CN114340583A - 油包水型组合物 - Google Patents
油包水型组合物 Download PDFInfo
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- CN114340583A CN114340583A CN202080061383.7A CN202080061383A CN114340583A CN 114340583 A CN114340583 A CN 114340583A CN 202080061383 A CN202080061383 A CN 202080061383A CN 114340583 A CN114340583 A CN 114340583A
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- oil
- water
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- phase
- silicone
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Abstract
本发明提供在混配了疏水化粉体的油相中,粉体的凝集/沉降不易发生的油包水型组合物。因此本发明涉及的油包水型组合物,其特征在于,包含:硅油/油相的质量比为0.65以上的油相;被分散在上述油相中,通过有机硅系表面处理剂进行了处理的有机硅处理粉体;将上述有机硅处理粉体分散在油相中的聚甘油改性有机硅分散剂;被分散在上述油相中的水相;以及将上述水相分散在油相中的乳化剂,有机硅处理粉体/总粉体的质量比为0.7以上。
Description
相关申请
本申请主张2019年9月5日申请的日本专利申请2019-161685号的优先权,将其内容并入到本文中。
技术领域
本发明涉及油包水型组合物、特别是其疏水化粉体分散性的改良。
背景技术
疏水化粉体由于在其涂抹面上发挥耐水性,不易发生由汗等引起的脱落,因此被应用于各种化妆品等。例如为了减轻紫外线对皮肤带来的影响,广泛应用防晒化妆品,它们被大致区分为使用紫外线散射粉体作为紫外线屏蔽剂的产品、和使用有机紫外线吸收剂作为紫外线屏蔽剂的产品。
有机紫外线吸收剂大部分被分类为酯油,能够溶解于油相,容易在皮肤上均匀地涂抹,但另一方面也有时对皮肤具有刺激性。
与此相对,在紫外线散射粉体中,通常使用微粒氧化锌、微粒二氧化钛,通过粒径的调整来使可见光的透射性提高,同时获得紫外线的散射效果。进而,紫外线散射粉体为了获得耐水性,粉体表面被疏水化处理,被混配于油相的情况多。
然而,进行了疏水化处理的无机粉体在油相中也易于发生凝集/沉降,也有时成为组合物的白浊/不均匀化、肌肤应用时的泛白的原因。
现有技术文献
专利文献
专利文献1:日本特许第4536538号
专利文献2:日本特开2006-213619号
专利文献3:日本特许第4881961号
专利文献4:日本特开2010-159229号
发明内容
发明所要解决的课题
本发明是鉴于上述现有技术而提出的,其所要解决的课题是提供在混配了疏水化粉体的油相中,粉体的凝集/沉降不易发生的油包水型组合物。
用于解决课题的方法
为了解决上述课题,本发明涉及的油包水型组合物,其特征在于,包含:
硅油/油相的质量比为0.65以上的油相;
被分散在上述油相中,通过有机硅系表面处理剂进行了处理的有机硅处理粉体;
将上述有机硅处理粉体分散在油相中的聚甘油改性有机硅分散剂;
被分散在上述油相中的水相;以及
将上述水相分散在油相中的乳化剂,
有机硅处理粉体/总粉体的质量比为0.7以上。
此外,在上述组合物中,
水相在组合物中为20~35质量%,
油相在组合物中为20~40质量%,
此外有机硅处理紫外线散射粉体在组合物中为10~35质量%是优选的。
此外,在上述组合物中,水相的平均乳化粒径为10μm以下是优选的。
此外,在上述组合物中,进一步包含有机改性粘土矿物是优选的。
此外,在上述组合物中,
有机硅处理粉体的表面处理剂为聚二甲基硅氧烷处理剂、氢化聚二甲基硅氧烷处理剂、辛基乙氧基硅烷处理剂中的任一处理剂是优选的。
此外,在上述组合物中,乳化剂为聚醚改性有机硅乳化剂是优选的。
此外,在上述组合物中,除聚甘油改性有机硅分散剂以外的分散剂在组合物中小于0.5质量%是优选的。
此外,在上述组合物中,环状硅氧烷在组合物中小于10质量%是优选的。
此外,在上述组合物中,聚甘油改性有机硅为双丁基聚二甲基硅氧烷聚甘油-3是优选的。
发明的效果
本发明涉及的油包水型组合物通过在以硅油为主的油相中分散有机硅处理粉体,使用聚甘油改性有机硅分散剂作为其分散剂,并且通过将水相分散在油相中,从而可以将上述有机硅处理粉体稳定地维持在组合物中,抑制凝集/沉降。
具体实施方式
以下,说明本发明的适合的实施方式。
本发明涉及的油包水型组合物,是使水相、和有机硅处理粉体各自独立地分散在油相中而成的组合物。
[油相]
在本发明中,分散介质为油相,特别是在本发明中在以硅油作为主体,并包含其它油性成分的情况下,硅油/油相的质量比为0.65以上,优选为0.75以上是适合的。
作为硅油,可例示二甲基聚硅氧烷、八甲基硅氧烷、十甲基四硅氧烷、甲基氢聚硅氧烷、甲基苯基聚硅氧烷、六甲基环状三聚硅氧烷、八甲基环状四聚硅氧烷、十甲基环状五聚硅氧烷等。
另外,在包含环状硅氧烷的情况下,优选其混配量在组合物中为10质量%以下。
作为其它油性成分,可举出各种液体油脂、酯油、烃油、固体油脂等。
作为液体油脂,可例示例如,鳄梨油、山茶籽油、海龟油、澳洲坚果籽油、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、落瓣油茶籽油、蓖麻油、亚麻籽油、红花油、草棉籽油、紫苏油、大豆油、花生油、茶籽油、日本榧树油、米糠油、白花泡桐油、日本桐油、霍霍巴籽油、胚芽油、三甘油等。
作为酯油,可例示例如,肉豆蔻酸异丙酯、辛酸鲸蜡基酯、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、肉豆蔻酸肉豆蔻基酯、油酸癸酯、二甲基辛酸己基癸基酯、乳酸鲸蜡基酯、乳酸肉豆蔻基酯、乙酰化羊毛脂、硬脂酸异鲸蜡基酯、异硬脂酸异鲸蜡基酯、异壬酸异壬酯、12-羟基硬脂酸胆甾醇酯、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、苹果酸二异硬脂基酯、二-2-庚基十一烷酸甘油酯、三-2-乙基己酸三羟甲基丙烷酯、三异硬脂酸三羟甲基丙烷酯、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酯、2-乙基己酸鲸蜡基酯、棕榈酸2-乙基己基酯、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、油酸油基酯、乙酰甘油酯、棕榈酸2-庚基十一烷基酯、己二酸二异丁酯、N-月桂酰-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-乙基己基酯、肉豆蔻酸2-己基癸基酯、棕榈酸2-己基癸基酯、己二酸2-己基癸基酯、癸二酸二异丙酯、琥珀酸2-乙基己基酯、柠檬酸三乙酯等。
作为烃油,可例示液体石蜡、地蜡、角鲨烷、姥鲛烷、石蜡、纯地蜡、角鲨烯、凡士林、微晶蜡、聚乙烯蜡、费托蜡等。
[有机硅处理粉体]
在本发明中,作为有机硅处理粉体,特别是可举出进行了有机硅表面处理的无机粉体。
优选可举出实施了有机硅处理的二氧化钛和/或氧化锌。
在使用这些有机硅处理粉体作为紫外线散射剂的情况下,从紫外线散射效果方面考虑,二氧化钛、氧化锌优选为被调制为微粒状的物质。作为微粒二氧化钛,优选可以举出平均一次粒径为1~100nm的微粒,此外作为微粒氧化锌,可以举出平均一次粒径为1~100nm的微粒。然而不限定于此。
有机硅化处理的方法没有特别限制,可以利用公知的方法进行处理。可举出例如使用了甲基氢聚硅氧烷、甲基氢聚硅氧烷/二甲基聚硅氧烷共聚物、二甲基聚硅氧烷等有机硅类的处理;使用了辛基三乙氧基硅烷、己基三甲氧基硅烷等硅烷化合物的处理。
作为特别优选的有机硅化处理,可举出聚二甲基硅氧烷处理、氢化聚二甲基硅氧烷处理、辛基乙氧基硅烷处理。
有机硅处理粉体的混配量,相对于本发明涉及的组合物为10~35质量%,优选为15~30质量%。如果混配量小于10质量%,则耐水性等作为有机硅处理粉体的效果不能充分获得,另一方面,如果超过35质量%,则担心以经时的变臭和粗糙感为代表的使用性的恶化。
作为上述有机硅化处理剂,没有特别限定,可以使用以往公知的物质。其中优选为有机硅化合物,优选为例如,二甲基聚硅氧烷(聚二甲基硅氧烷)、甲基苯基聚硅氧烷、甲基氢聚硅氧烷等各种硅油、甲基三甲氧基硅烷、乙基三甲氧基硅烷、己基三甲氧基硅烷、辛基三甲氧基硅烷等各种烷基硅烷、三氟甲基乙基三甲氧基硅烷、十七氟癸基三甲氧基硅烷等各种氟烷基硅烷等。可以将它们单独使用,或混合使用二种以上。
[聚甘油改性有机硅分散剂]
在本发明中,作为有机硅处理粉体的分散剂,需要使用聚甘油改性有机硅分散剂。
作为该聚甘油改性有机硅分散剂,优选为在主骨架具有聚甘油骨架,在其两末端具有硅氧烷链的物质。该两末端有机硅聚甘油虽然形成油包水型组合物的、作为所谓乳化剂的能力几乎没有,但在本发明中在使有机硅处理粉体分散在油相中时发挥优异的能力。
更具体而言,优选使用具有以下结构的物质。
m=30~100,优选为50~70(在试验例中使用的物质为平均60)
n=1~5,优选为2~3(在试验例中使用的物质为平均3)
在本发明中聚甘油改性有机硅分散剂虽然与有机硅处理粉体的混配量有关,但优选在组合物中为0.5~5质量%,优选为1~3质量%。
另外,在混配除聚甘油改性有机硅分散剂以外的分散剂的情况下,优选在组合物中小于0.5质量%。
[水相]
在本发明中,在外相的油相中分散有构成内相的水相,通过内水相的存在而抑制有机硅处理粉体的沉降。
作为水相所包含的成分,可例示水、和醇、水溶性高分子等。
作为醇类,可例示乙醇、异丙醇等低级醇、异硬脂醇、辛基十二烷醇、己基癸醇等高级醇、乙二醇、丙二醇、1,3-丁二醇、双丙甘醇、聚丁二醇等多元醇等。
作为水溶性高分子,可举出2-丙烯酰胺-2-甲基丙烷磺酸(以下,简写为“AMPS”)的均聚物、或共聚物。共聚物为与乙烯基吡咯烷酮、丙烯酰胺、丙烯酸钠、丙烯酸羟基乙酯等共聚单体形成的共聚物。即,可例示AMPS均聚物、乙烯基吡咯烷酮/AMPS共聚物、二甲基丙烯酰胺/AMPS共聚物、丙烯酰胺/AMPS共聚物、丙烯酸钠/AMPS共聚物等。
进一步可例示羧基乙烯基聚合物、聚丙烯酸铵、聚丙烯酸钠、丙烯酸钠/丙烯酸烷基酯/甲基丙烯酸钠/甲基丙烯酸烷基酯共聚物、角叉菜聚糖、果胶、甘露聚糖、凝胶多糖、硫酸软骨素、淀粉、糖原、***胶、透明质酸钠、黄蓍胶、黄原胶、硫酸粘多糖、羟基乙基瓜尔胶、羧基甲基瓜尔胶、瓜尔胶、葡聚糖、硫酸角质、刺槐豆胶、琥珀酰聚糖、壳多糖、脱乙酰壳多糖、羧基甲基壳多糖、琼脂等。
在本发明中,水相具有抑制上述有机硅化粉体在组合物中凝集/沉降的效果,其混配量在组合物中为10~35质量%,优选为20~30质量%。
[乳化剂]
在本发明中,作为使水相分散在油相中的油包水型乳化剂,可举出低HLB的乳化剂,但特别适合地,优选使用相对于硅氧烷骨架以侧基状地结合了聚氧化乙烯基的聚醚改性有机硅。
p=30~50
q=1~3
r=2~4
a=3~12
b=7~13
聚醚改性率:约20重量%
另外,在本发明中油包水型乳化剂的混配量优选在组合物中为0.5~7质量%,优选为2~5质量%。
在本发明的油包水型组合物中,除上述必需成分以外,可以根据需要适当混配通常化妆品、药品等皮肤外用剂中所使用的成分,例如美白剂、保湿剂、抗氧化剂、油性成分、其它紫外线吸收剂、表面活性剂、增稠剂、醇类、粉末成分、着色剂、水性成分、水、各种皮肤营养剂等,通过常规方法来制造。
本发明的油包水型组合物可以通过油包水型乳化组合物的制造所使用的通常的方法来调制。可举出例如,将油相部适当加热而使其均匀溶解,用均质混合机使有机硅处理粉体分散于油相部后,一边在该油相部中慢慢添加另行调制的水相部,一边使用均质混合机使其乳化的方法等。
以下,在具体的实施方式的说明之前,对制造方法、评价方法进行说明。
[制造方法]
在使用均质混合机进行了混合的油性成分中使粉末分散后,添加已充分混合了的水性成分,从而获得了组合物。
[评价方法]
在模拟皮肤PMMA板(SPFMASTER-PA01)上以2mg/cm2的量滴加,用手指涂抹60秒,干燥15分钟而形成了涂膜。以未涂抹的板作为对照,利用株式会社日立制作所社制U-3500型自记录分光光度计测定上述涂膜的吸光度(400~280nm),由所得的测定数据求出吸光度累计值、300nm的吸光度。此外,制作厚度10微米~50微米的任意的均匀的膜,通过目视确认了相同膜厚的样品的透明度。
此外,透明度通过以下基准评价。
A:极其透明
B:透明
C:虽然透明但有一点白色
D:透明感少,有白色
以下,对本发明的具体的实施方式进行说明。
首先,本发明人等在油包水型组合物中混配疏水化处理粉体时,研究了其分散性。
将结果示于表1中。
表1(A)
表1(B)
如果将上述表1的试验例1-1~1-3进行对比可知,进行了有机硅处理(氢化聚二甲基硅氧烷被覆处理)的试验例1-1、1-2几乎未确认到凝集体的形成,组合物的透明度高,但进行了硬脂酸处理的试验例1-3中透明度降低,确认到粉体的凝集。同样地,如果将试验例1-4~1-6进行对比可知,果然在氢化聚二甲基硅氧烷被覆(试验例1-4)时未确认到凝集体的形成,在三乙氧基辛基硅烷被覆(试验例1-5)和棕榈酸糊精酯被覆(试验例1-6)时确认到凝集体的形成,透明度降低了。
基于以上结果可知,在本发明中,疏水化处理需要是有机硅处理。
接下来本发明人等对有机硅处理粉体/总粉体的质量比进行了研究。
如表1(B)的试验例1-7~1-9所示那样,如果有机硅处理粉体/总粉体为小于0.7,则确认到透明性的降低。因此,有机硅处理粉体/总粉体优选为0.7以上。
此外,本发明人等对油相中的硅油的质量比进行了研究。将结果示于表2中。
表2
根据表2可知,基本上本发明的油相优选为硅油,但在包含其它油分(癸二酸二异丙酯)的情况下,优选硅油的质量比为0.65以上,优选为0.75以上。
进一步本发明人等进行了使有机硅处理粉体分散在油相中的分散剂的研究。将结果示于表3中。
表3
从上述表3可知,特别适合使用聚甘油改性有机硅分散剂,异硬脂酸等一般的分散剂得不到充分的分散效果。
本发明人等对油包水型组合物中的水相比进行了研究。将结果示于表4中。
表4
另外,关于粉末的再分散性,如以下那样评价。
C:即使数次振动也不会再分散
B:如果数次振动则再分散
A:如果振动1、2次则再分散
由表4明确了,如果组合物中的水相小于20质量%则发生粉末的结块。因此,本发明涉及的油包水型组合物的水相优选为20质量%以上。
Claims (9)
1.一种油包水型组合物,其特征在于,包含:
硅油/油相的质量比为0.65以上的油相;
被分散在所述油相中,通过有机硅系表面处理剂进行了处理的有机硅处理粉体;
将所述有机硅处理粉体分散在油相中的聚甘油改性有机硅分散剂;
被分散在所述油相中的水相;以及
将所述水相分散在油相中的乳化剂,
有机硅处理粉体/总粉体的质量比为0.7以上。
2.如权利要求1所述的油包水型组合物,其特征在于,
水相在组合物中为20~35质量%,
油相在组合物中为20~40质量%,
此外有机硅处理紫外线散射粉体在组合物中为10~35质量%。
3.如权利要求1或2所述的油包水型组合物,其特征在于,
水相的平均乳化粒径为10μm以下。
4.如权利要求1~3中任一项所述的油包水型组合物,其特征在于,
进一步包含有机改性粘土矿物。
5.如权利要求1~4中任一项所述的油包水型组合物,其特征在于,
有机硅处理粉体的表面处理剂是聚二甲基硅氧烷处理剂、氢化聚二甲基硅氧烷处理剂、辛基乙氧基硅烷处理剂中的任一处理剂。
6.如权利要求1~5中任一项所述的油包水型组合物,其特征在于,乳化剂为聚醚改性有机硅乳化剂。
7.如权利要求1~6中任一项所述的油包水型组合物,其特征在于,除聚甘油改性有机硅分散剂以外的分散剂在组合物中小于0.5质量%。
8.如权利要求1~7中任一项所述的油包水型组合物,其特征在于,环状硅氧烷在组合物中小于10质量%。
9.如权利要求1~8中任一项所述的油包水型组合物,其特征在于,聚甘油改性有机硅是双丁基聚二甲基硅氧烷聚甘油-3。
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JP2012246446A (ja) * | 2011-05-30 | 2012-12-13 | Dow Corning Toray Co Ltd | 新規液状オルガノポリシロキサン及びその利用 |
JP2013010935A (ja) * | 2011-05-30 | 2013-01-17 | Dow Corning Toray Co Ltd | モノ−又はジ−グリセリン誘導体変性オルガノポリシロキサンエラストマー及びその利用 |
JP2017071602A (ja) * | 2015-10-09 | 2017-04-13 | 株式会社 資生堂 | 噴霧型日焼け止め化粧料 |
WO2018225768A1 (ja) * | 2017-06-08 | 2018-12-13 | 株式会社 資生堂 | 油中水型乳化化粧料 |
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