CN102686207B - 含水的粉状组合物 - Google Patents
含水的粉状组合物 Download PDFInfo
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- CN102686207B CN102686207B CN201080059489.XA CN201080059489A CN102686207B CN 102686207 B CN102686207 B CN 102686207B CN 201080059489 A CN201080059489 A CN 201080059489A CN 102686207 B CN102686207 B CN 102686207B
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- water
- powder composition
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- silica
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- 229920002554 vinyl polymer Polymers 0.000 description 1
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- 239000011719 vitamin A Substances 0.000 description 1
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Classifications
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
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- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0216—Solid or semisolid forms
- A61K8/0233—Distinct layers, e.g. core/shell sticks
- A61K8/0237—Striped compositions
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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- A61K8/04—Dispersions; Emulsions
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- A61K8/11—Encapsulated compositions
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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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Abstract
粉状组合物,其包含:a)至少一种核壳颗粒形式的粉末,所述核包含液态水或液态水相,并且所述壳包含疏水性或疏水化的颗粒;和b)至少一种包含载体和分别位于所述载体之中和/或之上的以下物质的粉末以下物质:b1)至少部分可溶于水的液体和/或b2)水反应性基质。由上述粉状组合物制备乳膏状组合物的方法,其中所述粉状组合物通过能量输入而活化,所述能量输入的形式是压力、剪切、温度、振动和/或添加溶剂,并且所述能量输入足以从所述核-壳材料释放所述液态水或所述液态水相,然后,a)所述液态水或液态水相从所述载体溶解或冲洗所述至少部分可溶于水的液体,和/或b)所述液态水或液态水相活化所述载体之中和/或之上的水反应性基质,然后从所述载体溶解或冲洗经活化而得的产物。
Description
技术领域
本发明涉及含水的粉状组合物和由此粉状组合物制备乳膏状(creamy)组合物的方法。
背景技术
水含量高的固体化妆品制剂,例如粉剂,是本领域已知的。一些专利申请的依据是久为人知的事实:在疏水性粉末例如疏水性二氧化硅粉末的存在下,水可被分散成小液滴并被疏水性材料包围,由此防止液滴重新结合。以此方式形成称为"干水"的水含量高的粉状物质(Fine Particles series no.11,Evonik Degussa)。基于"干水"的化妆品制剂在Seifen,Fette,Wachse8(2003),第1-8页中有述。这些是当擦在皮肤上时液化的自由流动的精细粉剂。基于此原理的含水的可液化的粉状组合物还在数项专利申请和专利中公开。
US 4274883公开了疏水性二氧化硅的水分散体,其由0.1-50份疏水性二氧化硅、在特定的情况中不超过3份湿润剂和99.9-50份水组成。它通过剧烈混合疏水性二氧化硅与水以已知的"干-水-相"为中间步骤进行制备。在还可使用湿润剂的特定的情况中,不产生"干-水-相"。疏水性二氧化硅的分散体可在没有额外的步骤或材料的情况下与橡胶胶乳混合。
DE-A-1467023公开了使用包含化妆品配料替代纯水制备干水的用途。
EP-A-1206928公开了含水的粉状组合物,其包含包有疏水性颗粒的水凝胶核。
JP 2000-309505公开了通过涂擦液化的化妆品粉剂,其包含2重量%-20重量%的比表面积至少60m2/g的疏水性二氧化硅和水包油型乳液组合物。
EP-A-1235554公开了化妆品或药物粉剂至液体组合物,其包含其中含有水和水溶性聚合物的疏水性包覆的二氧化硅颗粒,所述组合物包含小于1%的油。
EP-A-1386599公开了制备包含包有疏水性粉末的含水组分的干水的方法,用以形成能够在涂擦使用时液化的粉末状态,其包括将疏水性粉末和含水组分加入中空的容器在其内形成疏水性封闭空间,然后在疏水性中空容器中高速搅拌形成精细的小水滴,而后使精细小液滴的表面均一地吸附疏水性粉末。
WO 01/85138A2公开了包封系统,其包含:含有至少5重量%水的含水液体的核,以及包围所述核形成稳定包封颗粒的包封剂,所述包封剂包含至少一层接触并包围所述核的疏水性颗粒,所述核和疏水性颗粒提供体积加权平均粒径为0.05-25微米的被包封的系统,至少25%的被包封的颗粒是球形并且可支撑其本身的重量。
EP-A-855177公开了美白粉剂,其包含0.1重量%-7重量%的比表面积至少80m2/g并且疏水度至少50%的三甲基硅氧基化的二氧化硅、5重量%-40重量%的多元醇、50重量%-94重量%水和0.01重量%-5重量%的美白成分。
WO 2005/058256公开了乳膏状或糊状稠度的化妆品制剂,其包含50重量%-95重量%水、疏水化的二氧化硅粉末、至少一种化妆品相关的活性成分,或者水溶性或在含水介质中可分散或乳化的添加剂,以及粘度调节剂。通过随着混合连续地向至少一种化妆品相关的活性成分的溶液或分散体添加疏水化的二氧化硅粉末并且继续混合直至达到糊状稠度,制备上述制剂。
虽然现有技术包括例如包封水的构思,此构思的问题是,取决于添加剂的性质例如添加剂的极性和链长,可添加的同时保持稳定粉末的添加剂的量为0重量%-3重量%。配方局限于0重量%-3重量%的添加剂,并且限制添加剂,减小最初构思的可行性。即使在已尝试此构思的工业的指导下,仍然不能克服关于添加剂种类或添加剂量的限制。
发明详述
因此,本发明一个目的是提供克服过去困难的构思。该构思不应局限于化妆品用途,而是应该还可用于其它工业如个人护理或家用护理。
本发明提供粉状组合物,其包含:
a)至少一种核壳颗粒形式的粉末,所述核包含液态水或液态水相,并且所述壳包含疏水性或疏水化的颗粒,和
b)至少一种包含载体和以下物质的粉末,以下物质分别位于所述载体之中和/或之上:
b1)至少部分可溶于水的液体和/或
b2)水反应性基质。
所述可溶于水的液体和水反应性基质通过毛细作用/吸收/吸附可逆地结合至载体,并且可被核壳颗粒的液态水或液态水相从载体部分或完全地冲洗或溶解。载体本身可以是水溶性的或者非水溶性的。
作为本发明的组合物的组成部分的核壳颗粒是指包含液态水或液态水相的粉状材料,但是其中疏水性或疏水化的颗粒的壳阻止单个水滴的聚集。该壳在通过压力、剪切、温度、振动和/或添加一种或多种溶剂或者一种或多种表面活性剂活化时能够从核释放液态水相或液态水。这些种类的核壳颗粒称为“干水”。水相可以是水溶液、水分散体或水乳液。
疏水性颗粒应理解为疏水性颗粒本身,而疏水化的颗粒是通过使亲水性颗粒的表面与疏水性表面改性剂反应而得的那些。通常在颗粒表面的反应基团如羟基与表面改性剂的反应基团之间形成共价键。
“疏水性”通常是指与水仅略有相互作用或无相互作用并且对水的亲和性小或为零。甲醇润湿性可用来定量衡量疏水性。本发明的壳颗粒的甲醇润湿性应为至少40,优选50-80,更优选60–70。为了测定甲醇润湿性,在每种情况中,将0.2g(±0.005g)疏水性或疏水化的颗粒称入透明离心管中。将8.0ml份的含有10体积%、20体积%、30体积%、40体积%、50体积%、60体积%、70体积%或80体积%甲醇的甲醇/水混合物加入每个样品中。摇动管30秒,然后在2500min-1下离心5分钟。甲醇润湿性定义为相对于沉积物体积100%,甲醇的体积百分比。该值越高,疏水性越高。
本发明中可使用的核壳颗粒的疏水性或疏水化的壳包括例如无机粉末,例如滑石、高岭土、云母、绢云母、白云石、金云母、合成云母、锂云母(lepidolite)、黑云母、锂云母(lithia mica)、蛭石、碳酸镁、碳酸钙、硅酸铝、硅酸钡、硅酸钙、硅酸镁、硅酸锶、钨酸金属盐、镁、二氧化硅、沸石、硫酸钡、煅烧硫酸钙、磷酸钙、氟磷灰石、羟磷灰石、二氧化钛、热解法二氧化钛、氧化铝和热解法氧化铝。
在这些形成三维网状物的疏水化的二氧化硅颗粒中,聚集的结构是优选的壳材料。所述二氧化硅可以是沉淀二氧化硅或热解法二氧化硅,优选后者。热解法二氧化硅通过火焰水解或火焰氧化法获得。它的纯度高于99重量%,通常高于99.8重量%。热解法二氧化硅通常形成聚集初始颗粒的三维网状物。热解法二氧化硅初始颗粒在它们的表面具有羟基并且无孔。
沉淀和热解法二氧化硅颗粒以及适合用作壳颗粒的其它颗粒是需要在下一步骤中被疏水化的亲水性颗粒。此步骤的工序是本领域技术人员已知的。
适合的表面改性剂可以是以下硅烷,其可单独地或作为混合物使用。
有机硅烷(RO)3Si(CnH2n+1)和(RO)3Si(CnH2n-1),其中R=烷基,例如甲基、乙基、正丙基、异丙基、丁基,并且n=1-20。
有机硅烷R'x(RO)ySi(CnH2n+1)和R'x(RO)ySi(CnH2n-1),其中R=烷基,例如甲基、乙基、正丙基、异丙基、丁基;R'=烷基,例如甲基、乙基、正丙基、异丙基、丁基;R'=环烷基;n=1-20;x+y=3、x=1、2;y=1、2。
卤代有机硅烷X3Si(CnH2n+1)和X3Si(CnH2n-1),其中X=Cl、Br;n=1-20。
卤代有机硅烷X2(R')Si(CnH2n+1)和X2(R')Si(CnH2n-1),其中X=Cl、Br,R'=烷基,例如甲基、乙基、正丙基、异丙基、丁基;R'=环烷基;n=1-20。
卤代有机硅烷X(R')2Si(CnH2n+1)和X(R')2Si(CnH2n-1),其中X=Cl、Br;R'=烷基,例如甲基、乙基、正丙基、异丙基、丁基;R'=环烷基;n=1-20。
有机硅烷(RO)3Si(CH2)m-R',其中R=烷基,例如甲基、乙基、丙基;m=0–20,R'=甲基、芳基例如-C6H5、取代的苯基、C4F9、OCF2-CHF-CF3、C6F13、OCF2CHF2、Sx-(CH2)3Si(OR)3。
有机硅烷(R")x(RO)ySi(CH2)m-R',其中R"=烷基、x+y=3;环烷基,x=1、2,y=1、2;m=0.1-20;R'=甲基、芳基例如C6H5、取代的苯基、C4F9、OCF2-CHF-CF3、C6F13、OCF2CHF2、Sx-(CH2)3Si(OR)3、SH、NR'R''R″′,其中R'=烷基、芳基;R''=H、烷基、芳基;R'''=H、烷基、芳基、苄基、C2H4NR″″R″″′,其中R″″=H、烷基,R″″′=H、烷基。
卤代有机硅烷X3Si(CH2)m-R',其中X=Cl、Br;m=0-20;R'=甲基、芳基例如C6H5、取代的苯基、C4F9、OCF2-CHF-CF3、C6F13、O-CF2-CHF2、Sx-(CH2)3Si(OR)3,其中R=甲基、乙基、丙基、丁基,并且x=1或2、SH。
卤代有机硅烷RX2Si(CH2)mR',其中X=Cl、Br;m=0-20;R'=甲基、芳基例如C6H5、取代的苯基、C4F9、OCF2-CHF-CF3、C6F13、O-CF2-CHF2、-OOC(CH3)C=CH2、-Sx-(CH2)3Si(OR)3,其中R=甲基、乙基、丙基、丁基,并且x=1或2,SH。
卤代有机硅烷R2XSi(CH2)mR',其中X=Cl、Br;m=0-20;R'=甲基、芳基例如C6H5、取代的苯基、C4F9、OCF2-CHF-CF3、C6F13、O-CF2-CHF2、-Sx-(CH2)3Si(OR)3,其中R=甲基、乙基、丙基、丁基并且x=1或2,SH。
硅氮烷R'R2SiNHSiR2R',其中R、R'=烷基、乙烯基、芳基。
环聚硅氧烷D3、D4、D5及它们的同系物,其中D3、D4和D5是指含有3、4或5个-O-Si(CH3)2型单元的环聚硅氧烷,例如,八甲基环四硅氧烷=D4。
Y-O[[-SiRR’-O]m-[SiR”R”’-O]n]u-Y型聚硅氧烷或硅油,其中R=烷基;R'=烷基、芳基、H;R''=烷基、芳基;R'''=烷基、芳基、H;Y=CH3、H、CzH2z+1其中z=1-20,Si(CH3)3、Si(CH3)2H、Si(CH3)2OH、Si(CH3)2(OCH3)、Si(CH3)2(CzH2z+1)并且z=1-20,m=0、1、2、3、…,n=0、1、2、3、…,u=0、1、2、3、…。
可优选以下化合物作为表面改性剂:辛基三甲氧基硅烷、辛基三乙氧基硅烷、六甲基二硅氮烷、十六烷基三甲氧基硅烷、十六烷基三乙氧基硅烷、二甲基聚硅氧烷、九氟己基三甲氧基硅烷、十三氟辛基三甲氧基硅烷、十三氟辛基三乙氧基硅烷。可特别优选使用六甲基二硅氮烷、辛基三乙氧基硅烷和二甲基聚硅氧烷。
本发明的粉状组合物的壳颗粒可以是BET表面积优选为30m2/g-500m2/g,更优选100m2/g-350m2/g的疏水化的二氧化硅颗粒。由于与表面改性剂反应,这些颗粒可包含0.1重量%-15重量%,通常0.5重量%-5重量%的碳。
可用作壳材料的典型实例是:R104(八甲基环四硅氧烷;150m2/g;55);R106(八甲基环四硅氧烷;250m2/g;50);R202(聚二甲基硅氧烷;100m2/g;75);R805(辛基硅烷;150m2/g;60);R812(六甲基二硅氮烷;260m2/g;60);R812S (六甲基二硅氮烷;220m2/g;65);R8200(六甲基二硅氮烷;150m2/g;65)。
括号内的说明是指表面改性剂、以及按照本说明书给出的方法测得的近似BET表面积和近似甲醇润湿性。
特别有用的壳颗粒材料是通过使BET表面积为270-330m2/g的亲水性热解法二氧化硅颗粒与六甲基二硅氮烷反应获得的疏水化的二氧化硅颗粒。所得的疏水化的二氧化硅颗粒的BET表面积为200-290m2/g,碳含量为2重量%-4重量%,甲醇润湿性为至少50,更优选50-70。
还可有益地使用紧密或颗粒形式的疏水化的热解法二氧化硅颗粒。
要讨论的核壳颗粒的另一部分是核。所述核包含液态水,并且是液态水本身的形式,或者液态水溶液形式、包含液态水的乳液或水分散体。在液态水溶液或乳液的情况中溶解或乳化的材料,或者在水分散体的情况中固体材料,应选自既不显著降低所述核的表面张力也不润湿所述壳的疏水性或疏水化的颗粒的那些材料。对于液态水溶液,这是指该溶液不应包含大于10重量%的被溶解的材料,优选包含不大于3重量%的被溶解的材料。液态水本身是最优选的核材料。
所述核可由包含至多10重量%的化合物的液态水相组成,可使用在化妆品、个人护理或家庭护理中典型使用的化合物,只要它们既不降低所述核的表面张力也不润湿所述壳的疏水性或疏水化的颗粒。与包含至少部分可溶于水的液体和/或水反应性基质的载体一起讨论典型实例。
所述核壳颗粒的水含量通常占所述核壳颗粒的75重量%-95重量%。
本发明的粉状组合物包含紧邻核壳颗粒的粉末,其由至少另一种其它粉末组成,其定义为包含分别位于载体之中和/或之上的至少部分可溶于水的液体或水反应性基质的载体。
在所述核壳颗粒通过压力、剪切、温度、振动和/或添加一种或多种溶剂或者一种或多种表面活性剂活化的情况中,所述可溶于水的液体能够部分或完全地从载体被该核壳颗粒的核材料冲洗或者溶解。这意味着可溶于水的液体部分或完全地从载体被所述核的水或水相溶解。或者,可溶于水的液体可部分或完全地从载体被所述核的水或水相冲洗。
同样适用于水反应性基质。水反应性基质是不溶于水或者仅可少量溶解的材料。当被水或水相活化时,它被转化成基本上或完全可溶的反应产物。
所述载体优选选自二氧化硅、二氧化硅-金属氧化物的混合氧化物如二氧化硅-氧化铝混合氧化物、二氧化硅-二氧化钛混合氧化物、层状硅酸盐、淀粉、中空玻璃球、尼龙、糖、环糊精和多糖。
在本发明的一个特别的实施方案中,所述载体选自热解法二氧化硅或沉淀二氧化硅,利用亲水性和疏水化的形式获得良好的结果。
在本发明的另一个特定的实施方案中,所述载体是沉淀二氧化硅,所述沉淀二氧化硅具有以下特征:
a)BET表面积为50-1000m2/g,优选100-700m2/g,更优选150-500m2/g,
b)通过激光衍射测得的粒度d50为2-100μm,优选3-20μm,更优选4-10μm,和
c)DBP(邻苯二甲酸二丁基酯)吸收为200-400,优选250-350gDBP/100g二氧化硅)。
对干燥后的物质,按照ISO 5794-1附录D测定BET表面积,按照ASTM690-1992测定粒度d50,按照ASTM D 2414测定DBP吸收。
具体的沉淀二氧化硅包括BET表面积为400-500m2/g,粒度d50为4-6μm并且DBP吸收为300-350g DBP/100g二氧化硅的材料。此外,另一种材料的BET表面积为150-250m2/g,粒度d50为4-7μm并且DBP吸收为250-300g DBP/100g二氧化硅。典型的实例是均来自Evonik Degussa的500LS和22LS。
至少部分可溶于水的液体和/或水反应性基质与载体的重量比取决于多种因素,例如可溶于水的液体的粘度、载体的结构包括孔径、孔体积和BET表面积。通常为10-90,优选60-75。
包含至少部分水溶性液体和/或水反应性基质的载体与核壳颗粒的重量比通常为1:1-1:9。
通过例如透射电子显微镜测定的载体和核壳颗粒的平均粒度通常可彼此独立地为2-20μm。可优选核壳颗粒的平均粒度是载体平均粒度的50%-150%。
核壳颗粒的核的水相和/或分别在载体之中和/或之上的至少部分可溶于水的液体和/或水反应性基质包含以下材料中的至少一种:紫外光保护过滤物质(UV light protection filters)、抗氧化剂、增湿物质(moisturizingsubstances)、除臭剂、止汗剂活性化合物、生物源物质(biogenic substances)、驱虫剂活性化合物、漂白剂抗氧化剂、漂白剂、抗细菌物质、抗真菌物质、调味剂、芳香剂、酸、碱、酶或它们的混合物。
根据本发明,紫外光保护过滤物质是有机物质,其在室温下呈液态或者结晶并且能够吸收紫外线,再以波长较长的辐射形式释放吸收的能量,例如热。紫外光过滤物质可以是油溶性或水溶性的。油溶性物质是例如:
-3-亚苄基樟脑和3-亚苄基降樟脑及它们的衍生物,
-4-氨基苯甲酸衍生物,优选4-(二甲基氨基)苯甲酸(2-乙基己基)酯、4-(二甲基氨基)苯甲酸(2-辛基)酯和4-(二甲基氨基)苯甲酸戊基酯,
-肉桂酸酯,优选4-甲氧基肉桂酸(2-乙基己基)酯、4-甲氧基肉桂酸丙基酯、4-甲氧基肉桂酸异戊基酯、2-氰基-3,3-苯基肉桂酸(2-乙基己基)酯(氰双苯丙烯酸辛酯,octocrylene)
-水杨酸酯,优选水杨酸(2-乙基己基)酯、水杨酸(4-异丙基苄基)酯、水杨酸(3,3,5-环己基)酯
-二苯甲酮衍生物,优选2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-4'-甲基二苯甲酮、2,2'-二羟基-4-甲氧基二苯甲酮
-苄基丙二酸酯(esters of benzalmalonic acid),优选4-甲氧基苄基丙二酸二(2-乙基己基)酯
-三嗪衍生物,例如2,4,6-三苯胺基-(对甲酰基-2'-乙基-1'-己氧基)-1,3,5-三嗪、辛基三嗪酮和二辛基丁酰胺基三嗪酮
-丙烷-1,3-二酮,例如1-(4-叔丁基苯基)-3-(4'-甲氧基苯基)丙烷-1,3-二酮
可用的水溶性物质是:
-2-苯基苯并咪唑-5-磺酸及其碱金属盐、碱土金属盐、铵盐、烷基铵盐、烷醇铵盐和葡糖铵盐
-二苯甲酮的磺酸衍生物,优选2-羟基-4-甲氧基二苯甲酮-5-磺酸及其盐
-3-亚苄基樟脑的磺酸衍生物,例如,4-(2-氧代-3-亚冰片基甲基)苯磺酸和2-甲基-5-(2-氧代-3-亚冰片基)磺酸及其盐。
典型的UV-A滤过剂是苯甲酰基甲烷衍生物,例如,1-(4'-叔丁基苯基)-3-(4'-甲氧基苯基)丙烷-1,3-二酮、4-叔丁基-4'-甲氧基二苯甲酰基甲烷、1-苯基-3-(4'-异丙基苯基)-丙烷-1,3-二酮。
当然,UV-A和UV-B过滤物质还可混合使用。特别有利的组合包括,苯甲酰基甲烷的衍生物如4-叔丁基-4'-甲氧基二苯甲酰基甲烷和2-氰基-3,3-苯基肉桂酸(2-乙基-己基)酯(氰双苯丙烯酸辛酯)与肉桂酸酯优选4-甲氧基肉桂酸(2-乙基己基)酯和/或4-甲氧基肉桂酸丙基酯和/或4-甲氧基肉桂酸异戊基酯组合。这样的组合有利地与水溶性过滤物质例如2-苯基苯并咪唑-5-磺酸及其碱金属盐、碱土金属盐、铵盐、烷基铵盐、烷醇铵盐和葡糖铵盐组合。
除了上述有机物质之外,不溶性光保护色素,即精细分散的金属氧化物粉末的原样或者疏水化的形式和盐也可用于此目的。适合的金属氧化物粉末或疏水化的金属氧化物粉末的实例可以是二氧化钛粉末、氧化锌粉末和/或含有元素Si、Ti、Al、Zn、Fe、B、Zr和/或Ce的这些混合氧化物粉末。
典型的实例是:被包覆的二氧化钛例如UV-Titan M212、M 262和X 111(Kemira);TiO2P25、PF2、T 805和T 817(Evonik Degussa)、微二氧化钛MT-150W、MT-100AQ、MT-100SA、MT-100HD、MT-100TV(Tayca)、Eusolex TM T2000(Merck)、氧化锌中性H&R和氧化锌NDM(Haarmann&Reimer)以及Z-Cote和Z-Cote HP1(BASF)。
还可使用分散体,例如,TEGO Sun TAQ 40,40重量%浓度的疏水化的二氧化钛水分散体(Evonik Goldschmidt)。
作为本发明的粉状组合物的组成部分的典型抗氧化剂可以是:
-氨基酸如甘氨酸、组氨酸、酪氨酸或色氨酸及它们的衍生物,
-咪唑如尿刊酸)及它们的衍生物,
-肽,例如D,L-肌肽、D-肌肽、L-肌肽及它们的衍生物,
-类胡萝卜素、胡萝卜素、α-胡萝卜素、β-胡萝卜素、番茄红素及它们的衍生物,
-绿原酸及它们的衍生物,
-脂酮酸及它们的衍生物
-螯合剂如α-羟基-脂肪酸、棕榈酸、植酸,
-α-羟基酸如柠檬酸、乳酸、苹果酸
-不饱和脂肪酸及它们的衍生物如γ-亚麻酸、亚油酸、油酸,
-叶酸及它们的衍生物,
-泛醌和泛醇及它们的衍生物,
-维生素C及衍生物如棕榈酸抗坏血酸基酯、磷酸抗坏血酸基酯、乙酸抗坏血酸基酯,
-生育酚及衍生物如维生素E、乙酸维生素E,
-维生素A及衍生物如棕榈酸维生素A
-甘露糖及它们的衍生物,
-超氧化物岐化酶。
保湿性物质可选自乙二醇、丁二醇、2,3-丁二醇、丙二醇、二丙二醇、三丙二醇、己二醇、丙三醇、二丙三醇、葡萄糖、果糖、乳糖、蔗糖、麦芽糖、甘露醇、甘露糖、PEG-4至PEG-800、如PEG-4、PEG-6、PEG-7、PEG-8、PEG-9、PEG-10、PEG-12、PEG-14、PEG-16、PEG-18、PEG-20、山梨糖醇、聚甘油山梨糖醇、脲、木糖醇及它们的混合物。
除臭剂和止汗剂活性的化合物可以是选自以下的至少一种:
-收敛剂金属盐,例如水合氯化铝、羟基乳酸铝、水合氯化铝锆和锌盐
-抑菌剂,例如壳聚糖、苯氧基乙醇、葡萄糖酸氯己定或5-氯-2-(2,4-二氯苯氧基)-苯酚
-酶抑制剂,例如
i)柠檬酸三烷基酯,例如柠檬酸三甲酯、柠檬酸三丙基酯、柠檬酸三异丙基酯、柠檬酸三丁基酯和柠檬酸三乙基酯;
ii)固醇硫酸酯或磷酸酯,例如羊毛固醇、胆固醇、菜油固醇、豆固醇及谷固醇硫酸酯和磷酸酯,
iii)二元羧酸及其酯,例如,戊二酸、戊二酸单乙基酯、戊二酸二乙基酯、己二酸、己二酸单乙基酯、己二酸二乙酯、丙二酸和丙二酸二乙酯,
iv)羟基羧酸及其酯,例如柠檬酸、苹果酸、酒石酸或酒石酸二乙酯;或者
v)4-羟基苯甲酸及其盐和酯,N-(4-氯苯基)-N'-(3,4-二氯苯基)脲、2,4,4'-三氯-2'-羟基-二苯基醚(Triclosan)、4-氯-3,5-二甲基-苯酚、2,2'-亚甲基-双(6-溴-4-氯苯酚)、3-甲基-4-(1-甲基乙基)-苯酚、2-苄基-4-氯苯酚、3-(4-氯苯氧基)-1,2-丙二醇、丁基甲酸(3-碘-2-丙炔基)酯、氯己定、3,4,4'-三氯二苯基脲百里酚、百里香油、丁香酚、丁香油、薄荷醇、薄荷油、法尼醇、苯氧基乙醇、甘油单己酸酯、甘油单辛酸酯、甘油单月桂酸酯、双甘油单己酸酯(DMC)、水杨酸N-烷基酰胺例如水杨酸N-辛基酰胺或水杨酸N-癸基酰胺。
-吸收剂或除臭剂如乙酸苄酯、乙酸(对叔丁基环己基)酯、乙酸芳樟酯、乙酸苯乙基酯、苯甲酸芳樟酯、甲酸苄酯、丙酸烯丙基环己基酯、丙酸苏合香脂和水杨酸苄基酯、苄基乙基醚、柠檬醛、香茅醛、香茅氧基乙醛、兔耳草醛、羟基香茅醛、紫罗兰酮、甲基柏木酮、茴香脑、香茅醇、丁香酚、异丁香酚、牛儿醇、芳樟醇、苯基乙醇、萜品醇或萜烯。
生物源物质可选自生育酚、生育酚乙酸酯、生育酚棕榈酸酯、抗坏血酸、(脱氧)核糖核酸及其分裂产物、β-葡聚糖、视黄醇、红没药醇、尿囊素、植烷三醇、泛醇、泛酸、水果酸(fruit acids)、α-羟基酸、氨基酸、神经酰胺、假神经酰胺、精油、植物提取物例如李属提取物(prunus extract)、bambara坚果提取物和复合维生素中的至少一种。
驱虫剂活性化合物可选自N,N-二乙基-间-甲苯酰胺、1,2-戊二醇、3-(N-正丁基-N-乙酰基-氨基)-丙酸乙基酯,和乙酰氨基丙酸丁基酯。
适合于本发明的漂白剂的实例是氢醌、过氧化锌、脲过氧化物、过氧化氢和/或有机过氧化物。
在本发明的一个具体的实施方案中,所述核壳颗粒的核是水,所述壳由疏水化的热解法二氧化硅颗粒组成,所述疏水化的热解法二氧化硅颗粒由BET表面积为30-500m2/g的亲水性的热解法二氧化硅反应而得。
此外,在本发明的一个有利的实施方案中,所述疏水化的热解法二氧化硅颗粒是通过使BET表面积270-330m2/g的亲水性热解法二氧化硅与六甲基二硅氮烷反应而得的,得到的疏水化的热解法二氧化硅颗粒,其BET表面积为200-290m2/g,碳含量为2重量%-4重量%并且甲醇润湿性为至少50。
该具体的实施方案还可包含作为载体的沉淀二氧化硅,其BET表面积为400-500m2/g,经激光衍射测得的粒度d50为4-6μm,并且DBP(邻苯二甲酸二丁基酯)吸收为300–350g DBP/100g二氧化硅。
该具体的实施方案还可包含作为载体的沉淀二氧化硅,其BET表面积为150-250m2/g,经激光衍射测得的粒度d50为4-7μm,并且DBP(邻苯二甲酸二丁基酯)吸收为250-300g DBP/100g二氧化硅。
另外,该具体的实施方案还可包含分别位于所述载体之中和/或之上的作为至少部分可溶于水的液体和/或水反应性基质的紫外光保护过滤物质、抗氧化剂、增湿物质、除臭剂、止汗剂活性化合物、生物源物质、驱虫剂活性化合物、漂白剂抗氧化剂、漂白剂、抗细菌物质、抗真菌物质、调味剂、芳香剂、酸、碱、酶或它们的混合物。
本发明的另一目的是由本发明的粉状组合物制备乳膏状组合物的方法。此粉状组合物通过能量输入而活化,所述能量输入的形式是压力、剪切、温度、振动和/或添加溶剂,该能量输入足以从核-壳材料释放液态水或液态水相,然后,
a)所述液态水或液态水相从所述载体溶解或冲洗至少部分可溶于水的液体,和/或
b)所述液态水或液态水相活化所述载体之中和/或之上的水反应性基质,然后从所述载体溶解或冲洗经活化而得的产物。
“乳膏状”应理解为是指从更似液体组合物至更似凝胶组合物至乳膏状组合物。
已概括地描述本发明,可参照仅以说明而非限制为目的提供的某些具体实施例进一步理解本发明。
实施例
实施例1:现有技术的粉状-乳膏状-粉状粉底(powder foundation)
为了制备干水制剂,将77.5重量%的去离子(DI)水与10.48重量%的来自The Dow Chemical Company的Carbowax聚乙二醇400NF、5.27重量%的来自Chemsil Silicones,Inc.的DM-20(20cPs)、1.75重量%的来自Kobo的铁氧化物色素AC-5Red R516P、AC-5 Yellow LL-100P、AC-5Black BL-100P和AC-5TiO2CR-50一起加入#KSB5ER4型KitchenAid混合机中。将R812S以5.0重量%加在水/PEG/二甲聚硅氧烷/色素混合物上。在混合机上紧密加盖,在最高挡(液化)以9,700RPM混合混合物1分钟。在1分钟的混合过程中,从左至右以50-60度角倾斜整个混合机保持10秒。
在约30分钟后,产品是在底部具有明显分离的乳膏/摩丝状。由于在与疏水性二氧化硅混合时没有形成稳定分离的小液滴,添加PEG和二甲聚硅氧烷的方法失败。认为润滑剂大幅降低水的表面张力以至它能够克服液滴与R812S之间的界面张力。
实施例2:本发明的粉状-乳膏状-粉状粉底
为了按照本发明制备新的粉状-乳膏状粉底制剂,通过将42.9重量%的来自The Dow Chemical Company的PEG聚乙二醇400NF、21.4重量%的来自Chemsil Silicones的DM-20(20cPs)、28.6重量%去离子(DI)水和7.1重量%的来自Kobo的AC-5铁氧化物色素混合产生PEG/二甲聚硅氧烷/色素/DI水稀释液。然后采用金属刮刀通过手工低剪切混合,在3-4加料步骤中将此溶液加入22LS中。所得的粉末产品是由70重量%润滑剂/色素溶液液体和30重量%载体组成的混合物。现将此粉末产品称为液体/载体。
通过添加5重量%的R812S、20重量%铁氧化物AC-5色素和75重量%的DI水制得干水。在混合机上紧密加盖,在最高挡(液化)以9,700RPM混合混合物1分钟。在1分钟混合的过程中,从左至右以50-60度角倾斜整个混合机保持约10秒。
然后将35重量%的液体/载体与65重量%干水混合物温和混合(翻滚、搅拌或调入)以制备最终的粉状-乳膏状粉底。
然后将此粉末储藏在塑料容器中。能够产生粉状组合物并且保持粉状。
实施例3:现有技术的粉状-乳膏状维生素油膏(rub)
称量13.71重量%的润滑剂聚乙二醇(来自的The Dow ChemicalCompany的PEG聚乙二醇400NF)、2.75重量%维生素E(JEENInternational Corp.)、78.54重量%的DI水和5.0重量%R812S并置于KSB5ER4型KitchenAid混合机中,以其最高速度(9,700rpm,液化)混合1分钟。在1分钟混合的过程中,从左至右以45度角倾斜混合机在每侧保持约10秒。
在约半小时后,最终产品呈在底部具有明显分离的乳膏状/摩丝状。
实施例4:本发明的粉状-乳膏状维生素油膏
配制71.4重量%聚乙二醇(来自The Dow Chemical Company的PEG聚乙二醇400NF)、14.3重量%维生素E(来自JEEN InternationalCorp.)和14.3重量%DI水的液体混合物。然后该液体混合物用来制备64.0重量%液体混合物,以36.0重量%22LS为载体。在3-4加料步骤中,将液体混合物缓慢加入22LS中,利用低剪切混合(在此情况中手工混合)直至混合均一。
然后将所得的粉末(30重量%)温和地混合(翻滚、搅拌或调入)入70重量%干水中。
然后将粉末储藏在塑料容器中。
表1:实施例1–4的配方的成分[重量%]
Claims (17)
1.粉状组合物,其包含:
a)至少一种核壳颗粒形式的粉末,所述核包含液态水或液态水相,并且所述壳包含疏水性或疏水化的颗粒,和
b)至少一种包含载体和以下物质的粉末,以下物质分别位于所述载体之中和/或之上:
b1)至少部分可溶于水的液体和/或
b2)水反应性基质,所述水反应性基质不溶于水,并且当被水或水相活化时,所述水反应性基质被转化成可溶于水的反应产物,
其中,所述载体的形式为沉淀二氧化硅,所述沉淀二氧化硅具有以下特征:
i)BET表面积为50-1000m2/g,
ii)经激光衍射测得的粒度d50为3-20μm,并且
iii)邻苯二甲酸二丁基酯DBP吸收为200-400g DBP/100g二氧化硅。
2.权利要求1的粉状组合物,其中所述壳颗粒包含或由疏水化的二氧化硅颗粒组成。
3.权利要求2的粉状组合物,其中所述疏水化的二氧化硅颗粒是聚集的热解法二氧化硅颗粒。
4.权利要求2的粉状组合物,其中所述疏水化的二氧化硅颗粒的BET表面积为30m2/g-500m2/g。
5.权利要求2的粉状组合物,其中所述疏水化的二氧化硅颗粒是通过使BET表面积270-330m2/g的亲水性热解法二氧化硅与六甲基二硅氮烷反应而得的,得到的疏水化的热解法二氧化硅颗粒的BET表面积为200-290m2/g,碳含量为2重量%-4重量%,并且甲醇润湿性为至少50。
6.权利要求1的粉状组合物,其中所述核由包含90重量%以上的水的液态水相组成。
7.权利要求1的粉状组合物,其中所述核壳颗粒的水含量为75重量%-95重量%。
8.权利要求1的粉状组合物,其中所述包含至少部分可溶于水的液体和/或水反应性基质的载体与所述核壳颗粒的重量比为1:1-1:9。
9.权利要求1的粉状组合物,其中所述载体和所述核壳颗粒的平均粒度为2-20μm。
10.权利要求9的粉状组合物,其中所述核壳颗粒的平均粒度是所述载体的平均粒度的50%-150%。
11.权利要求1的粉状组合物,其中a)所述核壳颗粒的核的水相和/或b)分别位于所述载体之中和/或之上的所述至少部分可溶于水的液体和/或水反应性基质包含选自如下的至少一种材料:紫外光保护过滤物质、抗氧化剂、增湿物质、除臭剂、止汗剂活性化合物、生物源物质、驱虫剂活性化合物、漂白剂、抗细菌物质、抗真菌物质、调味剂、芳香剂、酸、碱、酶或它们的混合物。
12.权利要求1的粉状组合物,其中所述核壳颗粒的核是水,并且所述壳由疏水化的热解法二氧化硅颗粒组成,所述疏水化的热解法二氧化硅颗粒由BET表面积为30-500m2/g的亲水性的热解法二氧化硅反应而得。
13.权利要求12的粉状组合物,其中所述疏水化的热解法二氧化硅颗粒是通过使BET表面积为270-330m2/g的亲水性热解法二氧化硅与六甲基二硅氮烷反应而得的,得到的疏水化的热解法二氧化硅颗粒的BET表面积为200-290m2/g,碳含量为2重量%-4重量%,并且甲醇润湿性为至少50。
14.权利要求12的粉状组合物,其中所述载体的形式是沉淀二氧化硅,该沉淀二氧化硅的BET表面积为400-500m2/g,经激光衍射测得的粒度d50为4-6μm,并且邻苯二甲酸二丁基酯DBP吸收为300-350g DBP/100g二氧化硅。
15.权利要求12的粉状组合物,其中所述载体的形式是沉淀二氧化硅,该沉淀二氧化硅的BET表面积为150-250m2/g,经激光衍射测得的粒度d50为4-7μm,并且邻苯二甲酸二丁基酯DBP吸收为250-300g DBP/100g二氧化硅。
16.权利要求12-15中任一项的粉状组合物,其还包含分别位于所述载体之中和/或之上的作为至少部分可溶于水的液体和/或水反应性基质的紫外光保护过滤物质、抗氧化剂、增湿物质、除臭剂、止汗剂活性化合物、生物源物质、驱虫剂活性化合物、漂白剂、抗细菌物质、抗真菌物质、调味剂、芳香剂、酸、碱、酶或它们的混合物。
17.由权利要求1的粉状组合物制备乳膏状组合物的方法,其中所述粉状组合物通过能量输入而活化,所述能量输入的形式是压力、剪切、温度、振动和/或添加溶剂,并且所述能量输入足以从所述核-壳材料释放所述液态水或所述液态水相,然后,
a)所述液态水或液态水相从所述载体溶解或冲洗所述至少部分可溶于水的液体,和/或
b)所述液态水或液态水相活化所述载体之中和/或之上的水反应性基质,然后从所述载体溶解或冲洗经活化而得的产物。
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US8647653B2 (en) | 2014-02-11 |
CN102686207A (zh) | 2012-09-19 |
BR112012018812B1 (pt) | 2020-12-15 |
KR101431932B1 (ko) | 2014-08-19 |
CA2785753A1 (en) | 2011-06-30 |
WO2011076518A1 (en) | 2011-06-30 |
CA2785753C (en) | 2016-12-06 |
US20130022656A1 (en) | 2013-01-24 |
EP2515829B1 (en) | 2016-08-10 |
EP2515829A1 (en) | 2012-10-31 |
JP5746210B2 (ja) | 2015-07-08 |
MX2012007285A (es) | 2012-07-30 |
JP2013515689A (ja) | 2013-05-09 |
KR20120091389A (ko) | 2012-08-17 |
BR112012018812A2 (pt) | 2020-09-01 |
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