CN100354340C - Polyether silioxane network composition - Google Patents

Abstract

The present invention relates to a composition of a reaction product comprising a formula of MaM<H>bM<E>cDdD<H>eD<E>fTgT<H>hT<E>iQj, wherein M=R<1>R<2>R<3>SiO<1/2>, M<H>=R<4>R<5>HSiO<1/2>, M<E>=R<6>R<7>R<E>SiO<1/2>, D=R<8>R<9>SiO<2/2>, D<H>=R<10>HSiO<2/2>, D<E>=R<11>R<E>SiO<2/2>, T=R<12>SiO<3/2>, T<H>=HSiO<3/2>, T<E>=R<E>SiO<3/2> and Q=SiO<4/2>; R<1>, R<2>, R<3>, R<8>, R<9> and R<12> are independent from each other and are respectively monovalent hydrocarbon radicals containing 1 to 60 carbon atoms, and R<4>, R<5> and R<10> are independent from each other and are respectively monovalent hydrocarbon radicals or hydrogen containing 1 to 60 carbon atoms; R<6>, R<7> and R<11> are independent from each other and are respectively monovalent hydrocarbon radicals or R<E> containing 1 to 60 carbon atoms, and each R<E> is an independent monovalent hydrocarbon radical which comprises one or more oxirane ports containing 1 to 60 carbon atoms. Stoichiometric ratio subscripts of a, b, c, d, e, f, g, h, i and j are zero or positive values conforming to the following conditions: a+b+c>1, b+e+h>1, c+f+i>1, and b+e+h>c+f+i, and moreover, a+b+c=2 under the condition of d+e+f+g+h+i+j=0.

Description

Polyether siloxane copolymer group of networks compound

Invention field

The present invention relates to polysiloxane composition, relate more specifically to contain the composition of polysiloxane polymer network, described siloxane polymer network comprises the crosslinked bonding that derives from epoxy compounds or ethylene oxide moiety.

Background of invention

Personal care industry is very prosperous aspect the multi-usage product of multiple mixture of ingredients, and wherein every kind of composition has performance very important for end formulation or that wish in end formulation.A kind of characteristic of hope provides the ability of soft and smooth initial perception and keeps high and shear the viscosity of attenuation, thisly feels that soft and smooth initial perception derives from the low molecular weight polysiloxane in the prescription, for example octamethylcyclotetrasiloxane or decamethylcyclopentaandoxane.Though these low molecular weight polysiloxane provide the sensory features of wishing, they still are the liquid of low viscosity, high workability.Therefore, they are not easy to remain in the prescription, but separate easily or flow out specific container or when being used for concrete purposes, uncontrollably flow through skin.And, wish to obtain initial soft and smooth sensation and sensation smooth, the low residue thing is provided when drying.Have been found that the polymer siloxane gel that in Y 7175, prepares the give prescription volatility of wishing, the sensation of low viscosity polysiloxane, provide high viscosity and slick soft and smooth sensation simultaneously, for example referring to United States Patent (USP) 5,760,116,5,493,041 and 4,987,169.

Such polymer siloxane gel prepares by hydrosilylation reactions usually, and this reaction needed is used SiH functional group and ethylene linkage end group, to form crosslinked siloxane polymer.Therefore, have only the siloxane structure of the siloxane groups of the vinyl functional that can introduce the hydrogenation silyl and choose wantonly can be used for making these materials.In addition, the restriction of the method for this generation across-linked siloxane polymer can be incorporated into the scope of the organo-functional group of wishing in the polymer architecture, and the introducing of these organo-functional groups can produce the additional performance advantage in the prescription of complexity.Therefore, the trial of introducing organo-functional group comprises the unsaturated organic group compatible with hydrosilylation reactions in crosslinked siloxane polymer.

Summary of the invention

A kind of composition comprises M _aM ^H _bM ^E _cD _dD ^H _eD ^E _fT _gT ^H _hT ^E _iQ _jReaction product,

Wherein:

M＝R ¹R ²R ³SiO _1/2；

M ^H＝R ⁴R ⁵HSiO _1/2；

M ^E＝R ⁶R ⁷R ^ESiO _1/2；

D＝R ⁸R ⁹SiO _2/2；

D ^H＝R ¹⁰HSiO _2/2；

D ^E＝R ¹¹R ^ESiO _2/2；

T＝R ¹²SiO _3/2；

T ^H＝HSiO _3/2；

T ^E=R ^ESiO _3/2And

Q＝SiO _4/2；

R wherein ¹, R ², R ³, R ⁸, R ⁹And R ¹²Be the monovalence alkyl that contains 1-60 carbon atom independently of each other; R ⁴, R ⁵And R ¹⁰Be monovalence alkyl or the hydrogen that contains 1-60 carbon atom independently of each other; R ⁶, R ⁷, R ¹¹Be monovalence alkyl or the R that contains 1-60 carbon atom independently of each other ^EEach R ^EBe the monovalence alkyl that contains the ethylene oxide moiety of one or more 1-60 of comprising carbon atom independently; Stoichiometric ratio subscript a, b, c, d, e, f, g, h, i and j be 0 or meet following condition on the occasion of a+b+c＞1; B+e+h＞1; C+f+i＞1; B+e+h＞c+f+i; And when d+e+f+g+h+i+j=0, a+b+c=2.In a preferred embodiment, reaction product of the present invention is the polyether siloxane copolymer network.In another preferred embodiment, reaction product of the present invention is the polyether siloxane copolymer network with the compound that contains the volatile low-molecular-weight polysiloxane.These compositions are used for various personal care compositions.

Detailed Description Of The Invention

Composition of the present invention comprises the reaction product of the epoxy functionalized hydride siloxane molecule with following formula:

M _aM ^H _bM ^B _cD _dD ^H _eD ^E _fT _gT ^H _hT ^z _iQ _j

Wherein:

M＝R ¹R ²R ³SiO _1/2；

M ^H＝R ⁴R ⁵HSiO _1/2；

M ^E＝R ⁶R ⁷R ^ESiO _1/2；

D＝R ⁸R ⁹SiO _2/2；

D ^H＝R ¹⁰HSiO _2/2；

D ^E＝R ¹¹R ^ESiO _2/2；

T＝R ¹²SiO _3/2；

T ^H＝HSiO _3/2；

T ^B=R ^ESiO _3/2And

Q＝SiO _4/2；

R wherein ¹, R ², R ³, R ⁸, R ⁹And R ¹²Be the monovalence alkyl that contains 1-60 carbon atom independently of each other; R ⁴, R ⁵And R ¹⁰Be monovalence alkyl or the hydrogen that contains 1-60 carbon atom independently of each other; R ⁶, R ⁷, R ¹¹Be monovalence alkyl or the R that contains 1-60 carbon atom independently of each other ^BEach R ^BBe the monovalence alkyl that contains the ethylene oxide moiety of one or more 1-60 of comprising carbon atom independently; Stoichiometric ratio subscript a, b, c, d, e, f, g, h, i and j be 0 or meet following condition on the occasion of a+b+c＞1; B+e+h＞1; C+f+i＞1; B+e+h＞c+f+i; And when d+e+f+g+h+i+j=0, a+b+c=2.

A kind of method of producing composition of the present invention be make have following formula molecule under the hydrosilylation reactions condition with contain the unsaturated molecular reaction of ethylenic of one or more ethylene oxide moieties, the stoichiometric condition of this reaction is the molar weight of the molar weight of oxyethane less than the hydrogenation silicomethane:

M _aM ^H _b，D _dD ^H _e，T _gT ^H _h，Q _j

Wherein, definition and relation as hereinafter defined (and with above defined consistent).Phrase used herein " the unsaturated molecule of ethylenic that contains one or more ethylene oxide moieties " is meant and has one or more inside, carbon-carbon double bond that hang or the end, the ternary oxygen heterocyclic ring (chemically, phrase " ternary oxygen heterocyclic ring " can exchange with oxyethane or epoxy construction in this article and use) that has one or more inside, that hang or end simultaneously.By such definition the simplest illustrational chemical structure be:

And comprise by the illustrational alicyclic structure of following formula:

Here, subscript k can be 0 or positive integer, more preferably is generally the positive integer in about 10 scopes of 0-.The ethylene linkage part and oxyethane (epoxy) part that should be noted that these two kinds of structures of enumerating all are in the end.More generally chemical structure is:

Wherein, R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷And R ¹⁸Be selected from hydrogen and the monovalence alkyl that contains 1-60 carbon atom, Q independently of one another _mBe divalence or the trivalent hydrocarbon radical that contains 1-60 carbon atom, Q _nBe the bivalent hydrocarbon radical that contains 1-60 carbon atom, subscript m and n are 0 or 1 independently of one another, and meet the following conditions: work as Q _mDuring for trivalent, R ¹³Or R ¹⁴One of do not exist and R ¹⁶And RR ¹⁸Can be each other cis or trans.

Therefore, it is as follows to prepare a kind of possible route of synthesis of reaction product of the present invention:

Make M _aM ^H _bD _dD ^H _e, T _gT ^H _h, Q _j+ α reacts under the hydrosilylation condition, to produce M _aM ^H _bM ^B _cD _dD ^H _eD ^E _fT _gT ^H _hT ^E _iQ _j, at this moment, stoichiometric coefficient α is less than the summation of b '+e '+h '.Should be noted that stoichiometric coefficient b, e and h determine to contain hydride species M in reactant and product ^H, D ^HAnd T ^HAnd it is interrelated in this mode, but because some groups that contain hydride with the unsaturated molecular reaction of the ethylenic that contains one or more ethylene oxide moieties, so must obtain following relational expression: b '+e '+h '＞b+e+h and b+c+e+f+h+I=b '+e '+h '.The acetylene analogue that should be noted that the molecule that contains the unsaturated oxyethane of ethylenic will produce similar material, and these similar materials will react and form similar product.Therefore, phrase used herein " the unsaturated molecule of ethylenic that contains one or more oxyethane " also comprises the unsaturated molecule of acetylene bond formula that contains one or more ethylene oxide moieties.Phrase " the unsaturated molecule of acetylene bond formula that contains one or more ethylene oxide moieties " is meant and contains one or more inside, carbon carbon triple bond that hang or the end, the ternary oxygen heterocyclic ring (chemically, phrase " ternary oxygen heterocyclic ring " can exchange with oxyethane or epoxy construction in this article and use) that has one or more inside, that hang or end simultaneously.When epoxy compounds was the ethylenic epoxy compounds, a specific examples was:

R then ^EAs substituting group, become:

All definition are defined identical with the front.When epoxy compounds was acetylene bond formula epoxy compounds, specific examples was:

R then ^EAs substituting group, become:

Or

All definition are defined consistent with the front.

The precursor molecule that contains the hydrogenation silicomethane, M _aM ^H _b, D _dD ^H _e, T _gT ^H _h, Q _jCan prepare by various techniques known in the art.The siloxanes that epoxy replaces connects the epoxy compounds that vinyl or allyl group replace and prepares containing by using hydrosilylation reactions with usual method on the siloxanes of SiH.The siloxanes that contains SiH is known in the art and structurally can is straight chain, side chain or cyclic.The epoxy compounds that useful vinyl or allyl group replace comprises 4-vinyl epoxy hexane, allyl glycidyl ether, limonene monoepoxide, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, monocycle oxidation norbornadiene and 1,2-epoxy-9-decene.Be applicable to that the noble metal catalyst of making epoxysilicone also is known in the art, and contain the complex compound of rhodium, ruthenium, palladium, osmium, iridium and/or platinum.

Many platinum catalysts that are used for this SiH alkene addition reaction (hydrosilation or hydrosilylation) are known, and such platinum catalyst can be used for the present invention's reaction.When the needs optical transparency, preferred platinum catalyst is those soluble platinic compound catalyzer in reaction mixture.Platinic compound can be selected from has molecular formula (PtCl ₂Alkene) and H (PtCl ₃Alkene) those compounds, as United States Patent (USP) 3,159, described in 601, this patent is incorporated herein by reference in this article.Other can be used for the cyclopropane complex compound that platinum material is a platinum chloride that contains in the composition of the present invention, and as United States Patent (USP) 3,159,662 is described, and this patent is incorporated herein by reference in this article.In addition, contain platinum material and can be the complex compound that the composition reaction that is selected from alcohol, ether, aldehyde and composition thereof by 2 moles in Platinic chloride and maximum every gram platinum forms, as United States Patent (USP) 3,220,972 is described, and this patent is incorporated herein by reference in this article.The catalyzer of advantageous applications is described in the United States Patent (USP) 3,715,334,3,775,452 and 3,814,730 of Karstedt.Other background that relates to this area can be referring to " the Homogeneous Catalysis ofHydrosilation by Transition Metals " of J.L.Spier, in Advances inOrganometallic Chemistry, volume 17, the 407-447 page or leaf, F.G.A.Stone and R.West editors, published by the Academic Press (New York, 1979).Those skilled in the art can easily determine the significant quantity of platinum catalyst.In general, the significant quantity scope is about 0.1-50 part/1,000,000 part total organopolysiloxane composition.

M _aM ^H _bM ^E _cD _dD ^H _eD ^E _fT _gT ^H _hT ^E _iQ _jReaction product produces polymer network, and this is considered to polyether siloxane copolymer network (perhaps silicone-polyether copolymer network).Term used herein " network " is meant the structure of the three-dimensional extension that comprises interconnective polyether siloxane copolymer chain.Preferably, contain liquid in the space of network.Term " space " about network is used to refer to the interior space of network, i.e. space between the polyether siloxane copolymer chain of network in this article.Used term polyethers comprises that two or more epoxy compoundss partly form the reaction product of one or more ehter bonds (it forms crosslinked) between siloxane chain or part in the polyether siloxane copolymer network range.

In a preferred embodiment, the polyether siloxane copolymer network is the cross-linked network that is insoluble in the liquid ingredient of silicone composition of the present invention, and still, it is can be by described liquid swollen.The crosslinked amount that exists in cross-linked network can characterize with respect to the degree of swelling that described network shows in described liquid.In another preferred embodiment, the crosslinking structure of described network can make this network effectively by low-molecular-weight siloxane liquid swelling, decamethylcyclopentaandoxane for example, the 1.01-5000 that swells to its initial volume from its initial volume doubly, more preferably 2-1000 doubly, even volume after the 5-500 swelling doubly more preferably.The initial volume of described network for example can to stay the primary volume, promptly not have the volume of the polyether siloxane copolymer network of liquid by extracting or evaporating all liquid components from silicone composition of the present invention, measure.

Term used herein " alkyl " comprises aliphatic alkyl, alicyclic alkyl and aromatic hydrocarbyl.

This paper is meant that about the used term of alkyl " monovalence " each group of this group can form a covalent linkage, term " divalence " is meant that each group of this group can form two covalent linkage, and term " trivalent " is meant that each group of this group can form three covalent linkage.In general, univalent perssad can be expressed as by totally remove a hydrogen atom from saturated hydrocarbon compound by the group of this compound deriving, divalent group can be expressed as by totally remove two hydrogen atoms from saturated hydrocarbon compound by the group of this compound deriving, and the trivalent group can be expressed as by totally remove three hydrogen atoms from saturated hydrocarbon compound by the group of this compound deriving.For example, ethyl is CH ₂CH ₃Group is a univalent perssad; Dimethylene is-(CH ₂) ₂-be divalent group; And ethane three bases promptly

Be the trivalent group, its each can be expressed as from stable hydrocarbon ethane and totally remove one or more hydrogen atom deutero-groups.

Term used herein " aliphatic alkyl " is meant the alkyl of straight or branched, preferably each group contains 1-60 carbon atom, it can be saturated or undersaturated, and can be randomly replaced by one or more atoms or functional group or interrupt, for example carboxyl, cyano group, hydroxyl, halogen and oxygen base.As long as these functional groups can not disturb the cationic cure mechanism of epoxy compounds or ethylene oxide moiety; suitable univalent aliphatic series alkyl can comprise for example alkyl; thiazolinyl; alkynyl; hydroxyalkyl; the cyano group alkyl; carboxyalkyl; alkoxyl group; oxa alkyl; alkyl-carbonyl oxa-thiazolinyl; carbamyl and haloalkyl; as methyl; ethyl; sec-butyl; the tertiary butyl; octyl group; decyl; dodecyl; hexadecyl; stearyl-; vinyl; propenyl; butenyl; hydroxypropyl; cyanoethyl; butoxy; 2; 5; 8-trioxa decyl; carboxymethyl; chloromethyl and 3; 3,3-fluoro propyl group.Suitable divalence aliphatic alkyl comprises for example alkylene of straight or branched, for example methylene radical, dimethylene, trimethylene, decamethylene, ethyl 1,2-ethylidene, 2-methyl trimethylene, 2,2-dimethyl trimethylene, oxa-alkylene with straight or branched, as methylene radical oxidation propylene.Suitable trivalent aliphatic alkyl comprises for example alkane three base as 1,1,2 ethane, three bases, 1,2,4-butane three bases, 1,2,8-octane three bases, 1,2,4-hexanaphthene three bases and oxa-alkane three bases as 1,2,6-three bases-4-oxa-hexane.

Term used herein " alkyl " is meant saturated straight or branched monovalence alkyl.In a preferred embodiment, univalent alkyl is selected from the straight or branched alkyl that each group contains 1-60 carbon atom, for example methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, decyl, dodecyl.

Term used herein " thiazolinyl " is meant the monovalence end unsaturated alkyl of straight or branched, and preferably each group contains 2-10 carbon atom, as vinyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl and ethenylphenyl.

Term used herein " alicyclic alkyl " is meant the group that contains one or more stable hydrocarbon rings, preferably each ring contains 4-12 carbon atom, each group can randomly be replaced by one or more alkyl, halogeno-group or other functional group on one or more rings, wherein each alkyl preferably contains 2-6 carbon atom, and it can be a condensed ring under the situation of the monovalence alicyclic alkyl that contains two or more rings.Suitable monovalence alicyclic alkyl comprises for example cyclohexyl and ring octyl group.Suitable bivalent hydrocarbon radical comprises saturated or undersaturated divalence monocycle alkyl as 1, the 4-cyclohexylene.Suitable trivalent alicyclic alkyl comprises and for example encircles alkylidene group three base as 1-dimethylene-2,4-cyclohexylene, 1-methyl ethylidene-3-methyl-3,4-cyclohexylene.

Term used herein " aromatic hydrocarbyl " is meant that each group contains the alkyl of one or more aromatic rings, it randomly can be replaced by one or more alkyl, halogeno-group or other functional group on aromatic ring, wherein each alkyl preferably contains 2-6 carbon atom, and it can be a condensed ring under the situation of the monovalence aromatic hydrocarbyl that contains two or more rings.Suitable monovalence aromatic hydrocarbyl comprises for example phenyl, tolyl, 2,4,6-trimethylphenyl, 1,2-isopropyl methyl phenyl, 1-pentalene base, naphthyl, anthryl, oxymethoxyallylbenzene and chavicol and aralkyl such as 2-phenylethyl.Suitable divalent aromatic alkyl for example comprises the divalence mononuclear aromatics as 1,2-phenylene, 1,4-phenylene, 4-methyl isophthalic acid, 2-phenylene, phenylmethylene.Suitable trivalent aromatic hydrocarbyl comprises for example trivalent mononuclear aromatics such as 1-trimethylene-3,5-phenylene.

In a kind of embodiment preferred, epoxy functionalized organosilicone compounds reacts by make epoxy functionalized organosilicone compounds polymerization under the cationoid polymerisation condition, preferably, react under the existence of preferred volatile siloxane liquid at liquid.In one embodiment, epoxy functionalized organosilicone compounds polymerization in the presence of liquid directly forms silicone compounds of the present invention.In another embodiment, the polymerization in the presence of first kind of liquid or liquid mixture of epoxy functionalized organosilicone compounds, form the polyether siloxane copolymer network, make formed network with second kind of liquid or liquid mixture swelling then, form polysiloxane compound of the present invention.Second kind of liquid or liquid mixture can be identical or different with first kind of liquid mixture.Randomly, before adding second kind of liquid, first kind of solvent can be discharged the network after polymerization, for example by evaporation.As the scheme of other replacement, epoxy functionalized organosilicone compounds is not having polymerization under the condition of liquid, and to form the polyether siloxane copolymer network, this network is with liquid or liquid mixture swelling, to form polysiloxane compound of the present invention then.In another embodiment, the polymerization of epoxy functionalized organo-siloxane is carried out with the excessive hydrogenation silicone functionalities of q.s, make after polymerization to have remaining hydride that it can be suitable under the condition of hydrosilylation and one or more alkenyl-functional groups compounds reactions subsequently.This can be used as under the situation of cationic curing inhibitor at the alkenyl functional compound be particularly advantageous.Such alkenyl compound contains those can be as the compound of the functional group of the inhibitor of cationic cure mechanism, for example alkali.In another embodiment, add a small amount of spissated hydride siloxane or hydrosilanes compound, to improve polymerization velocity.

The cationoid polymerisation condition produces by an acidic catalyst that adds energy polymeric rings oxygen groups, for example add acidic  salt and some as lewis acidic metal-salt such as aluminum chloride and iron trichloride, the triflates that perhaps adds lanthanum is referring to PCT International Application No. WO 0008,087.The acid catalyzed polymerisation of epoxy compounds is the known method that is formed with organic polymer, and has been applied to epoxy functionalized silicone compounds, to be formed for the siloxanes polyalkylene oxides segmented copolymer of various uses, described purposes is the release coat on paper for example, for example referring to United States Patent (USP) 4,279,717, and combine the plastic composition that forms coating and modification with organism, for example referring to United States Patent (USP) 5,354,796 and 5,663,752.Must note in advance, if promptly cationoid polymerisation is at annular siloxane such as D ₃, D ₄Or D ₅Deng existence under carry out, used acid catalyzed intensity should make the cationoid polymerisation of epoxy compounds part take place but the polymerization of annular siloxane can obviously not take place.

In a kind of embodiment preferred, the polymerization under the cationic curing condition that produces by interaction of epoxy functionalized organosilicone compounds with platinum and the compound that contains SiH.This synthesis of epoxy compounds reaction path is described in United States Patent (USP) 5,128, and 431 and the J.Polymer Sci. of J.V.Crivello and N.Fan, Part A:Polymer Chemistry is in the 1853-1863 page or leaf (1997).As if in the present embodiment, reaction kinetics depends on the existence of trace molecular oxygen.

The crosslinked structure of polyether siloxane copolymer combination of network deposits yields of the present invention, it has a certain amount of steric hindrance owing to crosslinked.This steric hindrance often stops reaction even continues to finish with the long reaction times, therefore may keep a certain amount of remaining functional group.This remnants functional group provide by with do not resemble the functionalized molecule reaction that is subjected to the steric hindrance restriction the polyether siloxane copolymer network or must carries out chemical passivation and in the polyether siloxane copolymer network, introduce the ability of other functional group.Wish that remaining functional group in a reason of chemically passivation is, in the course of processing of these materials as usefulness low-molecular-weight siloxane compound (perhaps low molecular weight polysiloxane liquid) swollen polyether siloxane copolymer network, described low-molecular-weight siloxane compound is generally D ₃, D ₄, D ₅, D ₆Or the M ' D ' that hereinafter defines _qT ' _sM ', processing often destroys network under shear conditions, reduces the sterically hindered level, therefore owing to there is the remaining functional group of Chemical exposure, further crosslinking reaction is taken place.In the known polysiloxane that solidifies the crosslinked addition polymerization that occurs in the addition polymerization that takes place by hydrosilylation in back.These materials are by first hydrosilylation preparation of the oxyethane or the epoxy compounds of hydrogenation silicomethane and alkene or alkynes.Therefore, the precious metal hydrosilylation catalysts will be present in the reaction mixture or in the gap of polyether siloxane copolymer network.This catalyzer can be used for further being aggregated in oxyethane or the epoxy compounds part of introducing in the reaction product that produces polyether siloxane copolymer network of the present invention (a plurality of part).By design promptly use be lower than stoichiometry or since the steric hindrance that reaction is finished hinder the further reaction that the remaining functional group that keeps can be as described herein or be neutralized or be suppressed.United States Patent (USP) 5,977,280 and 5,929,164 all are incorporated herein by reference, and they have illustrated by for example phosphine, amine and organic sulfide such as organic sulfide and thiol treatment are carried out this neutralization of hydrosilylation catalysts with strong precious metal complexing ligand.But though they make the passivation of precious metal hydrosilylation catalysts, some in these strong complexing ligands are deleterious, so their application in some purposes must avoid, for example personal care applications.Therefore, the amino acid ester of sulfur-bearing is strong precious metal complexing ligand, and methyl methionine, methionine(Met) ethyl ester, acthiol-J, ethycysteine and halfcystine dimethyl ester have been preferred for such precious metal passivation.Should be noted that the natural protein that contains easy destructive disulfide linkage also can be used for the used noble metal catalyst of passivation, for example yolk etc.Sulfur-containing amino acid, polypeptide etc. also can be used for passivation precious metal hydrosilylation catalysts similarly.

Polymkeric substance synthetic method provides and introduce multiple organo-functional group in the copolymerization structure.Therefore, for example organic epoxy compounds of other organo-functional group, epoxysilicone, end unsaturated organic compound and alkenyl siloxane compound can be used for copolymer-modified to gained.

In a selective embodiment, under the polymeric reaction condition of selecting, by to can with the reaction mixture of epoxy functionalized organo-siloxane copolymerization in introduce the organic functional compound, in the polymerization process of epoxy functionalized organo-siloxane, in described network, introduce organo-functional group.

In one embodiment, being aggregated under one or more organic epoxy compoundss existence of epoxy functionalized organo-siloxane carried out, described organic epoxy compounds can with epoxy functionalized hydride siloxane copolymerization under polymerizing condition, form blended polyalkylene oxides unit.Additional organic epoxy compounds can contain different substituting groups, with the multipolymer of further modification gained.Suitable organic epoxy compounds for example comprises oxyethane, propylene oxide, butylene oxide ring, cyclohexene oxide, Racemic glycidol and and epoxy oils such as epoxidised soya-bean oil.

In another embodiment, one or more hydroxy functional compounds that are aggregated in of epoxy functionalized organo-siloxane carry out under existing, described hydroxy functional compound under polymerizing condition can with epoxy functionalized hydride siloxane copolymerization, make product copolymer-modified.Suitable hydroxy functional compound for example comprises that polyethers, organic alcohol that water, hydroxyl are ended comprise that the organopolysiloxane polymer of organic diol, methyl alcohol functional siloxane and hydroxyl-functional comprises polyether siloxane copolymer.

In another embodiment, being aggregated under one or more alkylidene group functional compounds existence of epoxy functionalized organo-siloxane carried out, described alkylidene group functional compound under polymerizing condition can with epoxy functionalized hydride siloxane copolymerization, make product copolymer-modified.Suitable alkylidene group functional compound comprises alkylidene group functional organic compounds such as hexadiene and alkylidene group functional polysiloxane compound such as vinyldimethicone.For example, the siloxanes that uses platinum and hydrogenation to replace therein produces in the embodiment of the cationoid reaction condition that makes the epoxide group reaction, and the functional compound of alkylidene group can add by hydrosilylation easily, as mentioned above.

Polysiloxane composition can be processed under low or high-shear to regulate the viscosity and the sensory feel of composition.For example, can by make composition through in by the time high shear force realize this point.For example, can use Sonolator equipment, Gaulin Homogenizer or MicroFluidizer equipment to apply high shear force.Randomly, before shearing, in polysiloxane composition, add one or more liquid.

In a preferred embodiment, polysiloxane composition of the present invention is a solid, has the emulsus denseness usually, and wherein, copolymer networks is as making liquid agglomerative means, so that reversibly give the solid characteristic for liquid.When static, this polysiloxane composition shows the solid gel Substance Properties.Polysiloxane composition high stability of the present invention and anti-synerisis, be that said composition shows very little or do not have liquid effusive trend from composition, and give and comprise personal care composition high stability and the anti-dewatering shrinkage of this polysiloxane composition as component.High stability and anti-dewatering shrinkage make the aging prolongation of such polysiloxane composition and personal care composition.But, be subjected to shearing force by making polysiloxane composition, for example, by making said composition friction between finger, liquid may discharge from network, with the sensory feel characteristic of liquid ingredient that described polysiloxane material is provided.

The liquid that is applicable to the liquid ingredient of composition of the present invention is at room temperature or near under the room temperature, for example about 20-50 ℃, with the following mixture of an about normal atmosphere, and comprise for example polyorganosiloxane fluid, hydrocarbon liquid, ester, alcohol, Fatty Alcohol(C12-C14 and C12-C18), dibasic alcohol and organic alcohol for the compound of liquid or two or more compounds.In a preferred embodiment, the liquid ingredient of composition of the present invention shows at 25 ℃ and is lower than approximately 1, and 000cSt preferably is lower than about 500cSt, more preferably is lower than about 250cSt, most preferably is lower than the viscosity of 100cSt.

In a preferred embodiment, liquid ingredient of the present invention comprises emollient compound.The suitable emollients compound comprises any liquid that softener character can be provided, in the time of promptly on being coated on skin, often remain on skin surface or in the stratum corneum of skin as lubricant, reduce shattered crack and improve the outward appearance of skin.Emollient compound is normally known and comprise for example hydrocarbon such as Permethyl 99A., isohexadecane and hydrogenant polyisobutene, organic wax such as Jojoba wax, polyorganosiloxane fluid such as D5, dimethyl polysiloxane, two phenyl propyl dimethyl polysiloxane, ester such as PIVALIC ACID CRUDE (25) octyl group dodecane ester and oleic oil alkene ester, and lipid acid and pure as oleyl alcohol and different tetradecyl alcohol.

In a highly preferred embodiment, liquid ingredient of the present invention comprises polyorganosiloxane fluid, more preferably shows the polyorganosiloxane fluid of softener performance, preferably low molecular weight polysiloxane liquid or low-molecular-weight siloxane compound.Suitable polyorganosiloxane fluid comprises for example formula D _rCyclic polysiloxanes, wherein, D, R ⁸And R ⁹Be as defined above, R preferably ⁸And R ⁹Be selected from the monovalence alkyl of 1-60 carbon atom, methyl more preferably, r is an integer, wherein 3≤r≤12, for example hexamethyl cyclotrisiloxane (" D ₃"), octamethylcyclotetrasiloxane (" D ₄"), decamethylcyclopentaandoxane (" D ₅") and ten diformazan basic rings, six siloxanes (" D ₆") and have formula M ' D ' _qT ' _sThe organopolysiloxane of the straight or branched of M ', wherein:

M ' is R ¹⁹ ₃SiO _1/2

D ' is R ²⁰ ₂Si _2/2

T ' is R ²¹SiO _3/2

R ¹⁹, R ²⁰And R ²¹Be alkyl, the aryl or aralkyl that contains 1-60 carbon atom independently of one another;

Q and s are 0-300 independently of one another, preferably 0-100, more preferably 0-50, the most preferably integer of 0-20.

In a preferred embodiment, in the polysiloxane composition of the present invention, per 100 weight parts (" pbw ") polysiloxane composition comprises 0.1-99pbw, 0.5pbw-30pbw more preferably, still more preferably polyether siloxane copolymer network and the 1-99.9pbw of 1-15pbw, 70-99.5pbw more preferably, the also described liquid of 85-99pbw more preferably.

Polyether siloxane copolymer group of networks compound of the present invention can use or use with the form of the polysiloxane component in emulsion with prepared form.Just as generally known, emulsion comprises at least two kinds of immiscible phases, and one of them is a successive, and another kind is discontinuous.Other emulsion can be to have the liquid or solid that changes viscosity.In addition, the particle size of emulsion can make them become microemulsion and can be transparent at enough hour microemulsion of particle size.In addition, also can prepare the emulsion of these emulsions, it generally is called multiple emulsion.These emulsions can be:

1) aqueous emulsion, wherein, discontinuous phase comprises water and external phase comprises polyether siloxane copolymer network of the present invention;

2) aqueous emulsion, wherein, external phase comprises polyether siloxane copolymer network of the present invention and discontinuous phase comprises water;

3) nonaqueous emulsion, wherein, discontinuous phase comprises non-water hydroxylic solvent and external phase comprises polyether siloxane copolymer network of the present invention;

4) nonaqueous emulsion, wherein, external phase comprises non-water hydroxyl organic solvent and discontinuous phase comprises polyether siloxane copolymer network of the present invention.

The nonaqueous emulsion that comprises the polysiloxane phase is described in United States Patent (USP) 6,060, and in the common pending application US series number 09/033,788 that on March 3rd, 546 and 1998 proposed, its content here specifically is incorporated herein by reference.

Term used herein " non-water hydroxyl organic compound " is meant that at room temperature for example about 25 ℃ and an about normal atmosphere be the organic compound that contains hydroxyl of liquid down, and for example alcohol, dibasic alcohol, polyhydroxy-alcohol and polymkeric substance are pure and their mixture.The organic hydroxylic solvent of non-water is selected from room temperature for example about 25 ℃ and an about normal atmosphere and be the organic compound that closes hydroxyl of liquid down, comprises alcohol, dibasic alcohol, polyhydroxy-alcohol, polymkeric substance is pure and their mixture.Preferably, non-water hydroxyl organic solvent is selected from ethylene glycol, ethanol, propyl alcohol, Virahol, propylene glycol, dipropylene glycol, tripropylene glycol, butyleneglycol, isobutyl glycol, methyl propanediol, glycerine, Sorbitol Powder, polyoxyethylene glycol, polypropylene glycol one alkyl oxide, polyoxyalkylene multipolymer and their mixture.

In case obtain the form of hope, no matter be only to be any or its version of polysiloxane phase, the anhydrous mixture that contains this polysiloxane phase, the aqueous mixture that contains this polysiloxane phase, water-in-oil emulsion, O/w emulsion or two kinds of nonaqueous emulsions, the material of gained normally has good feel feature and the absorbefacient high viscosity creme of highly volatile silicones.It can be blended into the prescription that is used for hair nursing, skin care, antiperspirant, sun-screening agent, makeup, coloured makeup, wormer, Metabolism Vitamins and Hormones carrier, fragrance carrier etc.

Can use polyether siloxane copolymer network of the present invention and include but not limited to wherein add usually the reodorant of polysiloxane component by the personal care applications of the polysiloxane composition of the present invention of its acquisition, antiperspirant, antiperspirant/deodorant, shave and use goods, skin lotion, wetting Agent for Printing Inks, toning agent, the bathing goods, cleaning article, hair-care goods such as shampoo, amendment, mousse, hair jelly, hair dye, the hair coloring goods, the bleaching hair agent, the curly hair goods, the hair straighteners, manicure preparations such as nail varnish, nail polish remover, nail polish paste and lotion, the epidermis tenderizer, protection cream such as sunscreen, wormer and anti-aging goods, colour cosmetic such as lipstick, foundation cream, wipe face powder, eyeliner, eye shadow, kermes, makeup, mascara and other personal care formulations, and the drug delivery system that is applied to the pharmaceutical composition topical application of skin.

In a preferred embodiment, personal care composition of the present invention also comprises one or more personal care compositions.Suitable personal care composition for example comprises softener, wetting agent, wetting Agent for Printing Inks, pigment comprises the mica of pearly pigment such as pearl white and titanium dioxide coating, tinting material, spices, sterilant, sanitas, antioxidant, biocide, anti-mycotic agent, antiperspirant, exfoliants, hormone, enzyme, medical compounds, VITAMIN, salt, ionogen, alcohol, polyvalent alcohol, ultra-violet absorber, plant milk extract, tensio-active agent, silicone oil, organic oil, wax, membrane-forming agent, thickening material such as fumed silica or hydrated SiO 2, granular filler such as talcum, kaolin, starch, treated starch, mica, nylon, clay such as bentonite and organically-modified clay.

Suitable personal care composition passes through one or more said components and polyether siloxane copolymer network with methods known in the art, polysiloxane composition form preferably of the present invention, mixing prepares.Suitable personal care composition can be single-phase form or emulsion form, comprise that oil-in-water, water-in-oil can be the anhydrous emulsions of discontinuous phase or external phase with polysiloxane wherein mutually, and multiple emulsion, for example water-in-oil bag fat liquor and water-in-oil-in-water compositions.

In a useful embodiment, antiperspirant composition comprises polyether siloxane copolymer network of the present invention and one or more active antiperspirants.Suitable antiperspirant for example comprises special topic (U.S.Food and DrugAdministration ' the s October 10 in the 10 days October in 1993 of united States food and drug administration, 1993 Monograph) halogenide of active antiperspirant composition of the I class of listing for the antiperspirant goods that are used for human purposes that need not to write out a prescription such as aluminium, the hydroxyhalide of aluminium is Wickenol CPS 325 for example, and the mixture or the mixture of they and oxyhalogenation zirconium and hydroxyl zirconium halide, Wickenol CPS 325 zirconium for example, the aluminum glycinate zirconium composite, glycine tetrachloro hydration (tetrachlorhydrex) aluminium zirconium.

In the useful embodiment of another kind, skin care compositions comprises the polyether siloxane copolymer network, polysiloxane composition form preferably of the present invention, and carrier, for example silicone oil or organic oil.This skin care compositions randomly can also comprise softener, for example tri-glyceride, wax ester, effective for treatment of premature ejaculation or alkenyl esters or polyhydroxy alkyl ester and one or more are usually used in the known component of skin care compositions, pigment for example, VITAMIN such as vitamin A, vitamins C and microorganism E, sun-screening agent or sun screening compound such as titanium dioxide, zinc oxide, oxybenzone, styracin octyl group methoxyl group ester, butyl methoxydibenzoylmethane, para-amino benzoic acid and octyl dimethyl aminobenzoic acid.

In the useful embodiment of another kind, color make-up composition such as lipstick, makeup or mascara composition comprise the polyether siloxane copolymer network, polysiloxane composition form preferably of the present invention and tinting material such as pigment, water-soluble dye or lipid-soluble dye.

In the useful embodiment of another kind, composition of the present invention and spices are united use.These spices can be the flavor compounds of flavor compounds, micro encapsulation, perhaps the compound of the release fragrance of pure compound or micro encapsulation.Compatible especially with composition of the present invention is the silicon-containing compound that discharges fragrance, as United States Patent (USP) 6,046, and 156,6,054,547,6,075,111,6,077,923,6,083,901 and 6,153, described in 578, all these patents here specifically are incorporated herein by reference.

The use of composition of the present invention is not limited to personal care composition, and other goods also can be considered as wax, rumbling compound and fabric with compositions-treated of the present invention.

Embodiment

The Experiment Preparation of polyether siloxane copolymer group of networks compound

Preparation embodiment 1

494.5 grams had proximate composition M ^HD ₃₀₀D ^H ₄M ^HHydride liquid and 5.5 gram vinyl cyclohexene oxides, 1500 gram decamethylcyclopentaandoxane (D ₅) and 0.1 gram platinum divinyl tetramethyl disiloxane catalyst solution mixing.Gained mixture heating up to 80 ℃.After 2 hours, add another part platinum catalyst.This material was heated 4 hours altogether at 80 ℃.Like this, obtain the gelatinous mass ExpMJO-07-391 of solids content about 26%.Then with 567 gram ExpMJO-07-391 and the other D of 1433 grams ₅Mix.Then the gained material is passed through the Gaulin homogenizer twice with 4500psi.The solid load of gained material ExpMJO-07-401 is about 7.3%, and viscosity is 24,200cps.This material has very soft and smooth sensation when rubbing on skin.

Preparation embodiment 2

300 grams had proximate composition M ^HD ₃₃₇D ^H _11.8M ^HHydride liquid and 3.94 gram vinyl cyclohexene oxides, the 37 grams Gulgtene C30+ alhpa olefin cut (AlphaOlefin Fraction) (hereinafter being defined as the substituting group of C30+ form), the 1022.8 gram decamethylcyclopentaandoxane (D that derive from Chevron ₅) and 0.1 gram platinum divinyl tetramethyl disiloxane catalyst solution mixing.The gained mixture produces ExpMJO-07-433 80 ℃ of heating 8 hours.The solid load of this material is about 25.5%.Then 587.5 gram ExpMJO-07-433 are restrained other D with 1412.5 ₅Swelling is passed through the Gaulin homogenizer with 4500psi then.The solid load of gained material ExpMJO-07-434 is about 7.4%, and viscosity is 45,000cps.It also has very soft and smooth sensation when rubbing on skin.

Preparation embodiment 3

300 grams had proximate composition M ^H _1.73D ₃₈₈D ^H _6.9M _0.27Hydride liquid and 3.00 gram vinyl cyclohexene oxides, the 9 grams Gulgtene C30+ alhpa olefin cut, the 936 gram decamethylcyclopentaandoxane (D that derive from Chevron ₅) and 0.1 gram platinum divinyl tetramethyl disiloxane catalyst solution mixing.The gained mixture produces the solid load about 25.7% of this material of ExpMJO-07-422. 80 ℃ of heating 8 hours.Then 591.4 gram ExpMJO-07-422 are restrained other D with 1408.6 ₅Swelling is passed through the Gaulin homogenizer with 4500psi then.The solid load of gained material ExpMJO-07-437 is about 7.26%, and viscosity is 39,000cps.

Preparation embodiment 4

300 grams had proximate composition M ^H _1.73D ₃₈₈D ^H _6.9M _0.27Hydride liquid and 3.00 gram vinyl cyclohexene oxides, 3 gram C-16/18 alhpa olefin cuts, 918 gram decamethylcyclopentaandoxane (D ₅) and 0.1 gram platinum divinyl tetramethyl disiloxane catalyst solution mixing.The gained mixture produces ExpMJO-07-424 80 ℃ of heating 8 hours.The solid load of this material about 25.7%.Then 591.4 gram ExpMJO-07-424 are restrained other D with 1408.6 ₅Swelling is passed through the Gaulin homogenizer with 4500psi then.The solid load of gained material ExpMJO-07-438 is about 7.57%, and viscosity is 39,500cps.

Preparation embodiment 5

300 grams had proximate composition M ^HD ₃₃₇D ^H _11.8M ^HHydride liquid and 4.89 gram vinyl cyclohexene oxides, the 26.4 grams Gulftene C30+ alhpa olefin cut, the 733 gram decamethylcyclopentaandoxane (D that derive from Chevron ₅) and 0.08 gram platinum divinyl tetramethyl disiloxane catalyst solution mixing.The gained mixture produces ExpMJO-07-464 80 ℃ of heating 6 hours.The solid load of this material about 30.84%.Then 533 gram ExpMJO-07-464 are restrained other D with 967 ₅Swelling is passed through the Gaulin homogenizer with 4500psi then.The solid load of gained material ExpMJO-07-465 is about 11%, and viscosity is 200,000cps.

Preparation embodiment 6

300 grams had proximate composition MD ₁₀₀D ^H _10.5The hydride liquid of M and 13.53 gram vinyl cyclohexene oxides, 34.84 grams derive from Gulftene C30+ alhpa olefin cut, the 647 gram decamethylcyclopentaandoxane (D of Chevron ₅) and 0.10 gram platinum divinyl tetramethyl disiloxane catalyst solution mixing.The gained mixture produces ExpMJO-07-477 80 ℃ of heating 6 hours.The solid load of this material about 35.25%.Then 533 gram ExpMJO-07-477 are restrained other D5 swelling with 947, pass through the Gaulin homogenizer with 4500psi then.The solid load of gained material ExpMJO-07-482 is about 12.69%, and viscosity is 16,500cps.

Preparation embodiment 7

316.4 grams had proximate composition M ^HD ₂₀₀D ^H _10.5M ^HHydride liquid and 7.56 gram vinyl cyclohexene oxides, 7.00 gram 4-allyl group-2-methoxyl group-phenol, 840 gram decamethylcyclopentaandoxane (D ₅) and 0.09 gram platinum divinyl tetramethyl disiloxane catalyst solution mixing.The gained mixture produces ExpMJO-08-537 80 ℃ of heating 6 hours.Then 418 gram ExpMJO-08-537 are restrained other D with 582 ₅Swelling is passed through the Gaulin homogenizer with 8000psi then.The solid load of gained material ExpMJO-08-540 is about 12%, and viscosity is 198,000cps.

Preparation embodiment 8

300 grams had proximate composition M ^HD ₃₃₇D ^H _11.8M ^HHydride liquid and 3.94 gram vinyl cyclohexene oxides, 905.4 gram decamethylcyclopentaandoxane (D ₅) and 0.1 gram platinum divinyl tetramethyl disiloxane catalyst solution mixing.The gained mixture is in 80 ℃ of heating 4 hours and well blend.Take out a small amount of agglomerative sample of reaction mixture and analyze with FTIR.This analysis clearlys show and has remaining SiH.The diisopstearate, the 100 gram D that add 30 gram TriMethylolPropane(TMP)s, one allyl ethers then ₅With 1 Pt mixture of catalysts.The material of gained was 80 ℃ of reheat 2 hours.When this heating finished, the acquisition solid load was 25.1% gel (gel E).The FTIR analysis revealed, SiH extends (about 2140cm ^-1) size obviously reduce.

Preparation embodiment 9: show the embodiment that dense hydride siloxane adds

300 grams had proximate composition M ^H _1.73D ₃₈₈D ^H _6.9M _0.27Hydride liquid and 3.00 gram vinyl cyclohexene oxides, 4.00 gram 4-allyl group-2-methoxyl group-phenol, the 20.8 grams Gulftene C30+ alhpa olefin cut, the 984 gram decamethylcyclopentaandoxane (D that derive from Chevron ₅) and 0.1 gram platinum divinyl tetramethyl disiloxane catalyst solution mixing.The gained mixture was 80 ℃ of heating 1 hour, and well blend.At this moment, the mixture that adds the methylhydrogenpolysi,oxane and the 5 gram decamethylcyclopentaandoxane of 4 gram trimethyl silyls termination.With making the reaction mixture gelling in 3 minutes.Heat 5 hours continuously to guarantee complete reaction.

Preparation embodiment 10

300 grams had proximate composition M ^HD ₂₀₀D ^H _10.5M ^HHydride liquid and 7.22 gram vinyl cyclohexene oxides, the 34.1 grams Gulftene C30+ alhpa olefin cut, the 796 gram decamethylcyclopentaandoxane (D that derive from Chevron ₅) and 0.085 gram platinum divinyl tetramethyl disiloxane catalyst solution mixing.The gained mixture produces ExpMJO-07-481 80 ℃ of heating 6 hours.Then 562 gram ExpMJO-07-481 are restrained other D with 938 ₅With the Isopar C solution swelling of 1.0 grams, 10% methyl two (hydrogenated tallow) amine, then with 4500psi by the Gaulin homogenizer.The solid load of gained material ExpMJO-07-484 is about 11.58%, and viscosity is 85,000cps.

Use the Experiment Preparation of the make-up composition of polyether siloxane copolymer group of networks compound

Makeup embodiment 1

Composition wt% wt%

A (contrast) B (embodiment 1)

Stearyl alcohol 15 15

Hydrogenant Viscotrol C 55

Permethyl 99A. 10 10

SF1202 45 35

Talcum 11

Al?Zr?Trichlorohydrex?Gly?24 24

(glycine three aluminum chlorhydrate's zirconiums)

ExpMJO-07-465 0 10

By stearyl alcohol, hydrogenated castor oil, Permethyl 99A., SF1202 and ExpMJO-07-465 heating are melted until jelling agent, prepare these anti-sweat medicated rolls.In batching, add glycine three aluminum chlorhydrate's zirconiums and be mixed to even at 70 ℃.At 60 ℃ antiperspirant is poured in the container.Estimate the hardness of the whiteness of antiperspirant, the ability that keeps liquid, sensation, medicated roll then.Imitate human consumer's application method by antiperspirant being coated on the dark-coloured vinyl slide glass, measure whiteness.The vinyl test slides air drying 15 minutes, and by External Observation ding white ware degree.The contrast antiperspirant showed the intensive whiteness within 5-10 after the coating minute.Compare with comparative sample, the whiteness of antiperspirant B reduces.When medicated roll was exerted pressure with thumb, antiperspirant B also showed the ability of excellent maintenance cosmetics liquid.It has also improved the consistency and elasticity of the medicated roll of this prescription.In addition, it also provides slick skin feel for Powdered goods.Prescription B is also by providing better and more uniform matrix and the growth that reduces the stearyl alcohol crystalline matrix have improved the crystallization of organic gelling agent.

Makeup embodiment 2

Composition A B (embodiment 2)

Part A wt% wt%

Propylene glycol 42.2 42.2

Hydroxypropylcellulose 0.5 0.5

DBS 2 2

Part B

30% glycine pentachloro-hydration 30 30

The propylene glycol solution of aluminium zirconium

Portion C

SF1202 10 0

ExpMJO-07-465 0 10

SF1555 15 15

40% dimethyl polysiloxane 0.3 0.3

The D of copolyol ₅Solution

By propylene glycol being heated to 80 ℃ and slowly be sprayed at and prepare these transparent antiperspirants in the hydroxypropylcellulose (HPC) and adjust.Behind the HPC homodisperse, add DBS this mixture heating up to 130 ℃ and in batching.This diol mixture will is cooled to 100 ℃, adds the solution of antiperspirant activeconstituents this moment.Polysiloxane mutually or portion C mix separately and be heated to 80 ℃, slowly introduce the dibasic alcohol phase to this polysiloxane in mutually then.

Compare with control sample, the clear antiperspirant B among the present invention does not have synersis and improves the hardness of medicated roll.With control sample relatively, it obtains antiperspirant activeconstituents good favourable smooth on skin and evenly adheres to.

Makeup embodiment 3 and 4

Composition A B (embodiment 3) C D (embodiment 4)

Part A Wt% Wt% Wt% Wt%

SF1202 21.65 11.65 19.2 9.9

Permethyl 99A. 8.7 8.7

Caprylic/capric 3.6 3.6

Witepsol W-S 55

Dimethyl polysiloxane 9.3 9.3

Phenyl trimethylammonium polysiloxane 9.3 9.3

Oleic acid Sorbitol Powder 1.5 1.5 1.4 1.4

40% dimethyl polysiloxane 3.75 3.75 3.5 3.5

The D5 solution of copolyol

ExpMJO-07-465 10

ExpMJO-07-434 9.3

Part B

Ferric oxide (red, yellow, black) 2.34 2.34 2.18 2.18

TiO ₂ 8.73 8.73 8.11 8.11

10% dimethyl polysiloxane 6.63 6.63 6.15 6.15

The D5 solution of copolyol

Portion C

Deionized water 37.75 37.75 34.98 34.98

Butyleneglycol 55 4.65 4.65

Xanthan gum 0.1 0.1 0.1 0.1

C _11-15?Pareth-7 0.25 0.25 0.23 0.23

Sal epsom 0.9 0.9

Parameter foundation cream A foundation cream B foundation cream C foundation cream D

(embodiment 3) (embodiment 4)

Level of coverage ¹-excellent-excellent

Glossiness 3.2 3.2 17.2 11.6

5 flush cycle NA NA wash out part and wash out,

Residual foundation cream

After outward appearance ²Be powdery

Attention: 1=compares the degree that covers with comparative sample.Prescription A is the contrast of prescription B,

Prescription C is the contrast of prescription D.

2=comes for the outward appearance that is coated in the foundation cream on the vinyl slide glass after 5 circulations of flushing

Test formulations C and D.Anti-washability method is described among the AS TM D1913.

These foundation creams are by at room temperature prepare part A and part B uniform mixing together.When joining in the oil phase, water (portion C) produces emulsion.The foundation cream sample is with 24 microns the spreadability of thickness evaluation on the vinyl slide glass.Estimate easy degree, outward appearance, level of coverage and the gloss in the process of smearing, sprawled of all foundation creams.After 12 hours, use Grossmeters to measure gloss.In this research, prescription B estimates with respect to prescription A (contrast), and prescription D estimates with respect to prescription C (contrast).

Outward appearance by being reduced in line on the vinyl slide glass and defective and by being reduced in the gloss of initially drying in the process, prescription B has obtained excellent even covering.But prescription A and B did not show the difference of glossiness after 12 hours.Prescription B gives exquisite soft and smooth sense and has the powdery FINAL APPEARANCE.Compare with the prescription A (contrast) that shows synersis simultaneously, the foundation cream B among the present invention has improved in the stability of room temperature after one week.

Prescription D obtains the similar benefit described in prescription B.In addition, it also provides anti-washability, and this makes personal care product for perspire or more durable in the swimming process.Prescription D has control glossy ability, as shown in above-mentioned result.

Makeup embodiment 5 and 6

Prepare these two embodiment illustrate the organopolysiloxane gel among the present invention the organic phase capacitive and it and present INCI D5 by name (with) the elastomerics gel of dimethyl polysiloxane/vinyl-dimethyl based polysiloxane cross-polymer (SFE839) relatively.

Makeup embodiment 5

Form outward appearance

25% vaseline is liquid in SFE 839

25% vaseline is in the ExpMJO-07-465 gel

When vaseline mixed with SFE839, prescription lost its structure and becomes opaque liquid mixture.The uncompatibility of this explanation vaseline and SFE839.On the other hand, when vaseline was blended in the gel of the present invention, this gel had the ability that keeps the product globality, had shown the consistency of this gel and vaseline.

Makeup embodiment 6

Form outward appearance

50% Cetearyl methyl polysiloxane is incompatible in SFE839

50% Cetearyl methyl polysiloxane is compatible in ExpMJO-07-465

The Cetearyl methyl polysiloxane is the polysiloxane that a kind of straight chained alkyl replaces, and it provides wettability by produce closed blocking layer on skin to prescription.When this polysiloxane wetting Agent for Printing Inks combined with described new gel, it showed good consistency, and SFE839 then can not.In addition, gel according to the present invention is easier to be mixed with cosmetic composition, because it need be by needed high shear mixing of SFE839 or longer mixing time.

Makeup embodiment 7

This skin treatment gel by all the components listed below of combination at room temperature until evenly preparing.This gel is applicable to temperature-sensitive and non-thermally sensitized activeconstituents as the delivery system of skin treatment and it, because it does not need heating in manufacturing processed.In this prescription, do not exist water guaranteed using up before ascorbic effectiveness.

Composition weight %

Poly methyl silsesquioxane (Tospear12000B) 0.5

Vitamins C 1

Hydrogenant poly decene 10

ExpMJO-07-434 88.5

Makeup embodiment 8

The lip processing that comprises following composition is used for delineate, the weather resistance and the sensation of preserving moisture.

Composition weight %

ExpMJO-07-465 89

Phenyl propyl dimethylsilane oxygen base silicon ester 10

PA-12 1

Makeup embodiment 9

Make soft and smooth refreshing body water by part A being combined and is heated to 80 ℃.In independent container, part B is mixed and be heated to 75 ℃.When part A and part B are added to a time-out under high shear mixing, form emulsion.This refreshing body water provides light and slick skin feel.

Composition

Part A wt%

ExpMJO-07-465 10

Caprylic/capric triglyceride 5

C _30-45Alkyl-dimethyl based polysiloxane 5

Stearin (with) PEG-100 stearate 4

Part B

Water is an amount of

Xanthan gum 0.1

Glycerine 2

Sanitas, color, spices 1

Makeup embodiment 10-13

The refreshing body water of water tolerance that is used for various personal care products prepares by at room temperature part A and part B being combined.Described refreshing body water is applied on the glass slide then and uses and test water-fast degree in the method described in the ASTM D1913.The anti-impact degree of washing is to wash the flush cycle number of times that needs when feeling well body water fully off.Use the refreshing body water B-E of new gel of the present invention to show water tolerance effect as follows.

Composition A B C D E

Makeup embodiment contrasts 10 11 12 13

Part A wt% wt% wt% wt% wt%

Oleic acid Sorbitol Powder 0.6 0.6 0.6 0.6 0.6

10% dimethyl gathers silica 10 10 10 10 10

The D5 solution of alkane copolyol

SF1202 16 4 4 4 4

ExpMJO-07-401 0 12 0 0 0

ExpMJO-07-437 0 0 12 0 0

ExpMJO-07-434 0 0 0 12 0

ExpMJO-07-438 0 0 0 0 12

Part B

Glycerine 11111

Sodium-chlor 11111

Quaternium-15 0.1 0.1 0.1 0.1 0.1

Water is an amount of an amount of

Anti-washability result

The prescription flush cycle

A (contrast) 5

B 15

C 15

D 15

E 10

Makeup embodiment 14

The shampoo that comprises following composition is that hair fiber is given soft and smooth sensation.This shampoo prepares with two kinds of methods, and a kind of is directly to add organopolysiloxane gel in shampoo, and another kind is in advance organopolysiloxane gel to be mixed with at least a tensio-active agent and water until forming emulsion and add this organopolysiloxane gel emulsion in shampoo.

This shampoo is by mixing the following preparation that becomes to assign in order.

Form wt%

Texapon Special 35

Cocamidopropyl trimethyl-glycine 5

Water 56.6

Sanitas 0.01

CALCIUM ACRYLATE/C _10-30Alkyl acrylate copolymer 0.8

Sodium hydroxide is adjusted to pH7.5

ExpMJO-07-465 2.5

Citric acid is adjusted to pH6

Makeup embodiment 15

The hair conditioner of this daily use provides flexibility, oilness and denseness.

Form wt%

Deionized water 93

Natvosol 1.5

Organopolysiloxane gel emulsion 2

Cetrimonium?chloride 3

Sanitas, toner, spices are an amount of

Makeup embodiment 16

Staying amendment on the hair has reduced and flies out and increase denseness and volume.

Form wt%

ExpMJO-07-465 50

Dimethyl polysiloxane copolyol 5

Permethyl 99A. 45

Makeup embodiment 17

This pliable solid antiperspirant contains organopolysiloxane gel, anti-synersis agent, thickening material and sensory intensifier.This gel shows excellent organic phase capacitive.Itself and organic thickening agent are used in combination to obtain ideal tissue and hardness.

Become portioning/Wt

(％)

D5 (SF1202) 37.0

Dimethyl polysiloxane (SF96-10) 8.0

Phenylformic acid C _12-15Alkyl ester 8.0

Hydrogenant Viscotrol C (70 ℃ of molten points) 7.0

C _18-36Acid glycerol three esters 7.0

ExpMJO-07-484 5.0

Talcum 3.0

Glycine tetrachloro hydrated aluminum zirconium 25.0

Makeup embodiment 18

This polysiloxane lipstick contains the organopolysiloxane gel of softening lip.Two kinds of polysiloxane are arranged, i.e. SF1528 and ExpMJO-07-484, their produce unique soft and smooth sensation.The adding sun-screening agent is used for sun protection in can following this prescription.

Become portioning/Wt

(％)

D5 (with)

The PEG/PPG-20/15 dimethyl polysiloxane

(SF1528)

ExpMJO-07-484 20.0

C _18-36Acid glycerol three esters 40.0

Ceresine 5.0

Polyethylene 3.0

Permethyl 99A. 5.0

D﹠amp; The red No.7 Ca of C color lake 20.0

7.0

The material of listing with SFxxxx is available from GE Silicones, 260 Hudson RiverRoad, the polysiloxane material of Waterford NY 12188.

These embodiment only are used to illustrate in essence, in any case can not think the appended claim of restriction.Be appreciated that those skilled in the art can produce the theme that this paper comprises and the considerable change of content, this is because which is a ordinary skill in the literal or reasonable range of claims.

Claims (10)

1. composition that comprises reaction product with following formula:

M _aM ^H _bM ^E _cD _dD ^H _eD ^E _fT _gT ^H _hT ^E _iQ _j

Wherein:

M＝R ¹R ²R ³SiO _1/2；

M ^H＝R ⁴R ⁵HSiO _1/2；

M ^E＝R ⁶R ⁷R ^ESiO _1/2；

D＝R ⁸R ⁹SiO _2/2；

D ^H＝R ¹⁰HSiO _2/2；

D ^E＝R ¹¹R ⁸SiO _2/2；

T＝R ¹²SiO _3/2；

T ^H＝HSiO _3/2；

T ^E=R ^ESiO _3/2And

Q＝SiO _4/2；

R wherein ¹, R ², R ³, R ⁸, R ⁹And R ¹²Be the monovalence alkyl that contains 1-60 carbon atom independently of each other; R ⁴, R ⁵And R ¹⁰Be monovalence alkyl or the hydrogen that contains 1-60 carbon atom independently of each other; R ⁶, R ⁷, R ¹¹Be monovalence alkyl or the R that contains 1-60 carbon atom independently of each other ^EEach R ^EBe the monovalence alkyl that contains the ethylene oxide moiety of one or more 1-60 of comprising carbon atom independently; Stoichiometric ratio subscript a, b, c, d, e, f, g, h, i and j be 0 or meet following condition on the occasion of a+b+c＞1; B+e+h＞1; C+f+i＞1; B+e+h＞c+f+i; And when d+e+f+g+h+i+j=0, a+b+c=2.

2. the composition of claim 1, wherein, R ^EHave following formula:

Wherein, R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷And R ¹⁸Be selected from hydrogen and the monovalence alkyl that contains 1-60 carbon atom, Q independently of one another _mBe divalence or the trivalent hydrocarbon radical that contains 1-60 carbon atom, Q is the bivalent hydrocarbon radical that contains 1-60 carbon atom, and subscript m and n are 0 or 1 independently of one another, and meet the following conditions: work as Q _mDuring for trivalent, R ¹³Or R ¹⁴One of do not exist.

3. claim 1 or 2 composition, wherein, R ^EBe selected from 4-vinyl cyclohexene oxide, allyl glycidyl ether, limonene monoepoxide, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, monocycle oxidation norbornadiene and 1,2-epoxy-9-decene.

4. the composition of claim 2, wherein, R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷And R ¹⁸Be that hydrogen and m and n are 0.

5. the composition of claim 3, wherein, R ^EBe 4-vinyl cyclohexene oxide.

6. each composition of aforementioned claim, wherein, R ¹, R ², R ³, R ⁸, R ⁹And R ¹²Be independently selected from methyl, ethyl, sec-butyl, the tertiary butyl, octyl group, decyl, dodecyl, hexadecyl, stearyl-, vinyl, propenyl, butenyl, hydroxypropyl, cyanoethyl, butoxy, 2; 5; 8-trioxa decyl, carboxymethyl, chloromethyl, C30+ and 3; 3, the 3-fluoropropyl.

7. aqueous emulsion, wherein, discontinuous phase comprises water and continuous items and comprises according to each composition of aforementioned claim.

8. aqueous emulsion, wherein, the moisture and discontinuous phase of external phase contains each the composition of with good grounds claim 1-6.

9. nonaqueous emulsion, wherein, discontinuous phase contains non-water hydroxylic solvent and external phase and comprises each composition according to claim 1-6.

10. nonaqueous emulsion, wherein, external phase comprises non-water hydroxylic solvent and discontinuous phase and comprises each composition according to claim 1-6.