• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    An alternating copolymer comprising a repeating unit ofα,ω-organohydrogensiloxane residue (A) and a repeating unitof a glycerol derivative residue(B)having 1 to 11 hydroxylgroups, the copolymer having the number of a repeating unit(AB) of from 2 to 100.
    公开号:EP1496080A1
    申请号:EP20040076938
    申请日:2004-07-06
    公开日:2005-01-12
    发明作者:Tetsuo Silicone-Electric Materials R.C. Nakanishi；Toshiki Silicone-Electric Materials R. C. Tanaka；Kiyomi Shin-Etsu Chemical Co. Ltd. Tachibana
    申请人:Shin Etsu Chemical Co Ltd；
    IPC主号:A61K8-00
    专利说明:
    [0001] This application claims benefits of Japanese Patentapplication No. 2003-192572 filed on July 7, 2003, JapanesePatent application No. 2003-194500 filed on July 9, 2003, andJapanese Patent application No. 2004-189229 filed on June 28,2004,the contents of which are hereby incorporated byreference. FIELD OF THE INVENTION
    [0002] This invention relates to an alternating copolymer oforganopolysiloxane with glycerol derivative and to a cosmeticcomprising the same as an oil agent or an emulsifier. DESCRIPTION OF THE PRIOR ART
    [0003] Human secretions such as sweat, tears and sebum cause makeupruns. Especially, in makeup cosmetics, an oil agent containedin cosmetics along with sebum secreted from the skin causesexcessive wetting of cosmetic powder, which results in seriousmakeup runs. In order to reduce the amount of cosmetic oilremaining on the skin, an attempt was made to use a volatileoil such as octamethylcyclotetrasiloxane ordecamethylcyclopentasiloxane as a part of the oil ingredientsto be added.
    [0004] Generally, an oily cosmetic has good affinity to skin anddurability, but it tends to give a user uncomfortable feelingsuch as oily, tacky, heavy or thick feeling. To reduce theoiliness, use has been made of a silicone oil which extends wellon the skin and gives refreshed feeling. By incorporating thesilicone oil, the oiliness is indeed reduced. However, negativeproperties of the silicone oil such as poor affinity and lackof moisturizing function prevail and the good affinity of an oily cosmetic is lost, too. In addition, satisfactory shinyfinish was not obtained.
    [0005] Although polysiloxanes have good properties as oily agentsused for cosmetics, properties concerning feeling are notsatisfactory such as affinity with skin, moisturized feelingand dryness.
    [0006] In makeup cosmetics such as foundation, water repellencyhas not been improved enough. In skin-care cosmetics such asa milky lotion, an oily agent is desired which has a light feeling,good water repellency, good usability and affinity to the skin.
    [0007] Meanwhile, a silicone oil obtained by modifying adimethylpolysiloxane with fluoroalkyl groups described inJapanese Patent Application (JPA) Laid-Open No.2-295912 has ahigher oil repellency than dimethylpolysiloxane.
    [0008] As the content of the floroalkyl groups increases, the oilrepellency increases, but a heavier feeling to the skin occurs.Further, solubility in octamethylcyclotetrasiloxane ordecamethylcyclopentasiloxane decreases, which is inconvenientin preparing cosmetic. To get enough solubility, thefloroalkyl groups should be decrease, which in turn decreasethe oil repellency and the affinity to the skin.
    [0009] Recently, in a water-in-oil type emulsion (w/o emulsion)composition, a silicone oil is used. Such a w/o emulsioncontaining the silicone oil is difficult to obtain by using aconventionally used emulsifier such as polyoxyalkylene fattyacid ester.
    [0010] As a surfactant for the aforesaid w/o emulsion, use of apolyoxyalkylene-modified organopolysiloxane, i.e.,polyether-modified silicone which has a good compatibility with a silicone oil is proposed in JPA Laid-Open No.61-293903, JPALaid-Open No.61-293904, JPA Laid-Open No.62-187406, JPALaid-Open No.62-215510, and JPA Laid-Open No.62-216635.
    [0011] To prepare an emulsion for a cosmetic application, an esteroil and a hydrocarbon oil are often used together with a siliconeoil as a mixture. With the aforesaid polyether-modifiedsilicone, an emulsion of such a mixed oil system is difficultto prepare due to a lack of emulsifying capability of thepolyether-modified silicone.
    [0012] To solve this problem, it is proposed in JPA Laid-Open No.61-90732 to use the following organopolysiloxane as anemulsifier which has a long alkyl chain and a polyoxyalkylenegroup.
    [0013] The above organopolysiloxane compound is a good emulsifierfor a mixed oil system containing relatively large amount ofester oil or hydrocarbon oil, but not good enough to preparea stable emulsion of a system containing relatively large amountof silicone oil.
    [0014] As shown in the formula (5), in an organopolysiloxanecompound having a polyoxyalkylene group, the polyoxyalkylenegroup is usually grafted to the organopolysiloxane chain. Othertype of organopolysiloxane is known which has a polyoxyalkylenegroup (A) bonded to one or both terminals of a siloxaneresidue (B) to form (AB) type or (ABA) type organopolysiloxane. In Japanese Patents No.3061434, No.3071222, and No.3283277, anorganopolysiloxane having a repeating unit of (AB) is disclosed.It is described that the organopolysiloxane functions as anantistatic agent, which is attributed to the polyalkylene group,and can be used for skin cosmetics as well as hair cosmetics.
    [0015] In an application of a skin cleaning agent, cleaning ofmakeup cosmetics containing large amount of solid oil such asa lipstick, foundation, eye shadow, eyeliner, and mascara isan issue. A cleaning agent comprising an ordinary soap cannotclean these cosmetic completely, because the soap cannotdissolve or emulsify the solid oil.
    [0016] To clean such oily cosmetics, a cleaning agent mainlycomposed of an oily material has been used. However, suchcleaning agent is not enough to clean a makeup cosmetic designedto give a durable and long lasting makeup or the one containingcyclic silicones or a film forming polymer intended to be usedin summer when people sweat a lot. In a hair cosmetic, a highlypolymerized silicone or a polymer having a high film formingcapability is used to protect hair, to add hair bounce or smoothfeeling.
    [0017] To clean such a durable makeup or film forming polymer onhair, a cleaning agent containing a nonionic surfactant or apolyethe- modified silicone is used. However, as film formingcapability increases, a cleaning agent having a higher cleaningcapability is desired.
    [0018] Meanwhile, various kinds of glycerol-modified siliconeshave been reported to solve poor moisturization property andaffinity to the skin.
    [0019] For example, glycerol-modified silicones are described inJPA Laid-Open No.6-157236, JPA Laid-Open No.9-71504 and JP Kokoku No.62-34039; glycerol- and fluoroalkyl-modifiedsilicones in JPA Laid-Open No.10-310504, No.10-310505,No.10-310506, No.10-310507, No.10-310508, and No.10-310509;monoglycerol- modified silicones and a cosmetic comprising thesame in Japanese Patent Publication (JP) No. 2613124, JPNo.2844453, JP Kokoku No.8-22811, JP No.2587797, and JPNo.2601738. All of the glycerol-modified silicones areintended to suppress drying property of the silicone andtackiness of glycerol.
    [0020] As a silicone modified with a compound having hydroxylgroups, a polyalcohol-modified silicone is also known whereinthe polyalcohol is sucrose or polysacharide. In JP No.3172787,a modified silicone having a sucrose residue is described andits application as an emulsifier is described in JP No.3229396,JPA Laid-Open No.7-41414, and Laid-Open No.7-41416.
    [0021] All of the modified silicones are intended to suppressdrying property of the silicone with the polyalcohol includingglycerol and to suppress tackiness of glycerol with thesilicone.
    [0022] The aforesaid known glycerol-modified silicones aresuperior to a conventional polyether-modified silicone in thatthey do not get viscous or show tackiness when mixed with water.However, one drawback with the glycerol-modified silicones isan availability of a raw material polyglycerol having reactivefunctional groups such as an aliphatic unsaturated group to bereacted with a silicone. For example, in preparing aglycerol-modified silicone by reacting the glycerol derivativecompound represented by the formula below with an SiH bond ofa silicone, miscibility of the compound with the silicone andhence a reaction rate significantly decrease with increasingthe repetition number of "d", due to increasing viscosity andhyrdophilicity of the glycerol derivative.
    [0023] To avoid such decrease in the reaction rate, a large amountof a reaction solvent is required, which decreases yield pervolume and hence cost performance. Said problem of poormiscibility is critical in modification of a silicone with apolyglycerol having higher degree of polymerization. Generally,modification with a polyglycerol having a molecular weight over5,000 is very difficult. Particularly, in modifying thesilicone with a small amount of polyglycerol derivative, thepolyglycerol derivative tends to exist in a separate phase fromthe silicone or precipitates, making a reaction product cloudy.
    [0024] Another drawback is that a hydroxyl group in a polyglycerolhaving an aliphatic unsaturated group tends to react with SiHgroup to hinder the addition reaction of the unsaturated groupwith SiH group and decrease a shelf life of themodified-silicone product.
    [0025] Such dehydrogenation reaction of SiH with OH group can besuppressed by reacting α,ω-organohydrogensiloxane, which hasa higher reactivity in the addition reaction, with a glycerolderivative having one aliphatic unsaturated bond. However, itcannot prevent a reaction product from being cloudy. To preparea glycerol-modified silicone with a higher molecular weight,a polyglycerol with a higher molecular weight is required,because reaction sites of α,ω-organohydrogensiloxane arelimited to the terminals. Such a high molecular weightpolyglycerol is less miscible with the siloxane.
    [0026] By using the triglycerol of the formula below with its OH groups being blocked, the dehydrogenation can be avoided.However, to release the blocking group after the reaction witha silicone, very severe reaction conditions are required, whichcauses a scission of the silicone chain, so that desiredreaction product may not be obtained reproducibly.
    [0027] Thus, a purpose of the present invention is to provide aglycerol-modified silicone having a good compatibility with oilagents conventionally used for a cosmetic and a good emulsifyingactivity to be advantageously used for a cosmetic and to providea method of producing the same without the aforesaid problemsin producing a glycerol-modified silicone. SUMMARY OF THE INVENTION
    [0028] As the result of extensive studies, the present inventorshave found that a polyglycerol-modified silicone having ahigher molecular weight than a conventional one can be obtained,without getting the polyglycerol-modified silicone cloudy, bysubjecting α,ω-organohydrogensiloxane and a glycerolderivative to an alternating addition reaction, which glycerolderivative has a relatively low molecular weight and analiphatic unsaturated group at both terminals. In addition,it has been found that polyclycerol-modified silicones withvarious contents of glycerol can be prepared by varying a ratioof a degree of polymerization of the siloxane to that of thepolyglycerol.
    [0029] Thus, the present invention is an alternating copolymercomprising a repeating unit of α,ω-organohydrogensiloxaneresidue (A) and a repeating unit of a glycerol derivativeresidue (B) having 1 to 11 hydroxyl groups, the copolymer havingthe number of a repeating unit (AB) of from 2 to 100.
    [0030] Another aspect of the present invention is a process forpreparing the aforesaid alternating copolymer comprising a stepof reacting α,ω-organohydrogensiloxane having an SiH bond atboth terminals with a glycerol derivative having an aliphaticunsaturated bond at both terminals.
    [0031] The alternating copolymer of the present invention is clear,and a cosmetic comprising the copolymer has a reduced tackiness,while maintaining affinity to the skin, light spreadability onthe skin to give a moisturized sensation. The applied cosmeticon the skin is durable and has a shiny finish of anexpensive-looking.
    [0032] A cosmetic comprising the alternating copolymer of thepresent invention as an emulsifier is very stable and thequality thereof does not change with temperature change orpassage of time.
    [0033] Moreover, the alternating copolymer may be added to a paintto prevent blocking or to improve flatness, smoothness andabrasion resistance of an applied paint. BRIEF DESCRIPTION OF THE DRAWING
    [0034] Fig. 1 is an IR chart of the present alternating copolymer5 prepared in the example 5. PREFERRED EMBODIMENT OF THE INVENTION
    [0035] The present copolymer is an alternating copolymercomprising a repeating unit of α,ω-organohydrogensiloxaneresidue (A) and a repeating unit of a glycerol derivativeresidue(B)having 1 to 11 hydroxyl groups. The silicone,α, ω-organohydrogensiloxane, is an organopolysiloxane having ahydrogen atom at both terminals. The glycerol derivativeresidue (B) has one hydroxyl group when the glycerol derivativeis monoglycerol derivative, or 2 to 11, preferably 2 to 5, andmore preferably 2 to 4 hydroxyl groups when the glycerolderivative is polyglycerol derivative. It is considered,without intending to limit the invention, that the alternatinglocations of the residue (A) with residue (B) is one of thereasons for the clearness, good emulsifying activity andmiscibility with an oily agent. The number of the repeating unit(AB) ranges from 2 to 100, preferably 3 to 30, from the viewpointsof fluidity and solubility at room temperature.
    [0036] Preferably, the repeating unit (AB) is represented by thefollowing formula(1).
    [0037] In formula (1), R1 and R2 are monovalent organic functionalgroups which do not have an aliphatic unsaturated bond. R1 maybe the same or different and is a group having 1 to 10 carbonatoms selected from the group consisting of alkyl, aryl, aralkyl,amino-substituted alkyl, and carboxyl-substituted alkyl, partof which hydrogen atoms may be replaced with halogen atoms.Examples of R1 include alkyl groups such as methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups;cycloalkyl groups such as cyclopentyl and cyclohexyl groups;aryl groups such as phenyl and tolyl groups; aralkyl groups suchas benzyl and phenetyl groups; amino-alkyl groups such as3-aminopropyl, and 3-[(2-aminoethyl)amino]propyl group;carboxyl-substituted alkyl group such as 3-carboxylpropylgroup; and trifluoropropyl and nonafluorooctyl groups.
    [0038] R2 may be the same or different and is an alkyl group having11 to 30 carbon atoms part of which hydrogen atoms may be replacedwith halogen atoms, such as undecyl, dodecyl, tridecyl,tetradecyl, hexadecyl, octadecyl, behenyl and partlyfluorinated alkyl groups.
    [0039] In formula (1), Q is a divalent organic group having 3 to20 carbon atoms and may comprise an ether bond and/or an esterbond such as - (CH2) 2-, - (CH2) 3-, -CH2CH (CH3) CH2-, - (CH2) 4-,- (CH2) 5-, - (CH2) 6-, - (CH2) 7-, - (CH2) 8-, - (CH2) 2-CH (CH2CH2CH3)--CH2-CH (CH2CH3) -, - (CH2) 3-O- (CH2) 2-, - (CH2) 3-O- (CH2) 2-O- (CH2) 2-,- (CH2)3-O-CH2CH (CH3) -, and -CH2-CH (CH3) -COO (CH2) 2-, among which- (CH2) 3- is preferred.
    [0040] In formula (1), G is a mono- or poly-glycerol residue. Typically, G may have a following chemical structure of (2),(3) or (4). In these formula, s, t, u, and v are integers offrom 0 to 10. Examples of G include residue of monoglycerol,diglycerol, triglycerol, tetraglycerol, octaglycerol,decaglycerol, hexadecaglycerol, and octadecaglycerol. A partof hydroxyl groups may be replaced with alkoxyl groups or estergroups.
    [0041] Preferably, s, t, u, and v are integers of from 1 to 9, andmore preferably s, t, and u+v are integers of from 1 to 4.
    [0042] Referring back to formula (1), a is an integer of from 2 to 100, preferably, from 10 to 60 and b is an integer of from0 to 100. Preferably, b is 10 to 50 % of a, that is from 1 to50, in order for the alternating copolymer to be miscible withboth a silicone oil and an ester oil. In formula (1), c is aninteger of from 2 to 100, preferably, from 3 to 30. If c is largerthan said upper limit, a copolymer may be too viscous to handleeasily. A copolymer with c being smaller than said lower limitmay not give a stable emulsion.
    [0043] The present alternating copolymer can be prepared bysubjecting the α,ω-orgnohydrogenpolysiloxane of the formula(5) shown below and mono- or polyglycerol derivative to anaddition reaction in the presence of a platinum or rhodiumcatalyst, which mono- or polyglycerol derivative has anunsaturated group at both terminals, for example, triglyceroldially ether of the formula (i) or (ii).
    [0044] Triglycerol dially ether of the formula (i) or (ii) may beprepared by adding 2 molar allylglycidyl ether dropwise to 1molar triglycerol and subjecting the mixture to an additionreaction. Preferably, the reaction is carried out at atemperature of 60 to 120 degrees C. After the reaction, thecatalyst is neutralized and, then, volatile substances havinga lower boiling point than that of triglycerol dially ether areremoved by distillation.
    [0045] Triglycerol dially ether thus obtained is considered to bea mixture of the compounds of the formulae (i) and (ii) whichis typically a pale yellow liquid having a viscosity of 330 mm2/s,hydroxyl number of 523 KOH mg/g, unsaturation of 6.13 meq/g.The hydroxyl number and unsaturation are nearly equal totheoretical values of 525 and 6.24, respectively, indicatingthat the dially ether obtained by the aforesaid method has twounsaturated groups per molecule.
    [0046] A dially ether with a higher molecular weight can be preparedin the same manner as described above, by using diglycerol ortriglycerol in place of glycerol.
    [0047] A ratio of α,ω-orgnohydrogenpolysiloxane of the formula (5)and the polyglycerol dially ether of the formula (i) and/or (ii)is such that a molar ratio of SiH group of theα,ω-orgnohydrogenpolysiloxane to CH=CH2 group of thepolyglycerol dially ether, SiH/ CH=CH2, is equal to or greaterthan 0.5 and smaller than 1.5, preferably equal to or greaterthan 0.8 and smaller than 1.2.
    [0048] The aforesaid addition reaction is preferably carried outin the presence of a platinum or rhodium catalyst. Preferredcatalysts are chloroplatinic acid, alcohol-modifiedchloroplatinic acid, and chloroplatinic acid-vinyl siloxanecomplex.
    [0049] The amount of the catalyst may be an effective amount, but500 ppm or less, particularly, 20 ppm or less as platinum orrhodium are preferred. The aforesaid addition reaction may becarried out in an organic solvent if necessary. Examples of theorganic solvent include aliphatic alcohols such as methanol,ethanol, 2-propanol, and butanol; aromatic hydrocarbons suchas toluene and xylene; aliphatic or alicyclic hydrocarbons suchas n-pentane, n-hexane, and cyclohexane; and halogenatedhydrocarbons such as dichloromethane, chloroform, and carbontetrachloride. When such solvent is used, the addition reactionis preferably carried out for 1 to 10 hours while refluxing thesolvent.
    [0050] After the addition reaction, unreacted allyl ether groupmay be killed by hydrogenation, or alkylation to reduce odor.An antioxidant such as tocopherol or BHT may be added to thecopolymer.
    [0051] The present alternating copolymer may be suitably used asan emulsifier or an oil agent in various products for externalapplication, for example, cosmetics such as emulsified productslike milky lotions; makeup products such as lipsticks and oilyfoundation; skin-care products; hair care products; and drugsfor external application.
    [0052] In the cosmetic, the present copolymer may be incorporatedin an amount of from 0.1 to 70 wt%, preferably from 1 to 50 wt%relative to a total weight of the cosmetic.
    [0053] In the cosmetic, commonly used oil agent, in addition tothe present copolymer, may be incorporated which may be solid,semi-solid, or liquid, at an ambient temperature. Examples ofthe oil agent include natural fats, oils from animals or plantsand semi-synthetic oils, such as avocado oil, linseed oil, almond oil, Ibota wax, perilla oil, olive oil, cacao butter,kapok wax, kaya oil, carnauba wax, Glycyrrhiza oil, candelillawax, beef tallow, neat's-foot oil, beef bone fat, hydrogenatedbeef tallow, apricot kernel oil, spermaceti wax, hydrogenatedoil, wheat germ oil, sesame oil, rice germ oil, rice bran oil,sugar cane wax, sasanqua oil, safflower oil, shear butter,Chinese tung oil, cinnamon oil, jojoba wax, squalane, olivesqualane, squalene, shellac wax, turtle oil, soybean oil, teaseed oil, camellia oil, evening primrose oil, corn oil, lard,rapeseed oil, Japanese tung oil, rice bran oil, germ oil, horsefat, persic oil, palm oil, palm kernel oil, castor oil,hydrogenated castor oil, castor oil fatty acid methyl ester,sunflower oil, grape oil, bayberry wax, jojoba oil, macadamianut oil, beeswax, mink oil, cottonseed oil, cotton wax, Japanesewax, Japanese wax kernel oil, montan wax, coconut oil,hydrogenated coconut oil, tri-coconut oil fatty acid glyceride,mutton tallow, peanut oil, lanolin, liquid lanolin,hydrogenated lanolin, lanolin alcohol, hard lanolin, lanolinacetate, isopropyl lanolate, POE lanolin alcohol ether, POElanolin alcohol acetate, lanolin fatty acid polyethylene glycol,POE hydrogenated lanolin alcohol ether, and egg yolk oil. Theterm "POE" means polyoxyethylene.
    [0054] The oil agent may be a hydrocarbon oil such as linear,branched and volatile hydrocarbons. Examples include α-olefinoligomers, light isoparaffin, light liquid isoparaffin,ozokerite, synthetic squalane, vegetable squalene, ceresin,paraffin, paraffin wax, polyethylene wax,polyethylene-polypropylene wax, liquid paraffin, pristane,polyisobutylene, microcrystalline wax, and Vaseline.
    [0055] The oil agent may be a higher fatty acid such as lauric acid,myristic acid, palmitic acid, stearic acid, behenic acid,undecylenic acid, oleic acid, linoleic acid, linolenic acid,arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and12-hydroxystearic acid.
    [0056] The oil agent may be a higher alcohol such as lauryl alcohol,myristyl alcohol, palmityl alcohol, stearyl alcohol, behenylalcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol,hexyldodecanol, octyl dodecanol, cetostearyl alcohol,2-decyltetradecinol, cholesterol, phytosterol, POEcholesterol ether, monostearyl glycerin ether (batyl alcohol) ,and monooleyl glyceryl ether (cerakyl alcohol).
    [0057] The oil agent may be an ester oil such as diisobutyl adipate,2-hexyldecyl adipate, di-2-heptylundecyl adipate, isononylisononate, isotridecyl isononate, N-alkyl glycolmonoisostearate, isocetyl isostearate, trimethylolpropanetriisostearate, ethylene glycol di-2-ethylhexanoate, cetyl2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate,pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate,octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate,decyl oleate, neopentyl glycol dioctanoate, neopentyl glycoldicaprirate, triethyl citrate, 2-ethylhexyl succinate, amylacetate, ethyl acetate, butyl acetate, isocetyl stearate, butylstearate, diisopropyl sebacinate, di-2-ethylhexyl sebacinate,cetyl lactate, myristyl lactate, isopropyl palmitate,2-ethylhexyl palmitate, 2-hexyldecyl palmitate,2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate,dipentaerythritol fatty acid esters, isopropyl myristate,octyldodecyl myristate, 2-hexyldecyl myristate, myristylmyristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyllaurate, 2-octyldodecyl N-lauroyl-L-glutamate, anddiisostearyl malate; and a glyceride oil, for example,acetoglyceryl, glycerol triisooctanoate, glyceryltriisostearate, glyceryl triisopalmitate, glycerylmonostearate, glyceryl di-2-heptylundecanoate, glyceryltrimyristate, and diglyceryl myristate isostearate.
    [0058] The oil agent may be a silicone oil, for example, a linearorganopolysiloxane having a low to high viscosity such asdimethylpolysiloxane, methylphenylpolysiloxane,methylhydrogenpolysiloxane, dimethylsiloxane /methylphenylsiloxane copolymer; a cyclic siloxane such asoctamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane,tetramethyltetrahydrogencyclotetrasiloxane,tetramethyltetraphenylcyclotetrasiloxane,tetramethyltetratrifluoropropylsiloxane, andpentamethylpentatrifluoropropylsiloxane; a branched siloxanesuch as trimethylsiloxymethylsiloxane,tristrimethylsiloxysilane, tetrakistrimethylsiloxysilane,tristrimethylsiloxyphenylsilane; silicone gum such as gummydimethylpolysiloxane having a high degree of polymerization,gummy dimethylsiloxane/methylphenylsiloxane copolymer and asolution thereof in a cyclic siloxane; trimethylsiloxysilicateand a solution thereof in a cyclic siloxane; a higheralkoxy-modified silicone such as stearoxy silicone; a higherfatty acid-modified silicone alkyl-modified silicone,amino-modified silicone, and fluorine-modified silicone.
    [0059] The oil agent may be a fluorinated oil such asperfluoropolyethers, perfluorodecaline, and perfluorooctane.
    [0060] These oil agents may be incorporated in the cosmetic inan amount of from 1 to 99 wt% based on a total weight of thecosmetic.
    [0061] The cosmetics of the present invention may furthercomprise one or more of a compound having alcoholic hydroxylgroup besides the copolymer of the present invention and thehigher alcohol mentioned above. Examples of the compound havingalcoholic hydroxyl group include lower monoalcohols such as ethanoland isopropanol; sugar alcohols such as sorbitol andmaltose; sterols such as cholesterol, sitosterol, phytosterol,and lanosterol; polyalcohols such as butylene glycol, propyleneglycol, butylene glycol, and pentyl glycol. The compound maybe incorporated in the cosmetic in an amount of from 0.1 to 98wt% based on a total weight of the cosmetic.
    [0062] The cosmetics of the present invention may comprise oneor more water-soluble or water-swelling polymer. Examples ofthe water-soluble or water-swelling polymer include plantpolymers such as gum Arabic, tragacanth gum, arabinogalactan,locust bean gum (carob gum) , guar gum, karaya gum, carrageenan,pectin, agar, quince seed (i.e., marmelo), starch from rice,corn, potato or wheat, algae colloid, trant gum and locust beangum; bacteria-derived polymers such as xanthan gum, dextran,succinoglucan, and pullulan; animal-derived polymers such ascollagen, casein, albumin, and gelatin; starch-derivedpolymers such as carboxymethyl starch and methylhydroxypropylstarch; cellulose polymers such as methyl cellulose, ethylcellulose, methylhydroxypropyl cellulose, carboxymethylcellulose, hydroxymethyl cellulose, hydroxypropyl cellulose,nitrocellulose, sodium cellulose sulfate, sodiumcarboxymethyl cellulose, crystalline cellulose, and cellulosepowder; alginic acid-derived polymers such as sodium alginateand propylene glycol alginate; vinyl polymers such as polyvinylmethylether, and carboxyvinyl polymer; polyoxyethylenepolymers; polyoxyethylene/polyoxypropylene copolymers;acrylic polymers such as sodium polyacrylate, polyethylacrylate, and polyacrylamide; synthetic water-solublepolymers such as polyethyleneimine and other kind of cationicpolymers; semi-synthetic water-soluble polymers such assilicone-modified pulllan; and water-soluble inorganicpolymers such as, bentonite, aluminum magnesium silicate,montmorillonite, beidellite, notronite, saponite, hectorite,and silicic anhydride. The examples of the water-soluble polymer further include film forming agents such as polyvinylalcohol and polyvinyl pyrrolidone. The water-soluble orwater-swelling polymer may be incorporated in the cosmetic inan amount of from 0.01 to 25 wt% based on a total weight of thecosmetic.
    [0063] The present cosmetic may further comprise water, mineralwater, seawater, deep-sea water, and rose water according toa purpose of the cosmetic. The water may be incorporated in anamount of from 1 to 99 wt% based on a total weight of the cosmetic.
    [0064] The present cosmetic may further comprise any powder andcoloring agents which are commonly used in cosmetics may be usedin the present invention, regardless of the shape (spherical,rod-like, acicular, tubular, irregular, scaly or spindle forms),particle size (size of fume, fine particles or pigment grade),and particle structure (porous and non-porous), such as, forexample, inorganic powder, organic powder, surface activatingmetal salt powder, colored pigments, nacreous pigments,metallic powder pigments, and natural dyes.
    [0065] Specific examples of the inorganic powders includetitanium oxide, zirconium oxide, zinc oxide, cerium oxide,magnesium oxide, barium sulfate, calcium sulfate, magnesiumsulfate, calcium carbonate, magnesium carbonate, talc, mica,kaolin, sericite, white mica, synthetic mica, phlogopite,lepidolite, biotite, lithia mica, silicic acid, silicicanhydride, aluminum silicate, magnesium silicate, aluminummagnesium silicate, calcium silicate, barium silicate,strontium silicate, metal salts of tungstenic acid,hydroxyapatite, vermiculite, higilite, bentonite,montmorillonite, hectolitre, zeolite, ceramics powder,calcium secondary phosphate, alumina, aluminum hydroxide,boron nitride, and silica.
    [0066] Examples of the organic powders include polyamide powder,polyester powder, polyethylene powder, polypropylene powder,polystyrene powder, polyurethane, benzoguanamine powder,polymethylbenzoguanamine powder, tetrafluoroethylene powder,polymethylmethacrylate powder, cellulose, silk powder, nylonpowder such as Nylon 12 and Nylon 6, spherical siliconeelastomer powder having crosslinked dimethylsiliconestructure (see Japanese Laid-Open Patent Application No.3-93834), spherical polymethylsilsesquioxane powder(seeJapanese Laid-Open Patent Application No. 3-47848), sphericalsilicone elastomer powder with its surface coated withpolymethylsilsesquioxane (see Japanese Laid-Open PatentApplication No. 7-196815) styrene/acrylic acid copolymer,divinylbenzene/styrene copolymer, vinyl resin, urea resin,phenol resin, fluororesin, acrylic resin, melamine resin, epoxyresin, polycarbonate resin, microcrystalline fiber powder,starch powder, and lauroyl lysine.
    [0067] Examples of the surface activating metal salt powders(metal soaps) include zinc stearate, aluminum stearate, calciumstearate, magnesium stearate, zinc myristate, magnesiummyristate, zinc cetyl phosphate, calcium cetyl phosphate, andzinc/sodium cetyl phosphate.
    [0068] Examples of the colored pigments include inorganic redpigments such as iron oxide, iron hydroxide, and iron titanate,inorganic brown pigments such as γ-iron oxide, inorganic yellowpigments such as iron oxide yellow and loess, inorganic blackpigments such as iron oxide black and carbon black, inorganicviolet pigments such as manganese violet and cobalt violet,inorganic green pigments such as chromium hydroxide, chromiumoxide, cobalt oxide, and cobalt titanate, inorganic bluepigments such as Prussian blue and ultramarine blue, lakes oftar pigments, lakes of natural dyes, and synthetic resin powdercomplexes thereof.
    [0069] Examples of the nacreous pigments include titaniumoxide-coated mica, bismuth oxychloride, titanium oxide-coatedbismuth oxychloride, titanium oxide-coated talc, fish scales,and titanium oxide-coated colored mica and examples of metallicpowder pigments include aluminum powder, copper powder andstainless steel powder.
    [0070] Examples of the tar pigments include Red No. 3, Red No. 104,Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205,Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230,Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, YellowNo. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, BlueNo. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, GreenNo. 201, Green No. 204, Green No. 205, Orange No. 201, OrangeNo. 203, Orange No. 204, Orange No. 206, and Orange No. 207.Examples of the natural dyes include carminic acid, laccaic acid,carthamin, brazilin, and crocin.
    [0071] Powders which absorb or scatter UV ray may be used, too,such as titanium oxide fine powder, fine powder of titaniumoxide containing iron, zinc oxide fine powder, cerium oxide finepowder and a mixture thereof.
    [0072] These powders can be subjected to compounding or surfacetreatment with common oil agents, conventional silicone oils,fluorine-containing compounds or surfactants prior to use, asfar as such treatment does not adversely affect the presentcosmetic. If necessary, two or more powders may be used.
    [0073] The present cosmetic may further comprise one or more orsurfactant. The surfactant may be anionic, cationic,non-ionic or amphoteric. There is not any particular limitationand any surfactant that can be used in common cosmetics may beused.
    [0074] Examples of the anionic surfactants include fatty acid soaps,such as sodium stearate and triethanolamine palmitate,alkylether carboxylic acids and salts thereof, salts of aminoacids and fatty acids, alkylsulfonic acids, alkenesulfonates,sulfonates of fatty acid esters, sulfonates of fatty acid amides,sulfonates of alkylsulfonate-formalin condensates,alkylsulfates, sulfates of secondary higher alcohols,alkyl/allyl ether sulfates, sulfates of fatty acid esters,sulfates of fatty acid alkylolamides, and sulfates of TurkeyRed oil, alkyl phosphates, ether phosphates, alkylallyletherphosphates, amide phosphates, and N-acylamino surfactants.
    [0075] Examples of the cationic surfactants include amine saltssuch as salts of alkylamine, polyamine and amino alcohol fattyacid derivatives, alkyl quaternary ammonium salts, aromaticquaternary ammonium salts, pyridium salts and imidazoliumsalts.
    [0076] Examples of the nonionic surfactants include sorbitanfatty acid esters, glycerin fatty acid esters, polyglycerinfatty acid esters, propylene glycol fatty acid esters,polyethylene glycol fatty acid esters, sucrose fatty acidesters, polyoxyethylene alkylethers, polyoxypropylenealkylethers, polyoxyethylene alkylphenylether,polyoxyethylene fatty acid esters, polyoxyethylene sorbitanfatty acid esters, polyoxyethylene sorbitol fatty acid esters,polyoxyethylene glycerin fatty acid esters, polyoxyethylenepropylene glycol fatty acid esters, polyoxyethylene castor oil,polyoxyethylene hydrogenated castor oil, polyoxyethylenephytostanolether, polyoxyethylene phytosterolether,polyoxyethylene cholestanolether, polyoxyethylenecholesterylether, polyoxyalkylene-modifed organopolysiloxane(see Japanese Patent No. 2137062 and Japanese Laid-open PatentApplication No. 7-330907), polyglycerin-modified organopolysiloxane (Japanese Laid-open Patent Application No.62-34039,and Japanese Patent Application Nos. 2613124, 2844453,and 2002-179798), polyoxyalkylene / alkylco-modified-organopolysiloxane (Japanese Laid-open Patent Nos.61-90732 and 9-59386) alknolamide, sugar ethers, and sugaramides.
    [0077] Examples of the amphoteric surfactants include betaine,aminocarboxylates, and imidazoline derivatives. A desirableamount of the surfactant to be added ranges from 0.1 to 20 wt%,preferably from 0.2 to 10 wt%, relative to a total weight ofthe cosmetic.
    [0078] The present cosmetic may further comprise one or more ofa crosslinked organopolysiloxane. Preferably, the crosslinkedorganopolysiloxane is swelled with a silicone having aviscosity of from 0.65 to 100.0 mm2 / sec in a larger amountby weight than the amount of the crosslinked organopolysiloxaneitself. This crosslinked organopolysiloxane can be obtained byreacting a SiH bond of organohydrogenpolysiloxane withcrosslinking agent having reactive vinylic unsaturated groupat molecular terminal. Further, the crosslinkedorganopolysiloxane may have at least one residue selected fromthe group consisting of polyoxyalkylene residue, alkyl residue,aryl residue, and fluoroalkyl residue. Examples of thecrosslinked organopolysiloxane, though not limited to these,include KSG-15, KSG-16, KSG-18, KSG-210, and KSG-710, all ofwhich are in a gel from swelled with a silicone oil andcommercially available from Shin-Etsu Chemical Co.
    [0079] The crosslinked organopolysiloxane swelled with an oilagent other than the silicone having a viscosity of from 0.65to 100.0 mm2 / sec may be used, too. Examples of such crosslinkedorganopolysiloxane, though not limited to these, includeKSG-310, KSG-320, KSG-330, KSG-340, KSG-41, KSG-42, KSG-43, KSG-44, KSG-810, KSG-820, KSG-830, and KSG-840, all of whichare in a gel from swelled with a hydrocarbon oil or triglycerideoil and commercially available from Shin-Etsu Chemical Co.
    [0080] The present cosmetic may further comprise one or more ofconventional silicone resins. One of the preferred siliconeresins is acrylic silicone resin such as acryl/silicone graftcopolymer and acryl/silicone block copolymer. The acrylicsilicone resin may have at least a residue selected from thegroup consisting of pyyrolidone residue, long alkyl chainresidue, polyoxyalkylene residue, fluoroalkyl residue, andanionic residue such as carboxylic acid residue.
    [0081] The silicone resin is preferably a network silicone compound,such as MQ resin, MDQ resin, MT resin, MDT resin, and MDTQ resin.Each M, D, T, and Q means R3SiO0.5 unit, R2SiO unit, RSiO1.5 unit,and siO2 unit, respectively, which nomenclature is commonly usedin the silicone industry. MT resin and MDT resin are generallyknown network silicone compounds. The network silicone compoundmay have MDQ or MDTQ moiety. These silicone resins arecommercially available in the form of a solution inoctamethylcyclotetrasiloxane. The network silicone compoundmay have at least a residue selected from the group consistingof pyyrolidone residue, long alkyl chain residue,polyoxyalkylene residue, fluoroalkyl residue and aminoresidue.
    [0082] The present cosmetic may comprise one or more of anoil-soluble gelling agent and clay mineral modified withorganic compounds.
    [0083] Examples of the oil-soluble gelling agent include metalsoaps such as aluminum stearate, magnesium stearate, and zincmyristate; α-amino acid derivatives such as N - lauroyl-L-glutamic acid, α, γ- di - n - butylamine; dextrin fatty acidesters such as dextrin palmitate, dextrin stearate, and dextrin2-ethylhexane palmitate; sucrose fatty acid esters such assucrose palmitate and sucrose stearate; fatty acid esters offructo-oligosaccharide such as inulinstearate, and2-ethylhexanoic ester of fructo-oligosaccharide ; benzylidenederivatives of sorbitol such as monobenzylidene sorbitol anddibenzylidene sorbitol; clay minerals modified with an organicmoiety such as dimethylbenzyldodecylammonium montmorilloniteclay, dimethyldioctadecylammonium montmorillonite.The present cosmetic may comprise one or more of organic UVabsorbents. Examples of the organic UV absorbents include UVabsorbents of benzoate type, such as p-aminobenzoic acid, ethyldihydroxypropyl p-aminobenzoate, glyceryl p-aminobenzoate,and octyl p-dimethylaminobenzoate; anthranilic acid type UVabsrobents such as methyl anthranilate; UV absorbents ofsalicylic acid type, such as methyl salicylate, octylsalicylate, and triethanol amine salt of salicylic acid;cinnamic acid type UV absorbents, such as octylp-methoxycinnamate, diethanol amine salt ofp-methoxyhydroxycinnamic acid, and dimethocycinnamic acid/isooctanoicacid gryceride; benzophenone type UV absorbents,such as 2,4-dihydroxybenzophenon,2,2',4,4'-tetrahydroxybenzophenon,2-hydroxy-4-methyoxybenzophenon,2-hydroxy-4-methoxypenzophenon-5-sulfonic acid,2,2'-dihydroxy-4-methoxypenzophenon, and2-hydroxy-4-N-octoxybenzophenon;UV absorbents of urocanic acid type, such as ethyl urocanate;UV absorbents of dibenzoylmethane type, such as4-tert-butyl-4'-methoxydibenzoylmethane, 4-isopropyldibenzoylmethane; 3-(4-methylbenzylidene)camphor,octyltriazone, e-ethylhexyl-2-cyano-3,3-diphenylacrylate,2-phenyl-benzoimidasole-5-sulfate,4-(3,4-dimethoxypnehylmethylene)-2,5-dioxo-1-imidazolidine, and 2-ethylhexylpropionate. The UV absorber may be encapsulatedin a polymer powder. The aforesaid powders which absorb orscatter UV ray may be used, for example, titanium oxide finepowder, fine powder of titanium oxide containing iron, zincoxide fine powder, cerium oxide fine powder and a mixturethereof.
    [0084] The present cosmetic may further comprise antiseptics orantibacterial agents. Examples of the antiseptics orantibacterial agents include alkyl paraoxybenzoates, benzoicacid, sodium benzoate, sorbic acid, potassium sorbate, andphenoxyethanol may be used. For the antibacterial agents,benzoic acid, salicylic acid, carbolic acid, sorbic acid,paraoxybenzoic acid alkyl esters, parachloromethacresol,hexachlorophene, benzalkonium chloride, chlorohexydinechloride, trichlorocarbanilide, triclosan, photosensitizer,and phenoxyethanol.
    [0085] Antioxidants may be incorporated in the cosmetic such astocopherol, butylhydroxyanisole, dibutylhydroxytoluene and, phytic acid.
    [0086] The present cosmetic may further comprise, in an amount notto adversely affect the invention, antiperspirant such asaluminum chlorohydrate, aluminum chloride, aluminumsesquichlorohydrate, zirconyl hydroxy chloride, aluminumzirconium hydroxychloride and aluminum zirconium glycine; pHregulators such as lactic acid, citric acid, glycolic acid,succinic acid, tartaric acid, dl-malic acid, potassiumcarbonate, sodium hydrogen carbonate and ammonium hydrogencarbonate; chlating agents such as alanine, sodium , sodiumpolyphosphate, sodium metaphosphate, phosphoric acid;refrigerants such as L-menthol and camphor; andanti-inflammatory agents include allantoin, glycyrrhetinicacid, glycyrrhizinic acid, tranexamic acid, and azulene.
    [0087] The present cosmetic may further comprises skin-beautifyingcomponents in an amount not to adversely affect the invention,such as whitening agents such as placenta extract, arbutin,glutathione and Yukinoshita extract, kojic acid, placentaextract, sulfur, ellagic acid, linoleic acid, tranexamic acid;cell activators, such as royal jelly, photosensitizers,cholesterol derivatives, calf blood extract, α-hydroxy acid andβ-hydroxy acid ; rough and dry skin improvers; bloodcirculation improvers, such as nonylic acid vanillyl amide,benzyl nicotinate, β-butoxyethyl nicotinate, capsaicin,zingerone, cantharis tincture, ichtammol, caffeine, tannicacid, α-borneol, tocopheryl nicotinate, inositolhexanicotinate, cyclandelate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthin and gamma -oryzanol; skinastringents, such as zinc oxide and tannic acid; andanti-seborrheic agents, such as sulfur and thianthol; and skincolorants such as α-hydroxyacetone.
    [0088] The present cosmetic may further comprises vitamins in anamount not to adversely affect the invention, e.g. vitamin Asuch as vitamin A oil, retinol, retinyl acetate and retinylpalmitate; vitamin B2 such as riboflavin, riboflavin butyrateand flavin adenine nucleotide, vitamin B6 such as pyridoxinehydrochloride, pyridoxine dioctanoate and pyridoxinetripalmitate, vitamin B12 and its derivatives, and vitamin B15and its derivatives; vitamin C, such as L-ascorbic acid,L-ascorbate dipalmitate, sodium (L-ascorbic acid)-2-sulfateand dipotassium L-ascorbic acid diphosphate; vitamin D, suchas ergocalciferol and cholecarciferol; vitamin E, such as alpha-tocopherol, beta -tocopherol, gamma -tocopherol, dl- alpha-tocopheryl acetate, dl- alpha -tocopheryl nicotinate and dl-alpha-tocopheryl succinate; vitamin H; vitamin P; nicotinicacids, such as nicotinic acid, benzyl nicotinate and nicotinic acid amide; pantothenic acids, such as calcium pantothenate,D-pantothenyl alcohol, pantothenyl ethyl ether andacetylpantothenyl ethyl ether; and biotin.
    [0089] The present cosmetic may further comprises amino acids suchas glycine, valine, leucine, isoleucine, serine, threonine,phenylaranine, alginine, lysine, aspartic acid, glutamic acid,cystine, cysteine, methionine, and tryptophan; examples of thenucleic acids include deoxyribonucleic acid; and examples ofthe hormones include estradiol and ethenyl estradiol.
    [0090] The present cosmetic may be in various forms such as liquid,milky lotion, cream, solid, paste, powder, lamella, gel, mousse,stick or spray. EXAMPLES
    [0091] The present invention will be further explained in detailbelow by referring to the examples, though not be limited tothese examples. In the examples, "%" means "% by weight" unlessotherwise specified.
    [0092] Triglycerol diallyl ether was prepared by adding allyglycidyl ether dropwise to glycerol in the presence of analkaline catalyst at 80 degrees C. After the reaction, thecatalyst was neutralized and the reaction mixture was subjectedto distillation to remove substances with low boiling points.Triglycerol diallyl ether obtained was a pale yellow liquidhaving a viscosity of 330 mm2/s, a hydroxyl value of 523 KOHmg/g,a unsaturation of 6.13 meq/g, which might be a mixture of theaforesaid isomers of the formula (i) and (ii).Example 1. Preparation of Alternating Copolymer 1
    [0093] In a reactor, 200 g of methylhydrogenpolysiloxanerepresented by the following average compositional formula, 256g of triglycerol dially ether, 400 g of isopropyl alcohol (IPA) , and 0.9 g of a 0.5 wt% solution of chloroplatinic acid in IPAwere placed and subjected to a reaction for 8 hours whilerefluxing IPA.
    [0094] After cooling, the reaction mixture liquid was transferredto an autoclave to which 15 g, weighed in water, of Raney nickelwas added. Then, hydrogen gas was introduced in the autoclaveand a reaction was carried out at 120 degrees C for 3 hours whilemaintaining a pressure of the hydrogen gas at 0.5 MPa. Afterremoving the catalyst by filtration, the reaction mixture wassubjected to vacuum distillation to remove volatile substances.The organopolysiloxane/polyglycerol alternating copolymerthus obtained was clear and colorless liquid having a viscosityof 39 Pa.s and a refractive index of 1.4576, both at 25 degreesC. Example 2. Preparation of Alternating Copolymer 2
    [0095] In a reactor, 300 g of methylhydrogenpolysiloxane representedby the following average compositional formula, 143 g oftriglycerol dially ether, 300 g of isopropyl alcohol (IPA) , and0.75 g of a 0. 5 wt% solution of chloroplatinic acid in IPA wereplaced and subjected to a reaction for 8 hours while refluxingIPA.
    [0096] After cooling, the reaction mixture liquid was transferredto an autoclave to which 15 g, weighed in water, of Raney nickelwas added. Then, hydrogen gas was introduced in the autoclaveand a reaction was carried out at 120 degrees C for 3 hours whilemaintaining a pressure of the hydrogen gas at 0.5 MPa.
    [0097] After removing the catalyst by filtration, the reactionmixture was subjected to vacuum distillation to remove volatilesubstances. The organopolysiloxane/polyglycerol alternatingcopolymer thus obtained was clear and colorless liquid havinga viscosity of 24 Pa.s and a refractive index of 1.4345, bothat 25 degrees C. Example 3. Preparation of Alternating Copolymer 3
    [0098] In a reactor, 300 g of methylhydrogenpolysiloxanerepresented by the following average compositional formula, 67g of triglycerol dially ether, 300 g of isopropyl alcohol (IPA) ,and 0.75 g of a 0.5 wt% solution of chloroplatinic acid in IPAwere placed and subjected to a reaction for 8 hours whilerefluxing IPA.
    [0099] After cooling, the reaction mixture liquid was transferredto an autoclave to which 15 g, weighed in water, of Raney nickelwas added. Then, hydrogen gas was introduced in the autoclaveand a reaction was carried out at 120 degrees C for 3 hours while maintaining a pressure of the hydrogen gas at 0.5 MPa.
    [0100] After removing the catalyst by filtration, a little amountof aldehydes were decomposed with hydrochloric acid. Then, thereaction mixture was neutralized and subjected to vacuumdistillation to remove volatile substances. Theorganopolysiloxane/polyglycerol alternating copolymer thusobtained was clear and colorless liquid having a viscosity of44 Pa.s and a refractive index of 1.4200, both at 25 degreesC. Example 4. Preparation of Alternating Copolymer 4
    [0101] In a reactor, 300 g of methylhydrogenpolysiloxanerepresented by the following average compositional formula, 28g of triglycerol dially ether, 300 g of isopropyl alcohol (IPA) ,and 0.75 g of a 0.5 wt% solution of chloroplatinic acid in IPAwere placed and subjected to a reaction for 8 hours whilerefluxing IPA.
    [0102] After cooling, the reaction mixture liquid was transferredto an autoclave to which 15 g, weighed in water, of Raney nickelwas added. Then, hydrogen gas was introduced in the autoclaveand a reaction was carried out at 120 degrees C for 3 hours whilemaintaining a pressure of the hydrogen gas at 0.5 MPa.
    [0103] After removing the catalyst by filtration, a little amountof aldehydes were decomposed by hydrochloric acid. Then, thereaction mixture was neutralized and subjected to vacuum distillation to remove volatile substances. Theorganopolysiloxane/polyglycerol alternating copolymer thusobtained was clear and colorless liquid having a viscosity of46 Pa.s and a refractive index of 1.4108, both at 25 degreesC. Example 5. Preparation of Alternating Copolymer 5
    [0104] In a reactor, 300 g of methylhydrogenpolysiloxane with amethyl group being replaced with a dodecyl group representedby the following average compositional formula, 29 g oftriglycerol dially ether, 300 g of isopropyl alcohol (IPA) , and0.75 g of a 0.5 wt% solution of chloroplatinic acid in IPA wereplaced and subjected to a reaction for 8 hours while refluxingIPA.
    [0105] After cooling, the reaction mixture liquid was transferredto an autoclave to which 15 g, weighed in water, of Raney nickelwas added. Then, hydrogen gas was introduced in the autoclaveand a reaction was carried out at 120 degrees C for 3 hours whilemaintaining a pressure of the hydrogen gas at 0.5 MPa.
    [0106] After removing the catalyst by filtration, a little amountof aldehydes were decomposed by hydrochloric acid. Then, thereaction mixture was neutralized and subjected to vacuumdistillation to remove volatile substances. Theorganopolysiloxane/polyglycerol alternating copolymer thus obtained was clear and pale yellow liquid having a viscosityof 7 Pa.s and a refractive index of 1.4337, both at 25 degreesC.
    [0107] The alternating copolymer prepared in Example 5 was analyzedwith an FT-IR spectrometer SP2000, ex Perkin Elmer, in a thinfilm coated on a KBr pellet. The presence of OH groups and Si-O-Sibonds in the alternating copolymer were confirmed by strongbands around 3400cm-1 assigned as O-H stretching and 1100-1000cm-1 assigned as Si-O-Si antisymmetric stretching. The presenceof methyl groups and Si-C bonds were confirmed by bands around2960 cm-1 assigned as CH3 antisymmetric stretching, 1250 cm-1assigned as CH3 symmetric deformation, and 840 cm-1 assignedas Si-C antisymmetric stretching. Comparative Example 1. Preparation of a Silicone HavingGlycerol Residues at Both Terminals
    [0108] In a reactor, 300 g of methylhydrogenpolysiloxanerepresented by the following average compositional formula, 122g of triglycerol dially ether, 300 g of isopropyl alcohol (IPA) ,and 0.75 g of a 0.5 wt% solution of chloroplatinic acid in IPAwere placed and subjected to a reaction for 8 hours whilerefluxing IPA.
    [0109] After cooling, the reaction mixture liquid was transferredto an autoclave to which 15 g, weighed in water, of Raney nickelwas added. Then, hydrogen gas was introduced in the autoclave and a reaction was carried out at 120 degrees C for 3 hours whilemaintaining a pressure of the hydrogen gas at 0.5 MPa.
    [0110] After removing the catalyst by filtration, a little amountof aldehydes were decomposed by hydrochloric acid. Then, thereaction mixture was neutralized and subjected to vacuumdistillation to remove volatile substances. The reactionproduct, which has a glycerol residue at both terminals, wasopaque and pale brown liquid having a viscosity of 69 Pa. s anda refractive index of 1.4285, both at 25 degrees C.
    [0111] The alternating copolymer 3 and the silicone prepared inComparative Example 1 were analyzed with GPC using THF as aneluent. A weight average molecular weight of the alternatingcopolymer 3 was 90,000 and that of the silicone of comparativeexample 1 was 3,500. Comparing with the silicone having aglycerol residue at both terminals, the present alternatingcopolymer has an excellent clarity in spite of the highermolecular weight. Comparative Example 2. Preparation of Silicone Having GlycerolResidues at Both Terminals
    [0112] In a reactor, 300 g of methylhydrogenpolysiloxanerepresented by the following average compositional formula, 47g of triglycerol dially ether, 300 g of isopropyl alcohol (IPA) ,and 0.75 g of a 0.5 wt% solution of chloroplatinic acid in IPAwere placed and subjected to a reaction for 8 hours whilerefluxing IPA.
    [0113] After cooling, the reaction mixture liquid was transferredto an autoclave to which 15 g, weighed in water, of Raney nickelwas added. Then, hydrogen gas was introduced in the autoclaveand a reaction was carried out at 120 degrees C for 3 hours whilemaintaining a pressure of the hydrogen gas at 0.5 MPa.
    [0114] After removing the catalyst by filtration, a little amountof aldehydes were decomposed by hydrochloric acid. Then, thereaction mixture was neutralized and subjected to vacuumdistillation to remove volatile substances. The reactionproduct, which was a silicone modified with glycerol at bothends, was opaque and pale brown liquid having a viscosity of233 Pa.s and a refractive index of 1.4150, both at 25 degreesC.
    [0115] The alternating copolymer 4 and the silicone prepared inComparative Example 2 were analyzed with GPC using THF as aneluent. A weight average molecular weight of the alternatingcopolymer 4 was 82,000 and that of the silicone in ComparativeExample 2 was 4,500. Comparing with the silicone having aglycerol residue at both terminals, the present alternatingcopolymer has an excellent clarity in spite of the highermolecular weight. Example 6. to 8. and Comparative Examples 3, 4 :Oily Foundation
    [0116] Oil-based foundations as seen in the following Table 1 wereprepared and evaluated. Oil-based Foundation Components Ex*.6 Ex.7 Ex.8 C*.3 C.4 1. Starch fatty acid ester 6.0 ← ← ← ←2. Ceresine 7.0 ← ← ← ← 3. Polybutene 4.0 ← ← ← ← 4. Liquid paraffin 34.0 ← ← ← ← 5. Alternating copolymer 1 6.0 ← ← ← ← 6. Alternating copolymer 2 6.0 7. Alternating copolymer 4 6.0 8. Dimetylpolysiloxane(6cs) 6.0 9. Dimetylpolysiloxane(100cs) 6.0 10. Titanium oxide 33.0 ← ← ← ← 11. Titanated mica 3.0 ← ← ← ← 12. Inorganic colored pigment 7.0 ← ← ← ← 13. Antiseptic q.l. ← ← ← ← 14. Perfume q.l. ← ← ← ←
    [0117] In the table, the numerals represent wt% based on a total weightof the foundation. Preparation Method
    [0118] Step 1 Components 1 - 4 and one of Components 5-9 weredissolved while heating. Step 2 Components 10 - 14 were mixed with the resultingmixture from Step 1. Step 3 The resulting mixture from Step 2 was dispersedhomogeneously with a three-roller mill. Step 4 The resulting mixture from Step 3 was dissolved whileheating, degassed, and then poured into a metal plate, followedby cooling.Evaluation
    [0119] The foundations were graded by a panel of 50 women in termsof evaluation items shown in table 2 according to the following criteria. Grading criteria
    [0120] Point 5 Excellent Point 4 good Point 3 fair Point 2 poor Point 1 very poor
    [0121] The averaged grades over the 50 women are as seen in the table2 where each capital letter means as follows: A 4.5 points or higher B 3.5 points or higher and lower than 4.5 points C 2.5 points or higher and lower than 3.5 points D lower than 2.5 points Evaluation Item Ex.6 Ex.7 Ex.8 C*.3 C.4 Product gloss A A A C C Spreadability A A A A C Affinity A A A C B Settleability A A A D C Non-tackiness A A A A B Moisturized feel A A A D C Beautifulness of finish A A A B A Durability A A A D C Over-all grading A A A D C
    [0122] As can be seen in Table 2, the foundations of Examples 6 to8 comprising the present organopolysiloxane/polyglycerolalternating copolymer were superior to those of Comparative Examples 3 and 4 in gloss, spreadability, affinity to skin,settleability, and non-tackiness and gave moisturized andbeautiful finish with an excellent durability. Example 9 , 10 and Comparative Examples 5, 6 : Lipstick
    [0123] Components Ex.9 Ex.10 C.5 C.6 1. Micro crystalline wax 6.0 ← ← ← 2. Synthetic hydrocarbon wax 8.0 ← ← ← 3. Cerecine wax 5.0 ← ← ← 4. Candellila wax 2.0 ← ← ← 5. Pentaerythritol rosinate 5.0 ← ← ← 6. Cetyl 2-ethylhexanoate 20.0 ← ← ← 7. Glyceryl trioctanoate 25.0 ← ← ← 8. Alternating copolymer 3 10.0 ← ← ← 9. Alternating copolymer 5 10.0 10.Methylphenylpolysiloxane10.0 11. Diisostearyl malate 10.0 12. Pigment 5.0 ← ← ← 13. Titanated mica 15.0 ← ← ← 14. Perfume q.l. ← ← ←
    [0124] In the table, the numerals represent wt% based on a total weightof the lipstick. Preparation Method
    [0125] Step 1 : All of the components except perfume were dissolvedwhile heating. Step 2 After degassing the dissolved mixture obtained in Step1, Component 14 was added and the resulting mixturewas poured into a container to form a lipstick.Evaluation
    [0126] The lipsticks thus obtained were evaluated in the samemanner as in Examples 6 to 8 except that the grading items werethose shown in table 4. Evaluation Item Ex.9 Ex.10 C.5 C.6 Gloss A A A D Non-tackiness during wearing A A B D Affinity during wearing A A D B Non-tackiness after wearing A A B D Affinity after wearing A A D B No color transfer A A C C No color fading A A C C No color blurring A A D B Over-all grading A A D C
    [0127] As is evident from Table 4, the lipsticks of Examples 9 and10 comprising the present organopolysiloxane/polyglycerolalternating copolymer had more shiny gloss of the productsurface and had non-tackiness during and after wearing,comparing with the silicones in Comparative Examples 5 and 6.The present invention comprising the present copolymer had anexcellent affinity to the lips with no color transferring, colorfading, or color blurring. Example 11: Lipstick
    [0128] Components wt% 1. Candelilla wax 8.0 2. Polyethylene wax 8.0 3. Acrylic silicone resin containing long alkyl chain 12.0 4. Metylphenylpolysiloxane 3.0 5. Isotridecyl isononanate 20.0 6. Glyceryl isostearate 16.0 7. Alternating copolymer 2 0.5 8. Octadecyldimethylbenzyl ammonium-modified mont-morillonite 0.5 9. Polyglyceryl triisostearate 27.5 10. Red No. 202 treated with graft copolymer of acrylic - silicone type 0.8 11. Iron oxide red treated with graft copolymer of acrylic - silicone type3) 1.5 12. Iron oxide yellow treated with graft copolymer of acrylic - silicone type3) 1.0 13. Iron oxide black treated with graft copolymer of acrylic - silicone type3) 0.2 14. Titanium oxide treated with graft copolymer of acrylic - silicone type3) 1.0 15. Antiseptic q.l. 16. Perfume q.l. (Preparation)
    [0129] Step 1 Components 1 - 8 and a portion of Component 9 were mixedwhile heating to dissolve. Step 2 Components 10 - 16 and the rest of Component 9 weremixed homogeneously, and then the resulting mixture was added to the mixture from Step 1 to obtain ahomogeneous mixture.
    [0130] The lipstick thus obtained had a shiny gloss on its surface,extended lightly, had a non-tacky and non-powdery touch, andleft to the lips refreshed and lightweight feel. The appliedlipstick had good water resistance, water repellency and wasdurable and stable. Example 12: Brushing Spray
    [0131] Components wt% 1. Isopropyl myristate 0.8 2. Stearyltrimethylammonium chloride 0.05 3. Alternating copolymer 1 0.5 4. Aluminum magnesium silicate 0.1 5. Zinc oxide treated with oil 3.0 6. Ethanol 25.0 7. Perfume q.l. 8. Propellent Balance (Preparation Method)
    [0132] Step 1 Components 1 - 7 were mixed. Step 2 The resulting mixture from Step 1 was put in an aerosolcan, to which Component 8 was put to obtain a brushingagent.
    [0133] The brushing spray thus obtained gave a shiny and smooth finish.It also demonstrated a good dispersibility of powder duringapplication and made hair shiny and easy to comb. Example 13: Roll-on Antiperspirant
    [0134] Components wt% 1. Crosslinked polyether-modified silicone 20.0 2. Dimethylpolysiloxane (6 mm2 / sec at 25 degrees 10.0 C) 3. Crosslinked dimethylpolysiloxane 14.3 4. Decamethylcyclopentasiloxane 30.0 5. Alternating copolymer 4 0.5 6. Organo-modified Bentonite 0.2 7. Aluminum Zirconium Tetrachlorohydrate 20.0 8. Zinc oxide treated with dimethylmethylhydrogen 5.0 9. Perfume q.l. (Preparation Method)
    [0135] Step 1 Components 1 -6 were mixed. Step 2 To the resulting mixture from Step 1, Components 7 -9 were added to disperse homogeneously.
    [0136] The roll-on antiperspirant spread lightly on the skin,gave a refreshed feeling, and had a non-tacky and non-greasytouch. It did not show quality change with temperature changeand with time, showing good properties for use and stability. Example 14: Cleansing Composition
    [0137] Components wt% 1. POE (10) Sorbitan monolaureate 30.0 2. Sodium chloride 1.0 3. Purified water 49.0 4. Alternating copolymer 1 20.0 Preparation MethodComponents 1 - 4 were mixed.
    [0138] The cleansing composition thus obtained was clear and had goodcompatibility with lipstick and/or foundation to show highcleansing effect. It spread well in use. After use, the skinwas moisturized and non-tacky. Example 15: Makeup Remover
    [0139] Components wt% 1. POE (6) Sorbitan Monolaureate 5.0 2. Alternating copolymer 1 5.0 3. Alternating copolymer 2 15.0 4. Ethanol 10.0 5. Glycerin 2.0 6. Dipropylene Glycol 3.0 7. Sodium Glutamate 0.5 8. Antiseptic q.l. 9. Perfume q.l. 10. Purified water 59.5 (Preparation Method)
    [0140] Step 1: Components 1 - 8 and 10 were combined and dissolvedhomogeneously. Step 2: To the resulting mixture from Step 1, Component 9 wasadded to obtain a makeup remover.
    [0141] Upon using the makeup remover thus obtained, the makeupremover was found to be compatible with cosmetics and sebum andhave good cleansing effect. It spread well in use. After use,the skin was moisturized and non-tacky. Example 16: Polyalcohol-in-Oil Emulsified Cosmetic
    [0142] Components wt% 1. Crosslinked dimethylpolysiloxane 30.0 2. decamethylcyclopentasiloxane 15.0 3. Dimethylpolysiloxane (6 mm2 / sec at 25 degrees C) 7.0 4. Alternating copolymer 3 3.0 5. Dimethyldistearylammonium hectorite 2.0 6. Antiseptic q.l. 7. Perfume q.l. 8. Sodium chloride 0.05 9. 1,3-butylene glycol 42.95 (Preparation Method)
    [0143] Step 1: Components 1 - 5 and 7 were mixed homogeneously. Step 2: Components 6, 8, and 9 were mixed. Step 3: The resulting mixture from Step 2 was added to theresulting mixture from Step 1 to emulsifyhomogeneously.
    [0144] The polyalcohol-in-oil emulsified cosmetic thusobtained was stable, spread lightly on the skin and had anon-tacky and non-greasy touch. After use, the skin wasmoisturized. Example 17: Solid Emulsified Blush of Polyalcohol-in-Oil Type
    [0145] Components wt% 1. Crosslinked dimethylpolysiloxane 5.0 2. Decamethylcyclopentasiloxane 5.0 3. Dimethylpolysiloxane (6 mm2 / sec at 25 degrees C) 19.7 4. Cetyl Isooctanoate 15.0 5. Paraffin wax (mp; 80 degrees C) 12.0 6. Alternating copolymer 3 3.0 7. Dimethyldisearylammonium hectorite 0.2 8. Powder treated for hydrophobicity 25.0 9. Antiseptic q.l. 10. Perfume q.l. 11. 1,3-Dibutylene glycol 15.0 (Preparation Method)
    [0146] Step 1: Components 1 -7 and 11 were heated to 80 degrees C tomix homogeneously. Step 2: Component 8 was added to the resulting mixture fromStep 1 and dispersed homogeneously. Step 3: Components 9, 10, and 12 were heated to 80 degrees Cand the resulting mixture was added to the mixture fromStep 2 to pour into a metal plate to cool down.
    [0147] The solid emulsified blush of polyalcohol-in-oil was stable,spread lightly on the skin, and had a non-tacky and non-greasytouch. After use, the skin was moisturized. Example 18: Creamy Lipstick
    [0148] Components wt% 1. Palmitic acid / dextrin ethylhexanoate 9.0 2. Glyceryl triisooctanoate 22.0 3. Bentonite 0.7 4. Alternating copolymer 4 1.5 5. M3T-C6 42.0 6. 1,3-butylene glycol 5.0 7. Sodium chloride 0.5 8. Purified water 19.3 9. Coloring pigment q.l. (Preparation Method)
    [0149] Step 1: Portions of Components 1 and 2 and Components 3 - 5were mixed to dissolve. Step 2: To the rest of Component 2, Component 9 was added todisperse with rollers. Step 3: To the resulting mixture from Step 2, the mixture fromStep 1 was added and mixed homogeneously. Step 4: Components 6 - 8 were mixed while heating. Step 5: The resulting mixture from Step 4 was added to themixture from Step 3 to emulsify.
    [0150] The lipstick thus obtained was a long wearing creamylipstick of w/O type, spread lightly, and had a non-tacky andnon-greasy touch. Example 19: Eye Liner
    [0151] Components wt% 1. Octamethylcyclotetrasiloxane 53.5 2. Alternating copolymer 4 3.0 3. Network silicone resin 15.0 4. Dimethylstearyammonium hectolite 3.0 5. Silicone-treated iron oxide black 10.0 6. 1,3 - butylene glycol 5.0 7. Sodium sulfate 0.5 8. Antiseptic q.l. 9. Perfume q.l. 10. Purified water 10.0 (Preparation Method)
    [0152] Step 1: Components 1 - 4 were mixed while heating, andComponent 5 was added to disperse homogeneously. Step 2: Components 6 - 9 were mixed. Step 3: While stirring, the resulting mixture from Step 2 wasadded portionwise to the resulting mixture from Step1 to obtain an eye liner.
    [0153] The eye liner thus obtained spread lightly on the skin, waseasy to draw, gave a refreshed and non-tacky feeling. It didnot show quality change with temperature change or with time,showing superior properties for use and stability. It had goodwater resistance as well as sweat resistance and the makeupcoverage lasted long. Example 20: Eye Shadow
    [0154] Components wt% 1. Decametylpentasiloxane 15.0 2. Dimethylpolysiloxane 10.0 3. Alternating copolymer 4 2.0 4. PEG(10) laurylether 0.5 5. Silicone-treated chromium oxide 6.2 6. Silicone-treated ultramarine blue1) 4.0 7. Silicone-treated titanium-coated mica1) 6.0 8. Sodium chloride 2.0 9. Propylene glycol 8.0 10. Antiseptic q.l. 11. Perfume q.l. 12. Purified water 46.3 (Preparation Method)
    [0155] Step 1: Components 1 - 4 were mixed, and Component 5 - 7 wereadded to disperse homogeneously. Step 2: Components 8 - 10 and Component 12 were dissolvedhomogeneously. Step 3: While stirring, the resulting mixture from Step 2 wasadded portionwise to the resulting mixture from Step1 to emulsify, to which Component 11 was added to obtainan eye shadow.
    [0156] The eye shadow thus obtained spread lightly on the skin,was non-greasy and non-powdery. It gave a moisturized andrefreshed feeling to the users. It also had good waterresistance, water repellency and good sweat resistance. Thecoverage lasted long. It did not show quality change withtemperature change or with time, showing superior stability. Example 21: Suntan Milky Lotion
    [0157] Components wt% 1. Emulsifier composition 6.0 2. Dimethylpolysiloxane (6 mm2 / sec at 25 degrees C) 49.0 3. 1,3-butylene glycol 5.0 4. Sodium dehydroacetate 0.2 5. Antioxidant q.l. 6. Antiseptic q.l. 7. Perfume q.l. 8. Purified water 39.8 (Preparation Method)
    [0158] Step 1 Component a was dissolved in Component c and Componentb was added. Step 2 The resulting mixture from Step 1 was stirred for anhour with a disperser and then ethanol was evaporatedwith a evaporator. Step 3 The resulting mixture from Step 2 was dried overnightat 50 degrees C to obtain an emulsified composition,Component 1. Step 4 Component 1, obtained in Step 3, was mixed withComponent 2. Step 5 Components 3 - 6 and 8 were mixed homogeneously. Step 6 Under stirring, the resulting mixture from Step 4 wasadded portionwise to the resulting mixture from Step5 to emulsify and then Component 7 was added to obtaina suntan milky lotion.
    [0159] The suntan milky lotion thus obtained spread lightlyon the skin, had a fine texture and a non-tacky and non-greasytouch, left skin moisturized, hydrated and refreshed feelingto the users, was water-proof and the coverage wore long. Itdid not also show quality change with temperature change or withtime, showing superior stability. Example 22: Suncut Cream
    [0160] Components wt% 1. Decamethylcyclepentasiloxane 17.5 2. Acrylic silicone resin / decamethylcyclopentasiloxane 12.0 3. Glyceryl triisooctanoate 5.0 4. Octyl para-methoxycinnamate 6.0 5. Cross-linked polyether-modified silicone 5.0 6. Alternating copolymer 5 1.0 7. Zinc oxide treated for lipophilicity 20.0 8. Sodium chloride 0.5 9. 1,3-butylene glycol 2.0 10. Antiseptic q.l. 11. Perfume q.l. 12. Purified water 31.0 (Preparation Method)
    [0161] Step 1: To a portion of Component 1, Component 2 was added andmixed homogeneously, to which Component 7 was addedand dispersed with a beads mill. Step 2: The rest of Component 1 and Components 3 - 6 werecombined to mix homogeneously. Step 3: Component 8 - 10 and 12 were mixed to dissolvehomogeneously. Step 4: To the resulting mixture from Step 2, the mixture fromStep 3 was added and emulsified, to which the mixturefrom Step 1 and Component 11 were added to obtain asuncut cream.
    [0162] The suncut cream thus obtained spread lightly on the skin,had a non-tacky touch, demonstrated good affinity with skin,clung tightly to the skin, and gave a shiny finish. It also exhibited a long lasting coverage and no quality change wasobserved with temperature change or with time. Example 23: Suntan Cream
    [0163] Components wt% 1. Decamethylcyclepentasiloxane 15.0 2. Dimethylpolysiloxane (6 mm2 / sec at 25 degrees C) 5.0 3. Stearyl-modified acrylic silicone 0.5 4. Alternating copolymer 4 6.0 5. Palmitic acid 0.2 6. Dimethyloctyl paraaminobenzoic acid 0.5 7. Kaoline 0.5 8. Iron oxide red 0.2 9. Iron oxide yellow 0.3 10. Iron oxide black 0.1 11. Titanium oxide coated mica 1.0 12. Sodium L-glutamate 3.0 13. 1,3-butylene glycol 5.0 14. Dioctadecyldimethyl ammonium chloride 0.1 15. Antioxidant q.l. 16. Antiseptic q.l. 17. Perfume q.l. 18. Purified water 62.1 (Preparation Method)
    [0164] Step 1: Components 1 - 7 and Components 16 - 17 were dissolvedwhile heating. Step 2: After stirring Component 15 and a portion of Component19 while heating, Components 8 - 12 were added to disperse. Step 3: Components 13 - 14 and the remaining portion ofComponent 19 were dissolved homogeneously andcombined with the resulting mixture from Step 2. Step 4: While stirring, the resulting mixture from Step 3 wasadded portionwise to the resulting mixture from Step1 to emulsify and cooled, to which Component 18 wasadded to obtain a suntan cream.
    [0165] The suntan cream thus obtained spread lightly on the skin, hada fine texture and a non-tacky and non-greasy touch, andprovided moisturized, hydrated and refreshed feeling to theusers. It also clung tightly to the skin and gave a long lastingcoverage. It did not show quality change with temperature changeor with time, such as separation or flocculation of the power,showing good stability. Example 24: Suncut Milky Lotion
    [0166] Components wt% 1. Decamethylcyclopentasiloxane 3.0 2. Dimethylpolysiloxane with a viscosity of 6 mm2 / sec) 5.0 3. Glyceryl triisooctanoate 5.0 4. Alternating copolymer 3 1.0 5. Crosslinked polyether-modified silicone 3.0 6. Titanium oxide / decamethylcyclopentasiloxane dispersion 25.0 7. Zinc oxide / decamethylcyclopentasiloxane dispersion 35.0 8. Dipropyleneglycol 3.0 9. Sodium citrate 0.5 10. Antiseptic q.l. 11. Perfume q.l. 12. Purified water 19.5 (Preparation Method)
    [0167] Step 1 Components 1 - 5 were combined to mix homogeneously. Step 2 Components 8, 10 and 12 were combined to dissolve. Step 3 To the resulting mixture from Step 1, the mixture fromStep 2 was added, and then Component 6, 7 and 11 wereadded to obtain a suncut milky lotion.
    [0168] The suncut milky lotion spread lightly on the skin, had anon-tacky touch, exhibited a good affinity with skin, clungtightly to the skin, and gave a shiny finish. The coverage lastedlong and no quality change was observed with temperature changeor with time. Example 25: Foundation
    [0169] Components wt% 1. Decamethylcyclopentasiloxane 45.0 2. Dimethylpolysiloxane with a viscosity of 6 mm2 / sec) 5.0 3. Alternating copolymer 2 1.5 4. Alternating copolymer 4 0.5 5. Hectorite modified with dimethyldistearylammonium salt 4.0 6. Titanium dioxide treated for hydrophobicity1) 10.0 7. Talc treated for hydrophobicity1) 6.0 8. Mica treated for hydrophobicity1) 6.0 9. Iron oxide red treated for hydrophobicity 1.6 10. Iron oxide yellow treated for hydrophobicity1) 0.7 11. Iron oxide black treated for hydrophobicity1) 0.2 12. Dipropylene glycol 5.0 13. Methyl paraoxybenzoate 0.3 14. 2-amino-2-methyl-1,3-propanediol 0.2 15. Hydrochloric acid 0.1 16. Perfume q.l. 17. Water 13.9 (Preparation Method)
    [0170] Step 1: Components 1 - 5 were mixed while heating andComponents 6 - 11 were added to obtain a homogeneousmixture. Step 2: Components 12 - 15 and Component 17 were dissolvedwhile heating (pH of the aqueous system: 9.0). Step 3: While stirring, the resulting mixture from Step 2 wasadded portionwise to the resulting mixture from Step1 to emulsify and cooled, to which Component 16 wasadded to obtain foundation.
    [0171] The foundation thus obtained spread lightly on the skin,had a fine texture and a non-tacky and non-greasy touch, andprovided moisturized, hydrated and refreshed feeling to theusers. The makeup coverage lasted long and it did not showquality change with temperature change or with time, showinggood stability. Example 26: Liquid Foundation
    [0172] Components wt% 1. Decamethylcyclopentasiloxane 16.0 2. Dimethylpolysiloxane with a viscosity of 6 mm2 / sec) 8.0 3. Octyl paramethoxycinnamate 3.0 4. 12-hydroxysteatic acid 1.0 5. Alternating copolymer 5 2.0 6. Fluorinated silicone 5.0 7. Spherical silicone resin powder 3.0 8. Fine particle titanium oxide treated with a fluorine compound3) 8.0 9. Mica titanium treated with a fluorine compound3) 1.0 10. Titanium oxide treated with a fluorine compound3) 5.0 11. Iron oxide red treated with a fluorine compound 0. 9 12. Iron oxide yellow treated with a fluorine compound3) 2.0 13. Iron oxide black treated with a fluorine compound3) 1.0 14. Ethanol 15.0 15. Glycerin 3.0 16. Magnesium sulfate 1.0 17. Antiseptic q.l. 18. Perfume q.l. 19. Purified water 25.1 (Preparation Method)
    [0173] Step 1: Components 7 - 13 were mixed homogeneously. Step 2: Components 1 - 6 were mixed while heating to 70 degreesC, to which the resulting mixture from Step 1 was added to obtain a homogeneous dispersion. Step 3. Components 14 - 17 and Component 19 were heated to 40degrees C and added portionwise to the resultingmixture from Step 2 to emulsify and cooled, to whichComponent 18 was added to obtain a liquid foundation.
    [0174] The foundation thus obtained spread lightly on the skin,was non-tacky, and gave a refreshed feeling to the users. Itdid not show quality change with temperature change or with time,showing superior stability. Example 27: Hair Cream
    [0175] Components wt% 1. Decamethylcyclopentasiloxane 10.0 2. Methyphenylpolysiloxane 5.0 3. Squalane 4.0 4. Network silicone resin 1.0 5. Glyceryl dioleate 2.0 6. Alternating copolymer 4 4.0 7. Sodium sorbitol sulfate 2.0 8. Sodium chondroitin sulfate 1.0 9. Sodium hyaluronate 0.5 10. Propylene glycol 3.0 11. Antiseptic 1.5 12. Vitamin E acetate 0.1 13. Antioxidant q.l. 14. Perfume q.l. 15. Purified water 65.9 (Preparation Method)
    [0176] Step 1: Components 1-6 and Components 11 - 13 were mixed whileheating. Step 2: Components 7-10 and Component 15 were mixed to dissolve. Step 3: While stirring, the resulting mixture from Step 2 wasadded portionwise to the resulting mixture from Step1 to emulsify and after cooled, Component 15 was addedto obtain a hair cream.
    [0177] The hair cream thus obtained spread lightly on the skin,demonstrated a non-tacky and non-greasy touch and gave hair amoisturized and refreshed feeling. It also had good waterresistance and repellency, and good sweat resistance and thecoverage lasted long. It showed no quality change withtemperature change or with time, showing good stability. Example 28: Hair Cream
    [0178] Components wt% 1. Dissolved silicone gum (400,000 mPa sec) 18.0 2. Silicone network resin 6.0 3. Glyceryl tri-2-ethylhexenoic acid 8.0 4. Vaseline 5.0 5. Stearyl alcohol 2.0 6. Sorbitan monoleaate 2.0 7. Alternating copolymer 4 2.0 8. Glycerol 5.0 9. Sodium chloride 0.5 10. Perfume q.l. 11. Purified water 51.5 (Preparation Method)
    [0179] Step 1 Components 1 -7 were mixed while heating. Step 2 Components 8 - 9 and 11 were mixed and stirred. Step 3 While stirring, to the resulting mixture from Step 2,the resulting mixture from Step 1 was added portionwiseto emulsify, to which Component 10 was added to obtaina hair cream.
    [0180] The hair cream thus obtained spread lightly on the skin,had a non-tacky and non-greasy touch, left moisturized,hydrated, and refreshed feeling, and gave hair shiny gloss andsmoothness. It was also found that it had a good setting effectfor hair. Example 29: Moisturizing Cream
    [0181] Components wt% 1. Decamethylcyclopentasiloxane 10.0 2. Methylphenylpolysiloxane 3.0 3. Liquid paraffin 5.0 4. Stearoxy-modified silicone 8.0 5. Alternating copolymer 4 2.0 6. Spherical organopolysilxane elastomer powder 2.5 7. Silica treated for hydrophobicity 2.0 8. Zinc Stearate 2.0 9. Vitamin E acetate 3.0 10. Polyethylene glycol 400 1.0 11. Sodium lactate 1.0 12. 1,3-butylene glycol 5.0 13. Antiseptic q.l. 14. Perfume q.l. 15. Purified water 55.5 (Preparation Method)
    [0182] Step 1 Components 1 - 5, 8, and 9 were mixed homogeneously,to which the Components 6 - 7 were added and dispersedhomogeneously. Step 2 Components 10 - 13 and 15 were combined to dissolve. Step 3 The resulting mixture from Step 2 was added portionwiseto that from Step 1 and cooled, to which Component 14was added to obtain a moisturizing cream.
    [0183] The moisturizing cream thus obtained spread lightly on the skin,had a non-tacky touch and gave skin moisturized and hydratedfeel. It did not show quality change with temperature changeor with time, showing good stability. Example 30: Hand cream
    [0184] Components % 1. Decamethylcyclepentasiloxane 30.0 2. Liquid paraffin 10.0 3. Gummy amino-modified silicone(amine equivalent weight;70000g/mol) 15.0 4. Alternating copolymer 3 4.0 5. Distearyldimethyl ammonium chloride 0.8 6. Vitamin E acetate 0.1 7. Polyethylene glycol 4000 1.0 8. Glycerin 10.0 9. Aluminum magnesium silicate 1.2 10. Antiseptic q.l. 11. Perfume q.l. 12. Purified water 27.9 (Preparation Method)
    [0185] Step 1: Components 1 and 3 were mixed to dissolve while heating,and Components 2, 4 - 6 and 10 were added while heating. Step 2: Components 7 - 9 and Component 12 were mixed underheating. Step 3: The resulting mixture from Step 2 was added portionwiseto the resulting mixture from Step 1 to emulsify andcooled, to which Component 11 was added to obtain ahand cream.
    [0186] The hand cream thus obtained spread lightly on the skin, wasnon-sticky, and gave the users a refreshing feel. It protectedskin when working with water and did not show quality changewith temperature change or with time, showing superiorstability. Example 31: O/W Cream
    [0187] Components wt% 1. Acrylic silicone resin/ decamethylpentasiloxane 10.0 2. Stearyl-modified acrylic silicone 8.0 3. Cetanol 1.0 4. Glyceryl triisostearate 5.0 5. Stearic acid 3.0 6. Glyceryl monostearate 1.5 7. Alternating copolymer 2 0.7 8. Sorbitan sesquioleate 0.5 9. Polyoxyethylene sorbitan monooleate 1.0 10. Sodium hydroxide (1% aqueous solution) 10.0 11. 1,3-butylene glycol 5.0 12. Antiseptic q.l. 13. Perfume q.l. 14. Purified water 54.3 (Preparation Method)
    [0188] Step 1: Components 1 - 9 were mixed and dissolved whileheating. Step 2: Components 10 - 12 and Component 14 were mixed andheated. Step 3: The resulting mixture from Step 2 was added to theresulting mixture from Step 1 to emulsify, to whichComponent 13 was added to obtain an O/W hand cream.
    [0189] The O/W cream thus obtained was non-tacky, spread lightly onthe skin, had a high affinity with skin, clung tightly to theskin, and gave a shiny finish. It provided a long lastingcosmetic coverage and superior stability and did not showquality change with temperature change or with time. Example 32: Milky Lotion
    [0190] Components wt% 1. Decamethylcyclopentasiloxane 15.0 2. Mehtylphenylpolysiloxane 5.0 3. Squalene 5.0 4. Pentaerythritol tetra-2-ethylhexanoate 5.0 5. Alternating copolymer 4 3.0 6. Spherical organopolysilxane elastomer powder 2.0 7. Hydrophobic silica 0.5 8. Magnesium ascorbate 1.0 9. Sodium chloride 1.0 10. Polyethylene glycol 11000 1.0 11. Propylene glycol 8.0 12. Antiseptic q.l. 13. Perfume q.l. 14. Purified water 53.5 (Preparation Method)
    [0191] Step 1: Components 1 - 5 were mixed homogeneously andComponents 6 - 7 were added to disperse homogeneously. Step 2: Components 8 - 10 were added to Component 14 to dissolve,to which a homogeneous mixture of Components 11 and12, was added. Step 3: The resulting mixture from Step 2 was added portionwiseto the resulting mixture from Step 1 to emulsify andcooled, to which Component 13 was added to obtain amilky lotion.
    [0192] The milky lotion thus obtained spread lightly on the skin, waslight and non-tacky, and did not show quality change withtemperature change or with time, showing superior stability andproperties for use. Example 33: Beautifying Liquid
    [0193] Components wt% 1. Decamethylcyclopentasiloxane 12.0 2. Glyceryl triisooctanoate 10.0 3. Alternating copolymer 4 2.0 4. Alternating copolymer 5 0.2 5. Glycerin 10.0 6. Magnesium ascorbate phosphate 3.0 7. Sodium chloride 2.0 8. Antiseptic q.l. 9. Perfume q.l. 10. Purified water 60.8 (Preparation Method)
    [0194] Step 1: Components 1 - 4 were mixed while. Step 2: Components 5 - 8 and Components 10 were heated todissolve homogeneously. Step 3: While stirring the resulting mixture from Step 2 wasadded portionwise to the resulting mixture from Step1 to emulsify to obtain a beautifying liquid.
    [0195] The beautifying liquid thus obtained spread lightly on the skin,had a fine texture and a non-tacky touch, and providedmoisturized and non-tacky feel to users. It did not show qualitychange with temperature change or with time, showing goodstability. Example 34: Antiperspirant
    [0196] Components wt% 1. Octamethylcyclopentasiloxane 30.0 2. Alternating copolymer 4 1.0 3. Polyoxyethylenesorbitan monooleate (20 E.O.) 0.5 4. Aluminum zirconium tetrachlorohydrate glycine salt 20.0 5. Purified water 48.5 (Preparation Method)
    [0197] Step 1: Components 1 and 2 were mixed. Step 2: Component 4 was dissolved in Component 5, to whichComponent 3 was added. Step 3: While stirring, the resulting mixture from Step 2 wasadded portionwise to the resulting mixture from Step1 to emulsify to obtain an antiperspirant.
    [0198] The antiperspirant thus obtained could be extendedlightly on the skin, had a non-tacky and non-greasy touch, didnot leave too much white powdery residue, and gave a refreshedfeeling to the users. It did not show quality change withtemperature change or with time, showing superior stability. Example 35: Cleansing Cream
    [0199] Components wt% 1. Dimethylpolysiloxane with a viscosity of 6 mm2 / sec) 5.0 2. Methylphenylpolysiloxane 5.0 3. Liquid paraffin 8.0 4. Jojoba oil 2.0 5. Alternating copolymer 4 2.5 6. Alternating copolymer 5 0.5 7. Dextrin fatty acid ester 0.8 8. Aluminum monostearate 0.2 9. Aluminum chloride 1.0 10. Glycerin 10.0 11. Antiseptic q.l. 12. Perfume q.l. 13. Purified water 65.0 (Preparation Method)
    [0200] Step 1 Components 1 - 8 were blended while heating. Step 2 Components 9 - 11 and 13 were dissolved while heating. Step 3 While stirring, the resulting mixture from the Step2 was added portionwise to that from Step 1 and cooled,to which Component 12 was added to obtain a cleansingcream.
    [0201] The cleansing cream thus obtained spread lightly on theskin, had a fine texture and a non-tacky and non-greasy touch, and left skin moisturized, hydrated and refreshed feeling. Italso had high cleansing effect and did not show a quality changewith temperature change and with time, showing superiorstability. Example 36 Treatment Gel
    [0202] Components wt% 1. Ethanol 20.0 2. Alternating copolymer 3 0.5 3. Glyceryl triisooctanoate 3.0 4. Stearoxy-modified silicone 2.0 5. Silicone composite powder 8.0 6. Carboxy vinyl polymer (1% aqueous solution) 20.0 7. Triethanol amine 0.2 8. Antiseptic q.l. 9. Perfume q.l. 10. Purified water 46.3 (Preparation Method)
    [0203] Step 1 Components 1 - 5 were combined and dispersed. Step 2 Components 6 - 8 and 10 were mixed to obtain ahomogeneous mixture. Step 3 The resulting mixture from the Step 1 was added to thatfrom the Step 2, to which Component 8 was added to mixhomogeneously.
    [0204] The treatment gel thus obtained spread lightly on the skin, hada non-tacky and non-greasy touch, and left skin moisturized,hydrated and refreshed feeling. It also had high affinity with skin and did not show quality change with temperature changeor with time, showing superior stability. Example 37: Wash-off Pack
    [0205] Components wt% 1. Dimethylpolysiloxane with a viscosity of 6 mm2 / sec) 3.0 2. Alternating copolymer 2 2.0 3. Kaolin 30.0 4. Carboxy vinylpolymer 0.4 5. 1,3-butylene glycol 10.0 6. Glycerin 20.0 7. Triethanolamine 0.4 8. Antiseptic q.l. 9. Perfume q.l. 10. Purified water 34.2 (Preparation Method)
    [0206] Step 1 Components 1, 2 and 8 were mixed. Step 2 Components 4 - 7 and 10 were mixed homogeneously andthen Component 3 was added to mix. Step 3 To the resulting mixture from Step 2, that from Step1 was added to emulsify, to which Component 9 was addedto obtain a paste of wash-off pack.
    [0207] The wash-off pack thus obtained spread lightly on the skin, washighly effective in washing the skin, and left skin moisturized,non-tacky, and smooth feels after washing off. It had goodproperties for use and superior stability. Example 38: Deodorant
    [0208] Components wt% 1. Decamethylcyclopentasiloxane 12.0 2. Dimethylpolysiloxane with a viscosity of 6 mm2 / sec) 4.0 3. Alternating copolymer 4 1.0 4. Propylene glycol 31.0 5. Triclosan 0.1 6. Glycerin 15.0 7. Antiseptic q.l. 8. Perfume q.l. 9. Purified water 36.8 (Preparation Method)
    [0209] Step 1: Components 1 - 3 were mixed. Step 2: Components 5 was dissolved in Component 4, and thenComponents 6 - 9 were mixed. Step 3: Under a vigorous stirring, the resulting mixture fromStep 2 was added to the resulting mixture from Step1 to emulsify. Step 4: 65 parts by weight of the resulting mixture from Step3 and 35 parts by weight of a propellant (a mixtureof n-butane, isobutane, and propane) were put in anaerosol can to obtain a deodorant.
    [0210] The deodorant thus obtained demonstrated no sagging when usedat a high concentration and was non-tacky and light. Itprovided a long lasting effect, showing good properties for use. Example 39: O / W / O Milky Lotion
    [0211] Components wt% 1. Cross-linked polyether-modified silicone) 3.0 2. Alternating copolymer 5 1.0 3. Gryceryl trioctanoate 14.0 4. Cross-linked alkyl-modified silicone compound 5.0 5. Sucrose monostearate 3.0 6. Glycerin 5.0 7. 1,3-butylene glycol 5.0 8. Antiseptic q.l. 9. Purified water 60.0 10. Macadamia nut oil 2.0 11. Cetyl alcohol 2.0 12. Perfume q.l. (Preparation Method)
    [0212] Step 1 Components 1 - 4 were mixed homogeneously. Step 2 Components 5 - 9 were mixed while heating to obtaina homogeneous mixture. Step 3 Components 10 -12 were mixed while heating. Step 4 The resulting mixture from Step 3 was added to thatfrom Step 2 while stirring to emulsify and cool. Step 5 The resulting mixture from Step 4 was added to thatfrom Step 1 while stirring to emulsify.
    [0213] The milky lotion thus obtained spread lightly on the skin,had a non-tacky and non-greasy touch, and gave a transparentfinish. The coverage wore long and it did not show quality changewith temperature change or with time. It was a superior O / W/ O type milky lotion with good properties for use and stability. Example 40: O / W / O Type Liquid Foundation
    [0214] Components wt% 1. Cross-linked polyether-modified silicone 4.0 2. Alternating copolymer 4 1.0 3. Propylene glycol decanoate 5.0 4. Isopropyl myristate 5.0 5. Pigment 10.0 6. Hydrogenated phospholipid from egg yolk 1.0 7. Glycerin 2.0 8. 1,3-butylene glycol 10.0 9. Antiseptic q.l. 10. Purified water 52.0 11. Squalane 5.0 12. Cetyl alcohol 5.0 13. Perfume q.l. (Preparation Method)
    [0215] Step 1 Components 1 -4 were mixed homogeneously. Step 2 Components 5 - 10 were mixed while heating to obtaina homogeneous mixture. Step 3 Components 11 - 13 were mixed while heating. Step 4 The resulting mixture from Step 3 was added to thatfrom Step 2 while stirring to emulsify and cool. Step 5 The resulting mixture from Step 4 was added to thatfrom Step 1 while stirring to emulsify.
    [0216] The liquid foundation thus obtained spread lightly on the skin,had a non-tacky and non-greasy touch and gave a transparentfinish. It gave a long lasting coverage and no quality changewas observed with temperature change and with time. It was asuperior O / W / O type liquid foundation with good propertiesfor use and stability. Example 41: W/O Type Cream
    [0217] Components wt% 1. Alkyl-modified crosslinked polyether-modified silicone 6.0 2.Liquid paraffins 13.5 3.Macadamia nuts oil 4.0 4.Alternating copolymer 5 1.5 5.Sodium citrate 0.2 6.Propylene glycol 8.0 7.Glycerol 3.0 8.Antiseptics q.l. 9.Perfume q.l. 10. Purified water 60.8 (Preparation Procedures)
    [0218] Step 1: Components 1 to 4 were mixed. Step 2: Components 5 to 10 were mixed to dissolve and theresulting mixture was added to the mixture obtained in Step 1. The resulting mixture was emulsified.
    [0219] The cream thus obtained was found to be non-tacky,non-oily, lightly extendable, to have an affinity the skin,cling to skin, gives shiny finish. It could also provide coolfeeling for skin. Example 42: W/O Type Cream
    [0220] Components wt% 1. Alkyl-modified crosslinked polyether-modified silicone 7.0 2.Liquid paraffins 13.5 3.Macadamia nuts oil 5.0 4.Alternating copolymer 5 0.5 5.Composite powder of hybrid silicone 3.0 6.Sodium citrate 0.2 7.Propylene glycol 8.0 8.Glycerol 3.0 9.Antiseptics q.l. 10.Perfume q.l. 11. Purified water 59.8 Preparation method
    [0221] Step 1:Components 1 to 5 were mixed. Step 2:Components 6 to 11 were mixed to dissolve and theresulting mixture was added to the mixture obtained in Step 1. The resulting mixture was emulsified.
    [0222] The cream thus obtained was found to be non-tacky, non-oily,lightly extendable, to have an affinity the skin, cling to skin,gives mat finish. It could also provide cool feeling for skin. Example 43: O/W Type Cream
    [0223] Components wt% 1.Crosslinked dimethylpolysiloxane 8.0 2.Crosslinked methylphenylpolysiloxane 2.0 3.Isotridecyl isononanate 5.0 4.Dipropylene glycol 7.0 5.Glycerol 5.0 6.Methylcellulose(2% aqueous solution) 7.0 7.Polyacrylamide emulsifier 2.0 8.Alternating copolymer 1 0.5 9.Guanine 1.0 10.Antiseptics q.l. 11.Perfume q.l. 12. Purified water 62.5 (Preparation method)
    [0224] Step 1:Components 4 to 11 were mixed. Step 2 : Components 1 to 3 were mixed to dissolve and the resultingmixture was added to the mixture obtained in Step 1 to emulsify.
    [0225] The cream thus obtained was found to have a fine texture,moisturized feel and be non-tacky, non-oily, lightly extendable,and cling to skin to gives a mat finish. It could also providecool feeling for skin. Example 44: W/O Cream
    [0226] Components % 1.Crosslinked polyglycerol-modified siloxane 7.0 2.Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 10.0 3.Alternating copolymer 4 0.5 4.Dipropylene glycol 10.0 5.Sodium citrate 0.2 6.Ethanol 5.0 7.Antiseptics q.l. 8.Perfume q.l. 9. Purified water 67.8 (Preparation method)
    [0227] Step 1:Components 1 to 3 were mixed while heating. Step 2:Components 4 to 10 were mixed to dissolve and the resulting mixture was added to the mixture obtained in Step 1to emulsify.
    [0228] The cream thus obtained was found to give non-tacky, non-oilyfeel. It extended lightly to give a moisturized feel. It clungto the skin to gives a cool feeling and mat finish. Example 45: W/O Makeup Base
    [0229] Components wt% 1.Crosslinked polyether-modified siloxane 5.0 2.Crosslinked dimethylpolysiloxane 1.0 3.Alternating copolymer 4 0.5 4.Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 6.0 5.Dimethylpolysiloxane(20 mm2/sec, 25 degrees C) 2.0 6.Decamethylpenatsiloxane 3.0 7.Titanium oxide dispersed in cyclopentasiloxane 10.0 8.Dipropylene glycol 5.0 9. Sodium citrate 0.2 10.Methylcellulose(2% aqueous solution) 2.5 11.Ethanol 3.0 12.Antiseptics q.l. 13.Perfume q.l. 14. Purified water 62.8 (Preparation method)
    [0230] Step 1:Components 1 to 7 were mixed while heating. Step 2:Components 8 to 15 were mixed to dissolve and theresulting mixture was added to the mixture obtained in Step 1to emulsify.
    [0231] The cream thus obtained was found to be non-tacky, non-oily.It was extended lightly, cling to skin to gives a cool feelingand mat finish. In addition, the applied cream have a UVprotection effect and lasted long. Example 46: O/W Type Cream
    [0232] Components wt% 1.Alkyl-crosslinked dimethylpolysiloxane) 2.0 2.Crosslinked dimethylpolysiloxane 15.0 3.Decamethylpentasiloxane 10.0 4. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 18.0 5. Alternating copolymer 1 0.7 6.Propylene glycol 3.0 7.Polyacrylamide mixture 0.8 8. Xanthan gum(2% aqueous solution) 8.0 9.Antiseptics q.l. 10.Perfume q.l. 1. Purified water 42.5 (Preparation method)
    [0233] Step 1:Components 1 to 4 were mixed while heating. Step 2:Components 8 to 15 were mixed to dissolve and theresulting mixture was added to the mixture obtained in Step 1to emulsify.
    [0234] The cream thus obtained had a fine texture and extended lightlyon the skin to give an non-tacky, non-oily, and moisturized feel.The applied cream lasted long. The quality of the cream did notchange with temperature change and with time. Example 47: Powder Foundation
    [0235] Components wt% 1.Vaseline 2.5 2.Squalane 3.0 3. Alternating copolymer 5 0.5 4. Glyceryl trioctanoate 2.0 5. Mica treated with silicone 40.0 6. Talc treated with silicone Balance 7. Titanium oxide treated with silicone 10.0 8. Titanium oxide fine powder treated with silicone 5.0 9. Barium oxide treated with silicone 10.0 10.Pigment q.1. 11. Phenyl-modified hybrid silicone composite powder 2.0 12.Silicone powder 2.5 13.Antiseptics q.l. 14.Perfume q.l. (Preparation Procedures)
    [0236] Step 1: Components 4 to 13 were mixed to be homogeneous. Step 2: Components 1 to 3 were mixed and the resulting mixturewas added to the mixture obtained in Step 1. Step 3: To the mixture obtained in Step 2, component 14 was addedand the resulting mixture was pressed in a mold to prepare afoundation.
    [0237] The foundation thus obtained was found to have a finetexture with non-tacky touch and spread lightly. It had anaffinity to the skin and clung to the skin to give a shiny finish. Example 48: Cream Foundation
    [0238] Components wt% 1.Crosslinked polyether-modified silicone 5.0 2. Alternating copolymer 3 0.5 3. Glyceryl trioctanoate 4.0 4. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 5.0 5. Decamethylpentasiloxane 6.0 6.Phenyl-modified hybrid silicone composite powder 2.5 7.Pigment 8.0 9. Acrylic silicone resin 5.0 9. Dipropylene glycol 5.0 10.Sodium citrate 0.2 11.Antiseptics q.l. 12.Perfume q.l. 13.Purified water 59.3 (Preparation Procedures)
    [0239] Step 1: Components 1 to 6 were mixed while heating. Step 2: Components 9 to 13 were mixed to dissolve and theresulting mixture was added to the mixture obtained in Step 1. Step 3: To the mixture obtained in Step 2, components 7 and 8were added and homogeneously mixed.
    [0240] The cream foundation thus obtained was found to have annon-tacky touch and spread lightly. It had an affinity to the skin and clung to the skin to give a mat finish. Example 49: W/O Compact Foundation
    [0241] Components wt% 1. Ceresin wax 5.5 2.Microcrystalline wax 1.0 3.Liquid paraffin 3.0 4.Alkyl-crosslinked dimethylpolysiloxane 9.0 5. Polypropylene glycol Dicaprate 3.0 6.Alternating copolymer 5 1.0 7.Dimethylpolysiloxane (6 mm2/sec, 25 degrees C) 15.5 8.Titanium oxide treated with oil 10.0 9.Pigment q.l. 10.Lecithin 0.3 11. Polyoxyethylene sorbitan monooleate 0.5 12.Dipropylene glycol 8.0 13.Sodium citrate 0.2 14. Purified water Balance (Preparation method)
    [0242] Step 1:Components 1 to 7 were mixed while heating. Step 2:Components 8 to 12 were homogeneously mixed. Step 3:Components 13 and 14 were mixed, to which the mixtureobtained in Step 2 was added and heated to be homogeneous. Step 4: The mixture obtained in Step 3 and the mixture obtainedin Step 2 were added and emulsified.
    [0243] The compact foundation thus obtained was found to be non-tacky,non-oily in spite of a relatively large amount of oilycomponents. It extended lightly, clung to the skin to gives acool feeling. The applied foundation lasted long. Example 50: Eye shadow
    [0244] Components wt% 1. Cerisite 40.0 2. Mica 10.0 3. Talc Balance 4. Titanium dioxide 10.0 5. Titanium dioxide fine powder 5.0 6. Magnesium stearate 3.0 7. Pigment q.1. 8. Octyldodecanol 3.0 9. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 4.0 10. Alternating copolymer 5 6.0 11.Antiseptics q.l. 12.Perfume q.l. (Preparation method)
    [0245] Step 1:Components 8 to 11 were mixed while heating. Step 2: The mixture of components 1 to 7 were made to which themixture obtained in Step 1 was added to make a homogeneousmixture.
    [0246] The eye shadow thus obtained was found to be non-tacky, non-oily.It spreads lightly on the skin, clung to the skin to give a shinyfinish. The applied eye shadow lasted long. Example 51: Powder Eyebrow
    [0247] Components wt% 1.Vaseline 2.5 2. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 1.5 3. Alternating copolymer 5 0.5 4. Glyceryl trioctanoate 4.0 5. Mica treated with silicone 40.0 6. Talc treated with silicone Balance 7. Titanium oxide treated with silicone 10.0 8. Barium oxide treated with silicone 15.0 9. Pigment treated with silicone q.1. 9. Hybrid silicone composite powder 1.5 12.Spherical polymethylsylsesquioxane powder 2.5 13.Antiseptics q.l. 14.Perfume q.l. (Preparation Procedures)
    [0248] Step 1: Components 5 to 12 were mixed to make a homogeneousmixture. Step 2: Components 1 to 3 were mixed and the resulting mixturewas added to the mixture obtained in Step 1. Step 3: To the mixture obtained in Step 2, component 13 was addedand the resulting mixture was pressed in a mold to prepare apowder eyebrow.
    [0249] The eyebrow thus obtained was found to be non-tacky. It spreadlightly and clung to the skin to give a shiny finish. The appliedeyebrow lasted long. Example 52: Hair cream
    [0250] Components wt% 1. Alternating copolymer 4 2.0 2. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 5.0 3. Decamethylcyclopentasiloxane 8.0 4. Stearyltrimethylammonium chloride 1.5 5. Glycerol 3.0 6. Propylene glycol 5.0 8. Hydroxyethyl cellulose 0.2 9.Antiseptics q.l. 10.Perfume q.l. 11.Purified water 75.3 (Preparation Procedures)
    [0251] Step 1: Components 1 to 3 were mixed while heating. Step 2: Components 4 to 8 and 10 were mixed to make a homogeneousmixture. Step 3: To the mixture obtained in Step 2, the mixture obtainedin Step 1 was added to make an emulsion. After cooling theemulsion, component 9 was added.
    [0252] The hair cream thus obtained spread lightly to make the hairsoft, smooth, easy to arrange, moisturized and shiny. Example 53: Conditioning Mousse
    [0253] Components wt% 1. Alternating copolymer 3 0.5 2. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 2.0 3. Crosslinked dimethylpolysiloxane 0.5 4. Glyceryl trioctanoate 1.5 5. Glycerol 3.0 6. Stearyldimethylbenzylammonium chloride 0.5 7. Polyoxyethylene hardened castor oil 0.5 8. Ethanol 7.0 9.Antiseptics q.l. 10.Perfume q.l. 11.Purified water 75.3 12.Liquified petroleum gas 5.0 (Preparation Procedures)
    [0254] Step 1: Components 1 to 4 were mixed while heating. Step 2: Components 5 to 9 and 11 were mixed to make a homogeneousmixture. Step 3: To the mixture obtained in Step 2, the mixture obtainedin Step 1 was added to make an emulsion. After cooling theemulsion, component 10 was added. Step 4: The mixture obtained in Step 3 was packed in a cancontaining aerosol.
    [0255] The mousse thus obtained gave moisturized, soft, smooth andnon-greasy touch. It had an affinity to the hair and clung tothe hair to give mat finish. Example 54: W/O Type Antiperspirant
    [0256] Components wt% 1. Crosslinked polyether modified silicone 8.0 2. Alternating copolymer 3 1.0 3. Decamethylcyclopentasiloxane 7.0 4. Glyceryl trioctanoate 8.0 5. 1,3-butylene glycol 5.0 6. Sodium citrate 0.2 7. Aluminum cholohydrate 20.0 8.Perfume q.l. 9.Purified water 50.8 (Preparation Procedures)
    [0257] Step 1: Components 1 to 4 were mixed while heating. Step 2: A mixture of Components 5,6, and 9 were made to whichcomponents 7 and 8 were added and dissolved. Step 3: To the mixture obtained in Step 2, the mixture obtained in Step 1 was added to make an emulsion.
    [0258] The antiperspirant thus obtained spread lightly to giverefreshed, cool, non-tacky, and non-greasy touch. It did notchange with time or temperature. Example 55: W/O Type UV Cut Cream
    [0259] Components wt% 1. Silicone treated zinc oxide 20.0 2. Acrylic silicone resin 12.0 3. Decamethylcyclopentasiloxane 20.0 4. Glyceryl trioctanoate 3.0 5. Crosslinked polyether modified silicone 7.0 6. Polyether modified silicone 1.0 7. Alkyl/polyether-modified silicone 0.5 8. Alternating copolymer 5 0.5 9. Methoxy octylcinnamete 6.0 10.Sodium citrate 0.2 11. Dipropylene glycol 3.0 12.Antiseptics q.l. 13.Perfume q.l. 14.Purified water 26.8 (Preparation Procedures)
    [0260] Step 1: A part of component 1 and components 4 to 9 were mixedwhile heating. Step 2: A mixture of components 10to 12 and 14 were made whichmixture was added to the mixture obtained in Step 1 to make anemulsion. Step 3: To the emulsion obtained in Step 2, components 1,2, therest of component 3 and component 13 were added to make ahomogeneous mixture.
    [0261] The UV cut cream thus obtained spread lightly to give refreshed,cool, non-tacky touch. It gave a transparent finish which lastedlong. In addition, it did not change with time or temperature. Example 56: W/O Type UV Cut Milky Lotion
    [0262] Components wt% 1. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 5.0 2. Glyceryl trioctanoate 2.0 3. Crosslinked polyglycerol-modified silicone 6.0 4. Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone 0.5 5. Alternating copolymer 3 0.5 6.Titanium dioxide dispersed in decamethylcyclopentasiloxane 30.0 7.Zinc oxide dispersed in decamethylcyclopentasiloxane 30.0 8.Dipropylene glycol 3.0 9.Sodium citrate 0.2 10.Antiseptics q.l. 11.Perfume q.l. 12.Purified water 22.8 (Preparation procedures)
    [0263] Step 1: Components 1 to 5 were mixed while heating. Step 2: A mixture of components 8 to 10 and 12 were made whichmixture was added to the mixture obtained in Step 1 to make anemulsion by stirring. Step 3: To the emulsion obtained in Step 2, components 6, 7, and11 were added to make a homogeneous mixture.
    [0264] The UV cut milky lotion thus obtained spread lightly to giverefreshed, non-tacky and non-greasy touch. It gave atransparent finish which lasted long. In addition, it did notchange with time or temperature. Example 57: W/O/W Type Cream
    [0265] Components wt% 1.Cetyl isooctanoate 5.0 2.Crosslinked polyether-modified silicone 6.0 3.Alternating copolymer 4 0.5 4.Decamethylcyclopentasiloxane 4.5 5.Mthylglucose dioleate 1.5 6.Isohexadecane 3.5 7.Magnesium sulfate 0.5 8.Propylene glycol 5.0 9.Purified water 39.5 10.Cetylalcohol 1.0 11.PEG-10 Soya seterol 2.0 12.Antiseptics q.l. 13.Perfume q.l. 14.Purified water 131.0 (Preparation procedures)
    [0266] Step 1: Components 7 to 9 were mixed. Step 2: A mixture of components 1 to 6 were made which mixturewas added to the mixture obtained in Step 1 to make an emulsionby stirring. Step 3: A mixture of components 10 to 12 and 14 were made towhich the emulsion obtained in Step 2 was added to make anemulsion. Step 4: To the emulsion obtained in Step 3, component 13 wasadded to make a homogeneous mixture.
    [0267] The cream thus obtained spread lightly to give refreshed,non-tacky and non-greasy touch. It gave a transparent finishwhich lasted long. In addition, it did not change with time ortemperature. Example 58: W/O Type Cream
    [0268] Components wt% 1. Alkyl crosslinked polyglycerol-modified siliconel 3.0 2.Alkyl Crosslinked dimethylpolysiloxane 2.0 3.Alkyl/polyclycerol-modified silicone 0.5 4.Alternating copolymer 5 0.5 5.Squalane 14.0 6.Macadamia nuts oil 3.0 7.Hybrid silicone composite powder 2.0 8.Sodium citrate 0.2 9. Sodium chloride 0.5 10.Dipropylene glycol 8.0 11.Glycerol 4.0 12.Antiseptics q.l. 13.Perfume q.l. 14. Purified water 62.3 (Preparation procedures)
    [0269] Step 1:Components 1 to 7 were mixed. Step 2:Components 8 to 14 were mixed. Step 3: The mixture obtained in Step 2 was added to the mixtureobtained in Step 1 and emulsified by stirring.
    [0270] The cream thus obtained was found to be non-tacky, non-oily, andspread lightly to give refreshed feeling. It clung to skin togive mat finish. Example 59: W/O Type Cream
    [0271] Components wt% 1. Crosslinked polyglycerol-modified silicone 5.0 2. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 11.5 3. Alternating copolymer 4 0.5 4.Dipropylene glycol 10.0 5.Sodium citrate 0.2 6.Sodium chloride 0.5 7.Ethanol 5.0 8.Antiseptics q.l. 9.Perfume q.l. 10. Purified water 67.3 (Preparation procedures)
    [0272] Step 1: Components 1 to 3 were mixed. Step 2: Components 4 to 10 were mixed which was then added tothe mixture obtained in Step 1 to make an emulsion by stirring.
    [0273] The cream thus obtained spread lightly to give refreshed,non-tacky and non-greasy touch. It had an excellent affinityto the skin to moisturized the skin. Example 60: W/O Type Milky Lotion
    [0274] Components wt% 1. Polyether-modified silicone 1.5 2. Alternating copolymer 3 0.5 3. Dextrin fatty acid ester 0.2 4. Stearic acid ester of fructo-oligosaccharide 1.8 5. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 6.0 6.Decamethylcyclopentapolysiloxane 22.0 7.1,3-butylene glycol 7.0 8.Sodium citrate 0.2 9.Ethanol 5.0 10.Antiseptics q.l. 11.Perfume q.l. 12. Purified water 55.8 (Preparation Procedures)
    [0275] Step 1: Components 1 to 6 were mixed while heating. Step 2: A mixture of components 7 to 12 were made which mixturewas added to the mixture obtained in Step 1 to make an emulsionby stirring.
    [0276] The milky lotion thus obtained was non-tacky and non-greasy.It spread lightly and clung to the skin to give refreshed andmoisturized feel. Example 61: O/W Cream
    [0277] Components wt% 1. Alternating copolymer 1 2.0 2. Crosslinked dimethylpolysiloxane 28.0 3.Decamethylcyclopentasiloxane 10.0 4. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 5.0 5.Polyglycerol-modified silicone 0.7 6. 1,3-butylene glycol 3.0 7.Polyacrylamide type mixture 0.8 8. Polyoxyethylene hardened castor oil 0.5 9.Water soluble polymer(5% aqueous solution) 10.0 10. Sodium chloride 0.1 11.Antiseptics q.l. 10.Perfume q.l. 11.Purified water 39.9 (Preparation Procedures)
    [0278] Step 1: Components 1 to 4 were mixed. Step 2: Components 5 to 13 were mixed to make a solution. Step 3: To the solution obtained in Step 2, the mixture obtainedin Step 1 was added to make an emulsion by stirring.
    [0279] The cream thus obtained had fine texture and spread lightly onthe skin to give non-tacky, non-greasy, moisturized andrefreshed feeling. The applied cream lasted long. The cream didnot change with time or temperature. Example 62: Lipstick
    [0280] Components wt% 1. Candelilla wax 4.0 2. Polyethylene wax 2.0 3.Microcrystalline wax 3.0 4.Ceresin 7.0 4. Acrylate / dimethylsilicone copolymer 15.0 5. Alternating copolymer 5 0.5 6. Polyglycerol-modified silicone 2.0 7.Hydrogenated polyisobutene 15.0 8.Maleic acid diisostearate 12.0 9. Macadamia nut oil 30.0 10. Isotridecyl isononanate 10.0 11. Glyceryl triisostearate 4.0 12. Pigment q.l. 13. Antiseptic q.l. 16. Perfume q.1. (Preparation procedures)
    [0281] Step 1 Components 1 - 10 and 13 were mixed while heating to melt. Step 2 Components 11 and 12 was mixed to make a homogeneousmixture. Step 3: Component 14 and the mixture obtained in Step 2 wereadded to the melt obtained in Step 1 to make homogeneousmixture which was molded.
    [0282] The lipstick thus obtained spread lightly on the lips to givea non-tacky, non-powdery and moisturized feel. The appliedlipstick had good water resistance and water repellency andlasted long. Example 63: Liquid Foundation
    [0283] Components wt% 1.Crosslinked polyether-modified silicone 3.0 2.Alternating copolymer 4 0.5 3.Crosslinked dimethylpolysiloxane 5.0 4.Polyether-modified silicone 1.0 5. Clay minerals modified with organic compounds 1.2 6. Glyceryl trioctanoate 5.0 7. Dimethylpolysiloxane(6 mm2/sec, 25 degrees C) 6.5 8.Decamethylcyclopentasiloxane 21.6 9.Pigment treated with organopolysiloxane 10.0 10.Acrylic silicone resin 1.5 11.Dipropylene glycol 5.0 12.Sodium citrate 0.2 13. Antiseptic q.l. 14. Perfume q.l. 15. Purified water 59.3 (Preparation procedures)
    [0284] Step 1: Components 1 to 6, a part of component 7 and 8 weremixed. Step 2: The rest of component 7 and 8, components 9, and 10were mixed. Step 3: Components 11 to 15 were mixed to make a solution. Step 4: The solution obtained in Step 3 was added to the mixtureobtained in Step 1 to make an emulsion by stirring. Step 5: The mixture obtained in Step 2 was added to the emulsionobtained in Step 4 to make a homogeneous mixture.
    [0285] The foundation thus obtained was non-tacky and spreadlightly on the skin to give a mat and stable finish clung tothe skin. Example 64: Creamy Eye shadow
    [0286] Components wt% 1. Acrylate / dimethylsilicone copolymer 10.0 2. Acrylate / dimethylsilicone copolymer 2.0 3. Alternating copolymer 4 0.3 4.Polyglycerol-modified silicone) 1.5 5.Decamethylcyclopentasiloxane 20.0 6. Clay minerals modified with organic compounds 1.2 7. Cetyl isooctanoate 3.0 8. Polyamide 3.0 9. Talc 4.0 10.Pigment treated with acrylic silicone resin 20.0 11. Ethanol 5.0 12.Purified water 30.0 (Preparation method)
    [0287] Step 1:Components 1 to 10 were mixed. Step 2:A mixture of components 10 and 11 was made which was addedto the mixture obtained in Step 1 to make a homogeneous mixture.
    [0288] The eye shadow thus obtained was non-tacky and spread lightlyon the skin to give a shiny finish which clung to the skin andlasted long. Example 65: Wrinkle Cover Cream
    [0289] Components wt% 1. Crosslinked polyether-modified silicone 5.0 2.Crosslinked dimetylpolysiloxane 55.0 3.Crosslinked dimetylpolysiloxane 15.0 4.Alternating copolymer 2 2.0 5.Decamethylcyclopentasiloxane 13.0 6.Hybrid silicone composite powder 8.0 7.Spherical polymethylsylsesquioxane powder 2.0 (Preparation Procedures)
    [0290] Step 1: Components 1 to 7 were mixed to make a homogeneousmixture.
    [0291] The cream thus obtained was non-tacky and non-greasy. It gavea moisturized, mat and stable finish. INDUSTRIAL APPLICABILITY
    [0292] The organopolysiloxane/polyglycerol alternating copolymerof the present invention is clear and compatible withconventional oil agents. It is a good emulsifier, too, to givea stable emulsion. A cosmetic comprising the copolymer has goodaffinity to the skin to give a non-tacky and non-greasy touch.The applied cosmetic is durable and has a shiny finish of anexpensive-looking.
    权利要求:
    Claims (12)
    [1]
    An alternating copolymer comprising a repeating unit ofα, ω-organohydrogensiloxane residue (A) and a repeating unitof a glycerol derivative residue(B)having 1 to 11 hydroxylgroups, the copolymer having the number of a repeating unit(AB) of from 2 to 100.
    [2]
    The copolymer according to claim 1, wherein the repeatingunit (AB) is represented by the following formula (1),
    [3]
    The copolymer according to claim 2, wherein b is an integerof at least 1.
    [4]
    The copolymer according to claim 2 or 3, wherein G isrepresented by the following formula (2),
    [5]
    The copolymer according to claim 2 or 3, wherein G isrepresented by the following formula (3).
    [6]
    The copolymer according to claim 2 or 3, wherein G isrepresented by the following formula (4).
    [7]
    The copolymer according to any one of claims 2 to 6, whereinQ is a propylene group.
    [8]
    A cosmetic comprising the copolymer according to any oneof claims 1 to 7.
    [9]
    The cosmetic according to claim 8, wherein the cosmetic isa skin-care cosmetic, a hair cosmetic, an antiperspirant,a makeup cosmetic, or a UV protecting cosmetic.
    [10]
    The cosmetic according to claim 8 or 9, wherein the cosmeticis in a form of liquid, milky lotion, cream, solid, paste,gel, powder, lamella, mousse, or spray.
    [11]
    An emulsifier comprising the copolymer according to any oneof claims 1 to 7.
    [12]
    A process for preparing the copolymer according to any ofclaims 1 to 7 comprising a step of reactingα,ω-organohydrogensiloxane having an SiH bond at bothterminals with a glycerol derivative having an aliphaticunsaturated bond at both terminals.
    类似技术:
    公开号 | 公开日 | 专利标题
    US7771709B2|2010-08-10|Alternating copolymer of organopolysiloxane with grycerol derivative and a cosmetic comprising the same
    EP1065234B1|2002-11-27|Silicones for powder treatment powders having surface treated with said silicones, and cosmetic materials containing said powders
    EP1481660B1|2008-02-20|Cosmetic
    EP1062944B1|2004-03-03|Cosmetic material
    US8592547B2|2013-11-26|Organopolysiloxane, a method of preparing the same and a cosmetic comprising the same
    US9090755B2|2015-07-28|Organopolysiloxane polymer, pasty composition, and cosmetic preparation containing the composition
    US9023969B2|2015-05-05|Powder surface-treated with an organopolysiloxane having carboxyl groups, a dispersion of the same, and a cosmetic comprising the same
    US7285290B2|2007-10-23|Hydrophilized powder and a composition comprising the same
    US6790451B2|2004-09-14|Cosmetic material
    EP1072627B1|2003-03-19|Silicone compound and cosmetic materials containing the same
    US7713520B2|2010-05-11|Cosmetic comprising a silicone polymer
    EP1416016B1|2008-08-13|Powder composition, a dispersion of powder in oil, and a cosmetic preparation comprising polyglycerine modified silicone
    EP2103301B1|2013-02-13|Polyglycerin-modified silicone and a cosmetic comprising the same
    US8912354B2|2014-12-16|Organopolysiloxane and cosmetic containing the same
    EP1291376A1|2003-03-12|Silicone polymer, silicone composition, and cosmetic preparation containing the same
    EP1314415A1|2003-05-28|Cosmetics
    JP2003146832A|2003-05-21|Cosmetic
    同族专利:
    公开号 | 公开日
    EP1496080B1|2006-04-26|
    DE602004000738T2|2007-05-16|
    JP5037782B2|2012-10-03|
    US20050008600A1|2005-01-13|
    JP2005042097A|2005-02-17|
    DE602004000738D1|2006-06-01|
    US7771709B2|2010-08-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4431789A|1981-03-13|1984-02-14|Shin-Etsu Chemical Co., Ltd.|Novel organopolysiloxane having alcoholic hydroxy groups and a method for the preparation thereof|
    EP0492657A1|1990-12-28|1992-07-01|Nippon Unicar Company Limited|Cosmetic formulations|
    EP1112733A1|1999-12-08|2001-07-04|Shin-Etsu Chemical Co., Ltd.|Lipstick composition containing hydrophilic crosslinked silicone|EP1579845A2|2004-03-22|2005-09-28|L'oreal|Cosmetic composition comprising a polyglycerolated silicone elastomer|
    EP1597969A1|2004-05-19|2005-11-23|Shin-Etsu Chemical Company, Ltd.|Glycerol-modified silicone spreading agent and a composition comprising the same|
    FR2873033A1|2004-07-16|2006-01-20|Oreal|Anhydrous cosmetic composition, useful in skin care, lip care and make-up composition, comprises liquid fatty phase, gelling agent for the liquid fatty phase, and silicone polymer|
    FR2873035A1|2004-07-16|2006-01-20|Oreal|COSMETIC COMPOSITION COMPRISING A DEFINED SILICONE POLYMER AND A FILMOGENIC AGENT.|
    FR2873032A1|2004-07-16|2006-01-20|Oreal|Anhydrous cosmetic composition, useful in e.g. make-up, lipand/or skin care composition, comprises a silicone polymer in a medium|
    FR2873031A1|2004-07-16|2006-01-20|Oreal|Anhydrous cosmetic composition useful as skin care or make-up composition and lipstick comprises at least one silicone polymer and at least one surfactant, in a physiological medium|
    FR2873034A1|2004-07-16|2006-01-20|Oreal|Cosmetic composition for making up or caring for keratin materials e.g. skin and nail comprises at least one hydrocarbon ester containing less than 40 carbon atoms and at least one silicone polymer, and volatile oil|
    WO2006038933A1|2004-09-30|2006-04-13|Kimberly-Clark Worldwide, Inc.|Skin cooling compositions|
    WO2006038965A1|2004-09-30|2006-04-13|Kimberly-Clark Worldwide, Inc.|Skin cooling compositions|
    WO2007064687A1|2005-12-02|2007-06-07|The Procter & Gamble Company|Water in oil emulsion compositions containing siloxane elastomers|
    EP1795233A2|2005-12-08|2007-06-13|L'oreal|Cosmetic composition comprising an ester of dimerdilinoleic acid and polyol and a silicon containing surfactant|
    WO2007086022A2|2006-01-25|2007-08-02|The Procter & Gamble Company|Water-in-oil emulsion composition|
    WO2007133769A2|2006-05-15|2007-11-22|The Procter & Gamble Company|Water in oil emulsion compositions containing sunscreen actives and siloxane elastomers|
    DE102008032066A1|2008-07-08|2010-01-14|Byk-Chemie Gmbh|Polyhydroxy-functional polysiloxanes as anti-adhesive and dirt-repellent additives in coatings, polymeric molding compounds and thermoplastics, process for their preparation and their use|
    WO2010059466A1|2008-11-24|2010-05-27|The Procter & Gamble Company|Cosmetic compositions|
    US8080239B2|2005-01-17|2011-12-20|Shiseido Co., Ltd.|Cosmetic|
    US20120024759A1|2010-08-02|2012-02-02|Momentive Performance Materials Inc.|Compositions and methods for separating emulsions using the same|
    EP2377512A3|2010-04-14|2015-03-18|Shin-Etsu Chemical Co., Ltd.|Water-releasing cosmetic makeup material|
    CN108047452A|2017-12-20|2018-05-18|山东东岳有机硅材料股份有限公司|A kind of levelling agent super high molecular weight Siloxane-Oxyalkylene Copolymers and preparation method and application|NL134016C|1963-08-27||||
    JPH0512979B2|1986-03-18|1993-02-19|Shiseido Co Ltd||
    JP3061434B2|1990-05-07|2000-07-10|日本ユニカー株式会社|Hair cosmetics|
    JP3071222B2|1990-12-28|2000-07-31|日本ユニカー株式会社|Skin cosmetics|
    JP3283277B2|1991-12-16|2002-05-20|日本ユニカー株式会社|Organopolysiloxane composition|
    JPH0625369A|1992-05-15|1994-02-01|Nippon Paint Co Ltd|Aqueous silicone-modified resin|
    JP3389271B2|1992-11-13|2003-03-24|株式会社コーセー|Cosmetics|
    JP3635127B2|1994-07-08|2005-04-06|日本ペイント株式会社|Block polymer and method for producing the same, surface modifier, coating material composition, multilayer coating film and method for forming multilayer coating film|
    JP3513682B2|1995-09-08|2004-03-31|信越化学工業株式会社|Oily cosmetics|
    JP3799110B2|1996-11-08|2006-07-19|東レ・ダウコーニング株式会社|Thickening agent containing silicone block alternating copolymer|
    JPH10310506A|1997-05-09|1998-11-24|Kose Corp|Low irritant cosmetic|
    JP3496133B2|1997-05-09|2004-02-09|株式会社コーセー|Modified powder and cosmetic containing it|
    JP3533554B2|1997-05-09|2004-05-31|株式会社コーセー|Powder cosmetics|
    JPH10310507A|1997-05-09|1998-11-24|Kose Corp|Oily cosmetic|
    JPH10310509A|1997-05-09|1998-11-24|Kose Corp|Hair cosmetic|
    JP3533553B2|1997-05-09|2004-05-31|株式会社コーセー|Emulsified cosmetic|
    JPH11158282A|1997-11-27|1999-06-15|Toagosei Co Ltd|Production of curable resin, and curable resin composition|
    JP5057413B2|1999-08-03|2012-10-24|東レ・ダウコーニング株式会社|Organic cross-linked particles, suspension thereof, and production method thereof|
    JP4371480B2|1999-08-03|2009-11-25|東レ・ダウコーニング株式会社|Organic cross-linked particles, their suspensions, and methods for their production|
    JP4700158B2|1999-11-16|2011-06-15|東レ・ダウコーニング株式会社|Method for producing emulsion and method for producing oil composition|
    JP2002260962A|2000-12-14|2002-09-13|Mitsubishi Paper Mills Ltd|Electric double-layer capacitor|
    JP3969728B2|2001-09-04|2007-09-05|信越化学工業株式会社|Pasty composition, cosmetic using the composition, and method for producing the composition|
    EP1550687B1|2002-09-12|2012-05-23|Shin-Etsu Chemical Company, Ltd.|Novel organopolysiloxane polymer, pasty composition, and cosmetic preparation containing the composition|
    JP2004169015A|2002-11-01|2004-06-17|Shin Etsu Chem Co Ltd|Powder composition, powder dispersion in oil and cosmetic containing them|ES2486790T3|2005-01-17|2014-08-19|Shin-Etsu Chemical Co., Ltd.|Cosmetic|
    JP4567585B2|2005-01-17|2010-10-20|株式会社資生堂|Cosmetics|
    JP5043304B2|2005-03-15|2012-10-10|株式会社コーセー|Gel composition and cosmetic containing the same|
    JP4777813B2|2005-03-31|2011-09-21|株式会社コーセー|Film-forming composition for cosmetics and cosmetics containing the same|
    JP4566135B2|2005-06-01|2010-10-20|株式会社資生堂|Water-in-oil type skin external composition|
    AU2006267870A1|2005-07-08|2007-01-18|The Procter & Gamble Company|Lipophilic personal care composition|
    US20070092462A1|2005-10-24|2007-04-26|Julio Gans Russ|Cosmetic compositions|
    JP4866066B2|2005-11-18|2012-02-01|花王株式会社|Cosmetics|
    JP4566124B2|2005-12-14|2010-10-20|株式会社資生堂|Water-in-oil emulsified cosmetic|
    JP4684895B2|2006-01-07|2011-05-18|日本メナード化粧品株式会社|Sunscreen cosmetics|
    EP1813262A1|2006-01-19|2007-08-01|Wella Aktiengesellschaft|Stable oil-in-water and water/oil/water multiple emulsions and hair treating compositions comprising them|
    US7790701B2|2006-04-19|2010-09-07|Gelest Technologies, Inc.|Silicon-based tocopherol derivatives|
    CN101472979B|2006-05-19|2012-01-04|陶氏康宁东丽株式会社|Polyether-modified organopolysiloxane, diorganopolysiloxane-polyether block copolymer, their production methods, and cosmetic preparation|
    DE102006031152A1|2006-07-04|2008-01-10|Byk-Chemie Gmbh|Polyhydroxy-functional polysiloxanes as anti-adhesive and dirt-repellent additives in coatings, polymeric molding compounds and thermoplastics, process for their preparation and their use|
    US8030267B2|2006-09-11|2011-10-04|Shiseido Company Ltd.|Silica composite capsules obtained by blending water-soluble silane derivative, composition containing the same, and transparent gel-form composition|
    JP4965975B2|2006-11-20|2012-07-04|花王株式会社|Water-in-oil emulsified cosmetic|
    KR101445902B1|2007-06-04|2014-09-29|더 프록터 앤드 갬블 캄파니|Multi-formulation cosmetic compositions|
    US20080311058A1|2007-06-18|2008-12-18|Connopco, Inc., D/B/A Unilever|Stable high internal phase emulsions and compositions comprising the same|
    JP2009209139A|2008-02-07|2009-09-17|Shiseido Co Ltd|Solid powder cosmetic|
    JP5307433B2|2008-03-31|2013-10-02|株式会社コーセー|High internal water phase oil-in-water emulsified cosmetic|
    US8425882B2|2008-04-01|2013-04-23|Conopco, Inc.|In-shower and bath compositions|
    JP4766720B2|2008-06-12|2011-09-07|株式会社資生堂|Oil-in-oil cosmetics|
    CN102227205A|2008-11-28|2011-10-26|花王株式会社|Hydrogel particles|
    JP5583906B2|2008-12-22|2014-09-03|東レ・ダウコーニング株式会社|Partially hydrocarbon group-blockedglycerol-modified polysiloxane, method for producing the same, and cosmetics containing the polysiloxane|
    JP2010144157A|2008-12-22|2010-07-01|Dow Corning Toray Co Ltd|Emulsified product, method for producing the same, and cosmetic raw material comprising the emulsified product|
    JP5430142B2|2008-12-22|2014-02-26|東レ・ダウコーニング株式会社|Method for producing emulsion|
    US8299127B2|2009-03-11|2012-10-30|Conopco, Inc.|Method and composition for evenly applying water soluble actives|
    EP2492300B1|2009-10-23|2018-10-03|Dow Corning Toray Co., Ltd.|Novel organopolysiloxane copolymer|
    CN102648264B|2009-10-23|2015-08-19|道康宁东丽株式会社|For thickening material or the jelling agent of the raw material based on oil|
    WO2011049248A1|2009-10-23|2011-04-28|東レ・ダウコーニング株式会社|Novel co-modified organopolysiloxane|
    JP5841311B2|2009-12-21|2016-01-13|東レ・ダウコーニング株式会社|Oily raw material thickener or gelling agent, gel composition containing the same, and method for producing cosmetic or external preparation|
    US9980897B2|2010-04-30|2018-05-29|Dow Corning Toray Co., Ltd.|Organopolysiloxane and powder treatment agent, preparation for external use and cosmetic comprising the same|
    CN102947369B|2010-04-30|2015-01-28|道康宁东丽株式会社|Organopolysiloxane and use thereof as surfactant, powder treatment agent, thickening agent of oil-based raw material or gelling agent. gel and emulsion compositions, as well as, preparations for external use and cosmetics comprising the same|
    JP5368394B2|2010-08-11|2013-12-18|信越化学工業株式会社|Novel organopolysiloxane compound and cosmetic containing the same|
    US8821839B2|2010-10-22|2014-09-02|Conopco, Inc.|Compositions and methods for imparting a sunless tan with a vicinal diamine|
    US8398959B2|2010-12-06|2013-03-19|Conopco, Inc.|Compositions and methods for imparting a sunless tan with functionalized adjuvants|
    JP5575685B2|2011-03-29|2014-08-20|信越化学工業株式会社|Organopolysiloxane and cosmetics containing the same|
    JP5795212B2|2011-07-29|2015-10-14|信越化学工業株式会社|Novel block-type organopolysiloxane and cosmetic containing the same|
    US8961942B2|2011-12-13|2015-02-24|Conopco, Inc.|Sunless tanning compositions with adjuvants comprising sulfur comprising moieties|
    JP6355224B2|2011-12-27|2018-07-11|東レ・ダウコーニング株式会社|Method for producing low-odor glycerin derivative-modified silicone or composition containing the same|
    JP6369888B2|2011-12-27|2018-08-08|東レ・ダウコーニング株式会社|Novel liquid organopolysiloxane and use thereof|
    JP6105920B2|2011-12-27|2017-03-29|東レ・ダウコーニング株式会社|Co-modified organopolysiloxane, emulsifier for water-in-oil emulsion containing the same, external preparation and cosmetic|
    JP6313540B2|2011-12-27|2018-04-18|東レ・ダウコーニング株式会社|Diglycerin derivative-modified silicone, emulsifier for water-in-oil emulsion containing the same, external preparation and cosmetic|
    US8680225B1|2012-04-02|2014-03-25|Surfatech Corporation|Terminal silicone polyglycerol polyesters|
    JP6184711B2|2012-03-30|2017-08-23|株式会社コーセー|Oily cosmetics|
    EP2940063A4|2012-12-28|2016-05-18|Dow Corning Toray Co Ltd|Manufacturing method for high-purity glycerol derivative-modified silicone|
    WO2014104257A1|2012-12-28|2014-07-03|東レ・ダウコーニング株式会社|Method for manufacturing high-purity organosilicon compound|
    JP6392669B2|2012-12-28|2018-09-19|東レ・ダウコーニング株式会社|Method for producing transparent or translucent liquid glycerin derivative-modified silicone composition|
    JPWO2015162906A1|2014-04-21|2017-04-13|東レ・ダウコーニング株式会社|Method for producing liquid high-purity polyhydric alcohol derivative-modified silicone or composition thereof|
    JP6560151B2|2016-03-28|2019-08-14|信越化学工業株式会社|Organopolysiloxane, cosmetic, and method for producing organopolysiloxane|
    WO2017169278A1|2016-03-28|2017-10-05|信越化学工業株式会社|Organopolysiloxane, cosmetic material, and method for producing organopolysiloxane|
    JP2017193529A|2016-04-14|2017-10-26|株式会社 資生堂|Cosmetic|
    JP6460504B1|2018-05-31|2019-01-30|株式会社コスモビューティー|Water-in-oil emulsion composition|
    法律状态:
    2004-11-26| PUAI| Public reference made under article 153(3) epc to a published international application that has entered the european phase|Free format text: ORIGINAL CODE: 0009012 |
    2005-01-12| AK| Designated contracting states|Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
    2005-01-12| AX| Request for extension of the european patent|Extension state: AL HR LT LV MK |
    2005-06-22| 17P| Request for examination filed|Effective date: 20050421 |
    2005-09-28| AKX| Designation fees paid|Designated state(s): DE FR GB |
    2005-10-06| GRAP| Despatch of communication of intention to grant a patent|Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
    2006-01-27| GRAS| Grant fee paid|Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
    2006-03-10| GRAA| (expected) grant|Free format text: ORIGINAL CODE: 0009210 |
    2006-04-26| AK| Designated contracting states|Kind code of ref document: B1 Designated state(s): DE FR GB |
    2006-04-26| REG| Reference to a national code|Ref country code: GB Ref legal event code: FG4D |
    2006-06-01| REF| Corresponds to:|Ref document number: 602004000738 Country of ref document: DE Date of ref document: 20060601 Kind code of ref document: P |
    2006-12-15| ET| Fr: translation filed|
    2007-03-02| STAA| Information on the status of an ep patent application or granted ep patent|Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
    2007-03-02| PLBE| No opposition filed within time limit|Free format text: ORIGINAL CODE: 0009261 |
    2007-04-04| 26N| No opposition filed|Effective date: 20070129 |
    2016-06-13| REG| Reference to a national code|Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
    2017-06-13| REG| Reference to a national code|Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
    2018-06-12| REG| Reference to a national code|Ref country code: FR Ref legal event code: PLFP Year of fee payment: 15 |
    2021-07-30| PGFP| Annual fee paid to national office [announced via postgrant information from national office to epo]|Ref country code: FR Payment date: 20210611 Year of fee payment: 18 |
    2021-08-31| PGFP| Annual fee paid to national office [announced via postgrant information from national office to epo]|Ref country code: GB Payment date: 20210609 Year of fee payment: 18 |
    2021-11-30| PGFP| Annual fee paid to national office [announced via postgrant information from national office to epo]|Ref country code: DE Payment date: 20210608 Year of fee payment: 18 |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2003192572||2003-07-07||
    JP2003192572||2003-07-07||
    JP2003194500||2003-07-09||
    JP2003194500||2003-07-09||
    JP2004189229||2004-06-28||
    JP2004189229A|JP5037782B2|2003-07-07|2004-06-28|Novel alternating organopolysiloxane-glycerin derivative copolymer and cosmetic containing the same|
    [返回顶部]