-05-03 Dow Corning Corporation Resin modified elastomers
JP3979922B2 (en) 2002-11-08 2007-09-19 信越化学工業株式会社 Hydrophilized powder and composition containing the same
US20040180032A1 (en) 2003-03-15 2004-09-16 Manelski Jean Marie Long wearing cosmetic composition
ATE371434T1 (en) 2003-03-27 2007-09-15 Dow Corning DELAYED RELEASE COMPOSITIONS
AU2003236256A1 (en) * 2003-04-14 2004-11-04 Shin-Etsu Chemical Co., Ltd. Organopolysiloxane hair treatment agent and hair cosmetic containing the treatment agent
US20040228821A1 (en) 2003-05-16 2004-11-18 The Procter & Gamble Company Personal care products comprising active agents in a gel network
JP4219843B2 (en) * 2004-04-08 2009-02-04 信越化学工業株式会社 Curable siloxane-based composition
CN100532432C (en) 2004-04-12 2009-08-26 陶氏康宁公司 Silsesquioxane resin wax
JP5199231B2 (en) 2006-03-21 2013-05-15 ダウ・コーニング・コーポレイション Silicone polyether elastomer gel
US8110630B2 (en) 2006-03-21 2012-02-07 Dow Corning Corporation Silicone elastomer gels
US20090317343A1 (en) 2006-12-29 2009-12-24 Shaow Lin Personal Care Compositions Containing Silicone Elastomer Gels
JP2010540721A (en) 2007-09-26 2010-12-24 ダウ・コーニング・コーポレイション Silicone organic elastomer gel from organopolysiloxane resin

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040092655A1 (en) * 2001-04-02 2004-05-13 Takayoshi Otomo Mouldable silicone gel compositions
WO2003093369A1 (en) * 2002-05-01 2003-11-13 Dow Corning Corporation Compositions having improved bath life

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1996644A2 *

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8273840B2 (en) 2006-03-21 2012-09-25 Dow Corning Corporation Silicone polyether elastomer gels
US8920783B2 (en) 2006-03-21 2014-12-30 Dow Corning Corporation Silicone-organic elastomer gels
WO2008085360A3 (en) * 2006-12-29 2009-03-12 Dow Corning Personal care compositions containing silicone elastomer gels
WO2008085360A2 (en) * 2006-12-29 2008-07-17 Dow Corning Corporation Personal care compositions containing silicone elastomer gels
US8236890B2 (en) 2007-09-25 2012-08-07 Dow Corning Corporation Emulsions of silicone elastomer and silicone organic elastomer gels
US8541011B2 (en) 2007-09-26 2013-09-24 Dow Corning Corporation Silicone organic elastomer gels from organopolysiloxane resins
US8222363B2 (en) 2007-09-26 2012-07-17 Dow Corning Corporation Silicone organic elastomer gels from organopolysiloxane resins
EP2271702A2 (en) * 2008-04-30 2011-01-12 Dow Corning Toray Co., Ltd. Silicon-containing particles, method for manufacturing thereof, oil composition, ceramic material, and method for manufacturing thereof
WO2009133765A2 (en) 2008-04-30 2009-11-05 Dow Corning Toray Co., Ltd. Silicon-containing particles, method for manufacturing thereof, oil composition, ceramic material, and method for manufacturing thereof
US8450231B2 (en) 2008-04-30 2013-05-28 Dow Corning Toray Company, Ltd. Silicon-containing particles, method for manufacturing thereof, oil composition, ceramic material, and method for manufacturing thereof
JP2011516681A (en) * 2008-04-30 2011-05-26 東レ・ダウコーニング株式会社 Silicon-containing particles, method for producing the same, oil composition, ceramic, and method for producing the same
DE102009049721A1 (en) 2008-10-22 2010-04-29 Beiersdorf Ag Cosmetic formulation, useful e.g. for permanent browning of skin, comprises e.g. siloxane elastomers, obtained from reaction of organohydrogen siloxane with substances or mixtures containing e.g. aliphatic unsaturated groups
EP2181699A1 (en) 2008-10-22 2010-05-05 Beiersdorf AG Cosmetic formula with siloxane elastomers for improving microbiological stability
WO2010046096A3 (en) * 2008-10-22 2010-06-17 Beiersdorf Ag Hair care preparations comprising novel siloxane elastomers
DE102009050237A1 (en) 2008-10-22 2010-10-21 Beiersdorf Ag Cosmetic formulation with siloxane elastomers for improved shaving
EP2181698A3 (en) * 2008-10-22 2010-06-02 Beiersdorf AG Cosmetic formula with siloxane elastomers and particulate material
EP2181698A2 (en) 2008-10-22 2010-05-05 Beiersdorf AG Cosmetic formula with siloxane elastomers and particulate material
DE102008053786A1 (en) 2008-10-22 2011-12-15 Beiersdorf Ag Hair care preparations with novel siloxane elastomers
DE102008053782A1 (en) 2008-10-22 2010-06-10 Beiersdorf Ag Use of ABC siloxane elastomers obtained from reacting organohydrogen siloxane with substance containing e.g. hydrocarbon, and hydrosilylation catalyst, in cosmetic shaving preparations to improve sliding and cutting capacity while shaving
EP2179721A1 (en) 2008-10-22 2010-04-28 Beiersdorf AG Cosmetic formula with new siloxane elastomers
DE102008053791A1 (en) 2008-10-22 2010-04-29 Beiersdorf Ag Cosmetic formulation with siloxane elastomers and particulate matter
DE102008053788A1 (en) 2008-10-22 2010-04-29 Beiersdorf Ag Cosmetic formulation with siloxane elastomers to improve microbiological stability
WO2010046096A2 (en) * 2008-10-22 2010-04-29 Beiersdorf Ag Hair care preparations comprising novel siloxane elastomers
DE102008053789A1 (en) 2008-10-22 2010-04-29 Beiersdorf Ag Cosmetic formulation with novel siloxane elastomers
US20120156148A1 (en) * 2009-09-03 2012-06-21 Naoki Shikano Pituitous Silicone Fluids
US9181434B2 (en) * 2009-09-03 2015-11-10 Dow Corning Corporation Pituitous silicone fluids
WO2012027143A1 (en) 2010-08-23 2012-03-01 Dow Corning Corporation Saccharide siloxane copolymers and methods for their preparation and use
WO2012027144A1 (en) 2010-08-23 2012-03-01 Dow Corning Corporation Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use
WO2012027145A1 (en) 2010-08-23 2012-03-01 Dow Corning Corporation Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use
US8668916B2 (en) 2010-09-24 2014-03-11 Conopco, Inc. HIPE-gelation process for making highly concentrated, spherical biopolymer gel particle suspensions
WO2015167963A1 (en) 2014-04-28 2015-11-05 Dow Corning Corporation Cross-linked composition and cosmetic composition comprising the same
US10357445B2 (en) 2014-04-28 2019-07-23 Dow Silicones Corporation Cross-linked composition and cosmetic composition comprising the same
WO2016164289A1 (en) * 2015-04-08 2016-10-13 Dow Corning Corporation Pituitous silicone fluid composition
US10933011B2 (en) 2016-03-14 2021-03-02 Dow Silicones Corporation Composition and method of preparation
WO2018165434A1 (en) 2017-03-08 2018-09-13 Dow Silicones Corporation Long lasting cosmetic composition comprising silicone elastomer
CN115926464A (en) * 2022-11-15 2023-04-07 清远高能结加改性材料科技有限公司 Preparation method of silicon rubber reinforced particles and reinforced rubber powder
CN115926464B (en) * 2022-11-15 2023-09-26 清远高能结加改性材料科技有限公司 Preparation method of silicon rubber reinforced particles and reinforced rubber powder

Also Published As

Publication number Publication date
JP2009530477A (en) 2009-08-27
EP1996644A2 (en) 2008-12-03
WO2007109260A3 (en) 2008-07-17
KR101364818B1 (en) 2014-02-19
JP5172821B2 (en) 2013-03-27
KR20080108104A (en) 2008-12-11
US8110630B2 (en) 2012-02-07
EP1996644B1 (en) 2015-09-02
US20100172849A1 (en) 2010-07-08
EP1996644B9 (en) 2015-12-09

Similar Documents

Publication Publication Date Title
EP1996644B1 (en) Silicone elastomer gels
EP2001934B1 (en) Silicone-organic elastomer gels
EP2001933B1 (en) Silicone polyether elastomer gels
EP2194954B1 (en) Personal care compositions containing silicone-organic gels from polyalkyloxylene crosslinked silicone elastomers
US20090317343A1 (en) Personal Care Compositions Containing Silicone Elastomer Gels
US20100303743A1 (en) Personal Care Compositions Containing Hydrophobic Silicone-Organic Gel Blends
US20090053301A1 (en) Silicone vesicles containing actives
US20230248635A1 (en) Chemically cross-linked elastomers formed by michael addition and compositions comprising such elastomers
GB2453952A (en) Personal care composition containing siloxane based polyamid elastomers

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780007575.4

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2007753516

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2009501505

Country of ref document: JP

Ref document number: 12293571

Country of ref document: US

Ref document number: 1020087022919

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: DE