Method for preparing a silicone emulsion containing elastomeric polysiloxane having quaternary ammonium groups

Object of This Invention:

[0001 ] 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. In particular this invention is to provide this silicone emulsion which is significantly useful for personal care products with better feeling

Background Art:

[0002] Silicone emulsions are well known and used in various applications such as industries (textile, antifoaming, process, etc.), cosmetic, pharmaceutical, and the like.

[0003] 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.

[0004] In personal care application, 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.

10005] US Patent No. 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.

[0006] 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.

[0007] Those silicone emulsions described in the above patents were not fully satisfactory in personal care application. In particular it was desirable to improve smoothness and softness more, when a silicone emulsions was used in shampoo application.

Summary Of The Invention

[0008] 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.

[0008] 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. In particular it is significantly useful for personal care application to provide excellent combing properties to personal care products such as shampoo, conditioner, and the like.

[0010] In the present invention, it provides 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.

[0011 ] In a preferred embodiment, the organic quaternary ammonium compound having epoxide groups is glycidyl trimethylammonium chloride or glycidyl trimethylammonium bromide.

[0012] In a preferred embodiment, 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.

[0013] In a preferred embodiment, the aqueous polar phase consists of water.

[0014] In a preferred embodiment, the aqueous polar phase comprises water and a polar organic compound.

10015] In a preferred embodiment, the polar organic compound is selected from the group consisting of monohydroxy alcohols, diols, triols, glycerol esters, and polyglycols.

[0016] In a preferred embodiment, 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.

[0017] In the present invention, it 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:

(i) preparing a first mixture containing polyorganosiloxane having amino groups in their molecule, and a polydiorganosiloxane having an organo group which is not reactive with the polyorganosiloxane having amino group, an organic quaternary ammonium compound below-mentioned and a crosslinking agent below-mentioned;

(ii) preparing a second mixture by adding a crosslinking agent for the polydioganosiloxane having amino groups, a surfactant and a first portion of an aqueous polar phase to the first mixture;

(iii) preparing a third mixture by adding the balance of the aqueous polar phase to the second mixture;

(iv) preparing a fourth mixture by adding an organic quaternary ammonium compound to the third mixture; and

(v) heating the fourth mixture.

[0018] In the present invention, it 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.

[0020] In a preferred embodiment, 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.

[0021 ] 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. 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.

[0022] [Component (i)]

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 in all cases y has an average value that is not greater than one tenth the average value of x. 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.

[0023] 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.

[0025] 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 .

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. Preferably, 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.

[0027] 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. For example, and with reference to the particular amine functional polysiloxane used in the examples, the amine functional polysiloxane was a trimethylsiloxy terminated dimethyl / methylaminoethylaminoisobutyl siloxane copolymer with a viscosity of 3,000

2 centistoke (mm /s), a DP of 390, with a mol percent amine content of 2.3 mol percent of aminoethylaminoisobutyl groups.

[0028] [Component (N)]

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.

[0030] A preferred group of halohydrin functional quaternary ammonium compounds is represented by:

(X ¹ ) CH ₂ CH(OH)YN ⁺ (R ⁴ )(R ⁵ )(R ⁶ )X ^"

where 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; and X ^" is a counter ion, especially chloride or bromide. Specific examples from this group are

3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl dimethyldodecyl ammonium chloride, 3-chloro-2-hydroxypropyl dimethyloctadecyl ammonium chloride and the corresponding bromides.

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.

[0031 ] [Component (Ni)]

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.

vV i Other polyglycidyl ethers of alkane polyols, polyglycidyl ethers of poly(alkylene glycols), diepoxy alkanes, diepoxy aralkanes, and polyphenol polyglycidyl ethers, may also be used herein.

[0033] Two especially preferred organic epoxides containing at least two epoxy groups are shown below, in which n is a positive integer determining the molecular weight of the epoxide.

Butanediol Diglycidyl Ether

Poly(propylene glycol) Diglycidyl Ether

[0034] When it is desirable to use 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.

I 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 (mwβ/s) and weight average molecular weights of about 300 - 6,000.

[0036] Chlorohydrins may be used in place of or in conjunction with the epoxides. As is know in the art, 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.

Cl

OH

[0037] Chlorohydrins can be converted into epoxides by the action of 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.

^o In addition, 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.

[Component (iv)]

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.

[0040] 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.

[0041 ] [Component (v)]

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.

[0042] Generally, 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^). ^cet yl (Ciβ) ^an ^ ^stea|r yl (Ci δ)- While the value of "p" may range from 1 to about 100, its value is typically in the range of about 12 to about 40. Some examples of 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. These and other 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. Most preferred are 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. These and other quaternary ammonium salts are commercially available under tradenames such as ADOGEN, ARQUAD, TOMAH, and VARIQUAT.

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. Among the various types of 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 naphthalene sulfonic acids with formaldehyde; sodium octahydro anthracene sulfonate; alkali metal alkyl sulfates such as sodium lauryl (dodecyl) sulfate (SDS); ether sulfates having alkyl groups of eight or more carbon atoms; and alkylaryl sulfonates having one or more alkyl groups of eight or more carbon atoms. 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.

[0045] 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.

[Component (vi)]

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.

10047] 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)CH2θH,

2-methyl-1 ,3-propane diol HOCH2CH(CH3)CH2θH, and glycerol; glycerol esters such as glyceryl triacetate (triacetin), glyceryl tripropionate (tripropionin), and glyceryl tributyrate (tributyrin); and polyglycols such as polyethylene glycols and polypropylene glycols among which are PPG-14 butyl ether C4Hg[OCH(CH3)CH2]i4θH. In applications other than personal care, these and other non-aqueous polar solvents may be employed.

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. Generally, 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. Typically, however, 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. While 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.

[0049] [Optional Components]

Since emulsions are susceptible to microbiological contamination, 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.

[0050] 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.

[0051 ] Another optional component of the composition which can be included is 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.

[0052] 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.

[0053] If 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.

[0054] [Alternate Components]

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;

(B) cosurfactants such as betaines, monoalkylalkanolamides, dialkylalkanolamides, amine oxides, amine glycinates, amine propionates, amine sultaines, and mixtures thereof;

(C) polyhydric alcohols such as glycerin and sorbitol.

[0055] 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.

[0056] Some examples of additional alternate components which can be included in personal care products containing the emulsion compositions are suspending agents and thickeners.

[0057] 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. Specific examples include 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.

3:~ 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.

[005Sj 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. In particular, 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.

[Preparation]

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;

(iv) 0.01-90 percent by weight of the polydiorganosiloxane having an organo radical which is not reactive with the above components (i), (ii) and (iii); (v) 0.01 -90 percent by weight of the surfactant, preferably 2-40 percent by weight, more preferably 5-20 percent by weight; and

(vi) the balance to 100 percent by weight being the aqueous polar phase. 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.

[0061 ] 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. However, it is generally preferred to mix all of the reactants together and to heat them at the temperature higher than the room temperature to 100 ⁰ C for a few minutes to a few hours. A catalyst is typically not necessary but under some circumstance, an appropriate catalyst may be employed. In this regard, it has been found that in general, 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."

S5] 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.

It is also useful in textile application to impart smoothness and antistatic property to textile.

Exaπigjes

[0067] The following examples are set forth in order to illustrate the invention in more detail.

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.,

USA) Component V-2: Surfactant - Tergitol® 15-S-30 (available from Dow Chemical

Co., USA)

[Practical Example 1 ] A silicone emulsion of this invention ("Invention Emulsion A") was prepared by the process comprising the following steps in amounts of the components as shown in Table 1.

1. Into a reaction vessel were placed Component I and Component IV-1 , which was mixed under agitation of 500 rpm for 10 minutes.

2. Under agitation of 500 rpm, Component III, Component V-1 , Component V-2, glacial acetic acid and 14.6 grams of water were added and mixed for 15 minutes to form homogeneous mixture.

3. 128.6 grams of water was added and mixed for another 30 minutes under agitation of 500 rpm

4. After heated up to the temperature of 70 ⁰ C, an aqueous solution composed of 4 grams of Component Il and 12 grams of water were added and heated at the temperature of 70 ⁰ C for 2 hours under agitation of 400 rpm.

5. To the mixture cooled down to the room temperature were added an aqueous solution composed of 0.6 gram of acetic acid and 2.5 grams of water. After the addition it was agitated at the same rate as in the step 4 above for 1.5 hours to obtain a silicone emulsion of this invention.

This Invention Emulsion A was an opaque white emulsion and had the particle sizes as shown in TABLE 1

[0070] [Practical Example 2]

The 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:

• Component IV-2 was substituted for Component IV-1 in the first step thereof.

• The amounts of water added were changed to 30 grams and 123.1 grams in the steps 2 and 3 thereof respectively. An opaque white emulsion was obtained with particle sizes shown in TABLE 1. 1 ] [Comparative Example 1 ]

Referring to amounts of the components shown in TABLE 1 , 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 Example 2]

Referring to amounts of the components shown in TABLE 1 , another silicone emulsion containing trimethylsiloxy-terminated polydimethylsilxoane having the viscosity of 60,000 mPa.s at 25 ⁰ C ("Comparative Emulsion B") was prepared by the process of Example 1 for comparative purpose.

• Component V-1 was substituted for Component I and Component III in the steps 1 and 2 thereof.

• The amount of water was increased to 147.3 grams in the step 3 thereof.

• The step 4 thereof was omitted.

Comparative Emulsion B obtained had the particle sizes shown in TABLE 1

[0073] TABLE 1

[0074] [Application Examples]

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.

[0075] [Treatment with Shampoo Test Samples on Hair Switch]:

Shampoo Test Samples were applied to hair switch which was commercially available on market for the purpose of testing evaluation in accordance with the process as follows:

1. Hair switch was washed with 40 ⁰ C tap water for 15 seconds.

2. 0.2 gram per gram of the hair switch of a solution containing 9 % (active) of sodium lauryl sulfate was applied to the hair switch. The hair switch was stroked through for 30 seconds by hand and rinsed with 40 ⁰ C tap water for 30 seconds.

3. The hair switch was hanged on clip and combed through, and then was let dry overnight at the atmosphere (24 ⁰ C and 50 % humidity).

4. 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.

5. The hair switch was combed and hanged on horizontal bar overnight to be dried at the same atmosphere as above-mentioned to obtain Test Sample of Treated Hair Switch. 76] [Measurement of Dry Combing Force]:

• Dry Combing Force required to comb Test Sample of Treated Hair Switch was measured to determine the ease of dry combing with use of a combing machine made by Jau Chyuan Machinery Corp., where a plastic comb with 8 teeth/cm was moved from the top to down at the rate of 5.0 cm/second.

• The force was reported as an Average Combing Load ("ACL"). The lower is the number of the ACL, the better is the effect imparted by the hair care sample being tested. The ACL baselines are initially established using untreated hair switches that have been washed by the above steps of from No. 1 to No. 3. The effectiveness of treatment can then be expressed as percentage reduction in ACL, calculated by the formula:

% = (untreated hair ACL - treated hair ACL) x 100 / untreated ACL 77] [Sensory Evaluation for Smoothness, Softness and Combing]:

• Test Sample of Treated Hair Switch was tested for sensory evaluation.

• 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".

• Wet hair switches were evaluated in the same manner above, except that the hair switch was placed under running tap water (3 litters per minute) at the temperature of 35 to 40 ⁰ C prior to the evaluation.

• The evaluation was carried out as multiple pairwise comparison, and accumulation of ranking were shown in TABLE 3.

• According to statistical analysis (Friedman pairwise ranking test), we were able to determine the significant level of the difference.

[0078] TABLE 2

Dry Combing Force Reduction (%) 52 47 50 54

* ¹ Shampoo Base is described below.

[007Sj Table 2 shows Invention Emulsion A improved Combing Force

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.

10080] TABLE 3

*1 Shampoo Base:

* ² 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)

10081 ] From Table 3, it is clear that a shampoo containing silicone emulsion of this invention showed better Combing Force Reduction rate than the shampoo containing the Comparative Emulsion A on 80 % confidence level, but a bit worse than the shampoo containing the Comparative Emulsion D, although difference therebetween was not significant. On the other hand, the Sensory Evaluation Results evidences much improvements over the conventional silicone emulsions as follows:

• 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.