CN110769802A - 固体粉末化妆品 - Google Patents
固体粉末化妆品 Download PDFInfo
- Publication number
- CN110769802A CN110769802A CN201880041549.1A CN201880041549A CN110769802A CN 110769802 A CN110769802 A CN 110769802A CN 201880041549 A CN201880041549 A CN 201880041549A CN 110769802 A CN110769802 A CN 110769802A
- Authority
- CN
- China
- Prior art keywords
- powder
- titanium dioxide
- mass
- elastomer
- carboxyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 168
- 239000002537 cosmetic Substances 0.000 title claims abstract description 69
- 239000007787 solid Substances 0.000 title claims abstract description 41
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- 239000004408 titanium dioxide Substances 0.000 claims abstract description 95
- 239000002245 particle Substances 0.000 claims abstract description 91
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 62
- 229920001971 elastomer Polymers 0.000 claims abstract description 48
- 239000000806 elastomer Substances 0.000 claims abstract description 47
- 125000003277 amino group Chemical group 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 40
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- 238000010304 firing Methods 0.000 claims description 73
- 239000000126 substance Substances 0.000 claims description 34
- 238000012360 testing method Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229920001558 organosilicon polymer Polymers 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
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Abstract
本发明所要解决的课题在于,提供冲击稳定性、妆容和使用性优异、维持遮盖力、并且更能透过长波长区域的光的功能(红色光选择透过功能)优异的固体粉末化妆品。固体粉末化妆品的特征在于包含:1~30质量%的二氧化钛粉体,该二氧化钛粉体是表观上的平均粒径为100nm以上且低于500nm、通过X射线衍射法测定的平均微晶直径为15~30nm、比表面积为10~30m2/g、且具有呈放射状突出的针状的突起凝结而成的形状的粒子,且形状的短径与长径之比(长径/短径)为1.0以上且低于2.5;5~30质量%的球状粉末;以及5~40质量%的由下述(A)成分和(B)成分构成的弹性体或金属皂表面处理过的粉末。弹性体由下述(A)成分和(B)成分构成:(A)具有氨基的有机硅聚合物;(B)具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物,且氨基与羧基的摩尔比在Y/X=0.1~1.2(Y是(B)成分所含的羧基的摩尔量,X是(A)成分所含的氨基的摩尔量)的范围。
Description
关联申请
本申请要求2017年6月26日申请的日本专利申请2017-124674号的优先权,并将其纳入本申请中。
技术领域
本发明涉及固体粉末化妆品,特别是涉及妆容和使用性优异、维持遮盖力、并且更能透过长波长区域的光的功能(红色光选择透过功能)优异的固体粉末化妆品。
背景技术
二氧化钛由于折射率高、白色度、遮盖力、着色力优异,而被广泛用作涂料、塑料等的白色颜料。另外,二氧化钛通过控制其粒径或光活性度,作为遮蔽紫外线的物质,也可作为紫外线吸收剂或紫外线遮蔽剂而利用于化妆品或催化剂等的用途,因此近年来正在盛行在这些用途中的研究开发。
已知如果将由许多二氧化钛形成的球藻状的特定平均一次粒径的二氧化钛的小球状粒子所形成的表观上的特定平均粒径的二氧化钛粉体用于化妆品,则会成为可赋予以往的二氧化钛所没有的良好的光滑性或优异的耐光性的功能性材料(专利文献1)。
另外,已知含有1~15质量%的平均粒径为0.2~0.4μm、平均摩擦系数(MIU值)为0.4~0.6的金红石(Rutile)型氧化钛凝聚粒子和1~40质量%的半固体油分的唇用化妆品,其具有光泽、抑制唇纹的显眼、持妆性优异(专利文献2)。
另外,已知作为用作化妆品的色料,通过掺混在可见光区域也为长波长侧的光(波长630~700nm)的吸收率少的色料,使肌肤内部的透光性接近于无妆肌肤,可实现自然的妆容(专利文献3)。
如此,作为提高光的长波长侧的光的透过率的二氧化钛,已知开发出下述的金红石型氧化钛:呈棒状粒子取向凝聚成束状的粒子形态,取向凝聚而成的粒子的表观平均长轴长度为80~300nm,取向凝聚而成的粒子的表观平均短轴长度为30~150nm,以表观平均长轴长度/表观平均短轴长度表示的表观平均轴比为1.1~4,比表面积为120~180m2/g,即为短条状或稻草束状的金红石型氧化钛,且透明性以及紫外线遮蔽能力均高(专利文献4)。
然而,该二氧化钛是棒状粒子的凝聚体,二次凝聚体中的空隙也多,因此表观折射率下降,实际掺混在化妆品中时遮盖力不充分。另外,由于目标着重点放在紫外线防御上,所以二次凝聚体的表观粒径也低于100nm,明显小于基于Mie理论的使氧化钛的散射效果最大化的粒径,因此这也成为遮盖力小的主要原因。
另一方面,已报道通过将粉体表面用有机聚硅氧烷衍生物处理,涂布于肌肤时的使用感触会有所改善。
但是,即使在该有机聚硅氧烷衍生物处理粉体中掺混以往的二氧化钛,肌肤的斑点等的遮盖力也高,但相反地,在为了提高遮盖力而大量掺混二氧化钛的情况下,会使妆容变得不自然,肌肤上的凹凸较无妆肌肤更为显眼。
鉴于这样的情形,期望开发掺混二氧化钛、耐冲击性和使用性优异、并且涂布于肌肤时形成自然的妆容的固体粉末化妆品。
现有技术文献
专利文献
专利文献1:日本特开2000-191325号公报;
专利文献2:日本特开2010-24189号公报;
专利文献3:日本特开2006-265134号公报;
专利文献4:日本特开2010-173863号公报;
专利文献5:日本特开2012-239039号公报。
发明内容
发明所要解决的课题
因此,本发明是鉴于上述以往技术而进行的发明,其所要解决的课题在于提供耐冲击性和使用性优异、且维持遮盖力、并且更能透过长波长区域的光的功能(红色光选择透过功能)优异的固体粉末化妆品。
用于解决课题的手段
本发明人为了解决上述课题而进行了深入研究,结果发现:烧制特定的二氧化钛,而制成特定的粒径、特定的微晶直径和特定的比表面积的二氧化钛,其充分具有化妆品所要求的遮盖力、并且红色光选择透过功能优异。而且,可知在该二氧化钛中掺混有经过特定的表面处理的滑石和球状粉末而得的物质,其使用性和耐冲击性优异、并且涂布于肌肤时具有自然的妆容和不泛白。
即,本发明所涉及的固体粉末化妆品的特征在于包含:
1~30质量%的二氧化钛粉体,该二氧化钛粉体的特征在于,其是表观上的平均粒径为100nm以上且低于500nm、通过X射线衍射法测定的平均微晶直径为15~30nm、比表面积为10~30m2/g、且具有呈放射状突出的针状的突起凝结而成的形状的粒子,且形状的短径与长径之比(长径/短径)为1.0以上且低于2.5;
5~30质量%的球状粉末;以及
5~40质量%的由下述(A)成分和(B)成分构成的弹性体或金属皂表面处理过的粉末;
弹性体由下述(A)成分和(B)成分构成:
(A) 具有氨基的有机硅聚合物
(B) 具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物
且氨基与羧基的摩尔比在Y/X=0.1~1.2(Y是(B)成分所含的羧基的摩尔量,X是(A)成分所含的氨基的摩尔量)的范围。
在上述固体粉末化妆品中,(A)成分适合为下述通式(1)所示的侧链型氨基改性硅氧烷。
[化学式1]
(通式(1)中,X为碳数1~18的烷基,R、R’为烷基)
在上述固体粉末化妆品中,固体粉末化妆品的特征在于,(B)成分为下述通式(2)所示的具有羧基的有机硅聚合物或下述通式(3)所示的具有羧基的丙烯酸聚合物。
[化学式2]
(式中,R1和R2表示甲基或下述的[化学式3]所示的基团,在1分子中含有1~100个该基团,y表示1~50,000的整数)
[化学式3]
[化学式4]
本发明所涉及的固体粉末化妆品的特征在于包含:
1~30质量%的金红石型二氧化钛粉体,该金红石型二氧化钛粉体的通过X射线衍射法测定的平均微晶直径为15~30nm,比表面积为10~30m2/g,且450nm的反射率的值为650nm的反射率的值的1.3倍以上,色差(△E)为22以下;
5~30质量%的球状粉末;以及
5~40质量%的由下述(A)成分和(B)成分构成的弹性体或金属皂表面处理过的粉末;
弹性体由下述(A)成分和(B)成分构成:
(A) 具有氨基的有机硅聚合物
(B) 具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物
且氨基与羧基的摩尔比在Y/X=0.1~1.2(Y是(B)成分所含的羧基的摩尔量,X是(A)成分所含的氨基的摩尔量)的范围。
需要说明的是,色差(△E)是将二氧化钛粉体以成为5%浓度的方式分散混合于硝化纤维素清漆中,将所得的分散物在黑白的遮盖率试纸JIS-K5400上以0.101μm的膜厚进行涂布、干燥而得到试验样品。将所得的试验样品利用分光测色仪对白与黑纸上的涂膜表面分别进行测色。算出Hunter Lab色空间中的色差(△E)。
本发明所涉及的固体粉末化妆品的特征在于包含:
1~30质量%的二氧化钛粉体,该二氧化钛粉体是将满足下述(a)~(c)的于粒子表面具有针状突起的金红石型二氧化钛进行烧制所得的金红石型二氧化钛粉体,其表观上的平均粒径为100nm以上且低于500nm,通过X射线衍射法测定的平均微晶直径为15~30nm,比表面积为10~30m2/g;
(a) 表观上的平均粒径为100nm以上且低于500nm
(b) 通过X射线衍射法测定的平均微晶直径为1~25nm
(c) 比表面积为40~200m2/g
5~30质量%的球状粉末;以及
5~40质量%的由下述(A)成分和(B)成分构成的弹性体或金属皂表面处理过的粉末;
弹性体由下述(A)成分和(B)成分构成:
(A) 具有氨基的有机硅聚合物
(B) 具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物
且氨基与羧基的摩尔比在Y/X=0.1~1.2(Y是(B)成分所含的羧基的摩尔量,X是(A)成分所含的氨基的摩尔量)的范围。
本发明所涉及的固体粉末化妆品的特征在于包含:
1~30质量%的二氧化钛粉体,该二氧化钛粉体的特征在于,其是将满足下述(a)~(c)的于粒子表面具有针状突起的金红石型二氧化钛烧制所得的金红石型二氧化钛粉体,且烧制后的金红石型二氧化钛粉体的比表面积相对于烧制前为8~50%;
(a) 表观上的平均粒径为100nm以上且低于500nm
(b) 通过X射线衍射法测定的平均微晶直径为1~25nm
(c) 比表面积为40~200m2/g
5~30质量%的球状粉末;以及
5~40质量%的由下述(A)成分和(B)成分构成的弹性体或金属皂表面处理过的粉末;
弹性体由下述(A)成分和(B)成分构成:
(A) 具有氨基的有机硅聚合物
(B) 具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物
且氨基与羧基的摩尔比在Y/X=0.1~1.2(Y是(B)成分所含的羧基的摩尔量,X是(A)成分所含的氨基的摩尔量)的范围。
在上述固体粉末化妆品中,二氧化钛的烧制温度适合为500~800℃。
在上述固体粉末化妆品中,二氧化钛的烧制温度适合为550~750℃。
发明效果
根据本发明,可提供冲击稳定性、妆容和使用性优异、维持遮盖力、并且更能透过长波长区域的光的功能(红色光选择透过功能)优异的固体粉末化妆品。
附图说明
[图1]是表观上的平均粒径的算出方法。
[图2]是表示金红石型颜料级氧化钛(*1)、氧化钛B(未烧制)、和将氧化钛B在700、900℃下烧制而得的物质的分光反射率的图。
[图3]是表示通过TEM观察在各烧制温度下烧制的二氧化钛B的形状变化的图。
[图4]是表示旋转窑(Rotary Kiln)中的烧制温度变化所致的氧化钛B的遮盖力变化的图。
[图5]是表示旋转窑中的烧制温度变化所致的氧化钛B的烧制温度变化而导致的红色透过性变化的图。
具体实施方式
本发明所涉及的二氧化钛粉体的特征在于,其是将棒状或针状粒子以放射状取向凝聚而成的于粒子表面具有针状突起的二氧化钛在500~800℃、更优选550~750℃下烧制而得的二氧化钛粉体,其通过X射线衍射法测定的平均微晶直径为15~30nm,二氧化钛的表观上的平均粒径为100nm以上且低于500nm、更优选为200~400nm,比表面积为10~30m2/g。
[用于母核的二氧化钛]
用于母核的二氧化钛的晶型,由于晶体结构的不同,有锐钛矿型(Anatase Type)和金红石型(Rutile Type)。在此,用于本发明的二氧化钛的晶型,由于光催化活性低、折射率高,因此需要为遮盖力高的金红石型。
用于母核的二氧化钛,使用具有红色光透过功能的二氧化钛。若考虑在烧制后一般会发生收缩现象,从实现本发明所得的由二氧化钛的散射所致的遮盖力和优异的红色光透过功能的观点出发,则用于母核的二氧化钛的表观的平均粒径希望优选为100nm以上且低于500nm、更优选为200~400nm。
作为用于母核的金红石型二氧化钛的形状,例如可举出:茧状、稻草束状、短条状、球状、针状、棒状等。在本发明中,优选为棒状或针状粒子以放射状取向凝聚而成的于粒子表面具有针状突起的形状。
用于母核的二氧化钛的比表面积,从因烧制而有效率地提高表观折射率的观点出发,希望为40~200m2/g。
用于母核的金红石型二氧化钛,优选通过X射线衍射法测定的平均微晶直径为1~25nm。
用于母核的二氧化钛可为市售品。例如可举出钛工业株式会社制的ST700系列。其中,可举出ST710等。
[用于本发明的二氧化钛粉体]
用于本发明的二氧化钛粉体可通过将用于母核的二氧化钛进行烧制而得到。
烧制温度根据进行烧制的装置,希望为下述的温度条件:从烧制前存在的粒子表面以放射状突出的针状突起是通过烧制而凝结的粒子,通过烧制发生凝结,而使针状粒子间存在的空隙减少,且针状粒子彼此烧结,通过X射线衍射法测定的平均微晶直径不会过度地增大。由此,能够兼具充分的遮盖力和红色光选择透过功能。
用于本发明的二氧化钛粉体的特征在于,从存在烧制前的粒子表面以放射状突出的针状突起是通过烧制而凝结的粒子的形状。而且,其特征在于,该粒子的短径与长径之比(长径/短径)为1.0以上且低于2.5。更优选为1.0~2.0。
适当的烧制温度根据烧制装置而不同,在利用作为一般烧制炉的马弗炉(MuffleFurnace)或旋转窑进行烧制的情况下,希望在500~800℃、更优选在550~750℃的范围进行烧制。若低于500℃,则不会充分减少烧制前所存在的空隙,所以遮盖力不充分,若超过800℃,则烧结过度地进行,而失去红色光选择透过功能。
本发明的二氧化钛通过X射线衍射法测定的平均微晶直径需要为15~30nm。
在上述微晶直径低于15nm的情况下,由于无法得到充分的遮盖力,因此不优选。另外,在超过30nm的情况下,烧结进行,会失去充分的红色光选择透过功能,从这一方面考虑不优选。
另外,本发明的二氧化钛粉体,从有效地实现散射所致的遮盖力和优异的红色透过功能的观点出发,表观上的平均粒径需要为100nm以上且低于500nm、更优选为200~400nm。
用于本发明的二氧化钛粉体的比表面积是表示所得的氧化钛粒子的空隙率降低和烧结进行的指标,成为母核的二氧化钛粉体的烧制后的比表面积与烧制前(100%)相比,优选成为8~50%的范围。更优选为8~30%。
另外,本发明的二氧化钛粉体的比表面积需要为10~30m2/g。若低于10m2/g,则烧结进行,会失去充分的红色光选择透过功能,从这一方面考虑不优选。另外,若超过30m2/g,则过度地存在空隙,无法达成充分的遮盖力,从这一方面考虑不优选。
本发明的二氧化钛粉体,也可在烧制后进行表面处理。通过进行表面处理,可得到粘度、对油的分散性、防水性所伴随的持妆性提高、且使用性优异的二氧化钛。
作为可用作表面处理剂的无机物,例如可举出:铝、硅、锌、钛、锆、铁、铈和锡等金属的含合氧化物或氧化物。对可用于此的上述金属盐没有特别限定。
作为可用作表面处理剂的有机物,例如在用氢氧化铝或氧化铝等金属氧化物、金属氢氧化物进行表面处理后,为了附加亲油性,可以列举:硬脂酸、油酸、异硬脂酸、肉荳蔻酸、棕榈酸、二十二烷酸(behenic acid)等脂肪酸;甲基氢聚硅氧烷、聚二甲基硅氧烷、烷基(C8~C18等)三烷氧基硅烷、氨基改性硅氧烷、羧基改性硅氧烷等有机硅化合物;全氟烷基烷基磷酸盐等氟化合物;糊精肉荳蔻酸酯、糊精棕榈酸酯、月桂酰基赖氨酸、月桂酰基谷氨酸酯等氨基酸衍生物等。
相对于二氧化钛粉体,若这些表面处理剂为1~10质量%,则遮蔽力高,因此优选。
用于本发明的二氧化钛粉体,可广泛地掺混于化妆品、颜料、墨水、涂料等中。
相对于粉末化妆品的总重量,用于本发明的二氧化钛的掺混量为1~30质量%、更优选为5~15质量%。若少于1质量%,则有无法得到掺混本发明的二氧化钛所致的效果的情形,若超过30质量%,则有妆容变得不自然的情形。
[球状粉末]
对于本发明的化妆品,所掺混的球状粉末的原材料如果是可掺混于通常化妆品中的球状粉末的原材料则没有特别限定。可示例:弹性球状粉末(例如,Refill、Urepearl、塑料粉末)、聚乙烯、聚丙烯、聚苯乙烯、聚甲基丙烯酸甲酯、聚酰胺树脂(尼龙)、氨基甲酸乙酯、有机硅树脂、有机硅橡胶、有机硅树脂被覆橡胶、聚四氟乙烯、二氧化硅(Silica)、苯乙烯与丙烯酸的共聚物树脂、苯并胍胺树脂、纤维素等。
而且,该球状粉末可实施表面处理。表面处理例如可举出:有机硅化合物处理、氟改性有机硅化合物处理、氟化合物处理、高级脂肪酸处理、高级醇处理、脂肪酸酯处理、金属皂处理、氨基酸处理、磷酸烷基酯处理等。
作为球状粉末的市售品,例如可举出:KSP100(信越化学工业株式会社制)、KSP-300(信越化学工业株式会社制)、Nylon SP-500(Toray株式会社制)、D-400(东色PIGMENT株式会社制)等。
另外,就使用感触而言,该球状粉末的粒径(平均粒径)适合于1~30μm的范围内、特别适合于3~20μm的范围内。本发明的化妆品中可掺混1种或2种以上球状粉末。
相对于化妆品,本发明的化妆品中的球状粉末的掺混量为5~30质量%、适合为10~20质量%。若该掺混量超过30质量%,则有成形性极端地变差的倾向,若低于5质量%,则难以对制品赋予充分的伸展性。
本发明所用的滑石是进行弹性体处理或金属皂处理后使用。在化妆品中,弹性体处理或金属皂处理滑石的掺混量优选为5~40质量%、更优选为15~35质量%。若多于40质量%,则有化妆品的卸除变差的情形。若少于5质量%,则有无法得到具有充分的耐冲击性的化妆品的情形。
[弹性体处理滑石]
用于将本发明所用的滑石进行弹性体处理的弹性体,可通过下述方法而得到。
本发明所涉及的弹性体是将具有氨基的有机硅聚合物与具有羧基的有机硅聚合物进行混合并加热而制造的弹性体。
(A) 具有氨基的有机硅聚合物
本发明所用的(A)具有氨基的有机硅聚合物是下述通式(1)所示的侧链型氨基改性硅氧烷。
[化学式5]
(通式(1)中,X为碳数1~18的烷基,R、R’为烷基)
通式(1)中,若m为20~2000,则由于所得的弹性体的硬度适合,因此优选。若低于20,则会有不形成弹性体的情形,从这一方面考虑不优选。另外,若超过2000,则有产生操作困难、制造困难的情形,从这一方面考虑不优选。
通式(1)中,若n为1~100,则由于所得的弹性体的硬度适合,因此优选。若低于1,则会有不形成弹性体的情形,从这一方面考虑不优选。另外,若超过100,则会有弹性体过硬的情形,从这一方面考虑不优选。
通式(1)中,R适合使用烷基链,就量产性的理由而言,优选为丙基。
通式(1)中,R’适合使用烷基链,就量产性的理由而言,优选为乙基。
(A)具有氨基的有机硅聚合物的氨基当量若为500g/mol~20000g/mol,则由于所得的弹性体的硬度适合,因此优选。若氨基当量低于500,则会有弹性体过硬的情形,从这一方面考虑不优选。另外,若氨基当量超过20000,则会有不形成弹性体的情形,从这一方面考虑不优选。
作为(A)具有氨基的有机硅聚合物的市售品,例如可举出:KF-8004、KF-8005S、KF-867S(信越化学工业公司制)、XF42-B1989(MOMENTIVE公司制)、ADM1650、ADM1370(旭化成Wacker Silicone公司制)、SF8452C、SS3551(Toray Dow Corning公司制)等。
上述氨基当量表示:相对于含氨基的物质,表示每1摩尔氨基的该物质的重量的数值。
(B) 具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物
本发明所用的(B)具有羧基的有机硅聚合物是下述通式(2)所示的羧基当量为1000g/mol~40000g/mol的侧链型羧基改性硅氧烷。
本发明所用的(B)具有羧基的丙烯酸聚合物是下述通式(3)所示的羧基当量为200g/mol~1000g/mol的侧链型羧基改性丙烯酸聚合物。
上述羧基当量表示:相对于含羧基的物质,表示每1摩尔羧基的该物质的重量的数值。
通式(2)是由下述的化学式2和化学式3构成。
[化学式6]
(式中,R1和R2表示甲基或下述的[化学式3]所示的基团,在1分子中含有1~100个该基团,y表示1~50,000的整数)
[化学式7]
通式(3)是由下述的化学式4构成。
[化学式8]
(通式(3)中,m/(m+n)=0~0.5)
作为通式(2)所示的具有羧基的有机硅聚合物的市售品,例如可举出SENSASIL PCA(Croda公司制)等。
通式(3)所示的具有羧基的丙烯酸聚合物可使用公知的方法进行合成。
具体例可举出:将12-甲基丙烯酰胺十二烷酸(MAD)/2-丙烯酰胺-2-甲基丙磺酸(AMPS)共聚物(90/10)、12-甲基丙烯酰胺十二烷酸(MAD)18.50g(65.37mmol)、2-丙烯酰胺-2-甲基丙磺酸(AMPS:Sigma-Aldrich Japan公司制)1.50g(7.24mmol)、氢氧化钠0.29g(7.25mmol)、偶氮双异丁腈(NACALAI TESQUE公司制)0.30g(1.83mmol)溶解于甲醇60.0g中。偶氮双异丁腈是依据常规方法从甲醇重结晶后使用。使氩气鼓泡60分钟进行脱气,用隔膜(Septum)盖住容器,在60℃下加热20小时进行聚合。在聚合反应结束后,将反应溶液滴加到大大过量的二乙醚中,通过吸引过滤(抽滤)回收沉淀物。减压干燥后,得到无规状的MAD/AMPS共聚物(90/10)15.2g(收率:75.1%)。重均分子量为50000。
(B)成分的羧基当量若为200~40000,则由于所得的弹性体的硬度适合,因此优选。若低于200,则会有弹性体过硬的情形,从这一方面考虑不优选。另外,若超过40000,则会有不形成弹性体的情形,从这一方面考虑不优选。
(A)具有氨基的有机硅聚合物中的氨基、与(B)具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物的羧基的摩尔比必须为Y/X=0.1~1.2(Y是(B)成分所含的羧基的摩尔量,X是(A)成分所含的氨基的摩尔量)。更优选为0.1~0.8。若低于0.1,则会有不形成弹性体的情形,因此不优选。另外,若大于1.2,则会有不形成弹性体的情形,因此不优选。
相对于滑石,被覆于滑石的弹性体的量为0.5~20质量%、更优选为1~15质量%。若掺混超过20质量%,则会有产生滑石的熔接或粉末化妆品成形性降低的情形,从这一方面考虑不优选。另外,若掺混量低于0.5质量%,则会有无法得到改善感触的效果的情形,从这一方面考虑不优选。
[弹性体处理滑石的制造方法]
本发明所涉及的弹性体处理滑石可通过将滑石与(A)具有氨基的有机硅聚合物进行混合的步骤;以及将(B)具有羧基的有机硅聚合物混合、加热的步骤而得到。
弹性体处理滑石可通过公知的被覆粉末的制造方法而得到。具体例可举出:在亨舍尔混合机中加入滑石、(A)具有氨基的有机硅聚合物,以低速混合10分钟。然后,在其中加入(B)具有羧基的有机硅聚合物,以低速混合10分钟,进行加热,由此可得到本发明的弹性体被覆无机粉末。
另外,即使(A)成分与(B)成分的添加顺序相反,仍可得到本发明所涉及的弹性体被覆无机粉末。
[金属皂处理滑石]
本发明所用的金属皂处理滑石可使用经过各式各样的金属皂处理的滑石。作为金属皂处理,例如可举出:癸基三硅氧烷羧酸锌等的癸基三硅氧烷羧酸金属处理、硬脂酸钙处理、硬脂酸镁处理等。
例如,癸基三硅氧烷羧酸金属处理滑石是用羧基癸基三硅氧烷衍生物的金属盐对滑石进行表面处理而得的滑石。作为羧基癸基三硅氧烷衍生物的金属盐,上述衍生物的末端羧基全部或一部分形成金属盐。作为所涉及的2价或3价金属原子,例如可举出:Zn、Mg、Ca、Ba、Mn、Fe、Co、Al、Ni、Cu、V、Mo、Nb、Ti等。在这些2价或3价金属原子中,可特别适合使用Zn或Mg。
本发明所用的羧基癸基三硅氧烷是羧酸改性有机硅的一种,且由下述通式(4)表示。
[化学式9]
其化学名称为3-(10-羧基癸基)-1,1,1,3,5,5,5-七甲基三硅氧烷,且属于公知的羧基改性硅氧烷。本发明中,优选使用“DOW CORNING TORAY OP-1800MF CARBOXY FLUID(TorayDow Corning)”等的市售品。
相对于滑石,被覆于滑石的金属皂处理的量为0.5~20质量%、更优选为1~15质量%。若掺混超过20质量%,则会有产生滑石的熔接或粉末化妆品的成形性降低的情形,从这一方面考虑不优选。另外,若掺混量低于0.5质量%,则会有无法得到感触的改善效果的情形,从这一方面考虑不优选。
[癸基三硅氧烷羧酸锌处理滑石的制造方法]
癸基三硅氧烷羧酸锌处理滑石可通过公知的被覆粉末的制造方法而得到。如果举出具体例,则可通过以下的干式法和湿式法这2种方法来实施。但是,并不限定于这些方法。
干式法
将上述化学式5的有机硅氧烷衍生物在1%氢氧化钠水溶液中转换为钠盐后,进一步添加1%氯化锌水溶液而进行盐交换,调制该有机硅氧烷衍生物的Zn盐。然后,将滑石15g、上述有机硅氧烷衍生物的Zn盐5g进行粉碎混合。
湿式法
依序添加滑石100g、1%氢氧化钠水溶液30.5g、上述化合物1的有机硅氧烷衍生物3g、1%氯化锌水溶液156ml,并使混合物分散。至此为止的反应在70℃下进行。其后,通过过滤而将经表面处理的粉体分离,水洗,干燥(105℃,12小时),使用粉碎机进行粉碎。
更优选采用通过湿式法进行的表面处理。湿式法中,其混合温度优选为60~80℃。另外,混合时间根据处理量、粉体种类而不同,但通常优选为1~3小时。
在此,弹性体处理、金属皂处理也可以是滑石以外的粉末。
作为无机粉末,例如可举出:滑石、氮化硼、绢云母、天然云母、煅烧云母、合成云母、合成绢云母、氧化铝、云母、高岭土、膨润土、蒙脱石、碳酸钙、碳酸镁、磷酸钙、硅酸酐、氧化镁、氧化锡、氧化铁、氧化钇、氧化铬、氧化锌、氧化铈、氧化铝、氧化镁、氢氧化铬、绀青(普鲁士蓝)、群青、磷酸钙、氢氧化铝、硫酸钡、硫酸镁、硅酸、硅酸铝镁、硅酸钙、硅酸钡、硅酸镁、硅酸铝、硅酸锶、碳化硅、氟化镁、钨酸金属盐、铝酸镁、偏硅酸铝酸镁、氯羟基铝、粘土、沸石、羟磷灰石、陶瓷粉末、尖晶石、莫来石(Mullite)、堇青石、氮化铝、氮化钛、氮化硅、镧、钐、钽、铽、铕、钕、Mn-Zn铁氧体、Ni-Zn铁氧体、碳化硅(Silicon Carbide)、钛酸钴、钛酸钡、钛酸铁、钛酸锂钴、铝酸钴、含锑氧化锡、含锡氧化铟、磁铁矿、铝粉、金粉、银粉、铂粉、铜粉、贵金属胶体、铁粉、锌粉、钴蓝、钴紫、钴绿、低价氧化钛、微粒氧化钛、蝶状硫酸钡、花瓣状氧化锌、四脚状氧化锌(Tetrapod Zinc Oxide)、微粒氧化锌;作为珍珠颜料:氧化钛被覆云母、氧化钛被覆云母、氧化钛被覆合成云母、氧化钛被覆二氧化硅、氧化钛被覆合成云母、氧化钛被覆滑石、氧化锌被覆二氧化硅、氧化钛被覆着色云母、氧化铁红被覆云母钛、氧化铁红/氧化铁黑被覆云母钛、胭脂红被覆云母钛、绀青被覆云母钛等。
这些之中,优选使用云母、绢云母、高岭土、氧化钛、氧化铁、氧化锌等。
作为有机粉体,可示例:聚酯粉末、聚乙烯粉末、聚丙烯粉末、聚甲基丙烯酸甲酯粉末、聚苯乙烯粉末、聚氨酯粉末、苯并胍胺粉末、聚甲基丙烯酸甲酯粉末、聚甲基苯并胍胺粉末、聚四氟乙烯粉末、纤维素、蚕丝粉末(Silk Powder)、尼龙粉末、尼龙12粉末、尼龙6粉末、苯乙烯/丙烯酸共聚物粉末、二乙烯基苯/苯乙烯共聚物粉末、乙烯基树脂粉末、尿素树脂粉末、酚醛树脂粉末、氟树脂粉末、丙烯酸树脂粉末、三聚氰胺树脂粉末、环氧树脂粉末、聚碳酸酯树脂粉末、微晶纤维粉体、淀粉粉末、月桂酰基赖氨酸粉末等。
作为表面活性剂金属盐粉体,可示例:硬脂酸锌、硬脂酸铝、硬脂酸钙、硬脂酸镁、肉豆蔻酸锌、肉豆蔻酸镁、鲸蜡醇磷酸锌、鲸蜡醇磷酸钙、鲸蜡醇磷酸锌钠等。
[其他成分]
本发明所涉及的固体粉末化妆品中,在不损及本发明的效果的范围内,可根据需要适当掺混其他成分,例如:酯、阴离子表面活性剂、阳离子表面活性剂、两性表面活性剂、非离子表面活性剂、保湿剂、水溶性高分子、增稠剂、皮膜剂、紫外线吸收剂、金属离子封锁剂、低级醇、多元醇、糖、氨基酸、有机胺、高分子乳剂、pH调节剂、皮肤营养剂、维生素、抗氧化剂、抗氧化助剂、香料、水等,根据目标的剂型,可通过常规方法进行制造。
以下举出具体的可掺混的成分,可将上述必须掺混成分与下述成分的任意1种或2种以上进行掺混,来调制固体粉末化妆品。
作为阴离子表面活性剂,例如可举出:脂肪酸皂(例如,月桂酸钠、棕榈酸钠等);高级烷基硫酸酯盐(例如,月桂基硫酸钠、月桂基硫酸钾等);烷基醚硫酸酯盐(例如,POE-月桂基硫酸三乙醇胺、POE-月桂基硫酸钠等);N-酰基肌氨酸(例如,月桂酰基肌氨酸钠等);高级脂肪酸酰胺磺酸盐(例如,N-肉豆蔻酰基-N-甲基牛磺酸钠、椰子油脂肪酸甲基牛磺酸钠、月桂基甲基牛磺酸钠等);磷酸酯盐(POE-油基醚磷酸钠、POE-硬脂基醚磷酸酯等);磺基琥珀酸盐(例如,二-2-乙基己基磺基琥珀酸钠、单月桂酰基单乙醇酰胺聚氧乙烯磺基琥珀酸钠、月桂基聚丙二醇磺基琥珀酸钠等);烷基苯磺酸盐(例如,直链十二烷基苯磺酸钠、直链十二烷基苯磺酸三乙醇胺、直链十二烷基苯磺酸等);高级脂肪酸酯硫酸酯盐(例如,氢化椰子油脂肪酸甘油硫酸钠等);N-酰基谷氨酸盐(例如,N-月桂酰基谷氨酸单钠、N-硬脂酰基谷氨酸二钠、N-肉豆蔻酰基-L-谷氨酸单钠等);硫酸化油(例如,土耳其红油等);POE-烷基醚羧酸;POE-烷基烯丙基醚羧酸盐;α-烯烃磺酸盐;高级脂肪酸酯磺酸盐;仲醇硫酸酯盐;高级脂肪酸烷醇酰胺硫酸酯盐;月桂酰基单乙醇酰胺琥珀酸钠;N-棕榈酰基天冬氨酸二(三乙醇胺);酪蛋白钠等。
作为阳离子表面活性剂,例如可举出:烷基三甲基铵盐(例如,硬脂基三甲基氯化铵、月桂基三甲基氯化铵等);烷基吡啶鎓盐(例如,氯化鲸蜡基吡啶鎓等);二硬脂基二甲基氯化铵二烷基二甲基铵盐;氯化聚(N,N’-二甲基-3,5-亚甲基哌啶鎓);烷基季铵盐;烷基二甲基苄基铵盐;烷基异喹啉鎓盐;二烷基吗啉鎓盐;POE-烷基胺;烷基胺盐;多胺脂肪酸衍生物;戊醇脂肪酸衍生物;苯扎氯铵(Benzalkonium Chloride);苄索氯铵(BenzethoniumChloride)等。
作为两性表面活性剂,例如可举出:咪唑啉系两性表面活性剂(例如,2-十一烷基-N,N,N-(羟乙基羧甲基)-2-咪唑啉钠、2-椰油酰基-2-咪唑啉鎓氢氧化物-1-羧基乙氧基二钠盐等);甜菜碱系表面活性剂(例如,2-十七烷基-N-羧甲基-N-羟乙基咪唑啉鎓甜菜碱、月桂基二甲基氨基乙酸甜菜碱、烷基甜菜碱、酰胺甜菜碱、磺基甜菜碱等)等。
作为亲油性非离子表面活性剂,例如可举出:脱水山梨糖醇脂肪酸酯类(例如,脱水山梨糖醇单油酸酯、脱水山梨糖醇单异硬脂酸酯、脱水山梨糖醇单月桂酸酯、脱水山梨糖醇单棕榈酸酯、脱水山梨糖醇单硬脂酸酯、脱水山梨糖醇倍半油酸酯、脱水山梨糖醇三油酸酯、脱水山梨糖醇五-2-乙基己酸二甘油酯、脱水山梨糖醇四-2-乙基己酸二甘油酯等);甘油聚甘油脂肪酸类(例如,单棉籽油脂肪酸甘油酯、单芥酸甘油酯、倍半油酸甘油酯、单硬脂酸甘油酯、α,α’-油酸焦谷氨酸甘油酯、甘油苹果酸单硬脂酸酯等);丙二醇脂肪酸酯类(例如,单硬脂酸丙二醇酯等);氢化蓖麻油衍生物;甘油烷基醚等。
作为亲水性非离子表面活性剂,例如可举出:POE-脱水山梨糖醇脂肪酸酯类(例如,POE-脱水山梨糖醇单油酸酯、POE-脱水山梨糖醇单硬脂酸酯、POE-脱水山梨糖醇单油酸酯、POE-脱水山梨糖醇四油酸酯等);POE-山梨糖醇脂肪酸酯类(例如,POE-山梨糖醇单月桂酸酯、POE-山梨糖醇单油酸酯、POE-山梨糖醇五油酸酯、POE-山梨糖醇单硬脂酸酯等);POE-甘油脂肪酸酯类(例如,POE-甘油单硬脂酸酯、POE-甘油单异硬脂酸酯、POE-甘油三异硬脂酸酯等的POE-单油酸酯等);POE-脂肪酸酯类(例如,POE-二硬脂酸酯、POE-单二油酸酯(POE-monodioleate)、二硬脂酸乙二醇酯等);POE-烷基醚类(例如,POE-月桂基醚、POE-油基醚、POE-硬脂基醚、POE-二十二烷基醚、POE-2-辛基十二烷基醚、POE-胆甾烷醇醚(POE-cholestanol ether)等);Pluronic型类(例如,Pluronic等);POE/POP-烷基醚类(例如,POE/POP-鲸蜡基醚、POE/POP-2-癸基十四烷基醚、POE/POP-单丁基醚、POE/POP-氢化羊毛脂、POE/POP-甘油基醚等);四POE/四POP-乙二胺缩合物类(例如,Tetronic等);POE-蓖麻油氢化蓖麻油衍生物(例如,POE-蓖麻油、POE-氢化蓖麻油、POE-氢化蓖麻油单异硬脂酸酯、POE-氢化蓖麻油三异硬脂酸酯、POE-氢化蓖麻油单焦谷氨酸单异硬脂酸二酯、POE-氢化蓖麻油马来酸酯等);POE-蜂蜡/羊毛脂衍生物(例如,POE-山梨糖醇蜂蜡等);烷醇酰胺(例如,椰子油脂肪酸二乙醇酰胺、月桂酸单乙醇酰胺、脂肪酸异丙醇酰胺等);POE-丙二醇脂肪酸酯;POE-烷基胺;POE-脂肪酸酰胺;蔗糖脂肪酸酯;烷基乙氧基二甲基氧化胺;三油醇磷酸酯等。
作为保湿剂,例如可举出:聚乙二醇、丙二醇、甘油、1,3-丁二醇、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(Charonic Acid)、去端肽胶原蛋白(Atelocollagen,缺端胶原)、12-羟基硬脂酸胆甾醇酯、乳酸钠、胆汁酸盐、d1-吡咯烷酮羧酸盐、环氧烷衍生物、短链可溶性胶原蛋白、二甘油(EO)PO加成物、刺梨提取物、西洋蓍草提取物、草木樨提取物等。
作为天然的水溶性高分子,例如可举出:植物系高分子(例如,阿拉伯树胶、黄蓍胶、半乳聚糖、瓜尔胶、角豆树胶、刺梧桐树胶、角叉菜胶、果胶、琼脂、榅桲籽(Marmelo)、藻类胶体(褐藻提取物)、淀粉(大米、玉米、马铃薯、小麦)、甘草酸等);微生物系高分子(例如,黄原胶、葡聚糖、琥珀酰聚糖、茁霉多糖等);动物系高分子(例如,胶原蛋白、酪蛋白、白蛋白、明胶等)等。
作为半合成的水溶性高分子,例如可举出:淀粉系高分子(例如,羧甲基淀粉、甲基羟丙基淀粉等);纤维素系高分子(甲基纤维素、乙基纤维素、甲基羟丙基纤维素、羟乙基纤维素、纤维素硫酸钠、羟丙基纤维素、羧甲基纤维素、羧甲基纤维素钠、结晶纤维素、纤维素粉末等);海藻酸系高分子(例如,海藻酸钠、海藻酸丙二醇酯等)等。
作为合成的水溶性高分子,例如可举出:乙烯系高分子(例如,聚乙烯醇、聚乙烯甲醚、聚乙烯吡咯烷酮、羧基乙烯基聚合物等);聚氧乙烯系高分子(例如,聚乙二醇20,000、40,000、60,0000的聚氧乙烯聚氧丙烯共聚物等);丙烯酸系高分子(例如,聚丙烯酸钠、聚丙烯酸乙酯、聚丙烯酰胺等);聚乙烯亚胺;阳离子聚合物等。
作为增稠剂,例如可举出:阿拉伯树胶、角叉菜胶、刺梧桐树胶、黄蓍胶、角豆树胶、榅桲籽(Marmelo)、酪蛋白、糊精、明胶、果胶酸钠、海藻酸钠、甲基纤维素、乙基纤维素、CMC、羟乙基纤维素、羟丙基纤维素、PVA、PVM、PVP、聚丙烯酸钠、羧基乙烯基聚合物、刺槐豆胶、瓜尔胶、罗望子胶、二烷基二甲基铵硫酸纤维素、黄原胶、硅酸铝镁、膨润土、锂蒙脱石、硅酸A1Mg(Veegum)、合成锂皂石(Laponite)、硅酸酐等。
作为紫外线吸收剂,例如可举出:苯甲酸系紫外线吸收剂(例如,对氨基苯甲酸(以下简称为PABA)、PABA单甘油酯、N,N-二丙氧基PABA乙酯、N,N-二乙氧基PABA乙酯、N,N-二甲基PABA乙酯、N,N-二甲基PABA丁酯、N,N-二甲基PABA乙酯等);邻氨基苯甲酸系紫外线吸收剂(例如,N-乙酰基邻氨基苯甲酸高薄荷酯等);水杨酸系紫外线吸收剂(例如,水杨酸戊酯、水杨酸薄荷酯、水杨酸高薄荷酯、水杨酸辛酯、水杨酸苯酯、水杨酸苄酯、对异丙醇苯基水杨酸酯等);肉桂酸系紫外线吸收剂(例如,甲氧基肉桂酸辛酯、肉桂酸乙基-4-异丙酯、肉桂酸甲基-2,5-二异丙酯、肉桂酸乙基-2,4-二异丙酯、肉桂酸甲基-2,4-二异丙酯、对甲氧基肉桂酸丙酯、对甲氧基肉桂酸异丙酯、对甲氧基肉桂酸异戊酯、对甲氧基肉桂酸辛酯(对甲氧基肉桂酸2-乙基己酯)、对甲氧基肉桂酸2-乙氧基乙酯、对甲氧基肉桂酸环己酯、α-氰基-β-苯基肉桂酸乙酯、α-氰基-β-苯基肉桂酸2-乙基己酯、单-2-乙基己酰基-二对甲氧基肉桂酸甘油酯等);二苯甲酮系紫外线吸收剂(例如,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、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);3-(4’-甲基亚苄基)-d,1-樟脑、3-亚苄基-d,1-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;二亚苄基吖嗪(Dibenzalazine);二茴香酰甲烷(Dianisoyl Methane);4-甲氧基-4’-叔丁基二苯甲酰基甲烷;5-(3,3-二甲基-2-亚降冰片基)-3-戊烷-2-酮、二吗啉代哒嗪酮(ジモルホリノピリダジノ);丙烯酸2-乙基己基-2-氰基-3,3-二苯酯;2,4-双{[4-(2-乙基己氧基)-2-羟基]-苯基}-6-(4-甲氧基苯基)-(1,3,5)-三嗪等。
作为金属离子封锁剂,例如可举出:1-羟基乙烷-1,1-二膦酸、1-羟基乙烷-1,1-二膦酸四钠盐、依地酸二钠、依地酸三钠、依地酸四钠、柠檬酸钠、聚磷酸钠、偏磷酸钠、葡糖酸、磷酸、柠檬酸、抗坏血酸、琥珀酸、依地酸、乙二胺羟乙基三乙酸三钠等。
作为低级醇,例如可举出:乙醇、丙醇、异丙醇、异丁醇、叔丁醇等。
作为多元醇,例如可举出:二元醇(例如,乙二醇、丙二醇、三亚甲基二醇、1,2-丁二醇、1,3-丁二醇、四亚甲基二醇、2,3-丁二醇、五亚甲基二醇、2-丁烯-1,4-二醇、己二醇、辛二醇等);三元醇(例如,甘油、三羟甲基丙烷等);四元醇(例如,1,2,6-己三醇等的季戊四醇等);五元醇(例如,木糖醇等);六元醇(例如,山梨糖醇、甘露糖醇等);多元醇聚合物(例如,二甘醇、一缩二丙二醇、三甘醇、聚丙二醇、四甘醇、二甘油、聚乙二醇、三甘油、四甘油、聚甘油等);二元的醇烷基醚类(例如,乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、乙二醇单苯醚、乙二醇单己醚、乙二醇单2-甲基己醚、乙二醇异戊醚、乙二醇苄醚、乙二醇异丙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚等);二元醇烷基醚类(例如,二甘醇单甲醚、二甘醇单乙醚、二甘醇单丁醚、二甘醇二甲醚、二甘醇二乙醚、二甘醇丁醚、二甘醇甲基乙醚、三甘醇单甲醚、三甘醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇异丁醚、丙二醇异丙醚、一缩二丙二醇甲醚、一缩二丙二醇乙醚、一缩二丙二醇丁醚等);二元醇醚酯(例如,乙二醇单甲醚乙酸酯、乙二醇单乙醚乙酸酯、乙二醇单丁醚乙酸酯、乙二醇单苯醚乙酸酯、乙二醇二己二酸酯、乙二醇二琥珀酸酯、二甘醇单乙醚乙酸酯、二甘醇单丁醚乙酸酯、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、丙二醇单丙醚乙酸酯、丙二醇单苯醚乙酸酯等);甘油单烷基醚(例如,鲛肝醇(Chimyl Alcohol)、鲨油醇(Selachyl Alcohol)、鲨肝醇(Batyl Alcohol)等);糖醇(例如,山梨糖醇、麦芽糖醇、麦芽三糖、甘露糖醇、蔗糖、赤藓糖醇、葡萄糖、果糖、淀粉分解糖、麦芽糖、木糖醇、淀粉分解糖还原醇等);Glysolid(グリソリッド);四氢糠醇;POE-四氢糠醇;POP-丁醚;POP/POE-丁醚;三聚氧丙烯甘油基醚;POP-甘油基醚;POP-甘油基醚磷酸酯;POP/POE-季戊四醇醚、聚甘油等。
作为单糖,例如可举出:三碳糖(例如,D-甘油醛、二羟基丙酮等);四碳糖(例如,D-赤藓糖、D-赤藓酮糖、D-苏糖、赤藓糖醇等);五碳糖(例如,L-阿拉伯糖、D-木糖、L-来苏糖、D-阿拉伯糖、D-核糖、D-核酮糖、D-木酮糖、L-木酮糖等);六碳糖(例如,D-葡萄糖、D-塔罗糖、D-阿洛酮糖(D-psicose)、D-半乳糖、D-果糖、L-半乳糖、L-甘露糖、D-塔格糖(D-tagatose)等);七碳糖(例如,庚醛糖、庚酮糖(ヘプロ-ス)等);八碳糖(例如,辛酮糖等);脱氧糖(例如,2-脱氧-D-核糖、6-脱氧-L-半乳糖、6-脱氧-L-甘露糖等);氨基糖(例如,D-葡糖胺、D-半乳糖胺、唾液酸、氨基糖醛酸、胞壁酸等);糖醛酸(例如,D-葡糖醛酸、D-甘露糖醛酸、L-古罗糖醛酸、D-半乳糖醛酸、L-艾杜糖醛酸等)等。
作为寡糖,例如可举出:蔗糖、龙胆三糖、伞形糖(Umbelliferose)、乳糖、车前糖(Planteose)、异剪秋罗糖(Isolychnose)类、α,α-海藻糖(α,α-trehalose)、棉籽糖(Raffinose)、剪秋罗糖(Lychnose)类、Umbilicin(ウンビリシン)、水苏糖(Stachyose)、毛蕊花糖(Verbascose)类等。
作为多糖,例如可举出:纤维素、榅桲籽、硫酸软骨素、淀粉、半乳聚糖、硫酸皮肤素(Dermatan Sulfate)、糖原(Glycogen)、阿拉伯树胶、硫酸乙酰肝素(Heparan Sulfate)、透明质酸、黄蓍胶、硫酸角质素(Keratan Sulfate)、软骨素、黄原胶、硫酸粘液素(MucoitinSulfate)、瓜尔胶、葡聚糖、硫酸角质(Keratosulfate)、刺槐豆胶、琥珀酰聚糖、卡洛宁酸等。
作为氨基酸,例如可举出:中性氨基酸(例如,苏氨酸、半胱氨酸等);碱性氨基酸(例如,羟基赖氨酸等)等。另外,作为氨基酸衍生物,例如可举出:酰基肌氨酸钠(月桂酰基肌氨酸钠)、酰基谷氨酸盐、酰基β-丙氨酸钠、谷胱甘肽、吡咯烷酮羧酸等。
作为有机胺,例如可举出:单乙醇胺、二乙醇胺、三乙醇胺、吗啉、三异丙醇胺、2-氨基-2-甲基-1,3-丙二醇、2-氨基-2-甲基-1-丙醇等。
作为高分子乳剂,例如可举出:丙烯酸树脂乳剂、聚丙烯酸乙酯乳剂、丙烯酸树脂溶液、聚丙烯酸烷基酯乳剂、聚乙酸乙烯酯树脂乳剂、天然橡胶乳胶等。
作为pH调节剂,例如可举出:乳酸-乳酸钠、柠檬酸-柠檬酸钠、琥珀酸-琥珀酸钠等的缓冲剂等。
作为维生素类,例如可举出:维生素A、B1、B2、B6、C、E及其衍生物、泛酸及其衍生物、生物素等。
作为抗氧化剂,例如可举出:生育酚类、二丁基羟基甲苯、丁基羟基茴香醚、没食子酸酯类等。
作为抗氧化助剂,例如可举出:磷酸、柠檬酸、抗坏血酸、马来酸、丙二酸、琥珀酸、富马酸、脑磷脂、六偏磷酸盐(酯)、植酸(phytic acid)、乙二胺四乙酸等。
作为其他可掺混的成分,例如可举出:防腐剂(对羟基苯甲酸乙酯、对羟基苯甲酸丁酯、氯苯甘醚、苯氧乙醇等);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,胎盘提取物、虎耳草提取物、熊果苷等);各种提取物(例如,黄柏、黄连、紫草、芍药、当药、桦木(Birch)、鼠尾草、枇杷、人参、芦荟、锦葵、鸢尾草、葡萄、薏苡仁、丝瓜、百合、藏红花、川芎、松球、小连翘、芒柄花、蒜、辣椒、陈皮、当归、海藻等);活化剂(赋活剂)(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(ノニル酸ワレニルアミド)、烟酸苄酯、烟酸β-丁氧基乙酯、辣椒素、姜油酮、斑螫酊(Cantharides Tincture)、鱼石脂(Ichthammol)、单宁酸、α-茨醇(α-冰片,α-borneol)、生育酚烟酸酯、六烟酸肌醇酯、环扁桃酯(Cyclandelate)、桂利嗪(Cinnarizine)、妥拉唑林(Tolazoline)、乙酰胆碱(Acetylcholine)、维拉帕米(Verapamil)、千金藤素(Cepharanthine)、γ-谷维素(γ-oryzanol)等);抗脂溢剂(例如,硫黄、二甲噻蒽(Thianthol)等);抗炎药(例如,氨甲环酸、硫代牛磺酸、亚牛磺酸(Hypotaurine,次牛磺酸)等)等。
而且,还可适当掺混:依地酸二钠、依地酸三钠、柠檬酸钠、聚磷酸钠、偏磷酸钠、葡糖酸、苹果酸等金属封锁剂,咖啡因、单宁、维拉帕米、氨甲环酸及其衍生物,甘草、木梨(カリン)、日本鹿蹄草等的各种草药(生药)提取物,生育酚乙酸酯、甘草次酸(グリチルレジン酸)、甘草酸(グリチルリチン酸)及其衍生物或其盐等的药剂,维生素C、抗坏血酸磷酸镁、抗坏血酸葡糖苷、熊果苷、曲酸等的美白剂,精氨酸、赖氨酸等的氨基酸及其衍生物,果糖、甘露糖、赤藓糖醇、海藻糖、木糖醇等的糖类等。
作为本发明所涉及的固体粉末化妆品的产品形态,可采用粉末化妆品范畴内的所有产品形态。具体而言,可为粉底、眼影、腮红、爽身粉(Body Powder)、粉剂香水(PerfumePowder)、婴儿爽身粉(Baby Powder)、粉饼(Pressed Powder)、除臭粉(DeodorantPowder)、扑粉等产品形态。
[固体粉末化妆品的制造方法]
〈干式的制造方法〉
将无机粉末成分、油性成分和其他成分预先在亨舍尔混合机(Henschel Mixer)中混合后,用粉碎机(Pulverizer)粉碎2次。然后,将所得的混合物填充于树脂制的中型器皿中,用公知的方法进行干式压制成形,可得到在化妆品中掺混有本发明的氧化钛的固体形状的粉末化妆品。
〈其他制造方法〉
作为将本发明的氧化钛掺混于化妆品中的制造方法,可使用公知的方法。例如也可通过下述制造方法适当地得到:日本专利第5422092号所记载的将使用挥发性溶剂的浆料进行干燥而制作的制造方法、日本专利第5972437号所记载的将使用挥发性溶剂的浆料填充后除去而制作的制造方法。
实施例
对于本发明,以下举出实施例以更详细地叙述,但本发明不限于这些实施例。在没有特别记载的情况下,掺混量以相对于掺混其成分的体系的质量%表示。
在说明实施例之前,先对在本发明中使用的二氧化钛的试验的评价方法进行说明。
评价(1):平均微晶直径的测定方法
将试样通过X射线衍射装置(Geigerflex,理学电机公司制)进行测定,通过应用谢乐(Scherrer)公式算出平均微晶直径。
评价(2):遮盖力的评价
将二氧化钛粉末以成为5%浓度的方式分散混合于硝化纤维素清漆中,将所得的分散物在黑白的遮盖率试纸JIS-K5400上以0.101μm的膜厚进行涂布、干燥,得到试验样品。将所得的试验样品利用分光测色仪(CM-2600,Konica Minolta公司制)对白与黑纸上的涂膜表面分别进行测色。算出Hunter Lab色空间中的色差(△E),并将其设为遮盖力而进行评价。需要说明的是,△E越高则表示遮盖力越小,△E越低则表示遮盖力越大。
ΔE=
(评价基准)
×:25<△E
△:22<△E≤25
○:△E≤22
评价(3):红色透过性的评价
红色透过性是指,通过与上述遮盖力相同方式在黑纸上的测定所得的各波长的分光反射率中,算出波长为450nm下的反射率与波长为650nm下的反射率比(波长为450nm下的反射率/波长为650nm下的反射率:R450/R650)。
R450/R650越高,则表示红色透过性越高,R450/R650越低,则表示红色透过性越低。
(评价基准)
×:R450/R650≤1.3
△:1.3<R450/R650≤1.35
○:1.35<R450/R650≤1.4
◎:1.4<R450/R650
评价(4):比表面积的测定方法
每单位质量的比表面积可通过作为相当于国际标准ISO 5794/1(附录D)的TheJournal of the American Chemical Society、60卷、309页、1938年2月所记载的BET(Brunauer-Emmet-Teller)法而公知的氮气吸附法来求得。
评价(5):表观的平均粒径的测定方法
用图1所示的方法,求取粒子的长轴与短轴的长度的平均值。
[用于母核的氧化钛的选定]
首先,本发明人使用可作为市售品获取的颜料级金红石型和锐钛矿型的氧化钛,采用上述评价方法进行评价。将结果示于表1。
[表1]
*1:Tipaque CR-50(石原产业公司制、表观上的平均粒径:200nm、形状:不定形)
*2:Bayertitan A(拜耳公司制、表观上的平均粒径:400nm、形状:不定形)
金红石型的颜料级氧化钛与锐钛矿型的颜料级氧化钛,红色透过性均低。另外,即使将它们在高温下烧制,红色透过性也低。
本发明人对于使用红色透过性高的金红石型氧化钛能否制造遮盖力优异的制品进行了研究。
本发明人使用专利文献(日本特开2010-173863号公报)的方法,合成了针状粒子以放射状取向凝聚而成的于粒子表面具有针状突起的2种粒径不同的二氧化钛。
将所得的氧化钛分别称为氧化钛A(比表面积:101m2/g、微晶直径:5nm、表观上的平均粒径:0.2~0.3μm、针状突起形状)、氧化钛B(比表面积:117m2/g、微晶直径:11nm、表观上的平均粒径:0.3μm、针状突起形状)。
另外,将作为市售品(ST-730:钛工业株式会社制)的针状粒子以放射状取向凝聚而成的于粒子表面具有针状突起的二氧化钛称为氧化钛C(比表面积:98m2/g、微晶直径:6nm、表观上的平均粒径:0.5μm、针状突起形状)。
另外,将作为市售品(ST-750:钛工业株式会社制)的针状粒子以放射状取向凝聚而成的于粒子表面具有针状突起的二氧化钛称为氧化钛D(84m2/g、微晶直径:8.6nm、表观上的平均粒径:1.0μm、针状突起形状)。
另外,将作为市售品(MT062;Tayca工业株式会社制)的粒子为针状的氧化钛称为氧化钛E(比表面积:47m2/g、微晶直径:23.3nm、表观上的平均粒径:65nm、针状突起形状)。
使用各二氧化钛,通过以下的方法得到了二氧化钛粉体。将所得的二氧化钛粉末采用上述评价方法进行评价,研究了烧制前的二氧化钛的种类与烧制温度的关系。将结果示于表2~表6。
(二氧化钛粉体的制造方法)
将用于母核的二氧化钛100g放入石英制的坩锅中,在马弗炉中在各温度下进行烧制1小时,由此得到了二氧化钛粉末。
氧化钛A(比表面积:101m2/g、微晶直径:5nm、表观上的平均粒径:0.2~0.3μm、针状突起形状)
[表2]
氧化钛B(比表面积:117m2/g、微晶直径:11nm、表观上的平均粒径:0.3μm、针状突起形状)
[表3]
氧化钛C(比表面积:98m2/g、微晶直径:6nm、表观上的平均粒径:0.5μm、针状突起形状)
[表4]
氧化钛D(84m2/g、微晶直径:8.6nm、表观上的平均粒径:1μm、针状突起形状)
[表5]
氧化钛E(比表面积:47m2/g、微晶直径:23.3nm、表观上的平均粒径:65nm、针状突起形状)
[表6]
试验例 | 5-1 | 5-2 | 5-3 | 5-4 |
形状 | 针状 | 针状 | 针状 | 针状 |
短径与长径之比 | 3.3 | 3.3 | 3.3 | 3.2 |
表观的粒径/nm | 65 | 65 | 65 | 65 |
微晶直径/nm | 23.3 | 23.3 | 24.3 | 26.9 |
比表面积/m<sup>2</sup>/g | 47 | 44 | 40 | 19 |
烧制温度/℃ | - | 350 | 630 | 720 |
红色透过性 | ◎ | ◎ | ◎ | ◎ |
遮盖力 | × | × | × | × |
就氧化钛A~C而言,遮盖力均会通过使烧制温度上升而提高。由于比表面积随着温度的上升而减少,因此可知,烧制前所存在的以放射状取向凝聚的针状粒子彼此凝结,因而减少存在于粒子中的空隙。这会引起表观折射率提高,遮盖力提高。但是,红色透过性会逐渐减少。特别是在高温下烧制时会产生过度烧结,最初的红色透过性显著降低。
特别是,关于平均粒径大的氧化钛C,在700℃下几乎丧失了红色透过性。
另外,与氧化钛A~C同样地为针状粒子以放射状取向凝聚而成的氧化钛D,虽然与氧化钛A~C同样地为随着烧制温度上升而比表面积减少,但是由于表观粒径显著较大,所以遮盖力的提高极为微小。而且,关于红色透过性,也由于表观粒径显著较大,因此无论在烧制前后,均为低红色透过性,无法得到所期望的红色透过性。
另外,关于烧制前的平均粒径较小且为由单一的针状粒子构成的氧化钛E,即使在烧制后形状也无大的变化,虽然维持了红色透过性,但遮盖力完全没有提高。
而且,研究了不同形状的二氧化钛。
另外,将作为市售品(TT055(A);石原产业株式会社制)的粒子为粒状的二氧化钛称为氧化钛F(比表面积:37m2/g、微晶直径:24.8nm、表观上的平均粒径:50nm、粒状)。
另外,将作为市售品(ST643:钛工业株式会社制)的棒状粒子以稻草束状取向凝聚而成的二氧化钛称为氧化钛G(比表面积:132m2/g、微晶直径:8.6nm、表观上的平均粒径:200nm、稻草束状)。
氧化钛F(比表面积:37m2/g、微晶直径:24.8nm、表观上的平均粒径:50nm、粒状)
[表7]
试验例 | 6-1 | 6-2 | 6-3 | 6-4 |
形状 | 粒状 | 粒状 | 粒状 | 粒状 |
短径与长径之比 | 1.7 | 1.7 | 1.7 | 1.7 |
表观的粒径 | 50 | 50 | 50 | 50 |
微晶直径 | 24.8 | 25.1 | 24.8 | 26.5 |
比表面积 | 37 | 38 | 32 | 35 |
烧制温度 | - | 350 | 630 | 720 |
红色透过性 | ◎ | ◎ | ◎ | ◎ |
遮盖力 | × | × | × | × |
由试验例6-1~6-4可知,在将粒状的氧化钛在350~720℃下烧制的情况下,微晶直径没有变化,就比表面积、微晶直径而言均无法成为本发明的烧制后的氧化钛。
因此,虽然具有红色透过性,但无法得到所期望的遮盖力。
氧化钛G(比表面积:132m2/g、微晶直径:8.6nm、表观上的平均粒径:200nm、稻草束状)
[表8]
试验例 | 7-1 | 7-2 | 7-3 | 7-4 |
形状 | 稻草束 | 稻草束 | 稻草束 | 稻草束 |
短径与长径之比 | 2.5 | 2.5 | 2.5 | 2.5 |
表观的粒径 | 200 | 200 | 200 | 200 |
微晶直径 | 8.6 | 8.7 | 9.9 | 11.1 |
比表面积 | 132 | 79 | 34 | 39 |
烧制温度 | - | 350 | 630 | 720 |
红色透过性 | △ | △ | △ | △ |
遮盖力 | × | △ | △ | △ |
试验例7-1所用的氧化钛与本发明的用于母核的二氧化钛同样地满足(a)表观上的平均粒径、(b)通过X射线衍射法测定的平均微晶直径、(c)比表面积,但是粒子表面不具有针状突起。而且,由于短径/长径之比大至2.5,所以即使在烧制后也无法实现充分的红色透过性和遮盖力。
由这些研究可知,适合作为用于本发明的母核的氧化钛,从遮盖性的提升和红色透过性的维持的观点出发,为可允许的温度范围较广的氧化钛B。
将测定金红石型的颜料级氧化钛(*1)和氧化钛B(未烧制、烧制温度:700℃、900℃)的分光反射率的结果示于图2。需要说明的是,测定是将二氧化钛粉末以浓度成为5%的方式分散混合于硝化纤维素清漆中,并将所得的分散物在黑白的遮盖率试纸JIS-K5400上以0.101μm的膜厚进行涂布、干燥,而得到试验样品。将所得的试验样品利用分光测色仪(CM-2600、Konica Minolta公司制),对黑纸上的涂膜表面分别进行测色,得到分光反射率。
然后,对于二氧化钛B,拍摄未烧制者、烧制者(烧制温度:300℃、500℃、700℃、900℃)的TEM影像。将结果示于图3。
另外,对于二氧化钛B,测定基于旋转窑的烧制温度变化的遮蔽力、红色透过性。将结果分别示于图4、图5。
由以上的结果,在于马弗炉中烧制的情况下,适合的温度为500~800℃,特别是更希望为500~700℃。
其次,本发明人以氧化钛B作为母核,在500~800℃的范围仔细研究了烧制温度。即,本发明人将改变了烧制温度的二氧化钛粉体利用上述评价方法进行评价。将结果示于表5、表6。
烧制在更接近量产、烧制效率高的旋转型烧制炉(旋转窑)中进行。
一般而言,旋转型烧制炉的烧制效率高,已知在以低于用静置下烧制的马弗炉烧制的情形的温度下,可得到同样的烧制状态。
[表9]
[表10]
比表面积是表示所得的氧化钛粒子的空隙率降低和烧结进行的指标,用于本发明的二氧化钛优选为通过将成为母核的二氧化钛粉体进行烧制而使其比表面积成为相较于烧制前(100%)为8~30%的范围。
由这些的结果可知,遮盖力和红色透过性优异的是,烧制温度优选为550~700℃、更优选为575~660℃。
[癸基三硅氧烷羧酸锌处理滑石的制造方法]
最初,本发明人使用上述化学式(4)的Zn盐作为有机硅氧烷衍生物,对滑石(商品名JA68R,浅田制粉株式会社制)实施表面处理,调制表面处理粉体。
[弹性体处理滑石的制造方法]
在亨舍尔混合机中,加入(C)滑石和具有羧基的有机硅聚合物,以低速混合10分钟。然后,在其中加入具有氨基的有机硅聚合物,以低速混合10分钟,加热,由此得到弹性体处理滑石。
[表11]
[固体粉末化妆品]
而且,本发明人使用表6的在烧制温度660℃下所得的二氧化钛,并通过下述的表面处理方法得到疏水化处理的二氧化钛,将掺混有该二氧化钛的固体粉末化妆品分别通过常规方法进行调整。然后,将所得的化妆品利用下述评价方法进行评价。
[二氧化钛粉体的表面处理方法]
将所得的二氧化钛粉体分散于离子交换水中,加温后,使其吸附硬脂酸3质量%,然后通过脱水、洗净、干燥而得到表面处理二氧化钛。
[固体粉末化妆品的制造方法]
[固体粉末化妆品的制造方法]
〈干式的制造方法〉
将无机粉末成分、油性成分和其他成分预先在亨舍尔混合机中混合后,用粉碎机粉碎2次。然后,将所得的混合物填充于树脂制的中型器皿中,用公知的方法进行干式压制成形,可得到在化妆品中掺混有本发明的氧化钛的固体形状的粉末化妆品。
〈其他制造方法〉
作为将本发明的氧化钛掺混于化妆品中的制造方法,可使用公知的方法。例如也可通过下述制造方法适当地得到:日本专利第5422092号所记载的将使用挥发性溶剂的浆料进行干燥而制作的制造方法、日本专利第5972437号所记载的将使用挥发性溶剂的浆料填充后除去而制作的制造方法。
[固体粉末化妆品的评价方法]
评价(6):自然的妆容
10名专业评审员将试样涂布于面部,评价涂布后的使用感。
A:10名评审员中7名以上回答为妆容自然
B:10名评审员中5名以上且低于7名回答为妆容自然
C:10名评审员中低于5名回答为妆容自然
评价(7):铺展性良好的程度
10名专业评审员将试样涂布于面部,评价涂布后的使用感。
A:10名评审员中7名以上回答为铺展性良好
B:10名评审员中5名以上且低于7名回答为铺展性良好
C:10名评审员中低于5名回答为铺展性良好
评价(8):不泛白
10名专业评审员将试样涂布于面部,评价涂布后的使用感。
A:10名评审员中7名以上回答为不泛白
B:10名评审员中5名以上且低于7名回答为不泛白
C:10名评审员中低于5名回答为不泛白
评价(9):没有颜色不均匀
10名专业评审员将试样涂布于面部,评价涂布后的使用感。
A:10名评审员中7名以上回答为没有颜色不均匀
B:10名评审员中5名以上且低于7名回答为没有颜色不均匀
C:10名评审员中低于5名回答为没有颜色不均匀
评价(10):冲击稳定性
将固体粉末化妆品设置于化妆品用的粉盒容器中,以化妆品面朝下的状态使其从50cm的高度掉落至金属板上,研究直到破裂为止的次数。针对各化妆品,试验数(N)=3的平均值为5次以上即评价为具有充分的耐冲击性。
○…5次以上
×…低于5次
[表12]
试验例 | 8-1 | 8-2 | 8-3 | 8-4 | 8-5 | 8-6 | 8-7 |
癸基三硅氧烷羧酸锌处理滑石 | 至100% | 至100% | 至100% | ||||
有机硅弹性体处理滑石 | 至100% | 至100% | |||||
支链烷基硅氧烷处理滑石(*1) | 至100% | ||||||
滑石(*2) | 至100% | ||||||
合成氟金云母(*3) | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
合成氟金云母铁(*4) | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
硫酸钡 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
氮化硼(*5) | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
颜料级二氧化钛(*6) | 10 | 10 | |||||
本发明二氧化钛(烧制后) | 10 | 10 | 10 | 10 | |||
烧制前二氧化钛 | 10 | ||||||
微粒二氧化钛(*7) | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
有机硅处理氧化铁红(*8) | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
有机硅处理氧化铁黄(*9) | 1.75 | 1.75 | 1.75 | 1.75 | 1.75 | 1.75 | 1.75 |
有机硅处理氧化铁黑(*10) | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
球状氨基甲酸乙酯粉末(*11) | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
球状有机硅粉末(*12) | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
珍珠(云母钛) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
防腐剂 | 适量 | 适量 | 适量 | 适量 | 适量 | 适量 | 适量 |
半固体硅油 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
硅油 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
酯油 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
甲氧基肉桂酸辛酯 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
抗氧化剂 | 适量 | 适量 | 适量 | 适量 | 适量 | 适量 | 适量 |
合计 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
冲击稳定性(掉落稳定性5次以上) | ○ | ○ | ○ | × | × | ○ | ○ |
自然的妆容 | A | A | A | A | A | C | C |
斑点、雀斑的遮盖 | A | A | C | A | A | A | A |
肌理的显眼 | A | A | C | A | A | A | A |
铺展性良好的程度 | A | A | A | A | A | A | A |
不泛白 | A | A | A | A | A | B | B |
没有颜色不均匀 | A | A | A | A | A | A | A |
[表13]
试验例 | 8-8 | 8-9 | 8-10 | 8-11 | 8-12 | 8-13 |
癸基三硅氧烷羧酸锌处理滑石 | 至100% | 至100% | 至100% | 至100% | 3 | 45 |
有机硅弹性体处理滑石 | ||||||
支链烷基硅氧烷处理滑石(*1) | ||||||
滑石(*2) | 至100% | 至100% | ||||
合成氟金云母(*3) | 5 | 5 | 5 | 5 | 5 | 5 |
合成氟金云母铁(*4) | 10 | 5 | 10 | 5 | 10 | 5 |
硫酸钡 | 3 | 3 | 3 | 3 | 3 | 3 |
氮化硼(*5) | 5 | 5 | 5 | 5 | 5 | 5 |
颜料级二氧化钛(*6) | ||||||
本发明二氧化钛(烧制后) | 0.6 | 32 | 10 | 10 | 7 | 7 |
烧制前二氧化钛 | ||||||
微粒二氧化钛(*7) | 1 | 1 | 1 | 1 | 1 | 1 |
有机硅处理氧化铁红(*8) | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
有机硅处理氧化铁黄(*9) | 1.75 | 1.75 | 1.75 | 1.75 | 1.75 | 1.75 |
有机硅处理氧化铁黑(*10) | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
球状氨基甲酸乙酯粉末(*11) | 7 | 7 | 1 | 24 | 5 | 5 |
球状有机硅粉末(*12) | 8 | 8 | 2 | 8 | 7 | 7 |
珍珠(云母钛) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
防腐剂 | 适量 | 适量 | 适量 | 适量 | 适量 | 适量 |
半固体硅油 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
硅油 | 1 | 1 | 1 | 1 | 1 | 1 |
酯油 | 5 | 5 | 5 | 5 | 5 | 5 |
甲氧基肉桂酸辛酯 | 5 | 5 | 5 | 5 | 5 | 5 |
抗氧化剂 | 适量 | 适量 | 适量 | 适量 | 适量 | 适量 |
合计 | 100 | 100 | 100 | 100 | 100 | 100 |
冲击稳定性(掉落稳定性5次以上) | ○ | ○ | ○ | × | × | ○ |
自然的妆容 | B | C | A | A | A | A |
斑点、雀斑的遮盖 | C | A | A | A | A | A |
肌理的显眼 | B | A | A | A | A | B |
铺展性良好的程度 | A | A | C | A | A | B |
不泛白 | A | C | A | A | A | A |
没有颜色不均匀 | A | A | A | A | A | B |
(*1)三好化成株式会社制BAE-Talc JA-68R
(*2)浅田制粉制Talc JA-68R
(*3)Topy工业株式会社制PDM-9WA
(*4)Topy工业株式会社制PDM-FE
(*5)默克株式会社制Ronaflair Boroneige SF-12
(*6)石原产业株式会社制Tipaque CR-50
(*7)Tayca株式会社制MT-100TV
(*8)大东化成工业株式会社制OTS-2氧化铁红No.216P
(*9)大东化成工业株式会社制OTS-2 STN-1
(*10)大东化成工业株式会社制OTS-2 BL-100
(*11)东色PIGMENT株式会社制D-400
(*12)信越化学株式会社制KSP-100
由试验例7-1~7-2可知,使用本发明的二氧化钛和本发明的表面处理滑石的固体粉末化妆品,可高掺混球状粉末,而使用性和冲击稳定性优异,并且涂布于肌肤时具有自然的妆容和不泛白。
由试验例7-3可知,在将用于母核的二氧化钛直接使用的情况下,在斑点、雀斑的遮盖力、肌理的显眼的方面较差。
由试验例7-4~7-5可知,在使用本发明所代表的未实施金属皂表面处理的粉末的情况下,在冲击稳定性的方面较差。
由试验例7-6~7-7可知,在使用以往的颜料级氧化钛的情况下,涂布于肌肤时在自然的妆容和不泛白的方面较差。
由试验例7-8可知,若本发明的二氧化钛的量较本发明的范围少,则在斑点/雀斑的遮盖的方面较差,无法得到自然的妆容。
由试验例7-9可知,若本发明的二氧化钛的量较本发明的范围多,则在自然的妆容、不泛白的方面较差。
由试验例7-10可知,若球状粉末的量较本发明的范围少,则在铺展性良好的程度的方面较差。
由试验例7-11可知,若球状粉末的量较本发明的范围多,则在冲击稳定性的方面较差。
由试验例7-12可知,若进行弹性体处理或金属皂处理后所用的滑石的量较本发明的范围少,则在冲击稳定性的方面较差。
由试验例7-13可知,若进行弹性体处理或金属皂处理后所用的滑石的量较本发明的范围多,则化妆品的卸除变差,且在铺展性良好的程度的方面较差。
Claims (8)
1.固体粉末化妆品,其特征在于,该固体粉末化妆品包含:
1~30质量%的二氧化钛粉体,该二氧化钛粉体的特征在于,其是表观上的平均粒径为100nm以上且低于500nm、通过X射线衍射法测定的平均微晶直径为15~30nm、比表面积为10~30m2/g、且具有呈放射状突出的针状的突起凝结而成的形状的粒子,且形状的短径与长径之比(长径/短径)为1.0以上且低于2.5;
5~30质量%的球状粉末;以及
5~40质量%的由下述(A)成分和(B)成分构成的弹性体或金属皂表面处理过的粉末;
弹性体由下述(A)成分和(B)成分构成:
(A) 具有氨基的有机硅聚合物
(B) 具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物
且氨基与羧基的摩尔比在Y/X=0.1~1.2的范围,其中,Y是(B)成分所含的羧基的摩尔量,X是(A)成分所含的氨基的摩尔量。
2.权利要求1所述的固体粉末化妆品,其特征在于,(A)成分为下述通式(1)所示的侧链型氨基改性硅氧烷,
[化学式1]
通式(1)中,X为碳数1~18的烷基,R、R’为烷基。
4.固体粉末化妆品,其特征在于,该固体粉末化妆品包含:
1~30质量%的金红石型二氧化钛粉体,该金红石型二氧化钛粉体的通过X射线衍射法测定的平均微晶直径为15~30nm,比表面积为10~30m2/g,且450nm的反射率的值为650nm的反射率的值的1.3倍以上,色差△E为22以下;
5~30质量%的球状粉末;以及
5~40质量%的由下述(A)成分和(B)成分构成的弹性体或金属皂表面处理过的粉末;
弹性体由下述(A)成分和(B)成分构成:
(A) 具有氨基的有机硅聚合物
(B) 具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物
且氨基与羧基的摩尔比在Y/X=0.1~1.2的范围,其中,Y是(B)成分所含的羧基的摩尔量,X是(A)成分所含的氨基的摩尔量,
需要说明的是,色差△E是将二氧化钛粉体以成为5%浓度的方式分散混合于硝化纤维素清漆中,将所得的分散物在黑白的遮盖率试纸JIS-K5400上以0.101μm的膜厚进行涂布、干燥而得到试验样品,将所得的试验样品利用分光测色仪对白与黑纸上的涂膜表面分别进行测色,算出Hunter Lab色空间中的色差△E。
5.固体粉末化妆品,其特征在于,该固体粉末化妆品包含:
1~30质量%的二氧化钛粉体,该二氧化钛粉体是将满足下述(a)~(c)的针状粒子以放射状取向凝聚而成的于粒子表面具有针状突起的金红石型二氧化钛烧制所得的金红石型二氧化钛粉体,其表观上的平均粒径为100nm以上且低于500nm,通过X射线衍射法测定的平均微晶直径为15~30nm,比表面积为10~30m2/g;
(a) 表观上的平均粒径为100nm以上且低于500nm
(b) 通过X射线衍射法测定的平均微晶直径为1~25nm
(c) 比表面积为40~200m2/g
5~30质量%的球状粉末;以及
5~40质量%的由下述(A)成分和(B)成分构成的弹性体或金属皂表面处理过的粉末;
弹性体由下述(A)成分和(B)成分构成:
(A) 具有氨基的有机硅聚合物
(B) 具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物
且氨基与羧基的摩尔比在Y/X=0.1~1.2的范围,其中,Y是(B)成分所含的羧基的摩尔量,X是(A)成分所含的氨基的摩尔量。
6.固体粉末化妆品,其特征在于,该固体粉末化妆品包含:
1~30质量%的二氧化钛粉体,该二氧化钛粉体的特征在于,其是将满足下述(a)~(c)的于粒子表面具有针状突起的金红石型二氧化钛烧制所得的金红石型二氧化钛粉体,且烧制后的金红石型二氧化钛粉体的比表面积相对于烧制前为8~50%;
(a) 表观上的平均粒径为100nm以上且低于500nm
(b) 通过X射线衍射法测定的平均微晶直径为1~25nm
(c) 比表面积为40~200m2/g
5~30质量%的球状粉末;以及
5~40质量%的由下述(A)成分和(B)成分构成的弹性体或金属皂表面处理过的粉末;
弹性体由下述(A)成分和(B)成分构成:
(A) 具有氨基的有机硅聚合物
(B) 具有羧基的有机硅聚合物或具有羧基的丙烯酸聚合物
且氨基与羧基的摩尔比在Y/X=0.1~1.2的范围,其中,Y是(B)成分所含的羧基的摩尔量,X是(A)成分所含的氨基的摩尔量。
7.权利要求5或6所述的固体粉末化妆品,其特征在于,二氧化钛的烧制温度为500~800℃。
8.权利要求7所述的固体粉末化妆品,其特征在于,二氧化钛的烧制温度为550~750℃。
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TW201904555A (zh) | 2019-02-01 |
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WO2019003756A1 (ja) | 2019-01-03 |
CN110769802B (zh) | 2023-11-07 |
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