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Publication numberCN1934168 A
Publication typeApplication
Application numberCN 200580008339
PCT numberPCT/US2005/007967
Publication date21 Mar 2007
Filing date10 Mar 2005
Priority date16 Mar 2004
Also published asCN100532431C, DE602005017597D1, EP1735368A1, EP1735368B1, US20070132113, US20110262375, WO2005090444A1
Publication number200580008339.5, CN 1934168 A, CN 1934168A, CN 200580008339, CN-A-1934168, CN1934168 A, CN1934168A, CN200580008339, CN200580008339.5, PCT/2005/7967, PCT/US/2005/007967, PCT/US/2005/07967, PCT/US/5/007967, PCT/US/5/07967, PCT/US2005/007967, PCT/US2005/07967, PCT/US2005007967, PCT/US200507967, PCT/US5/007967, PCT/US5/07967, PCT/US5007967, PCT/US507967
InventorsDM欣特曼, JB霍斯特曼, LA斯塔克-卡斯莱, GM维贝尔
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Alkyl-phenyl silsesquioxane resins compositions
CN 1934168 A
Abstract  translated from Chinese
公开了一种组合物,其包含粉末和烷基-苯基倍半硅氧烷树脂。 Discloses a composition comprising a powder and alkyl - phenyl silsesquioxane resin. 这些组合物尤其可用于各种个人或医疗护理用组合物,以提高在局部施加之后粉末的耐久性和亲和性。 These compositions are particularly useful in a variety of personal or medical care composition for topical application to increase the powder after the durability and affinity.
Claims(10)  translated from Chinese
1.一种组合物,其包含:(A)粉末,和(B)烷基-苯基倍半硅氧烷树脂,其包括至少60mol%具有通式(R′SiO3/2)x(C6H5SiO3/2)y的甲硅烷氧基单元,其中x和y的数值为0.05-0.95,和R′是具有2-8个碳原子的单价烃基。 1. A composition, comprising: (A) powder, and (B) alkyl - phenyl silsesquioxane resin comprising at least 60mol% having the general formula (R'SiO3 / 2) x (C6H5SiO3 / 2) y siloxy units, wherein the numerical values of x and y is 0.05 to 0.95, and R 'is a monovalent hydrocarbon group having 2-8 carbon atoms.
2.权利要求1的组合物,其中烷基-苯基倍半硅氧烷树脂包括下述单元:(i)(R13SiO1/2)a(ii)(R22SiO2/2)b(iii)(R3SiO3/2)c(iv)(SiO4/2)d(v)(R′SiO3/2)x和(vi)(C6H5SiO3/2)y,其中R1、R2和R3独立地为具有1-8个碳原子的烷基、芳基、醇基或氨基,R′是具有2-8个碳原子的单价烃基,a、b、c和d的数值为0-0.4,x和y的数值为0.05-0.95,条件是x+y的数值等于或大于0.60,和a+b+c+d+x+y=1。 The composition of claim 1, wherein the alkyl - phenyl silsesquioxane resin comprising the units: (i) (R13SiO1 / 2) a (ii) (R22SiO2 / 2) b (iii) (R3SiO3 / 2) c (iv) (SiO4 / 2) d (v) (R'SiO3 / 2) x and (vi) (C6H5SiO3 / 2) y, wherein R1, R2 and R3 are independently having 1 to 8 carbon atoms, alkyl group, an aryl group, an alcohol group or an amino group, R 'is a monovalent hydrocarbon group having 2-8 carbon atoms, the value a, b, c and d is 0 to 0.4, x and y values of 0.05 to 0.95, the proviso that x + y is equal to or greater than the value of 0.60, and a + b + c + d + x + y = 1.
3.权利要求1的组合物,其中R′是丙基。 The composition of claim 1, wherein R 'is propyl.
4.权利要求1的组合物,进一步包含:(C)挥发性硅氧烷或有机溶剂。 The composition of claim 1, further comprising: (C) a volatile siloxane or organic solvent.
5.一种个人护理用产品,其包含权利要求1的组合物。 A personal care product comprising the composition of claim 1.
6.权利要求5的个人护理用产品,其中该个人护理用产品是化妆产品。 Personal care according to claim 5 with a product, wherein the personal care product is a cosmetic product.
7.权利要求6的个人护理用产品,其中化妆产品是口红或粉底。 Claim 6 of personal care products, wherein the cosmetic product is a lipstick or foundation.
8.一种家庭护理用产品,其包含权利要求1的组合物。 A household care product comprising the composition of claim 1.
9.一种机动车护理用产品,其包含权利要求1的组合物。 A motor vehicle with a care product, comprising the composition of claim 1.
10.一种医疗护理用产品,其包含权利要求1的组合物。 10. A medical care use product, comprising the composition of claim 1.
Description  translated from Chinese
烷基-苯基倍半硅氧烷树脂组合物 Alkyl - phenyl silsesquioxane resin composition


[0001]没有。 [0001] No.

发明领域 Field of the Invention

[0002]本发明提供含粉末和烷基-苯基倍半硅氧烷树脂的组合物。 [0002] The present invention provides a powder and alkyl-containing - compositions phenyl silsesquioxane resin. 可将本发明的组合物掺入到各种个人、家庭、机动车或医疗护理用组合物中,以便在局部施加之后提高粉末的耐久性和亲和性。 The compositions of the invention may be incorporated into a variety of personal, household, or medical care vehicle composition, so that after topical application to improve the durability of the powder and affinity.

发明背景 Background of the Invention

[0003]通式RnSiO(4-n)/2的硅氧烷树脂,其中R是烷基和n通常小于1.8,是一族重要的硅氧烷聚合物,因为它们在许多商业应用,例如粘合剂组合物和涂料应用中使用。 [0003] the general formula RnSiO (4-n) silicone resin / 2, wherein R is an alkyl group and n is generally less than 1.8, are an important family of silicone polymers because they are in many commercial applications, such as adhesion compositions and coatings used in the application. 发现被称为MQ树脂的一个特别亚组的硅氧烷树脂(因为它们主要包括通式R3SiO1/2的“M”单元和通式SiO2的“Q”单元)在化妆配方中是有用的。 Found that the silicone resin is a special subgroup called MQ resins (since they include "M" units of the formula SiO2 "Q" units of the general formula R3SiO1 / 2) is useful in cosmetic formulations. 特别地,MQ树脂常用于“延长的磨耗(extended wear)”或“抗转移(transfer resistant)”化妆配方中。 In particular, MQ resin used in the "extended wear (extended wear)" or "anti-transfer (transfer resistant)" cosmetic formulations. 在这些配方中,在施加之后,MQ树脂提高颜料或其它配方活性成分对皮肤的亲和性,从而产生更长久和因此延长的磨耗的产品。 In these formulations, after application, MQ resins enhance the pigments or other formulation of the active ingredient to the skin affinity, and thus resulting in longer extended wear product.

[0004]在US6071503、US6074654、US6139823、US6340466、WO97/17058和WO97/17059中可找到使用MQ树脂的抗转移化妆组合物的代表性实例,这些专利公开了含有机硅氧烷树脂和流体二有机硅氧烷树脂与挥发性载体的结合物的组合物。 [0004] In US6071503, US6074654, US6139823, US6340466, WO97 / 17058 and WO97 / 17059 can be found using the MQ resin transfer resistant cosmetic composition of representative examples, these patents disclose silicone containing organic resin and a two fluid silicone resin composition with a volatile carrier conjugate.

[0005]US5330747教导了使用由含三甲基甲硅烷基封端的树脂共聚物、硅烷醇封端的聚二有机硅氧烷流体和含苯基的聚硅氧烷流体的压敏粘合剂组合物得到的成膜剂,具有提高的耐久性的化妆品。 [0005] US5330747 teaches the use of a polydiorganosiloxane fluid containing copolymer resin by trimethylsiloxy-terminated, silanol-terminated and phenyl-containing polysiloxane fluid pressure sensitive adhesive composition The resulting film-forming agent, having improved durability of the cosmetic.

[0006]US5800816公开了一种具有改进的抗转移的化妆组合物,其包含:a)约0.1-60wt%三甲基化氧化硅,b)约0.1-60wt%在25℃下粘度为0.5-100厘泊的挥发性溶剂,c)0.1-60wt%在25℃下粘度为200-1,000,000厘泊的非挥发性油,d)0.1-80wt%的化妆品可接受的载体。 [0006] US5800816 discloses a cosmetic composition having improved transfer resistance comprising: a) from about 0.1-60wt% trimethylated silica, b) from about 0.1-60wt% at a viscosity of 0.5 to 25 ℃ volatile solvent 100 centipoise, c) 0.1-60wt% at 25 ℃ under non-volatile oil having a viscosity of 200-1,000,000 centipoise, d) 0.1-80wt% of a cosmetically acceptable carrier.

[0007]US5837223和US6036947教导了抗转移高光泽的化妆棒状组合物,其包含以组合物的总重量计,a)10-70%在25℃下粘度为0.5-20厘泊的挥发性溶剂,b)0.5-40%的guerbet酯,和c)0.1-20%的甲硅烷氧基硅酸酯聚合物。 [0007] US5837223 and US6036947 teach transfer resistant high luster cosmetic stick composition, comprising the composition total weight, a) 10-70% at 25 ℃ viscosity of 0.5 to 20 centipoise at a volatile solvent, b) 0.5-40% of guerbet ester, and c) 0.1-20% of siloxy silicate polymer.

[0008]GB2319527公开了基于高分子量聚二有机硅氧烷化合物的释放芳香的非挥发性聚硅氧烷,其中该聚合物中的至少一个或多个有机取代基是衍生于芳香醇的基团。 [0008] GB2319527 discloses a polydiorganosiloxane based on the high molecular weight compound releasing an aromatic non-volatile silicone, wherein the at least one or more of the polymer is an organic substituent derived from an aromatic alcohol groups .

[0009]日本已审专利公开1994-72085教导了具有改进的耐水性和耐久性的化妆组合物,其含有有机硅氧烷树脂、挥发性硅油和化妆粉末。 [0009] Japanese Examined Patent Publication No. 1994-72085 teaches having improved water resistance and durability of cosmetic composition containing an organic silicone resin, a volatile silicone oil, and make-up powder.

[0010]在皮肤护理配方中,需要改进的硅氧烷树脂,所述硅氧烷树脂提供至少与目前在化妆品配方中使用的MQ树脂相当的延长的磨耗和抗转移性能,但具有改进的光泽(即非消光)。 [0010] In skin care formulations, a need for improved silicone resin, the silicone resin is present to provide at least the MQ resin used in cosmetic formulations considerably extended wear and transfer resistance properties, but having improved gloss (i.e. non-matte). 此外,需要改进苯基倍半硅氧烷树脂在常用个人护理溶剂内的溶解度。 In addition, the need to improve the solubility of phenyl silsesquioxane resin in a solvent commonly used in personal care.

[0011]发明人已发现,通过结合烷基(R′SiO3/2)单元和苯基(C6H5SiO3/2)甲硅烷氧基单元的改进的硅氧烷树脂。 [0011] The inventors have found that by combining an alkyl (R'SiO3 / 2) units and phenyl (C6H5SiO3 / 2) siloxy units modified silicone resin. 所得硅氧烷树脂(下文称为烷基-苯基倍半硅氧烷树脂)改进在局部施用到皮肤上之后粉末的亲和性。 The resulting silicone resin (hereinafter referred to as alkyl - phenyl silsesquioxane resin) improvement after topical application to the skin powder affinity. 特别地,含本发明的烷基-苯基倍半硅氧烷树脂的化妆品配方比单独的苯基倍半硅氧烷树脂具有改进的耐久性。 In particular, the present invention containing alkyl - phenyl silsesquioxane resin cosmetic applications than a separate phenyl silsesquioxane resins having improved durability.

发明概述 Summary of the Invention

[0012]本发明涉及包含下述物质的组合物:(A)粉末,和(B)烷基-苯基倍半硅氧烷树脂,其包括至少60mol%具有通式(R′SiO3/2)x(C6H5SiO3/2)y的甲硅烷氧基单元,其中x和y的数值为0.05-0.95,和R′是具有2-8个碳原子的单价烃基。 [0012] The present invention relates to a composition comprising the following substances: (A) powder, and (B) alkyl - phenyl silsesquioxane resin comprising at least 60mol% having the general formula (R'SiO3 / 2) x (C6H5SiO3 / 2) y siloxy units, wherein the numerical values of x and y is 0.05 to 0.95, and R 'is a monovalent hydrocarbon group having 2-8 carbon atoms.

[0013]可将本发明的组合物掺入到各种个人、家庭、机动车或医疗护理用组合物中。 [0013] The compositions of the invention may be incorporated into a variety of personal, household, or medical care vehicle composition. 烷基-苯基倍半硅氧烷树脂改进在局部施用含本发明组合物的配方之后粉末或颜料在皮肤上的耐久性和亲和性。 Alkyl - phenyl silsesquioxane resins improvement after topical application of compositions of the invention containing a powder formulation or pigment on the skin durability and affinity.


[0014]本发明涉及包含下述物质的组合物:(A)粉末,和(B)烷基-苯基倍半硅氧烷树脂,其包括至少60mol%具有通式(R′SiO3/2)x(C6H5SiO3/2)y的甲硅烷氧基单元,其中x和y的数值为0.05-0.95,和R′是具有2-8个碳原子的单价烃基。 [0014] The present invention relates to a composition comprising the following substances: (A) powder, and (B) alkyl - phenyl silsesquioxane resin comprising at least 60mol% having the general formula (R'SiO3 / 2) x (C6H5SiO3 / 2) y siloxy units, wherein the numerical values of x and y is 0.05 to 0.95, and R 'is a monovalent hydrocarbon group having 2-8 carbon atoms.

[0015]组分(A)是粉末,它在此处定义为粒度为0.02-50微米的干燥粒状物。 [0015] Component (A) is a powder, it is defined herein as a particle size of 0.02 to 50 microns dry particulate matter. 该粒状物可被着色或者未着色(例如白色)。 The particulate matter may be colored or not colored (e.g. white). 合适的粉末包括羟基氯化铋、钛酸酯化云母、煅制氧化硅、球形氧化硅珠、聚甲基丙烯酸甲酯珠、微粉化特氟隆、氮化硼、丙烯酸酯聚合物、硅酸铝、淀粉辛烯基琥珀酸铝、膨润土、硅酸钙、纤维素、白垩、玉米淀粉、硅藻土、漂白土、甘油基淀粉、锂蒙脱石、水化氧化硅、高岭土、硅酸镁铝、碳酸镁、氢氧化镁、氧化镁、硅酸镁、三硅酸镁、麦芽糖糊精、蒙脱石、微晶纤维素、大米淀粉、氧化硅、滑石、云母、二氧化钛、月桂酸锌、肉豆蔻酸锌、新癸酸锌、松香酸锌、硬脂酸锌、聚乙烯、氧化铝、硅镁土、碳酸钙、硅酸钙、葡聚糖、高岭土、尼龙、氧化硅甲硅烷基化物(silica silylate)、蚕丝粉末、serecite、大豆粉、氧化锡、氢氧化钛、磷酸三镁、胡桃壳粉末、或其混合物。 Suitable powders include bismuth oxychloride, titanate esterification mica, fumed silica, spherical silica beads, polymethylmethacrylate beads, micronized teflon, boron nitride, acrylate polymers, silicate aluminum, aluminum starch octenylsuccinate, bentonite, calcium silicate, cellulose, chalk, corn starch, diatomaceous earth, fuller's earth, glyceryl starch, hectorite, hydrated silica, kaolin, magnesium silicate aluminum, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium silicate, magnesium trisilicate, maltodextrin, montmorillonite, microcrystalline cellulose, rice starch, silica, talc, mica, titanium dioxide, zinc laurate, zinc myristate, zinc neodecanoate, zinc rosinate, zinc stearate, polyethylene, alumina, attapulgite, calcium carbonate, calcium silicate, dextran, kaolin, nylon, silica silylated thereof (silica silylate), silk powder, serecite, soy flour, tin oxide, titanium hydroxide, trimagnesium phosphate, walnut shell powder, or mixtures thereof. 以上提及的粉末可以单独或结合用卵磷脂、氨基酸、矿物油、硅油或各种其它试剂表面处理,这种处理涂布粉末的表面并使得颗粒本质上疏水。 Powder mentioned above can be used alone or in combination with lecithin, amino acids, mineral oil, silicone oil, or various other surface treatment agents, such treatment powder applied to the surface and such that the particles essentially hydrophobic.

[0016]粉末组分(A)还包括各种有机和无机颜料。 [0016] powder component (A) also include various organic and inorganic pigments. 有机颜料通常是各种芳族类型,其中包括偶氮、靛青类、三苯基甲烷、蒽醌和黄嘌呤染料(表示为D&C和FD&C蓝、褐、绿、橙、红、黄等)。 The organic pigments are generally various aromatic types including azo, indigoid, triphenylmethane, anthraquinone, and xanthine dyes (denoted as D & amp; C and FD & amp; C blue, brown, green, orange, red, yellow etc.). 无机颜料通常由检定的着色添加剂的不溶金属盐(称为Lakes或铁的氧化物)组成。 Inorganic pigments are generally insoluble salts by accredited coloring additives (called Lakes or iron oxide). 粉状着色剂,例如炭黑、铬或铁的氧化物,群青、焦磷酸锰、铁蓝和二氧化钛、通常作为与着色颜料的混合物形式使用的珠光剂,或者通常作为与着色颜料的混合物形式使用且常用于化妆工业的一些有机染料可加入到该组合物中。 Powder colorants such as carbon black, chromium or iron oxides, ultramarine, manganese pyrophosphate, iron blue, and titanium dioxide, pearlescent agents generally used as a mixture with colored pigments used, or generally used as a coloring pigment in the form of a mixture with and is commonly used in the cosmetic industry, some organic dyes may be added to the composition. 也可添加粉状无机或有机填料。 Can also be added powdered inorganic or organic fillers. 这些粉状填料可选自滑石、云母、高岭土、锌或钛的氧化物,钙或镁的碳酸盐、氧化硅、球形二氧化钛、玻璃或陶瓷珠,衍生于具有8-22个碳原子的羧酸的金属皂、非膨胀合成聚合物粉末、膨胀粉末和来自天然有机化合物例如谷类淀粉(它可以交联或者可以不交联)的粉末。 The powdery filler selected from talc, mica carbonate, kaolin, zinc or titanium oxides, calcium or magnesium, silica, spherical titanium dioxide, glass or ceramic beads, derived from 8 to 22 carbon atoms having a carboxyl of acid metallic soaps, non-expanded synthetic polymer powders, expanded powders and from natural organic compounds such as cereal starches (which may be crosslinked or may not be crosslinked) powder. 尤其可提及滑石、云母、氧化硅、高岭土、尼龙粉末(尤其ORGASOL)、聚乙烯粉末、特氟隆、淀粉、氮化硼、共聚物微球,例如EXPANCEL(NobelIndustrie)、POLYTRAP和有机硅树脂粉末或微珠(例如获自Toshiba的TOSPEARL)。 In particular, mention may be made of talc, mica, silica, kaolin, nylon powders (in particular ORGASOL), polyethylene powder, Teflon, starch, boron nitride, copolymer microspheres such as EXPANCEL (NobelIndustrie), POLYTRAP and silicone resins powder or beads (e.g. available from Toshiba the TOSPEARL).

[0017]组分(B)是一种烷基-苯基倍半硅氧烷树脂,其包括至少60mol%具有通式(R′SiO3/2)x(C6H5SiO3/2)y的甲硅烷氧基单元,其中x和y的数值为0.05-0.95,和R′是具有2-8个碳原子的单价烃基。 Siloxy-phenyl silsesquioxane resin comprising at least 60mol% having the general formula (R'SiO3 / 2) x (C6H5SiO3 / 2) y - A [0017] Component (B) is an alkyl unit, wherein the numerical values of x and y is 0.05 to 0.95, and R 'is a monovalent hydrocarbon group having 2-8 carbon atoms. 此处所使用的x和y表示在烷基-苯基倍半硅氧烷树脂内存在的(R′SiO3/2)和(C6H5SiO3/2)甲硅烷氧基单元(即T-烷基和T-苯基甲硅烷氧基单元)相对于彼此的摩尔分数。 Where x and y denote used in alkyl - phenyl silsesquioxane resins in the memory (R'SiO3 / 2) and (C6H5SiO3 / 2) siloxy units (i.e. alkyl and T- T- phenyl siloxy units) relative to each mole fractions. 因此,(R′SiO3/2)和(C6H5SiO3/2)甲硅烷氧基单元的摩尔分数各自可独立地在0.05-0.95间变化。 Therefore, mole fraction (R'SiO3 / 2) and (C6H5SiO3 / 2) siloxy units each can independently vary from 0.05 to 0.95. 然而,所存在的(R′SiO3/2)和(C6H5SiO3/2)甲硅烷氧基单元的组合必需总计占在烷基-苯基倍半硅氧烷树脂内存在的所有甲硅烷氧基单元的至少60mol%,或者80mol%,或者95mol%。 However, (R'SiO3 / 2) (C6H5SiO3 / 2) and the present combination of siloxy units in the account of the required total alkyl - phenyl silsesquioxane resins in the memory of all siloxy units of at least 60mol%, or 80mol%, or 95mol%.

[0018]R′可以是直链或支链烷基,例如乙基、丙基、丁基、戊基、己基、庚基或辛基。 [0018] R 'may be linear or branched alkyl, e.g., ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. 优选R′是丙基。 Preferably R 'is propyl.

[0019]烷基-苯基倍半硅氧烷树脂可含有额外的甲硅烷氧基单元,例如本领域通常已知且还在此处分别作为M、D、T和Q单元使用的(i)(R13SiO1/2)a,(ii)(R22SiO2/2)b,(ii)(R3SiO3/2)c或(iv)(SiO4/2)d单元。 [0019] alkyl - phenyl silsesquioxane resins can contain additional siloxy units such as are generally known in the art and also here, respectively, as M, D, T and Q units used (i) (R13SiO1 / 2) a, (ii) (R22SiO2 / 2) b, (ii) (R3SiO3 / 2) c, or (iv) (SiO4 / 2) d units. 存在于烷基-苯基倍半硅氧烷树脂内的每一单元的含量可表达为存在于烷基-苯基倍半硅氧烷树脂内的所有甲硅烷氧基单元的总摩尔数的摩尔分数。 Present in the alkyl group - the phenyl silsesquioxane resin content of each unit may be expressed as present in the alkyl group - the phenyl silsesquioxane resins of all siloxy units of moles of the total moles scores. 因此,本发明的烷基-苯基倍半硅氧烷树脂包括下述单元:(i)(R13SiO1/2)a Accordingly, the present invention is an alkyl - phenyl silsesquioxane resin comprising the units: (i) (R13SiO1 / 2) a

(ii)(R22SiO2/2)b(iii)(R3SiO3/2)c(iv)(SiO4/2)d(v)(R′SiO3/2)x和(vi)(C6H5SiO3/2)y,其中R1、R2和R3独立地为具有1-8个碳原子的烷基、芳基、醇基(carbinol)或氨基,R′是具有2-8个碳原子的单价烃基,a、b、c和d的数值为0-0.4,x和y的数值为0.05-0.95,条件是x+y的数值等于或大于0.60,和a+b+c+d+x+y=1。 (Ii) (R22SiO2 / 2) b (iii) (R3SiO3 / 2) c (iv) (SiO4 / 2) d (v) (R'SiO3 / 2) x and (vi) (C6H5SiO3 / 2) y, wherein R1, R2 and R3 are independently an alkyl group having 1-8 carbon atoms, an aryl group, an alcohol group (carbinol) or an amino group, R 'is a monovalent hydrocarbon group having 2-8 carbon atoms, a, b, c, and The value of d is 0 to 0.4, x and y values of 0.05 to 0.95, provided that x + y is equal to or greater than the value of 0.60, and a + b + c + d + x + y = 1.

[0020]在烷基-苯基倍半硅氧烷树脂的单元内的R1、R2和R3独立地为具有1-8个碳原子的烷基、芳基、醇基或氨基。 [0020] In the group - R1 within unit phenyl silsesquioxane resins of, R2 and R3 are independently an alkyl group having 1-8 carbon atoms, an aryl group, an alcohol group or an amino group. 烷基可例举甲基、乙基、丙基、丁基、戊基、己基和辛基。 The alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl. 芳基可例举苯基、萘基、苄基、甲苯基、二甲苯基、联苯基、甲基苯基、2-苯乙基、2-苯基-2-甲基乙基、氯代苯基、溴代苯基和氟代苯基,其中芳基典型地为苯基。 The aryl group may include phenyl, naphthyl, benzyl, tolyl, xylyl, biphenyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chloro phenyl, substituted phenyl and fluoro-bromophenyl, wherein aryl is typically phenyl.

[0021]对于本发明的目的来说,“醇基”定义为含有至少一个与碳键合的羟基(COH)的任何基团。 [0021] For the purposes of the present invention, "an alcohol" is defined as containing at least one carbon-bonded hydroxyl (COH) of any group. 因此,醇基可含有大于一个COH基,例如 Thus, alcohol groups may contain more than one COH group, e.g.

[0022]不含芳基的醇基具有至少3个碳原子,或者含有芳基的醇基具有至少6个碳原子。 [0022] The alcohol group free of aromatic groups having at least 3 carbon atoms, or an aryl group having an alcohol containing at least 6 carbon atoms. 具有至少3个碳原子的不含芳基的醇基可例举具有通式R4OH的基团,其中R4是具有至少3个碳原子的二价烃基,或者具有至少3个碳原子的二价烃氧基。 Alcohol groups contain aromatic groups having at least 3 carbon atoms may include a group having the formula R4OH, wherein R4 is having at least 3 carbon atoms a divalent hydrocarbon group, or a divalent hydrocarbon having at least 3 carbon atoms, group. R4基可例举亚烷基,例如-(CH2)x-,其中x的数值为3-10,-CH2CH(CH3)-、-CH2CH(CH3)CH2-、-CH2CH2CH(CH2CH3)CH2CH2CH2-和-OCH(CH3)(CH2)x-,其中x的数值为1-10。 R4 group may include an alkylene group, e.g., - (CH2) x-, wherein x has a value of 3-10, -CH2CH (CH3) -, - CH2CH (CH3) CH2 -, - CH2CH2CH (CH2CH3) CH2CH2CH2-, and - OCH (CH3) (CH2) x-, wherein x has a value of 1-10.

[0023]具有至少6个碳原子的含芳基的醇基可例举具有通式R5OH的基团,其中R5是亚芳基,例如-(CH2)xC6H4-,其中x的数值为0-10,-CH2CH(CH3)(CH2)xC6H4-,其中x的数值为0-10,-(CH2)xC6H4(CH2)x-,其中x的数值为1-10。 [0023] The alcohol group containing an aryl group having at least 6 carbon atoms can be exemplified by a group having the formula R5OH wherein R5 is an arylene group, e.g., - (CH2) xC6H4-, wherein the value of x is 0-10 , -CH2CH (CH3) (CH2) xC6H4-, wherein x has a value of 0-10, - (CH2) xC6H4 (CH2) x-, wherein x has a value of 1-10. 含芳基的醇基典型地具有6-14个原子。 Alcohol group-containing aryl group typically has 6-14 atoms.

[0024]氨基可以是伯、仲或叔胺。 [0024] The amino group may be primary, secondary or tertiary amine. 胺可例举具有通式-R6NH2或-R6NHR7NH2的基团,其中R6是具有至少2个碳原子的二价烃基,和R7是具有至少2个碳原子的二价烃基。 Amine may, for example have the formula -R6NH2 or -R6NHR7NH2 group, wherein R6 is at least two carbon atoms having a divalent hydrocarbon group, and R7 is a divalent hydrocarbon group having at least 2 carbon atoms. R6基典型地为具有2-20个碳原子的亚烷基。 R6 group typically having 2 to 20 carbon atoms in the alkylene group. R6可例举亚乙基、亚丙基、-CH2CHCH3-、亚丁基、-CH2CH(CH3)CH2-、亚戊基、亚己基、3-乙基亚己基、亚辛基和亚癸基。 R6 may, for example ethylene, propylene, -CH2CHCH3-, butylene, -CH2CH (CH3) CH2-, pentamethylene, hexamethylene, 3-ethyl hexylene, octylene and decylene.

[0025]R7典型地为具有2-20个碳原子的亚烷基。 [0025] R7 typically having 2 to 20 carbon atoms in the alkylene group. R7可例举亚乙基、亚丙基、-CH2CHCH3-、亚丁基、-CH2CH(CH3)CH2-、亚戊基、亚己基、3-乙基亚己基、亚辛基和亚癸基。 R7 can be exemplified by ethylene, propylene, -CH2CHCH3-, butylene, -CH2CH (CH3) CH2-, pentamethylene, hexamethylene, 3-ethyl hexylene, octylene and decylene.

[0026]典型的氨基是-CH2CH2CH2NH2和-CH2(CH3)CHCH2(H)NCH3、-CH2CH2NHCH2CH2NH2、-CH2CH2NH2、-CH2CH2NHCH3、-CH2CH2CH2CH2NH2、-(CH2CH2NH)3H和-CH2CH2NHCH2CH2NHC4H9。 [0026] A typical amino is -CH2CH2CH2NH2 and -CH2 (CH3) CHCH2 (H) NCH3, -CH2CH2NHCH2CH2NH2, -CH2CH2NH2, -CH2CH2NHCH3, -CH2CH2CH2CH2NH2, - (CH2CH2NH) 3H and -CH2CH2NHCH2CH2NHC4H9.

[0027]典型地,R1是甲基,R2是甲基或苯基,和R3是甲基。 [0027] Typically, R1 is methyl, R2 is methyl or phenyl, and R3 is methyl.

[0028]烷基-苯基倍半硅氧烷树脂中的任何单独的D、T或Q硅氧烷单元也可含有羟基和/或烷氧基。 [0028] alkyl - phenyl silsesquioxane resin of any individual D, T or Q siloxane units can also contain hydroxyl and / or alkoxy. 常常在具有通式RnSiO(4-n)/2的硅氧烷树脂中发现这种含有羟基和/或烷氧基的硅氧烷单元。 Often having the general formula RnSiO (4-n) silicone resin / 2 found that contain hydroxy and / or alkoxy siloxane units. 在这些硅氧烷树脂中的羟基典型地来自于在硅氧烷单元上的可水解基团与水的反应。 Hydroxyl group in these silicone resins are typically derived from the reaction of siloxane units in the hydrolyzable group and water. 当使用烷氧基硅烷前体时,烷氧基来自于不完全水解,或者来自于醇与可水解基团的交换。 When the body prior to use alkoxysilane, an alkoxy group derived from incomplete hydrolysis, or from exchange of alcohol with hydrolysable groups. 典型地,存在于烷基-苯基倍半硅氧烷树脂中的全部羟基的重量百分数为最多10%,或者5%,或者3%。 Typically, in the presence of alkyl - phenyl silsesquioxane resin percentage weight of the total hydroxyl groups of up to 10%, or 5%, or 3%. 典型地,存在于烷基-苯基倍半硅氧烷树脂中的全部烷氧基的重量百分数为最多20%,或者最多10%,或者最多5%。 Typically, in the presence of alkyl - phenyl silsesquioxane resin in the alkoxy group of up to 20% weight percent, or at most 10%, or at most 5%.

[0029]没有限制烷基-苯基倍半硅氧烷树脂的分子量,但典型地数均分子量(MN)范围为5,00-10,000,或者1,000-5,000。 [0029] There is no limit alkyl - molecular weight of the phenyl silsesquioxane resin, but typically the number average molecular weight (MN) range 5,00-10,000, or 1,000-5,000.

[0028]可通过本领域已知的制备通式RnSiO(4-n)/2的硅氧烷树脂的任何一种方法,来制备本发明的烷基-苯基倍半硅氧烷树脂,其中R是烷基或芳基,n通常小于1.8。 [0028] known in the art may be prepared by the general formula RnSiO (4-n) A method of any of silicone resin / 2, the present invention is to prepare an alkyl - phenyl silsesquioxane resin, wherein R is an alkyl or aryl group, n is usually less than 1.8. 因此,可通过共水解烷基硅烷和苯基硅烷来制备烷基-苯基倍半硅氧烷树脂,其中烷基硅烷和苯基硅烷各自具有存在于硅烷分子内的三个可水解基团,例如卤素或烷氧基。 Accordingly, by co-hydrolysis of alkyl silanes and phenyl silanes to prepare alkyl - phenyl silsesquioxane resin, wherein the alkylsilane and phenylsilane are each present in the silane molecule having three hydrolyzable groups, such as halogen or alkoxy. 例如,可通过共水解丙基三甲氧基硅烷、丙基三乙氧基硅烷或苯基三丙氧基硅烷与苯基三甲氧基硅烷、苯基三乙氧基硅烷或苯基三丙氧基硅烷,获得烷基-苯基倍半硅氧烷树脂。 For example, by cohydrolysis trimethoxysilane, propyl triethoxysilane or phenyl tripropoxy silane and phenyl trimethoxysilane, phenyl triethoxysilane or phenyl tripropoxy silane, to obtain alkyl - phenyl silsesquioxane resin. 或者,可共水解丙基三氯硅烷与苯基三氯硅烷,产生本发明的烷基-苯基倍半硅氧烷树脂。 Alternatively, cohydrolysis propyl trichlorosilane and phenyl trichlorosilane, the present invention produce alkyl - phenyl silsesquioxane resin. 典型地,在醇或烃溶剂内进行共水解。 Typically, in an alcohol or hydrocarbon solvent cohydrolysis. 适合于这些目的的醇包括甲醇、乙醇、正丙醇、异丙醇、丁醇、甲氧基乙醇、乙氧基乙醇或类似的醇。 Alcohols suitable for these purposes include methanol, ethanol, n-propanol, isopropanol, butanol, methoxyethanol, ethoxyethanol or a similar alcohol. 也可同时使用的烃类溶剂的实例包括甲苯、二甲苯、或类似的芳烃;己烷、庚烷、异辛烷或类似的直链或部分支化的饱和烃;和环己烷或类似的脂族烃。 Examples of hydrocarbon can also be simultaneously used solvents include toluene, xylene, or similar aromatic hydrocarbons; hexane, heptane, isooctane, or similar linear or partially branched saturated hydrocarbons; and cyclohexane, or similar aliphatic hydrocarbons.

[0031]在共水解烷基硅烷和苯基硅烷的过程中,可通过使为在所得树脂内产生所需甲硅烷氧基单元而选择的额外的有机硅烷反应,将以上所述的额外的M、D、T和Q单元引入到烷基-苯基倍半硅氧烷树脂内。 Additional organic silane reaction [0031] In the co-hydrolysis of the alkylsilane and phenylsilane process, by reacting to generate the desired siloxy unit in the resulting resin selected, the above-described additional M , D, T and Q units introduced into the alkyl group - the phenyl silsesquioxane resin. 例如,使甲氧基三甲基硅烷、二甲氧基二甲基硅烷、三甲氧基甲基硅烷、四甲氧基硅烷(或者各自相应的乙氧基或氯代硅烷)反应将分别引入M、D、T或Q单元到烷基-苯基倍半硅氧烷树脂内。 For example, so-methoxy trimethyl silane, dimethoxy dimethyl silane, trimethoxy methyl silane, tetramethoxysilane (or their corresponding ethoxy or chlorosilane) were introduced into the reaction M , D, T or Q unit into the alkyl group - the phenyl silsesquioxane resin. 选择存在于共水解反应内的这些额外的硅烷量以满足以上所述的摩尔分数定义。 Select these additional silanes present in an amount within the co-hydrolysis reaction to meet the above definition of the mole fractions.

[0032]或者,可使用本领域已知的进行M、D、T和Q硅氧烷单元反应的任何方法,通过使烷基倍半硅氧烷和苯基倍半硅氧烷树脂反应,制备烷基-苯基倍半硅氧烷树脂。 [0032] Alternatively, known in the art may be carried out using M, D, T and Q any method siloxane units reaction, by reacting an alkyl silsesquioxane and phenyl silsesquioxane resin was prepared by reacting alkyl - phenyl silsesquioxane resin. 例如,可通过在催化剂存在下的缩合反应,使烷基倍半硅氧烷树脂和苯基倍半硅氧烷树脂反应。 For example, by condensation reaction in the presence of a catalyst, an alkyl silsesquioxane resin and a phenyl silsesquioxane resin reaction. 典型地,起始树脂包含在芳烃或硅氧烷溶剂内。 Typically, the starting resin is included in an aromatic hydrocarbon or siloxane solvent. 合适的缩合反应催化剂是碱催化剂,其中包括金属氢氧化物,例如氢氧化钾和氢氧化钠;金属盐,例如硅烷醇化物、羧酸盐和碳酸盐;氨;胺;和钛酸酯,例如钛酸四丁酯;及其组合。 Suitable condensation reaction catalysts are base catalysts including metal hydroxides such as potassium hydroxide and sodium hydroxide; metal salts such as silanolates, carboxylates, and carbonates; ammonia; amine; and a titanate, such as tetrabutyl titanate; and combinations thereof. 典型地,通过加热反应混合物到范围为50-140℃的温度,或者100-140℃,从而进行硅氧烷树脂的反应。 Typically, the reaction mixture by heating to a temperature in the range of 50-140 ℃, or 100-140 ℃, thereby performing the reaction of the silicone resin. 可以以间歇、半连续或连续的工艺进行该反应。 May be a batch, semi-continuous or continuous process to carry out the reaction.

[0033]本发明的烷基-苯基倍半硅氧烷树脂可例举:含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)3SiO1/2)a含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)2SiO2/2)b含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)SiO3/2)c含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y(SiO4/2)d含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)3SiO1/2)a(SiO4/2)d含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y [0033] The present invention is an alkyl - phenyl silsesquioxane resins can be exemplified: containing the following units propyl - phenyl silsesquioxane resin: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y propyl containing the following elements - phenyl silsesquioxane resins: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y ((CH3) 3SiO1 / 2) a propylene containing the following units of - phenyl sesqui silicone resin: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y ((CH3) 2SiO2 / 2) b containing the following units propyl - phenyl silsesquioxane resin: (CH3CH2CH2SiO3 / 2) x ( C6H5SiO3 / 2) y ((CH3) SiO3 / 2) c of the following units containing propyl - phenyl silsesquioxane resins: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y (SiO4 / 2) d containing propyl group comprising the units - phenyl silsesquioxane resins: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y ((CH3) 3SiO1 / 2) a (SiO4 / 2) d units containing propyl following - phenyl silsesquioxane resin: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y

((CH3)3SiO1/2)a((CH3)SiO3/2)c含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)3SiO1/2)a((CH3)2SiO2/2)b含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)2SiO2/2)b((CH3)SiO3/2)c含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)2SiO2/2)b(SiO4/2)d含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)SiO3/2)c(SiO4/2)d含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)3SiO1/2)a((CH3)2SiO2/2)b((CH3)SiO3/2)c,和(SiO4/2)d Propyl ((CH3) 3SiO1 / 2) a ((CH3) SiO3 / 2) c containing the following elements - phenyl silsesquioxane resins: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y ((CH3 ) 3SiO1 / 2) a ((CH3) 2SiO2 / 2) b containing the following units propyl - phenyl silsesquioxane resin: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y ((CH3) 2SiO2 / 2) b ((CH3) SiO3 / 2) c containing the following units propyl - phenyl silsesquioxane resin: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y ((CH3) 2SiO2 / 2) b propyl (SiO4 / 2) d containing the following elements - phenyl silsesquioxane resins: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y ((CH3) SiO3 / 2) c (SiO4 / 2) d containing the following units propyl - phenyl silsesquioxane resin: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y ((CH3) 3SiO1 / 2) a ((CH3) 2SiO2 / 2) b ((CH3 ) SiO3 / 2) c, and (SiO4 / 2) d

含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)(H2NCH2CH2CH2SiO2/2)b,含下述单元的丙基-苯基倍半硅氧烷树脂:(CH3CH2CH2SiO3/2)x(C6H5SiO3/2)y((CH3)(C6H5)SiO2/2)b其中a、b、c和d的数值为0-0.4,x和y的数值为0.05-0.95,条件是x+y的数值等于或大于0.60,和a+b+c+d+x+y的数值=1。 Propyl containing the following elements - phenyl silsesquioxane resins: (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y ((CH3) (H2NCH2CH2CH2SiO2 / 2) b, the following units containing propyl - phenyl silsesquioxane resin: wherein the numerical values (CH3CH2CH2SiO3 / 2) x (C6H5SiO3 / 2) y ((CH3) (C6H5) SiO2 / 2) b a, b, c, and d is 0-0.4, x and y value of 0.05 to 0.95, provided that x + y is equal to or greater than the value of 0.60, and a + b + c + d + x + y = 1 value.

[0034]任选地,可将烷基-苯基倍半硅氧烷树脂溶解在组分(C)溶剂内。 [0034] Optionally, the alkyl - phenyl silsesquioxane resin is dissolved in the component (C) a solvent. 可选择挥发性硅氧烷或有机溶剂作为任选的组分(C)用以溶解或分散烷基-苯基倍半硅氧烷树脂,之后与(A)粉末混合。 Alternatively volatile siloxane or organic solvent as an optional component (C) for dissolving or dispersing the alkyl - phenyl silsesquioxane resin, after mixing with (A) powder. 可选择任何挥发性硅氧烷或有机溶剂,条件是组分(B)可用所选溶剂分散或与之混溶。 Alternatively Any volatile siloxane or organic solvent, provided that the component (B) can be used in or miscible with the selected solvent dispersion. 挥发性硅氧烷溶剂可以是环状聚硅氧烷、直链聚硅氧烷或其混合物。 Volatile silicone solvent may be a cyclic polysiloxane, a linear polysiloxane, or mixtures thereof. 一些代表性的挥发性直链聚硅氧烷是六甲基二硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷、十四甲基六硅氧烷和十六甲基七硅氧烷。 Some representative volatile linear polysiloxanes are hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, fourteen and sixteen-methyl-siloxane methyl six seven siloxane. 一些代表性挥发性环状聚硅氧烷是六甲基环三硅氧烷、八甲基环四硅氧烷、十甲基环五硅氧烷和十二甲基环六硅氧烷。 Some representative volatile cyclic polysiloxanes are hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and twelve methylcyclopropyl six siloxane. 有机溶剂可以是酯,醇,例如甲醇、乙醇、异丙醇、丁醇或正丙醇,酮,例如丙酮、甲乙酮或甲基异丁基酮;芳烃,例如苯、甲苯或二甲苯;脂族烃,例如庚烷、己烷或辛烷;二元醇醚,例如丙二醇甲醚、二丙二醇甲醚、丙二醇正丁醚、丙二醇正丙醚或乙二醇正丁醚,乙酸酯,例如乙酸乙酯或乙酸丁酯,卤代烃,例如二氯甲烷、1,1,1-三氯乙烷或二氯甲烷、氯仿、二甲亚砜、二甲基甲酰胺、乙腈、四氢呋喃或脂族烃,例如石油溶剂、溶剂油、异十二烷、庚烷、己烷或石脑油。 The organic solvent may be an ester, an alcohol, such as methanol, ethanol, isopropanol, butanol or n-propanol, ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone; aromatic hydrocarbons, such as benzene, toluene or xylene; an aliphatic hydrocarbons, such as heptane, hexane or octane; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether or ethylene glycol n-butyl ether, acetates such as ethyl acetate acetate or butyl acetate, halogenated hydrocarbons such as methylene chloride, 1,1,1-trichloroethane, or methylene chloride, chloroform, dimethylsulfoxide, dimethylformamide, acetonitrile, tetrahydrofuran or aliphatic hydrocarbons , such as mineral spirits, mineral spirits, isododecane, heptane, hexane or naphtha. 典型地,溶剂是十甲基环五硅氧烷或异十二烷。 Typically, the solvent is decamethylcyclopentasiloxane or isododecane siloxane.

[0035]不存在对进行组分A)和B)的混合所需的特殊要求或条件。 [0035] there is no mixing required to carry out component A) and B) of the special requirements or conditions. 因此,可使用进行这种组合物的混合已知的任何方法。 Thus, any method of mixing known in such compositions may be used. 组分A)和B)可任选地包含在以上作为组分C)所述的溶剂内。 Components A) and B) may optionally be included in the above as the component C) of the solvent. 可以以间歇、半连续或连续工艺进行混合。 May be a batch, semi-continuous or continuous processes may be employed.

[0036]在混合物内组分A)与组分B)(即A/B)的重量比可从99∶1变化到1∶99,或者85∶15到15∶85。 Weight [0036] component in the mixture of A) to component B) (i.e. A / B) ratio changes from 99 to 1:99 or 85:15 to eighty-five past three p.m..

[0037]烷基-苯基倍半硅氧烷树脂可用于各种个人、家庭、机动车或医疗护理用组合物中。 [0037] alkyl - phenyl silsesquioxane resins can be used for a variety of personal, family, or medical care vehicle composition. 因此,它们可用于止汗剂、除味剂、护肤霜、皮肤护理洗剂、保湿剂、面部处理剂,例如痤疮或皱纹除去剂、个人和面部清洁剂、防晒剂、指甲抛光剂、化妆品、彩色化妆品、粉底、胭脂、口红、唇膏、眼线膏、染眉毛油和粉末。 Thus, they can be used for antiperspirants, deodorants, skin creams, skin care lotions, moisturizers, facial treatment agent, such as acne or wrinkle removers, personal and facial cleansers, sunscreens, nail polishes, cosmetics, color cosmetics, foundation, blush, lipstick, lipstick, eyeliner, mascara and powder. 此外,预期本发明的组合物可结合各种其它组分,以制备以下所述的个人护理产品。 In addition, the compositions of the present invention may be expected in connection with various other components, as described below to prepare a personal care product. 这些组分包括配制这种个人护理用产品常用的额外的表面活性剂、保湿剂、颜料、防晒剂、香料、润肤剂。 These components include the preparation of personal care products such additional conventional surfactants, moisturizers, pigments, sunscreens, fragrances, emollients.

[0038]烷基-苯基倍半硅氧烷树脂尤其可用于提高在局部施加化妆品或化妆品配方之后颜料的耐久性和亲和性。 [0038] alkyl - phenyl silsesquioxane resins are particularly useful for topical application to improve after a cosmetic or cosmetic formulations pigment durability and affinity.


[0039]列出下述实施例进一步阐述本发明的组合物和方法,但不打算解释为限制本发明。 [0039] The following examples are to further illustrate the compositions and methods of the invention described below, but is not intended to be construed as limiting the present invention. 实施例中的所有份数和百分数以重量为基础,且所有的测量在约23℃下进行,除非有相反指示。 EXAMPLE All parts and percentages are on a weight basis and all measurements were at about 23 ℃, unless indicated to the contrary.

[0040]使用在树脂内存在的甲硅烷氧基单元的符号M、D、T和Q,描述这些实施例的代表性烷基倍半硅氧烷树脂。 [0040] In the symbol M in the memory resin siloxy units, D, T and Q, describing these representative embodiments of the alkyl silsesquioxane resin. 下标进一步描述在该甲硅烷氧基单元上存在的烷基或苯基取代基。 Subscript further described on the siloxy units present in the alkyl or phenyl substituents. 此处所使用的Pr是CH3CH2CH2-,Ph是C6H5-,和NH2是-CH2CH2CH2NH2。 Pr used herein is CH3CH2CH2-, Ph is C6H5-, and NH2 is -CH2CH2CH2NH2. 下标描述在树脂内的甲硅烷氧基单元的摩尔分数。 Subscript described in a resin siloxy units of mole fraction. 因此,每一甲硅烷氧基单元的摩尔分数为0.50的烷基-苯基硅氧烷树脂在此处表示为TPr0.50TPh0.50。 Thus, the mole fraction of each siloxy units of 0.50 alkyl - phenyl siloxane resin represented here TPr0.50TPh0.50.

实施例1由甲氧基硅烷制备的TPr0.50TPh0.50硅氧烷树脂 Example 1 TPr0.50TPh0.50 silicone resin prepared by methoxysilane embodiment

[0041]在4颈反应烧瓶内装入991.50g苯基三甲氧基硅烷、821.60g丙基三甲氧基硅烷和0.52g FC-24。 [0041] In 4-necked reaction 991.50g phenyltrimethoxysilane charged into the flask, 821.60g trimethoxysilane and 0.52g FC-24. 该烧瓶配有空气驱动的搅拌叶片、温度计和具有冷凝器的Dean Stark分水器。 The flask was equipped with an air driven stirring blade, a thermometer and a Dean Stark trap with condenser. 然后,在5秒内添加323.26g水,并加热该混合物以除去所形成的甲醇。 Then, within 5 seconds added 323.26g of water, and heating the mixture to remove the methanol formed. 当除去80%的甲醇时,添加747.93g甲苯,产生60wt%的混合物。 When 80% of the methanol was removed, toluene was added 747.93g, generated 60wt% of the mixture. 重新开始加热以除去挥发物。 Re-start of heating to remove volatiles. 在除去大多数甲醇之后,添加162.15g水,以进一步水解任何残留的甲氧基。 After removal of most of the methanol, add 162.15g of water, to further hydrolysis any residual methoxy. 加热反应混合物到回流(75-115℃),以除去甲醇和水。 The reaction mixture was heated to reflux (75-115 ℃), to remove methanol and water. 在冷却所得树脂混合物之后,添加3.38g碳酸钙以中和所存在的FC-24,接着添加4g硫酸镁,以除去任何痕量的水。 After cooling the resulting resin mixture was added 3.38g of calcium carbonate to neutralize the presence of FC-24, followed by addition of 4g of magnesium sulfate, to remove any traces of water. 过滤该混合物,以除去盐并在150-155℃的油浴温度和0.4mmHg(53.3Pa)下,在旋转蒸发仪上汽提。 The mixture was filtered to remove salts and the oil bath temperature 150-155 ℃ and 0.4mmHg (53.3Pa) under, stripped in a rotary evaporator. 所得树脂在室温下是透明无色的固体。 The resulting resin at room temperature is a clear colorless solid.

实施例2由氯代硅烷制备的TPr0.70TPh0.30树脂 Example 2 TPr0.70TPh0.30 resin consisting chlorosilane prepared in

[0042]在5升4颈反应烧瓶内装入2136.52g去离子水和214.00g2-丙醇,并采用加热煲加热到70℃。 [0042] 5-liter, four-neck reaction flask was charged with deionized water and 2136.52g 214.00g2- propanol, and using heated pot was heated to 70 ℃. 在2L Erlenmeyer烧瓶内装入483.63g甲苯、291.70g苯基三氯硅烷PhSiCl3和572.10g丙基三氯硅烷PrSiCl3。 Charged 483.63g of toluene in a 2L Erlenmeyer flask, 291.70g phenyltrichlorosilane PhSiCl3 and 572.10g propyl trichlorosilane PrSiCl3. 然后将Erlenmeyer烧瓶内的试剂经滴液漏斗加入到反应烧瓶内,同时通过使用冰水浴在添加过程中维持温度74-78℃并改变添加速度。 Then the Erlenmeyer flask through the reagent inside the dropping funnel was added to the reaction flask while maintaining the temperature by using an ice bath during the addition 74-78 ℃ and changing the addition rate. 在加完之后,缓慢冷却反应混合物。 After completion of the addition, the reaction mixture was slowly cooled. 采用加热煲使冷却速度减慢,但不施加热量。 Pot by heating the cooling slowed, but not the application of heat. 在50℃下,将反应产物转移到4升分液漏斗中,除去水相。 At 50 ℃, the reaction product was transferred to a 4 l separatory funnel, the aqueous phase was removed. 将留在分液漏斗内的材料转移到3升三颈圆底烧瓶内,然后通过共沸除去其余的水。 The material is left in the separatory funnel is transferred to a 3 liter three-necked round bottom flask, and then removing the remaining water by azeotropic. 然后使用50.78g去离子水和21.61g 2-丙醇进行共沸洗涤。 Then using 50.78g of deionized water and 21.61g 2- propanol washed azeotropic. 再次通过共沸除去水。 By azeotropic removal of water again. 分析所得混合物的酸含量,表明基于溶液为148ppm HCl。 Analysis of the resulting mixture of acid content, indicating that the solution is based 148ppm HCl. 然后在125-130℃和0.3mmHg(40Pa)下,借助旋转蒸发仪,从所得反应混合物中经1小时除去挥发物。 Then at 125-130 ℃ and 0.3mmHg (40Pa), the means of a rotary evaporator, after one hour the volatiles were removed from the resulting reaction mixture. 将所得树脂溶解在乙酸丁酯内,产生75wt%固体的树脂溶液。 The resulting resin was dissolved in butyl acetate to produce 75wt% solids resin solution.

实施例3由氯代硅烷制备的TPr0.90TPh0.10树脂 Resin from Example 3 TPr0.90TPh0.10 chlorosilane prepared in

[0043]借助实施例2的工序,通过添加182.90g甲苯、103.76gPhSiCl3和784.20g PrSiCl3的混合物到在反应烧瓶中的2278.82g去离子水和229.10g 2-丙醇的混合物中,制备这一树脂。 [0043] With the step of Example 2, by adding 182.90g toluene, 103.76gPhSiCl3 784.20g PrSiCl3 to the mixture and the reaction mixture in the flask was 2278.82g deionized water and 229.10g 2- propanol, a solution of the resin . 用乙酸丁酯稀释所得树脂到75wt%的固体。 The resultant was diluted with butyl acetate to 75wt% resin solids.

[0044]这些材料通过NMR和GPC来表征,在Leneta图表上评价其光泽度和在挥发性溶剂内的35%固体下的粘性,评价在粉底(彩色化妆品)中的耐久性。 [0044] These materials are characterized by NMR and GPC, and evaluation of viscosity in the gloss volatile solvent at 35% solids in the Leneta chart, the durability was evaluated in the foundation (color cosmetic) in. 在表1中可发现NMR的表征,且可在表2中找到应用结果。 In Table 1 can be found in the NMR characterization, and application of the results can be found in Table 2.

实施例4由甲氧基硅烷制备的TPr0.45TPh0.45DNH20.05M0.05硅氧烷树脂 Example 4 TPr0.45TPh0.45DNH20.05M0.05 silicone resins prepared by methoxysilane embodiment

[0045]在四颈反应烧瓶内装入446.15g苯基三甲氧基硅烷、369.6g丙基三甲氧基硅烷、47.85g Me(EtO)2Si(PrNH2)和376.38g二甲苯。 [0045] Load 446.15g phenyltrimethoxysilane, 369.6g trimethoxysilane, 47.85g Me (EtO) 2Si (PrNH2) and 376.38g of xylene in a four-neck reaction flask. 该烧瓶配有空气驱动的搅拌叶片、温度计和冷凝器。 The flask was equipped with an air driven stirring blade, a thermometer and a condenser. 然后,添加116.0g水,并加热该混合物以除去所形成的醇。 Then, 116.0g of water, and heating the mixture to remove the alcohol formed. 添加44.0gMe3SiOEt、78.26g水和10.55g 1.0M的KOH(aq),并在Dean Stark分水器中汽提掉水和醇,同时在回流下加热。 Add 44.0gMe3SiOEt, 78.26g water and 10.55g 1.0M of KOH (aq), and Dean Stark trap stripped of water and alcohol, while heating under reflux. 汽提分离后,添加10.77g1.0M HCl,以中和KOH。 After stripping separation, add 10.77g1.0M HCl, to neutralize the KOH. 在除去大部分醇和水之后,过滤该材料,以除去盐,并在155-160℃的油浴温度和0.6mmHg(80Pa)下在旋转蒸发仪上汽提1小时。 After removal of most of the alcohol and water, the material was filtered to remove the salt, and the oil bath temperature 155-160 ℃ and 0.6mmHg (80Pa) at a rotary evaporator and stripped 1 hour. 所得树脂在室温下是透明的无色固体。 The resulting resin at room temperature is a clear colorless solid.

实施例5TPr0.30TPh0.70树脂 Example 5TPr0.30TPh0.70 Resin

[0045]使用与实施例2相类似的工序制备这一树脂。 [0045] similar to the step 2 of Example was prepared using this resin.

实施例6TPr0.32TPh0.31DNH20.05M0.33 EXAMPLE 6TPr0.32TPh0.31DNH20.05M0.33

[0046]使用与实施例4相类似的工序制备这一树脂。 [0046] a step similar to that used in Example 4 Preparation of the resin.

表1:NMR和GPC表征结果 Table 1: NMR and GPC characterization results

表2:应用结果 Table 2: Application results

粉底配方 Foundation formula

[0047]颜料预混物50wt%DC 245流体13.16wt%Carde AS二氧化钛(辛酰基硅烷处理)11.41wt%Carde AS红色氧化铁(辛酰基硅烷处理)18.26wt%Carde AS黄色氧化铁(辛酰基硅烷处理)7.17wt%Carde AS黑色氧化铁(辛酰基硅烷处理)工序:1)将DC 245流体置入Waring Blender内2)添加二氧化钛并通过按压脉冲钮2秒混合总计15秒3)添加红色氧化铁并混合它与二氧化钛4)继续与其它颜料混合5)当所有材料分散时,高速混合并切碎30秒,以研磨颜料6)将预混物置入圆的玻璃罐内并放置在桶辊上6小时。 [0047] Pigment premix 50wt% DC 245 fluid 13.16wt% Carde AS Titanium dioxide (caprylyl silane treated) 11.41wt% Carde AS Red Iron Oxide (caprylyl silane treated) 18.26wt% Carde AS Yellow Iron Oxide (caprylyl silane processing) 7.17wt% Carde AS black iron oxide (octanoyl silane treatment) process: 1) the DC 245 fluid placed within Waring Blender 2) add titanium dioxide and a total of 15 seconds 3) Add the red iron oxide by pressing the pulse button 2 seconds mixed mixing was continued for 5 and mixed it with other pigments and titanium dioxide 4)) When all materials are dispersed, and chopped 30 seconds high speed mixing, milling the pigment to 6) the premix into a round glass jar and placed within the barrel roll 6 hours.

A相20.50wt%颜料预混物7.50wt%DC5225C A phase 20.50wt% pigment premix 7.50wt% DC5225C

8wt%在溶剂内的50%树脂固体B相54.80wt%的DI水1.0wt%NaCl0.20wt%失水山梨醇聚氧乙烯(20)醚月桂酸酯用于油性粉底内液体水的工序:1)在辊上放置颜料分散体1小时。 8wt% within a 50% resin solids in solvent Phase B DI water 54.80wt% 1.0wt% NaCl0.20wt% sorbitan polyoxyethylene (20) ether laurate oily foundation for the liquid water within the steps of: 1 ) is placed on the roll pigment dispersion for one hour.

2)称取树脂和溶剂,制备50%固体的稀释液。 2) Weigh resin and a solvent to prepare a 50% solids dilution. 使用烘箱和滚轮混合。 Use oven and roll mix.

3)利用双刮刀、涡流形式的混合作用,组合A相内的成分,混合直到均匀。 3) the use of a double doctor blade, a vortex mixing action, the combination of ingredients within the phase A, mix until uniform.

4)使用磁搅拌器,在独立的烧杯内组合B相内的成分,混合直到均匀。 4) using a magnetic stirrer, in a separate beaker Phase B ingredients within the composition, mix until uniform.

5)增加A相的混合速度到1376rpm,并通过滴液漏斗非常缓慢地添加B相。 5) Increase mixing speed of Phase A to 1376rpm, and through the dropping funnel very slowly add Phase B. 这一添加应当花费10分钟。 This addition should take 10 minutes.

继续混合额外10分钟。 Mixing was continued for an additional 10 minutes.

粉底耐久性方法:加德纳磨耗试验机1.将胶原切割成3.5”3”的小片,将每一片放置在每一3”2.5”的聚碳酸酯块上,并放置在湿度腔室内过夜。 Foundation Durability Method: Gardner Abrasion Tester 1. The collagen was cut into 3.5 " 3" in small pieces, each piece is placed on each of the 3 " 2.5" polycarbonate blocks and placed in the humidity chamber overnight. 这一腔室必须处于恒定的98%相对湿度水平下。 This chamber must be at a constant 98% relative humidity level.

2.从腔室中取出胶原和块。 2. Remove the collagen and blocks from the chamber. 用Scotch胶带将胶原固定到块上,注意不要将任何胶带置于块表面的上部。 Collagen with Scotch tape fixed to the block, be careful not to put any tape upper block surface.

3.添加约1g粉底到胶原上,在该块的上部使之成珠粒。 3. Add about 1g foundation to the collagen, in the upper part of the block to make it into the beads. 使用#8迈耶绕线棒涂布器,通过在粉底珠粒上放置绕线棒,并向下铺涂到块的底部,从而用粉底涂布胶原。 Use a # 8 Meyer bar coater, wire bar by placing beads on the foundation, applied to the bottom of the block to the lower berth, thus coated with collagen foundation. 最终的涂层重量应当为约0.2g。 The final coating weight should be about 0.2g. 可能需要重复这一操作,以获得合适的涂层重量。 May need to repeat this operation in order to obtain a suitable coating weight. 从块料的侧面上除去任何材料。 Removing any material from the side surface of the block material.

4.使在胶原上的样品干燥。 4. The samples were dried in the collagen. 干燥时间随不同样品而不同。 Drying times vary with different samples. 全部样品在测试之前必须没有任何湿气。 All samples must be free of any moisture before testing. 使用分光光度计或色度计,相对于起始基线颜色,测量在胶原上的样品的颜色。 Using a spectrophotometer or colorimeter, with respect to the initial baseline color, measured on a collagen sample color. L*、a*和b*表示在三维空间内着色物体的位置。 L *, a * and b * indicates the position of the colored object in three-dimensional space.

5.将块以胶原面向上的方式放置在加德纳磨耗试验机上,从而确保块在测试仪内。 5. The collagen-oriented manner on the block is placed on the Gardner Abrasion Tester, thus ensuring blocks are within the tester. Velcro的柔软侧附着在攻击块(insult block),以便磨蚀或攻击在胶原上的粉底样品。 Soft side of Velcro is attached to the attack block (insult block), so that abrasion or attack the foundation sample on the collagen. 攻击块摩擦经过粉底样品。 Attack the Block friction through the foundation samples. 一次攻击由一次向后和向前的运动组成。 An attack by a backward and forward movement of components. 攻击在胶原上的粉底样品20次。 Attack on the foundation of collagen sample 20 times. 可在一定的时间间隔处停止该机器,以测量颜色。 The machine can be stopped at certain time intervals, to measure the color.

6.在粉底样品被攻击20次之后,以L*、a*和b*形式读取颜色,并计算颜色变化ΔE(参见下述方程式)。 6. After the foundation sample is attacked 20 times, with L *, a * and b * in the form of read color, and calculate the color change ΔE (see equation below). 可改变攻击的次数,涂层重量和反复次数,以配合待测试的材料的需要。 Can change the number of attacks, coat weight and the number of iterations to meet the needs of the material to be tested. 这取决于操作者的判断。 It depends on the operator's judgment.

ΔL*、Δa*和Δb*=在磨耗之后的数值-在磨耗之前在起始基线处的数值ΔE=(ΔL2+Δa*2+Δb*2)1/2在较大的ΔE情况下,除去更多的粉底,因此粉底不那么耐久。 ΔL *, Δa * and Δb * = value after abrasion - Before the start of wear in the baseline value at ΔE = (ΔL2 + Δa * 2 + Δb * 2) 1/2 in the larger ΔE case, remove More of the foundation, so the foundation is not so durable.

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International ClassificationA61Q5/06, A61K8/89, A61K8/58, C08G77/04, A61K8/891
Cooperative ClassificationA61Q1/02, A61K8/585, A61K8/891, A61Q1/06, C08G77/04
European ClassificationA61K8/891, A61Q1/06, C08G77/04, A61Q1/02, A61K8/58C
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