CN113518615B - 化妆料、加温使用化妆料及美容方法 - Google Patents
化妆料、加温使用化妆料及美容方法 Download PDFInfo
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- CN113518615B CN113518615B CN202080018099.1A CN202080018099A CN113518615B CN 113518615 B CN113518615 B CN 113518615B CN 202080018099 A CN202080018099 A CN 202080018099A CN 113518615 B CN113518615 B CN 113518615B
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Classifications
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- A—HUMAN NECESSITIES
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/87—Polyurethanes
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D34/00—Containers or accessories specially adapted for handling liquid toiletry or cosmetic substances, e.g. perfumes
- A45D34/04—Appliances specially adapted for applying liquid, e.g. using roller or ball
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- A—HUMAN NECESSITIES
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Abstract
本发明的课题是提供抑制发粘,在分配器工作时连续地吸起的化妆料。此外,提供具有温度响应性,高温稳定性高的加温使用化妆料。解决手段是使化妆料为含有(A)疏水改性聚醚氨基甲酸酯、(B)纤维素纳米纤维、和(C)水的化妆料,并且(A)与(B)的混配比率:在(A)<(B)的情况下,(A)+(B)的混配量相对于全部化妆料为0.75质量%以下,在(A)=(B)的情况下,(A)+(B)的混配量相对于全部化妆料为1.75质量%以下,在(A)>(B)的情况下,(A)+(B)的混配量相对于全部化妆料为2质量%以下。此外,使加温使用化妆料为在具有加热部的设备中使用的加温使用化妆料,并且含有在30℃以上会发生结构变化的温度响应性高分子、在70℃以下不会发生结构变化的高温稳定性高分子、和水。
Description
技术领域
本发明涉及含有疏水性聚醚氨基甲酸酯和纤维素纳米纤维的化妆料、含有温度响应性高分子和高温稳定性高分子的加温而使用的加温使用化妆料以及美容方法。
背景技术
一直以来,在化妆品中以制剂的稳定性、使用性的使用感觉的提高作为目的而混配了水溶性增稠剂,根据使用者的用途来调整该增稠剂的种类、混配量、组合。例如,在专利文献1中记载了包含纤维素纳米晶体、和羧基乙烯基聚合物、甲基丙烯酸烷基酯/丙烯酸共聚物、增稠性多糖类这样的水溶性高分子的化妆料。
一般而言如果混配增稠剂,则通过该化妆料的溶剂的挥发而增稠剂浓度上升。因此,起因于增稠剂的发粘显著发生,使用性变差。此外,如果增加增稠剂的混配量,则一般化妆料的触变性增加,因此由于化妆料对容器壁面的附着增加从而使得能够使用的量的减少、发生分配器的吸起不良等。特别是,在采用分配器吸起时,发生化妆料不会连续地吸起而成为混入了空气的断续的排出这样的问题。
化妆料被收容在瓶、管、罐、雾分配器等这样的各种容器形态中,但在开发用水溶性增稠剂进行了调整的化妆品时,除了增稠剂的选择以外还考虑了容器形态的设计是重要的。
另外,一直以来明确了,与常温下的化妆料的使用相比,加温而使用的情况下可获得更高的效果真实感,开始开发加温而使用的化妆料(以下,也称为加温使用化妆料)。在加温使用化妆料中,利用通过温度而物性变化的性质来控制了使用感的具有温度响应性的基剂是适合的。
然而,如果仅仅将以往的化妆料加温而使用,则有时化妆料的粘度下降,在使用中滴落、或有时产生分离等稳定性问题,为了满足使用者可以满足的使用条件,需要选择混配成分、特别是用于调整化妆料的粘度的增稠剂。
作为加温使用化妆料,开发了由水溶性增稠剂进行了调整的化妆料,例如,在专利文献2中记载了通过温度响应性高分子与水溶性增稠剂的组合而调整了使用感的化妆料。
现有技术文献
专利文献
专利文献1:日本特开2017-48181号公报
专利文献2:日本特开2012-240926号公报
发明内容
发明所要解决的课题
专利文献1为了抑制微细纤维素的凝集而制成均匀的化妆料,采用了特定的水溶性高分子,但因为化妆料对容器壁面的附着增加、分配器的吸起不良这样的与容器的关系,不选择增稠剂。
另一方面,在加温使用化妆料的领域中,对具有温度响应性的水溶性增稠剂、和不妨碍其温度响应性而使高温稳定性提高,没有任何研究。
本发明是鉴于上述课题而提出的,第一,目的在于提供通过在干燥时具有被膜性从而使化妆料的发粘消失,并且,在分配器工作时连续地吸起的化妆料。
此外,第二,目的在于提供具有温度响应性,并且高温稳定性高的加温使用化妆料。进一步,目的也在于提供应用加温使用化妆料的美容方法作为目的。
用于解决课题的方法
本发明的化妆料是下述化妆料,其含有:
(A)疏水改性聚醚氨基甲酸酯;
(B)纤维素纳米纤维;以及
(C)水,
(A)疏水改性聚醚氨基甲酸酯与(B)纤维素纳米纤维的混配比率:
在(A)<(B)的情况下,(A)+(B)的混配量相对于全部化妆料为0.75质量%以下,
在(A)=(B)的情况下,(A)+(B)的混配量相对于全部化妆料为1.75质量%以下,
在(A)>(B)的情况下,(A)+(B)的混配量相对于全部化妆料为2质量%以下。
优选(A)疏水改性聚醚氨基甲酸酯为(PEG-240/癸基十四醇聚醚-20/HDI)共聚物(即,PEG-240/HDI共聚物双-癸基十四醇聚醚-20醚(PEG-240/HDI Copolymer Bis-Decyltetradeceth-20Ether))。另外,PEG是聚乙二醇的缩写,HDI是1,6-己二异氰酸酯的缩写。
优选(B)纤维素纳米纤维为最大纤维直径为1000nm以下的微细纤维状纤维素。
优选本发明的化妆料被收容于分配器容器。
本发明的加温使用化妆料是在具有加热部的设备中使用的加温使用化妆料,其含有:
在30℃以上会发生结构变化的温度响应性高分子;
在70℃以下不会发生结构变化的高温稳定性高分子;以及
水。
优选温度响应性高分子为(A)疏水改性聚醚氨基甲酸酯,高温稳定性高分子为(B)纤维素纳米纤维。
优选温度响应性高分子的混配量多于高温稳定性高分子的混配量,并且高温稳定性高分子的混配量相对于全部化妆料为0.1质量%以上。
优选(A)疏水改性聚醚氨基甲酸酯为(PEG-240/癸基十四醇聚醚(Decyltetradeceth)/HDI)共聚物。
优选(B)纤维素纳米纤维为最大纤维直径为1000nm以下的微细纤维状纤维素。
优选本发明的加温使用化妆料在30~70℃的温度条件下使用。
优选加热部的热源为加热器或珀尔帖元件。
设备可以为具备喷雾装置的设备。
设备可以为具备探头的设备。
设备可以为具备收容加温使用化妆料的罐的设备。
本发明的美容方法将上述加温使用化妆料用加热部控制为40~70℃的温度范围而以雾状直接和/或间接地应用于皮肤。
本发明的美容方法将上述加温使用化妆料用加热部控制为30~48℃的温度范围而直接和/或间接地应用于皮肤。
发明的效果
本发明的化妆料是下述化妆料,其含有:
(A)疏水改性聚醚氨基甲酸酯;
(B)纤维素纳米纤维;以及
(C)水,
(A)疏水改性聚醚氨基甲酸酯与(B)纤维素纳米纤维的混配比率:
在(A)<(B)的情况下,(A)+(B)的混配量相对于全部化妆料为0.75质量%以下,
在(A)=(B)的情况下,(A)+(B)的混配量相对于全部化妆料为1.75质量%以下,
在(A)>(B)的情况下,(A)+(B)的混配量相对于全部化妆料为2质量%以下,因此可以赋予被膜性而发粘消失,并且,在分配器工作时连续地吸起。
本发明的加温使用化妆料是在具有加热部的设备中使用的加温使用化妆料,其含有:
在30℃以上会发生结构变化的温度响应性高分子;
在70℃以下不会发生结构变化的高温稳定性高分子;以及
水,
因此可以制成具有温度响应性,并且高温稳定性高的化妆料。
附图说明
图1为显示(A):(B)=100:0的加温使用化妆料的基于加温的弹性模量与应变的关系的图。
图2为显示(A):(B)=75:25的加温使用化妆料的基于加温的弹性模量与应变的关系的图。
图3为显示(A):(B)=50:50的加温使用化妆料的基于加温的弹性模量与应变的关系的图。
图4为显示(A):(B)=25:75的加温使用化妆料的基于加温的弹性模量与应变的关系的图。
图5为显示(A):(B)=0:100的加温使用化妆料的基于加温的弹性模量与应变的关系的图。
具体实施方式
首先,对本发明的化妆料进行说明。本发明的化妆料是下述化妆料,其含有:
(A)疏水改性聚醚氨基甲酸酯(以下也简称为(A));
(B)纤维素纳米纤维(以下也简称为(B));以及
(C)水,
(A)与(B)的混配比率:
在(A)<(B)的情况下,(A)+(B)的混配量相对于全部化妆料为0.75质量%以下,
在(A)=(B)的情况下,(A)+(B)的混配量相对于全部化妆料为1.75质量%以下,
在(A)>(B)的情况下,(A)+(B)的混配量相对于全部化妆料为2质量%以下。
以下,对各成分进行说明。
(A)疏水改性聚醚氨基甲酸酯
(A)疏水改性聚醚氨基甲酸酯为下述式(I)所示的疏水改性聚醚氨基甲酸酯。已知该共聚物为缔合性增稠剂,具有温度响应性。缔合性增稠剂是指为以亲水基部作为骨架,末端具有疏水性部分的共聚物,且在水性介质中共聚物的疏水性部分彼此缔合而显示增稠作用的物质。这样的缔合性增稠剂在水性介质中共聚物的疏水性部分彼此缔合,亲水部形成环状、桥状,显示增稠作用。
在上述式(I)中,R1、R2和R4各自独立地表示碳原子数2~4的亚烷基、或苯基亚乙基。优选为碳原子数2~4的亚烷基。
R3表示可以具有氨基甲酸酯键的碳原子数1~10的亚烷基。
R5表示碳原子数8~36、优选为12~24的直链、支链或仲烷基。
m为2以上的数。优选为2。
h为1以上的数。优选为1。
k为1~500的数。优选为100~300的数。
n为1~200的数。优选为10~100的数。
作为适合例,可举出上述式(I)所示的疏水改性聚醚氨基甲酸酯例如通过使R1-[(O-R2)k-OH]m(其中,R1、R2、k、m如上述定义的那样)所示的1种或2种以上聚醚多元醇、与R3-(NCO)h+1(其中,R3、h如上述定义的那样)所示的1种或2种以上多异氰酸酯、与HO-(R4-O)n-R5(其中,R4、R5、n如上述定义的那样)所示的1种或2种以上聚醚一元醇进行反应而获得的方法。
在该情况下,式(I)中的R1~R5通过所使用的R1-[(O-R2)k-OH]m、R3-(NCO)h+1、HO-(R4-O)n-R5来决定。上述3者的加入比没有特别限定,但来源于聚醚多元醇和聚醚一元醇的羟基、与来源于多异氰酸酯的异氰酸酯基的比优选为NCO/OH=0.8:1~1.4:1。
上述式R1-[(O-R2)k-OH]m所示的聚醚多元醇化合物通过使亚乙基氧化物、亚丙基氧化物、亚丁基氧化物、表氯醇等亚烷基氧化物、苯乙烯氧化物等与m元多元醇进行加聚而形成。
这里作为多元醇,优选为2~8元的多元醇,可举出例如乙二醇、丙二醇、丁二醇、1,6-己二醇、新戊二醇等2元醇;甘油、三羟基异丁烷、1,2,3-丁三醇、1,2,3-戊三醇、2-甲基-1,2,3-丙三醇、2-甲基-2,3,4-丁三醇、2-乙基-1,2,3-丁三醇、2,3,4-戊三醇、2,3,4-己三醇、4-丙基-3,4,5-庚三醇、2,4-二甲基-2,3,4-戊三醇、五甲基甘油、三羟甲基乙烷(pentaglycerine)、1,2,4-丁三醇、1,2,4-戊三醇、三羟甲基乙烷、三羟甲基丙烷等3元醇;季戊四醇、1,2,3,4-戊四醇、2,3,4,5-己四醇、1,2,4,5-戊四醇、1,3,4,5-己四醇等4元醇;阿东糖醇、阿拉伯糖醇、木糖醇等5元醇;二季戊四醇、山梨糖醇、甘露糖醇、艾杜糖醇等6元醇;蔗糖等8元醇等。
此外,通过加成的亚烷基氧化物、苯乙烯氧化物等来决定R2,但特别是为了容易获得,发挥优异的效果,优选为碳原子数2~4的亚烷基氧化物或苯乙烯氧化物。
加成的亚烷基氧化物、氧化苯乙烯等可以为均聚、2种以上的无规聚合或嵌段聚合。加成的方法可以为通常的方法。聚合度k为1~500。亚乙基在R2中所占的比例优选为全部R2的50~100质量%。
R1-[(O-R2)k-OH]m的分子量优选为500~10万,特别优选为1000~5万。
上述式R3-(NCO)h+1所示的多异氰酸酯只要在分子中具有2个以上异氰酸酯基,就没有特别限定。可举出例如,脂肪族二异氰酸酯、芳香族二异氰酸酯、脂环族二异氰酸酯、联苯二异氰酸酯、苯基甲烷的二-、三-、四异氰酸酯等。
作为脂肪族二异氰酸酯,可举出例如,二异氰酸亚甲酯、乙二异氰酸酯、丙二异氰酸酯、丁二异氰酸酯、戊二异氰酸酯、己二异氰酸酯、二丙基醚二异氰酸酯、2,2-二甲基戊烷二异氰酸酯、3-甲氧基己烷二异氰酸酯、辛二异氰酸酯、2,2,4-三甲基戊烷二异氰酸酯、壬二异氰酸酯、癸二异氰酸酯、3-丁氧基己烷二异氰酸酯、1,4-丁二醇二丙基醚二异氰酸酯、硫代二己基二异氰酸酯、间苯二亚甲基二异氰酸酯、对苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯等。
作为芳香族二异氰酸酯,可举出例如,间苯撑二异氰酸酯、对苯撑二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、二甲基苯二异氰酸酯、乙基苯二异氰酸酯、异丙基苯二异氰酸酯、联甲苯胺二异氰酸酯、1,4-萘二异氰酸酯、1,5-萘二异氰酸酯、2,6-萘二异氰酸酯、2,7-萘二异氰酸酯等。
作为脂环族二异氰酸酯,可举出例如,氢化苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯等。
作为联苯二异氰酸酯,可举出例如,联苯二异氰酸酯、3,3’-二甲基联苯二异氰酸酯、3,3’-二甲氧基联苯二异氰酸酯等。
作为苯基甲烷的二异氰酸酯,可举出例如,二苯基甲烷-4,4’-二异氰酸酯、2,2’-二甲基二苯基甲烷-4,4’-二异氰酸酯、二苯基二甲基甲烷-4,4’-二异氰酸酯、2,5,2’,5’-四甲基二苯基甲烷-4,4’-二异氰酸酯、环己基双(4-异氰酸酯基苯基)甲烷、3,3’-二甲氧基二苯基甲烷-4,4’-二异氰酸酯、4,4’-二甲氧基二苯基甲烷-3,3’-二异氰酸酯、4,4’-二乙氧基二苯基甲烷-3,3’-二异氰酸酯、2,2’-二甲基-5,5’-二甲氧基二苯基甲烷-4,4’-二异氰酸酯、3,3’-二氯二苯基二甲基甲烷-4,4’-二异氰酸酯、二苯甲酮-3,3’-二异氰酸酯等。
作为苯基甲烷的三异氰酸酯,可举出例如,1-甲基苯-2,4,6-三异氰酸酯、1,3,5-三甲基苯-2,4,6-三异氰酸酯、1,3,7-萘三异氰酸酯、联苯-2,4,4’-三异氰酸酯、二苯基甲烷-2,4,4’-三异氰酸酯、3-甲基二苯基甲烷-4,6,4’-三异氰酸酯、三苯基甲烷-4,4’,4”-三异氰酸酯、1,6,11-十一烷三异氰酸酯、1,8-二异氰酸酯-4-异氰酸酯甲基辛烷、1,3,6-己三异氰酸酯、二环庚烷三异氰酸酯、三(异氰酸酯苯基)硫代磷酸酯等。
此外,可以以这些多异氰酸酯化合物的二聚体、三聚体(异氰脲酸酯键)使用,此外,也可以使其与胺反应而作为缩二脲使用。
进一步,也可以使用使这些多异氰酸酯化合物、与多元醇反应了的具有氨基甲酸酯键的多异氰酸酯。作为多元醇,优选为2~8元的多元醇,优选为上述多元醇。另外,在使用3元以上的多异氰酸酯作为R3-(NCO)h+1的情况下,优选为该具有氨基甲酸酯键的多异氰酸酯。
上述式HO-(R4-O)n-R5所示的聚醚一元醇只要是直链和支链或仲1元醇的聚醚,就没有特别限定。这样的化合物可以通过将亚乙基氧化物、亚丙基氧化物、亚丁基氧化物、表氯醇等亚烷基氧化物、苯乙烯氧化物等与直链和支链或仲1元醇进行加聚来获得。
这里所谓直链醇,由下述式(II)表示。
R6-OH(II)
此外,这里所谓支链醇,由下述式(III)表示。
此外,所谓仲醇,由下述式(IV)表示。
因此,R5为在上述式(II)~(IV)中除去了羟基的基团。在上述式(II)~(IV)中R6、R7、R8、R10和R11为烃基或氟碳基,例如为烷基、烯基、烷基芳基、环烷基、环烯基等。
作为烷基,可举出例如,甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、异戊基、新戊基、叔戊基、己基、庚基、辛基、2-乙基己基、壬基、癸基、十一烷基、十二烷基、十三烷基、异十三烷基、肉豆蔻基、棕榈基、硬脂基、异硬脂基、二十烷基、二十二烷基、二十四烷基、三十烷基、2-辛基十二烷基、2-十二烷基十六烷基、2-十四烷基十八烷基、单甲基支链-异硬脂基等。
作为烯基,可举出例如,乙烯基、烯丙基、丙烯基、异丙烯基、丁烯基、戊烯基、异戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、十四碳烯基、油基等。
作为烷基芳基,可举出苯基、甲苯甲酰、二甲苯基、枯烯基、2,4,6-三甲苯基、苄基、苯乙基、苯乙烯基、肉桂基、二苯甲基、三苯甲基、乙基苯基、丙基苯基、丁基苯基、戊基苯基、己基苯基、庚基苯基、辛基苯基、壬基苯基、α-萘基、β-萘基等。
作为环烷基、环烯基,可举出例如,环戊基、环己基、环庚基、甲基环戊基、甲基环己基、甲基环庚基、环戊烯基、环己烯基、环庚烯基、甲基环戊烯基、甲基环己烯基、甲基环庚烯基等。
在上述式(III)中,R9为烃基、或氟化碳基,例如为亚烷基、亚烯基、烷基亚芳基、亚环烷基、亚环烯基等。
此外,R5为烃基或氟化碳基,其中优选为烷基,进一步其合计的碳原子数优选为8~36,特别优选为12~24。
此外,加成的亚烷基氧化物、苯乙烯氧化物等可以为均聚、2种以上的无规聚合或嵌段聚合。加成的方法可以为通常的方法。聚合度n为0~1000,优选为1~200,进一步优选为10~200为好。此外,如果亚乙基在R4中所占的比例优选为全部R4的50~100质量%,进一步优选为65~100质量%,则可获得对于本发明的目的良好的缔合性增稠剂。
作为制造上述式(I)所示的共聚物的方法,与通常的聚醚与异氰酸酯的反应同样地操作,例如,可以在80~90℃下加热1~3小时,使其反应而获得。
此外,在使R1-[(O-R2)k-OH]m所示的聚醚多元醇(a)、与R3-(NCO)h+1所示的多异氰酸酯(b)、与HO-(R4-O)n-R5所示的聚醚一元醇(c)反应的情况下,有时也副生除式(I)的结构的共聚物以外的物质。例如,在使用了二异氰酸酯的情况下,作为主生成物,生成式(I)所示的c-b-a-b-c型的共聚物,但此外,有时副生c-b-c型、c-b-(a-b)x-a-b-c型等的共聚物。在该情况下,特别是可以不将式(I)型的共聚物分离,而在包含式(I)型的共聚物的混合物的状态下使用于本发明。
作为特别优选的例子,可举出INCI名称为“PEG-240/HDI共聚物双-癸基十四醇聚醚-20醚(PEG-240/HDI COPOLYMER BISDECYLTETRADECETH-20ETHER)”的疏水改性聚醚氨基甲酸酯。该共聚物作为商品名“アデカノールGT-700”由株式会社ADEKA市售。
(B)纤维素纳米纤维
纤维素纳米纤维是指将来源于植物细胞壁的纤维素纤维进行分丝直到纳米级的纤维,优选为最大纤维直径为1000nm以下的微细纤维状纤维素。更详细而言,优选为数均纤维直径为2~100nm的纤维素纤维,且该纤维素具有纤维素I型晶体结构,并且纤维素分子中的葡萄糖单元的C6位的羟基被选择性地氧化而被改性为醛基或羧基,羧基的量为0.6~2.2mmol/g的微细的纤维素纤维。这是指上述纤维素纤维为将具有I型晶体结构的天然来源的纤维素固体原料进行表面氧化而微细化了的纤维。即,在天然纤维素的生物合成的过程中,几乎没有例外地首先形成被称为微原纤的纳米纤维,它们多束化而构成高级的固体结构,但为了减弱成为上述微原纤间的强凝集力的原动力的表面间的氢键,该羟基的一部分被氧化而被转变为醛基和羧基。
这里,构成纤维素纳米纤维的纤维素具有I型晶体结构,例如,可以由在通过广角X射线衍射图像测定而获得的衍射图谱中,在2θ=14~17°附近、与2θ=22~23°附近的2个位置具有典型的峰来鉴定。
此外,纤维素纳米纤维的最大纤维直径为1000nm以下,并且数均纤维直径为2~100nm,从分散稳定性方面考虑,优选数均纤维直径为3~80nm。即,通过上述数均纤维直径为2nm以上,从而可以更加抑制溶解于分散介质,通过数均纤维直径为100nm以下,从而可以抑制纤维素纤维的沉降,使由混配纤维素纤维带来的功能性充分表现。此外,同样地,通过使最大纤维直径为1000nm以下,从而可以抑制纤维素纤维的沉降,使由混配纤维素纤维带来的功能性充分表现。
纤维素纳米纤维的数均纤维直径和最大纤维直径,例如,可以如以下那样操作而测定。即,在纤维素纤维中加入水,使纤维素的固体成分为1质量%。将其使用超声波均化器、高压均化器、具有旋转速度15,000rpm以上的能力的搅拌器等进行了分散后,通过冷冻干燥而调制试样。可以将其通过扫描型电子显微镜(SEM)等进行观察,由所得的图像测定纤维素纤维的数均纤维直径和最大纤维直径而算出。
纤维素纳米纤维优选纤维素分子中的葡萄糖单元的C6位的羟基被选择性地氧化而被改性为醛基或羧基,羧基的量为0.6~2.2mmol/g。进一步,从保形性能、分散稳定性方面考虑,特别优选为0.6~2.0mmol/g的范围。即,通过上述羧基量为0.6mmol/g以上,从而使纤维素纤维的分散稳定性更良好,可以抑制沉降,通过羧基量为2.2mmol/g以下,从而可以适当保持水溶性而抑制发粘了的使用感。
纤维素纳米纤维的羧基量的测定,例如,可以通过电位滴定进行。即,使进行了干燥的纤维素纤维分散于水,加入0.01N的氯化钠水溶液,充分地搅拌而使纤维素纤维分散。接着,可以加入0.1N的盐酸溶液直到变为pH2.5~3.0,将0.04N的氢氧化钠水溶液以每分钟0.1ml的速度滴加,从所得的pH曲线由过剩的盐酸的中和点、与来源于该纤维素纤维的羧基的中和点之差算出羧基量。
另外,羧基量的调整如后述那样,可以通过控制在纤维素纤维的氧化工序中使用的共氧化剂的添加量、反应时间来进行。
纤维素纳米纤维优选仅纤维素纤维表面上的葡萄糖单元的C6位的羟基选择性地被氧化为醛基或羧基。是否仅该纤维素纤维表面上的葡萄糖单元的C6位的羟基被选择性地氧化为醛基或羧基,可以通过例如13C-NMR图来确认。即,在氧化前的纤维素的13C-NMR图中可以确认的相当于葡萄糖单元的伯羟基的C6位的62ppm的峰在氧化反应后消失,取而代之在178ppm出现来源于羧基的峰。这样操作可以确认仅葡萄糖单元的C6位羟基被氧化为醛基或羧基。
纤维素纳米纤维例如可以如以下那样操作而制作。即,首先,在使针叶树浆粕等天然纤维素分散于水而制成浆状的物质中,加入溴化钠、N-氧基自由基催化剂,进行充分搅拌使其分散、溶解。接着,加入次氯酸水溶液等共氧化剂,一边以保持pH10.5的方式滴加0.5N氢氧化钠水溶液一边进行反应直到未见pH变化。通过上述反应而获得的浆料为了除去未反应原料、催化剂等,通过进行水洗、过滤来精制,可以获得作为目标物质的、纤维表面被氧化了的特定的纤维素纤维的水分散体。另外,在作为化妆料而要求更高透明性的情况下,通过使用高压均化器、超高压均化器等具有强力分散力的分散装置进行处理,从而可以获得具有良好的透明性的化妆料。
作为上述N-氧基自由基催化剂,可举出例如,2,2,6,6-四甲基哌啶子基氧基自由基(TEMPO)、4-乙酰胺-TEMPO等。上述N-氧基自由基催化剂的添加为催化剂量就是充分的,优选为以0.1~4mmol/l,进一步优选以0.2~2mmol/l的范围添加于反应水溶液。
此外,作为上述共氧化剂,可举出例如,次卤酸或其盐、亚卤酸或其盐、高卤酸或其盐、过氧化氢、过有机酸等。它们单独使用或将二种以上并用。其中,优选为次氯酸钠、次溴酸钠等碱金属次卤酸盐。进而,在使用上述次氯酸钠的情况下,在溴化钠等溴化碱金属的存在下进行反应在反应速度方面是优选的。上述溴化碱金属的添加量相对于上述N-氧基自由基催化剂为约1~40倍摩尔量,优选为约10~20倍摩尔量。
另外,纤维素纳米纤维可以使用市售品,例如,作为商品名“レオクリスタC-2SP”,可以举出由第一工业制药株式会社市售的物质。
(A)成分与(B)成分的混配比率在(A)<(B)的情况下,(A)+(B)的混配量相对于全部化妆料为0.75质量%以下,在(A)=(B)的情况下,(A)+(B)的混配量相对于全部化妆料为1.75质量%以下,在(A)>(B)的情况下,(A)+(B)的混配量相对于全部化妆料为2质量%以下。通过(A)+(B)的混配量相对于全部化妆料分别为上述数值以下,从而可以制成在干燥时赋予被膜性从而化妆料的发粘消失,并且,在分配器工作时连续地吸起的化妆料。
(A)成分与(B)成分的混配比率在(A)<(B)的情况下,(A)+(B)的混配量相对于全部化妆料更优选为0.01~0.75质量%的范围,更优选为0.1~0.5质量%的范围。在(A)=(B)的情况下,(A)+(B)的混配量相对于全部化妆料更优选为0.02~1.75质量%的范围,更优选为0.2~1.5质量%的范围。在(A)>(B)的情况下,(A)+(B)的混配量相对于全部化妆料更优选为0.02~2质量%的范围,更优选为0.2~1.75质量%的范围。
本发明的化妆料在分配器工作时连续地吸起,因此可以作为收容于分配器容器的形态而适合使用。另外,分配器容器是通过不将容器倾斜而将设置于头部的按钮进行按压操作,从而每次取出规定量的容器内容物的容器。
接着,对本发明的加温使用化妆料进行说明。本发明的加温使用化妆料是在具有加热部的设备中使用的加温使用化妆料,其含有:
在30℃以上会发生结构变化的温度响应性高分子;
在70℃以下不会发生结构变化的高温稳定性高分子;以及
水。
以下,对各成分进行说明。
(在30℃以上会发生结构变化的温度响应性高分子)
在30℃以上会发生结构变化的温度响应性高分子(以下,也简称为温度响应性高分子)是指在30℃以上的温度下由高分子制成的结构体溶胀收缩。特别是指发生高分子的分子内、或分子间的疏水键增强而聚合物链凝集的结构变化的高分子。通过包含温度响应性高分子,可以发生由加温引起的化妆料的粘度降低。温度响应性高分子的会发生结构变化的温度范围更优选为30℃以上且小于80℃。
优选温度响应性高分子为(A)疏水改性聚醚氨基甲酸酯,其详细内容与上述同样。
(在70℃以下不会发生结构变化的高温稳定性高分子)
在70℃以下不会发生结构变化的高温稳定性高分子(以下,也简称为高温稳定性高分子)是指在70℃以下的温度下由高分子制成的结构体不溶胀收缩。特别是指在70℃以下的温度下该分子内、或分子间的凝集不发生而不会发生结构变化的高分子。通过包含高温稳定性高分子,从而没有由加温引起的化妆料的粘度降低,在使用中不会滴落、或分离,可以确保稳定性。高温稳定性高分子的不会发生结构变化的温度范围更优选为30℃以上且小于70℃。
优选高温稳定性高分子为(B)纤维素纳米纤维,其详细内容与上述同样。
通过将温度响应性高分子与高温稳定性高分子并用,从而可以调制在加温前后确保高温稳定性的同时也进行温度响应的加温使用化妆料。特别是,在加温前为各个高分子的物性被相加了的状态,但在加温后主要表现高温稳定性高分子的物性。因此,可以制成赋予由加温引起的变化,也同时可以确保高温稳定性的化妆料。
优选温度响应性高分子的混配量多于高温稳定性高分子的混配量,并且高温稳定性高分子的混配量相对于全部化妆料为0.1质量%以上。更优选为0.1~1质量%的范围。通过高温稳定性高分子的混配量为0.1质量%以上,从而可以使由混配高温稳定性高分子带来的增稠机制充分表现。
本发明的加温使用化妆料优选在30~70℃的温度条件下,更优选在36~66℃的温度条件下使用。通过在30~70℃的温度条件下使用,从而可以获得化妆料的高效果真实感。此外,本发明的加温使用化妆料由于将温度响应性高分子与高温稳定性高分子并用,因此即使加温,化妆料在使用中也不滴落,可以抑制分离。
使用本发明的加温使用化妆料的设备的加热部的热源没有特别限定,但优选为加热器或珀尔帖元件等。
使用加温使用化妆料的设备没有特别限定,可举出具备喷雾装置的设备,例如,安装了在将容器的内部保持于大气压的状态下能够喷雾的泵式喷嘴的分配器式喷雾器、将喷射剂填充在容器内的气雾剂式喷雾器、使网孔以高频率振动的超声波式喷雾器、使液柱从液面生成的超声波式喷雾器、使其它液体混合于化妆料的多流体混合式喷雾器(无论设备的内部、外部的混合)、通过由静电脉冲带来的冲击进行雾化的静电式喷雾器、从针尖用空气流进行雾化的气刷式喷雾器等。此外,可举出作为美容沙龙、美容医疗领域、家庭用美容设备等而使用的具备对皮肤的加温用温热探头的设备、具备收容加温使用化妆料的罐的设备、此外将该罐加温的设备等。
本发明的加温使用化妆料在用上述设备具体为美容沙龙、美容医疗领域、家庭用美容设备将化妆料以雾状直接和/或间接地应用于皮肤的情况下,可以应用于将化妆料控制为40~70℃的温度范围而使用的美容方法。此外,本发明的加温使用化妆料可以用于通过上述设备具体为加温用温热探头将化妆料控制为30~48℃的温度范围而直接和/或间接地应用于皮肤的美容方法。
这里,所谓间接地,是指在应用上述设备、加温使用化妆料的情况下,经由其以外的化妆料、化妆用具等而应用于皮肤,可举出例如,使加温后的加温使用化妆料包含于棉而应用于肌肤。
在本发明的化妆料和加温使用化妆料中可以混配通常混配于化妆料的成分,可举出水性成分、油性成分、粉末等。此外,本发明的化妆料和加温使用化妆料将水性成分作为主要的分散介质而构成,可以具有乳化结构。
作为水性成分,可举出水、水溶性成分等。作为水溶性成分,可举出例如低级醇、保湿剂、水溶性高分子(天然、半合成、合成、无机)等。另外,水溶性高分子是指不是增稠目的的物质。
作为低级醇,可例示乙醇、丙醇、丁醇、戊醇、己醇等。
作为保湿剂,可例示甘油,二甘醇、丁二醇、聚乙二醇、己二醇、木糖醇、山梨糖醇、麦芽糖醇、硫酸软骨素、透明质酸、硫酸粘液素、卡洛宁酸、缺端胶原、弹性蛋白、氨基酸、核酸、胆甾烯基-12-羟基硬脂酸酯、乳酸钠、胆汁酸盐、dl-吡咯烷酮羧酸盐、短链可溶性胶原、双甘油(EO)PO加成物、缫丝花提取物、蓍提取物、草木犀提取物等。另外,EO是氧化乙烯的缩写,PO是氧化丙烯的缩写。
作为天然的水溶性高分子,可例示阿拉伯树胶、黄蓍胶、半乳聚糖、瓜尔豆胶、刺槐豆胶、罗望子胶、角豆胶、刺梧桐树胶、角叉菜聚糖、果胶、琼脂、榅桲籽(榅桲)、海藻胶(褐藻提取物)、淀粉(米、玉米、马铃薯、小麦)、甘草酸等植物系水溶性高分子;黄原酸胶、葡聚糖、琥珀酰聚糖、普鲁兰糖等微生物系水溶性高分子;胶原、酪蛋白、白蛋白、明胶等动物系水溶性高分子等。
作为半合成水溶性高分子,可例示羧基甲基淀粉、甲基羟基丙基淀粉等淀粉系水溶性高分子;甲基纤维素、硝酸纤维素、乙基纤维素、甲基羟基丙基纤维素、羟基乙基纤维素、纤维素硫酸钠、羟基丙基纤维素、羧基甲基纤维素(CMC)、结晶纤维素、纤维素末等纤维素系水溶性高分子;藻酸钠、藻酸丙二醇酯等藻酸系水溶性高分子等。
作为合成水溶性高分子,可例示聚乙烯醇、聚乙烯基甲基醚、聚乙烯吡咯烷酮、羧基乙烯基聚合物(カーボポール)等乙烯基系水溶性高分子;聚乙二醇20,000、聚乙二醇4,000,000、聚乙二醇600,000等聚氧乙烯系水溶性高分子;聚氧乙烯聚氧丙烯共聚物等共聚系水溶性高分子;聚丙烯酸钠、聚丙烯酸乙酯、聚丙烯酰胺等丙烯酸系水溶性高分子、以及聚乙烯亚胺、阳离子聚合物等。
作为无机的水溶性高分子,可例示膨润土、硅酸AlMg(ビーガム)、合成锂皂石、锂蒙脱石、硅酸酐等。
作为粉末成分,可以使用疏水性粉末、亲水性粉末中的任一者。此外,不仅粉末本身为疏水性、亲水性的物质,而且可以将粉末表面进行疏水化、亲水化的处理。
作为粉末成分,可举出例如滑石、高岭土、云母、绢云母(sericite)、白云母、金云母、合成云母、红云母、黑云母、锂云母、蛭石、碳酸镁、碳酸钙、硅酸铝、硅酸钡、硅酸钙、硅酸镁、硅酸锶、钨酸金属盐、镁、二氧化硅、沸石、硫酸钡、烧成硫酸钙(烧石膏)、磷酸钙、氟磷灰石、羟基磷灰石、陶瓷粉末、金属皂(肉豆蔻酸锌、棕榈酸钙、硬脂酸铝等)、聚酰胺树脂粉末(尼龙粉末)、聚乙烯粉末、聚甲基丙烯酸甲酯粉末、聚苯乙烯粉末、苯乙烯与丙烯酸的共聚物树脂粉末、苯胍胺树脂粉末、聚四氟乙烯粉末、纤维素粉末等有机粉末、三甲基倍半硅氧烷粉末等有机硅粉末、氮化硼等无机粉末;二氧化钛、氧化锌等无机白色颜料;氧化铁(氧化铁红)、钛酸铁等无机红色系颜料;γ-氧化铁等无机褐色系颜料;氧化铁黄、黄土等无机黄色系颜料;氧化铁黑、炭黑、低价二氧化钛等无机黑色系颜料;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、藏青等无机蓝色系颜料;二氧化钛被覆云母、二氧化钛被覆氯氧化铋、二氧化钛被覆滑石、着色二氧化钛被覆云母、氯氧化铋、珠光石等珠光颜料;铝粉末、铜粉末等金属粉末颜料等。
作为将这些粉末成分进行疏水化处理的方法,作为疏水化处理方法,只要是可以赋予拨水性的方法,就可以为任何方法,该方法不限,可以使用例如气相法、液相法、高压釜法、机械化学法等通常的表面处理方法。作为疏水化处理剂,没有特别限定,可举出脂肪酸糊精处理粉末、三甲基甲硅烷氧基硅酸处理粉末、氟改性三甲基甲硅烷氧基硅酸处理粉末、甲基苯基甲硅烷氧基硅酸处理粉末、氟改性甲基苯基甲硅烷氧基硅酸处理粉末、二甲基聚硅氧烷、二苯基聚硅氧烷、甲基苯基聚硅氧烷等低粘度~高粘度油状聚硅氧烷处理粉末、胶状聚硅氧烷处理粉末、甲基含氢聚硅氧烷处理粉末、氟改性甲基含氢聚硅氧烷处理粉末、由甲基三氯硅烷、甲基三烷氧基硅烷、六甲基乙硅烷、二甲基二氯硅烷、二甲基二烷氧基硅烷、三甲基氯硅烷三甲基烷氧基硅烷等有机甲硅烷基化合物或它们的氟取代体得到的处理粉末、由乙基三氯硅烷、乙基三烷氧基硅烷、丙基三氯硅烷、丙基三烷氧基硅烷、己基三氯硅烷、己基三烷氧基硅烷、长链烷基三氯硅烷、长链烷基三乙氧基硅烷等有机改性硅烷或它们的氟取代体得到的处理粉末、氨基改性聚硅氧烷处理粉末、氟改性聚硅氧烷处理粉末、氟化烷基磷酸处理粉末等。
混配于本发明的化妆料和加温使用化妆料的油性成分只要是通常能够混配于化妆料的油性成分,就没有特别限定,可举出例如,油脂、蜡类、烃油、高级脂肪酸、高级醇、合成酯油、硅油等。
作为油脂,可例示鳄梨油、山茶油、月见草油、海龟油、澳洲坚果油、玉米糠油、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、亚麻子油、红花油、棉籽油、紫苏油、豆油、花生油、茶籽油、榧子油、米糠油、白桐油、日本桐油、霍霍巴油、胚芽油、三甘油、三辛酸甘油酯、三异棕榈酸甘油酯等液体油脂;可可脂、椰子油、马脂、硬化椰子油、棕榈油、牛脂、羊脂、硬化牛脂、棕榈仁油、猪脂、牛骨脂、木蜡仁油、硬化油、牛脚脂、木蜡、硬化蓖麻油等固体油脂等。
作为蜡类,可例示蜂蜡、小烛树蜡、棉蜡、巴西棕榈蜡、杨梅蜡、虫白蜡、鲸蜡、褐煤蜡、米糠蜡、羊毛脂、木棉蜡、乙酸羊毛脂、液体羊毛脂、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、紫胶蜡、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酯、POE加氢羊毛脂醇醚等。另外,POE是聚氧乙烯的缩写。
作为烃油,可例示液体石蜡、地蜡、角鲨烯、姥鲛烷、石蜡、纯地蜡、角鲨烯、凡士林、微晶蜡等。
作为高级脂肪酸,可例示月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山(山/>)酸、油酸、12-羟基硬脂酸、十一碳烯酸、妥尔油酸、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,可例示月桂醇、鲸蜡醇、硬脂醇、山醇、肉豆蔻醇、油醇、十六醇十八醇混合物等直链醇;单硬脂基甘油醚(鲨肝醇)、2-癸基十四醇、羊毛脂醇、胆固醇、植物甾醇、己基十二烷醇、异硬脂醇、辛基十二烷醇等支链醇等。
作为合成酯油,可例示肉豆蔻酸异丙酯、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、乙酸羊毛脂酯、硬脂酸异鲸蜡基酯、异硬脂酸异鲸蜡基酯、12-羟基硬脂基酸胆甾醇酯、二-2-乙基己基酸乙二醇酯、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-乙基己基酸三羟甲基丙烷酯、三异硬脂酸三羟甲基丙烷酯、四-2-乙基己基酸季戊四醇酯、三-2-乙基己基酸甘油酯、三异硬脂酸三羟甲基丙烷酯、鲸蜡基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、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、乙酸乙酯、乙酸丁酯、乙酸戊酯、柠檬酸三乙酯、克罗米通(C13H17NO)等。
作为硅油,可例示二甲基聚硅氧烷、甲基苯基聚硅氧烷、甲基含氢聚硅氧烷等链状聚硅氧烷;十甲基聚硅氧烷、十二甲基聚硅氧烷、四甲基四含氢聚硅氧烷等环状聚硅氧烷;形成了3维网状结构的硅树脂、硅橡胶等。
在乳化剂中,可以混配一般可以混配于水包油型的乳化化妆料的乳化剂。作为这样的乳化剂,在本发明中由HLB8以上的1种或2种以上构成的物质是适合的。混配例如选自甘油或聚甘油脂肪酸酯类、丙二醇脂肪酸酯类、POE失水山梨糖醇脂肪酸酯类、POE山梨糖醇脂肪酸酯类、POE甘油脂肪酸酯类、POE脂肪酸酯类、POE烷基醚类、POE烷基苯基醚类、POE/POP烷基醚类、POE蓖麻油或硬化蓖麻油衍生物、POE蜂蜡/羊毛脂衍生物、链烷醇酰胺类、POE丙二醇脂肪酸酯类、POE烷基胺、POE脂肪酸酰胺类中的1种或2种以上。
作为除上述例示的成分以外的其它可混配成分,可举出例如,防腐剂(对羟基苯甲酸乙酯、对羟基苯甲酸丁酯等);消炎剂(例如,甘草酸衍生物、甘草次酸衍生物、水杨酸衍生物、扁柏酚、氧化锌、尿囊素等);美白剂(例如,虎耳草提取物、熊果苷等);各种提取物(例如,黄柏、黄连、紫草根、芍药、当药、桦树(birch)、鼠尾草、枇杷、胡萝卜、芦荟、锦葵、鸢尾草、葡萄、薏苡仁、丝瓜、百合、藏红花、川芎、生姜、小连翘、芒柄花、蒜、辣椒、陈皮、当归、海藻等)、活化剂(例如,蜂王浆、感光素、胆固醇衍生物等);血液循环促进剂(例如,壬酸香草酰胺、烟酸苄酯、烟酸β-丁氧基乙酯、辣椒素、姜油酮、斑蝥酊、鱼石脂、单宁酸、α-冰片(龙脑)、生育酚烟酸酯、六烟酸肌醇酯、环扁桃酯、桂利嗪、妥拉唑啉、乙酰胆碱、维拉帕米、千金藤素、γ-谷维素等);抗脂溢剂(例如,硫黄、二甲硫蒽等);抗炎药(例如,氨甲环酸、硫代牛磺酸、亚牛磺酸等)等;紫外线吸收剂等。但是不限定于这些例示。
实施例
以下举出实施例进一步具体地说明本发明,但本发明不受此任何限定。混配量只要没有特别记载,就全部是质量%。
另外在本实施例中,(A)和(B)使用了下述化合物。
(A):疏水改性聚醚氨基甲酸酯:使用了上述式(I)所示的共聚物(其中在式中,R1、R2、R4分别为亚乙基,R3=1,6-亚己基,R5=2-十二烷基十二烷基,h=1,m=2,k=120,n=20)((PEG-240/癸基十四醇聚醚-20/HDI)共聚物:“アデカノールGT-700”;株式会社ADEKA制)。
(B):纤维素纳米纤维:使用了最大纤维直径为1000nm以下的微细纤维状纤维素(“レオクリスタC-2SP”;第一工业制药株式会社制)。另外,レオクリスタC-2SP是在97质量%的水中包含2质量%的微细纤维状纤维素、1质量%的苯氧基乙醇(防腐剂)的制品,本说明书和表所记载的质量%是指仅微细纤维状纤维素,不包含商品所包含的水、防腐剂。
[关于化妆料的实施例]
相对于总量,以仅(A)、(A)与(B)、和仅(B)分别成为2质量%、1.75质量%、0.75质量%的方式,以表4所示的处方混配化妆料,并且在各个浓度下,以(A)与(B)的混配比率成为下述表1~3所示的比率的方式调制,进行了下述被膜试验、分配器试验。将评价结果示于表1~3中。
(被膜试验)
通过以下基准判断了在φ50mm玻璃制培养皿中滴加各混配条件的样品10g,在使表面为平面的状态下在50℃下放置了24小时后的样品的状态。
A:从培养皿作为固体而能够剥落样品
C:具有粘着性而不能从培养皿剥落样品
(分配器试验)
通过以下基准判断了用0.7ml排出的分配器将各混配条件的样品的连续排出。
A:不混入空气而可以连续地排出
B:通过5次以内的按压操作而可以连续地排出
C:只能断续地排出
表1
表2
表3
表4
由被膜试验可知如果混配(B)则发粘被抑制。这是在表1所示的(A)单独的2质量%混配样品中得不到的结果。此外,由分配器试验可知(A)的混配比率越高则即使将(A)和(B)高混配也可以排出。相反在(B)的混配比率高的情况下排出变得困难。这意味着通过(B)的混配而化妆料接近于不连续体,即,弹性体。因此可知,通过将(A)与(B)组合,从而即使(A)为高混配,也可以制成没有发粘,并且,分配器能够排出的制剂。
即,其组合:
在(A)<(B)的情况下,(A)+(B)的混配量相对于全部化妆料为0.75质量%以下,
在(A)=(B)的情况下,(A)+(B)的混配量相对于全部化妆料为1.75质量%以下,
在(A)>(B)的情况下,(A)+(B)的混配量相对于全部化妆料为2质量%以下成为适当的值。
[关于加温使用化妆料的实施例]
相对于总量,以仅(A)、(A)和(B)、和仅(B)成为1质量%的方式,以表4所示的处方混配化妆料,并且以(A)与(B)的混配比率成为下述表5所示的比率的方式调制。关于调制出的各样品,使用アントンパール社制,应力控制型流变仪MCR301进行了动态粘弹性测定。测定条件是用φ25mm锥板使温度为30℃、60℃,测定了使应变从0.01上升直到5000时的储能弹性模量G’和损耗弹性模量G”。
一般而言在G’>G”的情况下(G”/G’=1以下的情况下)被认为是固体性质占优势的物性,在G”>G’的情况下(G”/G’=1以上的情况下)被认为是液体性质占优势的物性。特别是,由于应变小的情况下的性质有助于滴落、分离的稳定性,因此由应变值为1时的物性值判断。
将结果示于表5和图1~5中。另外,如图1的图下所记载地那样,在图1~5的图中,●表示30℃下G’,○表示30℃下的G”,▲表示60℃下的G’,△表示60℃下的G”。
/>
在仅(A)(=温度响应性高分子)的情况下,如果温度从30℃加温到60℃则弹性模量下降,损耗弹性模量G”优势变得显著(图1)。另一方面,在仅(B)(=纤维素纳米纤维)的情况下,在加温前后没有弹性模量的变化,该储能弹性模量G’显示高值(图5)。在(B)>(A)的情况下,(B)的物性占统治地位,在保持高弹性模量的状态下,在加温前后弹性模量的变化小(图4)。在(A)>(B)的情况下,在加温时弹性模量下降,并且,在高温时储能弹性模量G’也高而维持了固体性质(图2)。在(A)=(B)的情况下,在加温前后没有弹性模量的变化(图3)。由以上结果可知,为了控制在加温时粘度变化的使用感,同时使该温度稳定性更好,更优选如(A)>(B)那样,在加温时弹性模量下降,并且,在低的应变值下G’>G”。
(水分散化妆料的处方例)
以表6所示的处方,将除离子交换水以外的成分溶解、分散于离子交换水而制作出水分散化妆料的处方例1~12。
(乳化化妆料的处方例)
以表7所示的处方,将油性成分、水性成分分别溶解、混合后,在水性成分中混合油性成分使其乳化,制作出乳化化妆料的处方例1~5。
表7
(粉末混配化妆料的处方例)
以表8所示的处方,将油性成分、水性成分分别溶解、混合后,油亲和好的粉末分散于油性成分,水亲和好的粉末分散于水性成分,在水性成分中混合油性成分使其乳化,制作出粉末混配化妆料的处方例1~5。
表8
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Claims (11)
1.一种化妆料,其含有:
(A)疏水改性聚醚氨基甲酸酯;
(B)纤维素纳米纤维;以及
(C)水,
所述(A)疏水改性聚醚氨基甲酸酯与所述(B)纤维素纳米纤维的混配比率:
在(A)<(B)的情况下,(A)+(B)的混配量相对于全部化妆料为0.75质量%以下,
在(A)=(B)的情况下,(A)+(B)的混配量相对于全部化妆料为1.75质量%以下,
在(A)>(B)的情况下,(A)+(B)的混配量相对于全部化妆料为2质量%以下,
所述(A)疏水改性聚醚氨基甲酸酯为(PEG-240/癸基十四醇聚醚-20/HDI)共聚物,
所述(B)纤维素纳米纤维为最大纤维直径为1000nm以下的微细纤维状纤维素。
2.根据权利要求1所述的化妆料,其被收容于分配器容器。
3.一种加温使用化妆料,是在具有加热部的设备中使用的加温使用化妆料,其含有:
在30℃以上会发生结构变化的温度响应性高分子;
在70℃以下不会发生结构变化的高温稳定性高分子;以及
水,
所述温度响应性高分子为(A)疏水改性聚醚氨基甲酸酯,所述高温稳定性高分子为(B)纤维素纳米纤维,
所述(A)疏水改性聚醚氨基甲酸酯为(PEG-240/癸基十四醇聚醚-20/HDI)共聚物,
所述(B)纤维素纳米纤维为最大纤维直径为1000nm以下的微细纤维状纤维素。
4.根据权利要求3所述的加温使用化妆料,所述温度响应性高分子的混配量多于所述高温稳定性高分子的混配量,并且所述高温稳定性高分子的混配量相对于全部化妆料为0.1质量%以上。
5.根据权利要求3所述的加温使用化妆料,其在30~70℃的温度条件下使用。
6.根据权利要求3所述的加温使用化妆料,所述加热部的热源为加热器或珀尔帖元件。
7.根据权利要求3~6中任一项所述的加温使用化妆料,所述设备具备喷雾装置。
8.根据权利要求3~6中任一项所述的加温使用化妆料,所述设备具备探头。
9.根据权利要求3~6中任一项所述的加温使用化妆料,所述设备具备收容所述加温使用化妆料的罐。
10.一种美容方法,将权利要求3~9中任一项所述的加温使用化妆料用所述加热部控制为40~70℃的温度范围,以雾状直接和/或间接地应用于皮肤。
11.一种美容方法,将权利要求3~9中任一项所述的加温使用化妆料用所述加热部控制为30~48℃的温度范围,直接和/或间接地应用于皮肤。
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