WO2009033399A1 - Procédé de préparation d'une émulsion de silicone contenant un polysiloxane élastomère qui possède des groupes ammonium quaternaires - Google Patents

Procédé de préparation d'une émulsion de silicone contenant un polysiloxane élastomère qui possède des groupes ammonium quaternaires Download PDF

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WO2009033399A1
WO2009033399A1 PCT/CN2008/072230 CN2008072230W WO2009033399A1 WO 2009033399 A1 WO2009033399 A1 WO 2009033399A1 CN 2008072230 W CN2008072230 W CN 2008072230W WO 2009033399 A1 WO2009033399 A1 WO 2009033399A1
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group
quaternary ammonium
polyorganosiloxane
groups
mixture
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PCT/CN2008/072230
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English (en)
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Irene Li
Rongrong Fan
Xiaoqun He
Junjie Shen
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Dow Corning (Shanghai) Co., Ltd.
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Publication of WO2009033399A1 publication Critical patent/WO2009033399A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • 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
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Definitions

  • This invention is to provide a new silicone emulsion containing an elastomeric polysiloxane having quaternary ammonium groups and a polydiorganosiloxane having non-reactive organo group, which can show synergic effects of polydiorganosiloxane emulsion and quaternary ammonium group-containing polysiloxane emulsion.
  • this invention is to provide this silicone emulsion which is significantly useful for personal care products with better feeling
  • Silicone emulsions are well known and used in various applications such as industries (textile, antifoaming, process, etc.), cosmetic, pharmaceutical, and the like.
  • Silicone emulsion is obtained by emulsifying silicone in the presence of surfactant with use of mixing tools such as mixer, homogenizer, colloid mil and the like, or by emulsification polymerization of cyclic siloxane. Silicone emulsion with Oil-in-Water type or Water-in-Oil type and also with various particle sizes of from a few microns to so-called microemulsion may be prepared by selection of adequate components from various silicones and surfactants. These techniques are well known.
  • silicones become known for their improved conditioning ability and the distinctive feel they impart to hair.
  • Silicone emulsions having a typical polydimethylsiloxane have been used in this application.
  • Shampoo containing its conventional silicone emulsion could reduce combing force in dry condition, but needed improvement of combing in wet condition.
  • Amino-functional polydimethylsiloxane emulsion was added to the conventional silicone emulsion in order to improve said property.
  • 6,787,603 discloses preparation of silicone emulsion containing a quaternary ammonium functional silane or siloxane comprising reacting (i) an organic quaternary ammonium compound having epoxide grous or halohydrin group with (ii) a silane or siloxane having amino group in the presence of (iii) surfactant, the components (i) and (ii) being dispersed in (iv) an aqueous polar phase, and also teaches use of the silicone emulsion in personal care application.
  • a preparation of a silicon based quaternary ammonium functional composition was taught in US Patent No. 6,482,969. These patents may be cited as reference of reaction of (i) a polyorganosiloxane having amino group and (ii) an organic quaternary ammonium compound having epoxide group or halohydrin group of this invention.
  • WO 2004/104013 claims a method of preparing silicone emulsion containing elastomeric polysiloxane having quaternary ammonium groups.
  • WO 2004/103326 discloses personal care emulsion comprising elastomeric polysiloxane obtained by reaction of an amino-functional polyorganosiloxane and a quaternary ammonium compound in the presence of a crosslinking agent. This emulsion could improve the feeling characteristics but did not satisfy with combing force reduction.
  • This invention relates to a method for preparation of silicone emulsion containing elastomeric polyorganosiloxane having quaternary ammonium functionality.
  • the silicone emulsion containing the elastomeric polyorganosiloxane having quaternary ammonium functionality is obtained by concurrently reaction of polyorganosiloxane having amino group with an organic quaternary ammonium compound having epoxide group or halohydrin group and crosslinking of polyorganosiloxane having amino group with a crosslinker therefor in the presence of polydiorganosiloxane having an organo group which is not reactive with the another components such as the polyorganosiloxane having amino group, the organic quaternary ammonium compound and the crosslinker, and of surfactant, those components being dispersed in an aqueous polar phase.
  • the silicone emulsion prepared by the method of this invention may be used in various applications such as textile application, personal care application, and the like.
  • it is significantly useful for personal care application to provide excellent combing properties to personal care products such as shampoo, conditioner, and the like.
  • a method for preparing a silicone emulsion containing elastomeric polyorganosiloxanes having quaternary ammonium groups in their molecule comprising reacting (i) a polyorganosiloxane having amino groups in its molecule, (ii) an organic quaternary ammonium compound having epoxide group or halohydrin group in its molecule, with (iii) a crosslinking agent for the polyorganosiloxane (i), in the presence of (iv) a polydiroganosiloxane having an organo group which is not reactive with the components (i), (ii) and (iii), and of (v) a surfactant, the components (i) to (iv) being dispersed in (vi) an aqueous polar phase.
  • the organic quaternary ammonium compound having epoxide groups is glycidyl trimethylammonium chloride or glycidyl trimethylammonium bromide.
  • the organic quaternary ammonium compound having halohydrin groups is selected from the group consisting of (3-chloro-2-hydroxypropyl)trimethylammonium chloride, (3-chloro-2-hydroxypropyl)dimethyldodecylammonium chloride, (3-chloro-2-hydroxypropyl)dimethyloctadecylammonium chloride, (3-chloro-2-hydroxypropyl)trimethylammonium bromide, (3-chloro-2-hydroxypropyl)dimethyldodecylammonium bromide, and (3-chloro-2-hydroxypropyl)dimethyloctadecylammonium bromide.
  • the aqueous polar phase consists of water.
  • the aqueous polar phase comprises water and a polar organic compound.
  • the polar organic compound is selected from the group consisting of monohydroxy alcohols, diols, triols, glycerol esters, and polyglycols.
  • the crosslinking agent is selected from the group consisting of organic epoxides containing at least two epoxy groups, epoxy functional silicones containing at least two epoxy groups, and chlorohydrins.
  • the present invention also provides a method of preparing a silicone emulsion containing elastomeric polyorganosiloxane having nitrogen atoms as the oil phase of the emulsion, comprising the sequential steps of:
  • the present invention also provides a silicone emulsion containing elastomeric polyorganosiloxane having quaternary ammonium group prepared by any of the methods mentioned hereinabove. 10019] In the present invention, it also provides a personal care product containing a silicone emulsion prepared according to any of the methods mentioned hereinabove.
  • the personal care product is selected from the group consisting of antiperspirant, deodorant, skin cream, skin care lotion, moisturizer, facial treatment, acne remover, wrinkle remover, personal cleanser, facial cleanser, bath oil, perfume, cologne, sachet, sunscreen, pre-shave lotion, after-shave lotion, shaving soap, shaving lather, hair shampoo, hair conditioner, hair colorant, hair relaxer, hair spray, mousse, styling gel, permanent, depilatorie, cuticle coat, make-up, color cosmetic, foundation, blush, lipstick, eyeliner, mascara, oil remover, color cosmetic remover, bath powder, body powder, pharmaceutical, biocide, or biologically active substance.
  • This invention is directed to silicone emulsion useful for textile application and personal care applications, of certain oil-in-water (ONM) emulsions containing elastomeric polysiloxanes having quaternary ammonium groups as an oil phase.
  • ONM oil-in-water
  • the emulsion containing elastomeric polysiloxanes is obtained by reacting (i) polyorganosiloxanes having amino groups with (ii) organic quaternary ammonium compounds having epoxide or halohydrin groups in its molecule, and crosslinking the components (i) with (iii) a crosslinking agent, the reactions being carried out in the presence (iv) polyorganosiloxane having an organic group which is not reactive with the components (i), (ii) and (iii), and (v) a surfactant, the components (i) - (iv) being dispersed in (vi) an aqueous polar phase.
  • a polyorganosiloxane having amino groups employed as Component (i) in this invention has the formula: wherein R' denotes an alkyl group of 1 to 4 carbons or a phenyl group with the proviso that at least 50 percent of the total number of R' groups are methyl; Q denotes an amino functional substituent of the formula -R"Z wherein R" is a divalent alkylene radical of 2 to 6 carbon atoms and Z is a monovalent radical selected from the group consisting of -NR'"2, and -NR'"(CH2)bNR'"2; wherein R" denotes independently hydrogen or an alkyl group of 1 to 4 carbons, and b is a positive integer having a value of from 2 to 6; z has a value of 0 or 1 ; x has an average value of 20 to 3000; y has an average value of 0 to 100 when z is 1 , y has an average value of 1 to 100 when z is 0; with the proviso that
  • Suitable R groups are represented by and may be independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and phenyl, with the proviso that at least fifty percent of the R' groups are methyl. Most preferably, all R' is methyl.
  • the alkylene radicals represented by R" may include dimethylene, trimethylene, tetramethylene, pentamethylene, -CH2CH(CH3) CH2-, and
  • -CH2CH2CH(CH3)CH2- Dimethylene, trimethylene or an alkyl substituted trimethylene radical such as -CH2CH(CH3)CH2- is preferable.
  • Alkyl groups of 1 to 4 carbon atoms as represented by R'" include methyl, ethyl, propyl, isopropyl, butyl, and isobutyl.
  • Useful Z radicals include the unsubstituted amino group -ISIH2, alkyl substituted amino groups such as -NHCH3, -NHCH2CH2CH2CH3, and -N(CH2CH3)2; and aminoalkyl substituted amino group such as -NHCH2CH2NH2, -NH(CH 2 )6NH 2 , and -NHCH 2 CH 2 CH 2 N(CHS) 2 .
  • the polyorganosiloxane When z is zero, the polyorganosiloxane has only pendent amino functional substituents in the polymer chain. When z is one, the polyorganosiloxane may have only terminal amino functional substituents or both terminal and pendent amino functional substituents in the polymer chain.
  • x may vary from a value of 20 to 500, and y may vary from zero to 80 when z is one and may vary from one to 80 when z is zero. Most preferably, the value of x + y is in the range of 20 to 580.
  • the amine content i.e., the number of amino functional groups in the molecule of the polyorganosiloxane having amino group, is generally expressed as mol percent amine, and this is determined according to the relationship A/DP x 100, where A is the sum of integer y in the above formula for the polyorganosiloxane having amino group and the number of amino group located at the terminal, and the Degree of Polymerization (DP) is x + y + 2, which indicates the chain length of the amine functional polysiloxane.
  • the amine functional polysiloxane was a trimethylsiloxy terminated dimethyl / methylaminoethylaminoisobutyl siloxane copolymer with a viscosity of 3,000
  • An organic quaternary ammonium compound employed as Component(ii) in this invention may be the organic quaternary ammonium compound having epoxide groups and/or halohydrin group.
  • One preferred group of epoxy functional organic quaternary ammonium compounds is represented by the formula: where, Y is a divalent alkylene radical of up to 6 carbon atoms, preferably methylene; R 4 , R 5 and R 6 are independently monovalent hydrocarbon groups, especially those having up to 20 carbons and preferably methyl, dodecyl or octadecyl; and X " is a counter ion, especially chloride or bromide. Useful examples from this group are glycidyl trimethyl ammonium chloride and glycidyl trimethyl ammonium bromide. Non-terminal epoxides may also be used, but terminal epoxides (such as those of the group described here) are generally preferred. Combinations of epoxides may also be employed.
  • a preferred group of halohydrin functional quaternary ammonium compounds is represented by:
  • X 1 is a halogen, preferably chlorine or bromine
  • Y is a divalent alkylene radial of up to 6 carbon atoms, preferably methylene
  • R 4 , R 5 and R 6 are independently monovalent hydrocarbon groups, especially those having up to 20 carbons and preferably methyl, dodecyl or octadecyl
  • X " is a counter ion, especially chloride or bromide. Specific examples from this group are
  • Non-terminal halohydrins may also be used, but terminal halohydrins (such as those of the group here) are generally preferred. Some combination of these specific halohydrins, other members of the group described here and/or members of the previously recited group of epoxides may also be employed.
  • a crosslinking agent employed as Component (iii) in this invention is an organic epoxide containing at least two epoxy groups, which effects crosslinking of the polyorganosiloxane having amino group (i) to form elastomeric polysiloxanes.
  • It may include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerine diglycidyl ether, triglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether; 1 ,2,3,4-diepoxybutane; 1 ,2,4,5-diepoxypentane; 1 ,2,5,6-diepoxyhexane; 1 ,2,7,8-diepoxyoctane; 1 ,3-divinylbenzene diepoxide; 1 ,4-divinylbenzene diepoxide; 4,4'-isopropylidene diphenol diglycidyl ether, and hydroquinone diglycidyl ether.
  • polyglycidyl ethers of alkane polyols may also be used herein.
  • polyglycidyl ethers of poly(alkylene glycols) may also be used herein.
  • n is a positive integer determining the molecular weight of the epoxide.
  • an epoxy functional silicone containing at least two epoxy groups instead of an organic epoxide containing at least two epoxy groups, a suitable epoxy functional silicone of the general structure shown below can be used, in which m represents an integer of one or more. If desired, epoxy functional silicones can be used which contain pendant epoxy groups along the silicone polymer chain.
  • Such epoxy functional silicones are well known in the art and available commercially from silicone producers. Typically, such silicones have the viscosity ranging from 1 to about 200 centistoke (mw ⁇ /s) and weight average molecular weights of about 300 - 6,000.
  • Chlorohydrins may be used in place of or in conjunction with the epoxides.
  • a chlorohydrin is a compound containing both chloro and hydroxyl radicals, and in some cases, chlorohydrin has been defined as compounds having the chloro and the hydroxy groups on adjacent carbon atoms, i.e.
  • Chlorohydrins can be converted into epoxides by the action of a base.
  • a base In the presence of the hydroxide ion, a small proportion of the alcohol exists as an alkoxide, which displaces the chloride ion from the adjacent carbon atom to produce a cyclic ether.
  • organic epoxides and epoxy functional silicones containing a single epoxy group can also be included as an optional component in order to control the cross link density and the overall molecular weight of the elastomeric polyorganosiloxanes.
  • a polydiorganosiloxane having an organo group which is not reactive with the Components (i), (ii) and (iii) employed as Component (iv) in the present invention may be represented by the general formula: where R1 is a monovalent hydrocarbon groups selected from the group consisting of alkyl group containing 1 -6 carbon atoms such as methyl, ethyl, propyl radical with most preference of methyl radical, halogenated alkyl group such as 3,3,3-trifluoropropyl gradical and aromatic group such as phenyl, and a has a value sufficient to provide the viscosity in the range from 1 ,000 mPa.s to 1 ,000,000 mPa.s at temperature of 25 0 C.
  • the polydiorganosiloxane having the organo group described as R1 intends to mean that the polydiorganosiloxane does not react with the components (i), (ii) and (iii), but may contain another radical present as residue of the synthesis of the polydiorganosiloxane, which does not adversely effect the reactions.
  • the viscosity of such polysiloxanes generally ranges from 1 ,000 mPa.s to 1 ,000,000 mPa.s at temperature of 25, with preferable range from 50,000 mPa.s to 500,000 mPa.s.
  • the polydiorganosiloxane has linear structure of two-dimensional as above-mentioned, but it may contain three-dimensional structure or four-dimensional structure to the extent that such structure adversely effect elastomeric property.
  • Most preferable polydiorganosiloxane of Component (iv) is trimethylsilyl-terminated polydimethysilxaone having the viscosity in the above range.
  • the above lower limit and upper limit of the viscosity would correspond to about 350 and about 2,300 of the value a of the polymerization degree respectively, although we can not precisely say the value due to the molecular weight distribution.
  • a surfactant employed as Component (v) in the present invention may comprises a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, or a mixture of such surfactants. Most preferred however are nonionic surfactants.
  • the nonionic surfactant should be a non-silicon atom containing nonionic emulsifier. Most preferred are alcohol ethoxylates R 4 -(OCH2CH2)pOH, particularly fatty alcohol ethoxylates. Fatty alcohol ethoxylates typically contain the characteristic group -(OCH2CH2)pOH which is attached to fatty hydrocarbon residue R 4 which contains about eight to about twenty carbon atoms, such as lauryl (C ⁇ ).
  • suitable nonionic surfactants are polyoxyethylene (4) lauryl ether, polyoxyethylene (5) lauryl ether, polyoxyethylene (23) lauryl ether, polyoxyethylene (2) cetyl ether, polyoxyethylene (10) cetyl ether, polyoxyethylene (20) cetyl ether, polyoxyethylene (2) stearyl ether, polyoxyethylene (10) stearyl ether, polyoxyethylene (20) stearyl ether, polyoxyethylene (21 ) stearyl ether, polyoxyethylene (100) stearyl ether, polyoxyethylene (2) oleyl ether, and polyoxyethylene (10) oleyl ether.
  • fatty alcohol ethoxylates are commercially available under trademarks and tradenames such as ALFONIC®, BRIJ, GENAPOL®, NEODOL®, SURFONIC®, TERGITOL®, and TRYCOL.
  • Ethoxylated alkylphenols can also be used, such as ethoxylated octylphenol, sold under the trademark TRITON®.
  • Cationic surfactants useful in the present invention include compounds containing quaternary ammonium hydrophilic moieties in the molecule which are positively charged, such as quaternary ammonium salts represented by
  • R'R"R"'R""N + X- where R', R", R'", and R"" are alkyl groups containing 1 -30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soy; and X is halogen, i.e., chlorine or bromine.
  • X is halogen, i.e., chlorine or bromine.
  • dialkyldimethyl ammonium salts represented by R'R"N + (CH3)2X " , where R' and R" are alkyl groups containing 12-30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soy; and X is halogen.
  • Monoalkyltrimethyl ammonium salts can also be employed, and are represented by R'N + (CH3)3X ⁇ where R' is an alkyl group containing 12-30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soy; and X is halogen.
  • Some representative quaternary ammonium salts are dodecyltrimethyl ammonium bromide (DTAB), didodecyldimethyl ammonium bromide, dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, didocosyldimethyl ammonium chloride, dicoconutdimethyl ammonium chloride, ditallowdimethyl ammonium chloride, and ditallowdimethyl ammonium bromide.
  • DTAB dodecyltrimethyl ammonium bromide
  • didodecyldimethyl ammonium bromide dihexadecyldimethyl ammonium chloride
  • dihexadecyldimethyl ammonium bromide dioctadecyldimethyl ammonium chloride
  • anionic surfactant As the elastomeric polyorganosiloxane in the emulsion of this invention contains quaternary ammonium groups, it is not desirable to use the anionic surfactant per se, but may use a combination of another surfactant.
  • anionic surfactants which can be used are sulfonic acids and their salt derivatives; alkali metal sulfosuccinates; sulfonated glyceryl esters of fatty acids such as sulfonated monoglycerides of coconut oil acids; salts of sulfonated monovalent alcohol esters such as sodium oleyl isothionate; amides of amino sulfonic acids such as the sodium salt of oleyl methyl tauride; sulfonated products of fatty acid nitriles such as palmitonitrile sulfonate; sulfonated aromatic hydrocarbons such as sodium alpha-naphthalene monosulfonate; condensation products of
  • Some examples of commercial anionic surfactants useful in this invention include triethanolamine linear alkyl sulfonate sold under the tradename BIO-SOFT N-300 by the Stepan Company, Northfield, Illinois; sulfates sold under the tradename POLYSTEP by the Stepan Company; and sodium n-hexadecyl diphenyloxide disulfonate sold under the tradename DOWFAX 8390 by The Dow Chemical Company, Midland, Michigan.
  • Amphoteric surfactants which may also be used generally comprise surfactant compositions such as alkyl betaines, alkylamido betaines, and amine oxides, specific examples of which are known in the art.
  • An aqueous polar phase employed as Component (v) in the present invention and used in the process is most preferably an aqueous phase consisting of only water, or an aqueous phase containing water and a polar solvent.
  • the polar solvents especially preferred herein are those compounds determined to be cosmetically acceptable non-aqueous polar solvents, among which are monohydroxy alcohols such as ethyl alcohol and isopropyl alcohol; diols and triols such as propylene glycol, 1 ,2-hexanediol CH3(CH2)3CH(OH)CH2 ⁇ H,
  • glycerol esters such as glyceryl triacetate (triacetin), glyceryl tripropionate (tripropionin), and glyceryl tributyrate (tributyrin)
  • polyglycols such as polyethylene glycols and polypropylene glycols among which are PPG-14 butyl ether C4
  • the aqueous polar phase of the emulsion therefore, can consist of water, or a mixture of water and a polar solvent which is preferably a polar organic compound.
  • this component will be present in the composition in an amount to provide the balance of the composition to 100 percent, after taking in account the amounts of the other components used in formulating a suitable composition.
  • this component will comprise 0.1-99.8 percent by weight based on the total weight of the O/W or W/O composition, preferably 10-95 percent by weight.
  • mixtures of liquids may be used to form this single phase component of the composition, liquids should be miscible and capable of forming an essentially homogeneous mixture.
  • a preservative may be required as an optional component of the composition, and some representative compounds which can be used include formaldehyde, salicylic acid, phenoxyethanol, DMDM hydantoin (1 ,3-dimethylol-5,5-dimethyl hydantoin), 5-bromo-5-nitro-1 ,3-dioxane, methyl paraben, propyl paraben, sorbic acid, imidazolidinyl urea sold under the name GERMALL® Il by Sutton Laboratories, Chatham, New Jersey, sodium benzoate, 5-chloro-2-methyl-4-isothiazolin-3-one sold under the name KATHON CG by Rohm & Haas Company, Philadelphia, Pennsylvania, and 3-iodo-2-propynl-butylcarbamate sold under the name GLYCACIL® L by Lonza Incorporated, Fair Lawn, New Jersey.
  • a freeze/thaw stabilizer can be included as another optional component of the composition including compounds such as ethylene glycol, propylene glycol, glycerol, trimethylene glycol, and polyoxyethylene ether alcohols such as RENEX 30 sold by ICI Surfactants, Wilmington, Delaware.
  • a corrosion inhibitor such as an alkanolamine, an inorganic phosphate such as zinc dithiophosphate, an inorganic phosphonate, an inorganic nitrite such as sodium nitrite, a silicate, a siliconate, an alkyl phosphate amine, a succinic anhydride such as dodecenyl succinic anhydride, an amine succinate, or an alkaline earth sulfonate such as sodium sulfonate or calcium sulfonate.
  • a corrosion inhibitor such as an alkanolamine, an inorganic phosphate such as zinc dithiophosphate, an inorganic phosphonate, an inorganic nitrite such as sodium nitrite, a silicate, a siliconate, an alkyl phosphate amine, a succinic anhydride such as dodecenyl succinic anhydride, an amine succinate, or an alkaline earth sulfonate such as sodium
  • An additional optional component which can be used are low molecular weight polysiloxanes such as low molecular weight linear or cyclic volatile methyl siloxanes, or low molecular weight linear and cyclic volatile and non-volatile alkyl and aryl siloxanes. Most preferred, are low molecular weight linear and cyclic volatile methyl siloxanes. These compositions are well known in the art and reference may be had to US Patent 6,238,657 (May 29, 2001 ), for numerous specific examples of suitable compositions.
  • an optional component is included, it is generally present in an amount of 0.01 -0.1 percent by weight of each optional component, i.e., preservative, freeze/thaw stabilizer, or corrosion inhibitor.
  • compositions according to this invention When emulsion compositions according to this invention are used in particular product(s) intended for the personal care market, the compositions may be formulated to include one or more alternate components, for example: (A) conditioning agents such as cationic polymers, proteins, natural oils, elastomeric polyorganosiloxanes containing nitrogen atoms, hydrocarbons other than waxes, and mixtures thereof;
  • conditioning agents such as cationic polymers, proteins, natural oils, elastomeric polyorganosiloxanes containing nitrogen atoms, hydrocarbons other than waxes, and mixtures thereof;
  • cosurfactants such as betaines, monoalkylalkanolamides, dialkylalkanolamides, amine oxides, amine glycinates, amine propionates, amine sultaines, and mixtures thereof;
  • Products containing alternate components (A) are especially useful as conditioners, products containing (A) and (B) are especially useful as shampoos, and products containing (C) are especially useful as moisturizers.
  • Some examples of additional alternate components which can be included in personal care products containing the emulsion compositions are suspending agents and thickeners.
  • a suspending agent can be used at concentrations effective for suspending the silicone component of the emulsion composition or other water-insoluble material in dispersed form, in the personal care product.
  • Such suspending agents can include crystalline suspending agents which are categorized as acyl derivatives, long chain amine oxides, and mixtures thereof. These suspending agents include ethylene glycol esters of fatty acids, preferably having 16-22 carbon atoms.
  • polyacrylic acids crosslinked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of carboxylic acid-containing monomers and acrylic esters, crosslinked copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums, and crystalline long chain acyl derivatives.
  • the long chain acyl derivative are preferably ethylene glycol stearates, alkanolamides of fatty acids having 16-22 carbon atoms, or mixtures thereof.
  • S Thickeners can be used to facilitate the hand application of the personal care product to the hair, skin or other substrate, and are added in sufficient quantities to provide a more luxurious effect.
  • Representative thickening agents sodium alignate; gum arabic; guar gum; hydroxypropyl guar gum; PEG-150/decyl alcohol/SMDI copolymer; cellulose derivatives such as methylcellulose, hydroxypropyl methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose; starch and starch derivatives such as hydroxypropyl starch phosphate, hydroxyethylamylose and starch amylose; locust bean gum; electrolytes such as sodium chloride and ammonium chloride; saccharides such as fructose and glucose; and derivatives of saccharides such as PEG-120 methyl glucose dioleate.
  • Other alternate components for hair care and skin care products include fragrances, vitamins, ceramides, amino-acid derivatives, liposomes, and botanicals and/or plant extracts.
  • Other alternate components depending upon the particular use of the personal care product include glycols, vitamins A and E in their various forms, sunscreen agents, humectants, emollients, occlusive agents, and esters.
  • Other alternate components may be added to the personal care products containing the emulsion compositions of the invention, such as colorants, electrolytes, pH control agents, foam boosters and foam builders, foam stabilizers, antimicrobials, antioxidants, ultraviolet light absorbers, and medicaments.
  • such alternate components can be used in amounts of 0.1-5 parts by weight per 100 parts by weight of conditioning shampoo products, preferably 0.1-1 part by weight per 100 parts by weight.
  • the amount of each of the various components used in preparing emulsions according to the invention, based on the total weight of the composition, is: (i) 0.01-90 percent by weight of the organic quaternary ammonium compound having epoxide groups or halohydrin groups in its molecule; (ii) 0.01-90 percent by weight of the siloxane having amino groups in its molecule; (iii) 0.01-90 percent by weight of the crosslinking agent;
  • Emulsions can also be prepared by omitting component (iv), i.e., the polydiorganosiloxane having an organo radical which is not reactive the above components (i), (ii) and (iii), and its preparation thereof is described in the aforementioned prior patents.
  • the average molar ratio of both component (ii) of the organic quaternary ammonium compound and component (iii) to total amine hydrogen in the polyorganosiloxane of component (i), considering primary and secondary amines, is at least 1 : 10 and less than 10 : 10, with preferable range of 1 : 6 to 9 : 10.
  • the average molar ratio of component (ii) to component (iii) is in the range of 1 : 9 to 9 : 1.
  • the reaction can be made to take place by simply mixing all of the components (i), (ii) and (iii) together in the presence of the components (iv) and (v) in the aqueous polar phase, and this is the minimum requirement to obtain reaction, i.e., to perform the "reacting" step under the circumstances.
  • a catalyst is typically not necessary but under some circumstance, an appropriate catalyst may be employed.
  • tertiary amines do not add readily to epoxides. This can be improved if the reaction mixture is acidified, especially in stoichiometric proportions, or the tertiary amine is pretreated with an acid in order to convert it to its acid salt.
  • the emulsions can be prepared using simple propeller mixers, turbine-type mixers, Brookfield counter-rotating mixers, or homogenizing mixers. No special equipment or processing conditions are generally required.
  • Silicone emulsion prepared by the method of this invention has the same advantages as silicone emulsion containing an elastomeric polyorganosiloxane having quaternary ammonium groups only, and improve spreading of the elastomeric polyorganosiloxane on a substrate such as hair, skin, textile and the like.
  • the method of this invention provides the particle size of silicone emulsion of this invention in the range of from 0.1 micron to 10 microns or up to 30 microns, while the above silicone emulsion containing an elastomeric polyorganosiloxane having quaternary ammonium groups is called microemulsion. Thereby silicone emulsion of this invention has better performances than conventional silicone emulsion in personal care application.”
  • Silicone emulsion of this invention is useful in personal care application. It may be added to antiperspirant, deodorant, skin cream, skin care lotion, moisturizer, facial treatment, acne remover, wrinkle remover, personal cleanser, facial cleanser, bath oil, perfume, cologne, sachet, sunscreen, pre-shave lotion, after-shave lotion, shaving soap, shaving lather, hair shampoo, hair conditioner, hair colorant, hair relaxer, hair spray, mousse, styling gel, permanent, depilatorie, cuticle coat, make-up, color cosmetic, foundation, blush, lipstick, eyeliner, mascara, oil remover, color cosmetic remover, bath powder, body powder, pharmaceutical, biocide, or biologically active substance.
  • Components employed in the working examples are as follows: Component I: Trimethylsiloxy terminated amino functional siloxane having a degree of polymerization (DP) of about 390, and containing about 2.3 mole percent of aminoethyl aminoisobutyl methyl siloxane groups
  • Component II Glycidyltrimethylammonium chloride
  • Component III Octamethyl-3,5-bis (gamma-glycidoxypropyl) tetrasiloxane
  • Component IV-1 Trimethylsiloxy-terminated polydimethylsiloxane having the viscosity of 60,000 mPa.s at 25 0 C
  • Component IV-2 Trimethylsiloxy-terminated polydimethylsiloxane having the viscosity of 500,000 mPa.s at 25 0 C.
  • Component V-1 Surfactant - Tergitol® 15-S-5 (available from Dow Chemical Co.,
  • Component V-2 Surfactant - Tergitol® 15-S-30 (available from Dow Chemical
  • Emulsion A was an opaque white emulsion and had the particle sizes as shown in TABLE 1
  • Example 1 was repeated to prepare another silicone emulsion of this invention ("Invention Emulsion B") referring to amounts of the components shown in TABLE 1 , except that:
  • a silicone emulsion containing elastomeric polysiloxane having quaternary ammonium group (“Comparative Emulsion A”) was prepared in the absence of Component IV by the process of Example 1 for the purpose of comparison.
  • Component I, Component III and Component V-2 were mixed under agitation of 500 rpm for 10 minutes. Glacial acetic acid was admixed and then 15 grams of water was added. After homogeneous mixture was formed, 159.3 grams of water was added under agitation of 500 rpm. To the mixture the above steps 4 and 5 were applied, to obtain a comparative silicone emulsion ("Comparative Emulsion A").
  • the particle sizes of Comparative Emulsion A were shown in TABLE 1.
  • Comparative Emulsion B obtained had the particle sizes shown in TABLE 1 [0073] TABLE 1
  • the emulsions prepared by method of this invention were combined with Shampoo base to form Shampoo Test Samples in amount shown in Table 2 and Table 3.
  • the hair care samples were applied to hair for evaluation of performances.
  • the hair switch was treated with Shampoo Test Samples in amount of 0.2 gram per gram of the hair switch.
  • the treated hair switch was stroked through 30 seconds by hand and rinsed with tap water for 30 seconds.
  • ACL Average Combing Load
  • a group of panelists implemented the sensory evaluation by taking the hair switch test sample between its thumb and index finger and moving the fingers to perceive amount of resistant force for "Smoothness”; and by bending the hair between the index and middle fingers to perceive ease of bending for "Softness”; and by combing through the hair switch to perceive ease of removing the tangles from the hair switch by a comb for "Easy Combing".
  • Comparative Emulsion A Reduction over the Comparative Emulsion A called emulsion containing elastomeric polysiloxane having quaternary ammonium group, and also over Run 3, the mixture of Comparative Emulsion A and Comparative Emulsion B called trimethylsiloxy terminated polydimethylsiloxane emulsion. This result showed the effective performance of Invention Emulsion A can not be accomplished by simple mixing.
  • Comparative Emulsion C Silicone emulsion commercially available, containing 50 percents by weight of trimethylsiloxy terminated polydimethylsiloxane having the viscosity of 500,000 mPa.s and 10 percents by weight of polydimethylsiloxane having the viscosity of 5,000 mPa.s and containing 0.5 percent by mole of aminoethylaminoisobutyl radical, and the remainder of water, surfactants and preservatives.
  • Comparative Emulsion D Silicone emulsion commercially available, containing 65 percents by weight of trimethylsiloxy terminated polydimethylsiloxane having the viscosity of 500,000 mPa.s)
  • Run 5 was better than Run 7 (LSD 99%) and Run 8 (LSD 80%) in "Easy Dry Combing” evaluation.
  • “LSD” means Least Significant Difference.
  • Run 5 was better than Run 6, Run 7 and Run 8 with LSD of more than 95% in "Dry Smoothness" evaluation.
  • Run 5 was better than Run 7 (LSD 95%) and Run 8 (LSD 80%) in "Wet Smoothness" evaluation.
  • Run 5 was better than Run 6 (LSD 99%), Run 7 (LSD 80%) and Run 8 (LSD 99%) in "Ease Wet Combing" evaluation.

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Abstract

L'invention concerne un procédé de préparation d'une émulsion de silicone contenant un polyorganosiloxane élastomère qui possède une fonction ammonium quaternaire et un polydiorganosiloxane qui possède un groupe organique non réactif, selon lequel l'émulsion de silicone est obtenue par mise en réaction simultanée d'un polyorganosiloxane qui possède un groupe amino avec un composé organique d'ammonium quaternaire qui possède un groupe époxydé ou un groupe halogénohydrine et réticulation du polyorganosiloxane qui possède un groupe amino avec un de ses agents de réticulation en présence d'un polydiorganosiloxane, qui possède un groupe organique qui n'est pas réactif avec les autres composants tels que le polyorganosiloxane qui possède un groupe amino, le composé organique d'ammonium quaternaire et l'agent de réticulation, et d'un tensioactif. Selon l'invention, ces composants sont dispersés dans une phase aqueuse polaire. L'émulsion de silicone préparée par le procédé selon cette invention peut être utilisée dans diverses applications, telles que les textiles, les produits d'hygiène personnelle et analogues.
PCT/CN2008/072230 2007-09-13 2008-09-02 Procédé de préparation d'une émulsion de silicone contenant un polysiloxane élastomère qui possède des groupes ammonium quaternaires WO2009033399A1 (fr)

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WO2016123349A1 (fr) * 2015-01-28 2016-08-04 The Procter & Gamble Company Procédé de fabrication d'une nanoémulsion d'aminosilicium
GB2540236A (en) * 2015-12-21 2017-01-11 Oreal Hair cosmetic composition comprising silicones and surfactants and cosmetic treatment process
US9982223B2 (en) 2015-01-28 2018-05-29 The Procter & Gamble Company Amino silicone nanoemulsion
WO2019025233A1 (fr) * 2017-08-03 2019-02-07 Basf Se Compositions cosmétiques comprenant un polymère d'origine biologique
US10675238B2 (en) 2015-07-29 2020-06-09 Conopco, Inc. Hair composition

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EP2608860A1 (fr) 2010-08-23 2013-07-03 The Regents of the University of California Procédé d'extraction de composés organiques depuis des mélanges aqueux
CN104817847B (zh) * 2015-05-06 2018-08-17 广州天赐高新材料股份有限公司 一种抗菌有机硅弹性体乳液及其制备方法与应用
CN113402539B (zh) * 2021-06-18 2022-12-02 吉林奥来德光电材料股份有限公司 一种用于封装薄膜的化合物、包含其的组合物及封装薄膜的制备方法

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US20150073069A1 (en) * 2013-09-11 2015-03-12 Evonik Industries Ag Coating composition comprising polysiloxane quats
US9353289B2 (en) * 2013-09-11 2016-05-31 Evonik Degussa Gmbh Coating composition comprising polysiloxane quats
WO2016123349A1 (fr) * 2015-01-28 2016-08-04 The Procter & Gamble Company Procédé de fabrication d'une nanoémulsion d'aminosilicium
US9982223B2 (en) 2015-01-28 2018-05-29 The Procter & Gamble Company Amino silicone nanoemulsion
US10182980B2 (en) 2015-01-28 2019-01-22 The Procter & Gamble Company Method of making an amino silicone nanoemulsion
US10675238B2 (en) 2015-07-29 2020-06-09 Conopco, Inc. Hair composition
GB2540236A (en) * 2015-12-21 2017-01-11 Oreal Hair cosmetic composition comprising silicones and surfactants and cosmetic treatment process
GB2545806A (en) * 2015-12-21 2017-06-28 Oreal Hair cosmetic composition comprising silicones and surfactants, and cosmetic treatment process
GB2540236B (en) * 2015-12-21 2020-05-27 Oreal Hair cosmetic composition comprising silicones and surfactants, and cosmetic treatment process
GB2545806B (en) * 2015-12-21 2020-07-15 Oreal Hair composition and process for washing and/or conditioning hair
WO2019025233A1 (fr) * 2017-08-03 2019-02-07 Basf Se Compositions cosmétiques comprenant un polymère d'origine biologique

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