USRE38116E1 - Method of making siloxane-based polymides - Google Patents

Method of making siloxane-based polymides Download PDF

Info

Publication number
USRE38116E1
USRE38116E1 US10/035,497 US3549701A USRE38116E US RE38116 E1 USRE38116 E1 US RE38116E1 US 3549701 A US3549701 A US 3549701A US RE38116 E USRE38116 E US RE38116E
Authority
US
United States
Prior art keywords
siloxane
branched
linear
based polyamide
ethyl
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
US10/035,497
Inventor
Lenin James Petroff
Jay Brian Rose
Michael Ward Skinner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones Corp
Original Assignee
Dow Corning Corp
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 Corp filed Critical Dow Corning Corp
Priority to US10/035,497 priority Critical patent/USRE38116E1/en
Application granted granted Critical
Publication of USRE38116E1 publication Critical patent/USRE38116E1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair

Definitions

  • This invention is directed to an improvement in the method of making siloxane-based polyamides described in a prior copending application, U.S. Ser. No. 08/904,709, filed Aug. 1, 1997, and entitled “Cosmetic Composition Containing Siloxane-Based Polyamides as Thickening Agents”, hereafter referred to as the '709 application.
  • the present invention relates to a novel method of making siloxane-based polyamides.
  • the '709 application is directed to one type of a process for preparing siloxane-based polyamides.
  • the process according to the '709 application involves many steps, and this results in cost prohibitive products which are difficult to produce in commercial quantity.
  • a dimethyl hydride endblocked polydimethylsiloxane is first prepared containing the appropriate number of siloxane units to achieve a desired value of DP.
  • the carboxylic acid group of undecylenic acid is then protected through reaction with hexamethyldisilazane.
  • the dimethyl hydride endblocked polydimethylsiloxane and the protected undecylenic acid are reacted to produce a siloxane diacid, i.e., a carboxydecyl terminated polydimethylsiloxane.
  • This reaction is accomplished in the presence of a platinum catalyst, and the product is washed with methanol to remove the trimethylsilyl protecting group from the protected siloxane diacid.
  • the siloxane diacid is then reacted with an organic diamine to produce a siloxane-based polyamide.
  • the new process basically involves the addition of an olefinic acid with an organic diamine to produce an organic diamide.
  • an ⁇ SiH endblocked polysiloxane is added in the presence of a platinum catalyst, to produce a siloxane-based polyamide via hydrosilylation.
  • the resulting polymeric product is in the form of a high molecular weight thermoplastic polymer.
  • This invention relates to a method of forming a siloxane-based polyamides which are useful as thickening agents to formulate a wide variety of cosmetic compositions.
  • the polyamides of this invention are multiples of a unit represented by the following Formula A:
  • the degree of polymerization (DP) is 1-700, preferably 10-500, and more preferably 15-45.
  • DP represents an average value for degree of polymerization of the siloxane units in the polymer with greater or lesser DP values centered around the indicated DP value.
  • n is 1-500, particularly 1-100, and more particularly 4-25.
  • X is a linear or branched chain alkylene having 1-30 carbons, particularly 3-10 carbons, and more particularly 10 carbons.
  • Y is a linear or branched chain alkylene having 1-40 carbons, particularly 1-20 carbons, more particularly 2-6 carbons, and especially 6 carbons wherein
  • the alkylene group may optionally and additionally contain in the alkylene portion at least one of (i) 1-3 amide linkages; (ii) a C5 or C6 cycloalkane; or (iii) phenylene, optionally substituted by 1-3 members which are independently C1-C3 alkyls; and
  • the alkylene group itself may optionally be substituted by at least one of (i) hydroxy; (ii) a C3-C8 cycloalkane; (iii) 1-3 members which are independently C1-C3 alkyls; phenyl, optionally substituted by 1-3 members which are independently C1-C3 alkyls; (iv) a C1-C3 alkyl hydroxy; or (v) a C1-C6 alkyl amine; and
  • Y can be Z where Z is T(R 20 )(R 21 )(R 22 ) where R 20 , R 21 and R 22 are each independently linear or branched C1-C 10 alkylenes; and T is CR in which R is hydrogen, the group defined for R 1 -R 4 , or a trivalent atom such as N, P and Al.
  • R 1 -R 4 is independently methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by 1-3 members which are methyl or ethyl. More particularly, R 1 -R 4 are methyl or ethyl, especially methyl.
  • X, Y, DP, and R 1 -R 4 may be the same or different for each polyamide unit.
  • siloxane chain is meant a group of units such as:
  • R 30 and R 31 are each independently organic moieties; and each R 30 and R 31 are connected to silicon by a carbon-silicon bond.
  • the carbon numbers in the alkylene chain do not include the carbons in the extra segments or substitutions.
  • the polyamides must have a siloxane portion in the backbone and optionally may have a siloxane portion in a pendant or branched portion.
  • Formula A is representative of a linear homopolymer.
  • Variations of the invention include: (1) polyamides in which multiple values of DP, and of units X, Y, and R 1 -R 4 occur in one polymeric molecule, and wherein the sequencing of these units may be alternating, random or block; (2) polyamides in which an organic triamine or higher amine such as tris(2-aminoethyl)amine replaces the organic diamine in part, to produce a branched or crosslinked molecule; and (3) physical blends of any of (1) and (2) and/or linear homopolymers.
  • This invention is directed to a new and novel process for making siloxane-based polyamides.
  • the process eliminates costly steps and produces a polymer with higher molecular weights than achieved with the previous process in the '709 application.
  • average molecular weights as measured by gel permeation chromatography (GPC), using the process according to the '709 application were determined to be approximately 50,000.
  • the new process according to the present invention produces average molecular weights of approximately 65,000.
  • the process according to this invention is much faster than the particular process of the '709 application as well as other traditional processes for making siloxane-based polyamides.
  • the '709 application process takes approximately four days to make a finished siloxane-based polyamide polymer, while the new route according to the present invention takes approximately one day.
  • the thermoplastic polymer produced as a result of the instant process is ideal for the thickening of dimethylcyclosiloxanes, which renders it of benefit in a large number of personal care product applications.
  • the new, process involves the addition of an olefinic acid such as undecylenic acid H 2 C ⁇ CH(CH 2 ) 8 COOH to an organic diamine such as hexamethylene diamine H 2 N(CH 2 ) 6 NH 2 , to produce an organic diamide.
  • an organic diamide product is then reacted with an ⁇ SiH endblocked polysiloxane in the presence of a platinum catalyst to produce the siloxane-based polyamide.
  • Analysis using GPC confirm and indicate the achievement of high molecular weight growth using the process according to the present invention.
  • Some examples of compounds of Formula A include:
  • a particular subgroup of Formula I are compounds where R 1 , R 2 , R 3 and R 4 are each methyl.
  • Preferred polyamides of Formula I are:
  • DP is 10-500, particularly 15-45, and more particularly 29.
  • Another particular group contains polyamides of Formula I where X, Y, DP and R 1 -R 4 are the same in each unit of the polymer.
  • X, Y, n, and R 1 -R 4 have the meanings described above for Formula A; m is the same as the value defined for n; and n and m denote the total number of units enclosed within the brackets; with the individual units arranged with regular, alternating, block, or random sequencing.
  • R 5 -R 8 is the same group as defined for R 1 -R 4 ; DP1 and DP2 may be the same or different, and each can be independently the same as defined for DP.
  • the units denominated by n and m may be structured to form either block (regularly sequenced) or random copolymers.
  • a particular subgroup for compounds of Formula II may have methyl for all R groups. Another particular subgroup of compounds of Formula II may have DP1 equal to DP2. A third particular subgroup may have methyl for all R groups, and DP1 equal to DP2.
  • X, Y, m, n, R 1 -R 8 , DP1, DP2 have the same meanings as described above for Formula A and Formula II;
  • Y 1 is independently selected from the same group as defined for Y; and the units denominated by n and m may be structured to form either block (regularly sequenced) or random copolymers.
  • a particular subgroup of compounds of Formula III may have DP1 equal to DP2.
  • Another particular subgroup of compounds of Formula III may have methyl for all R groups.
  • a third particular subgroup may have methyl for all R groups, and DP1 equal to DP2.
  • X, Y, Y 1 , R 1 -R 8 , m, n, DP1, and DP2, are the same as defined above;
  • R 9 -R 12 are the same as defined for R 1 -R 8 ;
  • DP3 is the same as defined for DP;
  • p is the same as defined for m and n;
  • Z is T(R 20 )(R 21 )(R 22 ) where R 20 , R 21 and R 22 are each independently linear or branched C1-C10 alkylenes; and T is CR where R is hydrogen, the same as defined for R 1 -R 4 , or a trivalent atom such as N, P and Al.
  • Preferred values for p are 1-25, with more preferred values being 1-7.
  • Preferred units for R 1 -R 12 are methyl.
  • T is preferably N.
  • Particular values for DP1 to DP3 are 10-500, and more particularly 15-45.
  • R 20 , R 21 , and R 22 are preferably ethylene.
  • a preferred group representative of Z is (—CH 2 CH 2 ) 3 N.
  • X is —(CH 2 ) 10 —
  • Y is —(CH 2 )—
  • DP is 15-45
  • m is 5-20% of n+p
  • Z is (—CH 2 CH 2 ) 3 N.
  • Siloxane-based polyamides according to this invention (1) contain both siloxane groups and amide groups which facilitate the thickening of compositions containing volatile silicone fluids and non-volatile silicone fluids; (2) are non-flowable solids at room temperature; and (3) dissolve in a fluid which contains silicone at a temperature of 25-160° C., to form translucent or clear solutions at a temperature in this range.
  • the siloxane units in the siloxane-based polyamides must be in the main or backbone chain but can also optionally be present in branched or pendent chains.
  • the siloxane units occur in segments as described above.
  • the siloxane units can occur individually or in segments.
  • siloxane-based polyamides include:
  • polyamides of Formula A synthesized with at least a portion of an activated diacid, such as a diacid chloride, dianhydride, or diester, instead of the diacid;
  • a reaction scheme for making polyamides of Formula I according to the '709 application involves the condensation of a siloxane diacid with an organic diamine as shown below.
  • a dimethyl hydride endblocked polydimethylsiloxane such as one of the type shown below, is prepared containing the appropriate number of siloxane units “n” to achieve the desired value of DP.
  • siloxane diacid (product of Step (3)) is reacted with an organic diamine to produce a siloxane-based polyamide.
  • the siloxane diacid is shown below. This reaction may involve the use of a reaction solvent such as toluene or xylene.
  • siloxane-based polyamide which includes at least one repeating unit represented by the formula
  • X is a linear or branched C 1 -C 30 alkylene chain
  • Y is a linear or branched C 1 -C 20 alkylene chain
  • DP is an integer having a value of 10-500
  • n is an integer having a value of 1-500.
  • Suitable olefinic acids which can be used include undecylenic acid H 2 C ⁇ CH(CH 2 ) 8 COOH, acrylic acid H 2 C ⁇ CHCOOH, 3-butenoic acid (vinylacetic acid) H 2 C ⁇ CHCH 2 COOH, 4-pentenoic acid H 2 C ⁇ CHCH 2 COOH, and other olefinic acids with carbon chains of varying length.
  • Organic amines which can be used herein preferably include linear alkyl diamines such as hexamethylene diamine, ethylene diamine, and mixtures of linear alkyl diamines, as well as other amines such as decamethylene diamine.
  • hydrosilylation involves the reaction between a polysiloxane containing ⁇ Si—H groups, and a material containing unsaturation, e.g., vinyl groups.
  • a material containing unsaturation e.g., vinyl groups.
  • the process requires a catalyst to effect the reaction between the ⁇ SiH containing polysiloxane and the material containing unsaturation, i.e., the organic diamide in the case of the present invention.
  • Suitable catalysts are Group VIII transition metals, i.e., the noble metals. Such noble metal catalysts are described in U.S. Pat. No. 3,923,705, incorporated herein by reference to show platinum catalysts.
  • One preferred platinum catalyst is Karstedt's catalyst, which is described in Karstedt's U.S. Pat. Nos. 3,715,334 and 3,814,730, incorporated herein by reference.
  • Karstedt's catalyst is a platinum divinyl tetramethyl disiloxane complex typically containing about one weight percent of platinum in a solvent such as toluene.
  • Another preferred platinum catalyst is a reaction product of chloroplatinic acid and an organosilicon compound containing terminal aliphatic unsaturation. It is described in U.S. Pat. No. 3,419,593, incorporated herein by reference.
  • Most preferred as the catalyst is a neutralized complex of platinous chloride and divinyl tetramethyl disiloxane, for example as described in U.S. Pat. No. 5,175,325.
  • the noble metal catalyst can be used in an amount of from 0.00001-0.5 parts per 100 weight parts of the ⁇ SiH containing polysiloxane. Preferably, the catalyst should be used in an amount sufficient to provide 5-15 parts per million (ppm) Pt metal per total composition.
  • Carrying out of the process is simply a matter of combining the ⁇ SiH containing polysiloxane(s), the material containing unsaturation, i.e., the organic diamide, and the catalyst; and mixing these ingredients.
  • the reaction temperature can vary over a wide range, and the optimum temperature is dependent upon the concentration of the catalyst and the nature of the reactants. Ordinarily, it is best to keep the reaction temperature below about 300° C. Best results with most reactants can be obtained by initiating the reaction at about 80° C. to 180° C., and maintaining the reaction within reasonable limits of this range.
  • the process is carried out using approximately a 1:1 molar ratio of ⁇ Si—H containing polysiloxane and the material containing unsaturation. It is expected that useful materials may also be prepared by carrying out the process with an excess of either the ⁇ Si—H containing polysiloxane or the material containing unsaturation, but this would be considered a less efficient use of the materials.
  • the process can also be used to make other types of siloxane-based polyamides in which the repeating unit of the siloxane-based polyamide is represented by the formula
  • X is a linear or branched C 1 -C 30 alkylene chain
  • Y, Y 1 , and Y 2 are linear or branched C 1 -C 20 alkylene chains
  • DP1, DP2, and DP3 are integers each having values of 10-500
  • n, m, and p are integers each having values of 1-500
  • Z is represented by
  • R′, R′′, and R′′′ are linear or branched C 1 -C 10 alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by 1-3 members which are methyl or ethyl, or T is a trivalent atom such as N, P and Al; provided n is not the same as m, or Y is not the same as Y 1 , or DP1 is not the same as DP2.
  • siloxane-based polyamides Following are specific synthesis examples for forming siloxane-based polyamides according to the method of this invention. Unless otherwise indicated, the vacuums described in Examples 1-4 are in the range of 5-20 millimeters of mercury. While particular siloxane-based polyamides are disclosed or used in the following Examples, it is to be understood that other siloxane-based polyamides, for example, those made with a purified siloxane diacid, dianhydride, diester, or diacid chloride, may also be used.
  • the temperature was increased to 185 degrees C., and 279.2 g of a 30 DP dimethylhydrogen endblocked polydimethylsiloxane was added to the flask over a 30 minute period. After complete addition, a dean stark trap was used to replace the addition funnel on the flask, and the toluene was removed from the flask. After removal of the toluene, the materials were allowed to react for an additional period of one hour. Vacuum stripping was applied to the flask for 1 hour to ensure complete removal of any residual solvent. The temperature of the final siloxane-based polyamide was cooled to 150° C. and poured off while still in the melt form.
  • the temperature controller was increased to 120 degrees C., and 65 g of toluene, and 0.5 g of a solution containing platinum in the form of a complex of platinous chloride and divinyl tetramethyl disiloxane, were added to the flask.
  • the temperature was then increased to 185 degrees C., and 222.0 g of a 20 DP dimethylhydrogen endblocked polydimethylsiloxane was added to the flask over a 30 minute period.
  • a dean stark trap was used to replace the addition funnel on the flask, and the toluene was removed from the flask. After removal of the toluene, the materials were allowed to react for an additional period of one hour. Vacuum stripping was applied to the flask for 1 hour to ensure complete removal of any residual solvent.
  • the temperature of the final siloxane-based polyamide was cooled to 150° C. and poured off while still in the melt form.
  • the temperature was increased to 120 degrees C., and 65 g of toluene, and 0.5 g of a solution containing platinum in the form of a complex of platinous chloride and divinyl tetramethyl disiloxane were added to the flask.
  • the temperature was then increased to 185 degrees C., and 168.72 g of a 15 DP dimethylhydrogen endblocked polydimethylsiloxane was added to the flask over a 30 minute period.
  • a dean stark trap was used to replace the addition funnel on the flask, and the toluene was removed from the flask. After removal of the toluene, the materials were allowed to react for an additional period of one hour. Vacuum stripping was applied to the flask for 1 hour to ensure complete removal of any residual solvent.
  • the temperature of the final siloxane-based polyamide was cooled to 150° C. and poured off while still in the melt form.
  • the temperature was increased to 120 degrees C., and 65 g of toluene, and 0.5 g of a solution containing platinum in the form of a complex of platinous chloride and divinyl tetramethyl disiloxane, were added to the flask.
  • the temperature was then increased to 185 degrees C., and 150.97 g of a 10 DP dimethylhydrogen endblocked polydimethylsiloxane was added to the flask over a 30 minute period.
  • a dean stark trap was used to replace the addition funnel on the flask, and the toluene was removed from the flask. After removal of the toluene, the materials were allowed to react for an additional period of one hour. Vacuum stripping was applied to the flask for 1 hour to ensure complete removal of any residual solvent.
  • the temperature of the final siloxane-based polyamide was cooled to 150° C. and poured off while still in the melt form.
  • undecylenic acid acrylic acid, 3-butenoic acid (vinylacetic acid), and 4-pentenoic acid
  • olefinic acids it should be understood that other branched or straight-chain alkenoic acids C n H 2n-2 )O 2 O 2 can be employed in accordance with the method of the present invention.
  • the siloxane-based polyamides according to this present invention can be used as thickening agents in hair, skin, underarm, and cosmetic, product applications.
  • the siloxane units provide compatibility with silicone fluids such as cyclomethicones, while the amide linkages and the spacing and selection of the locations of the amide linkages, facilitate thickening and formation of such products.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Dermatology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Silicon Polymers (AREA)
  • Polyamides (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

A method of making siloxane-based polyamides which includes at least one repeating unit represented by the formula
Figure USRE038116-20030506-C00001
wherein X is a linear or branched C1-C30 alkylene chain; Y is a linear or branched C1-C20 alkylene chain; DP is an integer having a value of 10-500; n is an integer having a value 1-500. The method involves heating an intimate reaction mixture containing an olefinic acid and an organic diamine at a temperature greater than 100° C. and forming an organic diamide; and thereafter reacting the organic diamide with a hydride-terminated polydimethylsiloxane in the presence of a hydrosilylation catalyst to form the siloxane-based polyamide.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
REFERENCE TO A MICROFICHE APPENDIX
Not applicable.
FIELD OF THE INVENTION
This invention is directed to an improvement in the method of making siloxane-based polyamides described in a prior copending application, U.S. Ser. No. 08/904,709, filed Aug. 1, 1997, and entitled “Cosmetic Composition Containing Siloxane-Based Polyamides as Thickening Agents”, hereafter referred to as the '709 application.
BACKGROUND OF THE INVENTION
The present invention relates to a novel method of making siloxane-based polyamides.
There is a growing demand in the personal care arena for polymeric materials capable of thickening dimethylcyclosiloxanes in order to modify product viscosity in various market niche hair, skin, cosmetic, and underarm, applications.
The '709 application is directed to one type of a process for preparing siloxane-based polyamides. The process according to the '709 application involves many steps, and this results in cost prohibitive products which are difficult to produce in commercial quantity.
For example, in the '709 application process, a dimethyl hydride endblocked polydimethylsiloxane is first prepared containing the appropriate number of siloxane units to achieve a desired value of DP. The carboxylic acid group of undecylenic acid is then protected through reaction with hexamethyldisilazane. The dimethyl hydride endblocked polydimethylsiloxane and the protected undecylenic acid are reacted to produce a siloxane diacid, i.e., a carboxydecyl terminated polydimethylsiloxane. This reaction is accomplished in the presence of a platinum catalyst, and the product is washed with methanol to remove the trimethylsilyl protecting group from the protected siloxane diacid. The siloxane diacid is then reacted with an organic diamine to produce a siloxane-based polyamide.
Accordingly, a new process has been discovered herein that eliminates many of the otherwise costly steps involved in the process according to the '709 application.
The new process basically involves the addition of an olefinic acid with an organic diamine to produce an organic diamide. One the olefinic acid and the organic diamine are fully reacted, an ≡SiH endblocked polysiloxane is added in the presence of a platinum catalyst, to produce a siloxane-based polyamide via hydrosilylation. The resulting polymeric product is in the form of a high molecular weight thermoplastic polymer. The benefits of this process is that it allows for the production of a cost effective manufactured product in commercial quantity.
BRIEF SUMMARY OF THE INVENTION
This invention relates to a method of forming a siloxane-based polyamides which are useful as thickening agents to formulate a wide variety of cosmetic compositions. The polyamides of this invention are multiples of a unit represented by the following Formula A:
Figure USRE038116-20030506-C00002
where:
(1) The degree of polymerization (DP) is 1-700, preferably 10-500, and more preferably 15-45. DP represents an average value for degree of polymerization of the siloxane units in the polymer with greater or lesser DP values centered around the indicated DP value.
(2) n is 1-500, particularly 1-100, and more particularly 4-25.
(3) X is a linear or branched chain alkylene having 1-30 carbons, particularly 3-10 carbons, and more particularly 10 carbons.
(4) Y is a linear or branched chain alkylene having 1-40 carbons, particularly 1-20 carbons, more particularly 2-6 carbons, and especially 6 carbons wherein
(a) The alkylene group may optionally and additionally contain in the alkylene portion at least one of (i) 1-3 amide linkages; (ii) a C5 or C6 cycloalkane; or (iii) phenylene, optionally substituted by 1-3 members which are independently C1-C3 alkyls; and
(b) the alkylene group itself may optionally be substituted by at least one of (i) hydroxy; (ii) a C3-C8 cycloalkane; (iii) 1-3 members which are independently C1-C3 alkyls; phenyl, optionally substituted by 1-3 members which are independently C1-C3 alkyls; (iv) a C1-C3 alkyl hydroxy; or (v) a C1-C6 alkyl amine; and
(c) Y can be Z where Z is T(R20)(R21)(R22) where R20, R21 and R22 are each independently linear or branched C1-C 10 alkylenes; and T is CR in which R is hydrogen, the group defined for R1-R4, or a trivalent atom such as N, P and Al.
(5) Each of R1-R4 (collectively “R”) is independently methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by 1-3 members which are methyl or ethyl. More particularly, R1-R4 are methyl or ethyl, especially methyl.
(6) X, Y, DP, and R1-R4 may be the same or different for each polyamide unit.
By “siloxane chain” is meant a group of units such as:
Figure USRE038116-20030506-C00003
where R30 and R31 are each independently organic moieties; and each R30 and R31 are connected to silicon by a carbon-silicon bond.
The carbon numbers in the alkylene chain do not include the carbons in the extra segments or substitutions. Also, the polyamides must have a siloxane portion in the backbone and optionally may have a siloxane portion in a pendant or branched portion.
If repeated with no variations in the defined variables, Formula A is representative of a linear homopolymer. Variations of the invention include: (1) polyamides in which multiple values of DP, and of units X, Y, and R1-R4 occur in one polymeric molecule, and wherein the sequencing of these units may be alternating, random or block; (2) polyamides in which an organic triamine or higher amine such as tris(2-aminoethyl)amine replaces the organic diamine in part, to produce a branched or crosslinked molecule; and (3) physical blends of any of (1) and (2) and/or linear homopolymers.
These and other features of the invention will become apparent from a consideration of the detailed description.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
Not applicable.
DETAILED DESCRIPTION OF THE INVENTION
This invention is directed to a new and novel process for making siloxane-based polyamides. As it relates to the '709 application, the process eliminates costly steps and produces a polymer with higher molecular weights than achieved with the previous process in the '709 application. For example, average molecular weights as measured by gel permeation chromatography (GPC), using the process according to the '709 application were determined to be approximately 50,000. The new process according to the present invention produces average molecular weights of approximately 65,000.
In addition, the process according to this invention is much faster than the particular process of the '709 application as well as other traditional processes for making siloxane-based polyamides. The '709 application process takes approximately four days to make a finished siloxane-based polyamide polymer, while the new route according to the present invention takes approximately one day. The thermoplastic polymer produced as a result of the instant process is ideal for the thickening of dimethylcyclosiloxanes, which renders it of benefit in a large number of personal care product applications.
Basically the new, process involves the addition of an olefinic acid such as undecylenic acid H2C═CH(CH2)8COOH to an organic diamine such as hexamethylene diamine H2N(CH2)6NH2, to produce an organic diamide. This organic diamide product is then reacted with an ≡SiH endblocked polysiloxane in the presence of a platinum catalyst to produce the siloxane-based polyamide. Analysis using GPC confirm and indicate the achievement of high molecular weight growth using the process according to the present invention.
Some examples of compounds of Formula A include:
1) Polyamides of Formula I:
Figure USRE038116-20030506-C00004
 where X, Y, n, R1-R4, and DP are as defined for Formula A, A particular subgroup of Formula I are compounds where R1, R2, R3 and R4 are each methyl.
Preferred polyamides of Formula I are:
Figure USRE038116-20030506-C00005
where DP is 10-500, particularly 15-45, and more particularly 29. Another particular group contains polyamides of Formula I where X, Y, DP and R1-R4 are the same in each unit of the polymer.
2) Polyamides containing multiple siloxane block lengths as shown in Formula II:
Figure USRE038116-20030506-C00006
 where X, Y, n, and R1-R4 have the meanings described above for Formula A; m is the same as the value defined for n; and n and m denote the total number of units enclosed within the brackets; with the individual units arranged with regular, alternating, block, or random sequencing.
R5-R8 is the same group as defined for R1-R4; DP1 and DP2 may be the same or different, and each can be independently the same as defined for DP. The units denominated by n and m may be structured to form either block (regularly sequenced) or random copolymers.
A particular subgroup for compounds of Formula II may have methyl for all R groups. Another particular subgroup of compounds of Formula II may have DP1 equal to DP2. A third particular subgroup may have methyl for all R groups, and DP1 equal to DP2.
3) Polyamides synthesized from multiple diamines as shown in Formula III:
Figure USRE038116-20030506-C00007
 where X, Y, m, n, R1-R8, DP1, DP2 have the same meanings as described above for Formula A and Formula II; Y1 is independently selected from the same group as defined for Y; and the units denominated by n and m may be structured to form either block (regularly sequenced) or random copolymers.
A particular subgroup of compounds of Formula III may have DP1 equal to DP2. Another particular subgroup of compounds of Formula III may have methyl for all R groups. A third particular subgroup may have methyl for all R groups, and DP1 equal to DP2.
4) Polyamides synthesized with a trifunctional amine as shown in Formula IV:
Figure USRE038116-20030506-C00008
 where X, Y, Y1, R1-R8, m, n, DP1, and DP2, are the same as defined above; R9-R12 are the same as defined for R1-R8; DP3 is the same as defined for DP; p is the same as defined for m and n; Z is T(R20)(R21)(R22) where R20, R21 and R22 are each independently linear or branched C1-C10 alkylenes; and T is CR where R is hydrogen, the same as defined for R1-R4, or a trivalent atom such as N, P and Al.
Preferred values for p are 1-25, with more preferred values being 1-7. Preferred units for R1-R12 are methyl. T is preferably N. Particular values for DP1 to DP3 are 10-500, and more particularly 15-45. R20, R21, and R22 are preferably ethylene. A preferred group representative of Z is (—CH2CH2)3N.
One particular group of compounds of Formula IV is represented by the formula
Figure USRE038116-20030506-C00009
where X is —(CH2)10—, Y is —(CH2)—; DP is 15-45; m is 5-20% of n+p; and Z is (—CH2CH2)3N.
Siloxane-based polyamides according to this invention (1) contain both siloxane groups and amide groups which facilitate the thickening of compositions containing volatile silicone fluids and non-volatile silicone fluids; (2) are non-flowable solids at room temperature; and (3) dissolve in a fluid which contains silicone at a temperature of 25-160° C., to form translucent or clear solutions at a temperature in this range.
With regard to the siloxane units in the siloxane-based polyamides, the siloxane units must be in the main or backbone chain but can also optionally be present in branched or pendent chains. In the main chain the siloxane units occur in segments as described above. In the branched or pendent chains the siloxane units can occur individually or in segments.
Particular groups of siloxane-based polyamides include:
(a) polyamides of Formula I where the DP is 15-50;
(b) physical blends of two or more polyamides wherein at least one polyamide has a value for DP in the range of 15-50, and at least one polyamide has a value for DP in the range of 30-500;
(c) compounds of Formula II where (1) the value for DP1 is 15-50, and the value for DP2 is 30-500; and (2) the portion of the polyamide having DP1 is about 1-99 weight % based on the weight of the total polyamide content, and the portion of the polyamide having DP2 is about 1-99 weight %;
(d) physical blends of polyamides of Formula I made by combining (1) 80-99 weight % of a polyamide where n is 2-10, and especially where n is 3-6; and (2) 1-20 weight % of a polyamide where n is 5-500, especially where n is 6-100;
(e) polyamides of Formula III where at least one Y or Y1 contains at least one hydroxyl substitution;
(f) polyamides of Formula A synthesized with at least a portion of an activated diacid, such as a diacid chloride, dianhydride, or diester, instead of the diacid;
(g) polyamides of Formula A where X is —(CH2)3—; and
(h) polyamides of Formula A where X is —(CH2)10—.
THE PROCESS ACCORDING TO THE '709 APPLICATION
A reaction scheme for making polyamides of Formula I according to the '709 application involves the condensation of a siloxane diacid with an organic diamine as shown below.
(1) A dimethyl hydride endblocked polydimethylsiloxane, such as one of the type shown below, is prepared containing the appropriate number of siloxane units “n” to achieve the desired value of DP.
Figure USRE038116-20030506-C00010
(2) The carboxylic acid group of undecylenic acid is protected through reaction with hexamethyldisilazane (CH3)3—Si—NH—Si—(CH3)3. This step is shown below.
Figure USRE038116-20030506-C00011
(3) The dimethyl hydride endblocked polydimethylsiloxane and the protected undecylenic acid (the products of Steps (1) and (2)) are reacted to produce a siloxane diacid )carboxydecyl terminated polydimethylsiloxane). This reaction is accomplished in the presence of a platinum catalyst such as chloroplatinic acid, and the product is washed with methanol to remove the trimethylsilyl protecting group from the protected siloxane diacid shown below.
Figure USRE038116-20030506-C00012
where Q is
Figure USRE038116-20030506-C00013
(4) The siloxane diacid (product of Step (3)) is reacted with an organic diamine to produce a siloxane-based polyamide. The siloxane diacid is shown below. This reaction may involve the use of a reaction solvent such as toluene or xylene.
Figure USRE038116-20030506-C00014
Figure USRE038116-20030506-C00015
THE PROCESS ACCORDING TO THE PRESENT INVENTION
The simplified process of the present invention can be illustrated schematically with reference to the following reaction scenario in which an olefinic acid is reacted with an organic diamine to produce an organic diamide.
Figure USRE038116-20030506-C00016
The organic diamide is then in turn reacted with a hydride-terminated polydimethylsiloxane of the structure such as the one depicted below:
Figure USRE038116-20030506-C00017
in the presence of a hydrosilylation catalyst to form a siloxane-based polyamide which includes at least one repeating unit represented by the formula
Figure USRE038116-20030506-C00018
wherein X is a linear or branched C1-C30 alkylene chain; Y is a linear or branched C1-C20 alkylene chain; DP is an integer having a value of 10-500; n is an integer having a value of 1-500.
Suitable olefinic acids which can be used include undecylenic acid H2C═CH(CH2)8COOH, acrylic acid H2C═CHCOOH, 3-butenoic acid (vinylacetic acid) H2C═CHCH2COOH, 4-pentenoic acid H2C═CHCH2COOH, and other olefinic acids with carbon chains of varying length.
Organic amines which can be used herein preferably include linear alkyl diamines such as hexamethylene diamine, ethylene diamine, and mixtures of linear alkyl diamines, as well as other amines such as decamethylene diamine.
A platinum catalyzed hydrosilylation reaction is employed according to this invention. Generally, hydrosilylation involves the reaction between a polysiloxane containing ≡Si—H groups, and a material containing unsaturation, e.g., vinyl groups. Some attractive features of this mechanism are that no by-products are formed, and hydrosilylation will proceed even at room temperature. In the mechanism, crosslinking involves addition of ≡SiH across double bonds, i.e.,
≡SiH+CH2═R→≡SiCH2CH2—R.
The process requires a catalyst to effect the reaction between the ≡SiH containing polysiloxane and the material containing unsaturation, i.e., the organic diamide in the case of the present invention. Suitable catalysts are Group VIII transition metals, i.e., the noble metals. Such noble metal catalysts are described in U.S. Pat. No. 3,923,705, incorporated herein by reference to show platinum catalysts. One preferred platinum catalyst is Karstedt's catalyst, which is described in Karstedt's U.S. Pat. Nos. 3,715,334 and 3,814,730, incorporated herein by reference. Karstedt's catalyst is a platinum divinyl tetramethyl disiloxane complex typically containing about one weight percent of platinum in a solvent such as toluene. Another preferred platinum catalyst is a reaction product of chloroplatinic acid and an organosilicon compound containing terminal aliphatic unsaturation. It is described in U.S. Pat. No. 3,419,593, incorporated herein by reference. Most preferred as the catalyst is a neutralized complex of platinous chloride and divinyl tetramethyl disiloxane, for example as described in U.S. Pat. No. 5,175,325.
The noble metal catalyst can be used in an amount of from 0.00001-0.5 parts per 100 weight parts of the ≡SiH containing polysiloxane. Preferably, the catalyst should be used in an amount sufficient to provide 5-15 parts per million (ppm) Pt metal per total composition.
Carrying out of the process is simply a matter of combining the ≡SiH containing polysiloxane(s), the material containing unsaturation, i.e., the organic diamide, and the catalyst; and mixing these ingredients. The reaction temperature can vary over a wide range, and the optimum temperature is dependent upon the concentration of the catalyst and the nature of the reactants. Ordinarily, it is best to keep the reaction temperature below about 300° C. Best results with most reactants can be obtained by initiating the reaction at about 80° C. to 180° C., and maintaining the reaction within reasonable limits of this range.
Typically, the process is carried out using approximately a 1:1 molar ratio of ≡Si—H containing polysiloxane and the material containing unsaturation. It is expected that useful materials may also be prepared by carrying out the process with an excess of either the ≡Si—H containing polysiloxane or the material containing unsaturation, but this would be considered a less efficient use of the materials.
The process can also be used to make other types of siloxane-based polyamides in which the repeating unit of the siloxane-based polyamide is represented by the formula
Figure USRE038116-20030506-C00019
or by the formula
Figure USRE038116-20030506-C00020
wherein X is a linear or branched C1-C30 alkylene chain; Y, Y1, and Y2 are linear or branched C1-C20 alkylene chains; DP1, DP2, and DP3 are integers each having values of 10-500; n, m, and p are integers each having values of 1-500; Z is represented by
Figure USRE038116-20030506-C00021
wherein R′, R″, and R″′ are linear or branched C1-C10 alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by 1-3 members which are methyl or ethyl, or T is a trivalent atom such as N, P and Al; provided n is not the same as m, or Y is not the same as Y1, or DP1 is not the same as DP2.
EXAMPLES
Following are specific synthesis examples for forming siloxane-based polyamides according to the method of this invention. Unless otherwise indicated, the vacuums described in Examples 1-4 are in the range of 5-20 millimeters of mercury. While particular siloxane-based polyamides are disclosed or used in the following Examples, it is to be understood that other siloxane-based polyamides, for example, those made with a purified siloxane diacid, dianhydride, diester, or diacid chloride, may also be used.
Example 1
30 DP Polymer
A 500 ml three neck flask equipped with a thermometer, electrical stirrer, nitrogen sweep, and a condenser, was charged with 50.12 g of undecylenic acid, and 22.58 g of a 70% hexamethylene diamine mixture in water. The flask was immediately heated to 225 degrees C. and kept at this temperature for 2 hours. After 2 hours, a vacuum was applied to the system for 2 hours to remove any unreacted materials. Upon completion of vacuum stripping, the flask was reweighed to obtain the product weight. The temperature was increased to 120 degrees C., and 65 g of toluene, complex of platinous chloride and divinyl tetramethyl disiloxane, were added to the flask. The temperature was increased to 185 degrees C., and 279.2 g of a 30 DP dimethylhydrogen endblocked polydimethylsiloxane was added to the flask over a 30 minute period. After complete addition, a dean stark trap was used to replace the addition funnel on the flask, and the toluene was removed from the flask. After removal of the toluene, the materials were allowed to react for an additional period of one hour. Vacuum stripping was applied to the flask for 1 hour to ensure complete removal of any residual solvent. The temperature of the final siloxane-based polyamide was cooled to 150° C. and poured off while still in the melt form.
Example 2
20 DP Polymer
A 500 ml three neck flask equipped with a thermometer, electrical stirrer, nitrogen sweep, and a condenser, was charged with 55.0 g of undecylenic acid, and 24.77 g of a 70% hexamethylene diamine mixture in water. The flask was immediately heated to 225 degrees C., and kept at this temperature for 2 hours. After 2 hours, a vacuum was applied to the system for 2 hour to remove any unreacted materials. Upon completion of vacuum stripping, the flask was reweighed to obtain the product weight. The temperature controller was increased to 120 degrees C., and 65 g of toluene, and 0.5 g of a solution containing platinum in the form of a complex of platinous chloride and divinyl tetramethyl disiloxane, were added to the flask. The temperature was then increased to 185 degrees C., and 222.0 g of a 20 DP dimethylhydrogen endblocked polydimethylsiloxane was added to the flask over a 30 minute period. After complete addition, a dean stark trap was used to replace the addition funnel on the flask, and the toluene was removed from the flask. After removal of the toluene, the materials were allowed to react for an additional period of one hour. Vacuum stripping was applied to the flask for 1 hour to ensure complete removal of any residual solvent. The temperature of the final siloxane-based polyamide was cooled to 150° C. and poured off while still in the melt form.
Example 3
15 DP Polymer
A 500 ml three neck flask equipped with a thermometer, electrical stirrer, nitrogen sweep, and a condenser, was charged with 57.75 g of undecylenic acid, and 24.77 g of a 70% hexamethylene diamine mixture in water. The flask was immediately heated to 225 degrees C., and kept at this temperature for 2 hours. After 2 hours, a vacuum was applied to the system for 2 hours to remove any unreacted materials. Upon completion of vacuum stripping, the flask was reweighed to obtain the product weight. The temperature was increased to 120 degrees C., and 65 g of toluene, and 0.5 g of a solution containing platinum in the form of a complex of platinous chloride and divinyl tetramethyl disiloxane were added to the flask. The temperature was then increased to 185 degrees C., and 168.72 g of a 15 DP dimethylhydrogen endblocked polydimethylsiloxane was added to the flask over a 30 minute period. After complete addition, a dean stark trap was used to replace the addition funnel on the flask, and the toluene was removed from the flask. After removal of the toluene, the materials were allowed to react for an additional period of one hour. Vacuum stripping was applied to the flask for 1 hour to ensure complete removal of any residual solvent. The temperature of the final siloxane-based polyamide was cooled to 150° C. and poured off while still in the melt form.
Example 4
10 DP Polymer
A 500 ml three neck flask equipped with a thermometer, electrical stirrer, nitrogen sweep, and a condenser, was charged with 67.0 g of undecylenic acid, and 29.82 g of a 70% hexamethylene diamine mixture in water. The flask was immediately heated to 225 degrees C., and kept at this temperature for 2 hours. After 2 hours, a vacuum was applied to the system for 2 hours to remove any unreacted materials. Upon completion of vacuum stripping, the flask was reweighed to obtain the product weight. The temperature was increased to 120 degrees C., and 65 g of toluene, and 0.5 g of a solution containing platinum in the form of a complex of platinous chloride and divinyl tetramethyl disiloxane, were added to the flask. The temperature was then increased to 185 degrees C., and 150.97 g of a 10 DP dimethylhydrogen endblocked polydimethylsiloxane was added to the flask over a 30 minute period. After complete addition, a dean stark trap was used to replace the addition funnel on the flask, and the toluene was removed from the flask. After removal of the toluene, the materials were allowed to react for an additional period of one hour. Vacuum stripping was applied to the flask for 1 hour to ensure complete removal of any residual solvent. The temperature of the final siloxane-based polyamide was cooled to 150° C. and poured off while still in the melt form.
Although undecylenic acid, acrylic acid, 3-butenoic acid (vinylacetic acid), and 4-pentenoic acid, have been set forth as being representative examples of some suitable olefinic acids, it should be understood that other branched or straight-chain alkenoic acids CnH2n-2)O2O2 can be employed in accordance with the method of the present invention.
The siloxane-based polyamides according to this present invention can be used as thickening agents in hair, skin, underarm, and cosmetic, product applications. The siloxane units provide compatibility with silicone fluids such as cyclomethicones, while the amide linkages and the spacing and selection of the locations of the amide linkages, facilitate thickening and formation of such products.
Other variations may be made in compounds, compositions, and methods described herein without departing from the essential features of the invention. The embodiments of the invention specifically illustrated herein are exemplary only and not intended as limitations on their scope except as defined in the appended claims.

Claims (20)

I claim:
1. A method of making a siloxane-based polyamide which includes at least one repeating unit represented by the formula
Figure USRE038116-20030506-C00022
wherein X is a linear or branched C3 to C10 alkylene chain; Y is a linear or branched C1-C20 alkylene chain; R1-R4 are independently methyl, ethyl, propyl, isopropyl, a siloxane chain, phenyl, or phenyl substituted by 1-3 members which are methyl or ethyl; DP is an integer having a value of 10-500; and n is an integer having a value of 1-500;
the method comprising heating a reaction mixture containing an olefinic acid and an organic diamine at a temperature greater than 100° C. and forming an organic diamide; and thereafter reacting the organic diamide with a hydride-terminated polydimethylsiloxane in the presence of a hydrosilylation catalyst to form the siloxane-based polyamide.
2. A method according to claim 1 in which the organic diamine is a compound selected from the group consisting of hexamethylene diamine, ethylene diamine, and decamethylene diamine.
3. A method according to claim 1 in which the olefinic acid is a compound selected from the group consisting of undecylenic acid, acrylic acid, 3-butenoic acid, and 4-pentenoic acid.
4. A method according to claim 1 in which the siloxane-based polyamide has a number average molecular weight of from 4,000 to 200,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.
5. A method according to claim 4 in which the siloxane-based polyamide has a number average molecular weight of from 5,000 to 65,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.
6. A method according to claim 1 in which the repeating unit of the siloxane-based polyamide is represented by the formula
Figure USRE038116-20030506-C00023
wherein X is a linear or branched C3 to C10 alkylene chain; Y, Y1, and Y2 are linear or branched C1-C20 alkylene chains; DP1, DP2, and DP3 are integers each having values of 10-500; n, m, and p are integers each having values of 1-500; Z is represented by
Figure USRE038116-20030506-C00024
wherein R′, R″, and R″′ are linear or branched C1-C10 alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by 1-3 members which are methyl or ethyl, or T is a trivalent atom such as N, P and Al; provided n is not the same as m, or Y is not the same as Y1, or DP1 is not the same as DP2.
7. A method of making a siloxane-based polyamide which includes at least one repeating unit represented by the formula
Figure USRE038116-20030506-C00025
wherein X is a linear or branched C3 to C10 alkylene chain; Y is a linear or branched C1-C20 alkylene chain; R1-R4 are independently methyl, ethyl, propyl, isopropyl, a siloxane chain, phenyl, or phenyl substituted by 1-3 members which are methyl or ethyl; DP is an integer having a value of 10-500; and n is an integer having a value of 1-500;
the method comprising reacting an organic diamide with a hydride-terminated polydimethylsiloxane in the presence of a hydrosilylation catalyst to form the siloxane-based polyamide.
8. A method according to claim 7 in which the siloxane-based polyamide has a number average molecular weight of from 4,000 to 200,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.
9. A method according to claim 8 in which the siloxane-based polyamide has a number average molecular weight of from 5,000 to 65,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.
10. A method according to claim 7 in which the repeating unit of the siloxane-based polyamide is represented by the formula
Figure USRE038116-20030506-C00026
Figure USRE038116-20030506-C00027
wherein X is a linear or branched C3 to C10 alkylene chain; Y, Y1, and Y2 are linear or branched C1-C20 alkylene chains; DP1, DP2, and DP3 are integers each having values of 10-500; n, m, and p are integers each having values of 1-500; Z is represented by
Figure USRE038116-20030506-C00028
wherein R′, R″, and R′″ are linear or branched C1-C10 alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by 1-3 members which are methyl or ethyl, or T is a trivalent atom such as N, P and Al; provided n is not the same as m, or Y is not the same as Y1, or DP1 is not the same as DP2.
11. A method of making a siloxane-based polyamide which includes at least one repeating unit represented by the formula
Figure USRE038116-20030506-C00029
wherein X is a linear or branched C 3 -C 10 alkylene chain; Y is a linear or branched C 1 -C 20 alkylene chain; R 1 -R 4 are independently methyl, ethyl, propyl, isopropyl, a siloxane chain, phenyl, or phenyl substituted by 1-3 members which are methyl or ethyl; DP is an integer having a value of 10-500; and n is an integer having a value of 1-500;
the method comprising heating a reaction mixture containing an olefinic acid and an organic diamine at a temperature greater than 100° C. and forming an organic diamide; and thereafter reacting the organic diamide with an ≡SiH containing polysiloxane in the presence of a hydrosilylation catalyst to form the siloxane-based polyamide.
12. A method according to claim 11 in which the organic diamine is a compound selected from the group consisting of hexamethylene diamine, ethylene diamine, and decamethylene diamine.
13. A method according to claim 11 in which the olefinic acid is a compound selected from the group consisting of undecylenic acid, acrylic acid, 3-butenoic acid, and 4 -pentenoic acid.
14. A method according to claim 11 in which the siloxane-based polyamide has a number average molecular weight of from 4,000 to 200,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.
15. A method according to claim 14 in which the siloxane-based polyamide has a number average molecular weight of from 5,000 to 65,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.
16. A method according to claim 11 in which the repeating unit of the siloxane-based polyamide is represented by the formula
Figure USRE038116-20030506-C00030
or the formula
Figure USRE038116-20030506-C00031
wherein X is a linear or branched C 3 -C 10 alkylene chain; Y, Y 1 , and Y 2 are linear or branched C 1 -C 20 alkylene chains; DP1, DP2, and DP3 are integers each having values of 10-500; n, m, and p are integers each having values of 1-500; Z is represented by
Figure USRE038116-20030506-C00032
wherein R′, R″, and R′″ are linear or branched C 1 -C 10 alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by 1-3 members which are methyl or ethyl, or T is a trivalent atom such as N, P and Al; provided n is not the same as m, or Y is not the same as Y 1 , or DP1 is not the same as DP2.
17. A method of making a siloxane-based polyamide which includes at least one repeating unit represented by the formula
Figure USRE038116-20030506-C00033
wherein X is a linear or branched C 3 -C 10 alkylene chain; Y is a linear or branched C 1 -C 20 alkylene chain; R 1 -R 4 are independently methyl, ethyl, propyl, isopropyl, a siloxane chain, phenyl, or phenyl substituted by 1-3 members which are methyl or ethyl; DP is an integer having a value of 10-500; and n is an integer having a value of 1-500;
the method comprising reacting an organic diamide with an ≡SiH containing polysiloxane in the presence of a hydrosilylation catalyst to form the siloxane-based polyamide.
18. A method according to claim 17 in which the siloxane-based polyamide has a number average molecular weight of from 4,000 to 200,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.
19. A method according to claim 18 in which the siloxane-based polyamide has a number average molecular weight of from 5,000 to 65,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.
20. A method according to claim 17 in which the repeating time of the siloxane-based polyamide is represented by the formula
Figure USRE038116-20030506-C00034
or the formula
Figure USRE038116-20030506-C00035
wherein X is a linear or branched C 3 -C 10 alkylene chain; Y, Y 1 , and Y 2 are linear or branched C 1 -C 20 alkylene chains; DP1, DP2, and DP3 are integers each having values of 10-500; n, m, and p are integers each having values of 1-500; Z is represented by
Figure USRE038116-20030506-C00036
wherein R′, R″, and R′″ are linear or branched C 1 -C 10 alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by 1-3 members which are methyl or ethyl, or T is a trivalent atom such as N, P and Al; provided n is not the same as m, or Y is not the same as Y 1 , or DP1 is not the same as DP2.
US10/035,497 1998-07-13 2001-11-08 Method of making siloxane-based polymides Expired - Lifetime USRE38116E1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/035,497 USRE38116E1 (en) 1998-07-13 2001-11-08 Method of making siloxane-based polymides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/114,381 US5981680A (en) 1998-07-13 1998-07-13 Method of making siloxane-based polyamides
US10/035,497 USRE38116E1 (en) 1998-07-13 2001-11-08 Method of making siloxane-based polymides

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09/114,381 Reissue US5981680A (en) 1998-07-13 1998-07-13 Method of making siloxane-based polyamides

Publications (1)

Publication Number Publication Date
USRE38116E1 true USRE38116E1 (en) 2003-05-06

Family

ID=22354872

Family Applications (2)

Application Number Title Priority Date Filing Date
US09/114,381 Expired - Lifetime US5981680A (en) 1998-07-13 1998-07-13 Method of making siloxane-based polyamides
US10/035,497 Expired - Lifetime USRE38116E1 (en) 1998-07-13 2001-11-08 Method of making siloxane-based polymides

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US09/114,381 Expired - Lifetime US5981680A (en) 1998-07-13 1998-07-13 Method of making siloxane-based polyamides

Country Status (4)

Country Link
US (2) US5981680A (en)
EP (1) EP0974614B1 (en)
JP (1) JP4382196B2 (en)
DE (1) DE69901371T2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030105260A1 (en) * 2001-07-12 2003-06-05 Cook Leon Neal Methods for making silicone-organic copolymers
US20100210491A1 (en) * 2009-02-13 2010-08-19 Charles Piskoti Silicone Wax Emulsion and Method of Manufacture
US9872828B2 (en) 2014-05-21 2018-01-23 Dow Corning Corporation Emulsion of cross-linked aminosiloxane polymer
US9890253B2 (en) 2014-05-21 2018-02-13 Dow Corning Corporation Cross-linked aminosiloxane polymer and method of forming
WO2018165434A1 (en) 2017-03-08 2018-09-13 Dow Silicones Corporation Long lasting cosmetic composition comprising silicone elastomer

Families Citing this family (414)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2796271B1 (en) 1999-07-15 2002-01-11 Oreal COMPOSITION WITHOUT WAX STRUCTURED IN A RIGID FORM BY A POLYMER
FR2796272B1 (en) 1999-07-15 2003-09-19 Oreal COMPOSITION WITHOUT WAX STRUCTURED IN A RIGID FORM BY A POLYMER
FR2804018B1 (en) 2000-01-24 2008-07-11 Oreal COMPOSITION WITHOUT STRUCTURED TRANSFER IN RIGID FORM BY A POLYMER
US6451295B1 (en) 2000-08-31 2002-09-17 Colgate-Palmolive Company Clear antiperspirants and deodorants made with siloxane-based polyamides
DE60132805T2 (en) 2000-12-12 2009-01-29 L'oreal COSMETIC COMPOSITION USING A POLYMERIC MIXTURE
WO2002047623A1 (en) 2000-12-12 2002-06-20 L'oreal Sa Composition comprising at least one heteropolymer and at least one inert filler and methods for use
AU2001220877A1 (en) 2000-12-12 2002-06-24 L'oreal S.A. Cosmetic composition comprising heteropolymers and a solid substance and method of using same
WO2002047624A1 (en) 2000-12-12 2002-06-20 L'oreal Sa Cosmetic compositions containing at least one heteropolymer and at least one gelling agent and methods of using the same
US7276547B2 (en) 2000-12-12 2007-10-02 L'oreal S.A. Compositions comprising heteropolymers and at least one oil-soluble polymers chosen from alkyl celluloses and alkylated guar gums
US8080257B2 (en) 2000-12-12 2011-12-20 L'oreal S.A. Cosmetic compositions containing at least one hetero polymer and at least one film-forming silicone resin and methods of using
US6835399B2 (en) 2000-12-12 2004-12-28 L'ORéAL S.A. Cosmetic composition comprising a polymer blend
FR2817739B1 (en) 2000-12-12 2005-01-07 Oreal TRANSPARENT OR TRANSLUCENT COLORED COSMETIC COMPOSITION
US7025953B2 (en) 2001-01-17 2006-04-11 L'oreal S.A. Nail polish composition comprising a polymer
FR2819399B1 (en) 2001-01-17 2003-02-21 Oreal COSMETIC COMPOSITION CONTAINING POLYMER AND FLUORINATED OIL
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
WO2003006530A1 (en) * 2001-07-12 2003-01-23 Dow Corning Corporation Methods for making silicone-organic copolymers
AU2002331001A1 (en) * 2001-08-07 2003-02-24 Dow Corning Corporation Hair and skin care compositions containing siloxane-based polyamide copolymers
US6716420B2 (en) 2001-10-05 2004-04-06 L′Oreal Methods of use and of making a mascara comprising at least one coloring agent and at least one heteropolymer
US6815486B2 (en) * 2002-04-12 2004-11-09 Dow Corning Corporation Thermally conductive phase change materials and methods for their preparation and use
US8449870B2 (en) 2002-06-11 2013-05-28 Color Access, Inc. Stable cosmetic emulsion with polyamide gelling agent
US8333956B2 (en) 2002-06-11 2012-12-18 Color Access, Inc. Stable cosmetic emulsion with polyamide gelling agent
US7879316B2 (en) * 2002-06-12 2011-02-01 L'oreal Cosmetic composition containing a polyorganosiloxane polymer
US20030232030A1 (en) * 2002-06-12 2003-12-18 L'oreal Compositions containing at least one oil structured with at least one silicone-polyamide polymer, and at least one gelling agent and methods of using the same
US20030235548A1 (en) * 2002-06-12 2003-12-25 L'oreal Cosmetic composition for care and/or treatment and/or makeup of the emulsion type structured with silicone polymers
US20030235552A1 (en) * 2002-06-12 2003-12-25 L'oreal Cosmetic composition for care and/or makeup, structured with silicone polymers and film-forming silicone resins
US20050008598A1 (en) 2003-07-11 2005-01-13 Shaoxiang Lu Cosmetic compositions comprising a structuring agent, silicone powder and swelling agent
US6916464B2 (en) 2002-12-20 2005-07-12 L'oreal Sunscreen compositions
US6958155B2 (en) * 2002-06-12 2005-10-25 L'oreal Cosmetic compositions comprising at least one polysiloxane based polyamide
US20040120912A1 (en) * 2002-12-17 2004-06-24 L'oreal Compositions containing at least one oil structured with at least one silicone-polyamide polymer, and at least one crystalline silicone compound and methods of using the same
ES2346304T3 (en) * 2002-06-12 2010-10-14 L'oreal COSMETIC COMPOSITION OF CARE AND / OR STRUCTURED MAKEUP WITH SILICONE POLYMERS AND ORGANOGELIFYING AGENTS, IN A RIGID FORM.
FR2840807B1 (en) * 2002-06-12 2005-03-11 COSMETIC CARE AND / OR MAKEUP COMPOSITION, STRUCTURED BY SILICONE POLYMERS AND ORGANOGELATORS, IN RIGID FORM
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
US20040115154A1 (en) * 2002-12-17 2004-06-17 L'oreal Compositions containing at least one oil structured with at least one silicone-polyamide polymer, and at least one short chain ester and methods of using the same
US7329699B2 (en) 2003-07-11 2008-02-12 L'oreal Composition containing oil, structuring polymer, and coated silicone elastomer, and methods of making and using the same
US6743868B2 (en) * 2002-07-18 2004-06-01 Dow Corning Corporation Polyamide based thermoplastic silicone elastomers
US7008629B2 (en) 2002-07-22 2006-03-07 L'ORéAL S.A. Compositions comprising at least one heteropolymer and fibers, and methods of using the same
US8007772B2 (en) 2002-10-02 2011-08-30 L'oreal S.A. Compositions to be applied to the skin and the integuments
US6783692B2 (en) 2002-10-17 2004-08-31 Dow Corning Corporation Heat softening thermally conductive compositions and methods for their preparation
KR100969498B1 (en) * 2002-10-24 2010-07-13 다우 코닝 코포레이션 Siloxane-based amide modified nylon
US8728500B2 (en) * 2002-12-17 2014-05-20 L'oreal Composition containing a polyorganosiloxane polymer, a thickening agent and at least one volatile alcohol
AU2003290128A1 (en) * 2002-12-17 2004-07-09 L'oreal Care and/or make-up cosmetic composition structured with silicone polymers
US6838541B2 (en) * 2003-02-12 2005-01-04 Dow Corning Corporation Method of making siloxane-based polyamide elastomers
US20040191512A1 (en) * 2003-03-27 2004-09-30 Samuel Mooney Melt-spun synthetic fiber and process for producing the fiber
US20050019286A1 (en) * 2003-06-09 2005-01-27 Wang Tian Xian Stable cosmetic emulsion with polyamide
EP1651725A4 (en) * 2003-07-21 2006-09-20 Oreal Self-emulsifying copolymer
US20050158260A1 (en) * 2003-12-12 2005-07-21 L'oreal Cosmetic composition containing a polyorganosiloxane polymer
US20050163736A1 (en) * 2004-01-27 2005-07-28 Heng Cai Dual phase stick
US20050257715A1 (en) * 2004-04-08 2005-11-24 Christophe Dumousseaux Compositions for application to the skin, to the lips, to the nails, and/or to hair
US7981404B2 (en) 2004-04-08 2011-07-19 L'oreal S.A. Composition for application to the skin, to the lips, to the nails, and/or to hair
US20050287103A1 (en) * 2004-06-08 2005-12-29 Vanina Filippi Cosmetic composition comprising at least one ester and at least one film-forming polymer
US20060013791A1 (en) * 2004-07-16 2006-01-19 L'oreal Cosmetic composition comprising a defined silicone polymer and a film former
US20070274941A9 (en) * 2004-07-16 2007-11-29 Xavier Blin Two-coat cosmetic product comprising at least one silicone polymer
US20060034791A1 (en) * 2004-07-16 2006-02-16 L'oreal Cosmetic composition comprising a silicone polymer
FR2873035A1 (en) 2004-07-16 2006-01-20 Oreal COSMETIC COMPOSITION COMPRISING A DEFINED SILICONE POLYMER AND A FILMOGENIC AGENT.
FR2876011B1 (en) 2004-10-05 2006-12-29 Oreal METHOD FOR MAKE-UP A SUPPORT AND KIT FOR IMPLEMENTING SAID METHOD
US9649261B2 (en) 2004-10-05 2017-05-16 L'oreal Method of applying makeup to a surface and a kit for implementing such a method
ES2380626T3 (en) 2004-10-22 2012-05-16 L'oreal Cosmetic compositions containing a polyorganosiloxane polymer
EP1661549A1 (en) 2004-11-04 2006-05-31 L'oreal Cosmetic compositions and methods of use
EP1836237B1 (en) * 2004-12-01 2011-08-24 Dow Corning Corporation Silicone polyether-amide block copolymers
KR101164438B1 (en) * 2004-12-16 2012-07-13 다우 코닝 코포레이션 Amide-substituted silicones and methods for their preparation and use
US20060130248A1 (en) * 2004-12-21 2006-06-22 L'oreal Easily removable water resistant cosmetic makeup compositions
FR2879442B1 (en) 2004-12-21 2007-07-20 Oreal COSMETIC COMPOSITION FOR WATER-RESISTANT MAKE-UP AND EASILY CLEANSABLE
EP1833918B1 (en) 2004-12-23 2011-09-28 Dow Corning Corporation Crosslinkable saccharide-siloxane compositions, and networks, coatings and articles formed therefrom
US20060171910A1 (en) * 2004-12-30 2006-08-03 Audrey Ricard Cosmetic composition containing an alkoxylated alcohol ester and a hydrocarbon-based ester oil
US20060193801A1 (en) * 2005-01-31 2006-08-31 L'oreal Solid cosmetic composition textured with an organic copolymer
FR2881343B1 (en) 2005-01-31 2007-04-20 Oreal SOLID COSMETIC COMPOSITION FOR MAKE-UP AND / OR CARE
FR2881347A1 (en) * 2005-01-31 2006-08-04 Oreal COSMETIC COMPOSITION COMPRISING TWO SILICONE POLYMERS
US20060193808A1 (en) * 2005-02-04 2006-08-31 Frederic Auguste Composition for coating keratin fibers, comprising a fatty alcohol wax and a cellulose-based polymer
US20060216257A1 (en) * 2005-03-24 2006-09-28 L'oreal Makeup and/or care kit providing volumizing effect
EP1866397A2 (en) * 2005-03-29 2007-12-19 Arizona Chemical Company Compostions containing fatty acids and/or derivatives thereof and a low temperature stabilizer
JP5138579B2 (en) * 2005-04-06 2013-02-06 ダウ コーニング コーポレーション Organosiloxane composition
JP5122444B2 (en) 2005-05-23 2013-01-16 ダウ・コーニング・コーポレイション Personal care compositions comprising saccharide-siloxane copolymers
US7993662B2 (en) * 2005-06-14 2011-08-09 Kokyu Alcohol Kogyo Co., Ltd. Transparent solid oil cosmetics
WO2006134896A1 (en) * 2005-06-14 2006-12-21 Kokyu Alcohol Kogyo Co., Ltd. Transparent oily solid cosmetic
WO2007008575A1 (en) * 2005-07-13 2007-01-18 L'oreal Cosmetic compositions containing liposoluble polymers and tackifiers
EP1743627B1 (en) * 2005-07-13 2014-12-17 L'Oréal Highly resistant make up composition for the lips comprising a low molecular weight resin
FR2889952A1 (en) 2005-07-22 2007-03-02 Oreal COATING PROCESS
US8241617B2 (en) * 2005-08-01 2012-08-14 L'oréal Methods for removing make-up compositions from keratin materials
FR2889921B1 (en) 2005-08-30 2007-12-28 Oreal CONDITIONING AND APPLICATION ASSEMBLY COMPRISING A MAGNETIC DEVICE.
US7790148B2 (en) * 2005-09-02 2010-09-07 L'oreal Compositions containing silicone polymer, wax and volatile solvent
US7884158B2 (en) * 2005-09-06 2011-02-08 L'Oré´al Cosmetic compositions containing block copolymers, tackifiers and phenylated silicones
US20070093619A1 (en) * 2005-10-24 2007-04-26 L'oreal Compositions having enhanced cosmetic properties
WO2007054830A2 (en) * 2005-11-09 2007-05-18 L'oreal Composition for coating the eyelashes or the eyebrows, comprising a fatty-phase-structuring polymer containing polyorganosiloxane units
FR2892925B1 (en) * 2005-11-09 2007-12-14 Oreal COMPOSITION FOR COATING LAMPS IN FOAM FORM
US20070128233A1 (en) * 2005-12-05 2007-06-07 L'oreal Cosmetic composition having a unique cushiony texture
US9320693B2 (en) * 2005-12-21 2016-04-26 L'oreal Cosmetic composition with a volumizing effect
US20070196301A1 (en) 2005-12-21 2007-08-23 L'oreal Cosmetic composition with a volumizing effect
US7371464B2 (en) * 2005-12-23 2008-05-13 3M Innovative Properties Company Adhesive compositions
JP5144538B2 (en) 2005-12-23 2013-02-13 スリーエム イノベイティブ プロパティズ カンパニー Films containing thermoplastic silicone block copolymers
US20070149745A1 (en) * 2005-12-23 2007-06-28 3M Innovative Properties Company Polydiorganosiloxane-containing materials with oxalylamino groups
US7501184B2 (en) 2005-12-23 2009-03-10 3M Innovative Properties Company Polydiorganosiloxane polyoxamide copolymers
KR101309394B1 (en) * 2005-12-23 2013-09-17 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Multilayer films including thermoplastic silicone block copolymers
US8110630B2 (en) 2006-03-21 2012-02-07 Dow Corning Corporation Silicone elastomer gels
JP5424866B2 (en) 2006-03-21 2014-02-26 ダウ・コーニング・コーポレイション Silicone polyether elastomer gel
EP2001934B9 (en) 2006-03-21 2016-02-24 Dow Corning Corporation Silicone-organic elastomer gels
US8313735B2 (en) * 2006-10-30 2012-11-20 Oreal Long-wearing cosmetic product system for providing extended shine and gloss
US20080102049A1 (en) * 2006-10-30 2008-05-01 L'oreal Long-wearing cosmetic product system having high shine and gloss
EP2019678A4 (en) * 2006-05-23 2012-05-02 Dow Corning NOVEL SILICONE FILMOGENIC AGENT FOR RELEASE OF ACTIVE INGREDIENTS
US8198207B2 (en) * 2006-05-23 2012-06-12 Dow Corning Corporation Borane catalyst complexes with amide functional polymers and curable compositions made therefrom
FR2901698B1 (en) 2006-05-31 2008-08-08 Oreal COSMETIC COMPOSITION COMPRISING VINYL POLYMER AND OLEFIN COPOLYME
DE602007009830D1 (en) * 2006-06-07 2010-11-25 Dow Corning TREATMENT OF TEXTILES WITH SILICONE POLYETHERAMIDE BLOCK COPOLYMERS
FR2902006B1 (en) * 2006-06-13 2009-06-05 Oreal COSMETIC COMPOSITION FOR LIPS ASSOCIATING A SURFACTANT PHOSPHATE AND A SILICONE POLYMER
EP1935400B1 (en) 2006-12-19 2013-09-04 L'Oréal Composition for skin make-up comprising a resin, a block copolymer, a solid fat, and no volatile oils
FR2910809B1 (en) 2006-12-29 2009-02-13 Oreal COSMETIC COMPOSITION COMPRISING A BIS UREA DERIVATIVE.
KR20090094044A (en) * 2006-12-29 2009-09-02 다우 코닝 코포레이션 Personal care compositions containing silicone elastomer gels
FR2910807A1 (en) 2006-12-29 2008-07-04 Oreal COSMETIC COMPOSITION INCLUDING A DERIVATIVE OF BIS UREE.
MX2007016506A (en) 2006-12-29 2008-10-28 Oreal Composition containing a polyorganosiloxane polymer, a thickening agent and at least one volatile alcohol .
FR2911065B1 (en) 2007-01-04 2009-03-20 Oreal MAKE-UP KERATIN FIBER KIT.
US8658141B2 (en) * 2007-01-12 2014-02-25 L'oreal Cosmetic composition containing a block copolymer, a tackifier, a silsesquioxane wax and/or resin
EP1955692A1 (en) 2007-01-12 2008-08-13 L'oreal Use of active agents for increasing the ceramide content of the lips, as a protection agent for fragile lips
US20080171008A1 (en) * 2007-01-17 2008-07-17 L'oreal S.A. Composition containing a polyorganosiloxane polymer, a tackifier, a wax and a block copolymer
JP5197631B2 (en) * 2007-02-20 2013-05-15 ダウ コーニング コーポレーション Hydrogen-bonding polyorganosiloxane-based filler treatment agent
FR2915892B1 (en) 2007-05-10 2009-07-03 Oreal FOAM COMPOSITION COMPRISING A POLYMERIC STRUCTURANT
FR2915893B1 (en) 2007-05-10 2012-05-11 Oreal COSMETIC COMPOSITION IN THE FORM OF FOAM WITHOUT WAX
FR2915891B1 (en) * 2007-05-10 2012-05-11 Oreal FOAM COMPOSITION COMPRISING A SILICONE POLYMER
US20080318065A1 (en) * 2007-06-22 2008-12-25 Sherman Audrey A Mixtures of polydiorganosiloxane polyamide-containing components and organic polymers
US8063166B2 (en) 2007-06-22 2011-11-22 3M Innovative Properties Company Polydiorganosiloxane polyamide copolymers having organic soft segments
US7705101B2 (en) 2007-06-22 2010-04-27 3M Innovative Properties Company Branched polydiorganosiloxane polyamide copolymers
US7507849B2 (en) * 2007-06-22 2009-03-24 3M Innovative Properties Company Cyclic silazanes containing an oxamido ester group and methods of making these compounds
US7705103B2 (en) * 2007-06-22 2010-04-27 3M Innovative Properties Company Polydiorganosiloxane polyoxamide copolymers
FR2918271B1 (en) 2007-07-03 2009-11-13 Oreal COSMETIC COMPOSITION COMPRISING A SILICONE POLYMER AND A TACKIFYING RESIN HAVING CERTAIN ELASTICITY
US8222363B2 (en) * 2007-09-26 2012-07-17 Dow Corning Corporation Silicone organic elastomer gels from organopolysiloxane resins
FR2924939B1 (en) 2007-12-13 2010-02-26 Oreal METHOD FOR HAIR COLORING FROM A COMPOSITION COMPRISING A HYDROPHOBIC FILMOGENIC POLYMER, A PIGMENT AND A VOLATILE SOLVENT
FR2924940B1 (en) * 2007-12-13 2012-10-19 Oreal COSMETIC COMPOSITION COMPRISING MACADAMIA OIL AND A WAX.
US8431671B2 (en) 2008-03-26 2013-04-30 3M Innovative Properties Company Structured polydiorganosiloxane polyamide containing devices and methods
US20110039087A1 (en) * 2008-04-14 2011-02-17 Severine Cauvin Emulsions Of Dilatant Organopolysiloxanes
WO2009129175A1 (en) * 2008-04-14 2009-10-22 Dow Corning Corporation Emulsions of boron crosslinked organopolysiloxanes
FR2931670B1 (en) 2008-06-02 2015-05-22 Oreal POLYESTER COMPOSITIONS IN A FATTY PHASE AND USES THEREOF.
FR2932070B1 (en) 2008-06-10 2012-08-17 Oreal MAKE-UP AND / OR CARE OF LASHES
FR2932980B1 (en) 2008-06-27 2010-12-24 Oreal COSMETIC COMPOSITION FOR MAKE-UP AND / OR LIP CARE
FR2933866A1 (en) * 2008-07-21 2010-01-22 Oreal COSMETIC COMPOSITION WITH IMPROVED APPLICATION TIME
FR2934129B1 (en) * 2008-07-24 2014-05-02 Oreal COSMETIC TREATMENT PROCESS.
EP2157209B1 (en) * 2008-07-31 2014-10-22 Rohm and Haas Electronic Materials LLC Inhibiting Background Plating
FR2934493B1 (en) * 2008-08-01 2010-09-17 Oreal PROCESS FOR THE TATING OF HUMAN KERATIN FIBERS
WO2010025311A1 (en) * 2008-08-29 2010-03-04 Dow Corning Corporation Silicone-organic hybrid emulsions in personal care applications
US8734767B2 (en) 2008-10-22 2014-05-27 Dow Corning Corporation Aminofunctional endblocked silicone polyether copolymers in personal care compositions
CN101392063B (en) * 2008-10-31 2011-05-18 华南理工大学 Dimethyl silicone polymer-polyamide multi-block elastomer and production method thereof
BRPI0916036B8 (en) 2008-11-17 2017-06-06 Oreal cosmetic method to treat human perspiration, composition and anhydrous solid composition
EP2186544B1 (en) 2008-11-17 2013-07-10 L'Oréal Use of amorphous mineral expanded particles for improving perfume tenacity; perfuming composition thereof and process for treating human body odours using said composition.
FR2938764B1 (en) * 2008-11-24 2012-06-08 Oreal SOLID COSMETIC COMPOSITION FOR APPLICATION TO KERATIN FIBERS
FR2938763B1 (en) 2008-11-24 2012-09-28 Oreal SOLID COSMETIC COMPOSITION FOR APPLICATION TO KERATIN FIBERS
FR2939033B1 (en) 2008-12-02 2012-08-31 Oreal COSMETIC COMPOSITION FOR MAKE-UP AND / OR CARE OF KERATINIC MATERIALS, AND METHOD FOR MAKE-UP
FR2940115B1 (en) 2008-12-19 2012-06-15 Oreal KERATINIC MATERIAL COATING KIT COMPRISING A POLYSACCHARIDE AND A CHEMICAL CROSSLINKING AGENT
FR2940111B1 (en) 2008-12-19 2012-06-01 Oreal KERATINIC MATERIAL COATING KIT COMPRISING A POLYSACCHARIDE AND A IONIC OR DATIVE COMPLEXATION AGENT
FR2941375A1 (en) 2009-01-27 2010-07-30 Oreal COSMETIC COMPOSITION FOR IMPROVING THE SKIN SURFACE APPEARANCE
FR2943225B1 (en) 2009-03-17 2011-06-03 Oreal DEVICE FOR CONDITIONING AND APPLYING AT LEAST ONE SOLID COSMETIC COMPOSITION
FR2943254B1 (en) * 2009-03-18 2011-06-17 Oreal COSMETIC COMPOSITION COMPRISING A SILICONE POLYAMIDE, A SILICONE RESIN, AND AT LEAST 51% COLORING MATERIAL
GB0905204D0 (en) 2009-03-26 2009-05-13 Dow Corning Preparation of organosiloxane polymers
GB0905205D0 (en) 2009-03-26 2009-05-13 Dow Corning Preparation of organosiloxane polymer
FR2944958B1 (en) 2009-04-30 2011-07-08 Oreal WAX-IN-WATER EMULSION COMPRISING THE ASSOCIATION OF A GLUTAMIC ACID DERIVATIVE AND ALKYLPOLYGLYCOSIDE
WO2010146147A2 (en) 2009-06-18 2010-12-23 L'oreal Composition for treating keratin fibres comprising a block copolymer, a siloxane resin and a volatile solvent
FR2946876B1 (en) 2009-06-19 2011-07-29 Oreal COSMETIC MAKE-UP AND / OR CARE COMPOSITION COMPRISING A TACKIFYING RESIN, AND A PARTICULAR OIL ASSOCIATION
KR20120059599A (en) 2009-09-03 2012-06-08 다우 코닝 코포레이션 Pituitous silicone fluids
WO2011028765A1 (en) 2009-09-03 2011-03-10 Dow Corning Corporation Personal care compositions with pituitous silicone fluids
FR2949958B1 (en) 2009-09-11 2012-10-05 Oreal COSMETIC SET OF MAKE-UP AND / OR CARE OF KERATINIC MATERIALS
FR2949955B1 (en) 2009-09-11 2011-12-09 Oreal METHOD FOR MAKE-UP AND / OR CARE OF KERATINIC MATERIALS
FR2951717B1 (en) 2009-10-22 2012-04-20 Oreal USE OF A DIALKYLPHENYL-4-AMINOPIPERIDINE AS A TREATMENT AGENT FOR HUMAN PERSPIRATION; NOVEL COMPOUNDS, COMPOSITIONS CONTAINING SAME
FR2951639B1 (en) 2009-10-22 2011-11-04 Oreal USE OF ADENOSINE AND / OR ONE OF ITS DERIVATIVES AS A TREATMENT AGENT FOR HUMAN TRANSPIRATION
KR101925354B1 (en) 2009-10-23 2018-12-05 다우 코닝 도레이 캄파니 리미티드 Novel co-modified organopolysiloxane
CN102648264B (en) 2009-10-23 2015-08-19 道康宁东丽株式会社 Thickeners or gelling agents for oil-based materials
EP2491065B1 (en) 2009-10-23 2014-11-26 Dow Corning Corporation Hydrophilically-modified silicone compositions
WO2011049896A2 (en) 2009-10-23 2011-04-28 Dow Corning Corporation Silicone compositions comprising a swollen silicone gel
EP2492300B1 (en) 2009-10-23 2018-10-03 Dow Corning Toray Co., Ltd. Novel organopolysiloxane copolymer
KR101860085B1 (en) 2009-11-25 2018-05-21 다우 실리콘즈 코포레이션 Volatile cyclic siloxanes
JP5577081B2 (en) 2009-12-03 2014-08-20 東レ・ダウコーニング株式会社 New organopolysiloxane and cosmetics
FR2953715B1 (en) 2009-12-11 2012-02-17 Oreal ANHYDROUS FLUID FILTERING COMPOSITION COMPRISING AN OILY PHASE, A PARTICULAR TRIAZINE FILTER AND A RHEOLOGICAL AGENT THAT IS THICKENING OR GELIFYING OIL
US20110146702A1 (en) * 2009-12-17 2011-06-23 L'oreal Extending cosmetic composition comprising behenyl alcohol as thickener
FR2954140A1 (en) 2009-12-17 2011-06-24 Oreal COSMETIC OR DERMATOLOGICAL COMPOSITIONS BASED ON BACTERIOCINS AND PREBIOTICS
FR2954138B1 (en) 2009-12-17 2012-03-02 Oreal COSMETIC TREATMENT PROCESS FOR BODY ODORS USING BACTERIOCIN COMPOSITION
FR2954131B1 (en) 2009-12-18 2016-02-19 Oreal COSMETIC COMPOSITION COMPRISING A SUPRAMOLECULAR COMPOUND CAPABLE OF ESTABLISHING HYDROGEN BONDS, AND A PARTICULAR OIL
FR2954130B1 (en) 2009-12-18 2012-02-24 Oreal COSMETIC COMPOSITION COMPRISING A SUPRAMOLECULAR COMPOUND CAPABLE OF ESTABLISHING HYDROGEN BONDS, AND A PARTICULAR ADDITIONAL INGREDIENT
EP2353582A1 (en) 2009-12-18 2011-08-10 L'Oréal Cosmetic composition for eyelashes
JP5841311B2 (en) 2009-12-21 2016-01-13 東レ・ダウコーニング株式会社 Oily raw material thickener or gelling agent, gel composition containing the same, and method for producing cosmetic or external preparation
CN102686646B (en) 2009-12-24 2015-08-19 道康宁东丽株式会社 Surface treatment agent for powder used in cosmetics and cosmetics containing powder treated with the surface treatment agent
CN102665668B (en) 2009-12-24 2014-10-22 道康宁东丽株式会社 Copolymer having carbosiloxane dendrimer structure, and composition and cosmetic containing the same
JP5702402B2 (en) 2009-12-30 2015-04-15 スリーエム イノベイティブ プロパティズ カンパニー Moisture curable siloxane and siloxane polymer
US20110202028A1 (en) 2010-02-16 2011-08-18 Carlo Toro Release sheet material
US20110202029A1 (en) * 2010-02-16 2011-08-18 The Procter & Gamble Company Release sheet material
FR2958158B1 (en) 2010-03-30 2012-06-08 Oreal COSMETIC COMPOSITION BASED ON POLYESTER
JP5827790B2 (en) 2010-04-28 2015-12-02 東レ・ダウコーニング株式会社 Cosmetic and skin external preparation containing higher alcohol-modified silicone
WO2011136394A1 (en) 2010-04-30 2011-11-03 Dow Corning Toray Co., Ltd. Powder treatment agent comprising sugar alcohol -modified organopolysiloxane
EP2563844A1 (en) 2010-04-30 2013-03-06 Dow Corning Toray Co., Ltd. Organopolysiloxane and use thereof as surfactant, powder treatment agent, thickening agent of oil -based raw material or gelling agent. gel and emulsion compositions, as well as, preparations for external use and cosmetics comprising the same
CN102906161B (en) 2010-04-30 2014-10-22 道康宁东丽株式会社 Novel organopolysiloxane, surfactant, emulsion composition, powder treatment agent, thickening agent of oil-based raw material, gelling agent, gel composition, and cosmetic raw material comprising novel organopolysiloxane, as well as, preparation for external use and cosmetic comprising the same
FR2959932A1 (en) 2010-05-17 2011-11-18 Oreal MAKE-UP AND / OR CARE COMPOSITION OF KERATIN FIBERS HAVING IMPROVED HOLDING PROPERTIES
WO2011148325A1 (en) 2010-05-26 2011-12-01 L'oreal Cosmetic composition based on a supramolecular polymer and a silicone filler
WO2011148324A2 (en) 2010-05-26 2011-12-01 L'oreal Cosmetic composition based on a supramolecular polymer and a silicone compound
FR2960433B1 (en) 2010-05-26 2012-08-17 Oreal COSMETIC METHOD FOR MAKE-UP AND / OR CARE OF SKIN AND / OR LIP
FR2960434B1 (en) 2010-05-26 2012-08-17 Oreal COSMETIC COMPOSITION BASED ON A SUPRAMOLECULAR POLYMER AND AN ABSORBENT CHARGE
US8933134B2 (en) 2010-06-09 2015-01-13 L'oreal Compositions containing agar and a softening agent
FR2961093A1 (en) 2010-06-09 2011-12-16 Oreal COSMETIC COMPOSITION COMPRISING A POLYMER AND A 4-CARBOXY 2-PYRROLIDINONE DERIVATIVE, COSMETIC TREATMENT METHOD AND COMPOUND
FR2961396B1 (en) 2010-06-16 2013-03-15 Oreal PROCESS FOR MAKE-UP OR CARE OF KERATIN FIBERS USING RETRACTABLE FIBERS AND USE THEREOF
FR2961510A1 (en) 2010-06-17 2011-12-23 Oreal USE AS A TREATMENT AGENT FOR HUMAN PERSPIRATION; NOVEL AMINO ACID DERIVATIVES; COMPOSITIONS CONTAINING THEM
FR2961392A1 (en) 2010-06-17 2011-12-23 Oreal USE OF AMINO ACID DERIVATIVES AS A TREATMENT AGENT FOR HUMAN PERSPIRATION; NEW COMPOUNDS; COMPOSITIONS CONTAINING THEM
FR2961508A1 (en) 2010-06-17 2011-12-23 Oreal AMINO ACID DERIVATIVES; COMPOSITIONS CONTAINING THEM; USE AS A TREATMENT AGENT FOR HUMAN PERSPIRATION
FR2961509B1 (en) 2010-06-17 2014-01-31 Oreal AMINO ACID DERIVATIVES; COMPOSITIONS CONTAINING THEM; USE AS A TREATMENT AGENT FOR HUMAN PERSPIRATION
FR2962036B1 (en) 2010-07-02 2012-07-27 Oreal METHOD FOR COMPLEMENTING RELIEF IMPERFECTIONS IN HOLES
FR2962037B1 (en) 2010-07-02 2013-01-11 Oreal COSMETIC COMPOSITION COMPRISING AT LEAST ONE ORGANOPOLYSILOXANE ELASTOMER AND AT LEAST ONE TACKIFYING RESIN
KR20130099013A (en) 2010-07-30 2013-09-05 다우 코닝 도레이 캄파니 리미티드 Cosmetic for hair containing sugar alcohol-modified silicone
KR101856640B1 (en) 2010-07-30 2018-05-14 다우 코닝 도레이 캄파니 리미티드 Cosmetic for hair containing co-modified organopolysiloxane
EP2609140B1 (en) 2010-08-23 2014-06-11 Dow Corning Corporation Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use
EP2609141A1 (en) 2010-08-23 2013-07-03 Dow Corning Corporation Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use
US9192564B2 (en) 2010-08-23 2015-11-24 Dow Corning Corporation Saccharide siloxane copolymers and methods for their preparation and use
US8853372B2 (en) 2010-08-23 2014-10-07 Dow Corning Corporation Saccharide siloxanes stable in aqueous environments and methods for the preparation and use of such saccharide siloxanes
FR2964870B1 (en) 2010-09-17 2012-10-19 Oreal SOLID COSMETIC COMPOSITION OF MAKE-UP
FR2964871B1 (en) * 2010-09-17 2012-10-19 Oreal SOLID COSMETIC COMPOSITION OF MAKE-UP
EP2432035B1 (en) 2010-09-21 2017-05-31 Sun Chemical Corporation Improved method of stripping hot melt etch resists from semiconductors
FR2967905B1 (en) 2010-11-25 2013-07-12 Oreal PROCESS FOR TREATING TRANSPIRATION USING A CARBONYL COMPOUND WHICH CAN BE REACTED ACCORDING TO THE MAILLARD REACTION
FR2968957B1 (en) 2010-12-15 2020-06-19 L'oreal COSMETIC COMPOSITION COMPRISING A SUPRAMOLECULAR COMPOUND CAPABLE OF ESTABLISHING HYDROGEN BONES, A SILICONE OIL AND A WAX
FR2968938B1 (en) 2010-12-21 2013-06-21 Oreal ANHYDROUS AND SOLID COSMETIC COMPOSITION
FR2968935B1 (en) 2010-12-21 2012-12-28 Oreal USE OF HYDROPHOBIC AEROGEL PARTICLES AS DEODORANT ACTIVE; METHOD OF TREATING HUMAN BODILY ODORS
KR101830303B1 (en) 2010-12-27 2018-02-20 다우 코닝 도레이 캄파니 리미티드 Cosmetic containing liquid organopolysiloxane
US10076487B2 (en) 2010-12-30 2018-09-18 L'oreal Comfortable, long-wearing, transfer-resistant colored cosmetic compositions
US8945525B2 (en) 2010-12-30 2015-02-03 L'oreal Comfortable, long-wearing, transfer-resistant colored cosmetic compositions having high gloss and a non-tacky feel
US20120219516A1 (en) 2011-02-25 2012-08-30 L'oreal S.A. Cosmetic compositions having long lasting shine
KR101864579B1 (en) 2011-05-30 2018-06-07 다우 코닝 도레이 캄파니 리미티드 Organopolysiloxane elastomer modified with mono-/diglycerin derivative, and use therefor
WO2012175330A2 (en) 2011-06-20 2012-12-27 L'oreal Cosmetic use of a flocculant polymer as antiperspirant
FR2976805B1 (en) 2011-06-23 2013-07-12 Oreal COSMETIC COMPOSITION COMPRISING A SUPRAMOLECULAR COMPOUND CAPABLE OF ESTABLISHING HYDROGEN BONDS, AND TWO SEPARATE PARTICULATE SILICONE OILS
FR2978035B1 (en) 2011-07-22 2015-03-20 Oreal USE AS ANTITRANSPIRANT OF A MULTIVALENT CATION SALT WITHOUT ANTITRANSPIRANT ALUMINUM HALOGEN OR COMPOUND SUSCEPTIBLE TO REACT WITH THIS SALT TO PRODUCE ANTITRANSPIRANT EFFECT
WO2013013902A2 (en) 2011-07-22 2013-01-31 L'oreal Method for the treatment of human perspiration using a polyvalent cation salt and an anion salt
FR2978036B1 (en) 2011-07-22 2013-07-19 Oreal PROCESS FOR TREATING TRANSPIRATION USING AN ANHYDROUS COMPOSITION COMPRISING TWO REAGENTS PRODUCING IN-SITU ASSEMBLY ON THE SKIN A TRANSPIRING EFFECT
JP2013095834A (en) 2011-10-31 2013-05-20 Dow Corning Toray Co Ltd Long chain hydrocarbon-modified silicone/amino-modified silicone copolymer and use of the same
JP2013095835A (en) 2011-10-31 2013-05-20 Dow Corning Toray Co Ltd Long chain amide-modified silicone/amino-modified silicone copolymer and use of the same
JP2015500926A (en) 2011-11-29 2015-01-08 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ Amino-functional silicone emulsion for textile treatment
FR2983406B1 (en) 2011-12-05 2014-03-28 Oreal COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS
FR2984089B1 (en) 2011-12-20 2014-01-10 Oreal APPLICATION DEVICE COMPRISING A COMPOSITION BASED ON HYDROPHOBIC FILMOGENIC POLYMER AND A VOLATILE SOLVENT, PROCESS FOR TREATING KERATINOUS FIBERS USING THE SAME
WO2013093802A2 (en) 2011-12-20 2013-06-27 L'oreal Composition comprising a polyamide resin, a gelling system, a polar oil and an apolar oil
FR2984142B1 (en) 2011-12-20 2013-12-20 Oreal COMPOSITION COMPRISING A PARTICULAR ACRYLIC POLYMER AND SILICONE COPOLYMER, PROCESS FOR TREATING KERATINOUS FIBERS USING THE SAME
FR2984143B1 (en) 2011-12-20 2014-07-11 Oreal PROCESS FOR APPLYING A PARTICULAR ACRYLIC POLYMER PIGMENT COLORING COMPOSITION AND SILICONE COPOLYMER, AND APPROPRIATE DEVICE
FR2984132B1 (en) 2011-12-20 2014-08-01 Oreal PIGMENT COMPOSITION BASED ON PARTICULAR ACRYLIC POLYMER AND SILICONE COPOLYMER, COLORING PROCESS
FR2984140B1 (en) 2011-12-20 2014-06-20 Oreal COMPOSITION COMPRISING A FATTY PHASE, A STRUCTURING AGENT, A COMPOUND AND / OR A HYDROPHILIC ACTIVE INGREDIENT
FR2984698B1 (en) 2011-12-22 2014-01-24 Oreal LIP MAKE-UP KIT, COSMETIC PRODUCT APPLICATOR, AND MAKE-UP PROCESS USING THE SAME
FR2984699B1 (en) 2011-12-22 2014-01-24 Oreal LIP MAKE-UP KIT, COSMETIC PRODUCT APPLICATOR, AND MAKE-UP PROCESS USING THE SAME
JP6369888B2 (en) 2011-12-27 2018-08-08 東レ・ダウコーニング株式会社 Novel liquid organopolysiloxane and use thereof
FR2989889B1 (en) 2012-04-26 2016-12-30 Oreal COSMETIC COMPOSITION COMPRISING SILANE AND LIPOPHILIC THICKENER
FR2990850B1 (en) 2012-05-25 2014-05-16 Oreal COSMETIC COMPOSITION COMPRISING THE ASSOCIATION OF A LIPOPHILIC DERIVATIVE OF SALICYLIC ACID, AN ANTI-TRANSPIRANT ALUMINUM SALT OR COMPLEX, AND AN ACETIC N, DIACIDAL AMINO ACID SALT
WO2013190469A2 (en) 2012-06-19 2013-12-27 L'oreal Cosmetic process for making up and/or caring for the lips
FR2992195B1 (en) 2012-06-21 2014-11-07 Oreal COSMETIC COMPOSITION COMPRISING AN OIL, HYDROPHOBIC SILICA AEROGEL PARTICLES AND A HYDROCARBON SEQUENCE COPOLYMER PREFERABLY OBTAINED FROM AT LEAST ONE STYRENE MONOMER
FR2992211B1 (en) 2012-06-21 2014-10-31 Oreal LIQUID COSMETIC COMPOSITION COMPRISING OIL, HYDROPHOBIC SILICA AEROGEL PARTICLES, AND NON-POLYMERIC ORGANOGELER
FR2992207B1 (en) 2012-06-21 2014-10-31 Oreal COSMETIC COMPOSITION COMPRISING OIL, HYDROPHOBIC SILICA AEROGEL PARTICLES, AND SEMI-CRYSTALLINE POLYMER
FR2992206B1 (en) 2012-06-21 2014-07-18 Oreal COSMETIC COMPOSITION COMPRISING AN OIL, HYDROPHOBIC SILICA AEROGEL PARTICLES AND A HYDROCARBON RESIN
FR2992196B1 (en) 2012-06-21 2014-10-31 Oreal LIQUID COSMETIC COMPOSITION COMPRISING OIL, HYDROPHOBIC SILICA AEROGEL PARTICLES AND ETHYLENE COPOLYMER SEQUENCE
FR2992193B1 (en) 2012-06-21 2014-11-07 Oreal LIQUID COSMETIC COMPOSITION COMPRISING AN OIL, HYDROPHOBIC SILICA AEROGEL PARTICLES, AND A FUSION TEMPERATURE WAX GREATER THAN 60 ° C
FR2992215B1 (en) 2012-06-21 2014-10-31 Oreal ANHYDROUS COSMETIC COMPOSITION COMPRISING AN OIL, HYDROPHOBIC SILICA AEROGEL PARTICLES, A HYDROPHILIC ACTIVE INGREDIENT AND AT LEAST ONE SURFACTANT
FR2992559B1 (en) 2012-06-29 2014-06-20 Oreal BILOKE PROCESS FOR COLORING KERATIN FIBERS
FR2993453B1 (en) 2012-07-20 2016-05-13 Oreal COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS
JP5797618B2 (en) 2012-08-22 2015-10-21 東レ・ダウコーニング株式会社 Copolymer having carbosiloxane dendrimer structure, and composition and cosmetic containing the same
CN104661646B (en) 2012-10-11 2017-10-27 道康宁公司 Waterborne organic silicon polyethers microemulsion
FR2996759B1 (en) 2012-10-15 2015-01-16 Oreal COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS
FR2996762B1 (en) 2012-10-15 2014-11-21 Oreal COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS
FR2996757B1 (en) 2012-10-15 2015-01-02 Oreal COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS
FR2996756B1 (en) 2012-10-15 2020-06-05 L'oreal COSMETIC USE OF A SINGLE-UNSATURATED FATTY ACID OR ONE OF ITS SALTS AND / OR ITS ESTERS AS A DEODORING ACTIVE INGREDIENT
FR2998782B1 (en) 2012-11-30 2015-04-17 Oreal WATER-IN-OIL COSMETIC EMULSION, PARTICULARLY CONDITIONED IN THE FORM OF AEROSOL COMPRISING AT LEAST ONE VINYL POLYMER, AT LEAST ONE OLEFIN COPOLYMER AND AT LEAST ONE ANTI-TRANSPARENT ACTIVE INGREDIENT
WO2014087183A1 (en) 2012-12-04 2014-06-12 L'oreal Solid powdery cosmetic composition
JP6392669B2 (en) 2012-12-28 2018-09-19 東レ・ダウコーニング株式会社 Method for producing transparent or translucent liquid glycerin derivative-modified silicone composition
FR3002448B1 (en) 2013-02-25 2015-04-03 Oreal COSMETIC COMPOSITION OF GEL TYPE
FR3004343B1 (en) 2013-04-12 2015-06-19 Oreal COSMETIC COMPOSITION OF GEL TYPE
FR3004940B1 (en) 2013-04-26 2015-05-22 Oreal COSMETIC USE OF AN ESSENTIAL OIL OF SATUREJA MONTANA RICH IN GERANIOL AS ACTIVE DEODORANT
FR3011741B1 (en) 2013-10-11 2015-10-23 Oreal COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS
FR3011740B1 (en) 2013-10-11 2015-10-23 Oreal COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS
CN106232100B (en) 2014-04-28 2020-08-28 美国陶氏有机硅公司 Cross-linked composition and cosmetic composition comprising the same
EP2939655A1 (en) 2014-04-30 2015-11-04 L'Oréal Composition comprising microcapsules containing reflective particles
EP2939653A1 (en) 2014-04-30 2015-11-04 L'Oréal Composition comprising microcapsules containing particles with a high wet point
EP2939654A1 (en) 2014-04-30 2015-11-04 L'Oréal Composition comprising microcapsules containing silicone elastomer
FR3021533B1 (en) 2014-05-28 2017-09-15 Oreal COSMETIC COMPOSITION OF GEL TYPE
FR3023475B1 (en) 2014-07-09 2016-07-22 Oreal ANHYDROUS SOLID COSMETIC OR DERMATOLOGICAL COMPOSITION BASED ON BENEFICIAL AGENT RELEASE PARTICLES
FR3023477B1 (en) 2014-07-10 2017-11-24 Oreal COSMETIC USE OF SPICULISPORIC ACID AS DEODORANT ACTIVE
WO2016014127A1 (en) 2014-07-23 2016-01-28 Dow Corning Corporation Pituitous silicone fluid
FR3025097B1 (en) 2014-08-28 2016-12-23 Oreal GEL / GEL COMPRISING AT LEAST TWO LOOSE EFFECTS
FR3025075A1 (en) 2014-08-28 2016-03-04 Oreal NEW CARE AND / OR MAKE-UP DEVICE COMPRISING A GEL / GEL ARCHITECTURE COMPOSITION
FR3025096B1 (en) 2014-08-28 2016-12-23 Oreal GEL / GEL COMPOSITION CONTAINING ANTI-TRANSPARENT ACTIVE INGREDIENT
FR3025100B1 (en) 2014-08-28 2016-12-09 Oreal GEL-TYPE COSMETIC COMPOSITION IMPROVED
FR3025099B1 (en) 2014-08-28 2016-12-16 Oreal GEL-TYPE COSMETIC COMPOSITION IMPROVED AND NOT COLLAPSIBLE
FR3028753B1 (en) 2014-11-24 2018-01-05 L'oreal AQUEOUS OR HYDRO-ALCOHOLIC GEL OF SYNTHETIC PHYLLOSILICATES AS A VISCOSING AGENT, MATIFIING AND / OR HOMOGENIZING APPLICATION
FR3028751B1 (en) 2014-11-24 2018-01-05 L'oreal POWDER SYNTHETIC PHYLLOSILICATE AS A MATIFYING AGENT AND / OR HOMOGENIZING APPLICATION
FR3032613B1 (en) 2014-12-12 2017-02-17 Oreal DEODORANT EMULSION CONTAINING A MIXTURE OF ALKYLPOLYGLYCOSIDE AND FATTY ALCOHOL, AN ASSOCIATIVE NON-IONIC POLYURETHANE POLYETHER, A VOLATILE HYDROCARBON OIL
FR3030232A1 (en) 2014-12-18 2016-06-24 Oreal METHOD OF MAKE-UP OF COSMETIC COMPOSITIONS COMPRISING A HIGH CONTENT OF POLYMER IN DISPERSION OR SOLUTION
WO2016100830A1 (en) 2014-12-19 2016-06-23 Dow Corning Corporation Method of preparing functionalized particles
FR3031298A1 (en) 2015-01-07 2016-07-08 Oreal MASCARA SUNFLOWER WAX AND VOLATILE HYDROCARBON OIL
FR3031299A1 (en) 2015-01-07 2016-07-08 Oreal MICROCAR MASK OF CARNAUBA
FR3031297A1 (en) 2015-01-07 2016-07-08 Oreal MASCARA SOLVENTS VOLATILE HYDROCARBONS AND SILICONES
EP3280770A1 (en) 2015-04-08 2018-02-14 Dow Corning Corporation Pituitous silicone fluid composition
US10940099B2 (en) 2015-04-08 2021-03-09 Dow Silicones Corporation Pituitous silicone emulsions
US10441527B2 (en) 2015-04-08 2019-10-15 Dow Silicones Corporation Fluid compositions and personal care
FR3041252B1 (en) 2015-09-18 2019-01-25 Capsum STABLE DISPERSIONS OF DROPS COMPRISING A GELIFYING AGENT
US10793673B2 (en) * 2015-11-10 2020-10-06 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
CN108601716B (en) 2015-12-17 2021-11-16 莱雅公司 Gel/gel-type composition based on pigments coated with hydrophobic substances and liquid fatty acid and/or diol compounds
JP6652513B2 (en) 2016-03-03 2020-02-26 信越化学工業株式会社 Bioelectrode manufacturing method
EP3448350A1 (en) 2016-04-27 2019-03-06 Dow Corning Corporation Hydrophilic silanes
JP6549517B2 (en) 2016-05-09 2019-07-24 信越化学工業株式会社 Bioelectrode and method of manufacturing the same
CN109071820B (en) 2016-05-10 2021-08-17 美国陶氏有机硅公司 Silicone block copolymers with amino-functional end-capping groups and methods of making and using the same
JP2019529596A (en) 2016-07-28 2019-10-17 スリーエム イノベイティブ プロパティズ カンパニー Segmented silicone polyamide block copolymer and articles containing the same
EP3491047B1 (en) 2016-07-28 2021-09-15 3M Innovative Properties Company Segmented silicone polyamide block copolymers and articles containing the same
US10688034B2 (en) 2016-07-29 2020-06-23 L'oreal Long-wearing, transfer-resistant cosmetic composition having improved tackiness
US10687601B2 (en) 2016-07-29 2020-06-23 L'oreal Cosmetic care system
JP6744848B2 (en) 2016-09-13 2020-08-19 信越化学工業株式会社 Adhesive composition, bioelectrode, and method for producing bioelectrode
CN109715692B (en) 2016-09-19 2021-09-07 美国陶氏有机硅公司 Skin contact adhesive and methods of making and using the same
JP6816264B2 (en) 2016-09-19 2021-01-20 ダウ シリコーンズ コーポレーション Polyurethane-polyorganosiloxane copolymer and its preparation method
WO2018052647A1 (en) 2016-09-19 2018-03-22 Dow Corning Corporation Personal care compositions including a polyurethane-polyorganosiloxane copolymer
WO2018052648A1 (en) 2016-09-19 2018-03-22 Dow Corning Corporation Copolymer composition for personal care
JP6761384B2 (en) * 2016-09-29 2020-09-23 信越化学工業株式会社 Adhesive composition, bioelectrode, and method for manufacturing bioelectrode
JP6761386B2 (en) 2016-09-29 2020-09-23 信越化学工業株式会社 Adhesive composition, bioelectrode, method for producing bioelectrode, and salt
FR3057768B1 (en) 2016-10-26 2018-12-07 Capsum DOUBLE EMULSIONS COMPRISING A GELIFIED FAT PHASE
FR3057767B1 (en) 2016-10-26 2018-12-07 Capsum DOUBLE EMULSIONS WITH DOUBLE COACERVAT
FR3061006B1 (en) 2016-12-22 2020-10-02 Oreal SOLID COSMETIC COMPOSITION CONSISTING OF A SILICONE POLYAMIDE, A SILICONE RESIN AND A DISPERSE AQUEOUS PHASE
FR3061002B1 (en) 2016-12-23 2019-05-24 L'oreal COMPOSITION COMPRISING HYDROXYETHYLPIPERAZINE ETHANE SULFONIC ACID AND AT LEAST ONE ALKYLPOLYGLUCOSIDE
FR3061429B1 (en) 2016-12-29 2020-11-27 Oreal ANHYDROUS COMPOSITION INCLUDING A MAGNESIUM SALT
JP6919993B2 (en) 2017-01-06 2021-08-18 信越化学工業株式会社 Bioelectrode composition, bioelectrode and method for producing bioelectrode
US20180214370A1 (en) 2017-01-31 2018-08-02 L'oreal Topcoat for long-wear lip compositions
JP6966310B2 (en) 2017-02-06 2021-11-10 信越化学工業株式会社 Bioelectrode composition, bioelectrode, method for producing bioelectrode, and polymer compound
JP6892376B2 (en) 2017-02-14 2021-06-23 信越化学工業株式会社 Bioelectrode composition, bioelectrode, method for producing bioelectrode, and polymer compound
JP6836520B2 (en) 2017-02-14 2021-03-03 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for producing bioelectrode
FR3063899B1 (en) 2017-03-17 2019-04-19 Capsum COMPOSITIONS COMPRISING A FATTY PHASE AND AQUEOUS PHASE IN THE FORM OF SOLID SPHERES
FR3067930B1 (en) 2017-06-27 2020-01-10 Capsum DISPERSIONS COMPRISING AT LEAST ONE HYDROCARBON VOLATILE OIL
EP3646850A4 (en) 2017-06-28 2021-03-31 Dow Toray Co., Ltd. FILM MAKERS FOR COSMETICS AND COSMETICS WITH IT
FR3070858B1 (en) 2017-09-14 2020-02-21 Capsum DISPERSION WITH HIGH FAT PIGMENT DISPERSE PHASE
FR3072029A1 (en) 2017-10-09 2019-04-12 L'oreal METHOD FOR TREATING HUMAN TRANSPIRATION USING A CATION AND ANION IN THE PRESENCE OF A MODULATOR
JP7311505B2 (en) 2017-11-20 2023-07-19 ダウ シリコーンズ コーポレーション Crosslinked aminosilicone polymer and method of preparation and use thereof
FR3075053B1 (en) 2017-12-15 2020-07-10 L'oreal PIGMENT-BASED GEL / GEL-LIKE COMPOSITION OF AT LEAST ONE C3-C8 SATURATED LINEAR DIHYDROXYALKANE, OF SALICYLIC ACID IN FREE FORM
FR3076218B1 (en) 2017-12-28 2019-12-27 L'oreal GEL COMPOSITION COMPRISING AN AQUEOUS WAX (S) MICRODISPERSION
US20190262257A1 (en) 2018-02-28 2019-08-29 L'oreal Matte lip compositions
JP6839125B2 (en) 2018-04-02 2021-03-03 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for producing bioelectrode
WO2019243613A1 (en) 2018-06-22 2019-12-26 L' Oreal Emulsion comprising an alkylpolyglycoside and nacres, and makeup and/or care process using same
JP7111653B2 (en) 2018-06-25 2022-08-02 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for producing bioelectrode
JP7158335B2 (en) 2018-06-25 2022-10-21 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for producing bioelectrode
JP7099990B2 (en) 2018-06-26 2022-07-12 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for manufacturing bioelectrode
US11234606B2 (en) 2018-07-05 2022-02-01 Shin-Etsu Chemical Co., Ltd. Bio-electrode composition, bio-electrode, and method for manufacturing a bio-electrode
JP6966389B2 (en) 2018-07-12 2021-11-17 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for manufacturing bioelectrode
JP6966396B2 (en) 2018-08-23 2021-11-17 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for manufacturing bioelectrode
JP6966397B2 (en) 2018-08-27 2021-11-17 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for manufacturing bioelectrode
EP3853292A4 (en) 2018-09-17 2022-06-08 Elevance Renewable Sciences, Inc. FUNCTIONALIZED SILICONE POLYMERS, AND METHODS OF MAKING AND USE THEREOF
EP3853294A4 (en) * 2018-09-17 2022-06-08 Elevance Renewable Sciences, Inc. SEGMENTED SILICONE POLYMERS AND METHODS OF PRODUCTION AND USE THEREOF
FR3088205B1 (en) 2018-11-13 2020-10-30 Oreal TWO-COMPOSITION EYEBROW AND CONTOUR MAKEUP KIT; TWO-STEP MAKE-UP PROCESS
FR3088206B1 (en) 2018-11-13 2020-10-30 Oreal TWO-COMPOSITION EYEBROW AND CONTOUR MAKEUP KIT; TWO-STEP MAKE-UP PROCESS
FR3090325B1 (en) 2018-12-21 2021-01-01 Oreal COMPOSITION OF THE GEL / GEL TYPE CONTAINING PARTICLES OF BORON NITRIDE AND AT LEAST ONE PIGMENT ENCAPSULATED
FR3094224B1 (en) 2019-03-29 2021-05-28 Chanel Parfums Beaute Composition allowing the transfer of a colored pattern to the skin and uses
FR3094226B1 (en) 2019-03-29 2021-11-26 Chanel Parfums Beaute Long-lasting cosmetic composition
FR3094220B1 (en) 2019-03-29 2022-02-25 Chanel Parfums Beaute Peelable film-forming cosmetic composition
FR3094222B1 (en) 2019-03-29 2021-09-10 Chanel Parfums Beaute Long-lasting cosmetic composition
FR3094228B1 (en) 2019-03-29 2022-04-01 Chanel Parfums Beaute Primer for long-lasting makeup
CN113661183A (en) 2019-04-01 2021-11-16 陶氏东丽株式会社 Copolymer having carbosiloxane dendrimer structure, and composition containing the same, cosmetic raw material, film-forming agent, and cosmetic
JP7082082B2 (en) 2019-04-03 2022-06-07 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for manufacturing bioelectrode
JP7045768B2 (en) 2019-04-03 2022-04-01 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for manufacturing bioelectrode
FR3098107B1 (en) 2019-07-03 2022-07-29 Chanel Parfums Beaute Solid cosmetic composition
FR3098108B1 (en) 2019-07-03 2022-04-01 Chanel Parfums Beaute Long-lasting solid cosmetic composition
FR3098110B1 (en) 2019-07-03 2022-02-04 Chanel Parfums Beaute Solid cosmetic composition
FR3098109B1 (en) 2019-07-03 2022-02-04 Chanel Parfums Beaute Moisturizing solid cosmetic composition
US11241375B2 (en) 2019-09-30 2022-02-08 L'oréal Cosmetic composition comprising biodegradable polymers
CN114667299B (en) 2019-11-19 2024-03-29 美国陶氏有机硅公司 Silicosan and preparation method thereof
EP4061876A1 (en) 2019-11-19 2022-09-28 Dow Silicones Corporation Aqueous leather coating composition
CN114729062A (en) 2019-11-19 2022-07-08 美国陶氏有机硅公司 Method for preparing silicasan
EP4065630A1 (en) 2019-11-26 2022-10-05 Dow Silicones Corporation Processes for making polysiloxazanes and using same for producing amino-functional polyorganosiloxanes
FR3104027B1 (en) 2019-12-06 2021-11-26 Chanel Parfums Beaute Cosmetic composition with metallic effect
JP7411537B2 (en) 2020-01-22 2024-01-11 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for producing bioelectrode
JP7410065B2 (en) 2020-03-19 2024-01-09 信越化学工業株式会社 Bioelectrode, bioelectrode manufacturing method, and biosignal measurement method
JP7406516B2 (en) 2020-04-01 2023-12-27 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and bioelectrode manufacturing method
FR3113588B1 (en) 2020-08-28 2023-06-09 Oreal WATER-IN-OIL EMULSIONS CONTAINING LOW HLB SURFACTANT, SILICONE GUM AND SILOXYSILICATE RESIN
WO2021222764A1 (en) 2020-04-30 2021-11-04 L'oreal Water-in-oil emulsions containing surfactant, silicone gum and/or latex, and siloxysilicate resin
FR3112949B1 (en) 2020-07-29 2023-02-24 Oreal WATER-IN-OIL EMULSIONS CONTAINING LATEX AND SILOXYSILICATE RESIN
FR3110406B1 (en) 2020-05-21 2022-12-23 Capsum Stable dispersion without bark
FR3110405B1 (en) 2020-05-21 2022-05-13 Capsum Double stable emulsion without bark
EP4171754A1 (en) 2020-06-24 2023-05-03 L'oreal Long wear lip cosmetic system and topcoat
US11160735B1 (en) 2020-06-24 2021-11-02 L'oreal Long wear lip cosmetic system and topcoat
FR3113239B1 (en) 2020-08-10 2023-05-26 Oreal COSMETIC SYSTEM AND LONG-LASTING LIP TOPCOAT
JP7444821B2 (en) 2020-09-15 2024-03-06 信越化学工業株式会社 Bioelectrode composition, bioelectrode, bioelectrode manufacturing method, and silicon material particles
FR3114501B1 (en) 2020-09-29 2024-02-16 Oreal Keratin fiber makeup kit with two compositions; two-step makeup process
JP7524148B2 (en) 2020-10-13 2024-07-29 信越化学工業株式会社 Bioelectrode composition, bioelectrode, method for producing bioelectrode, polymer compound and composite
JP7569298B2 (en) 2020-11-05 2024-10-17 信越化学工業株式会社 Bioelectrode composition, bioelectrode, method for producing bioelectrode, and reaction complex
JP7507737B2 (en) 2020-11-26 2024-06-28 信越化学工業株式会社 Bioelectrode composition, bioelectrode, method for producing a bioelectrode, and reaction complex
FR3117831A1 (en) 2020-12-18 2022-06-24 L'oreal Cosmetic use of fatty chain derivatives of diglutamide lysine as a deodorant active ingredient
FR3117832A1 (en) 2020-12-21 2022-06-24 L'oreal Two-step makeup process comprising on the one hand an amino acid and on the other hand an acid dye and kit
EP4265657A4 (en) 2020-12-21 2024-11-27 Dow Toray Co., Ltd. Radical copolymer composition, production method therefor, and cosmetic or cosmetic ingredient containing radical copolymer composition
FR3117833A1 (en) 2020-12-21 2022-06-24 L'oreal Three-step makeup process comprising on the one hand a basic amino acid and on the other hand an acid dye and kit
FR3117867B1 (en) 2020-12-22 2024-03-08 Oreal Microdispersion of natural wax
FR3117804B1 (en) 2020-12-22 2024-03-01 Oreal METHOD FOR TREATING HUMAN SWEAT AND BODY ODOR USING MAGNESIUM OXIDE AND PHOSPHATE SALT
JP7611807B2 (en) 2021-01-06 2025-01-10 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for producing bioelectrode
FR3119317B1 (en) 2021-02-04 2024-05-03 Capsum Composition in the form of a stable macroscopic emulsion comprising a percentage of ingredients of natural origin greater than or equal to 95% according to standard ISO 16128
JP7627671B2 (en) 2021-04-16 2025-02-06 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for producing bioelectrode
CN117279981A (en) 2021-05-18 2023-12-22 美国陶氏有机硅公司 Methods for preparing polyepoxysilazane and using the same to produce amino-functional polyorganosiloxanes
FR3126314B1 (en) 2021-08-30 2024-03-08 Oreal long-lasting cosmetic composition comprising expanded perlite
FR3126875B1 (en) 2021-09-10 2023-08-11 Oreal Make-up kit comprising an aqueous make-up composition, and a fixing composition with a continuous oily phase with a hydrophobic film-forming polymer
FR3127404B1 (en) 2021-09-29 2023-10-13 Oreal Long-lasting diluted cosmetic composition comprising mixed sensory modifiers
FR3129286A1 (en) 2021-11-24 2023-05-26 Capsum MACROSCOPIC DISPERSION
FR3129590A1 (en) 2021-11-26 2023-06-02 Capsum SOLAR MACROSCOPIC DISPERSION WITHOUT BARK
FR3129593A1 (en) 2021-11-30 2023-06-02 L'oreal Aqueous care and/or makeup composition comprising a fatty acid monoester, a neutralized anionic surfactant, a VP/Eicosene copolymer, a semi-crystalline polymer and a latex
FR3130136A1 (en) 2021-12-14 2023-06-16 L'oreal Water-in-oil emulsions comprising a surfactant, a water-soluble vinyl polymer and an organosiloxane
FR3130134B1 (en) 2021-12-14 2023-12-22 Oreal Water-in-oil emulsions comprising a surfactant, an acrylic polymer and an organosiloxane
FR3134970B1 (en) 2022-04-28 2024-03-15 Oreal Makeup kit for eyebrows and the skin around the eyebrows comprising an anhydrous film-forming composition and a 3-layer makeup composition and makeup process
CN115505126B (en) * 2022-07-08 2023-06-06 橙天新材料(广州)有限公司 Preparation method of beta-end siloxane-based polydimethylsiloxane
JP7842716B2 (en) 2022-07-21 2026-04-08 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for manufacturing the same
JP2025541694A (en) 2022-11-30 2025-12-23 ダウ・東レ株式会社 Solid particles of organosilicon-functional copolymers, their manufacturing process, and cosmetics containing said solid particles
FR3144758A1 (en) 2023-01-10 2024-07-12 L'oreal Eyebrow makeup composition with a non-glycerol silicone resin, a glycerol silicone resin, a volatile hydrocarbon oil and a thickener
WO2024165693A1 (en) 2023-02-08 2024-08-15 Chanel Parfums Beaute Cosmetic composition comprising hydrophobic and hydrophilic treated pigments
FR3147707A1 (en) 2023-04-17 2024-10-18 L'oreal ANHYDROUS cosmetic composition, including OIL AND LAMELLAR MINERALS AND METHODS OF USE
WO2024182099A1 (en) 2023-02-27 2024-09-06 L'oreal Anhydrous cosmetic composition including oil and platy mineral, and methods of use
JP2024137755A (en) 2023-03-23 2024-10-07 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for producing bioelectrode
FR3148717A1 (en) 2023-05-15 2024-11-22 L'oreal Aqueous cosmetic composition comprising a fatty acid monoester, a neutralized anionic surfactant, a VP/Eicosene copolymer, a semi-crystalline polymer, a latex, a filler and a polyol
JP2025011039A (en) 2023-07-10 2025-01-23 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for producing bioelectrode
FR3152122B3 (en) 2023-08-17 2025-09-12 Oreal COMPOSITION IN THE FORM OF A WATER-IN-OIL EMULSION AND ASSOCIATED METHODS
FR3153747A1 (en) 2023-10-06 2025-04-11 L'oreal Aqueous composition comprising a fatty acid monoester, a neutralized anionic surfactant, a liquid polyester derived from a diol dimer and an unsaturated fatty acid dimer, a latex and a polyol
FR3154003A1 (en) 2023-10-16 2025-04-18 L'oreal Eyebrow makeup method with first felt-tip pen composition and second composition with a non-glycerolated silicone resin, a glycerolated silicone resin, a silicone polyamide
FR3154004A1 (en) 2023-10-16 2025-04-18 L'oreal Two-step eyebrow makeup process with a first composition of pencil lead type and a second composition with a non-glycerolated silicone resin, a glycerolated silicone resin, a silicone polyamide
FR3154607A1 (en) 2023-10-30 2025-05-02 L'oreal LIQUID MAKE-UP COMPOSITION COMPRISING SILICONE FILM-FORMING AGENTS, OILS, A SILICONE GUM AND PIGMENTS AND METHOD FOR USING IT
FR3156653A1 (en) 2023-12-15 2025-06-20 L'oreal Solid cosmetic composition comprising an indenic hydrocarbon resin, a silicone resin and a dispersed aqueous phase
FR3157183A1 (en) 2023-12-20 2025-06-27 L'oreal INVERSE EMULSION COMPRISING PULLULAN, AN APOLAR HYDROCARBON OIL, A SILICONE FILMLOGEN POLYMER, A COLORING MATERIAL AND MAKE-UP PROCESS
WO2025169011A1 (en) 2024-02-06 2025-08-14 L'oreal Non-solid cosmetic composition with an apolar volatile hydrocarbon oil, a solvent with an alcohol, acid, amine or amide function and a silicone elastomer with carboxylic acid functions
FR3160320B3 (en) 2024-03-25 2026-04-17 Oreal NON-SOLID COSMETIC COMPOSITION WITH A NON-POLAR VOLATILE HYDROCARBONATE OIL, A SOLVENT HAVING AN ALCOHOL, ACID, AMINE OR AMIDE FUNCTIONALITY AND A SILICONE ELASTOMER HAVING CARBOXYLIC ACID FUNCTIONS.
FR3159099A1 (en) 2024-02-09 2025-08-15 L'oreal Aqueous composition comprising a wax, a neutralized C12-C20 monoalkyl phosphate, a liquid polyester derived from a dimer diol and an unsaturated fatty acid dimer, a latex and a polyol
FR3161433A1 (en) 2024-04-17 2025-10-24 Chanel Parfums Beaute Process for the synthesis of bio-sourced solid fatty substances
JP2025174080A (en) 2024-05-16 2025-11-28 信越化学工業株式会社 Bioelectrode composition, bioelectrode, and method for manufacturing bioelectrode
FR3162356A1 (en) 2024-05-24 2025-11-28 Chanel Parfums Beaute Solid skincare and/or makeup composition
FR3165168A1 (en) 2024-07-30 2026-02-06 Chanel Parfums Beaute Solid cosmetic composition
FR3167545A1 (en) 2024-10-18 2026-04-24 L'oreal Composition comprising a polyester and a lipophilic silicone polymer

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3218344A (en) 1959-06-29 1965-11-16 Union Carbide Corp Alkoxy substituted organosilicon compounds
US3313773A (en) 1965-12-03 1967-04-11 Gen Electric Platinum addition catalyst system
US3392143A (en) 1967-05-15 1968-07-09 Gen Electric Polyamide compositions
US3746738A (en) 1972-03-28 1973-07-17 Union Carbide Corp Silicon containing polyazimides
US3892643A (en) 1973-05-02 1975-07-01 Hitachi Ltd Thermally curable compositions and process for curing said compositions
US4145508A (en) 1976-08-17 1979-03-20 Rhone-Poulenc Industries Polysiloxane thermoplastic elastomers
US5874069A (en) 1997-01-24 1999-02-23 Colgate-Palmolive Company Cosmetic composition containing silicon-modified amides as thickening agents and method of forming same
US5919441A (en) 1996-04-01 1999-07-06 Colgate-Palmolive Company Cosmetic composition containing thickening agent of siloxane polymer with hydrogen-bonding groups
US6051216A (en) 1997-08-01 2000-04-18 Colgate-Palmolive Company Cosmetic composition containing siloxane based polyamides as thickening agents

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE225644T1 (en) * 1996-04-01 2002-10-15 Colgate Palmolive Co COSMETIC COMPOSITION CONTAINING AMIDE AND SILICON MODIFIED WAXES

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3218344A (en) 1959-06-29 1965-11-16 Union Carbide Corp Alkoxy substituted organosilicon compounds
US3313773A (en) 1965-12-03 1967-04-11 Gen Electric Platinum addition catalyst system
US3392143A (en) 1967-05-15 1968-07-09 Gen Electric Polyamide compositions
US3746738A (en) 1972-03-28 1973-07-17 Union Carbide Corp Silicon containing polyazimides
US3892643A (en) 1973-05-02 1975-07-01 Hitachi Ltd Thermally curable compositions and process for curing said compositions
US4145508A (en) 1976-08-17 1979-03-20 Rhone-Poulenc Industries Polysiloxane thermoplastic elastomers
US5919441A (en) 1996-04-01 1999-07-06 Colgate-Palmolive Company Cosmetic composition containing thickening agent of siloxane polymer with hydrogen-bonding groups
US5874069A (en) 1997-01-24 1999-02-23 Colgate-Palmolive Company Cosmetic composition containing silicon-modified amides as thickening agents and method of forming same
US6051216A (en) 1997-08-01 2000-04-18 Colgate-Palmolive Company Cosmetic composition containing siloxane based polyamides as thickening agents

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030105260A1 (en) * 2001-07-12 2003-06-05 Cook Leon Neal Methods for making silicone-organic copolymers
US6800713B2 (en) * 2001-07-12 2004-10-05 Dow Corning Corporation Methods for making silicone-organic copolymers
US20100210491A1 (en) * 2009-02-13 2010-08-19 Charles Piskoti Silicone Wax Emulsion and Method of Manufacture
US9006157B2 (en) 2009-02-13 2015-04-14 Genesee Polymers Corp. Silicone wax emulsion and method of manufacture
US9872828B2 (en) 2014-05-21 2018-01-23 Dow Corning Corporation Emulsion of cross-linked aminosiloxane polymer
US9890253B2 (en) 2014-05-21 2018-02-13 Dow Corning Corporation Cross-linked aminosiloxane polymer and method of forming
US10059806B2 (en) 2014-05-21 2018-08-28 Dow Silicones Corporation Aminosiloxane polymer and method of forming
WO2018165434A1 (en) 2017-03-08 2018-09-13 Dow Silicones Corporation Long lasting cosmetic composition comprising silicone elastomer
US10918587B2 (en) 2017-03-08 2021-02-16 Dow Silicones Corporation Long lasting cosmetic composition comprising silicone elastomer

Also Published As

Publication number Publication date
EP0974614A3 (en) 2000-08-09
DE69901371T2 (en) 2002-12-05
JP4382196B2 (en) 2009-12-09
US5981680A (en) 1999-11-09
EP0974614B1 (en) 2002-05-02
EP0974614A2 (en) 2000-01-26
DE69901371D1 (en) 2002-06-06
JP2000038450A (en) 2000-02-08

Similar Documents

Publication Publication Date Title
USRE38116E1 (en) Method of making siloxane-based polymides
RU2193575C2 (en) Novel block copolymers and method of preparation thereof
JP2003335788A (en) Method for producing nitrogen-containing organic compound containing SiH group
JPH06172536A (en) Room temperature curing silicone sealant and its preparation
JP2678624B2 (en) Organosiloxane compound having amino group
CN101959938B (en) Method for producing silicone polyethers
US20020013441A1 (en) Process for the preparation of silarylenesiloxane-diorganosiloxane copolymers
AU737014B2 (en) Method for preparing polydiorganosiloxanes partially end-blocked with substituted silethylene groups
US6800713B2 (en) Methods for making silicone-organic copolymers
US5567790A (en) Method for the preparation of diphenylsiloxane-dimethylsiloxane copolymers
US5852153A (en) Trimethylsiloxy group-containing polysiloxane and a process for producing the same
JP4628672B2 (en) Method for producing silicone-organic copolymer
JPH0291083A (en) One-end reactive siloxane compound
US5274156A (en) Organosiloxane ethers
US5157095A (en) Hydrosilylation of unsaturated aliphatic isocyanates
JP2947596B2 (en) Silethynylsiloxane copolymer and method for producing the same
JP2533772B2 (en) Organopolysiloxane having phospholipid-like structure
JP2841268B2 (en) Amidobetaine-modified organo (poly) siloxane and method for producing the same
JPH072823B2 (en) Method for producing modified polyorgano-organosiloxane having comb-like or block-like structure
Jallouli et al. Polycarbosilanes containing siloxy and/or silanamine units by polycondensation using hydrosilylation
WO2001032750A1 (en) Fluoroelastomers for a wide temperature range of applications
JPH10182829A (en) Production of organopolysiloxane
JPH04331234A (en) Polysiloxane star polymer and its production
JPH05230077A (en) Novel reactive diamino silicone compound
JPH06172368A (en) Process for producing diaminoalkyldisiloxane and diaminoalkyldisiloxane containing N-alkenyl group

Legal Events

Date Code Title Description
FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12