CN101257888B - 仿晒化妆品 - Google Patents
仿晒化妆品 Download PDFInfo
- Publication number
- CN101257888B CN101257888B CN2005800514733A CN200580051473A CN101257888B CN 101257888 B CN101257888 B CN 101257888B CN 2005800514733 A CN2005800514733 A CN 2005800514733A CN 200580051473 A CN200580051473 A CN 200580051473A CN 101257888 B CN101257888 B CN 101257888B
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- Prior art keywords
- self
- tanning cosmetic
- mentioned
- oiliness
- acid
- Prior art date
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- 239000002537 cosmetic Substances 0.000 title claims abstract description 87
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 229940120503 dihydroxyacetone Drugs 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000008346 aqueous phase Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 14
- -1 silane compound Chemical class 0.000 claims description 36
- 239000004531 microgranule Substances 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 230000036541 health Effects 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 3
- 229920000800 acrylic rubber Polymers 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
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- 239000000463 material Substances 0.000 description 4
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 4
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- 229920002125 Sokalan® Polymers 0.000 description 3
- DRRMRHKHTQRWMB-UHFFFAOYSA-N [3-(2-ethylhexanoyloxy)-2,2-bis(2-ethylhexanoyloxymethyl)propyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(COC(=O)C(CC)CCCC)(COC(=O)C(CC)CCCC)COC(=O)C(CC)CCCC DRRMRHKHTQRWMB-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明提供一种仿晒化妆品,其中含有:0.2~20.0%质量二羟基丙酮;0.01~3.0%质量经疏水化处理的含金属粉末;相对于上述经疏水化处理的含金属粉末,以质量比计为5~20倍量的固体油分,该化妆品的特征在于:将上述含金属粉末用上述固体油分胶囊化而得到的油性微粒分散在溶解有二羟基丙酮的水相中。根据本发明,可以提供由珠光剂产生的演出效果和二羟基丙酮产生的长期染色效果可以并存、且保存稳定性和使用感优异的仿晒化妆品。
Description
技术领域
本发明涉及仿晒(self-tanning)化妆品。更详细而言,特别是涉及能够稳定混合珠光剂、使用感也优异的、含二羟基丙酮的仿晒化妆品。
背景技术
仿晒化妆品是指使皮肤着色的化妆品。染色剂产生的着色效果通常自涂布后数小时开始,维持最强着色效果1~2天,之后该效果递减,1周后回复到原来的肤色。
仿晒化妆品是指不必暴露于有害的紫外线下,而可以提供外观上自然且健康的日晒色皮肤的化妆品。作为具有持续着色效果的仿晒化妆品,已知有混合染色剂二羟基丙酮的仿晒化妆品(专利文献1~5)。
另一方面,作为身体用仿晒化妆品,从铺展性良好、易干燥的角度考虑,优选凝胶状仿晒化妆品。另外,为了美化皮肤而混合有珠光剂的仿晒化妆品非常受欢迎。
而且,在身体用仿晒化妆品中,要求象水凝胶状化妆品一样清爽、湿润的使用感。
专利文献1:日本特开平7-101843号公报
专利文献2:日本特开平7-101848号公报
专利文献3:日本特开2001-213747号公报
专利文献4:日本特开2002-338448号公报
专利文献5:日本特开2005-145860号公报
发明内容
发明所要解决的问题
然而,仿晒化妆品中混合的二羟基丙酮随时间而分解,存在着化妆品的色调发生变化、产生不愉快的臭气的问题。特别是二羟基丙酮,在混合无机金属氧化物等含金属粉末时极其不稳定。因此,非常难以制造将二羟基丙酮和颜料或珠光剂并用的水凝胶状化妆品。
鉴于上述问题,本发明人等反复进行深入研究,结果发现:若将珠光剂用固体油分胶囊化后混合到含有二羟基丙酮的水相中,则可防止二羟基丙酮的不稳定化,并且可以提供使用感也极其优异的水凝胶状仿晒化妆品,从而完成了本发明。
本发明的目的在于提供稳定性和使用感极其优异的、混合有珠光剂的仿晒化妆品。
解决问题的方法
即,本发明提供仿晒化妆品,其中含有:0.2~20.0%质量二羟基丙酮;0.02~3.0%质量经疏水化处理的含金属粉末;以及相对于上述经疏水化处理的含金属粉末,以质量比计为5~20倍量的固体油分,该仿晒化妆品的特征在于:将上述含金属粉末用上述固体油分胶囊化而得到的油性微粒分散在溶解有二羟基丙酮的水相中。
本发明还提供上述仿晒化妆品,其特征在于:上述含金属粉末为珠光剂。
本发明进一步提供上述仿晒化妆品,其特征在于:使上述固体油分在高温下熔化,向其中分散施行了疏水化处理的上述含金属粉末,将所得油相在搅拌下添加到水相中,然后骤冷,从而用上述固体油分使上述含金属粉末胶囊化,将该胶囊化的油性微粒分散在上述水相中。
本发明还提供上述仿晒化妆品,其特征在于:上述胶囊化的油性微粒中含有丙烯酸/丙烯酸烷基酯共聚物。
本发明进一步提供上述仿晒化妆品,其特征在于:上述胶囊化的油性微粒的粒径为50μm~0.5mm。
本发明还提供上述仿晒化妆品,其特征在于:上述水相中含有增粘剂。
本发明进一步提供上述仿晒化妆品,其特征在于:上述仿晒化妆品为身体用仿晒化妆品。
发明效果
(1)本发明的仿晒化妆品,可防止由珠光剂(一种含金属粉末)引起的二羟基丙酮的不稳定化。即,可以提供由珠光剂产生的演出效果和二羟基丙酮产生的长期染色效果可以并存、且保存稳定性和使用感优异的仿晒化妆品。
(2)本发明的仿晒化妆品,其使用感极其优异。即,由于是水凝胶状化妆品,因此铺展性好、清爽,具有湿润的使用感。
(3)本发明的仿晒化妆品,由于可以在具透明感的基质中稳定混合珠光剂,因此可以提供掺杂有颗粒的水凝胶一样的外观。
(4)本发明的仿晒化妆品干燥快,涂布后立即可以着装。因此,适合用作身体用仿晒化妆品。
实施发明的最佳方式
[二羟基丙酮]
本发明中使用的二羟基丙酮也简记作DHA,是仿晒化妆品中通常使用的公知化妆品原料(皮肤用染色剂)。其在仿晒化妆品中的含量要求为:相对于仿晒化妆品总量,二羟基丙酮为0.2~20.0%质量,优选为1.0~15.0%质量。若其含量不足0.2%质量,则无法得到仿晒效果。另一方面,若含量超过20.0%质量,则保存稳定性恶化。
本发明中使用的二羟基丙酮的纯度优选为90.0%质量以上,更优选为95.0%质量以上,进一步优选为97.0%质量以上。
本发明中,二羟基丙酮溶解于水相中含有。
[用固体油分胶囊化的含金属粉末]
本发明中使用的含金属粉末,按照公知的方法(参照例如日本特开2003-73230号公报),用固体油分使其胶囊化。用固体油分进行的胶囊化是指在包含固体油分的油性微粒中,使含金属粉末以内包化的状态存在的状态(不是含金属粉末仅附着在油性微粒表面的状态)。容易理解的例子为:口红等固体油脂中含有含金属粉末,且该粉末成为可分散于水相中的粒径的状态。
油性微粒中除了存在固体油分、含金属粉末以外,还可以存在其他油分或其他疏水性成分。
应说明的是,油性微粒分散在水相中,其平均粒径优选为50μm~0.5mm。
将含金属粉末胶囊化的固体油分在仿晒化妆品中的含量为:相对于经疏水化处理的含金属粉末的含量,以质量比计为5倍以上、20倍量以下。即,固体油分与经疏水化处理的含金属粉末的比例(质量比)为5/1~20/1。若固体油分与经疏水化处理的含金属粉末的质量比不足5/1,则含金属粉末的胶囊化不完全,保存稳定性恶化。在增加固体油分量的同时失去作为水凝胶状的使用感,因此从使用感的角度考虑,希望固体油分与含金属粉末的比例少,作为在仿晒化妆品中的含量也希望为30%质量以下。
经疏水化处理的含金属粉末在仿晒化妆品中的含量要求为0.02~3.0%质量,优选为0.1~2.0%质量。若其含量不足0.01%质量,则皮肤或基质的演出效果不足。另一方面,若含量超过3.0%质量,则由于胶囊化所必需的油分量变多,而表现为油性大的使用感,失去作为水凝胶状的使用感。
本发明中,含金属粉末是指金属原子化合物的粉末。例如包括:二氧化钛、氧化锌等无机白色系颜料;氧化铁(氧化铁红)、钛酸铁等无机红色系颜料;γ-氧化铁等无机黑色系颜料;锰紫、钴紫等无机紫色系颜料;氧化铬、氢氧化铬、钛酸钴等无机绿色系颜料;群青、绀青等无机蓝色系颜料;氧化钛包覆的云母、氧化铁包覆的云母、氧化钛包覆的氯氧化铋、氧化钛包覆的滑石粉、着色氧化钛包覆的云母、氯氧化铋、鱼鳞箔等珠光颜料;铝粉、铜粉等金属粉末颜料。
从皮肤或化妆品基质的演出效果的角度考虑,含金属粉末优选珠光剂。珠光剂可以使用一种或两种以上。珠光剂是指具有干扰色的粉末,可以列举如:云母钛、氧化钛包覆的合成云母、氧化钛和氧化硅包覆的云母、氧化钛包覆的玻璃薄片、氧化钛包覆的二氧化硅薄片、氧化钛包覆的氧化铝薄片、氧化钛薄片、二氧化硅包覆的铝等。
珠光剂等的含金属粉末,其表面必需进行疏水化处理。通过进行疏水化处理,可以高效率地在固体油分中被胶囊化。
对疏水化处理没有特别限定,采用公知方法进行处理。可以列举如:使用甲基氢聚硅氧烷、甲基氢聚硅氧烷/二甲基聚硅氧烷共聚物、二甲基聚硅氧烷等硅氧烷类进行的处理;使用辛基三乙氧基硅烷、己基三甲氧基硅烷等硅烷化合物进行的处理;使用棕榈酸、硬脂酸等脂肪酸进行的处理;使用上述脂肪酸的碱金属盐或碱土金属盐等进行的金属皂处理;使用全氟烷基磷酸二乙醇胺盐、全氟烷基三甲氧基硅烷等进行的氟处理等。本发明中,特别优选经二甲基聚硅氧烷处理的珠光剂。
[混合在油性微粒中的优选的任意含有成分]
包含固体油分的油性微粒中,从抑制油性胶囊聚集的角度考虑,特别优选混合丙烯酸/丙烯酸烷基酯(C10-30)共聚物(PEMULEN TR-2BF Goodrich公司)。
丙烯酸/丙烯酸烷基酯(C10-30)共聚物在仿晒化妆品中的含量,要求相对于仿晒化妆品中构成油性微粒的总油分量为0.02~4.0%质量,特别优选为0.3~0.4%质量。若其含量相对于总油分量不足0.02%质量,则油性微粒的微粒形成能力不足,油性微粒聚集,难以进行胶囊化。另一方面,若其含量超过4.0%质量,则增粘水相的效果过剩,难以制造胶囊。
[增粘剂]
优选在本发明的仿晒化妆品的水相中混合增粘剂。只要是通常化妆品中使用的增粘剂即可,没有特别限定。
但是,从与二羟基丙酮在水相中共存、可提供透明的外观、可以高浓度混合醇的角度考虑,优选日本特开2005-145860号公报中公开的包含微凝胶(microgel)的增粘剂。以下加以说明。
本发明中优选使用的“包含微凝胶的增粘剂”,是指在以有机溶剂或油分为分散介质、以水为分散相的组合物中,将水溶性烯键式不饱和单体溶解在分散相中,在分散相中采用称作反相乳液聚合法的聚合法进行自由基聚合而得到的合成高分子的微凝胶。“微凝胶”是指采用反相微乳聚合法制备的合成高分子电解质的微粒。本发明的包含微凝胶的增粘剂,在水、乙醇或水-乙醇混合溶液中膨胀,可以提供外观上肉眼观察呈均匀的高粘度溶液。
优选通过使用调节至特别适宜选择的亲水亲油平衡(HLB)的表面活性剂,使反相乳液聚合中的聚合系统形成单相微乳或微细W/O型乳剂的条件下,制备包含微凝胶的增粘剂。
“水溶性烯键式不饱和单体”优选将非离子性单体和离子性单体(阴离子性单体或阳离子性单体)并用。
非离子性单体优选通式(1)所示的二烷基丙烯酰胺。
通式(1):
(R1表示H或甲基;R2和R3分别独立表示甲基、乙基、丙基、异丙基)。
“离子性单体”优选通式(2)所示的阴离子性丙烯酰胺衍生物或通式(3)所示的阳离子性丙烯酰胺衍生物。
通式(2):
(R4和R5分别独立表示H或甲基;R6表示碳原子数为1~6的直链或支链烷基;X表示金属离子或NH3)。
通式(3):
(R7表示H或甲基;R8表示H或碳原子数为1~6的直链或支链烷基;R9表示碳原子数为1~6的直链或支链烷基;R10、R11、R12表示甲基或乙基;Y表示金属离子)。
特别优选的二烷基丙烯酰胺为:二甲基丙烯酰胺、二乙基丙烯酰胺。
特别优选的离子性丙烯酰胺衍生物为:2-丙烯酰胺-2-甲基丙磺酸及其盐。
特别优选的阳离子性丙烯酰胺衍生物为:N,N’-二甲氨基丙基丙烯酰胺甲基氯。
关于非离子性单体和离子性单体在聚合系统中的单体组成比(聚合系统的填料比),根据目标微凝胶的单体构成比而适当任意决定。微凝胶的单体构成比和聚合系统的填料比大致相同。非离子性单体和离子性单体在聚合系统中的填料比(摩尔比),通常以非离子性单体∶离子性单体=0.5∶9.5~9.5∶0.5、优选1∶9~9∶1、更优选7∶3~9∶1的范围供给共聚。最佳比例为非离子性单体∶离子性单体=8∶2。
任意选择上述水溶性烯键式不饱和单体,使增粘剂聚合。特别优选的增粘剂为:在水溶性烯键式不饱和单体中使用二甲基丙烯酰胺和2-丙烯酰胺-2-甲基丙磺酸,由这些单体共聚的二元共聚物的微凝胶。该情况下,不需要交联单体,通过自交联而得到发挥优异的增粘效果和使用感的增粘剂。应说明的是,也可以使用交联单体,此时优选通式(4)所示的交联单体,特别优选亚甲基双丙烯酰胺。
在二烷基丙烯酰胺和丙烯酰胺系离子性单体共聚而得到的微凝胶中进行自发交联反应,特别是即使作为第三成分的多官能性交联单体不进行共聚,也可得到化学性自交联的微凝胶,成为本发明中特别优选的增粘剂。
虽然不需要第三成分的多官能性交联单体,但是添加其进行共聚,也可以合成本发明中使用的微凝胶。多官能性交联单体优选通式(4)所示的单体,可以使用一种或两种以上通式(4)所示的交联单体进行交联。这些交联性单体必须在二烷基丙烯酰胺和离子性丙烯酰胺衍生物的聚合系统中能够高效率地获得交联结构。
通式(4):
作为优选的交联性单体,可以列举如:乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、聚氧乙烯二丙烯酸酯、聚氧乙烯二甲基丙烯酸酯、二甘醇二甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、N,N’-亚甲基双丙烯酰胺、N,N’-亚乙基双丙烯酰胺、三聚异氰酸三烯丙酯、季戊四醇二甲基丙烯酸酯等,可以使用选自其中的一种或两种以上。本发明中,特别优选使用N,N’-亚甲基双丙烯酰胺。
共聚物中,2-丙烯酰胺-2-甲基丙磺酸单元和二烷基丙烯酰胺单元的含量的摩尔比通常为2-丙烯酰胺-2-甲基丙磺酸单元∶二烷基丙烯酰胺单元=0.5∶9.5~9.5∶0.5,优选为1∶9~9∶1,更优选为3∶7~1∶9。最佳比为2-丙烯酰胺-2-甲基丙磺酸单元∶二烷基丙烯酰胺单元=2∶8。本发明中使用的增粘剂的粘性起因于根据强解离基团磺酰基的静电斥力引起的分子链的伸展和二烷基丙烯酰胺的自发交联反应或交联性单体形成的交联结构,若2-丙烯酰胺-2-甲基丙磺酸单元或其盐的含量相对于二烷基丙烯酰胺单元不足5%摩尔,则分子链的伸展无法充分发生,因此有时无法得到足够的粘度。
交联性单体的使用量优选以相对于2-丙烯酰胺-2-甲基丙磺酸或其盐与二烷基丙烯酰胺的总摩尔数为0.0001~2.0%摩尔的范围进行添加。以不足0.0001%摩尔制备的增粘剂有时无法得到交联效果。以超过2%摩尔制备时,由于交联密度太高,微凝胶无法充分膨胀,有时未发挥足够的增粘效果。
微凝胶的分子量为重均分子量10万~500万(PEG换算:通过GPC测定)左右,增粘剂根据求得的粘度进行调节。
本发明中用作增粘剂的微凝胶,可以在聚合后经由简单的沉淀纯化步骤,以粉末状态进行分离。
粉末状分离的微凝胶,容易分散于水或乙醇或水/乙醇的混合溶剂中并迅速膨胀,作为增粘剂而发挥功能。而且,具有可以提供透明基质的优点。
另外,通过将微凝胶中共聚的离子性单体选择强酸性的单体(例如含有磺酸残基的单体),也可以增粘用以往的卡波普(聚羧乙烯,carboxyvinyl polymer)无法增粘的酸性制剂。
并且,此微凝胶还可以是以往难以增粘或凝胶化的醇的增粘或凝胶化。特别是作为含有高浓度醇的组合物的增粘剂而发挥优异的效果。
另外,上述增粘剂在水相中发挥增粘或凝胶化的功能,大幅改善二羟基丙酮的染色性。并且,可以制造具有极其优异的使用感的仿晒化妆品。
将上述增粘剂混合到水相中。增粘剂的混合量可适当决定,并无限定。从使用感的角度考虑,优选的混合量为相对于仿晒化妆品总量为0.01~10%(质量百分率),更优选为0.1~5%(质量百分率)。
向仿晒化妆品中混合乙醇时,相对于仿晒化妆品总量,乙醇的含量为1~70%质量,优选为5~20%质量。但是,即使乙醇为30%质量以上的高配比时,例如混合30~50%质量的产品,也可以制造增粘效果优异的稳定组合物。当乙醇为高配比时,增粘剂的混合量稍微多一些,优选0.01~10%质量。
“仿晒化妆品的具体制造方法”
本发明的仿晒化妆品是将油性微粒(例如将象口红一样的固体油性组合物微粒化而得到的微粒)分散在水相中得到的组合物。但是,油性微粒大(优选平均粒径为50μm~0.5mm)并具有可目视确认的外观。而且,作为使用感,成为与含有油性颗粒的水凝胶同样优异的使用感。
构成油相的油分在常温下(15℃)为固体油分,必须在高温下将其熔化。例如,可以使用下述油分。
(1)作为“固体油脂”,可以列举如:可可脂、椰子油(coconut oil)、硬化椰子油、棕榈油、棕榈仁油、木蜡核油、硬化油、木蜡、硬化蓖麻油等。
(2)作为“蜡”,可以列举如:蜂蜡、小烛树蜡、棉蜡、巴西棕榈蜡、月桂子蜡、虫白蜡、鲸蜡、褐煤蜡、糠蜡、羊毛脂、木棉蜡、乙酸羊毛脂、液状羊毛脂、甘蔗蜡、羊毛脂脂肪酸异丙酯、月桂酸己酯、还原羊毛脂、霍霍巴蜡、硬质羊毛脂、虫胶蜡、POE羊毛脂醇醚、POE羊毛脂醇乙酸酯、POE胆固醇醚、羊毛脂脂肪酸聚乙二醇、POE氢化羊毛脂醇醚、纯地蜡、微晶蜡等。
另外,可以向上述固体油分中混合下述油分。
作为“液体油脂”,可以列举如:鳄梨油、山茶油、海龟油、夏威夷果油、玉米油、貂油、橄榄油、菜籽油、蛋黄油、芝麻油、杏仁油、小麦胚芽油、山茶花油、蓖麻油、亚麻籽油、红花油、棉籽油、紫苏子油、大豆油、花生油、茶籽油、椰子油(kaya oil)、米糠油、中国桐油、日本桐油、霍霍巴油、胚芽油、三甘油等。
作为“烃油”,可以列举如:液体石蜡、地蜡、鱼鲨烷、姥鲛烷、石蜡、鱼鲨烯、凡士林等。
作为“高级脂肪酸”,可以列举如:月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、二十二烷酸、油酸、十一碳烯酸、异硬脂酸、亚油酸、亚麻酸、二十碳五烯酸(EPA)、二十二碳六烯酸(DHA)等。
作为“高级醇”,可以列举如:直链醇(例如,月桂醇、鲸蜡醇、硬脂醇、二十二烷醇、肉豆蔻醇、油醇、十八醇十六醇混合物等);支链醇(例如,单十八烷基甘油醚(鲨肝醇)、2-癸基十四烷醇、羊毛脂醇、胆固醇、植物甾醇、己基十二烷醇、异硬脂醇、辛基十二烷醇等)等。
作为“酯油”,可以列举如:肉豆蔻酸异丙酯、辛酸十六烷基酯、肉豆蔻酸辛基十二烷基酯、棕榈酸异丙酯、硬脂酸丁酯、月桂酸己酯、肉豆蔻酸肉豆蔻酯、油酸癸酯、二甲基辛酸己基癸酯、乳酸十六烷酯、乳酸肉豆蔻酯、乙酸羊毛脂、硬脂酸异十六烷酯、异硬脂酸异十六烷酯、12-羟基硬脂酸胆固醇酯、二-2-乙基己酸乙二醇酯、二季戊四醇脂肪酸酯、单异硬脂酸N-烷基二醇酯、二癸酸新戊二醇酯、苹果酸二异硬脂酯、二-2-庚基十一烷酸甘油酯、三(2-乙基己酸)三羟甲基丙烷、三异硬脂酸三羟甲基丙烷、四-2-乙基己酸季戊四醇酯、三-2-乙基己酸甘油酯、三辛酸甘油酯、三异棕榈酸甘油酯、三异硬脂酸三羟甲基丙烷、十六烷基-2-乙基己酸酯、2-乙基己基棕榈酸酯、三肉豆蔻酸甘油酯、三-2-庚基十一烷酸甘油酯、蓖麻油脂肪酸甲酯、油酸油酯、乙酰甘油酯、棕榈酸2-庚基十一烷酯、己二酸二异丁酯、N-月桂酰基-L-谷氨酸-2-辛基十二烷基酯、己二酸二-2-庚基十一烷基酯、月桂酸乙酯、癸二酸二-2-乙基己酯、肉豆蔻酸2-己基癸酯、棕榈酸2-己基癸酯、己二酸2-己基癸酯、癸二酸二异丙酯、琥珀酸2-乙基己酯、枸橼酸三乙酯等。
作为“硅油”,可以列举如:链状聚硅氧烷(例如,二甲基聚硅氧烷、甲基苯基聚硅氧烷、二苯基聚硅氧烷等);环状聚硅氧烷(例如,八甲基环四硅氧烷、十甲基环五硅氧烷、十二甲基环六硅氧烷等);形成三维网状结构的硅氧烷树脂、硅橡胶、各种改性聚硅氧烷(氨基改性聚硅氧烷、聚醚改性聚硅氧烷、烷基改性聚硅氧烷、氟改性聚硅氧烷等)等。
将染色剂二羟基丙酮溶解在水相中。相对于仿晒化妆品总量,构成水相的水的含量通常为40~99%质量,优选50~95%质量。
水相中可以混合乙醇。另外,作为保湿成分,还优选混合甘油、山梨醇等多元醇类、透明质酸等多糖类、焦糖等染色剂类、依地酸盐等螯合剂类、焦亚硫酸钠等稳定化剂类、对羟基苯甲酸甲酯、苯氧乙醇等防腐剂类、吡咯烷酮羧酸等氨基酸类或其他水溶性成分。
<优选的制造方法>
本发明的仿晒化妆品,从得到长期保存稳定性优异的化妆品方面考虑,优选利用下述方法进行制造。
(1)将固体油分和液状油分混合,高温(因油相的种类而异,70~100℃)下将其熔化。混合油溶性活性剂时在此混合。
(2)向高温下熔化的上述油分中添加施行了疏水化处理的含金属粉末和丙烯酸/丙烯酸烷基酯共聚物(为水溶性活性剂,粉末状物质),充分分散。分散物作为油相部分。
(3)向高温下(油相的熔化温度以上)搅拌的一部分水(相对于油相部分为1倍以上)中缓慢添加油相部分,形成油性微粒(以下称作A部分)。
(4)通过一边搅拌A部分一边骤冷(冷却至油分的熔化温度以下),来制备将含金属粉末胶囊化的固体油性微粒。
(5)将羟基丙酮、增粘剂(根据需要还包括醇、多元醇类或各种水溶性成分)溶解于水中,得到由含有二羟基丙酮的水溶液形成的水相(水相)。
(6)将A部分混合到水相中,搅拌,使之均匀。由此,可以制造含有将含金属粉末胶囊化而得到的油性微粒(颗粒状物质)的水凝胶状仿晒化妆品。
搅拌的转数可以适当调整。转数越高,油性微粒越微细。低转数时,油性微粒有巨大化的可能性,但是当相对于生产规模旋转等级太低时,分散过程中会诱发油上浮或微粒的聚集。
优选桨式混合器(paddle mixer)等具有弱的搅拌力的搅拌装置。
作为油性微粒的粒径,必需为胶囊化的含金属粉末的粒径以上且2mm以下。更优选50μm~0.5mm。
上述粒径为含金属粉末的粒径以下时,无法抑制因含金属粉末和二羟基丙酮接触而引起的不稳定化。另外,因油性微粒的微细化而使透明性降低,因此也无法得到水凝胶状的外观。
上述粒径超过2mm时,使用时经胶囊化的颗粒状的含金属粉末油性微粒不易被破坏,含金属粉末在皮肤上不均匀,无法得到良好的皮肤演出效果。
将A部分混合到水相中,搅拌时的液温可根据构成油性微粒的油分组成进行适当调整。优选15~50℃,更优选20~45℃。上述搅拌时的液温在数值范围内时,可提供二羟基丙酮的稳定性更优异的化妆品。
搅拌中,可以使用桨式混合器、均化搅拌器、分散器等普通的乳化装置。优选搅拌力弱的桨式混合器。
本发明的仿晒化妆品中,在不损及本发明效果的范围内,可以混合其他成分。例如,可以根据需要适当混合保湿剂、水溶性高分子、增粘剂、皮膜剂、紫外线吸收剂、金属离子封闭剂、低级醇、多元醇、糖、氨基酸、有机胺、高分子乳液、pH调节剂、皮肤营养剂、维生素、抗氧剂、抗氧助剂、染料、香料,来制备本发明的仿晒化妆品。
<优选的商品形态>
本发明的仿晒化妆品,优选具有可视觉观察含有珠光剂的油性微粒的外观(在透明凝胶中可见颗粒状的外观)的身体用水性仿晒凝胶。
实施例
接下来,列举实施例,更具体地说明本发明。本发明并不受限于此。只要没有特别说明,则混合量为“%质量”。
按照“表1”~“表3”所示配方制造水凝胶状的仿晒化妆品,研究下述效果。
<外观·气味的稳定性评价>
在-20℃、-5℃、0℃、室温(25℃)、37℃、50℃各温度的恒温槽中维持各化妆品,1个月后目视观察色调和是否产生臭气,按下述评价基准综合评价外观和气味的稳定性。
“评价基准”
没有色调变化和臭气的发生 ○
有轻度色调变化或臭气的发生 △
色调变化或臭气的发生非常明显 ×
<粘度稳定性的评价>
在-20℃、-5℃、0℃、室温(25℃)、37℃、50℃各温度的恒温槽中维持各化妆品,1个月后按下述评价基准评价粘度稳定性。
“评价基准”
刚制造后未发生大的变化 ○
与刚制造后相比,仅在50℃下出现大的粘度下降 △
与刚制造后相比,在室温~50℃下出现大的粘度下降 ×
<染色效果的持续性评价>
在7名受试者的前腕部3×3cm2上涂布18μl化妆品,2小时后清洗,4天后按下述评价基准目视评价染色效果的持续性(长期着色效果)。
“评价基准”
保持染色效果使涂布的部位完全可以识别 ○
大体可以识别涂布部位,不能识别染色部位的边界线 △
完全回复至原来的肤色,无法识别涂布部位 ×
<使用感的评价>
在面部涂布各化妆品,按下述评价基准评价涂布时的使用感。
“评价基准”
象水凝胶一样的湿润使用感,干燥也快 ○
接近于乳液的使用感,油性大,干燥也慢 ×
<皮肤演出效果的评价>
在面部涂布各化妆品,按下述评价基准目视评价刚涂布后由珠光剂产生的皮肤演出效果。应说明的是,为了观察干扰光,评价在太阳光下进行。
“评价基准”
可以确认涂布前后的肤色变化,且可以确认由珠光剂
产生的光干扰效果 ○
可以确认涂布前后的肤色变化,但可以确认珠光剂的
不均匀 △
无法确认涂布前后的肤色变化 ×
[表1]
是否存在胶囊;是否进行疏水化处理; | 偏离DHA的含量 | 偏离珠光剂的含量(珠光剂和固体油分的质量比与实施例1相同) | ||||||
实施例1 | 比较例1 | 比较例2 | 比较例4 | 比较例5 | 比较例6 | 比较例7 | ||
A | 离子交换水 | 余量 | 余量 | 余量 | 余量 | 余量 | 余量 | 余量 |
甘油 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
依地酸盐 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | |
焦亚硫酸钠 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | |
二丙二醇 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
包含微凝胶的增粘剂 *1 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | |
二羟基丙酮 | 5 | 5 | 5 | 0.1 | 25 | 5 | 5 | |
乙醇(95度) | 4 | 4 | 4 | 4 | 4 | 4 | 4 | |
苯氧乙醇 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | |
B | 离子交换水 | 20 | - | - | 20 | 20 | 20 | 37 |
C | 山萮醇 | 0.375 | - | - | 0.375 | 0.375 | 0.005 | 1.55 |
二甲基聚硅氧烷 | 1.85 | - | - | 1.85 | 1.85 | 0.025 | 7.65 | |
甲基苯基聚硅氧烷 | 1 | - | - | 1 | 1 | 0.013 | 4.13 | |
四辛酸季戊四醇酯 | 3.9 | - | - | 3.9 | 3.9 | 0.052 | 16.12 | |
小烛树蜡 | 0.975 | - | - | 0.975 | 0.975 | 0.013 | 4.03 | |
D | 二甲硅油处理氧化钛包覆的云母 *2 | 0.75 | - | - | 0.75 | 0.75 | 0.01 | 3.1 |
氧化钛包覆的云母 *3 | - | - | 0.75 | - | - | - | - | |
(丙烯酸/丙烯酸烷基酯(C10-30))共聚物 *4 | 0.03 | - | - | 0.03 | 0.03 | 0.0004 | 0.12 | |
总计 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
油性微粒粒径 | 0.5mm | 0.5mm | 0.5mm | 0.5mm | 0.5mm | 0.5mm | 0.5mm | |
外观·气味稳定性 | ○ | ○ | × | ○ | × | ○ | ○ | |
粘度稳定性 | ○ | ○ | × | ○ | × | ○ | ○ |
染色效果的保持性 | ○ | ○ | ○ | × | ○ | ○ | ○ |
使用感 | ○ | ○ | ○ | ○ | ○ | ○ | × |
皮肤演出效果 | ○ | × | ○ | ○ | ○ | × | ○ |
[表2]
油和珠光剂的质量比的比较 | PEMULEN*4的含量的比较 | 油性微粒粒径的比较 | |||||
比较例8 | 比较例9 | 比较例10 | 比较例11 | 比较例12 | 比较例13 | ||
A | 离子交换水 | 余量 | 余量 | 余量 | 余量 | 余量 | 余量 |
甘油 | 3 | 3 | 3 | 3 | 3 | 3 | |
依地酸盐 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | |
焦亚硫酸钠 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | |
二丙二醇 | 5 | 5 | 5 | 5 | 5 | 5 | |
包含微凝胶的增粘剂 *1 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | |
二羟基丙酮 | 5 | 5 | 5 | 5 | 5 | 5 | |
乙醇(95度) | 4 | 4 | 4 | 4 | 4 | 4 | |
苯氧乙醇 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | |
B | 离子交换水 | 20 | 20 | 20 | 20 | 20 | 20 |
C | 山萮醇 | 0.375 | 0.138889 | 0.375 | 0.375 | 0.375 | 0.375 |
二甲基聚硅氧烷 | 1.85 | 0.685185 | 1.85 | 1.85 | 1.85 | 1.85 | |
甲基苯基聚硅氧烷 | 1 | 0.37037 | 1 | 1 | 1 | 1 | |
四辛酸季戊四醇酯 | 3.9 | 1.444444 | 3.9 | 3.9 | 3.9 | 3.9 | |
小烛树蜡 | 0.975 | 0.361111 | 0.975 | 0.975 | 0.975 | 0.975 | |
D | 二甲硅油处理氧化钛包覆的云母 *2 | 2 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 |
氧化钛包覆的云母 *3 | - | - | - | - | - | - | |
(丙烯酸/丙烯酸烷基酯(C10-30))共聚物 *4 | 0.03 | 0.03 | 0.00081 | 0.4 | 0.03 | 0.03 | |
总计 | 100 | 100 | 100 | 100 | 100 | 100 | |
油性微粒粒径 | 0.5mm | 0.5mm | - | - | 10μm | 3mm | |
外观·气味稳定性 | △ | △ | 无法制造 | 无法制造 | × | ○ | |
粘度稳定性 | × | × | × | ○ | |||
染色效果的保持性 | ○ | ○ | ○ | ○ | |||
使用感 | ○ | ○ | × | ○ | |||
皮肤演出效果 | ○ | ○ | ○ | △ |
[表3]
实施例2 | 实施例3 | 实施例4 | ||
A | 离子交换水 | 余量 | 余量 | 余量 |
甘油 | 3 | 3 | 3 |
依地酸盐 | 0.03 | 0.03 | 0.03 | |
焦亚硫酸钠 | 0.02 | 0.02 | 0.02 | |
二丙二醇 | 5 | 5 | 5 | |
聚丙烯酰胺 *5 | 0.8 | - | 0.8 | |
氯化甲基丙烯酸胆碱酯 *6 | - | 0.8 | - | |
二羟基丙酮 | 5 | 5 | 5 | |
乙醇(95度) | 4 | 4 | 4 | |
苯氧乙醇 | 0.35 | 0.35 | 0.35 | |
B | 离子交换水 | 20 | 20 | 20 |
C | 山萮醇 | 0.375 | 0.375 | 0.375 |
二甲基聚硅氧烷 | 1.85 | 1.85 | 1.85 | |
甲基苯基聚硅氧烷 | 1 | 1 | 1 | |
四辛酸季戊四醇酯 | 3.9 | 3.9 | 3.9 | |
小烛树蜡 | 0.975 | 0.975 | 0.975 | |
D | 二甲硅油处理氧化钛包覆的云母 *2 | 0.75 | 0.75 | - |
烷基改性硅氧烷树脂包覆的氧化铁红 *7 | - | - | 0.2 | |
烷基改性硅氧烷树脂包覆的氧化铁黄 *8 | - | - | 0.2 | |
烷基改性硅氧烷树脂包覆的氧化铁黑 *9 | - | - | 0.2 | |
(丙烯酸/丙烯酸烷基酯(C10-30))共聚物 *4 | 0.03 | 0.03 | 0.03 | |
总计 | 100 | 100 | 100 | |
油性微粒粒径 | 0.5mm | 0.5mm | 0.5mm | |
外观·气味稳定性 | ○ | ○ | ○ | |
粘度稳定性 | ○ | ○ | ○ | |
染色效果的保持性 | ○ | ○ | ○ | |
使用感 | ○ | ○ | ○ | |
皮肤演出效果 | ○ | ○ | ○ |
*1:下述合成例1制备的微凝胶
“合成例1 将40g二甲基丙烯酰胺(人制)和9g 2-丙烯酰胺-2-甲基丙磺酸(Sigma制)溶解在250g离子交换水中,用氢氧化钠调节至pH=7.0。向具备回流装置的1000ml三颈烧瓶中装入250g正己烷、8.2g聚氧乙烯(3)油醚(エマレツクス503,日本エマルシヨン制)和16.4g聚氧乙烯(6)油醚(エマレツクス506,日本エマルシヨン制),混合溶解,并进行N2置换。向此三颈烧瓶中添加单体水溶液,在N2气氛下一边搅拌一边用油浴加热至65℃~70℃。确认系统温度达到65℃~70℃时系统为半透明的微乳状态后,向聚合系统中添加2g过硫酸铵,引发聚合。一边搅拌一边将聚合系统在65℃~70℃下维持3小时,生成微凝胶。聚合结束后,向微凝胶悬浮液中加入丙酮,使微凝胶沉淀,继续用丙酮洗涤3次,除去残留单体和表面活性剂。将沉淀物过滤后减压干燥,得到白色粉末状的微凝胶干燥物。”
*2:SA-テイミカゴ-ルデンブロンズ:三好化成株式会社
*3:テイミカゴ-ルデンブロンズ:マ-ル社
*4:PEMULEN TR-2:日光ケミカルズ株式会社
*5:セピゲル305:セピツク社
*6:サルケアSC96:チバスペシヤリテイケミカルズ
*7:使1,3,5,7-四甲基环四硅氧烷和氧化铁红气相接触后,添加十四碳烯,过滤、洗涤后,干燥得到的物质
*8:使1,3,5,7-四甲基环四硅氧烷和氧化铁黄气相接触后,添加十四碳烯,过滤、洗涤后,干燥得到的物质
*9:使1,3,5,7-四甲基环四硅氧烷和氧化铁黑气相接触后,添加十四碳烯,过滤、洗涤后,干燥得到的物质
由上述“表1”~“表3”可知:本发明的实施例,防止了由珠光剂引起的二羟基丙酮的不稳定化。是保存稳定性极其优异的水凝胶状仿晒化妆品。使用感极其优异。即,该化妆品象凝胶等水系化妆品一样清爽,具有湿润的使用感。并且,该仿晒化妆品具透明感,相对于皮肤和化妆品基质具有演出效果,涂布时干燥快。
产业实用性
本发明的仿晒化妆品,是一种用于不必沐浴太阳光(紫外线)而将皮肤着色成日晒色的化妆品,具有珠光剂产生的演出效果和长期着色效果。优选用作使用感优异的身体用仿晒化妆品。
Claims (5)
1.仿晒化妆品,其中含有:0.2~20.0%质量二羟基丙酮;0.02~3.0%质量经疏水化处理的含金属粉末;以及相对于上述经疏水化处理的含金属粉末,以质量比计为5~20倍量的固体油分,该仿晒化妆品的特征在于:将上述经疏水化处理的含金属粉末用上述固体油分胶囊化而得到的油性微粒分散在溶解有二羟基丙酮的水相中,其中所述固体油分是固体油脂或蜡,所述疏水化处理是使用硅氧烷类或硅烷化合物进行的处理,并且上述胶囊化的油性微粒的粒径为50μm至0.5mm。
2.权利要求1的仿晒化妆品,其特征在于:上述含金属粉末为珠光剂。
3.权利要求1或2的仿晒化妆品,其特征在于:上述胶囊化的油性微粒中含有丙烯酸/丙烯酸烷基酯共聚物。
4.权利要求1或2的仿晒化妆品,其特征在于:上述溶解有二羟基丙酮的水相中含有包含微凝胶的增粘剂。
5.权利要求1或2的仿晒化妆品,其特征在于:上述仿晒化妆品为身体用仿晒化妆品。
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- 2005-09-05 EP EP05781582A patent/EP1932508A4/en not_active Withdrawn
- 2005-09-05 CN CN2005800514733A patent/CN101257888B/zh not_active Expired - Fee Related
- 2005-09-05 US US11/922,816 patent/US20090074823A1/en not_active Abandoned
- 2005-09-05 WO PCT/JP2005/016208 patent/WO2007029299A1/ja active Application Filing
- 2005-09-05 KR KR1020077029914A patent/KR101197489B1/ko not_active IP Right Cessation
- 2005-09-05 JP JP2007534202A patent/JPWO2007029299A1/ja active Pending
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Also Published As
Publication number | Publication date |
---|---|
WO2007029299A1 (ja) | 2007-03-15 |
KR20080047508A (ko) | 2008-05-29 |
KR101197489B1 (ko) | 2012-11-09 |
CN101257888A (zh) | 2008-09-03 |
EP1932508A1 (en) | 2008-06-18 |
EP1932508A4 (en) | 2012-08-29 |
JPWO2007029299A1 (ja) | 2009-03-12 |
US20090074823A1 (en) | 2009-03-19 |
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