CN108350012B - 新的糖衍生物胶凝剂 - Google Patents
新的糖衍生物胶凝剂 Download PDFInfo
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- CN108350012B CN108350012B CN201680062408.9A CN201680062408A CN108350012B CN 108350012 B CN108350012 B CN 108350012B CN 201680062408 A CN201680062408 A CN 201680062408A CN 108350012 B CN108350012 B CN 108350012B
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- oil
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Abstract
Description
技术领域
本发明涉及新的胶凝剂,详细地涉及包含烷基-糖衍生物的新的胶凝剂。
背景技术
由具有凝胶形成能力的物质(以下称胶凝剂)形成的三维网孔结构中含有流体的结构体被称为凝胶,通常流体为水时称为水凝胶(hydrogel),流体为水以外的有机液体(有机溶剂或油等)时称为有机凝胶或油凝胶。油凝胶(有机凝胶)在化妆品、医药品、农药、食品、粘接剂、涂料、树脂等领域中用于调节化妆品及涂料的流动性。另外,油凝胶(有机凝胶)还在例如将废油凝胶化而形成固体物质来防止水质污染等环境保护领域中广泛的应用。
关于胶凝剂的研究主要对高分子化合物进行,但是近年来,对于与高分子化合物相比更容易引入多种多样功能的低分子化合物的研究开发正在进行。如上所述,油凝胶(有机凝胶)已在广阔的领域中得到的应用,且被期待今后的应用领域继续扩大。因此,对于低分子化合物胶凝剂(以下有时称为低分子胶凝剂),面对油凝胶的用途扩展,要求其对广泛种类的有机溶剂都有凝胶形成能力。针对该课题,到目前为止,作为对各种有机溶剂仅以少量添加量即可形成稳定性优异的凝胶的低分子胶凝剂,提出了各种化合物。作为其一,例如报告了由各种单糖类衍生的糖衍生物由于相互间容易形成强氢键的结构,因而使各种有机溶剂发生凝胶化(非专利文献1)。还报告了使用了糖衍生物的低分子胶凝剂能够使水与油(亲水性有机溶剂和疏水性有机溶剂)两种溶剂以及它们的混合溶剂凝胶化(专利文献1)。
现有技术文献
专利文献
专利文献1:国际公开第2013/133419号
非专利文献
非专利文献1:S.Shinkai et al.,Chem.Eur.J.2001,7,No20,4327-4334
发明内容
发明所要解决的课题
到目前为止,虽然已提出了面向有机溶剂等非水性介质的包含低分子化合物的油胶凝剂,但存在着能够凝胶化的介质受限等问题,因此,在具有新用途、功能性的新的油凝胶的创制中,正在探索能够使各种介质凝胶化的新的低分子油胶凝剂的方案。
上述的糖衍生物的胶凝剂虽然可以通过改变糖的种类来使各种溶剂凝胶化,但反过来用一种糖衍生物使广泛种类的溶剂凝胶化就比较难,另外由非专利文献1记载的糖衍生物得到的凝胶不具备贮存稳定性。进而专利文献1所公开的胶凝剂虽然也可以使水和油(亲水性有机溶剂和疏水性有机溶剂)的混合溶剂凝胶化,但以光毒性为代表的安全性试验需要花费成本。
这样,虽然能够将水和油(疏水性有机溶剂)的混合溶剂凝胶化、形成水/油分散凝胶、即乳液凝胶(凝胶乳液)的胶凝剂在要求生物体安全性高的化妆品、药品基材中特别有用,但能够对广泛种类的溶剂确保凝胶化能力和生物体安全性的划时代的胶凝剂尚未出现。
另外一般在化妆品等用途中,O/W(水包油型)乳液由于在皮肤上的延展性轻、油性感弱,因而到目前为止在大量的化妆品中应用。另一方面,W/O(油包水型)乳液虽然与O/W型相比应用于皮肤时油性感较多,但适合要求耐水性(耐汗性)的用途,还能够长时间维持化妆的效果。另外W/O型乳液通过使分散相(内相)的水分量变多,还能够期待实现清爽的使用感。
因此近年来,对能够作为W/O型乳液凝胶获得上述乳液凝胶的胶凝剂的期望提高。
本发明是基于上述事实而做出的,其要解决的课题是提供不仅能够使各种种类的有机溶剂凝胶化,能够分别单独使水、亲水性有机溶剂和疏水性有机溶剂(油等)凝胶化,而且也能够使它们的混合溶剂、特别是水和疏水性有机溶剂(油)的混合溶剂凝胶化,且能够制备生物体安全性也优异的凝胶,并且能够制备W/O型的乳液凝胶的新的胶凝剂。
用于解决课题的方法
本发明人为了解决上述课题而进行了深入研究,结果发现,通过应用烷基-糖衍生物作为胶凝剂,令人惊讶地能够对各种溶剂形成凝胶,特别是能够将水和疏水性溶液(油)的混合溶剂凝胶化,从而完成了本发明
即,本发明作为第1观点,涉及胶凝剂,包含下述式(1)或式(2)所示的化合物,
式中,R1表示碳原子数9~20的直链状或支链状的烷基、碳原子数13~20的环状的烷基、或碳原子数9~20的直链状或支链状的烯基,
R2表示氢原子、碳原子数1~10的直链状或支链状的烷基、或可以具有取代基的芳基,
R3和R4表示羟基。
作为第2观点,涉及根据第1观点所述的胶凝剂,所述式(1)所示的化合物是式(3)所示的化合物,
式中,R1和R2与上述式(1)中所述的定义含义相同。
作为第3观点,涉及根据第1观点所述的胶凝剂,所述式(1)所示的化合物是式(4)所示的化合物,
式中,R1和R2与上述式(1)中所述的定义含义相同。
作为第4观点,涉及凝胶,由第1观点~第3观点的任一项所述的胶凝剂、和
疏水性有机溶剂、亲水性有机溶液、疏水性有机溶液或水溶液制成。
作为第5观点,涉及凝胶,由第1观点~第3观点的任一项所述的胶凝剂、
表面活性剂、和
疏水性有机溶剂、亲水性有机溶剂、水、亲水性有机溶液、疏水性有机溶液或水溶液制成。
作为第6观点,涉及根据第4观点或第5观点所述的凝胶,所述疏水性有机溶剂是选自植物油、酯类、硅油和烃类中的至少一种。
作为第7观点,涉及根据第4观点或第5观点所述的凝胶,所述疏水性有机溶液是第6观点中记载的疏水性有机溶剂与水的混合溶剂。
作为第8观点,涉及根据第5观点所述的凝胶,所述亲水性有机溶剂是选自甲醇、乙醇、2-丙醇、异丁醇、戊醇、己醇、1-辛醇、异辛醇、丙酮、环己酮、乙腈、二氧杂环己烷、甘油、丙二醇、乙二醇和二甲基亚砜中的至少一种。
作为第9观点,涉及根据第4观点或第5观点所述的凝胶,所述亲水性有机溶液是权利要求8中记载的亲水性有机溶剂与水的混合溶剂。
作为第10观点,涉及根据第4观点~第9观点的任一项所述的凝胶,是微粒进一步分散在凝胶内而成的。
作为第11观点,涉及根据第1观点~第3观点的任一项所述的胶凝剂,是离子液体的胶凝剂。
作为第12观点,涉及凝胶,由第1观点~第3观点的任一项所述的胶凝剂和离子液体制成。
作为第13观点,涉及化妆品基材或医疗用基材,包含第1观点~第3观点的任一项所述的胶凝剂。
作为第14观点,涉及权利要求1中记载的式(1)或式(2)所示的化合物的制造方法,其特征在于,
在原甲酸三乙酯、DMF、对甲苯磺酸存在下,通过一锅法进行制造工序,所述制造工序是使式R1-CHO所示的化合物与葡萄糖、甘露糖、半乳糖或它们的衍生物进行缩环反应,从而制造所述式(1)或式(2)所示的化合物的工序,
式R1-CHO中,R1表示碳原子数9~20的直链状或支链状的烷基、碳原子数13~20的环状的烷基、或碳原子数9~20的直链状或支链状的烯基。
作为第15观点,涉及包含下述式(7)或式(8)所示的化合物的胶凝剂,
式中,R5表示碳原子数13~20的直链状或支链状的烷基、碳原子数13~20的环状的烷基、或碳原子数13~20的直链状或支链状的烯基,
R2表示氢原子、碳原子数1~10的直链状或支链状的烷基、或可以具有取代基的芳基,
R3和R4表示羟基。
发明的效果
本发明的胶凝剂对水和油(疏水性有机溶剂)这样的各种溶剂具有凝胶形成能力,例如在水与亲水性有机溶剂的亲水性的混合溶剂、疏水性有机溶剂(油)这样的各种体系中能够形成凝胶,另外能够获得触变性优异的凝胶。
特别是本发明的胶凝剂能够由水与油(疏水性有机溶剂)的混合溶剂形成水/油分散凝胶,并且能够形成高含水率的W/O型乳液凝胶,能够提供给出优异的使用感的水/油分散凝胶。
进而本发明的胶凝剂能够将离子液体凝胶化,能够由离子液体与油的混合溶剂形成离子液体-油分散凝胶(凝胶乳液)。
并且本发明的胶凝剂在包含微粒的体系中也能够进行凝胶形成,由包含微粒的水与油(疏水性有机溶剂)的混合溶剂也能够形成水/油分散凝胶。
另外本发明的胶凝剂以葡萄糖、甘露糖、半乳糖或它们的衍生物这样的单糖类作为原料,不仅生物体安全性,而且能够将原料成本抑制得极低。
另外,根据本发明的制造方法,能够由葡萄糖、甘露糖、半乳糖的衍生物通过一锅法制造上述的胶凝剂,能够廉价且简便地制造成为胶凝剂的化合物。而且制造时不需要甲醇、金属催化剂,因此能够从反应后的体系中排除这样的刺激性化合物的残存,特别是能够制造适合作为针对化妆品基材、医疗用基材、以及食品用基材等要求高安全性的基材的胶凝剂的化合物。
附图说明
图1是实施例2中制备的配合了2wt%的葡萄糖衍生物:化合物[8]的KF995凝胶的照片。
图2是显示实施例6中制备的使用化合物[8]作为胶凝剂的配合了Tween20的水/KF995(KF995/水=2/8(vol/vol))凝胶(图2(a))、和配合了Span80的水/KF995(KF995/水=2/8(vol/vol))凝胶(图2(b))的凝胶外观和共焦点激光扫描显微镜像的照片。
图3是显示实施例7中制备的使用化合物[8]作为胶凝剂的KF995干凝胶(图3(a))、和50%乙醇凝胶(图3(b))的扫描型显微镜照片的图。
图4是显示实施例7中制备的使用化合物[8]作为胶凝剂的配合了Tween20的水/KF995(KF995/水=2/8(vol/vol))分散凝胶的扫描型显微镜照片的图(图4(a)为500倍、图4(b)为5000倍)。
图5是实施例8中制备的由配合了化合物[8]3wt%(图5(a))或2wt%(图5(b))的离子液体[BuMeIm][TFSI]形成的凝胶的照片。
图6是显示实施例10中制备的使用化合物[8]作为胶凝剂的离子液体[BuMeIm][TFSI]/角鲨烷(离子液体/角鲨烷=50/50(vol/vol))凝胶(图6(a))、和进一步配合了Tween20的离子液体[BuMeIm][TFSI]/角鲨烷(离子液体/角鲨烷=50/50(vol/vol))凝胶(图6(b))的共焦点激光扫描显微镜像的照片。
图7是显示实施例13中制备的使用化合物[8]作为胶凝剂、配合了钛和Span80的KF995/水=20/80(vol/vol)凝胶的共焦点激光扫描显微镜像的照片。
图8是显示实施例14中制备的粉底的外观的图。
具体实施方式
[胶凝剂]
本发明的胶凝剂包含下述式(1)或式(2)所示的化合物。
[式中,
R1表示碳原子数9~20的直链状或支链状的烷基、碳原子数13~20的环状的烷基、或碳原子数9~20的直链状或支链状的烯基,
R2表示氢原子、碳原子数1~10的直链状或支链状的烷基、或可以具有取代基的芳基,
R3和R4表示羟基。]
作为所述碳原子数9~20的直链状或支链状的烷基,可列举壬基、癸基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基和二十烷基等、以及这些基团支链化而成的基团。
作为所述碳原子数13~20的环状的烷基,不仅可列举仅由环状的烷基构成的基团(例如,环十三烷基、环十四烷基、环十五烷基、环十六烷基、环十七烷基、环十八烷基、环十九烷基、环二十烷基等),还可列举具有环戊基环、环己基环等环结构、且碳原子数为13~20的直链状和/或支链状的烷基。
作为所述碳原子数9~20的直链状或支链状的烯基,可列举壬烯基、癸烯基、十三烯基、十四烯基、十五烯基、十六烯基、十七烯基、十八烯基、十九烯基、二十烯基等、以及这些基团支链化而成的基团。
作为所述碳原子数1~10的直链状或支链状的烷基,可列举甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、异丙基、异丁基、仲丁基、叔丁基和2-乙基己基等。
作为所述芳基,可列举苯基、苄基、1-萘基、2-萘基、1-蒽基和1-菲基等。另外,该芳基可以具有取代基,作为这样的取代基,可列举可含有酯键、酰胺键和醚键的直链状、支链状或环状的烷基、卤素原子等。
从使用本发明的胶凝剂使后述的各种溶剂良好地凝胶化方面考虑,所述式(1)或(2)中,R2优选为氢原子、甲基、乙基,尤其优选为氢原子或甲基。
另外,R1可以是例如碳原子数为13以上的基团、或碳原子数为15以上基团,从单独使用后述的各种溶剂、或将这些溶剂混合时,能够不发生液体分离地获得透明性和均匀性高的凝胶这样的观点考虑,R1特别优选为碳原子数为17以上的直链烷基。另外通过使R1的碳原子数变大(使碳链长度变长),能够使亲水性有机溶剂比率的高的亲水性有机溶液形成凝胶。
所述(1)或式(2)所示的化合物可以通过公知的方法、例如具有上述R1基的醛与单糖反应来获得。
作为可以使用的单糖,只要是显示吡喃糖环结构的单糖就没有特别的限定,可列举阿洛糖、阿卓糖、葡萄糖、甘露糖、古洛糖、艾杜糖、半乳糖和塔罗糖等。
其中,从比较便宜和特别可期待生物体适合性方面考虑,作为单糖,优选葡萄糖、甘露糖、半乳糖,特别优选葡萄糖和甘露糖。
上述式(1)或(2)所示的化合物中,特别优选具有葡萄糖部分的下述式(3)所示的化合物、或具有甘露糖部分的下述式(4)所示的化合物。
[式中,R1和R2与上述式(1)中所述的定义含义相同。]
[式中,R1和R2与上述式(1)中所述的定义含义相同。]
上述式(3)所示的化合物中,优选下述式(5)所示的化合物。
[式中,R1与上述式(1)中所述的定义含义相同。]
另外,上述式(4)所示的化合物中,优选下述式(6)所示的化合物。
[式中,R1与上述式(1)中所述的定义含义相同。]
上述式(3)所示的化合物(葡萄糖型胶凝剂)在亲水性有机溶液和油(疏水性有机溶剂)的任一种中均具有凝胶形成能力,特别以能够对水/油混合溶剂形成水/油分散凝胶为最大的特征。
另外式(3)所示的化合物能够得到触变性优异的凝胶。并且还具有能够形成可以自己立起(具有自支撑性)的透明凝胶的特性。
此外上述式(1)或式(2)所示的化合物中,R1表示碳原子数13~20的直链状或支链状的烷基、碳原子数13~20的环状的烷基、或碳原子数13~20的直链状或支链状的烯基的化合物,即下述式(7)或式(8)所示的化合物也是本发明的对象。
[式中,
R5表示碳原子数13~20的直链状或支链状的烷基、碳原子数13~20的环状的烷基、或碳原子数13~20的直链状或支链状的烯基,
R2表示氢原子、碳原子数1~10的直链状或支链状的烷基、或可以具有取代基的芳基,
R3和R4表示羟基。]
[凝胶]
作为本发明的凝胶,可以通过利用上述胶凝剂使溶剂凝胶化来得到。具体来说,可以例示将规定量的胶凝剂加热溶解在溶剂中,并进行冷却这样的制造方法。通常,加热溶解时优选使其完全溶解。
此外,在本说明书中,凝胶化是指具有流动性的液体变成丧失流动性的状态。
使溶剂凝胶化时,本发明的胶凝剂的使用量,只要能发挥本发明的效果就没有特别的限定,但相对于被凝胶化的溶剂的质量通常为0.001~20质量%、例如0.02~5质量%。
作为所述溶剂,只要不妨碍凝胶化就没有特别的限定,作为优选的具体例子,可列举疏水性有机溶剂、亲水性有机溶剂、水、水和亲水性有机溶剂的混合溶剂(在本说明书中称为亲水性有机溶液)、疏水性有机溶剂和水的混合溶剂(在本说明书中称为疏水性有机溶液)、或在水中溶解有机酸或无机酸、或在水中溶解有无机盐或有机盐而形成的水溶液(在本说明书中称为水溶液)等。
本发明的凝胶可以包含所述胶凝剂、和疏水性有机溶剂、亲水性有机溶液、疏水性有机溶液或水溶液而形成,或者可以包含所述胶凝剂、表面活性剂、和疏水性有机溶剂、亲水性有机溶剂、水、亲水性有机溶液、疏水性有机溶液或水溶液而形成。
作为所述疏水性有机溶剂的优选具体例,可列举例如,橄榄油、椰油、蓖麻油、霍霍巴油或向日葵油等的植物油;乙酸乙酯、辛酸鲸蜡酯、肉豆蔻酸异丙酯或棕榈酸异丙酯等酯类;甲苯、二甲苯、正己烷、环己烷、辛烷、角鲨烷、角鲨烯、矿物油、硅油或氢化聚异丁烯等烃类;氯仿等卤代烃类等。
在这些物质中,作为所述疏水性有机溶剂,优选橄榄油、肉豆蔻酸异丙酯、甲苯、环己烷、角鲨烷、角鲨烯、直链状硅酮、环状硅酮、烷基改性硅酮、苯基改性硅酮、聚二甲基硅氧烷或聚二甲基硅氧烷醇等硅油和辛烷。
对于上述硅油,可以使用能够由東レ·ダウコーニング(株)获得的直链状硅氧烷(商品名:2-1184)、环状硅氧烷(十甲基环五硅氧烷(商品名:SH245)等)、烷基改性硅氧烷(商品名:SS-3408)、苯基改性硅氧烷(商品名:PH-1555)、聚二甲基硅氧烷(商品名:BY-11-0系列)、聚二甲基硅氧烷醇(商品名:CB-1556)等、以及能够从信越シリコーン(株)获得的十甲基环五硅氧烷(商品名:KF995)等。
所述亲水性有机溶剂是指可以在水中以任意比例溶解的有机溶剂,可列举醇、或丙酮、环己酮、乙腈、二氧杂环己烷、甘油和二甲基亚砜等。
所述醇优选为在水中自由溶解的水溶性醇,更优选列举碳原子数1至9的醇、多元醇、高级醇、甘油酯类。
具体来说,作为碳原子数1至9的醇,可列举甲醇、乙醇、2-丙醇、异丁醇、戊醇、己醇、1-辛醇、异辛醇等;作为多元醇,可列举乙二醇、丙二醇、聚丙二醇等;作为高级醇,可列举辛基十二烷醇、硬脂醇、油醇等;作为甘油酯类,可列举三辛酸甘油酯、三(辛酸/癸酸)甘油酯、硬脂酸甘油酯等。
在这些物质中,作为所述亲水性有机溶剂,优选甲醇、乙醇、2-丙醇、异丁醇、戊醇、己醇、1-辛醇、异辛醇、丙酮、环己酮、乙腈、二氧杂环己烷、甘油、丙二醇、乙二醇和二甲基亚砜,更优选甘油、丙二醇和乙二醇。
另外所述水溶液中使用的所述有机酸或无机酸可以单独使用也可以多种组合使用。
作为优选的有机酸的例子,可列举乙酸、柠檬酸、琥珀酸、乳酸、苹果酸、马来酸、富马酸及三氟乙酸。更优选为乙酸、柠檬酸、琥珀酸、乳酸、苹果酸,进一步优选为乙酸、柠檬酸、乳酸。
另外,作为优选的无机酸的例子,可列举盐酸、磷酸、碳酸、硫酸、硝酸和硼酸。更优选为盐酸、磷酸、碳酸、硫酸,进一步优选为盐酸、磷酸、碳酸。
进而所述水溶液中使用的所述无机盐或有机盐可以使用多种,但优选为1或2种。通过加入2种盐,还可期待水溶液具有缓冲能力。
作为优选的无机盐的例子,可以列举无机碳酸盐、无机硫酸盐、无机磷酸盐和无机磷酸氢盐。更优选为碳酸钙、碳酸钠、碳酸钾、硫酸钠、硫酸钾、硫酸镁、磷酸钾、磷酸钠、磷酸氢二钠或磷酸二氢钠,进一步优选为碳酸钙、硫酸镁、磷酸氢二钠或磷酸二氢钠。
另外,作为优选的有机盐的例子,可以列举无机乙酸盐、无机乳酸盐、无机柠檬酸盐这样的无机有机酸盐、有机胺的盐酸盐或有机胺乙酸盐。更优选为乙酸钠、乙酸钾、乳酸钠、乳酸钾、柠檬酸钠、柠檬酸钾、乙二胺盐酸盐、乙二胺四乙酸盐、三羟基甲基氨基甲烷盐酸盐。
相对于作为介质的所述的疏水性有机溶剂、亲水性有机溶剂、水、亲水性有机溶液、疏水性有机溶液或水溶液,本发明的胶凝剂可以按照0.001~20质量%、或者0.001~10质量%、优选为0.05~10质量%或者0.1~10质量%、例如0.02~5质量%或者0.1~5质量%的量使用。
将本发明的胶凝剂添加到作为介质的所述的疏水性有机溶剂、亲水性有机溶剂、水、亲水性有机溶液、疏水性有机溶液或水溶液等中,必要时进行加热搅拌使其溶解后,在室温下放置,从而可以得到凝胶。凝胶强度可以利用胶凝剂的浓度进行调节。
此外,利用本发明的胶凝剂形成的凝胶,可以在不损害胶凝剂的凝胶化能力的范围内,根据其应用用途等,根据需要混入各种添加剂(表面活性剂、紫外线吸收剂、保湿剂、防腐剂、抗氧化剂、香料、生理活性物质(药效成分)等有机化合物、和氧化钛、滑石、云母、水等无机化合物等)。
例如作为表面活性剂,可列举Tween(吐温)20、Span(司盘)80、蔗糖糖酯等非离子性表面活性剂、各种阴离子性表面活性剂、阳离子性表面活性剂等。
另外作为生理活性物质,可列举L-抗坏血酸、L-抗坏血酸2-磷酸酯3钠(维生素C衍生物)、甘氨酸、葡糖胺等。
[微粒]
另外本发明的凝胶还可以是进一步分散而包含有微粒的方式。
微粒是非常细小的颗粒,可以是呈球状的形状,也可以是长、宽、高的值不同的形状。另外,作为该颗粒的数均粒径,优选为0.1nm~20μm,更优选为1nm~2,000nm。
可以在本发明中使用的微粒是无机物、有机物的微粒、例如无机物可列举氧化钛、氧化锌、氧化铬、黑色氧化铁、红色氧化铁、黄色氧化铁、红铅、黑色氧化钛、氢氧化铬、钛酸锂钴、钴蓝、绿松石、钛黄、Fe-Zn-Cr系棕、Cu-Cr系黑、氧化铝、镉黄、镉红、铬黄绿、钼镉红、铬酸锌、锰紫、群青、铁蓝、磷酸钙、羟磷灰石、碳酸钙、碳酸镁、硫酸钡、铝粉、青铜粉、炭黑、氯氧化铋、云母钛、铅白、钛酸钡、钛酸锆酸锌、铁素体、镁橄榄石、氧化锆、锆石、莫来石、滑石、堇青石、氮化铝、氮化硅、高岭土、硅酸酐、硅酸铝镁、合成金云母、绢云母、滑石、云母等。有机物可列举麻纤维素粉、小麦淀粉、蚕丝粉、玉米淀粉、硬脂酸铝、硬脂酸锌、硬脂酸镁、硬脂酸钙、棕榈酸锌、肉豆蔻酸锌、肉豆蔻酸镁、十一碳烯酸锌、碳化硅、纤维素粉末、聚乙烯粉末、尼龙粉末、聚丙烯酸烷基酯、交联聚苯乙烯、甲基硅氧烷网状聚合物、聚氨酯、色淀红C、亮胭脂红6B、直接红498、直接黄K-5G、立索尔宝红B、永久红4R、萘酚红、坚牢黄G、双偶氮黄HR、吡唑啉酮橙、苯并咪唑酮胭脂红HF4C、苯并咪唑酮黄H3G、缩合偶氮红BR、缩合偶氮黄GR、酞菁蓝、酞菁绿、二蒽醌红、硫靛枣红、苝橙、苝红、喹吖啶酮洋红、二噁嗪紫、喹酞酮黄、偶氮甲碱黄、异吲哚啉酮黄G、二酮吡咯红、罗丹明B、沉淀罗丹明6、沉淀喹啉黄等。只要作为微粒存在,则对材质等不特别限定,另外也可以是它们的混合物、复合物。进而,如果考虑对光的散射特性、遮蔽特性、作为色材的耐久性,则可以是金属氧化物或它们的混合物或复合物。
在向本发明的凝胶中配合微粒的情况下,作为微粒的分散方法,为了进一步提高其分散效果从而能应对各种种类的微粒的分散,也可以联合使用机械分散处理。这里机械分散处理是指对凝集了的颗粒施加冲击、剪切等物理的力,解开凝集体使其分散的处理。作为例子,可列举:像超声波浴、超声波均质机等那样,通过消灭伴随粗密状态、膨胀而产生的空穴使凝集体变形从而破碎的方法;像高速搅拌器、胶体磨等那样利用由旋转翼与固定环之间的细微间隙产生的强剪切力、冲击力的方法;高压均质机等利用凝集体的高速冲撞的方法;珠磨机等利用与介质的冲撞、剪切、冲击、摩擦等而分散的方法等,但不特别限于这些。
在配合微粒的情况下,其配合量只要微粒能够均匀分散就无特别限制,但相对于要使其凝胶化的流体的体积,优选为0.1~20质量%(w/v%),进一步优选为0.5~10质量%(w/v%)。
[各种用途]
本发明的胶凝剂如上所述能够将各种溶剂凝胶化,另外也能够将水与油的混合溶剂凝胶化。因此本发明的胶凝剂和由其得到的凝胶能够在化妆品基材或医疗用基材、凝胶电解质、细胞培养基材、细胞或蛋白质等生物体分子保存用基材、外用基材、生物化学用基材、食品用基材、隐形眼镜、纸尿裤、人工执行器、干燥地农业用基材等各种领域的材料中使用。另外,能够作为酶等的生物反应器载体在研究、医疗、分析、各种产业中广泛利用。
[化妆品基材或医疗用基材]
本发明的化妆品基材或医疗用基材含有上述胶凝剂。
另外,本发明的化妆品基材或医疗用基材除了上述胶凝剂之外,还可以含有水、醇、多元醇、亲水性有机溶剂、疏水性有机溶剂、或它们的混合溶液。此外,作为所述醇、多元醇、亲水性有机溶剂和疏水性有机溶剂,可列举所述醇、多元醇、亲水性有机溶剂和疏水性有机溶剂中例示的化合物。
另外,本发明的化妆品基材或医疗用基材根据需要可含有一般在化妆品基材或医疗用基材中配合的生理活性物质和功能性物质等添加成分,作为这样的添加成分,可以列举油性基剂、保湿剂、触感提升剂、表面活性剂、高分子、增稠/胶凝剂、溶剂、喷射剂、抗氧化剂、还原剂、氧化剂、防腐剂、抗菌剂、杀菌剂、螯合剂、pH调节剂、酸、碱、粉末、无机盐、紫外线吸收剂、美白剂、维生素类及其衍生物类、生发用药剂、血液循环促进剂、刺激剂、激素类、抗皱剂、抗老化剂、紧致剂、冷感剂、温感剂、伤口愈合促进剂、刺激减缓剂、镇痛剂、细胞活化剂、植物/动物/微生物提取物、除痒剂、角质剥离/溶解剂、止汗剂、清凉剂、收敛剂、酶、核酸、香料、色素、着色剂、染料、颜料、消炎剂、抗炎剂、抗哮喘、抗慢性阻塞性肺病、抗变态反应、免疫调节剂、抗感染剂及抗真菌剂等。
另外,本发明的化妆品基材或医疗用基材可以包含上述胶凝剂和至少一种高分子化合物。
作为所述高分子化合物,可以列举明胶、海藻酸钠、海藻酸丙二醇酯、阿拉伯胶、聚乙烯醇、聚丙烯酸、聚丙烯酸钠、羧甲基纤维素、结冷胶、黄原胶、角叉胶聚苯乙烯、聚甲基丙烯酸甲酯、聚乙烯基吡咯烷酮、聚氧乙烯、聚乳酸、聚苯乙烯磺酸、聚丙烯腈、聚乙烯和聚对苯二甲酸乙二酯等。
如果例示这些添加成分,则作为油性基剂,可列举鲸蜡醇、肉豆蔻醇、油醇、月桂醇、鲸蜡硬脂醇、硬脂醇、芳烷醇、二十二烷醇、霍霍巴醇、鲛肝醇、单油烯基甘油醚、鲨肝醇、己基癸醇、异硬脂醇、2-辛基十二烷醇、二聚二醇等高级(多元)醇类;苄醇等芳烷醇及其衍生物;月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、异硬脂酸、二十二烷酸、十一碳烯酸、12-羟基硬脂酸、棕榈油酸、油酸、亚油酸、亚麻酸、芥酸、二十二碳六烯酸、二十碳五烯酸、异十六烷酸、反式异十一碳五烯酸、长链支链脂肪酸、二聚酸、氢化二聚酸等高级脂肪酸类、及其铝盐、钙盐、镁盐、锌盐、钾盐、钠盐等金属皂化物类、以及酰胺等含氮衍生物类;液体石蜡(矿物油)、重质液体异链烷烃、轻质液体异链烷烃、α-烯烃低聚物、聚异丁烯、氢化聚异丁烯、聚丁烯、角鲨烷、来自橄榄油的角鲨烷、角鲨烯、凡士林、固体石蜡等烃类;小烛树蜡、巴西蜡棕蜡、米糠蜡、木蜡、蜂蜡、褐煤蜡、地蜡、纯地蜡、石蜡、微晶蜡、凡士林、费托蜡、聚乙烯蜡、乙烯/丙烯共聚物等蜡类;椰油、棕榈油、棕榈核油、红花油、橄榄油、蓖麻油、鳄梨油、芝麻油、茶油、月见草油、小麦胚芽油、澳洲坚果油、榛子油、石栗油、玫瑰果油、白芒花油、波斯油、茶树油、薄荷油、玉米油、菜籽油、葵花籽油、小麦胚芽油、亚麻籽油、棉籽油、大豆油、花生油、米糠油、可可脂、乳木果油、氢化椰子油、氢化蓖麻油、霍霍巴油、氢化霍霍巴油等;牛脂、乳脂、马脂、蛋黄油、貂油、鳖油动物性油脂类;鲸蜡、羊毛脂、胸棘鲷油等动物性蜡类;液体羊毛脂、还原羊毛脂、吸附纯化羊毛脂、醋酸羊毛脂、醋酸羊毛脂、醋酸羊毛脂、羟乙基羊毛脂、聚氧乙烯羊毛脂、硬质羊毛脂脂肪酸、羊毛脂醇、羊毛脂醇乙酸酯、乙酸(十六烷基/羊毛脂基)酯等羊毛脂类;卵磷脂、磷脂酰胆碱、磷脂酰乙醇胺、磷脂酰丝氨酸、磷脂酰甘油、磷脂酰肌醇、鞘磷脂等鞘脂、磷脂酸、溶血卵磷脂等磷脂类;氢化大豆磷脂、部分氢化大豆磷脂、氢化卵黄磷脂、部分氢化卵黄磷脂等磷脂衍生物类;胆固醇、二氢胆固醇、羊毛固醇、二氢固醇、植物固醇、胆酸等固醇类;皂苷元类;皂苷类;乙酸胆固醇酯、壬酸胆固醇酯、异硬脂酸胆固醇酯、异硬脂酸胆固醇酯、油酸胆固醇酯、N-月桂酰-L-谷氨酸二(胆固醇基/二十二烷基/辛基十二烷基)酯、N-月桂酰-L-谷氨酸二(胆固醇基/辛基十二烷基)酯、N-月桂酰-L-谷氨酸二(植物固醇基/二十二烷基/辛基十二烷基)酯、N-月桂酰-L-谷氨酸二(植物固醇基/辛基十二烷基)酯、N-月桂酰肌氨酸异丙酯等酰基肌氨酸烷基酯、12-羟基异硬脂酸胆固醇酯、澳洲坚果油脂肪酸胆固醇酯、澳洲坚果油脂肪酸植物固醇酯、异硬脂酸植物固醇酯、软质羊毛脂脂肪酸胆固醇酯、硬质羊毛脂脂肪酸胆固醇酯、长链支链化脂肪酸胆固醇酯、长链α-羟基脂肪酸胆固醇酯等固醇酯类;磷脂-胆固醇复合体、磷脂-植物固醇复合体等脂质复合体;肉豆蔻酸辛基十二烷基酯、肉豆蔻酸己基癸基酯、异硬脂酸辛基十二烷基酯、棕榈酸十六烷基酯、棕榈酸辛基十二烷基酯、辛酸十六烷基酯、辛酸己基癸基酯、异壬酸异十三烷基酯、异壬酸异壬基酯、异壬酸辛酯、异壬酸异十三烷基酯、新戊酸异癸基酯、新戊酸异十三烷基酯、新戊酸异硬脂基酯、新癸酸辛基十二烷基酯、油酸油烯基酯、油酸辛基十二烷基酯、蓖麻油酸辛基十二烷基酯、羊毛脂脂肪酸辛基十二烷基酯、二甲基辛酸己基癸基酯、芥酸辛基十二烷基酯、异硬脂酸硬化蓖麻籽油、油酸乙酯、鳄梨油脂肪酸乙酯、肉豆蔻酸异丙酯、棕榈酸异丙酯、棕榈酸辛酯、异硬脂酸异丙酯、羊毛脂脂肪酸异丙酯、癸二酸二乙酯、癸二酸二异丙酯、癸二酸二辛酯、己二酸二异丙酯、癸二酸二丁基辛酯、己二酸二异丁基酯、琥珀酸二辛酯、柠檬酸三乙酯等一元醇羧酸酯类;乳酸十六烷基酯、苹果酸二异硬脂基酯、氢化蓖麻籽油单异硬脂酸酯等羟基酸酯类;三辛酸甘油酯、三油酸甘油酯、三异硬脂酸甘油酯、二异硬脂酸甘油酯、三(辛酸/癸酸)甘油酯、三(辛酸/癸酸/肉豆蔻酸/异硬脂酸)甘油酯、氢化松香三甘油酯(氢化酯胶)、松香三甘油酯(酯胶)、二十二酸二十烷二酸甘油酯、三羟甲基丙烷三辛酸酯、三羟甲基丙烷三异硬脂酸酯、新戊二醇二辛酸酯、新戊二醇二癸酸酯、2-丁基-2-乙基-1,3-丙二醇二辛酸酯、丙二醇二油酸酯、季戊四醇四辛酸酯、氢化松香季戊四醇、双三羟甲基丙烷三乙基己酸酯、双三羟甲基丙烷(异硬脂酸/癸二酸)酯、季戊四醇三乙基己酸酯、二季戊四醇(羟基异硬脂酸/异硬脂酸/松香酸)酯、二异硬脂酸二甘油酯、聚甘油四异硬脂酸酯、聚甘油-10九异硬脂酸酯、聚甘油-8十(芥酸/异硬脂酸/蓖麻油酸)酯、(己基癸酸/癸二酸)双甘油低聚脂、二异硬脂酸二醇(乙二醇二异硬脂酸酯)、二新戊酸3-甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇二新戊酸酯等多元醇脂肪酸酯类;二聚物二亚油酸二异丙酯、二聚物二亚油酸二异硬脂基酯、二聚物二亚油酸二(异硬脂基/植物固醇基)酯、二聚物二亚油酸(植物固醇基/二十二烷基)酯、二聚物二亚油酸(植物固醇基/异硬脂基/十六烷基/硬脂基/二十二烷基)酯、二聚物二亚油酸二聚物二亚油醇、二异硬脂酸二聚物二亚油醇、二聚物二亚油醇氢化松香缩合物、二聚物硬化蓖麻籽油二亚油酸酯、羟基烷基二聚物二亚油醇醚等二聚物酸或二聚物二醇的衍生物;椰油脂肪酸单乙醇酰胺(椰油酰胺MEA)、椰油脂肪酸二乙醇酰胺(椰油酰胺DEA)、月桂酸单乙醇酰胺(月桂酰胺MEA)、月桂酸二乙醇酰胺(月桂酰胺DEA)、月桂酸单异丙醇酰胺(月桂酰胺MIPA)、棕榈酸单乙醇酰胺(棕榈酰胺MEA)、棕榈酸二乙醇酰胺(棕榈酰胺DEA)、椰油脂肪酸甲基乙醇酰胺(椰油酰胺甲基MEA)等脂肪酸烷醇酰胺类;二甲硅油(二甲基聚硅氧烷)、高聚合二甲硅油(高聚合二甲基聚硅氧烷)、环甲硅油(环状二甲基硅氧烷、十甲基环五硅氧烷)、苯基三甲硅油、二苯基二甲硅油、苯基二甲硅油、硬脂氧基丙基二甲基胺、(氨基乙基氨基丙基甲硅油/二甲硅油)共聚物、聚二甲基硅氧烷醇、聚二甲基硅氧烷醇交联聚合物、硅氧烷树脂、硅橡胶纯胶料、氨基丙基二甲硅油和氨端聚二甲基硅氧烷(amodimethicone)等氨基改性硅氧烷、阳离子改性硅氧烷、聚二甲基硅氧烷共聚醇等聚醚改性硅氧烷、聚甘油改性硅氧烷、糖改性硅氧烷、羧酸改性硅氧烷、磷酸改性硅氧烷、硫酸改性硅氧烷、烷基改性硅氧烷、脂肪酸改性硅氧烷、烷基醚改性硅氧烷、氨基酸改性硅氧烷、肽改性硅氧烷、氟改性硅氧烷、阳离子改性和聚醚改性硅氧烷、氨基改性和聚醚改性硅氧烷、烷基改性和聚醚改性硅氧烷、聚硅氧烷-氧化烯共聚物等硅氧烷类;全氟癸烷、全氟辛烷、全氟聚醚等氟系油剂类作为优选物质。
作为保湿剂和/或触感提升剂,可列举甘油、1,3-丁二醇、丙二醇、3-甲基-1,3-丁二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、三羟甲基丙烷、季戊四醇、己二醇、双甘油、聚甘油、二甘醇、聚乙二醇、双丙甘醇、聚丙二醇、乙二醇-丙二醇共聚物等多元醇类及其聚合物;二甘醇单乙基醚(乙氧基二甘醇)、乙二醇单乙基醚、乙二醇单丁基醚、二甘醇二丁基醚等甘醇烷基醚类;聚甘油-10(二十烷二酸/四癸烷二酸)酯、聚甘油-10四癸烷二酸酯等水溶性酯类;山梨糖醇、木糖醇、赤藓醇、甘露糖醇、麦芽糖醇等糖醇类;葡萄糖、果糖、半乳糖、甘露糖、苏糖、木糖、阿拉伯糖、岩藻糖、核糖、脱氧核糖、麦芽糖、海藻糖、乳糖、棉子糖、葡糖酸、葡萄糖醛酸、环糊精类(α-、β-、γ-环糊精、和麦芽糖基化、羟基烷基化等的修饰环糊精)、β葡聚糖、几丁质、壳聚糖、肝素及其衍生物、果胶、阿拉伯半乳聚糖、糊精、葡聚糖、糖原、乙基葡糖苷、甲基丙烯酸葡萄糖基乙酯聚合物或共聚物等糖类及其衍生物类;透明质酸、透明质酸钠;硫酸软骨素钠;硫酸粘多糖、硫酸カロニン(charonin)、硫酸角质素、硫酸皮肤素;白桦提取物、石斑草多糖体;岩藻依聚糖;晚香玉多糖体或天然来源多糖体;柠檬酸、酒石酸、乳酸等有机酸及其盐;尿素及其衍生物;2-吡咯烷酮-5-羧酸及其钠等盐;甜菜碱(三甲基甘氨酸)、脯氨酸、羟脯氨酸、精氨酸、赖氨酸、丝氨酸、甘氨酸、丙氨酸、苯丙氨酸、酪氨酸、β-丙氨酸、苏氨酸、谷氨酸、谷氨酰胺、天冬酰胺、天冬氨酸、半胱氨酸、半胱氨酸、甲硫氨酸、亮氨酸、异亮氨酸、缬氨酸、色氨酸、组氨酸、牛磺酸等氨基酸类及其盐;胶原蛋白、鱼来源胶原蛋白、缺端胶原(Atelocollagen)、明胶,弹性蛋白、胶原蛋白分解肽、水解胶原蛋白、羟基丙基氯化铵水解胶原蛋白、弹性蛋白分解肽、角蛋白分解肽、水解角蛋白、贝壳硬蛋白分解肽、水解贝壳硬蛋白、蚕丝蛋白分解肽、水解蚕丝、月桂酰水解蚕丝钠、大豆蛋白分解肽、小麦蛋白分解肽、水解小麦蛋白、酪蛋白分解肽、酰基化肽等蛋白肽类及其衍生物;棕榈酰寡肽、棕榈酰五肽、棕榈酰四肽等酰基化肽类;甲硅烷基化肽类;乳酸菌培养液、酵母提取液、卵壳膜蛋白、牛下颌下腺粘蛋白、亚牛磺酸、芝麻木脂素糖苷、谷胱甘肽、白蛋白、乳清;氯化胆碱、磷酸胆碱;胎盘提取液、弹性蛋白、胶原蛋白、芦荟提取物、金缕梅水、丝瓜水、洋甘菊提取物、甘草提取物、紫草提取物、蚕丝提取物、缫丝花提取物、西洋耆草提取物、桉树提取物、草木犀提取物等动物提取成分、天然型神经酰胺(1、2、3、4、5、6型)、羟基神经酰胺、类神经酰胺、神经鞘糖脂、含有神经酰胺和糖神经酰胺的提取物等神经酰胺类作为优选的物质。
作为表面活性剂,可列举阴离子性表面活性剂、非离子性表面活性剂、阳离子性表面活性剂、两性表面活性剂、高分子表面活性剂等作为优选的物质。如果例示作为表面活性剂优选的物质,则作为阴离子性表面活性剂,可列举月桂酸钾、肉豆蔻酸钾等脂肪酸盐;十二烷基硫酸钠、十二烷基硫酸三乙醇胺、十二烷基硫酸铵等烷基硫酸酯盐;十二烷基聚醚硫酸钠、十二烷基聚醚硫酸三乙醇胺等聚氧乙烯烷基硫酸盐;椰油基甲基牛磺酸钠、椰油基甲基牛磺酸钾、月桂酰甲基牛磺酸钠、肉豆蔻酰甲基牛磺酸钠、月桂酰甲基丙氨酸钠、月桂酰肌氨酸钠、月桂酰肌氨酸三乙醇胺、月桂酰谷氨酸甲基丙氨酸钠等酰基N-甲基氨基酸盐;椰油基谷氨酸钠、椰油基谷氨酸三乙醇胺、月桂酰谷氨酸钠、肉豆蔻酰谷氨酸钠、硬脂酰谷氨酸钠、棕榈酰天冬氨酸双三乙醇胺、椰油基丙氨酸三乙醇胺等酰基氨基酸盐;十二烷基聚醚乙酸钠等聚氧乙烯烷基醚乙酸盐;月桂酰单乙醇酰胺琥珀酸钠等琥珀酸酯盐;脂肪酸烷醇酰胺醚羧酸盐;酰基乳酸盐;聚氧乙烯脂肪胺硫酸盐;脂肪酸烷醇酰胺硫酸盐;硬化椰油脂肪酸甘油硫酸钠等脂肪酸甘油酯硫酸盐;烷基苯聚氧乙烯硫酸盐;α-烯烃磺酸钠等烯烃磺酸盐;磺基琥珀酸十二烷基2钠、磺基琥珀酸二辛基钠等烷基磺基琥珀酸盐;磺基琥珀酸十二烷基聚醚2钠、单月桂酰单乙醇酰胺聚氧乙烯磺基琥珀酸钠、十二烷基聚丙二醇磺基琥珀酸钠等烷基醚磺基琥珀酸盐;十四烷基苯磺酸钠、十四烷基苯磺酸三乙醇胺等烷基苯磺酸盐;烷基萘磺酸盐;烷烃磺酸盐;α-磺基脂肪酸甲基酯盐;酰基羟基乙磺酸盐;烷基缩水甘油基醚磺酸盐;烷基磺基乙酸盐;十二烷基聚醚磷酸钠、双十二烷基聚醚磷酸钠、三十二烷基聚醚磷酸钠、单油醇聚醚磷酸钠等烷基醚磷酸酯盐;十二烷基磷酸钾等烷基磷酸酯盐;酪蛋白钠;烷基芳基醚磷酸盐;脂肪酸酰胺醚磷酸盐;磷脂酰甘油,磷脂酰肌醇,磷脂酸等磷脂类;羧酸改性硅氧烷、磷酸改性硅氧烷、硫酸改性硅氧烷等硅氧烷系阴离子性表面活性剂等作为优选的物质;作为非离子表面活性剂,可列举十二烷基聚醚(聚氧乙烯十二烷基醚)类、鲸蜡醇聚醚(聚氧乙烯十六烷基醚)类、硬脂醇聚醚(聚氧乙烯硬脂基醚)类、二十二烷醇聚醚类(聚氧乙烯二十二烷基醚)、异硬脂醇聚醚(聚氧乙烯异硬脂基醚)类、辛基十二烷醇聚醚(聚氧乙烯辛基十二烷基醚)类等各种聚氧乙烯加成数的聚氧乙烯烷基醚类;聚氧乙烯烷基苯基醚;聚氧乙烯硬化蓖麻籽油、聚氧乙烯蓖麻籽油、聚氧乙烯硬化蓖麻籽油单异硬脂酯、聚氧乙烯硬化蓖麻籽油三异硬脂酯、聚氧乙烯硬化蓖麻籽油单焦谷氨酸单异硬脂酸二酯、聚氧乙烯硬化蓖麻籽油马来酸等蓖麻籽油和硬化蓖麻籽油衍生物;聚氧乙烯植物固醇;聚氧乙烯胆固醇;聚氧乙烯胆甾烷醇;聚氧乙烯羊毛脂;聚氧乙烯还原羊毛脂;聚氧乙烯-聚氧丙烯十六烷基醚、聚氧乙烯-聚氧丙烯2-癸基十四烷基醚、聚氧乙烯-聚氧丙烯单丁基醚、聚氧乙烯-聚氧丙烯氢化羊毛脂、聚氧乙烯-聚氧丙烯甘油醚等聚氧乙烯-聚氧丙烯烷基醚;聚氧乙烯·聚氧丙二醇;PPG-9二甘油酯等(聚)甘油聚氧丙二醇;异硬脂酸甘油酯、异硬脂酸甘油酯、棕榈酸甘油酯、肉豆蔻酸甘油酯、油酸甘油酯、椰油脂肪酸甘油酯、单棉籽油脂肪酸甘油酯、单芥酸甘油酯、倍半油酸甘油酯、α,α’-油酸焦谷氨酸甘油酯、单异硬脂酸甘油苹果酸酯等甘油脂肪酸部分酯类;聚甘油-2异硬脂酸酯、聚甘油-3异硬脂酸酯、聚甘油-4异硬脂酸酯、聚甘油-5异硬脂酸酯、聚甘油-6异硬脂酸酯、聚甘油-8异硬脂酸酯、聚甘油-10异硬脂酸酯、聚甘油-6二异硬脂酸酯、聚甘油-10二异硬脂酸酯、聚甘油-2三异硬脂酸酯、聚甘油-10十异硬脂酸酯、聚甘油-2异硬脂酸酯、聚甘油-3异硬脂酸酯、聚甘油-4异硬脂酸酯、聚甘油-5异硬脂酸酯、聚甘油-6异硬脂酸酯、聚甘油-8异硬脂酸酯、聚甘油-10异硬脂酸酯、聚甘油-2二异硬脂酸酯(二异硬脂酸二甘油酯)、聚甘油-3二异硬脂酸酯、聚甘油-10二异硬脂酸酯、聚甘油-2三异硬脂酸酯、聚甘油-2四异硬脂酸酯、聚甘油-10十异硬脂酸酯、聚甘油-2油酸酯、聚甘油-3油酸酯、聚甘油-4油酸酯、聚甘油-5油酸酯、聚甘油-6油酸酯、聚甘油-8油酸酯、聚甘油-10油酸酯、聚甘油-6二油酸酯、聚甘油-2三油酸酯、聚甘油-10十油酸酯等聚甘油脂肪酸酯;单异硬脂酸乙二醇等乙二醇单脂肪酸酯;单异硬脂酸丙二醇等丙二醇单脂肪酸酯;季戊四醇部分脂肪酸酯;山梨糖醇部分脂肪酸酯;麦芽糖醇部分脂肪酸酯;麦芽糖醇醚;失水山梨糖醇单油酸酯、失水山梨糖醇单异硬脂酯、失水山梨糖醇单月桂酸酯、失水山梨糖醇单棕榈酸酯、失水山梨糖醇单硬脂酸酯、失水山梨糖醇倍半油酸酯、失水山梨糖醇三油酸酯、五(2-乙基己基酸)双甘油失水山梨糖醇酯、四(2-乙基己基酸)双甘油失水山梨糖醇酯等失水山梨糖醇脂肪酸酯;蔗糖脂肪酸酯、甲基糖苷脂肪酸酯、十一碳烯酸海藻糖酯等糖衍生物部分酯;辛基糖苷等烷基糖苷;烷基聚糖苷;羊毛脂醇;还原羊毛脂;聚氧乙烯二硬脂酸酯、聚乙二醇二异硬脂酯、聚氧乙烯单油酸酯、聚氧乙烯二油酸酯等聚氧乙烯脂肪酸单酯和二酯;聚氧乙烯-丙二醇脂肪酸酯;聚氧乙烯甘油单硬脂酸酯、聚氧乙烯甘油单异硬脂酯、聚氧乙烯甘油三异硬脂酯等聚氧乙烯单油酸酯等聚氧乙烯甘油脂肪酸酯;聚氧乙烯失水山梨糖醇单油酸酯、聚氧乙烯失水山梨糖醇单硬脂酸酯、聚氧乙烯失水山梨糖醇单油酸酯、聚氧乙烯失水山梨糖醇四油酸酯等聚氧乙烯失水山梨糖醇脂肪酸酯;聚氧乙烯山梨糖醇单月桂酸酯、聚氧乙烯山梨糖醇单油酸酯、聚氧乙烯山梨糖醇五油酸酯、聚氧乙烯山梨糖醇单硬脂酸酯等聚氧乙烯山梨糖醇脂肪酸酯;聚氧乙烯甲基糖苷脂肪酸酯;聚氧乙烯烷基醚脂肪酸酯;聚氧乙烯山梨糖醇蜂蜡等聚氧乙烯动植物油脂类;异硬脂基甘油酯醚、鲛肝醇、单油烯基甘油醚、鲨肝醇等烷基甘油酯醚类;多元醇烷基醚;聚氧乙烯烷基胺;四聚氧乙烯-四聚氧丙烯-乙烯二胺缩合物类;皂苷、槐糖脂等天然系表面活性剂;聚氧乙烯脂肪酸酰胺;椰油脂肪酸单乙醇酰胺(椰油酰胺MEA)、椰油脂肪酸二乙醇酰胺(椰油酰胺DEA)、月桂酸单乙醇酰胺(月桂酰胺MEA)、月桂酸二乙醇酰胺(月桂酰胺DEA)、月桂酸单异丙醇酰胺(月桂酰胺MIPA)、棕榈酸单乙醇酰胺(棕榈酰胺MEA)、棕榈酸二乙醇酰胺(棕榈酰胺DEA)、椰油脂肪酸甲基乙醇酰胺(椰油酰胺甲基MEA)等脂肪酸烷醇酰胺类;月桂胺氧化物、椰油胺氧化物、硬脂胺氧化物、二十二胺氧化物等烷基二甲基胺氧化物;烷基乙氧基二甲基胺氧化物;聚氧乙烯烷基硫醇;二甲硅油共聚醇等聚醚改性硅氧烷、聚硅氧烷-氧化烯共聚物、聚甘油改性硅氧烷、糖改性硅氧烷等硅氧烷系非离子性表面活性剂等作为优选的物质;作为阳离子性表面活性剂,可列举二十二烷基三甲基氯化铵、硬脂基三甲基氯化铵、西曲氯铵、十二烷基三甲基氯化铵等烷基三甲基氯化铵;硬脂基三甲基溴化铵等烷基三甲基溴化铵;二硬脂基二甲基氯化铵、二椰油基二甲基氯化铵等二烷基二甲基氯化铵;硬脂酰胺丙基二甲基胺、硬脂酰胺乙基二乙胺等脂肪酸酰胺胺及其盐;硬脂氧基丙基二甲基胺等烷基醚胺及其盐或季盐;乙基硫酸长链支链化脂肪酸(12~31)氨基丙基乙基二甲基铵、乙基硫酸羊毛脂脂肪酸氨基丙基乙基二甲基铵等脂肪酸酰胺型季铵盐;聚氧乙烯烷基胺及其盐或季盐;烷基胺盐;脂肪酸酰胺胍盐;烷基醚胺铵盐;烷基三亚烷基二醇铵盐;苯扎氯铵盐;苄索氯铵盐;氯化十六烷基吡啶鎓等吡啶鎓盐;
咪唑啉鎓盐;烷基异喹啉鎓盐;二烷基吗啉鎓盐;聚胺脂肪酸衍生物;氨基丙基二甲硅油和氨端聚二甲基硅氧烷等氨基改性硅氧烷、阳离子改性硅氧烷、阳离子改性和聚醚改性硅氧烷、氨基改性和聚醚改性硅氧烷等硅氧烷系阳离子性表面活性剂等作为优选的物质;作为两性表面活性剂,可列举十二烷基甜菜碱(十二烷基二甲基氨基乙酸甜菜碱)等N-烷基-N,N-二甲基氨基酸甜菜碱;椰油酰胺丙基甜菜碱、月桂酰胺丙基甜菜碱等脂肪酸酰胺烷基-N,N-二甲基氨基酸甜菜碱;椰油酰两性基乙酸钠、月桂酰两性基乙酸钠等咪唑啉型甜菜碱;烷基二甲基牛磺酸等烷基磺基甜菜碱;烷基二甲基氨基乙醇硫酸酯等硫酸型甜菜碱;烷基二甲基氨基乙醇磷酸酯等磷酸型甜菜碱;磷脂酰胆碱、磷脂酰乙醇胺、磷脂酰丝氨酸、鞘磷脂等鞘脂、溶血卵磷脂、氢化大豆磷脂、部分氢化大豆磷脂、氢化卵黄磷脂、部分氢化卵黄磷脂、氢氧化卵磷脂等磷脂类;硅氧烷系两性表面活性剂等作为优选的物质;作为高分子表面活性剂,可列举聚乙烯醇、海藻酸钠、淀粉衍生物、黄蓍胶、丙烯酸烷基酯/甲基丙烯酸烷基酯共聚物;硅氧烷系各种表面活性剂作为优选的物质。
作为高分子、增稠剂和/或胶凝剂、瓜耳胶、刺槐豆胶、クィーンスシード、角叉菜胶、半乳聚糖、阿拉伯树胶、塔拉胶、罗望子胶、红藻胶、刺梧桐树胶、黄蜀葵胶、伽罗胶、黄蓍胶、果胶、果胶酸和钠盐等盐、海藻酸和钠盐等盐、甘露聚糖;大米、玉米、马铃薯、小麦等的淀粉;黄原胶(キサンタンガム)、葡聚糖、琥珀酰葡聚糖、凝胶多糖、透明质酸及其盐、黄原胶(ザンサンガム)、支链淀粉、结冷胶、几丁质、壳聚糖、琼脂、褐藻提取物、硫酸软骨素、酪蛋白、胶原蛋白、明胶、白蛋白;甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基纤维素、羟丙基甲基纤维素、羧甲基纤维素及其钠等盐、甲基羟丙基纤维素、纤维素硫酸钠、二烷基二甲基铵纤维素硫酸酯、结晶纤维素、纤维素末等纤维素及其衍生物;可溶性淀粉、羧甲基淀粉、甲基羟基丙基淀粉、甲基淀粉等淀粉系高分子、淀粉羟基丙基三甲基氯化铵、玉米淀粉辛烯基琥珀酸铝等淀粉衍生物;海藻酸钠、海藻酸丙二醇酯等海藻酸衍生物;聚乙烯基吡咯烷酮(PVP)、聚乙烯醇(PVA)、乙烯基吡咯烷酮-乙烯醇共聚物、聚乙烯基甲基醚;聚乙二醇、聚丙二醇、聚氧乙烯-聚氧丙烯共聚物;(甲基丙烯酰氧乙基羧基甜菜碱/甲基丙烯酸烷基)共聚物、(丙烯酸酯类/丙烯酸硬脂基酯/甲基丙烯酸乙胺氧化物)共聚物等两性甲基丙烯酸酯共聚物;(二甲硅油/乙烯基二甲硅油)交联聚合物、(丙烯酸烷基/双丙酮丙烯酰胺)共聚物、(丙烯酸烷基/双丙酮丙烯酰胺)共聚物AMP;聚乙酸乙烯酯部分皂化物、马来酸共聚物;乙烯基吡咯烷酮/甲基丙烯酸二烷基氨基烷基酯共聚物;丙烯酸类树脂烷醇胺;聚酯、水分散性聚酯;聚丙烯酰胺;聚丙烯酸乙酯等聚丙烯酸酯共聚物、羧基乙烯基聚合物、聚丙烯酸及其钠盐等盐、丙烯酸-甲基丙烯酸酯共聚物;丙烯酸-甲基丙烯酸烷基酯共聚物;聚季铵盐(Polyquaternium)-10等阳离子化纤维素、聚季铵盐(Polyquaternium)-7等二烯丙基二甲基氯化铵-丙烯酰胺共聚物、聚季铵盐(Polyquaternium)-22等丙烯酸-二烯丙基二甲基氯化铵共聚物、聚季铵盐(Polyquaternium)-39等丙烯酸-二烯丙基二甲基氯化铵-丙烯酰胺共聚物、丙烯酸-阳离子化甲基丙烯酸酯共聚物、丙烯酸-阳离子化甲基丙烯酰胺共聚物、聚季铵盐(Polyquaternium)-47等丙烯酸-丙烯酸甲酯-甲基丙烯酰胺丙基三甲基氯化铵共聚物、氯化甲基丙烯酸胆碱酯聚合物;阳离子化低聚糖、阳离子化右旋糖酐、瓜耳胶羟基丙基三甲基氯化铵等阳离子化多糖类;聚乙烯亚胺;阳离子聚合物;聚季铵盐(Polyquaternium)-51等2-甲基丙烯酰氧乙基磷脂酰胆碱的聚合物和与甲基丙烯酸丁酯共聚物等的共聚物;丙烯酸类树脂乳液、聚丙烯酸乙酯乳液、聚丙烯酸烷基酯乳液、聚乙酸乙烯酯树脂乳液、天然橡胶胶乳、合成胶乳等高分子乳液;硝基纤维素;聚氨酯类和各种共聚物;各种硅氧烷类;丙烯酸类化合物-硅氧烷接枝共聚物等硅氧烷系各种共聚物;各种氟系高分子;12-羟基异硬脂酸及其盐;糊精棕榈酸酯、糊精肉豆蔻酸酯等糊精脂肪酸酯;硅酸酐、气相二氧化硅(超微粒无水硅酸)、硅酸铝镁、硅酸钠镁、金属皂化物、二烷基磷酸金属盐、膨润土、锂蒙脱石、有机改性粘土矿物、蔗糖脂肪酸酯、低聚果糖脂肪酸酯作为优选的物质。上述例示中,优选纤维素及其衍生物、海藻酸及其盐、聚乙烯醇、透明质酸及其盐、或胶原蛋白。
溶剂和/或喷射剂类,可列举乙醇、2-丙醇(异丙基醇)、丁醇、异丁醇等低级醇类;丙二醇、1,3-丁二醇、二甘醇、二丙二醇、异戊基二醇等二醇类;二甘醇单乙基醚(乙氧基二甘醇)、乙二醇单乙基醚、乙二醇单丁基醚、三乙二醇单乙基醚、二甘醇乙醚、二甘醇二丁基醚、丙二醇单乙基醚、二丙二醇单乙基醚等二醇醚类;乙二醇单乙基醚乙酸酯、二甘醇单乙基醚乙酸酯、丙二醇单乙基醚乙酸酯等二醇醚酯类;琥珀酸二乙氧基乙酯、乙二醇二琥珀酸酯等二醇酯类;苄醇、苄基氧乙醇、碳酸亚丙酯、碳酸二烷酯、丙酮、乙酸乙酯、N-甲基吡咯烷酮;甲苯;碳氟化合物、新一代氟利昂;LPG、二甲醚、二氧化碳等喷射剂作为优选的物质。
作为抗氧化剂,可列举生育酚(维生素E)、乙酸生育酚等生育酚衍生物;BHT、BHA;没食子酸丙酯等没食子酸衍生物;维生素C(抗坏血酸)和/或其衍生物;异抗坏血酸及其衍生物;亚硫酸钠等亚硫酸盐;亚硫酸氢钠等亚硫酸氢盐;硫代硫酸钠等硫代硫酸盐;焦亚硫酸氢盐;硫代牛磺酸,亚牛磺酸;硫代甘油、硫脲、巯基乙酸、半胱氨酸盐酸盐作为优选的物质。
作为还原剂,可列举巯基乙酸、半胱氨酸、半胱胺等作为优选的物质。
作为氧化剂,可列举过氧化氢水、过硫酸铵、溴酸钠、过碳酸作为优选的物质。
作为防腐剂、抗菌剂和/或杀菌剂,可列举对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯、对羟基苯甲酸丁酯等羟基苯甲酸及其盐或其酯;水杨酸;苯甲酸钠;苯氧基乙醇;1,2-戊二醇、1,2-己二醇等1,2-二醇;甲基氯异噻唑啉酮、甲基异噻唑啉酮等异噻唑啉酮衍生物;咪唑啉鎓脲;脱氢乙酸及其盐;酚类;三氯生等卤代联苯酚类、酸酰胺类、季铵盐类;三氯碳酰胺、吡啶硫酮锌、苯扎氯铵、苄索氯铵、山梨酸、氯己定、葡萄糖酸氯己定、氯卡宾、六氯酚;苯酚、异丙酚、甲酚、百里酚、对氯苯酚、苯基苯酚、苯基苯酚钠等其他酚类;苯乙醇、感光素类、抗菌性沸石、银离子作为优选的物质。
作为螯合剂,可列举EDTA、EDTA2Na、EDTA3Na、EDTA4Na等依地酸盐(乙二胺四乙酸盐);HEDTA3Na等羟乙基乙二胺三乙酸盐;喷替酸盐(二亚乙基三胺五乙酸盐);植酸;羟乙叉二磷酸等膦酸及其钠盐等盐类;草酸钠;聚天冬氨酸、聚谷氨酸等聚氨基酸类;聚磷酸钠、偏磷酸钠、磷酸;柠檬酸钠、柠檬酸、丙氨酸、二羟基乙基甘氨酸、葡萄糖酸、抗坏血酸、琥珀酸、酒石酸作为优选的物质。
作为pH调节剂、酸和/或碱,可列举柠檬酸、柠檬酸钠、乳酸、乳酸钠、乳酸钾、乙醇酸、琥珀酸、乙酸、乙酸钠、苹果酸、酒石酸、富马酸、磷酸、盐酸、硫酸、单乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、三异丙醇胺、2-氨基-2-甲基-1,3-丙二醇、2-氨基-2-羟基甲基-1,3-丙二醇、精氨酸、氢氧化钠、氢氧化钾、氨水、碳酸胍、碳酸铵作为优选的物质。
作为粉末、可列举云母、滑石、高岭土、绢云母、蒙脱石、高岭石、云母、白云母、金云母、合成云母、云母、黑云母、蛭石、碳酸镁、碳酸钙、硅酸铝、硅酸钡、硅酸钙、硅酸镁、硅酸锶、金属钨酸盐、镁、沸石、硫酸钡、煅烧硫酸钙、磷酸钙、氟磷灰石、羟磷灰石、陶瓷粉、膨润土、蒙脱石、粘土、泥、金属皂化物(例如,肉豆蔻酸锌、棕榈酸钙、异硬脂酸铝)、碳酸钙、红色氧化铁、黄色氧化铁、黑色氧化铁、群青、铁蓝、碳黑、氧化钛、微粒和超微粒氧化钛、氧化锌、微粒和超微粒氧化锌、氧化铝、二氧化硅、气相二氧化硅(超微粒无水硅酸)、云母钛、鱼鳞箔、氮化硼、光致变色颜料、合成氟金云母、微粒复合粉末、金、铝等各种大小和形状形状的无机粉末、以及将它们用氢硅氧烷、环状氢硅氧烷等硅氧烷或其他硅烷或钛偶联剂等各种表面处理剂进行处理而疏水化或亲水化而得的粉末等无机粉末;淀粉、纤维素、尼龙粉、聚乙烯末、聚甲基丙烯酸甲酯末、聚苯乙烯末、苯乙烯与丙烯酸的共聚物树脂粉末、聚酯末、苯胍胺树脂粉末、聚对苯二甲酸乙二酯-聚甲基丙烯酸甲酯叠层末、聚对苯二甲酸乙二酯-铝-环氧叠层末等、聚氨酯粉末、硅氧烷粉末、特氟龙(Teflon)(注册商标)粉末等各种大小和形状的有机系粉末和表面处理粉末、有机无机复合粉末作为优选的物质。
作为无机盐类,可列举食盐、並塩(由天日盐纯化而得的湿盐)、岩盐、海盐、天然盐等含氯化钠盐类;氯化钾、氯化铝、氯化钙、氯化镁、盐卤、氯化锌、氯化铵;硫酸钠、硫酸铝、硫酸铝钾(明矾)、硫酸铝铵、硫酸钡、硫酸钙、硫酸钾、硫酸镁、硫酸锌、硫酸铁、硫酸铜;磷酸1Na·2Na·3Na等磷酸钠类、磷酸钾类、磷酸钙类、磷酸镁类作为优选的物质。
作为紫外线吸收剂,可列举对氨基苯甲酸、对氨基苯甲酸单甘油酯、N,N-二丙氧基对氨基苯甲酸乙酯、N,N-二乙氧基对氨基苯甲酸乙酯、N,N-二甲基对氨基苯甲酸乙酯、N,N-二甲基对氨基苯甲酸丁基酯、N,N-二甲基对氨基苯甲酸甲基酯等苯甲酸系紫外线吸收剂;3,3,5-三甲基环己基-N-乙酰邻氨基苯甲酸酯等邻氨基苯甲酸系紫外线吸收剂;水杨酸及其钠盐、戊基水杨酸酯、水杨酸薄荷酯、3,3,5-三甲基环己基水杨酸酯、辛基水杨酸酯、苯基水杨酸酯、苄基水杨酸酯、对异丙醇苯基水杨酸酯等水杨酸系紫外线吸收剂;辛基肉桂酸酯、乙基-4-异丙基肉桂酸酯、甲基-2,5-二异丙基肉桂酸酯、乙基-2,4-二异丙基肉桂酸酯、甲基-2,4-二异丙基肉桂酸酯、丙基-对甲氧基肉桂酸酯、异丙基-对甲氧基肉桂酸酯、异戊基-对甲氧基肉桂酸酯、2-乙基己基-对甲氧基肉桂酸酯(对甲氧基肉桂酸辛酯)、2-乙氧基乙基-对甲氧基肉桂酸酯(西诺沙酯)、环己基-对甲氧基肉桂酸酯、乙基-α-氰基-β-苯基肉桂酸酯、2-乙基己基-α-氰基-β-苯基肉桂酸酯(奥克立林)、甘油单-2-乙基己酰-二对甲氧基肉桂酸酯、阿魏酸及其衍生物等肉桂酸系紫外线吸收剂;2,4-二羟基二苯甲酮、2,2’-二羟基-4-甲氧基二苯甲酮、2,2’-二羟基-4,4’-二甲氧基二苯甲酮、2,2’,4,4’-四羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮(氧苯酮-3)、2-羟基-4-甲氧基-4’-甲基二苯甲酮、2-羟基-4-甲氧基二苯甲酮-5-磺酸盐、4-苯基二苯甲酮、2-乙基己基-4’-苯基-二苯甲酮-2-甲酸酯、2-羟基-4-正辛氧基二苯甲酮、4-羟基-3-羧基二苯甲酮等二苯甲酮系紫外线吸收剂;3-(4’-甲基亚苄基)-d,l-樟脑、3-亚苄基-d,l-樟脑;2-苯基-5-甲基苯并噁唑;2,2’-羟基-5-甲基苯基苯并三唑;2-(2’-羟基-5’-叔辛基苯基)苯并三唑;2-(2’-羟基-5’-甲基苯基苯并三唑;联苄连氮;二茴香酰甲烷;5-(3,3-二甲基-2-降冰片烯叉)-3戊烷-2-酮;4-叔丁基甲氧基二苯甲酰甲烷等二苯甲酰甲烷衍生物;辛基三唑;尿刊酸和尿刊酸乙酯等尿刊酸衍生物;2-(2’-羟基-5’-甲基苯基)苯并三唑、1-(3,4-二甲氧基苯基)-4,4-二甲基-1,3-戊二酮、二甲氧基亚苄基二氧代咪唑烷丙酸2-乙基己酯等乙内酰脲衍生物、苯基苯并咪唑磺酸、对苯二亚甲基二樟脑磺酸、甲酚曲唑三硅氧烷、邻氨基苯甲酸甲酯、芸香苷及其衍生物、谷维素及其衍生物作为优选的物质。
作为美白剂,可列举熊果苷、α-熊果苷等氢醌配糖体及其酯类;抗坏血酸、抗坏血酸磷酸酯钠盐和抗坏血酸磷酸酯镁盐等抗坏血酸磷酸酯盐、抗坏血酸四异棕榈酸酯等抗坏血酸脂肪酸酯、抗坏血酸乙基醚等抗坏血酸烷基醚、抗坏血酸-2-糖苷等抗坏血酸糖苷及其脂肪酸酯类、抗坏血酸硫酸酯、磷酸生育酚酯抗坏血酸酯等抗坏血酸衍生物;曲酸、鞣花酸、氨甲环酸及其衍生物、阿魏酸及其衍生物、胎盘提取物、谷胱甘肽、谷维素、丁基间苯二酚、油溶性德国洋甘菊提取物、油溶性甘草提取物、西河柳提取物、虎耳草提取物等植物提取物作为优选的物质。
作为维生素类及其衍生物类,可列举视黄醇、乙酸视黄醇酯、棕榈酸视黄醇酯等维生素A类;硫胺素盐酸盐、硫胺素硫酸盐、核黄素、乙酸核黄素、盐酸吡哆素、吡哆素二辛酸酯、吡哆素二棕榈酸酯、黄素腺嘌呤二核苷酸、氰钴胺素、叶酸类、烟酰胺/烟酸苄酯等烟酸类、胆碱类等维生素B群类;抗坏血酸及其钠等的盐等维生素C类;维生素D;α、β、γ、δ-生育酚等维生素E类;泛酸、生物素等其他维生素类;抗坏血酸磷酸酯钠盐和抗坏血酸磷酸酯镁盐等抗坏血酸磷酸酯盐、抗坏血酸四异棕榈酸酯/异硬脂酸抗坏血酸酯/棕榈酸抗坏血酸酯/二棕榈酸抗坏血酸酯等抗坏血酸脂肪酸酯、抗坏血酸乙基醚等抗坏血酸烷基醚、抗坏血酸-2-糖苷等抗坏血酸糖苷及其脂肪酸酯、磷酸生育酚酯抗坏血酸酯等抗坏血酸衍生物;烟酸生育酚酯、乙酸生育酚酯、亚油酸生育酚酯、阿魏酸生育酚酯、生育酚磷酸酯等生育酚衍生物等维生素衍生物、三烯生育醇、其他各种维生素衍生物类作为优选的物质。
生发用药剂、血液循环促进剂和/或刺激剂,可列举日本绿龙胆提取物、辣椒酊、生姜酊、生姜提取物、斑蝥酊等植物提取物/酊类;辣椒素,壬酸伐雷酰胺,姜油酮、鱼石脂、单宁酸,冰片,环扁桃酸盐,桂利嗪,妥拉唑林,乙酰胆碱,维拉帕米,头孢哌醋、γ-谷维素、维生素E和烟酸生育酚/乙酸生育酚等衍生物、γ-谷维素、烟酸和烟酰胺/烟酸苄基酯·肌醇六烟酸酯、尼克醇等衍生物、尿囊素,感光素301、感光素401、卡普氯铵、十五烷酸单甘油酯,黄烷醇衍生物,豆甾醇或豆甾烷醇及其糖苷,米诺地尔作为优选的物质。
作为激素类,可列举雌二醇,雌酮,乙炔雌二醇,可的松,氢化可的松,泼尼松等。
作为抗皱剂、抗老化剂、紧致剂、冷感剂、温感剂、伤口愈合促进剂、刺激减缓剂、镇痛剂、细胞活化剂等其他药效剂,可列举视黄醇类、视黄酸类、视黄酸生育酚酯;乳酸、乙醇酸、葡萄糖酸、果酸、水杨酸及其配糖体/酯化物等衍生物、羟基癸酸、长链α-羟基脂肪酸、长链α-羟基脂肪酸胆固醇酯等α-或β-羟基酸类及其衍生物类;γ-氨基丁酸、γ-氨基-β-羟基丁酸;肉碱;肌肽;肌酸;神经酰胺类、鞘氨醇类;咖啡因、黄嘌呤等及其衍生物;辅酶Q10、胡萝卜素、番茄红素、虾青素、叶黄素、α-硫辛酸、铂纳米胶体、富勒烯类等抗氧化/活性氧去除剂;儿茶素类;槲皮素等黄酮类;异黄酮类;没食子酸和酯糖衍生物;单宁、芝麻素、原花青素、绿原酸、苹果多酚等多酚类;芸香苷和配糖体等衍生物;橙皮苷和配糖体等衍生物;木脂素配糖体;光甘草定、光甘草素、甘草苷、异甘草苷等甘草提取物相关物质;乳铁蛋白;志贺醇;姜醇;薄荷醇;雪松醇等香料物质及其衍生物;辣椒素,香草醛等和衍生物;二乙基甲苯酰胺等昆虫驱避剂;生理活性物质与环糊精类的复合体作为优选的物质。
作为植物、动物和/或微生物提取物类,可列举鸢尾花提取物、明日叶提取物、罗汉柏提取物、芦笋提取物、鳄梨提取物、甘茶提取物、甜扁桃提取物、药蜀葵提取物、山金车提取物、芦荟提取物、杏提取物、杏仁提取物、银杏提取物、寸蔻提取物、茴香提取物、姜黄提取物、乌龙茶提取物、熊果提取物、エイジツ提取物、紫锥菊叶提取物、毛叶香茶菜(エンメイソウ)提取物、黄芩提取物、黄柏提取物、黄连提取物、大麦提取物、高丽参提取物、小连翘提取物、粉花野芝麻(Lamium album var.barbatum)提取物、芒柄花提取物、豆瓣菜提取物、橙子提取物、海水干燥物、海藻提取物、柿叶提取物、火棘果提取物、水解弹性蛋白、水解小麦末水解蚕丝、野葛根提取物、德国洋甘菊提取物、油溶性德国洋甘菊提取物、胡萝卜根提取物、茵陈蒿提取物、燕麦提取物、カルカデ提取物、甘草提取物、油溶性甘草提取物、猕猴桃提取物、キオウ提取物、木耳提取物、金鸡纳提取物、黄瓜提取物、毛泡桐叶提取物、鸟苷、番石榴提取物、苦参提取物、栀子提取物、熊笹提取物、苦参提取物、核桃提取物、板栗提取物、葡萄柚提取物、铁线莲提取物、黑米提取物、黑砂糖提取物、黑醋、小球藻提取物、蘑菇提取物、龙胆提取物、童氏老鹳草提取物、红茶提取物、酵母提取物、香米提取物、咖啡提取物、牛蒡提取物、大米提取物、大米发酵提取物、米糠发酵提取物、稻胚芽油、紫草提取物、胶原蛋白、越橘提取物、细辛提取物、柴胡提取物、脐带提取液、番红花提取物、丹参提取物、肥皂草提取物、竹提取物(ササエキス)、山楂提取物、芫荽提取物、山椒提取物、香蕈提取物、地黄提取物、紫根提取物、紫苏提取物、椴木提取物、绣线菊提取物、孪叶豆提取物、芍药提取物、生姜提取物、菖蒲根提取物、白桦提取物、白云耳菇提取物、问荆提取物、甜菊提取物、甜菊发酵物、西河柳提取物、常春藤提取物、锐刺山楂提取物、西洋接骨木提取物、西洋耆草提取物、辣薄荷提取物、白花鼠尾草提取物、欧锦葵提取物、日本川芎提取物、日本绿龙胆提取物、山桑提取物、大黄提取物、大豆提取物、大枣提取物、百里香提取物、蒲公英提取物、地衣类提取物、茶提取物、丁香提取物、白茅提取物、陈皮提取物、茶树油、甜茶提取物、辣椒提取物、当归提取物、金盏花提取物、桃仁提取物、橙皮提取物、蕺菜提取物、番茄提取物、纳豆提取物、胡萝卜提取物、大蒜提取物、狗牙蔷薇提取物、玫瑰茄提取物、麦冬提取物、莲花提取物、欧芹提取物、桦木提取物、蜂蜜、金缕梅提取物、墙草提取物、毛叶香茶菜(ヒキオコシ)提取物、红没药醇、桧木提取物、双歧杆菌提取物、枇杷提取物、款冬提取物、款冬若芽提取物、茯苓提取物、假叶树提取物、葡萄提取物、葡萄籽提取物、蜂胶、丝瓜提取物、红花提取物、薄荷提取物、椴树提取物、牡丹提取物、啤酒花提取物、玫瑰花提取物、松提取物、欧洲七叶树提取物、观音莲(ミズバショウ)提取物、无患子提取物、香蜂花提取物、海蕴(モズク)提取物、桃子提取物、矢车菊提取物、桉树提取物、虎耳草提取物、柚子提取物、百合提取物、薏苡仁提取物、艾草提取物、薰衣草提取物、绿茶提取物、卵壳膜提取物、苹果提取物、博士茶(Rooibos tea)提取物、赤芝提取物、莴苣提取物、柠檬提取物、连翘提取物、紫云英提取物、玫瑰提取物、迷迭香提取物、罗马洋甘菊提取物、蜂王浆提取物、地榆提取物等提取物作为优选的物质。
作为止痒剂,可列举盐酸苯海拉明、马来酸氯苯那敏、樟脑、P物质抑制剂等。
作为角质剥离/溶解剂,可列举水杨酸、硫、间苯二酚、硫化硒、吡哆素等。
作为止汗剂,可列举羟基氯化铝、氯化铝、氧化锌、对苯酚磺酸锌等。
作为清凉剂,可列举薄荷醇、水杨酸甲酯等。
作为收敛剂,可列举柠檬酸、酒石酸、乳酸、硫酸铝钾、单宁酸等。
作为酶类,可列举超氧化物歧化酶、过氧化氢酶、溶菌酶氯化物、脂肪酶、木瓜蛋白酶、胰酶、蛋白酶等。
作为核酸类,可列举核糖核酸及其盐、脱氧核糖核酸及其盐、腺苷三磷酸二钠作为优选的物质。
作为香料,可列举乙酰柏木烯,戊基肉桂醛,烯丙基戊基乙醇酸酯,β-紫罗兰酮、龙涎酮(ISO E Super)、异丁基喹啉、鸢尾花油、イロン、吲哚、依兰油、十一碳醛、十一碳烯醛、γ-十一碳内酯、龙蒿脑、丁香油酚、橡木苔、红没药树脂、橙子油、丁香油酚、橙花素、半乳糖固体(ガラクソリッド)、香芹酚、L-香芹酮、樟脑、キャノン、胡萝卜籽油,丁香油,肉桂酸甲酯、香叶醇、香叶基腈、乙酸异冰片酯、乙酸香叶酯、乙酸二甲基苄基甲醇酯、乙酸苯乙烯酯、醋酸柏木酯、醋酸沙雷匹林、乙酸对叔丁基环己酯、乙酸香根酯、乙酸苄酯、乙酸芳樟酯、水杨酸异戊酯、水杨酸苄酯、檀香油、檀香醇、仙客来醛、环十五内酯、二氢茉莉酮酸甲酯、二氢月桂烯醇、茉莉净油、茉莉内酯、顺式茉莉酮、柠檬醛、香茅醇(シトロネノール)、香茅醛、肉桂树皮油、1,8-桉树脑、肉桂醛、苏合香树脂、柏木油、柏木烯、雪松醇、芹菜籽油、百里香油、大马酮、大马烯酮、百里香酚、晚香玉净油、癸醛、癸内酯、萜品醇、γ-萜品烯、女贞醛、橙花醇、壬醛、2,6-壬二烯醇、壬内酯、广藿香醇、香草净油、香草醛、罗勒油、广藿香油、羟基香茅醛、α-蒎烯、胡椒碱、苯乙醇、苯乙醛、苦橙叶油、己基肉桂醛、顺-3-己烯醇、秘鲁香脂、香根草油、香根草醇、薄荷油、胡椒油、洋茉莉醛、佛手柑油、苯甲酸苄酯、冰片、水松树脂、麝香酮、甲基壬基乙醛、γ-甲基壬酮、薄荷醇、L-薄荷醇、L-薄荷酮、桉树油、β-蒎烯酮、酸橙油、薰衣草油、D-柠檬烯、芳樟醇、新铃兰醛、铃兰醛、柠檬油、玫瑰净油、玫瑰氧化物、玫瑰油、迷迭香油、各种精油等合成香料和天然香料以及各种调合香料作为优选的物质。
作为色素、着色剂、染料和/或颜料,可列举褐色201号、黑色401号、紫色201号、紫色401号、蓝色1号、蓝色2号、蓝色201号、蓝色202号、蓝色203号、蓝色204号、蓝色205号、蓝色403号、蓝色404号、绿色201号、绿色202号、绿色204号、绿色205号、绿色3号、绿色401号、绿色402号、红色102号、红色104-1号、红色105-1号、红色106号、红色2号、红色201号、红色202号、红色203号、红色204号、红色205号、红色206号、红色207号、红色208号、红色213号、红色214号、红色215号、红色218号、红色219号、红色220号、红色221号、红色223号、红色225号、红色226号、红色227号、红色228号、红色230-1号、红色230-2号、红色231号、红色232号、红色3号、红色401号、红色404号、红色405号、红色501号、红色502号、红色503号、红色504号、红色505号、红色506号、橙色201号、橙色203号、橙色204号、橙色205号、橙色206号、橙色207号、橙色401号、橙色402号、橙色403号、黄色201号、黄色202-1号、黄色202-2号、黄色203号、黄色204号、黄色205号、黄色4号、黄色401号、黄色402号、黄色403-1号、黄色404号、黄色405号、黄色406号、黄色407号、黄色5号等法定色素;酸性红(Acid Red)14等其他酸性染料;Arianor Sienna Brown、Arianor Madder Red、Arianor Steel Blue、Arianor StrawYellow等碱性染料;HC Yellow 2、HC Yellow 5、HC Red 3、4-羟丙基氨基-3-硝基苯酚、N,N’-双(2-羟乙基)-2-硝基-对苯二胺、HC Blue 2、Basic Blue 26等硝基染料;分散染料;二氧化钛、氧化锌等无机白色颜料;氧化铁(红色氧化铁)、钛酸铁等无机红色系颜料;γ-氧化铁等无机褐色系颜料;黄色氧化铁、黄土等无机黄色系颜料;黑色氧化铁、低氧氧化钛等无机黑色系颜料;芒果紫、钴紫无机紫色系颜料;氧化铬、氢氧化铬、钛酸钴等无机绿色系颜料;群青、铁蓝等无机蓝色系颜料氧化钛涂层云母、氧化钛涂层铋氧氯化铋、氧化钛涂层滑石、有色氧化钛涂层云母、氧氯化铋、鱼鳞箔等珍珠颜料;铝粉、铜粉、金等金属粉末颜料;表面处理无机和金属粉末颜料;锆色淀、钡色淀或铝色淀等有机颜料;表面处理有机颜料;虾青素、茜素等蒽醌类、花青素、β-胡萝卜素、カテナール、辣椒红素、查尔酮、红花苷、槲皮素、藏红花素、叶绿素、姜黄素、胭脂虫红、紫草素等萘醌类、胭脂树橙、黄酮类、β-花青素、指甲花、血红蛋白、番茄红素、核黄素、芸香苷等天然色素/染料;对苯二胺、甲苯-2,5-二胺、邻氨基苯酚、间氨基苯酚、对氨基苯酚、间苯二胺、5-氨基-2-甲基苯酚、间苯二酚、1-萘酚、2,6-二氨基吡啶等及其盐等氧化染料中间体和耦合剂;二氢吲哚等自动氧化型染料;二羟基丙酮作为优选的物质。
作为消炎剂和/或抗炎剂,可列举甘草酸及其衍生物、甘草次酸衍生物、水杨酸衍生物、日扁柏醇、愈创薁、尿囊素、吲哚美辛、酮洛芬、布洛芬、双氯芬酸、洛索洛芬、塞来考昔、英夫利昔单抗、依那西普、氧化锌、醋酸氢化可的松、泼尼松、盐酸二苯胺、马来酸氯苯那敏;桃叶提取物、蒿叶提取物等植物提取物作为优选的物质。
作为抗哮喘、抗慢性阻塞性肺病、抗变态反应、免疫调节剂,可列举氨茶碱、茶碱、类固醇类(氟替卡松、倍氯米松等)、白三烯拮抗剂、血栓素抑制剂、色甘酸钠、β2激动剂(福莫特罗、沙美特罗、沙丁胺醇、妥洛特罗、克仑特罗、肾上腺素等)、噻托溴铵、异丙托铵、右美沙芬、二甲啡烷、溴己新、曲尼司特、酮替芬、氮卓斯汀、西替利嗪、氯苯那敏、美喹他嗪、他克莫司、环孢霉素、西罗莫司、甲氨蝶呤、细胞因子调节剂类、干扰素、奥马珠单抗、蛋白/抗体制剂作为优选的物质。
作为抗感染症剂、抗真菌剂,可列举奥司他韦和扎那米韦、伊曲康唑作为优选的物质。
此外,还可以以公知的组合和配合比/配合量含有化妆品原料基准、化妆品种别配合成分规格、日本化妆品工业联合会成分表示名称列表、INCI辞典(The InternationalCosmetic Ingredient Dictionary and Handbook)、准药品原料规格、日本药典、药品添加物规格、食品添加物公定书等记载的成分、和国际专利分类IPC属于A61K7和A61K8的分类的日本和其他国家专利公报和专利公开公报(包含日本公表公报、再公表)中记载的成分等公知的化妆料成分、药品成分、食品成分等。
作为一般市售化妆料,例如,作为洗涤成分添加表面活性剂和消毒剂,作为润肤成分添加多元醇和脂肪酸酯等油性基材,作为保湿成分添加保湿剂、油性基材和增稠剂,以及作为防止肌肤粗糙的成分添加消炎剂,进而添加防腐剂和稳定剂等,制造洗颜料、沐浴露、清洁剂等。进而可以通过添加粉末来调节粘度。
例如,作为基剂添加水和无机盐,作为保湿成分添加多元醇和脂肪酸酯等油性基材和植物提取物、增稠剂作为防止肌肤粗糙的成分添加消炎剂,以及作为功能性成分添加维生素类、美白剂、抗氧化剂、抗皱剂、抗老化剂、或紧致剂等,制造化妆水和美容液等。
例如,作为基剂添加水和胶凝剂,作为润肤成分添加多元醇和脂肪酸酯等油性基材,作为保湿成分添加保湿剂、油性基材和增稠剂、乳化剂,以及作为功能成分添加抗氧化剂等,制造霜剂。
例如,作为基剂添加水,作为润肤成分添加硅油、植物油、脂肪酸酯等油性基材,作为保湿成分添加多元醇等保湿剂、增稠剂、乳化剂以及作为功能性成分添加抗氧化剂等,制造眼部护理剂等。
例如,作为基剂添加水和无机盐,作为润肤成分添加硅油、脂肪酸酯、多元醇和脂肪酸等油性基材,作为保湿成分添加多元醇等油性基材和保湿剂,以及添加颜料,制造底妆、口红等。
例如,作为基剂添加胶凝剂和无机盐,作为润肤成分添加增稠剂、颜料、炼制油,以及添加粉末,制造腮红和粉底等。
例如,作为基剂添加酯等油性基材,作为润肤成分添加油脂等油性基材,以及添加增稠剂,制造卸甲水等。
进而,可以通过在上述制品中作为抗氧化剂添加烃和蜡,作为紫外线散射成分添加无机盐和粉末、以及紫外线吸收剂等,从而使其具有UV防护性能。
本发明的糖衍生物胶凝剂具有在化妆料中作为胶凝剂和/或增稠剂的功能,可以替换上述现有市售的化妆料的胶凝剂和/或增稠剂使用,使得比现有的化妆用品安全性、使用感更良好。
于是,作为包含本发明的糖衍生物胶凝剂的化妆料,可列举基础化妆料、彩妆化妆料、身体护理化妆料、芳香用化妆料、和毛发护理化妆料。但不限于这里例示的化妆料。
基础化妆品是指洗颜料、卸妆料、化妆水、乳液、美容液、面霜、面膜、眼部护理剂及其其他脸部皮肤护理用化妆品。
可列举例如,固体肥皂、洗颜泡沫、洗颜粉、和洗颜湿巾用途等的洗颜料;清洁泡沫、清洁霜、清洁乳、清洁露、清洁凝胶、清洁油和清洁面膜等卸妆料;脂质(リポソース)化妆水、柔软化妆水、收敛化妆水、洗涤用化妆水和多层式化妆水等化妆水;润肤露、保湿露、乳液、滋润露、滋润乳、皮肤保湿、保湿乳液、按摩露和面部用角质平滑剂等乳液;脂质体化妆水、保湿美容液、美白美容液、和防紫外线美容液等美容液;润肤霜、营养霜、滋润霜、雪花膏、保湿霜、晚霜、按摩霜、清洁霜、彩妆霜、打底霜、剃须霜、和面部用角质软化霜等霜剂;剥离面膜、粉末面膜、水洗面膜、油面膜、和清洁面膜等面膜;眼部精华、眼部凝胶、眼霜等眼部护理剂;面部用的UV护理乳液、防晒、防晒剂、防UV乳、阳光隔离剂、阳光隔离霜和防晒霜等UV护理剂;保湿凝胶等凝胶;面部去角质剂、瘦脸剂等其他基础化妆料。
作为彩妆化妆料,可列举底妆化妆料和焦点化妆料。
底妆化妆料是指用于衬托焦点的基础化妆料,是指妆底、遮瑕、粉底和扑面粉等。例如,彩妆底、打底霜、色彩控制妆底、防UV妆底等妆底;遮瑕粉和遮瑕霜、遮瑕液等遮瑕;粉底、防UV粉底、粉底霜、防UVカ粉底霜等粉底;散粉、粉饼、修容粉、白粉等扑面粉等。
焦点化妆料是指赋予肌肤色彩,使肌肤看起来美丽的化妆品,可列举例如,眼彩、眼线、睫毛膏、画眉料、腮红、唇彩、指甲油等。
可列举例如,眼彩粉、眼彩笔和眼影等眼彩;眼线笔、眼线液等眼线;卷翘睫毛膏、拉长睫毛膏、卷曲保持睫毛膏、和彩色睫毛膏等睫毛膏;眉笔、眉粉和眉液等画眉料;腮红粉和腮红霜等腮红;唇彩、唇膏、口红、液体唇彩(lip gloss)和唇线等唇彩;指甲油、护甲水(nail care)、亮油(nail top)、底油(base coat)、面油(top coat)、封层(over coat)、卸甲水、除光液、指甲油稀释液和指甲护理液等指甲油。
作为身体护理化妆料,可列举身体露/身体霜、唇霜、护手霜、UV护理剂、体毛处理剂、腿部护理剂、止汗防臭剂等。
可列举例如,身体露、身体油和身体喷雾等身体露;身体霜、身体乳、身体凝胶和身体慕斯等身体霜;保湿用唇霜、UV护理用唇霜和彩色唇霜等唇霜;护手霜和护手凝胶等护手霜;身体用的UV护理乳液、防晒、防晒剂、UV护理乳、阳光隔离剂、阳光隔离霜和防晒霜等UV护理剂;除毛霜、除毛慕斯、脱毛蜡、体毛脱色剂和体毛用剃须霜等体毛处理剂;腿部按摩剂、瘦腿剂、腿部去角质剂、足跟等脸部以外的角质除去剂、和润肤剂等腿部护理剂;除臭露、除臭粉、除臭喷雾、除臭棒等止汗防臭剂;除虫喷雾等驱虫剂。
作为芳香化妆料,可列举香水、香精、淡香精、淡香氛、古龙水、浓香水、香粉、香水皂、沐浴油。
作为头发护理化妆料,可列举香波、洗发/护发剂、发膜、头发定型剂、头发喷雾/亮发剂、生发/养发剂、烫发剂、染发剂。
可列举例如,香波油、香波霜、调理香波、头屑用香波、染发用香波、漂洗一体型香波等香波;洗发/护发剂、头屑/头皮护理洗发/护发剂、头屑/头皮控制洗发/护发剂等洗发/护发剂;损伤护理发膜、损伤护理发膜、头屑/头皮护理发膜和头屑/头皮控制发膜等发膜;发泡、发膏、发蜡、发胶、发水、发露、发油和发液等定型剂;头发定型喷雾、头发定型雾和亮发剂等头发喷雾/亮发剂、生发剂、养发剂、头发滋补剂和头发精华等生发/养发剂;直发烫发剂、卷发烫发剂、烫发前处理剂和烫发后处理剂等烫发剂;氧化染发剂、头发漂白剂、染发前处理剂、染发后处理剂和毛鳞片修复剂等染发剂。
[离子液体]
本发明的胶凝剂不仅能够使所述的疏水性有机机溶剂、亲水性有机溶剂形成凝胶,还能够使离子液体形成凝胶。
即,本发明以属于离子液体的胶凝剂的所述的胶凝剂为对象,进一步以由所述胶凝剂和离子液体制成的凝胶为对象。
作为上述离子液体,可以使用一般作为“离子液体”已知的物质,可列举例如,由选自咪唑鎓、吡啶鎓、哌啶鎓、吡咯烷鎓、鏻、铵和锍中的阳离子,和选自卤素、羧酸盐、硫酸盐、磺酸盐、硫氰酸盐、硝酸盐、铝酸盐、硼酸盐、磷酸盐、酰胺、锑酸盐、酰亚胺和甲基化物中的阴离子构成的离子液体。
例如,作为阳离子种,可列举1,3-二烷基咪唑鎓离子、1,2,3-三烷基咪唑鎓离子、N-烷基吡啶鎓离子、N-烷基哌啶鎓、四烷基铵离子、四烷基鏻离子、三烷基锍离子等。
另外,作为阴离子种,可列举四氟硼酸根(BF4 -)离子、六氟磷酸根(PF6 -)离子、三氟甲烷磺酸根(CF3SO3 -)离子、六氟锑酸根(SbF6 -)离子、双(三氟甲基磺酰)亚胺((CF3SO2)2N-)离子、双(氟磺酰)亚胺((FSO2)2N-)离子、三(三氟甲基磺酰)甲基化物((CF3SO2)3C-)离子、硝酸根(NO3 -)离子、三氟甲基甲酸根(CF3CO2 -)离子、乙酸根(CH3CO2 -)离子、氯铝酸根(Al2Cl7 -)离子等。
[凝胶电解质]
本发明的凝胶可以作为凝胶电解质使用。凝胶电解质是使包含有机溶剂或水的电解液(液体电解质)、以及所述的离子液体进行凝胶化而得到。对使用的胶凝剂和电解液没有特别的限制,根据使用进行适时选择即可。
例如,在包含所述有机溶剂的电解液的情况下,是在至少一种非质子性有机溶剂中溶解电解质盐而形成。
作为所述非质子性有机溶剂,可以列举乙二醇二甲醚、碳酸亚烷基酯、碳酸烷基酯、环状醚、酰胺类、腈类、酮类和酯类等,作为优选的具体例,可列举碳酸亚丙酯、碳酸亚乙酯、碳酸二乙酯、γ-丁内酯、1,2-二甲氧基乙烷、四氢呋喃、2-甲基四氢呋喃、二甲基亚砜、1,3-二氧戊环、甲酰胺、二甲基甲酰胺、1,4-二氧杂环己烷、乙腈、硝基甲烷、乙基单乙二醇二甲醚、磷酸三酯、三甲氧基甲烷、二氧戊环衍生物、环丁砜、3-甲基-2-噁唑烷酮、碳酸亚丙酯衍生物、四氢呋喃衍生物、乙醚和1,3-丙磺酸内酯等。这些有机溶剂可以单独使用或组合2种以上使用。
所述电解质盐由金属阳离子和抗衡阴离子组成,作为金属阳离子,可以列举Li+、Na+、K+等,作为其抗衡阴离子,可以列举ClO4 -、LiBF4 -、PF6 -、CF3SO3 -、CF3CO2 -、AsF6 -、SbF6 -、(CF3SO2)2N-、B10Cl10 2-、(1,2-二甲氧基乙烷)2ClO4 -、低级脂肪族羧酸盐、AlCl4 -、Cl-、Br-、I-、氯硼烷化合物和四苯基硼酸等。在这些物质中,作为优选的电解质盐,可以列举锂盐。这些电解质盐可以单独使用或组合2种以上使用。
[胶凝剂的制造法]
本发明另外还以制造作为所述本发明的胶凝剂的式(1)或式(2)表示的化合物的方法作为对象。
即,该制造方法的特征在于,在原甲酸三乙酯、DMF、对甲苯磺酸存在下,通过一锅法进行制造工序,所述制造工序是使式R1-CHO(式中,R1表示碳原子数9~20的直链状或支链状的烷基、碳原子数13~20的环状的烷基、或碳原子数9~20的直链状或支链状的烯基)所示的化合物与葡萄糖、甘露糖、半乳糖或它们的衍生物进行缩环反应,从而制造式(1)或式(2)所示的化合物的工序。
实施例
以下为了进一步表明本发明的特征而显示实施例,但本发明不受这些实施例限制。
以下显示作为下述实施例的合成原料使用的试剂。
1-十八烷醇、1-十四烷醇(特级)、1-十六烷醇(一级)、1-十二烷醇、乙基α-D-吡喃葡萄糖苷(食品分析用)、甲基α-D-吡喃甘露糖苷(特级)、甲基α-D-吡喃半乳糖苷一水合物、四丁基溴化铵、碳酸钾从和光纯药工业(株)获得,N-氯琥珀酰亚胺、2,2,6,6-四甲基哌啶-1-氧基、甲基α-D-吡喃葡萄糖苷、对甲苯磺酸一水合物、原甲酸三乙酯、1-十一碳醛、甲基β-D-吡喃葡萄糖苷0.5水合物从东京化成工业(株)获得。
另外作为反应溶剂使用的N,N-二甲基甲酰胺(DMF)(脱水、有机合成用)、二氯甲烷(特级)从和光纯药工业(株)获得,己烷(特级)从关东化学(株)获得。
反应后处理和纯化时使用的三乙胺(特级)、硫酸钠(特级)、碳酸氢钠(特级)、乙醇(特级)、乙腈(特级)、乙醚(特级)、氯化钠(特级)、甲苯(特级)从和光纯药工业(株)获得,己烷(特级)、乙酸乙酯(特级)、甲醇(特级)、氯仿(特级)从关东化学(株)获得。
水使用纯水。NMR测定用的氘代氯仿(含有0.03%TMS(四甲基硅烷))从シグマアルドリッチジャパン(株)获得。
以下显示下述凝胶化试验和乳液制备时使用的溶剂和试剂。
辛烷(特级)、环己烷(特级)、角鲨烯(特级)、甲苯(特级)、十二烷基硫酸钠(生化学用)、荧光素钠(特级)、罗丹明B(特级)、肉豆蔻酸异丙酯(特级)、橄榄油(一级)、乙醇(特级)、角鲨烷(特级)、聚氧乙烯(20)失水山梨糖醇单月桂酸酯(Tween 20相当品)、L-抗坏血酸、甘氨酸、L-抗坏血酸2-磷酸酯三钠从和光纯药工业(株)获得,二甲基亚砜(DMSO)、1-丁基-3-甲基咪唑鎓四氟硼酸盐([BuMeIm][BF4])、三甲基丙基铵双(三氟甲烷磺酰)酰亚胺盐([TMPA][TFSI])、十六烷基氯化吡啶鎓一水合物(CPC)、十六烷基三甲基溴化铵(CTAB)、磺基琥珀酸双(2-乙基己基)钠(AOT)、Span 80(失水山梨糖醇单油酸酯)、D-(+)-葡糖胺盐酸盐从东京化成工业(株)获得,氯仿(特级)、乙酸乙酯(特级)、乙腈(特级)、乙二醇(特级)、甲醇(特级)、1-乙基-3-甲基咪唑鎓双(三氟甲基磺酰)酰亚胺盐([EtMeIm][TFSI])、1-丁基-3-甲基碘化咪唑鎓([BuMeIm][I])、1-丁基-3-甲基咪唑鎓六氟磷酸盐([BuMeIm][PF6])、1-丁基-3-甲基咪唑鎓三氟甲磺酸盐([BuMeIm][CF3SO3])、1-丁基吡啶鎓双(三氟甲基磺酰)酰亚胺盐([BuPy][TFSI])、N-甲基-N-丙基哌啶鎓双(三氟甲烷磺酰)酰亚胺盐([P13][TFSI])从关东化学(株)获得,1-丁基-3-甲基咪唑鎓双(三氟甲基磺酰)酰亚胺([BuMeIm][TFSI])盐从シグマアルドリッチジャパン合同会社获得,1-己基-3-甲基咪唑鎓双(三氟甲基磺酰)酰亚胺盐[HeMeIm][TFSI]从メルク(株)获得,SH245(十甲基环五硅氧烷)从東レダウコーニング(株)获得,KF995(十甲基环五硅氧烷)从信越シリコーン(株)获得,霍霍巴油从株式会社良品计画获得,滑石DN-SH、钛DN-SH(2)、绢云母DN-MC(2)、DN-HAP(SH)从大日本化成(株)获得。水使用纯水。
另外以下显示各种测定、分析和聚合中使用的装置和条件。
(1)1H-NMR光谱
·装置:AVANCE500、ブルカー·バイオスピン(株)制
JNM-ECS 400、日本电子(株)制
(2)涡旋混合器
·装置:Voltex Genie 2、Scientific Industries社制
(3)共焦点激光扫描显微镜
·装置:LSM700、カールツァイス(株)制
(4)扫描型电子显微镜(SEM)
·装置:Inspect S50、FEI Company制
[实施例1:胶凝剂的合成]
<具有烃基的脂肪族醛(化合物[1]-[3])的合成>
《化合物[1]的合成》
在1-十四烷醇(10.7g,50mmol)、四丁基溴化铵(TBAB)(0.81g,2.5mmol)和2,2,6,6-四甲基哌啶-1-氧基(TEMPO)(0.39g,2.5mmol)的二氯甲烷100mL溶液中加入溶解有碳酸氢钠(4.2g,50mmol)和碳酸钾(0.69g,5.0mmol)的纯水100mL溶液,在室温下搅拌。在该溶液中加入N-氯琥珀酰亚胺(NCS)(8.0g,60mmol),在室温下搅拌1小时。搅拌后,分液有机层,将该有机层用纯水100mL洗涤3次。洗涤后,分液有机层,加入硫酸钠进行干燥,然后过滤除去硫酸钠,浓缩滤液。将残留物通过柱层析(二氧化硅凝胶,己烷:乙酸乙酯=100:0至95:5(v/v))纯化,获得目的物1-十四醛(化合物[1])。产率77%(8.2g),1H NMR(400MHz,CDCl3):δ9.77(1H,t,J=1.8Hz),2.42(2H,dt,J=1.8,7.3Hz),1.63(2H,quintet,J=7.3Hz),1.38-1.17(20H,m),0.88(3H,t,J=6.9Hz)。
《化合物[2]的合成》
在1-十六烷醇(24.4g,100mmol)、四丁基溴化铵(TBAB)(1.67g,5.2mmol)和2,2,6,6-四甲基哌啶-1-氧基(TEMPO)(0.79g,5.1mmol)的二氯甲烷200mL溶液中加入溶解有碳酸氢钠(8.47g,100mmol)和碳酸钾(1.42g,10.3mmol)的纯水200mL溶液,在室温下搅拌。在该溶液中加入N-氯琥珀酰亚胺(NCS)(16.1g,120mmol),在室温下搅拌1小时。搅拌后,分液有机层,将该有机层用纯水100mL洗涤3次。洗涤后,分液有机层,加入硫酸钠进行干燥,然后过滤除去硫酸钠,浓缩滤液。将残留物通过柱层析(二氧化硅凝胶,己烷:乙酸乙酯=100:0至95:5(v/v))纯化,获得目的物1-十六醛(化合物[2])。产率83%(20.0g),1H NMR(400MHz,CDCl3):δ9.76(1H,t,J=1.8Hz),2.42(2H,dt,J=1.8,7.3Hz),1.63(2H,quin,J=7.3Hz),1.37-1.19(24H,m),0.88(3H,t,J=6.9Hz)。
《化合物[3]的合成》
在1-十八烷醇(40.6g,150mmol)、四丁基溴化铵(TBAB)(2.42g,7.5mmol)和2,2,6,6-四甲基哌啶-1-氧基(TEMPO)(1.17g,7.5mmol)的二氯甲烷750mL溶液中加入溶解有碳酸氢钠(63.0g,750mmol)和碳酸钾(10.4g,75mmol)的纯水1.5L溶液,在室温下搅拌。在该溶液中加入N-氯琥珀酰亚胺(NCS)(22.0g,165mmol),在室温下搅拌2小时。搅拌后,分液有机层,将该有机层用纯水500mL洗涤3次。洗涤后,分液有机层,加入硫酸钠进行干燥,然后过滤除去硫酸钠,浓缩滤液。在浓缩物中加入乙腈200mL,室温下搅拌一夜。搅拌后,通过过滤获得白色粉末,进行减压干燥,得到目的物1-十八醛(化合物[3])。产率86%(34.4g),1H NMR(500MHz,CDCl3):δ9.76(1H,d,J=1.9Hz),2.42(2H,dt,J=7.3,1.9Hz),1.63(2H,quintet,J=7.3Hz),1.37-1.19(28H,m),0.88(3H,t,J=6.9Hz)。
<葡萄糖衍生物(化合物[4]-[8])的合成>
《化合物[4]的合成》
在室温下,在甲基α-D-吡喃葡萄糖苷(1.9g,10mmol)的DMF(10mL)悬浮溶液中加入对甲苯磺酸一水合物(46mg,0.24mmol)和原甲酸三乙酯(1.7mL,10mmol)。在室温下在该悬浮溶液中加入1-十一碳醛(1.7g,10mmol)的DMF(5mL)悬浮溶液。将加入了反应溶液的烧瓶与旋转蒸发器连接,将浴温设定为50℃,在将体系内减压至50hPa的同时使其旋转5小时。5小时后,放冷至室温,加入饱和碳酸氢钠水溶液,用乙酸乙酯提取,用饱和氯化钠水溶液洗涤。洗涤后,将提取液用硫酸钠干燥,过滤除去硫酸钠后,减压蒸馏除去溶剂。在残渣中加入己烷,在冰浴冷却的同时搅拌。将得到的悬浮液过滤,用冷己烷洗涤。将得到的粉末溶解在甲醇中,用水使其再结晶,得到目的物(化合物[4])。产率33%(1.2g)1H NMR(400MHz,CDCl3):δ4.76(1H,d,J=4.1Hz),4.54(1H,t,J=5.0Hz),4.13(1H,dd,J=4.8,10.3Hz),3.85(1H,dt,J=1.8,9.2Hz),3.68-3.54(2H,m),3.51(1H,t,J=10.1Hz),3.43(3H,s),3.26(1H,t,J=9.4Hz),2.66(1H,s),2.23(1H,d,J=9.6Hz),1.72-1.60(2H,m),1.45-1.34(2H,m),1.34-1.20(14H,m),0.88(3H,t,J=6.9Hz)。
《化合物[5]的合成》
在室温下,在甲基α-D-吡喃葡萄糖苷(7.8g,40mmol)的DMF(50mL)悬浮溶液中加入对甲苯磺酸一水合物(190mg,1mmol)、原甲酸三乙酯(6.7mL,40mmol)、1-十二烷醇(7.4g,40mmol)。将加入了反应溶液的烧瓶与旋转蒸发器连接,将浴温设定为50℃,在将体系内减压至50hPa的同时使其旋转6小时旋转。6小时后,放冷至室温,加入饱和碳酸氢钠水溶液,减压下浓缩。在残渣中加入甲苯(200mL)和水(200mL),在分液漏斗中剧烈震荡。分液有机层,用硫酸钠使其干燥,过滤除去硫酸钠后,减压蒸馏除去溶剂。在残渣中加入己烷(200mL)搅拌。将得到的悬浮液过滤,得到白色固体。在得到的白色固体中加入己烷(100mL),在用冰浴冷却的同时搅拌。将得到的悬浮液过滤,用冷己烷洗涤,使得到的粉末干燥,得到目的物(化合物[5])。产率63%(9.1g)1H NMR(400MHz,CDCl3):δ4.76(1H,d,J=4.1Hz),4.54(1H,t,J=5.0Hz),4.13(1H,dd,J=4.8,10.3Hz),3.84(1H,t,J=9.2Hz),3.68-3.54(2H,m),3.51(1H,t,J=10.3Hz),3.43(3H,s),3.26(1H,t,J=9.4Hz),2.65(1H,s),2.22(1H,d,J=9.6Hz),1.70-1.60(2H,m),1.44-1.34(2H,m),1.34-1.20(16H,m),0.88(3H,t,J=6.9Hz)。
《化合物[6]的合成》
在室温下,在甲基α-D-吡喃葡萄糖苷(1.9g,10mmol)的DMF(5mL)悬浮溶液中加入对甲苯磺酸一水合物(55mg,0.29mmol)、原甲酸三乙酯(1.7mL,10mmol)。在室温下在该悬浮溶液中加入1-十四醛(化合物[1])(2.1g,10mmol)的DMF(2.5mL)和己烷(12mL)溶液。将加入了反应溶液的烧瓶与旋转蒸发器连接,将浴温设定为40℃,在将体系内减压至50hPa的同时使其旋转5小时。5小时后,放冷至室温,加入饱和碳酸氢钠水溶液,将得到的沉淀物过滤,用水洗涤。将得到的固体通过柱层析(二氧化硅凝胶,己烷:乙酸乙酯=60:40至40:60(v/v))纯化,得到目的物(化合物[6])。产率31%(1.2g)1H NMR(400MHz,CDCl3):δ4.78(1H,d,J=4.1Hz),4.54(1H,t,J=5.0Hz),4.12(1H,dd,J=5.0,10.1Hz),3.85(1H,t,J=9.2Hz),3.68-3.54(2H,m),3.50(1H,t,J=10.3Hz),3.43(3H,s),3.25(1H,t,J=9.4Hz),2.84(1H,s),2.38(1H,d,J=9.6Hz),1.73-1.57(2H,m),1.44-1.34(2H,m),1.33-1.20(20H,m),0.88(3H,t,J=6.9Hz)。
《化合物[7]的合成》
在室温下,在甲基α-D-吡喃葡萄糖苷(0.8g,4mmol)的DMF(5mL)悬浮溶液中加入对甲苯磺酸一水合物(25mg,0.13mmol)、原甲酸三乙酯(0.7mL,4mmol)。在室温下在该悬浮溶液中加入1-十六醛(化合物[2])(1.0g,4mmol)的二氯甲烷(5mL)溶液。将加入了反应溶液的烧瓶与旋转蒸发器连接,将浴温设定为40℃,在将体系内减压至50hPa的同时使其旋转4小时旋转。4小时后,放冷至室温,加入饱和碳酸氢钠水溶液,得到的沉淀物过滤,用水洗涤。将得到的固体通过柱层析(二氧化硅凝胶,己烷:乙酸乙酯=60:40至40:60(v/v))纯化,得到目的物(化合物[7])。产率21%(0.35g)1H NMR(400MHz,CDCl3):δ4.76(1H,d,J=3.7Hz),4.54(1H,t,J=5.0Hz),4.12(1H,dd,J=4.8,10.3Hz),3.85(1H,t,J=9.4Hz),3.68-3.54(2H,m),3.51(1H,t,J=10.3Hz),3.43(3H,s),3.26(1H,t,J=9.4Hz),2.72(1H,s),2.28(1H,s),1.71-1.60(2H,m),1.44-1.34(2H,m),1.33-1.21(24H,m),0.88(3H,t,J=6.9Hz)。
《化合物[8]的合成-1》
在室温下,在甲基α-D-吡喃葡萄糖苷(19.4g,100mmol)、1-十八醛(化合物[3])(29.5g,110mmol)、对甲苯磺酸一水合物(1.05g,5.5mmol)的DMF(130mL)悬浮溶液中加入原甲酸三乙酯(14.7mL,100mmol)。将加入了反应溶液的烧瓶与旋转蒸发器连接,将浴温设定为70℃,在将体系内减压至220hPa的同时使其旋转5小时。5小时后,放冷至室温,加入三乙胺13.3mL,减压蒸馏除去反应溶剂。在残渣中加入乙醇350mL进行固液洗涤,过滤后,将白色粉末减压干燥。将该洗涤操作进行2次,得到目的物(化合物[8])。产率76%(33.7g)1H NMR(400MHz,CDCl3):δ4.76(1H,d,J=3.7Hz),4.54(1H,t,J=4.6Hz),4.13(1H,dd,J=5.0,10.1Hz),3.86(1H,t,J=9.2Hz),3.69-3.54(2H,m),3.51(1H,t,J=10.1Hz),3.43(3H,s),3.26(1H,t,J=9.2Hz),2.73(1H,br s),2.30(1H,br s),1.76-1.55(2H,m),1.50-1.14(30H,m),0.88(3H,t,J=6.4Hz)。
《化合物[8]的合成-2》
在室温下,在甲基α-D-吡喃葡萄糖苷(1.9g,10mmol)、1-十八醛(化合物[3])(2.7g,10mmol)、对甲苯磺酸一水合物(105mg,0.55mmol)的DMF(10mL)悬浮溶液中加入原甲酸三乙酯(1.7mL,10mmol)。将加入了反应溶液的烧瓶与旋转蒸发器连接,将浴温设定为70℃,在将体系内减压至220hPa的同时使其旋转5小时。5小时后,放冷至室温,加入饱和碳酸氢钠水溶液,滤出得到的沉淀物,用水(50mL)洗涤二次。在得到的残渣中加入己烷(30mL)进行固液洗涤,过滤后,将白色粉末减压干燥,得到目的物(化合物[8])。产率70%(3.1g)
<葡萄糖衍生物(化合物[9])的合成>
在室温下,在甲基β-D-吡喃葡萄糖苷0.5水合物(2.0g,10mmol)、1-十八醛(化合物[3])(2.7g,10mmol)、对甲苯磺酸一水合物(105mg,0.55mmol)的DMF(10mL)悬浮溶液中加入原甲酸三乙酯(2.5mL,15mmol)。将加入了反应溶液的烧瓶与旋转蒸发器连接,将浴温设定为70℃,在将体系内减压至220hPa的同时使其旋转5小时。5小时后,放冷至室温,加入饱和碳酸氢钠水溶液,滤出得到的沉淀物,用水(50mL)洗涤二次。在得到的残渣中加入乙醚(30mL)进行固液洗涤,过滤后,将白色粉末减压干燥,得到目的物(化合物[9])。产率81%(3.6g)1H NMR(400MHz,CDCl3):δ4.55(1H,d,J=5.0Hz),4.28(1H,t,J=7.8Hz),4.23-4.14(1H,m),3.80-3.69(1H,m),3.61-3.50(4H,m),3.48-3.40(1H,m),3.36-3.25(2H,m),2.73(1H,d,J=2.3Hz),2.62(1H,d,J=2.3Hz)1.74-1.56(4H,m),1.47-1.16(30H,m),0.88(3H,t,J=6.4Hz)。
<葡萄糖衍生物(化合物[10])的合成>
在室温下,在乙基α-D-吡喃葡萄糖苷(2.1g,10mmol)、1-十八醛(化合物[3])(2.7g,10mmol)、对甲苯磺酸一水合物(105mg,0.55mmol)的DMF(10mL)悬浮溶液中加入原甲酸三乙酯(1.7mL,10mmol)。将加入了反应溶液的烧瓶与旋转蒸发器连接,将浴温设定为70℃,在将体系内减压至220hPa的同时使其旋转5小时。5小时后,放冷至室温,加入饱和碳酸氢钠水溶液,滤出得到的沉淀物,用水(50mL)洗涤二次。在得到的残渣中加入乙醚(30mL)进行固液洗涤,过滤后,将白色粉末减压干燥,得到目的物(化合物[10])。产率74%(3.4g)1HNMR(400MHz,CDCl3):δ4.87(1H,d,J=4.1Hz),4.54(1H,t,J=5.0Hz),4.11(1H,dd,J=4.6,10.1Hz),3.90-3.73(2H,m),3.67(1H,dt,J=4.6,10.1Hz),3.60-3.45(3H,m),3.26(1H,t,J=9.6Hz),2.65(1H,s),2.20(1H,d,J=10.1Hz),1.75-1.53(5H,m),1.46-1.15(32H,m),0.88(3H,t,J=6.9Hz)。
<甘露糖衍生物(化合物[11])的合成>
在室温下,在甲基α-D-吡喃甘露糖苷(1.9g,10mmol)、1-十八醛(化合物[3])(2.7g,10mmol)、对甲苯磺酸一水合物(105mg,0.55mmol)的DMF(10mL)悬浮溶液中加入原甲酸三乙酯(1.7mL,10mmol)。将加入了反应溶液的烧瓶与旋转蒸发器连接,将浴温设定为70℃,在将体系内减压至220hPa的同时使其旋转5小时。5小时后,放冷至室温,加入饱和碳酸氢钠水溶液,滤出得到的沉淀物,用水(50mL)洗涤二次。在得到的残渣中加入乙醚(30mL)进行固液洗涤,过滤后,将白色固体减压干燥。将得到的固体通过柱层析(二氧化硅凝胶,己烷:乙酸乙酯=80:20至50:50(v/v)和氯仿:乙酸乙酯=50:50(v/v))进行纯化,得到目的物(化合物[11])。产率27%(1.2g)1H NMR(400MHz,CDCl3):δ4.74(1H,d,J=1.4Hz),4.58(1H,t,J=5.0Hz),4.17-4.07(1H,m),4.05-3.94(2H,m),3.71-3.56(3H,m),3.37(3H,s),2.55(1H,d,J=2.3Hz),2.51(1H,d,J=3.7Hz),1.69-1.60(2H,m),1.47-1.17(30H,m),0.88(3H,t,J=6.9Hz)。
<半乳糖衍生物(化合物[12])的合成>
在室温下,在甲基α-D-吡喃半乳糖苷一水合物(2.1g,10mmol)、1-十八醛(化合物[3])(2.7g,10mmol)、对甲苯磺酸一水合物(105mg,0.55mmol)的DMF(10mL)悬浮溶液中加入原甲酸三乙酯(3.3mL,20mmol)。将加入了反应溶液的烧瓶与旋转蒸发器连接,将浴温设定为70℃,在将体系内减压至220hPa的同时使其旋转5小时。5小时后,放冷至室温,加入饱和碳酸氢钠水溶液,用乙酸乙酯提取,用饱和氯化钠水溶液洗涤。分液有机层,加入硫酸钠进行干燥,然后过滤除去硫酸钠,浓缩滤液。在残留物中加入己烷(30mL)进行固液洗涤,过滤后,将白色固体减压干燥。将得到的固体通过柱层析(二氧化硅凝胶,己烷:乙酸乙酯=60:40至40:70(v/v))进行纯化,得到目的物(化合物[12])。产率55%(2.4g)1H NMR(400MHz,CDCl3):δ4.90(1H,d,J=3.2Hz),4.57(1H,t,J=5.0Hz),4.12(1H,d,J=12.4Hz),4.03(1H,t,J=3.7Hz),3.92-3.73(3H,m),3.60(1H,s),3.44(3H,s),2.37(1H,d,J=7.8Hz),2.10(1H,d,J=7.8Hz)1.76-1.65(2H,m),1.50-1.15(30H,m),0.88(3H,t,J=6.0Hz)。
[实施例2:胶凝剂的凝胶形成能力试验]
以实施例1中合成的化合物[4]-[12]作为胶凝剂,评价对各种溶剂的凝胶形成能力。
凝胶化试验如下进行。在4mL螺口样品管中加入胶凝剂和溶剂,在化合物[4]-[7]时,对于辛烷、角鲨烷、角鲨烯、肉豆蔻酸异丙酯(IPM)、橄榄油、KF995(十甲基环五硅氧烷)、乙二醇以120℃加热30分钟,对于霍霍巴油、甲苯、水以100℃加热30分钟,对于环己烷、乙酸乙酯、乙腈、DMSO(二甲基亚砜)、乙醇、乙醇/水(vol/vol)混合溶剂(75%乙醇(乙醇/水=75/25)、50%乙醇(乙醇/水=50/50)、25%乙醇(乙醇/水=25/75))以80℃加热30分钟,对于氯仿、甲醇以60℃加热30分钟。另一方面,在化合物[8]-[12]时,对于辛烷、角鲨烷、角鲨烯、肉豆蔻酸异丙酯(IPM)、橄榄油、霍霍巴油、KF995(十甲基环五硅氧烷)、甲苯、乙二醇、水以100℃加热30分钟,对于环己烷、乙酸乙酯、乙腈、DMSO(二甲基亚砜)、乙醇、乙醇/水(vol/vol)混合溶剂(75%乙醇(乙醇/水=75/25)、50%乙醇(乙醇/水=50/50)、25%乙醇(乙醇/水=25/75))以80℃加热30分钟,对于氯仿、甲醇以60℃加热30分钟。
将得到的各溶液冷却至室温,放置1小时,观察凝胶的形成(其中,在使用甲苯和乙酸乙酯的情况下根据化合物的种类而放置(放冷)24小时)。此外,将放冷后溶液的流动性丧失、即使将样品管倒置溶液也不流下的状态判断为“凝胶化”。凝胶化试验以胶凝剂的浓度:5.0、4.0、3.0、2.0、1.0、0.5、0.25、0.1wt%实施,将凝胶化所需的胶凝剂的最低浓度(wt%)作为最低凝胶化浓度。这里,表示浓度的单位的wt%是指wt/vol×100。将得到的结果示于表1。表中的数字表示最低凝胶化浓度(wt%),表中的符号表示形成的凝胶的状态(以下,本说明书中的其他表也同样)、透明的凝胶评价为“G”,半透明的凝胶评价为“TG”,浑浊的凝胶评价为“OG”,部分凝胶化且透明的凝胶评价为“P-G”,部分凝胶化且半透明的凝胶评价为“P-TG”,部分凝胶化且白浊的凝胶白浊“P-OG”,保持溶液状态时评价为“S”,生成沉淀时评价为“P”,另外,即使加热胶凝剂也不溶解形成不溶状态时评价为“IS”。另外未评价的溶剂表示为“-”。
表1.糖衍生物型胶凝剂(化合物[4]-[12])的凝胶化试验结果
溶剂 | 化合物[4] | 化合物[5] | 化合物[6] | 化合物[7] | 化合物[8] | 化合物[9] | 化合物[10] | 化合物[11] | 化合物[12] |
辛烷 | 0.5G | 1G | 1TG | 0.25TG | 2TG | 0.5TG | 2OG | 2G | 2OG |
环己烷 | S | S | S | 1TG | 2P-TG | 0.1TG | 2P-OG | 3TG | 3OG |
角鲨烷 | 0.25G | 0.25G | 1TG | 0.25G | 0.25TG | 0.05G | 0.25G | 0.1G | 1TG |
角鲨烯 | - | - | - | - | 5TG | 0.1G | 1G | 0.5G | 1TG |
霍霍巴油 | 2G | 1G | 0.5G | 0.5G | 0.25G | 0.25G | 0.25G | 1G | 0.5OG |
IPM | S | S | 2TG | 2TG | 2TG | 0.5TG | 2OG | 2G | 3OG |
橄榄油 | 5G | 5G | 2TG | 2TG | 2TG | 0.5G | 2TG | 2G | 2OG |
KF995 | 0.25G | 0.1G | 0.25G | 0.25TG | 0.25P-TG | 0.25G | 0.5TG | 0.25G | 1OG |
甲苯 | S | S | S | 5G | 5P-G* | 1G | 5P-OG* | 5P-OG* | 5P-TG* |
氯仿 | - | - | - | - | S | S | S | S | S |
乙酸乙酯 | - | - | - | - | S | 5OG | S | S | 5OG* |
乙腈 | S | S | S | 2OG | 5P-TG | 0.5G | 3OG | P | 2OG |
DMSo | S | S | S | S | P | 3TG | 4OG | S | 3TG |
乙二醇 | 5OG | 5TG | 1TG | 0.5TG | 0.5TG | 0.02G | 4OG | 0.05TG | P |
甲醇 | - | - | - | - | P | 3TG | 3OG | 2OG | 3OG |
乙醇 | S | S | S | S | P | 3TG | P | P | 3P-TG |
75%乙醇 | P | S | S | P | 2P-OG | 0.5TG | 1OG | 5OG | 2TG |
50%乙醇 | P | P | 0.5TG | 0.1G | 0.1TG | 0.05G | 0.05TG | 3OG | 1OG |
25%乙醇 | IS | 0.1G | 0.1TG | 2P-OG | IS | P | 5P-OG | P | P |
水 | 0.1P-TG | 1OG | IS | IS | IS | P | P | P | IS |
*号表示放冷24小时放冷的结果
如表1所示表明,糖衍生物型胶凝剂(化合物[4]-[12])对从非极性溶剂到质子性溶剂的广泛溶剂群显示凝胶化能力,化合物[4]-[12]作为低分子胶凝剂发挥功能。
进而,配合2wt%的葡萄糖衍生物:化合物[8]而形成的KF995凝胶具有能够自己立起的硬度(自支持性)(参照图1)。
[实施例3:触变性试验]
对于由葡萄糖衍生物型胶凝剂(化合物[8])制成的各种凝胶的触变性进行评价。触变性试验如下进行。通过与实施例2同样的方法改变胶凝剂的浓度而制备凝胶。然后,通过使用涡旋混合器从凝胶震荡成溶胶状态而使凝胶崩解,室温下静置一定时间(1.5小时)。静置一定时间后,将装入了溶液的样品管倒置,在溶液不流下的状态时判断为“有触变性”。表2显示确认了触变性的胶凝剂的最低浓度(wt%)。
表2.葡萄糖衍生物型胶凝剂(化合物[8])的触变性试验结果
※表中的数值表示确认了触变性的各溶剂凝胶化所需的胶凝剂(化合物)的最低浓度(wt%)。
如表2所示,确认了本发明的葡萄糖衍生物型胶凝剂(化合物[8])形成具有触变性的凝胶。
[实施例4:添加剂配合试验<配合表面活性剂时的凝胶化试验(1)>]
一般化妆品、准药品中要配合表面活性剂等各种添加剂,在配合了这样的添加剂的情况下也具有凝胶化能力的胶凝剂、特别是在配合了表面活性剂时具有凝胶化能力的胶凝剂如后所述可以期待容易地制备水-油分散系凝胶,因而能够设想对各种用途的展开,所示是非常有用的。
进而如果无论HLB值大小都能够使表面活性剂配合溶液凝胶化,则能期待用一种胶凝剂制备O/W分散系凝胶和W/O分散系凝胶的任一者。
以下,对于配合了HLB值大的Tween20(HLB=16.7)和HLB值小的Span80(HLB=4.3)时的本发明的胶凝剂的凝胶化能力进行讨论。
<表面活性剂配合试验>
配合表面活性剂时的凝胶化试验如下进行。
对于添加了非离子性表面活性剂聚氧乙烯(20)失水山梨糖醇单月桂酸酯(Tween20)(HLB=16.7)时的凝胶化能力进行讨论。首先将Tween20溶解在水中制备配合了1wt%的Tween20配合的水溶液。然后,在4mL的螺管中添加葡萄糖衍生物型胶凝剂(化合物[8])至规定浓度,加入之前制备的表面活性剂配合水溶液,在100℃加热30分钟。将得到的溶液冷却至室温冷却放置1小时,通过将螺管倒置而确认了凝胶的形成。结果示于表3。
接着研究添加非离子性表面活性剂Span80(HLB=4.3)时的凝胶化能力。在4mL的螺管中添加Span80至规定浓度(0.5wt%),并添加葡萄糖衍生物型胶凝剂(化合物[8])至规定浓度,加入油剂(角鲨烷、橄榄油、霍霍巴油、KF995),在120℃加热30分钟。将得到的溶液冷却至室温放置1小时,通过将螺管倒置而确认了凝胶的形成。结果示于表3。
表3.表面活性剂配合时凝胶化试验结果(1)
※表中的数值表示各溶剂凝胶化所需的胶凝剂(化合物)的最低浓度(wt%)。
※G:透明的凝胶、TG:半透明的凝胶、OG:浑浊的凝胶。
如表3所示,得到了本发明的胶凝剂在配合了非离子性表面活性剂Tween20的情况下能够形成水凝胶的结果。
此外,如之前的表1所示,化合物[8]的葡萄糖衍生物型胶凝剂不能单独形成水凝胶(水100%凝胶),通过联合使用胶凝剂和表面活性剂而形成水凝胶可以说是极有特征的例子。
另外如表3所示,确认了在任何油剂中配合Span80时都形成凝胶。该结果提示,在制备水-油分散系凝胶时,有能够形成W/O型的分散凝胶的可能性。
[实施例5:添加剂配合试验<配合表面活性剂时的凝胶化试验(2)>]
在本例中,对于作为各种表面活性剂配合非离子性表面活性剂(Tween20)、阴离子性表面活性剂[二(2-乙基己基)磺基琥珀酸钠(AOT)、十二烷基硫酸钠(SDS)]、和阳离子性表面活性剂[十六烷基三甲基溴化铵(CTAB)、十六烷基氯化吡啶鎓(CPC)]时的本发明的胶凝剂的凝胶化能力进行研究。
首先将上述各种表面活性剂溶解在水中制备0.5wt%的各种表面活性剂配合水溶液。然后,在4mL的螺管添加葡萄糖衍生物型胶凝剂(化合物[8])至规定浓度,加入之前制备的表面活性剂配合水溶液,在100℃加热30分钟。将得到的溶液冷却到室温,放置1天(Tween20为1小时),通过将螺管倒置而确认了凝胶的形成。结果示于表4。
表4.表面活性剂配合时凝胶化试验结果(2)
*室温放冷、1小时后
※表中的数值显示各溶剂凝胶化所需的胶凝剂(化合物)的最低浓度(wt%)。
※TG:半透明的凝胶、OG:浑浊的凝胶。
如表4所示,得到了本发明的胶凝剂在配合了非离子性表面活性剂、阴离子性表面活性剂、阳离子性表面活性剂的任一情况下均能够形成水凝胶的结果。
[实施例6:使用葡萄糖衍生物型胶凝剂(化合物[8])的水-油分散试验]
在化妆品、药品、食品、功能性材料等多种用途中要求使油剂与水均匀地分散化、且稳定化的乳液制备技术。
通过连续相的凝胶化来抑制液滴合一,成为乳液的稳定化中重要的因子之一。即,某种胶凝剂能够诱发W/O乳液和O/W乳液中的连续相的凝胶化,意味着该胶凝剂具有能够使W/O或O/W乳液稳定化的可能性。
在所述的实施例4和实施例5中确认了,不仅在表面活性剂配合时也具有凝胶形成能力,而且通过少量的表面活性剂Tween20添加还能够形成水凝胶(水100%凝胶)。进而实施例2中,得到了本发明的胶凝剂对疏水性有机溶剂(油剂)和乙醇配合水溶液(乙醇/水溶液)两者具有凝胶形成能力的结果。该结果提示,本发明的胶凝剂即使不使用表面活性剂也能够使水与油均匀地分散化、且稳定化。
于是,在本例中,为了确认本发明的胶凝剂能否将水与油剂的两溶剂均匀地分散,而进行了水-油分散试验。
<水-KF995分散凝胶制备试验>
水-油分散试验如下进行。4mL的带螺口样品管中加入葡萄糖衍生物型胶凝剂(化合物[8])、以及油剂(KF995)和水至规定浓度。另外在表面活性剂配合例中,Tween20是使用1wt%的Tween20水溶液代替水,Span80是在添加胶凝剂加入1wt%(但仅在KF995/水(2/8(vol/vol))时加入0.5wt%)。
将加入了上述胶凝剂等的混合溶液的样品管加热30分钟加热,使混合成分溶解。然后,使用涡旋混合器剪切后,室温静置1小时,观察分散状态。此外,将放冷后溶液的流动性丧失、即使将样品管倒置溶液也不流下、并且水与油均匀地分散的状态判断为“水/油分散凝胶”。将得到的结果示于表5。
表5.葡萄糖衍生物型胶凝剂[化合物[8]]的水-KF995分散凝胶制备试验
※表中的数值表示各溶剂凝胶化所需的胶凝剂(化合物)的浓度(wt%)。
※表中的括号内的数值表示加热温度(℃)和涡旋混合器的剪切时间(分钟)。
※斜线表示未实施。
如表5所示,在水-KF995分散凝胶制备中,单独使用胶凝剂(化合物[8])单独的情况、联合使用胶凝剂和表面活性剂(Tween20、Span80)的情况下,均能够形成水/油分散凝胶。
<使用共焦点激光扫描显微镜的分散凝胶的分散相和连续相的鉴定>
图2显示使用荧光色素荧光素钠5μM水溶液代替水与上述同样地制备的配合了表面活性剂的水/油分散凝胶的共焦点激光扫描显微镜观察结果。此外,作为水/油分散凝胶使用水-KF995(KF995/水=2/8(vol/vol))分散凝胶(胶凝剂的添加量参照表5参照),作为表面活性剂,配合1wt%的Tween20,或者1wt%的Span80。图中,发出荧光色的相(图像上看起来为白色的相)是水相。
如图2(a)所示,配合了1wt%的Tween20的水-KF995(KF995/水=2/8(vol/vol))分散凝胶是O/W乳液凝胶(分散相为KF995相、连续相为水相),另一方面,配合了1.0wt%的Span80的水-KF995(KF995/水=2/8(vol/vol))分散凝胶是W/O乳液凝胶(分散相为水相、连续相为KF995相)。
如之前实施例2的结果所示,本发明的胶凝剂中的化合物[8]等对100%水具有凝胶化能力,但在实施例4和实施例5中确认了通过在该体系中配合Tween20等表面活性剂能够形成水凝胶。并且上述O/W乳液凝胶形成的结果显示葡萄糖衍生物型胶凝剂(化合物[8])与Tween20的复合体参与乳液凝胶形。
另外,高含水率的W/O乳液凝胶一般在化妆品用途中不被汗、水冲掉,并且在皮肤上的延展性好,期待应用于同时具有清爽的使用感和耐水性的制品群,但已知乳液不稳定。
被认为这样难以制备的高含水率W/O乳液在使用本发明的胶凝剂、另外作为表面活性剂配合Span80时作为乳液凝胶获得,这样的结果可以说是通过本发明的胶凝剂获得的较大特征之一。
<葡萄糖衍生物型胶凝剂(化合物[8])的水-角鲨烷、水-IPM和水-霍霍巴油分散凝胶制备试验>
接着,使用本发明的胶凝剂(化合物[8]),另外作为油剂使用角鲨烷、IPM或霍霍巴油,按照之前的<水-KF995分散凝胶制备试验>步骤进行水-油分散凝胶制备试验。
得到的结果示于表6。
表6.葡萄糖衍生物型胶凝剂(化合物[8])的水-油分散凝胶制备试验
※表中的数值表示各溶剂凝胶化所需的胶凝剂(化合物)的浓度(wt%)。
※无添加剂时的加热温度为80℃、涡旋混合器的剪切时间为5分钟。
添加Tween20添加时的加热温度为100℃、涡旋混合器的剪切时间为3分钟。
添加Span80添加时的加热温度为80℃、涡旋混合器的剪切时间为5分钟。
※Tween20制成1wt%的Tween20溶液使用。
Span80在胶凝剂添加时直接添加至0.5wt%。
※斜线表示未实施。
根据表6,在各种油性基材中,仅使用胶凝剂(化合物[8])、和联合使用胶凝剂和Tween20时、以及联合使用胶凝剂和Span80时,能够进行水-油分散凝胶制备。该结果提示,葡萄糖衍生物型胶凝剂(化合物[8])能够在多样的油性基材中制备水-油分散凝胶。
<水溶性药剂内包水-油分散凝胶的制备>
接着,使用水溶性药剂水溶液代替水进行水-油分散凝胶制备。作为水溶性药剂,使用L-抗坏血酸(20%水溶液(pH2.0))、L-抗坏血酸2-磷酸酯三钠(40%水溶液(pH8.4))、甘氨酸(18%水溶液(pH6.1))、D-(+)-葡糖胺盐酸盐(25%水溶液(pH7.1))、葡萄糖衍生物型胶凝剂(化合物[8]和Span80各0.5wt%,油性基材使用KF995,水溶性液与油性基材的比例为80/20,使用它们制成括号内所示的规定浓度的水溶液,按照之前的<水-KF995分散凝胶制备试验>步骤进行水-油分散凝胶制备试验。将得到的结果示于表7。
表7.内包了水溶性药剂的水-油分散凝胶制备试验
L-抗坏血酸 | L-抗坏血酸2-磷酸酯三钠 | 甘氨酸 | 葡糖胺 |
○(0.5分钟) | ○(0.5分钟) | ○(1分钟) | ○(0.5分钟) |
※表中的括号内的数值表示涡旋混合器的剪切时间(分钟)。
根据表7,即使内包任一水溶性药剂,也能够制备稳定的水-油分散凝胶。另外,L-抗坏血酸水溶液为酸性(pH约2.0)、L-抗坏血酸2-磷酸酯三钠水溶液为碱性(pH约8.4),确认了能够在广泛的pH范围制备水-油分散凝胶。
[实施例7:各种凝胶的SEM观察]
<葡萄糖衍生物型胶凝剂(化合物[8])的KF995干凝胶和50%EtOH凝胶的SEM观察>
制备加入了0.25wt%的实施例1中制备的胶凝剂(化合物[8])的KF995凝胶后,在碳带上真空干燥24小时,将由此得到的干凝胶用扫描型显微镜(SEM)进行观察。
另外,制备加入了0.1wt%的上述胶凝剂的50%乙醇凝胶(乙醇/水=50/50(vol/vol)后,在碳带上装载该凝胶,在80Pa的减压下以SEM观察。
将得到的结果示于图3(图3(a):KF995干凝胶、(b):50%乙醇凝胶)。
根据图3所示的SEM图像,由胶凝剂(化合物[8])的KF995干凝胶(图3(a))和50%EtOH凝胶(图3(b))均得到纤维状的像。由此,确认了由葡萄糖衍生物型胶凝剂(化合物[8])制成的凝胶采取三维网眼结构。
<葡萄糖衍生物型胶凝剂(化合物[8])的配合了1%的Tween20的水-KF995分散凝胶的SEM观察>
接着,对于使用实施例1中制备的胶凝剂(化合物[8])制备的配合了1%的Tween20的水-KF995分散凝胶进行SEM观察。
使用2wt%的上述胶凝剂制备配合了1%的Tween20的水-KF995分散凝胶后,在碳带上装载该凝胶,在80Pa的减压下以SEM观察。将得到的结果示于图4(图4(a)500倍、(b)5000倍)。
根据图4所示的SEM图像,配合了的Tween20的水-KF995(KF995/水=2/8(vol/vol))分散凝胶得到了形成具有孔隙的海绵状结构的像。考虑该孔隙来源于由KF995相形成的分散相,即结果提示了由胶凝剂(化合物[8])和表面活性剂Tween20的复合体制成的纤维状结构体形成连续相,从而形成水-油分散凝胶。
[实施例8:离子液体的凝胶化评价]
以实施例1中合成的化合物[8]作为胶凝剂,评价对各种离子液体的凝胶形成能力。
在4mL的螺管中添加葡萄糖衍生物型胶凝剂(化合物[8])至规定浓度,在其中加入表8所示的各种离子液体,在100℃加热30分钟。将得到的溶液冷却至室温,放置1小时,通过将螺管倒置而确认了凝胶的形成。结果示于表8。
此外,以下的实施例中使用的离子液体(阳离子种·阴离子种)如下。
<阳离子种>
EtMeIm:1-乙基-3-甲基-咪唑鎓离子
BuMeIm:1-丁基-3-甲基-咪唑鎓离子
BuPy:N-丁基吡啶鎓离子
HeMeIm:1-己基-3-甲基-咪唑鎓离子
P13:N-甲基-N-丙基哌啶鎓离子
TMPA:N,N,N-三甲基-N-丙基铵离子
<阴离子种>
TFSI:双(三氟甲基磺酰)酰亚胺离子
PF6:六氟磷酸根离子
I:碘离子
CF3SO3:三氟甲烷磺酸根离子
BF4:四氟硼酸根离子
表8.对各种离子液体的凝胶形成能力
离子液体 | 凝胶形成结果 | 离子液体 | 凝胶形成结果 |
[EtMeIm][TFSI] | 1TG | [BuMeIm][BF<sub>4</sub>] | 5TG |
[BuMeIm][TFSI] | 2TG | [BuPy][TFSI] | 2TG |
[BuMeIm][PF<sub>6</sub>] | 1TG | [HeMeIm][TFSI] | 2TG |
[BuMeIm][I] | 1* | [P13][TFSI] | 1G |
[BuMeIm][CF<sub>3</sub>SO<sub>3</sub>] | 2TG | [TMPA][TFSI] | 1TG |
*离子液体自身的颜色浓,无法判断浊度。
※表中的数值表示各离子液体凝胶化所需的胶凝剂(化合物)的浓度(wt%)。
※G:透明的凝胶、TG:半透明的凝胶。
如表8所示,确认了本发明的胶凝剂能够将各种离子液体凝胶化。
另外,由配合了2wt%或3wt%的葡萄糖衍生物:化合物[8]的离子液体[BuMeIm][TFSI]形成的凝胶具有能自己立起的硬度(自支持性)(参照图5:图5(a)配合3wt%的化合物[8],(b)配合2wt%的化合物[8])。
[实施例9:电导率测定]
以实施例1中合成的化合物[8]作为胶凝剂,将其以各种浓度加入离子液体[BuMeIm][TFSI]中,在100℃加热30分钟。将得到的溶液注入电导率计的测定池,室温下放置1小时,进行电导率测定。
得到的结果示于表9。
·电导率测定步骤
〈测定仪器〉
株式会社堀场制作所便携式电导率计LAQUAtwin B-771
表9.电导率测定结果
※离子液体[BuMeIm][TFSI]、胶凝剂化合物[8]
如表9所示,关于使用本发明的胶凝剂得到的离子液体凝胶的电导率,并不大幅降低离子液体(胶凝剂浓度0wt%)的电导率,基本显示相同的值。
[实施例10:离子液体-油分散凝胶制备试验]
在4mL的带螺口样品管中加入葡萄糖衍生物型胶凝剂(化合物[8])至2wt%,并且以50/50(vol/vol)的比率加入离子液体[BuMeIm][TFSI]和角鲨烷。另外,作为胶凝剂加入0.25wt%的化合物[8]、并且加入Tween20至2wt%,以50/50(vol/vol)的比率加入离子液体[BuMeIm][TFSI]和角鲨烷。
将加入了上述胶凝剂等的混合溶液的样品管加热30分钟,使混合成分溶解。然后,使用涡旋混合器剪切后,室温静置1小时,观察分散状态。此外,将放冷后溶液的流动性丧失、即使将样品管倒置溶液也不流下、并且离子液体和角鲨烷均匀地分散的状态判断为“离子液体-油分散凝胶”。
其结果在离子液体-角鲨烷分散凝胶制备中,在单独使用胶凝剂(化合物[8])的情况、和联合使用胶凝剂和表面活性剂(Tween20)的情况下,都能够形成离子液体/油分散凝胶(凝胶乳液)。
<使用共焦点激光扫描显微镜的离子液体凝胶乳液的分散相和连续相的鉴定>
使用10μM罗丹明B配合离子液体[BuMeIm][TFSI]与上述同样地制备配合了2wt%的化合物[8]的罗丹明B配合离子液体[BuMeIm][TFSI]/角鲨烷=50/50(vol/vol)凝胶乳液,通过共焦点激光扫描显微镜观察进行观察。将得到的结果示于图6(a)。
同样地,制备配合了0.25wt%的化合物[8]、作为表面活性剂配合了2wt%的Tween20的罗丹明B配合离子液体[BuMeIm][TFSI]/角鲨烷=50/50(vol/vol)凝胶乳液,通过共焦点激光扫描显微镜观察进行观察。将得到的结果示于图6(b)。
图6中,发出荧光色的相(图像上看起来为明亮的白色的相)是离子液体相。
如图6也显示的那样,确认了仅配合了化合物[8]的凝胶乳液形成了离子液体/油(IL/O)凝胶乳液(分散相为离子液体相、连续相为角鲨烷相),另一方面,在联合使用了化合物[8]和Tweeen20的体系中,形成了油/离子液体(O/IL)凝胶乳液(分散相为角鲨烷相、连续相为离子液体相)。
<离子液体凝胶乳液的电导率测定>
对于配合2wt%的所述的化合物[8]、或配合0.25wt%的化合物[8]和2wt%的Tween20而制成的各离子液体[BuMeIm][TFSI]与角鲨烷的50/50(vol/vol)的凝胶乳液,按照上述[实施例9:电导率测定]的步骤测定电导率。
其结果是,仅配合了胶凝剂(化合物[8])的凝胶乳液的电导率为0μS/cm,另一方面,联合使用了胶凝剂和表面活性剂(Tween20)时的凝胶乳液的电导率为1.67mS/cm。
与之前的共焦点激光扫描显微镜的观察结果对比,确认了仅由电导率为0μS/cm的化合物[8]制成的凝胶乳液是IL/O乳液,因而由离子液体产生的电导性被遮蔽。另一方面,确认了由化合物[8]和Tween20制成的凝胶乳液是O/IL乳液,在凝胶乳液的状态下也显示电导性(1.67mS/cm)。
[实施例11:微粒分散体系中的凝胶形成能力试验(1)]
以实施例1中合成的化合物[8]作为胶凝剂,评价微粒分散体系中的凝胶形成能力。
微粒使用实施了硅氧烷处理(甲基氢聚硅氧烷处理)的粉末(商品名:滑石DN-SH、钛DN-SH(2)(微粒成分:氧化钛)、绢云母DN-MC(2)(微粒成分:云母)、DN-HAP(SH)(微粒成分:羟磷灰石)均使用大日本化成(株)制)。
在带螺口样品管中加入作为胶凝剂的合成例1中制备的化合物[8](10mg或20mg)、上述的各种微粒(50mg、钛DN-SH(2)为50mg或100mg)、KF995(1mL)。将其在80℃加热30分钟后,在室温下放冷1小时,通过将样品管倒置确认了凝胶的形成。结果示于表10。
表10.微粒分散凝胶形成结果(1)
*标记表示添加了100mg的钛DN-SH(2)时的结果。
如表10所示,确认了在分散了各种微粒的体系中也能够凝胶化。
[实施例12:微粒分散体系中的凝胶形成能力试验(2)]
在带螺口样品管中加入作为胶凝剂的化合物[8](40mg),KF995(1mL),和水、L-抗坏血酸水溶液(20%水溶液)、L-抗坏血酸2-磷酸酯三钠盐水溶液(40%水溶液)、或甘氨酸水溶液(18%水溶液)(分别为1mL)作为试样,或进一步加入实施了硅氧烷处理的微粒钛DN-SH(2)(100mg或200mg)作为试样(KF995与水等水系介质的比率:50/50(vol/vol)。将得到的各试样在80℃加热30分钟,接着用涡旋混合器震荡3分钟后,室温下放冷1小时,确认了凝胶的形成。结果示于表11。
表11.微粒分散凝胶形成结果(2)
*标记是使用200mg的钛DN-SH(2)时的结果。
如表11所示,确认了在任一体系中都能够进行凝胶乳液化。
[实施例13:微粒分散体系中的凝胶形成能力试验(3)]
进而,研究KF995与水的比率为20/80(vol/vol)时的高内相比凝胶乳液(分散相的体积分率的极大的乳液)制备。
在带螺口样品管中加入作为胶凝剂的化合物[8](10mg),KF995(0.4mL),水、L-抗坏血酸水溶液(20%水溶液)、L-抗坏血酸2-磷酸酯三钠盐水溶液(40%水溶液)、或甘氨酸水溶液(18%水溶液)(分别为1.6mL),以及实施了硅氧烷处理的微粒钛DN-SH(2)(100mg或200mg),或进一步加入Span80(10mg)作为试样(制备了仅为水、未配合Span80的试样)。将得到的各试样在80℃加热30分钟,接着用涡旋混合器震荡3分钟后,室温下放冷1小时,确认了凝胶的形成。结果示于表12。
表12.微粒分散凝胶形成结果(3)
*标记是加入了200mg的钛DN-SH(2)时的结果。
如表12所示,在KF995与水系介质的比率为20/80(vol/vol)的体系中,通过配合Sapn80,能够进行高内相比凝胶乳液化。
<使用共焦点激光扫描显微镜的微粒分散体系凝胶观察>
对于配合作为胶凝剂的化合物[8]0.5wt%、Span80 0.5wt%、以及实施了硅氧烷处理的微粒钛DN-SH(2)5wt%而制成的KF995/水=20/80(vol/vol)凝胶乳液,通过共焦点激光扫描显微镜进行观察。将得到的结果示于图7。
由之前的[实施例6]的<水-KF995分散凝胶制备试验>和<使用共焦点激光扫描显微镜的分散凝胶的分散相和连续相的鉴定>的结果确认,配合了Span80的水-KF995分散凝胶形成W/O乳液(分散相为水相、连续相为KF995相)。
并且如图7所示,确认了钛微粒分散在连续相(KF995相)中。
[实施例14:粉底制作]
按照下述表13将成分(A)总量自动研钵(ANM-1000型,日陶科学株式会社制)中搅拌混合15分钟。除了用于试验的化合物[8]以外,全部使用从株式会社オレンジフラワー购买的产品。然后,添加实现搅拌混合而制备的成分(B)(处方1~处方3加热溶解),进一步混合15分钟。将得到的粉末加入便携式盒(型号:cp-23、制造商:株式会社オレンジフラワー),使用平坦的板加固粉体。
将加入便携式盒中得到的粉底的外观示于图8。图8中(a)显示比较处方,(b)显示处方1,(c)显示处方2,(d)显示处方3。
表13.粉底处方
※1:黄色氧化铁、黑色氧化铁和红色氧化铁的总量为0.3g
如图8所示,确认了在比较处方、处方1~处方3的任一者中制作粉底。特别是确认了处方1~处方3的粉底中配合的各种粉体和油均匀地分散。尤其是在处方1和处方2中,得到了提示形成了不仅成形良好,而且获得了湿润的使用感的粉底的结果。
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