TW202346431A - 複合粒子、複合粒子的製造方法、及化粧料 - Google Patents
複合粒子、複合粒子的製造方法、及化粧料 Download PDFInfo
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- TW202346431A TW202346431A TW112112504A TW112112504A TW202346431A TW 202346431 A TW202346431 A TW 202346431A TW 112112504 A TW112112504 A TW 112112504A TW 112112504 A TW112112504 A TW 112112504A TW 202346431 A TW202346431 A TW 202346431A
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Classifications
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- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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- A—HUMAN NECESSITIES
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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- C—CHEMISTRY; METALLURGY
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Abstract
本發明是一種複合粒子,其於球狀有機樹脂粒子的表面附著有橡膠粒子,其特徵在於,該橡膠粒子以二氧化矽為黏合劑而固著於該有機樹脂粒子。由此,提供一種使橡膠粒子附著於有機樹脂粒子的表面而成之複合粒子及其製造方法、以及含有該複合粒子之化粧料,能夠賦予觸感柔軟或使用感順滑、具有延展性、且藉由光散射性而具有自然的粧感之效果。
Description
本發明關於一種複合粒子,具體而言,關於一種使橡膠粒子附著於有機樹脂粒子的表面而成之複合粒子及其製造方法、以及含有該粒子而成之化粧料。
聚醯胺樹脂、聚丙烯酸樹脂、聚苯乙烯樹脂、矽酮樹脂(聚有機倍半矽氧烷)等有機樹脂(塑膠)的球狀粒子被用於粉底等化粧品中,以賦予順滑的使用感及延展性。又,由於使光散射,因此,亦能夠賦予無不自然的光澤(油光)之自然的粧感之效果。該等粒子為樹脂(塑膠),故有觸感較硬之缺點。
微塑膠是一種微細有機物,不溶於水,為固體且直徑為5 mm以下,其對生態系統的影響令人擔憂,如微塑膠自身、含有或吸附之化學物質有可能被帶入食物鏈中等,全球範圍內也是關注度較高的問題,一部分國家當局正在檢討進行限制。製造成上述粒子之微塑膠由於尺寸非常小,因此,當流入河川、海洋、池沼等時難以回收。又,前述有機樹脂粒子在自然環境中分解得非常慢。因此,提出於化粧料中使用來自天然物之纖維素粒子(專利文獻1)。然而,纖維素粒子雖可生物降解,但有潤滑性較低、且觸感較硬之缺點。
於專利文獻2中,提出一種化粧料,其是使用使矽酮彈性體附著於粒子(母粒子)的表面而成之複合粒子。藉由矽酮彈性體的光擴散性,而提升自然的粧感,且可獲得柔軟濕潤的觸感。具體舉例將矽酮樹脂(聚有機倍半矽氧烷)作為黏合劑,以使矽酮彈性體固著於粒子表面。當該複合粒子的母粒子為有機樹脂時,相對於為無機粒子時而言,有時潤滑性較差,進而延展性變差而產生浮粉。一般認為其原因在於,母粒子的有機樹脂及黏合劑的矽酮樹脂沒有無機粒子硬。
[先前技術文獻]
(專利文獻)
專利文獻1:國際公開WO2020/004604號手冊
專利文獻2:日本特開2011-1332號公報
[發明所欲解決之問題]
本發明是鑒於上述情況而完成的,其目的在於提供一種使橡膠粒子附著於有機樹脂粒子的表面而成之複合粒子及其製造方法、以及含有該複合粒子之化粧料,能夠賦予觸感柔軟或使用感順滑、具有延展性、且藉由光散射性而具有自然的粧感之效果。
[解決問題之技術手段]
為了解決上述問題,於本發明中,
提供一種複合粒子,其於球狀有機樹脂粒子的表面附著有橡膠粒子,該橡膠粒子以二氧化矽為黏合劑而固著於該有機樹脂粒子。
若為此種複合粒子,則能夠賦予觸感柔軟或使用感順滑、具有延展性、且藉由光散射性而具有自然的粧感之效果。
又,較佳為相對於該有機樹脂粒子100質量份,該橡膠粒子的量為0.1~100質量份的範圍。
若為此種橡膠粒子的量,則能夠對化粧料賦予更顯著的柔軟的觸感或順滑的使用感、延展性、光散射性,且能夠使凝聚性較低。
又,較佳為相對於該橡膠粒子100質量份,該二氧化矽的量為10~1,000質量份的範圍。
若為此種二氧化矽的量,則能夠更切實地使橡膠粒子固著於有機樹脂粒子表面,且能夠對化粧料賦予柔軟的觸感。
又,較佳為該橡膠粒子為矽酮橡膠粒子。
於本發明中,可較佳地使用此種橡膠粒子。
又,較佳為該有機樹脂粒子為纖維素粒子。
於本發明中,可較佳地使用此種有機樹脂粒子。
又,於本發明中,提供一種複合粒子的製造方法,其是上述複合粒子的製造方法,
向將該有機樹脂粒子、該橡膠粒子、陽離子性物質、鹼性物質及水調配而成之混合液中添加四烷氧矽烷,使其進行水解及縮合反應,且,
使該陽離子性物質為陽離子性界面活性劑及/或陽離子性水溶性高分子。
如此,能夠製造本發明的複合粒子。
又,較佳為使該陽離子性物質為陽離子性界面活性劑及陽離子性水溶性高分子。
如此,能夠更切實地製造本發明的複合粒子。
又,較佳為相對於該混合液中的水100質量份,使該陽離子性物質的調配量為0.0001~2.0質量份的範圍。
如此,橡膠粒子附著於有機樹脂粒子的表面,且利用二氧化矽進行之固著較為充分。
又,較佳為相對於該混合液中的水100質量份,使該陽離子性界面活性劑的調配量為0.001~1.9質量份,且,相對於該混合液中的水100質量份,使該陽離子性水溶性高分子的調配量為0.0001~1.0質量份的範圍。
如此,橡膠粒子更切實地附著於有機樹脂粒子的表面,且利用二氧化矽進行之固著較為充分。
又,於本發明中,提供一種化粧料,其含有上述複合粒子。
本發明的化粧料是觸感柔軟或使用感順滑、具有延展性、且藉由光散射性而具有自然的粧感之化粧料。
(發明的效果)
根據本發明,可提供一種複合粒子及其製造方法、以及含有該複合粒子之化粧料,能夠賦予觸感柔軟或使用感順滑、具有延展性、且藉由光散射性而具有自然的粧感之效果。
如上所述,需要開發一種使橡膠粒子附著於有機樹脂粒子的表面而成之複合粒子及其製造方法、以及含有該複合粒子之化粧料,能夠賦予觸感柔軟或使用感順滑、具有延展性、且藉由光散射性而具有自然的粧感之效果。
本發明者針對上述問題反復進行努力研究,結果發現,以二氧化矽為黏合劑使橡膠粒子固著於球狀有機樹脂粒子的表面之複合粒子能夠對化粧料賦予觸感柔軟或使用感順滑、具有延展性、且藉由光散射性而具有自然的粧感之效果,從而完成本發明。
即,本發明是一種複合粒子,其於球狀有機樹脂粒子的表面附著有橡膠粒子,該橡膠粒子以二氧化矽為黏合劑而固著於該有機樹脂粒子。
又,本發明是一種複合粒子的製造方法,其是上述複合粒子的製造方法,向將該有機樹脂粒子、該橡膠粒子、陽離子性物質、鹼性物質及水調配而成之混合液中添加四烷氧矽烷,使其進行水解及縮合反應,且,使該陽離子性物質為陽離子性界面活性劑及/或陽離子性水溶性高分子。
以下,對本發明進行詳細說明,但本發明並不限於以下內容。
[複合粒子]
本發明的複合粒子是於球狀有機樹脂粒子的表面附著有橡膠粒子,橡膠粒子以二氧化矽為黏合劑而固著於有機樹脂粒子。
其體積平均粒徑可藉由庫爾特計數器法(電阻法)來測定。粒徑是藉由有機樹脂粒子的粒徑、橡膠粒子的粒徑、附著於有機樹脂粒子表面之橡膠粒子的量來決定。
[有機樹脂粒子]
本發明中使用之有機樹脂粒子是複合粒子的核心粒子。有機樹脂粒子可單獨使用一種或適當組合使用兩種以上,若為球狀,則可應用實質上可用於化粧料之粉體及整個粒徑範圍的粒子。
有機樹脂粒子的形狀為球狀。於本說明書中,「球狀」不僅是指粒子的形狀為正球狀,而且指最長軸的長度/最短軸的長度(縱橫比)平均通常為1.0~4.0、較佳為1.0~2.0、更佳為1.0~1.6、進而更佳為1.0~1.4的範圍之變形後之球。粒子的形狀可藉由利用光學顯微鏡、電子顯微鏡等觀察粒子來確認。粒子的結構可為無孔、多孔中的任一種。
體積平均粒徑較佳為0.5~50 μm的範圍,更佳為1~30 μm。若粒徑為0.5 μm以上,則可充分獲得賦予清爽感、順滑性等使用感或延展性的效果;而若為50 μm以下,則能夠降低粗糙感。再者,體積平均粒徑是藉由庫爾特計數器法(電阻法)來測定。
作為有機樹脂粒子,可列舉例如:聚乙烯;聚丙烯;聚苯乙烯;二乙烯苯樹脂;聚氯乙烯;甲基丙烯酸樹脂;聚四氟乙烯;甲基丙烯酸-苯乙烯共聚物;聚醯胺;聚碳酸酯;聚對苯二甲酸乙二酯、聚丁二酸丁二醇酯、聚羥基丁酸酯、聚己內酯等聚酯;纖維素;纖維素衍生物;海藻酸鈣;酚樹脂;三聚氰胺樹脂;苯并胍胺樹脂;環氧樹脂;聚胺基甲酸酯等粒子。
當需要可生物降解的特性時,可列舉聚丁二酸丁二醇酯、聚羥基丁酸酯、聚己內酯、纖維素、及乙酸纖維素或醋酸丙酸纖維素等纖維素衍生物的粒子等。進而,當需要來自天然物時,可列舉纖維素粒子。
[橡膠粒子]
本發明中使用之橡膠粒子是附著於作為複合粒子的核心之有機樹脂粒子的表面之粒子。橡膠粒子可單獨使用一種或適當組合使用兩種以上,且可應用實質上可用於化粧料之粉體及整個粒徑範圍的粒子。又,其幾何學態樣為通常用於化粧料的形狀即可,可為球狀、多面體狀、紡錘狀、針狀、板狀等中的任一形狀,且可為無孔、多孔中的任一種。
橡膠粒子的體積平均粒徑較佳為小於有機樹脂粒子。若小於作為核心粉體之有機樹脂粒子,則粉體的柔軟觸感或順滑的使用感、延展性、光散射性等特性會充分展現。體積平均粒徑較佳為0.05~5 μm的範圍,更佳為0.1~1 μm。再者,體積平均粒徑是藉由雷射繞射/散射法來測定。
構成橡膠粒子之橡膠較佳為不黏,其橡膠硬度較佳為在利用日本JISK6253所規定之A型硬度計測定時為5~95的範圍,更佳為10~70。若橡膠硬度為5以上,則凝聚性較低,能夠對化粧料賦予良好的潤滑性或延展性,因此,不會產生浮粉。若橡膠硬度為95以下,則能夠獲得柔軟的觸感。再者,橡膠硬度是指按照粒子的組成來製作日本JISK6253所規定之形狀、尺寸的試片並進行測定之值。
作為橡膠粒子,可列舉聚丁二烯橡膠、丙烯酸橡膠、胺基甲酸酯橡膠、矽酮橡膠、氟橡膠等的粒子。就容易獲得柔軟的觸感之方面而言,較佳為矽酮橡膠粒子。
矽酮橡膠較佳為由具有以式-(R
2SiO
2/2)
a-表示之線狀有機矽氧烷嵌段之硬化物組成。此處,式中的R為經取代或未經取代之碳數為1~30的一價烴基。a為5~5,000的正整數。
R的碳原子數為1~30,較佳為1~22,更佳為1~18。作為R,可列舉例如:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、癸基、十一烷基、十二烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基、二十三烷基、二十四烷基、三十烷基等烷基;苯基、甲苯基、萘基等芳基;苄基、苯乙基等芳烷基;乙烯基、烯丙基等烯基;環戊基、環己基、環庚基等環烷基;及與該等基團的碳原子鍵結之部分或全部氫原子經鹵素原子(氟原子、氯原子、溴原子、碘原子)等原子及/或丙烯醯氧基、甲基丙烯醯氧基、環氧基、環氧丙氧基、羧基等取代基取代之烴基等。較佳為碳數為1~18的烷基或苯基,較佳為所有R中的50莫耳%以上為甲基。
矽酮橡膠可由硬化性液態矽酮組成物獲得,其硬化可舉例利用加成反應、縮合反應、自由基反應等來進行。硬化性液態矽酮組成物是指含有具有上述硬化反應的反應性基團之成分(具有雙方的反應性基團之成分、具有一方的反應性基團之成分及具有另一方的反應性基團之成分)、及硬化觸媒或自由基產生劑之組成物。
當利用加成反應進行硬化而製成矽酮橡膠時,硬化性液態矽酮組成物可舉例(A)具有烯基之有機聚矽氧烷、(B)具有與矽原子鍵結之氫原子之有機氫聚矽氧烷、及含有加成反應用觸媒之組成物。
(A)成分是由下述平均組成式(1)
R
1 bR
2 cSiO
(4-b-c)/2(1)
表示、且於一分子中具有至少兩個烯基之有機聚矽氧烷。式中,R
1彼此獨立地為未經取代或經取代之不具有烯基之碳原子數為1~30的一價烴基。R
2彼此獨立地為碳原子數為2~6的烯基。b及c為滿足0<b<3、0<c≦3及0.1≦b+c≦3之正數。
既可單獨使用由平均組成式(1)表示之有機聚矽氧烷的一種,亦可併用兩種以上。
R
1的碳原子數為1~30,較佳為1~22,更佳為1~18。R
1可列舉針對上述R所列舉之基團中除烯基以外的一價烴基,R
1較佳為50莫耳%以上為甲基。R
2可列舉乙烯基、烯丙基、丙烯基、丁烯基、戊烯基、己烯基,較佳為乙烯基。b及c較佳為滿足0<b≦2.295、0.005≦c≦2.3、0.5≦b+c≦2.3之正數。
(A)成分在25℃的黏度較佳為100,000 mm
2/s以下,更佳為10,000 mm
2/s以下。若黏度為100,000 mm
2/s以下,則於下述矽酮橡膠粒子的水分散液的製作中,尤其容易獲得粒徑分佈較窄的矽酮微粒子。黏度的下限並無特別限定,為0.7 mm
2/s以上、尤其是2 mm
2/s以上即可。再者,於本發明中,動黏度的值可設為於25℃利用毛細管黏度計所測定之值。
又,(A)成分的結構可為直鏈狀、環狀及分支狀中之任一種,尤佳為直鏈狀或分支單元較少的分支狀。烯基的鍵結部位並無特別限制,亦可鍵結於分子的側鏈及末端的任一矽原子,尤佳為鍵結於直鏈狀有機聚矽氧烷的兩末端的矽原子。
作為直鏈狀結構,可列舉例如由下述通式(2)表示之結構。
(式中,R
1、R
2與上述相同,d為正數,e為0或正數,f為0、1、2或3,其中,e及f為滿足e+2×f≧2之數。)
作為分支狀結構,可列舉例如藉由R
1SiO
3/2單元而形成分支之由下述通式(3)表示之結構。
(式中,R
1、R
2與上述相同,g為正數,h為0或正數,i為正數,j為0、1、2或3,其中,h及j為滿足h+j≧1之數。)
作為藉由SiO
4/2單元而形成分支之結構,可列舉例如由下述通式(4)表示之結構。
(式中,R
1、R
2與上述相同,k為正數,l為0或正數,m為正數,n為0、1、2或3,其中,l及n為滿足1+n≧1之數。)
又,可舉例由下述單元式(5)表示且每一分子具有兩個以上烯基之結構。
[R
1 3SiO
1/2]
o[R
2(R
1)
2SiO
1/2]
p[SiO
4/2]
q[(OR
3)SiO
3/2]
r(5)
(式中,R
1、R
2與上述相同,R
3為氫原子或未經取代之碳原子數為1~6的一價烴基,o為0或正數,p為正數,q為正數,r為0或正數。)
(B)成分是由下述平均組成式(6)
R
4 sH
tSiO
(4-s-t)/2(6)
表示、且於一分子中具有至少兩個與矽原子鍵結之氫原子(稱為SiH基)之有機氫聚矽氧烷。式中,R
4彼此獨立地為未經取代或經取代之不具有烯基之碳原子數為1~30的一價烴基。s及t為滿足0<s<3、0<t≦3及0.1≦s+t≦3之數。
既可單獨使用由平均組成式(6)表示之有機聚矽氧烷的一種,亦可併用兩種以上。
R
4的碳原子數為1~30,較佳為1~22,更佳為1~18。R
4可列舉與R
1相同的一價烴基,較佳為80莫耳%以上為甲基,更佳為95%以上為甲基。s及t較佳為滿足0<s≦2.295、0.005≦t≦2.3及0.5≦s+t≦2.3之正數。
(B)成分在25℃的黏度較佳為100,000 mm
2/s以下,更佳為10,000 mm
2/s以下。若黏度為100,000 mm
2/s以下,則於下述矽酮橡膠粒子的水分散液的製作中,尤其容易獲得粒徑分佈較窄的矽酮微粒子。黏度的下限並無特別限定,為0.4 mm
2/s以上、尤其是2 mm
2/s以上即可。
又,(B)成分的結構可為直鏈狀、環狀、分支狀中的任一種,尤佳為直鏈狀或分支狀。又,與矽原子鍵結之氫原子的鍵結部位並無特別限制,亦可鍵結於分子的側鏈及末端的任一矽原子。
作為直鏈狀結構,可列舉例如由下述通式(7)表示之結構。
(式中,R
4與上述相同,u為正數,v為0或正數,w為0、1、2或3,其中,v及w為滿足v+2×w≧2之數。)
作為分支狀結構,可列舉例如藉由R
4SiO
3/2單元而形成分支之由下述通式(8)表示之結構。
(式中,R
4與上述相同,x為正數,y為0或正數,z為正數,a1為0、1、2或3,其中,y及a1為滿足y+a1≧1之數。)
作為藉由SiO
4/2單元而形成分支之結構,例如可舉例由下述通式(9)表示之結構。
(式中,R
4與上述相同,b1為正數,c1為0或正數,d1為正數,e1為0、1、2或3,其中,c1及e1為滿足c1+e1≧1之數。)
又,可列舉由下述單元式(10)表示、且每一分子具有兩個以上與矽原子鍵結之氫原子之結構。
[R
4 3SiO
1/2]
f1[H(R
4)
2SiO
1/3]
g1[SiO
4/2]
h1[(OR
5)SiO
3/2]
i1(10)
式中,R
4與上述相同,R
5為氫原子或未經取代之碳原子數為1~6的一價烴基,f1為0或正數,g1為正數,h1為正數,i1為0或正數。
如上所述,(A)成分是於一分子中具有兩個以上烯基之有機聚矽氧烷,(B)成分是於一分子中具有兩個以上與矽原子鍵結之氫原子之有機氫聚矽氧烷。其中,具有僅兩個烯基之(A)有機聚矽氧烷與具有僅兩個SiH基之(B)有機氫聚矽氧烷的組合除外。其原因在於,作為(A)成分之具有兩個烯基之有機聚矽氧烷與作為(B)成分之具有兩個SiH基之有機氫矽氧烷的組合會導致硬化物黏連,從而無法獲得矽酮橡膠。即,當(A)成分具有兩個烯基時,至少一(B)成分為具有三個以上SiH基之有機氫矽氧烷,並且,當(B)成分具有兩個SiH基時,至少一(A)成分為具有三個以上烯基之有機矽氧烷。
(B)成分相對於(A)成分之量較佳為(B)成分中的SiH基相對於(A)成分中的一價烯基之個數比為0.5~2之量,更佳為0.7~1.5之量。若調配SiH基的個數比在上述範圍內之量的(B)成分,則所獲得之矽酮橡膠硬化物不黏,並且,反應活性也適度。
加成反應用觸媒可列舉矽氫化反應中所使用之鉑族金屬系觸媒。可列舉例如:鉑(包括鉑黑)、銠、鈀等鉑族金屬單質;H
2PtCl
4·XH
2O、H
2PtCl
6·XH
2O、NaHPtCl
6·XH
2O、KHPtCl
6·XH
2O、Na
2PtCl
6·XH
2O、K
2PtCl
4·XH
2O、PtCl
4·XH
2O、PtCl
2、Na
2HPtCl
4·XH
2O(其中,式中,X為0~6的整數,較佳為0或6)等氯化鉑、氯鉑酸及氯鉑酸鹽;醇改性氯鉑酸;氯化鉑、氯鉑酸與烯烴的絡合物、氯鉑酸與含乙烯基矽氧烷的絡合物、鉑與含乙烯基矽氧烷的絡合物;使鉑黑、鈀等鉑族金屬擔載於氧化鋁、二氧化矽、碳等載體之化合物;銠-烯烴絡合物;三(三苯基膦)氯化銠(威爾金森觸媒)等。既可單獨使用一種,亦可併用兩種以上。
鉑族金屬系觸媒的調配量為作為矽氫化反應觸媒的有效量即可,相對於(A)成分與(B)成分的總量,鉑族金屬系觸媒中的鉑族金屬量換算為質量通常為0.1~500 ppm左右,較佳為0.5~200 ppm左右,更佳為1~100 ppm左右。
於矽酮橡膠中,亦可含有矽酮油、有機矽烷、無機系粉末、有機系粉末及抗氧化劑等。
於本發明中,附著於有機樹脂粒子的表面之橡膠粒子的密度並無特別限定。即,橡膠粒子既可稀疏地附著於有機樹脂粒子表面,亦可無間隙地被覆附著於有機樹脂粒子表面。又,既可於橡膠粒子彼此凝聚之狀態下附著,亦可為於無間隙地被覆附著於有機樹脂粒子表面之橡膠粒子上進而附著有橡膠粒子之結構。橡膠粒子的附著密度或狀態可利用電子顯微鏡來確認。
橡膠粒子的量並無特別限定,當需要更顯著的柔軟觸感或順滑的使用感、延展性、光散射性時,相對於有機樹脂粒子100質量份,較佳為0.1質量份以上,更佳為0.2質量份以上,進而較佳為0.5質量份以上,更佳為0.8質量份以上。又,就獲得低凝聚性、順滑的使用感、延展性之觀點而言,相對於有機樹脂粒子100質量份,較佳為100質量份以下,更佳為50質量份以下,進而較佳為20質量份以下,更佳為10質量份以下。
[二氧化矽]
本發明中所使用之二氧化矽是有機樹脂粒子與橡膠粒子的黏合劑。藉由製成以二氧化矽為黏合劑使橡膠粒子附著於有機樹脂粒子的表面而成之複合粒子,橡膠粒子固著於有機樹脂粒子表面,不易自有機樹脂粒子表面脫落,從而能夠賦予更良好的使用感。
二氧化矽的形狀既可為膜狀,亦可為粒狀,且其亦可部分或整面附著於有機樹脂粒子表面及/或橡膠粒子表面。
二氧化矽為由SiO
2單元組成之結構,其製法並無特別限定,較佳為如下述製造方法般,藉由四烷氧矽烷的水解及縮合反應來獲得。
二氧化矽的量並無特別限定,為了使橡膠粒子固著於有機樹脂粒子表面,相對於橡膠粒子100質量份,較佳為10質量份以上,更佳為20質量份以上,進而較佳為30質量份以上,更佳為50質量份以上。又,就獲得柔軟觸感之觀點而言,相對於橡膠粒子100質量份,較佳為1000質量份以下,更佳為800質量份以下,進而較佳為500質量份以下,更佳為350質量份以下。
[表面處理劑]
本發明的複合粒子亦可利用矽化劑、矽酮油、蠟類、石蠟類、有機氟化合物、界面活性劑等對粒子表面進行處理,以賦予、提高撥水性或提高在油劑中的分散性。
[複合粒子的製造方法]
本發明的以二氧化矽為黏合劑使橡膠粒子附著於有機樹脂粒子的表面而成之複合粒子可藉由向將有機樹脂粒子、橡膠粒子、陽離子性物質(陽離子性界面活性劑及/或陽離子性水溶性高分子)、鹼性物質及水調配而成之混合液中添加四烷氧矽烷,使其進行水解及縮合反應來獲得。
[有機樹脂粒子及橡膠粒子]
有機樹脂粒子及橡膠粒子使用的是於複合粒子部分所說明之粒子,亦可預先製備成水分散液或使用於水中合成之水分散液。
為了使有機樹脂粒子及橡膠粒子分散於水中,亦可向水分散液中調配界面活性劑及水溶性高分子。又,當使用於水中合成之水分散液時,亦可於水分散液中含有合成時使用之界面活性劑或水溶性高分子。
界面活性劑並無特別限定,較佳為非離子性界面活性劑、陽離子性界面活性劑、及/或兩性界面活性劑。
作為非離子性界面活性劑,可列舉聚氧乙烯烷基醚、聚氧乙烯聚氧丙烯烷基醚、聚氧乙烯烷基苯基醚、聚乙二醇脂肪酸酯、山梨醇酐脂肪酸酯、聚氧乙烯山梨醇酐脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯、甘油脂肪酸酯、聚氧乙烯甘油脂肪酸酯、聚甘油脂肪酸酯、丙二醇脂肪酸酯、聚氧乙烯蓖麻油、聚氧乙烯氫化蓖麻油、聚氧乙烯氫化蓖麻油脂肪酸酯、聚氧乙烯烷基胺、聚氧乙烯脂肪酸醯胺、聚氧乙烯改性有機聚矽氧烷、聚氧乙烯聚氧丙烯改性有機聚矽氧烷等。
作為陽離子性界面活性劑,並無特別限定,可列舉烷基三甲基銨鹽、二烷基二甲基銨鹽、聚氧乙烯烷基二甲基銨鹽、二聚氧乙烯烷基甲基銨鹽、三聚氧乙烯烷基銨鹽、烷基芐基二甲基銨鹽、烷基吡啶鎓鹽、單烷基胺鹽、單烷基醯胺基胺鹽等。
作為兩性界面活性劑,可列舉烷基二甲基氧化胺、烷基二甲基羧基甜菜鹼、烷基醯胺基丙基二甲基羧基甜菜鹼、烷基羥基磺基甜菜鹼、烷基羧甲基羥乙基咪唑鎓甜菜鹼等。
水溶性高分子並無特別限定,較佳為非離子性水溶性高分子及/或陽離子性水溶性高分子。
作為非離子性水溶性高分子,可列舉聚乙烯醇、聚丙烯醯胺、聚乙烯吡咯啶酮、聚環氧乙烷、聚甲基乙烯基醚、聚異丙基丙烯醯胺、甲基纖維素、羥丙基甲基纖維素、澱粉、瓜爾膠、黃原膠等。
作為陽離子性水溶性高分子,可列舉例如二甲基二烯丙基氯化銨的聚合物、乙烯基咪唑啉的聚合物、甲基乙烯基咪唑鎓氯化物的聚合物、丙烯酸乙基三甲基氯化銨的聚合物、甲基丙烯酸乙基三甲基氯化銨的聚合物、丙烯醯胺丙基三甲基氯化銨的聚合物、甲基丙烯醯胺丙基三甲基氯化銨的聚合物、表氯醇/二甲胺聚合物、次乙亞胺的聚合物、次乙亞胺的聚合物的四級化物、烯丙基胺鹽酸鹽的聚合物、聚離胺酸、陽離子澱粉、陽離子化纖維素、聚葡萄胺糖(chitosan)、及使具有非離子性基團或陰離子性基團之單體與它們共聚等所得之它們的衍生物等。
當將矽酮橡膠粒子用於橡膠粒子時,較佳為製作成矽酮橡膠粒子的水分散液來使用。
矽酮橡膠粒子的水分散液的製備方法並無特別限定,可使用周知的矽酮橡膠粒子的水分散液的製備方法。例如,可藉由利用上述界面活性劑及/或上述水溶性高分子,使於複合粒子部分所說明之硬化性液態矽酮組成物於水中乳化後,使其進行硬化反應來製造。
當利用加成反應進行硬化來製成矽酮橡膠粒子的水分散液時,可列舉以下方法:向由於複合粒子的部分所說明之具有烯基之有機聚矽氧烷(A)、具有與矽原子鍵結之氫原子之有機氫聚矽氧烷(B)所組成之硬化性液態矽酮組成物中,添加上述界面活性劑及/或上述水溶性高分子、及水進行乳化,製成乳液,之後,添加鉑系觸媒使其進行加成聚合。亦可為向硬化性液態矽酮組成物中預先調配鉑族金屬系觸媒之方法,此時,需要藉由溫度的調整、觸媒量的調整或控制劑的調配等,使得在乳化結束之前不進行反應。
於將有機樹脂粒子、橡膠粒子、陽離子性物質、鹼性物質及水調配而成之混合液中,相對於所調配之水100質量份,有機樹脂粒子較佳為3~150質量份,更佳為5~50質量份。若為3質量份以上,則製造效率較高;而若為150質量份以下,則水分散液(混合液)的動黏度不會過高,容易附著橡膠粒子。橡膠粒子的量為附著於有機樹脂粒子的表面之量即可。
[陽離子性物質]
於製造複合粒子時調配之陽離子性界面活性劑及/或陽離子性水溶性高分子具有促進水解後之四烷氧矽烷的縮合反應、且使二氧化矽生成之作用。又,推測具有使所生成之二氧化矽吸附於有機樹脂粒子及橡膠粒子表面之作用或使有機樹脂粒子與橡膠粒子相吸附之作用。
陽離子性界面活性劑及陽離子性水溶性高分子可單獨使用一種或適當組合使用兩種以上。就可使橡膠粒子較多地附著於有機樹脂粒子表面之方面而言,較佳為使用陽離子性界面活性劑及陽離子性水溶性高分子這兩者。
陽離子性界面活性劑可列舉於複合粒子的製造方法的說明中所述之化合物,較佳為烷基三甲基銨鹽,其中,更佳為月桂基三甲基銨鹽及鯨蠟基三甲基銨鹽。
陽離子性水溶性高分子可列舉於複合粒子的製造方法的說明中所述之化合物,其中,較佳為不使用具有非離子性基團之單體之聚合物,進而較佳為二甲基二烯丙基氯化銨的聚合物。
相對於混合液中所調配之水100質量份,陽離子性物質(陽離子性界面活性劑及/或陽離子性水溶性高分子)較佳為0.0001~2.0質量份、更佳為0.001~1.0質量份的範圍。若為0.0001質量份~2.0質量份的調配量,則橡膠粒子附著於有機樹脂粒子表面,且利用二氧化矽進行之固著較為充分。
進而,相對於混合液中所調配之水100質量份,較佳為陽離子性界面活性劑為0.001~1.9質量份,且陽離子性水溶性高分子為0.0001~1.0質量份,更佳為陽離子性界面活性劑為0.01~1.0質量份,且陽離子性水溶性高分子為0.001~0.5質量份,進而較佳為陽離子性界面活性劑為0.05~0.5質量份,且陽離子性水溶性高分子為0.01~0.2質量份。
再者,如上所述,當使用陽離子性界面活性劑及/或陽離子性水溶性高分子以預先使有機樹脂粒子及橡膠粒子分散於水中來製成水分散液時,若並非所需的種類及量的陽離子性界面活性劑及/或陽離子性水溶性高分子,則追加;而若為所需的種類及量,則無需追加。
陽離子性界面活性劑及/或陽離子性水溶性高分子亦可預先調配在有機樹脂粒子、橡膠粒子、鹼性物質及水的混合液中,亦可於下述添加四烷氧矽烷時同時添加。
[鹼性物質]
鹼性物質是用於四烷氧矽烷的水解及縮合反應之觸媒。
鹼性物質並無特別限定,可使用例如:氫氧化鉀、氫氧化鈉、氫氧化鋰等鹼金屬氫氧化物;氫氧化鈣、氫氧化鋇等鹼土類金屬氫氧化物;碳酸鉀、碳酸鈉等鹼金屬碳酸鹽;氨;氫氧化四甲銨、氫氧化四乙銨等氫氧化四烷銨;或單甲胺、單乙胺、單丙胺、單丁胺、單戊胺、二甲胺、二乙胺、三甲胺、三乙醇胺、乙二胺等胺類等。其中,就能夠藉由揮發而自所獲得之複合粒子的粉末容易地除去之方面而言,氨最合適。作為氨,可使用市售之氨水溶液。
鹼性物質的調配量較佳為至少使將該鹼性物質、有機樹脂粒子、橡膠粒子、陽離子性界面活性劑及/或陽離子性水溶性高分子、及水調配而成之混合液的pH為9.0~12.0之量,更佳為9.5~11.5之量。若添加pH為9.0~12.0之量的鹼性物質,則四烷氧矽烷的水解及縮合反應的進行及橡膠粒子向有機樹脂粒子表面之固著較為充分。
[四烷氧矽烷]
於本發明的複合粒子的製造方法中,向將有機樹脂粒子、橡膠粒子、陽離子性界面活性劑及/或陽離子性水溶性高分子、鹼性物質及水調配而成之混合液中添加四烷氧矽烷。
四烷氧矽烷藉由鹼性物質的觸媒作用進行水解及縮合反應,而成為二氧化矽。添加四烷氧矽烷後,藉由四烷氧矽烷的水解及縮合反應而生成之二氧化矽形成於有機樹脂粒子的表面及/或橡膠粒子的表面上,同時,會產生橡膠粒子向有機樹脂粒子表面之吸附,由此,成為橡膠粒子利用二氧化矽而固著於有機樹脂粒子表面之狀態。
四烷氧矽烷由Si(OR
6)
4表示。式中的R
6為烷基。作為烷基,較佳為碳數為1~6的烷基。具體而言,可列舉甲基、乙基、丙基、丁基、戊基、己基等,就反應性之方面而言,更佳為甲基、乙基。即,更佳為四甲氧矽烷、四乙氧矽烷,進而較佳為四甲氧矽烷。四烷氧矽烷亦可使用烷氧基部分或全部水解所得者。進而,亦可使用部分縮合者。
四烷氧矽烷的添加量並無特別限定,水解及縮合反應後的二氧化矽的量為相對於上述橡膠粒子之量即可。
[水解及縮合反應]
一邊攪拌將有機樹脂粒子、橡膠粒子、陽離子性界面活性劑及/或陽離子性水溶性高分子、鹼性物質及水調配而成之混合液,一邊添加四烷氧矽烷,進行水解及縮合反應。四烷氧矽烷可以逐漸滴加之方式添加,亦可以溶解於水中之形態或分散於水中之形態添加,亦可添加調配有醇等水溶性有機溶劑之溶液。
就防止有機樹脂粒子彼此及橡膠粒子彼此凝聚之觀點而言,攪拌較佳為使用槳翼、螺旋翼、後掠翼、錨型翼等緩慢地進行,攪拌強度需要為使有機樹脂粒子、橡膠粒子及四烷氧矽烷分散於混合液中之程度。
將四烷氧矽烷添加至混合液中時的溫度較佳為0~60℃,更佳為0~39℃。若該溫度為0℃以上,則無混合液凝固之虞;而若為60℃以下,則無所獲得之粒子發生凝聚之虞。
亦可向混合液中調配醇等水溶性有機溶劑,以提高有機樹脂粒子及橡膠粒子在水中的分散性或使橡膠粒子均勻附著於有機樹脂粒子表面。
當製成經矽化劑表面處理之粒子時,既可對複合粒子進行處理,亦可於將四烷氧矽烷添加至混合液中後,添加矽化劑進行處理。作為矽化劑,可列舉例如三甲基甲氧基矽烷、三甲基矽烷醇、六甲基二矽氮烷、甲基三甲氧基矽烷、苯基三甲氧基矽烷等。
較佳為四烷氧矽烷添加結束後,繼續攪拌一段時間,直至水解及縮合反應結束。為了促進反應,可於40~100℃加熱,亦可追加鹼性物質。之後,若有必要,亦可投入酸性物質加以中和。
水解及縮合反應後,除去水分。水分的除去可藉由例如於常壓下或減壓下加熱反應後的混合液來進行,具體而言,可列舉於加熱下靜置混合液而除去水分之方法、一邊於加熱下攪拌混合液使其流動一邊除去水分之方法、如噴霧乾燥器般將混合液噴霧使其分散於熱風氣流中之方法、利用流動熱介質之方法等。再者,作為該操作的預處理,可利用加熱脫水、加壓過濾等過濾分離、離心分離、傾析等方法將混合液濃縮,視需要亦可利用水或酒精等清洗混合液。
當藉由自反應後的混合液除去水分而獲得之粉體凝聚時,較佳為利用噴射磨機、球磨機、鎚磨機等粉碎機壓碎或分級。
[含有複合粒子之化粧料]
本發明的化粧料的特徵在於含有前述複合粒子。以下,對本發明的化粧料詳細地進行說明。再者,於本發明中,有時以化粧品標示名或化粧品成分國際命名法(International Nomenclature of Cosmetic Ingredient, INCI)記載成分名。當化粧品標示名與INCI對應時,有時省略英文記載。
本發明適用於各種化粧料,尤佳為護膚化粧料、彩粧化粧料、止汗化粧料、防紫外線化粧料等外用於皮膚之化粧料及毛髮化粧料等外用於毛髮之化粧料。作為護膚化粧料,可列舉例如化粧水、乳液、面霜、潔面乳、面膜、油液、按摩料、美容液、美容油、清潔劑、除臭劑、護手霜、潤唇膏、遮皺膏等。作為彩粧化粧料,可列舉例如粧前乳、遮瑕膏、散粉、粉餅、眼彩(eye color)、眼影(eye shadow)、睫毛膏、眼線液、眉筆、口紅等。作為止汗化粧料,可列舉例如滾珠型、霜型、溶液型、棒型等止汗化粧料。作為防紫外線化粧料,可列舉例如防曬油、防曬乳液、防曬霜等。作為毛髮化粧料,可列舉例如洗髮劑、潤髮乳、護髮素、定型劑等。
本發明的化粧料的形態例如可為粉體、油性液體、油包水型乳液、水包油型乳液、非水乳液、W/O/W型、O/W/O型等多重乳液等中的任一種。又,作為本發明的化粧料的性狀,可選擇液體狀、乳液狀、霜狀、固體狀、膏狀、凝膠狀、粉末狀、餅狀、多層狀、慕絲狀、噴霧狀、棒狀、鉛筆狀等各種性狀。
只要為含有必需成分之化粧料,便無特別限定,可應用於例如護膚品、粉底液、粉餅、遮瑕膏、口紅等、及對它們賦予防曬性能之各種產品。
本發明的化粧料可含有用於一般的化粧料之各種成分。可包括例如(1)油劑、(2)水性成分、(3)界面活性劑、(4)本發明以外的粉體、(5)由交聯型有機聚矽氧烷及室溫下為液態的油劑組成之組成物、(6)成膜劑、(7)紫外線吸收散射劑、(8)其他添加劑。它們可單獨使用一種或適當組合使用兩種以上。
(1)油劑
油劑既可為揮發性,亦可為非揮發性,亦可於室溫(25℃)為固體、半固體、液態中的任一種,可列舉例如矽酮油、矽酮蠟、天然動植物油脂類及半合成油脂、烴油、高級醇、脂肪酸、酯油、氟系油劑、紫外線吸收劑等。
本發明的複合粒子由於表面的橡膠粒子對各種液態油劑的吸油性較高,因此,藉由吸收液態油劑,而抑制油劑的黏連感或眩光,使用感的改善效果較高。又,可調整油的黏度,或獲得慕絲狀等各種性狀。亦可直接含有本發明中所使用之複合粒子作為化粧料成分,亦可另行製備包含複合粒子及該油性成分之油性凝膠組成物,以該油性凝膠組成物的形態製備含有該複合粒子及該油性成分之化粧料,以達到展現化粧料所需之使用感之目的。
·矽酮油
作為矽酮油,可列舉例如二甲聚矽氧烷(INCI)、三矽氧烷(INCI)、甲基三甲聚矽氧烷(INCI)、乙基三矽氧烷(INCI)、乙基甲聚矽氧烷(INCI)、己基二甲聚矽氧烷(INCI)等烷基改性矽酮、辛基甲聚矽氧烷(INCI)等長鏈烷基改性矽酮、苯基三甲聚矽氧烷(INCI)、二苯基二甲聚矽氧烷(INCI)、二苯基矽烷氧基苯基三甲聚矽氧烷(INCI)、四苯基二甲基二矽氧烷(INCI)、甲基氫聚矽氧烷等低黏度至高黏度的直鏈或分支狀的有機聚矽氧烷、環四矽氧烷(INCI)、環戊矽氧烷(INCI)、環己矽氧烷(INCI)等環狀有機聚矽氧烷、胺基封端二甲聚矽氧烷(INCI)、胺基丙基二甲聚矽氧烷(INCI)等胺基改性有機聚矽氧烷、PCA二甲聚矽氧烷(INCI)等吡咯啶酮改性有機聚矽氧烷、吡咯啶酮羧酸改性有機聚矽氧烷、高聚合度的膠狀二甲基聚矽氧烷、膠狀胺基改性有機聚矽氧烷、膠狀二甲基矽氧烷-甲基苯基矽氧烷共聚物等矽酮橡膠、及矽膠或橡膠的低黏度有機聚矽氧烷溶液、胺基酸改性矽酮、氟改性矽酮、矽酮樹脂及矽酮樹脂的溶解物等。
作為市售之矽酮油的示例,可列舉信越化學工業(股)(Shin-Etsu Chemical Co., Ltd.)製造之KF-96L-1cs、KF-96L-1.5cs、KF-96L-2cs、KF-96A-6cs、KF-4422、KF-54、KF-54HV、KF-56A、KF-995等。
·固體狀的油性成分
於本發明中,當欲使化粧料固化時,較佳為調配於25℃為固體狀的油性成分。作為於25℃為固體狀的油性成分,可列舉具有較佳為40℃以上、更佳為60~110℃的熔點之蠟、烴、酯、高級醇、高級脂肪酸,只要為通常可調配至化粧料中之原料,便無特別限定。
具體而言,可列舉:巴西棕櫚蠟(INCI: Copernicia Cerifera (Carnauba) Wax)、甘蔗蠟、堪地里拉蠟(INCI: Euphorbia Cerifera (Candelilla) Wax)、精製堪地里拉蠟、米蠟、木蠟、荷荷巴蠟、木棉蠟、米糠蠟、蠟楊梅果蠟、牛油樹油脂、可可脂、野漆果蠟(INCI: Rhus Succedanea Fruit Wax)、褐煤蠟(INCI: Montan Wax)、氫化蓖麻油異硬脂酸酯等植物性蠟、蜂蠟、牛脂、牛骨脂、豬脂(INCI: Lard)、馬脂(INCI: Horse Fat)、羊脂、羊毛脂(INCI: Lanolin)、中國蠟、蟲膠蠟、鯨蠟等動物性蠟、羊毛脂酯、羊毛脂脂肪酸酯、蜂蠟酸酯等半合成蠟、氫化蓖麻油、氫化椰子油等氫化油、固體石蠟、聚乙烯、純地蠟、天然地蠟、微晶蠟等烴系蠟、合成蜂蠟等蠟酯、二辛基十二烷醇月桂醯麩胺酸酯、二辛基十二烷醇月桂醯麩胺酸酯、二辛基十二烷醇月桂醯麩胺酸酯等胺基酸硬脂醇、硬脂酸、山萮酸等脂肪酸、及丙烯酸-聚矽氧接枝或嵌段共聚物的丙烯酸矽酮樹脂等聚矽氧蠟(信越化學工業(股)製造之丙烯酸-聚矽氧接枝共聚物:KP-561P、562P等)、或它們的衍生物,較佳為從它們中選擇之一種或兩種以上。
·天然動植物油劑及半合成油劑
作為天然動植物油劑及半合成油劑,可列舉鰐梨油(:標示名(INCI: Persea Gratissima (Avocado) Oil))、亞麻耔油(:標示名(INCI: Linum Usitatissimum (Linseed) Seed Oil))、甜杏仁油(:標示名(INCI: Prunus Amygdalus Dulcis (Sweet Almond) Oil))、紫蘇油(標示名)、橄欖油(:標示名(INCI: Olea Europaea (Olive) Fruit Oil))、加州榧樹油(:標示名(INCI: Torreya Californica (California Nutmeg) Oil))、亞香茅油(:標示名(INCI: Cymbopogon Nardus (Citronella) Oil))、日本榧樹籽油(:標示名(INCI: Torreya Nucifera Seed Oil))、杏仁油(:標示名(INCI: Kyounin Yu))、小麥胚芽油(:標示名(INCI: Triticum Vulgare (Wheat) Germ Oil))、芝麻油(:標示名(INCI: Sesamum Indicum (Sesame) Seed Oil))、小麥胚芽油(:標示名(INCI: Triticum Vulgare (Wheat) Germ Oil))、米胚芽油(:標示名(INCI: Oryza Sativa (Rice) Germ Oil))、米糠油(:標示名(INCI: Oryza Sativa (Rice) Bran Oil))、落瓣油茶籽油(:標示名(INCI: Camellia Kissi Seed Oil))、紅花油(:標示名(INCI: Carthamus Tinctorius (Safflower) Seed Oil))、大豆油(:標示名(INCI: Glycine Soja (Soybean) Oil))、茶籽油(:標示名(INCI: Camellia Sinensis Seed Oil))、山茶籽油(:標示名(INCI: Camellia Japonica Seed Oil))、月見草油(:標示名(INCI: Oenothera Biennis (Evening Primrose) Oil))、菜籽油(標示名)、玉米胚芽油(:標示名(INCI;Zea Mays (Corn) Germ Oil))、小麥胚芽油(:標示名(INCI: Triticum Vulgare (Wheat) Germ Oil))等胚芽油、杏核油(標示名)、棕櫚油(:標示名(INCI: Elaeis Guineensis (Palm) Oil))、棕櫚仁油(:標示名(INCI: Elaeis Guineensis (Palm) Kernel Oil))、蓖麻油(:標示名(INCI: Ricinus Communis (Castor) Seed Oil))、葵花籽油(:標示名(INCI: Helianthus Annuus (Sunflower) Seed Oil))、葡萄籽油(:標示名(INCI: Vitis Vinifera (Grape) Seed Oil))、荷荷巴籽油(:標示名(INCI: Simmondsia Chinensis (Jojoba) Seed Oil))、夏威夷堅果油(:標示名(INCI: Macadamia Ternifolia Seed Oil))、白芒花籽油(:標示名(INCI: Limnanthes Alba (Meadowfoam) Seed Oil))、棉籽油(:標示名(INCI: Gossypium Herbaceum (Cotton) Seed Oil))、椰子油(:標示名(INCI: Cocos Nucifera (Coconut) Oil))、花生油(:標示名(INCI: Arachis Hypogaea (Peanut) Oil))等天然植物油、鯊魚肝油(:標示名(INCI: Shark Liver oil))、鱈魚肝油(:標示名(INCI: Cod Liver Oil))、魚肝油(:標示名(INCI: Fish Liver Oil))、海龜油(:標示名(INCI: Turtle Oil))、貂油(:標示名(INCI: Mink Oil))、蛋黃油(:標示名(INCI: Egg Oil))等天然動物油、氫化椰子油(:標示名(INCI: Hydrogenated Coconut Oil))、液態羊毛脂(:標示名(INCI: Lanolin Oil))等半合成油脂等。
·烴油
作為烴油,可列舉例如直鏈狀或分支狀的烴油,既可為揮發性的烴油,亦可為非揮發性的烴油。具體而言,可列舉烯烴低聚物(INCI)、(C13,14)異構石蠟(INCI)等異構石蠟、異十二烷(INCI)、十一烷(INCI)、十二烷(INCI)、異十六烷(INCI)、氫化聚異丁烯(:標示名(INCI: Hydrogenated Polyisobutene))、鯊烷(INCI)、礦物油(INCI)、椰子烷烴(INCI)、(C13-15)烷烴(INCI)等烷烴等。
高級醇類
作為高級醇類,可列舉例如碳原子數較佳為6以上、更佳為10~30的醇類。作為高級醇類的具體例,可列舉月桂醇(INCI)、肉荳蔻醇(INCI)、棕櫚醇(INCI)、硬脂醇(INCI)、山萮醇(INCI)、油醇(INCI)、異硬脂醇(INCI)、辛基十二醇(INCI)、膽固醇(INCI)、植物固醇(INCI)、鯊肝醇(INCI)等。
·酯油
作為酯油,可列舉己二酸二異丁酯(:標示名(INCI: Diisobutyl Adipate))、己二酸二己基癸酯(標示名)、二(庚基十一烷醇)己二酸酯(:標示名(INCI: Diheptylundecyl Adipate))、異硬脂酸異硬脂(:標示名(INCI: Isostearyl Isostearate))等n-烷基乙二醇單異硬脂酸酯、異鯨蠟醇異硬脂酸酯(:標示名(INCI: Isocetyl Isostearate))、三羥甲基丙烷三異硬脂酸酯(:標示名(INCI: Trimethylolpropane Triisostearate))、乙二醇二乙基己酸酯(:標示名(INCI: Glycol Diethylhexanoate))、鯨蠟醇乙基己酸酯(:標示名(INCI: Cetyl Ethylhexanoate))、三羥甲基丙烷三(乙基己酸)酯(:標示名(INCI: Trimethylolpropane Triethylhexanoate))、季戊四醇四(乙基己酸)酯(:標示名(INCI: Pentaerythrityl Tetraethylhexanoate))、鯨蠟醇辛酸酯(:標示名(INCI: Cetyl Ethylhexanoate))、辛基十二醇硬脂醯氧基硬脂酸酯(:標示名(INCI: Octyldodecyl Stearoyl Stearate))等辛基十二烷基酯、油醇油酸酯(:標示名(INCI: Oleyl Oleate))、辛基十二烷醇油酸酯(:標示名(INCI: Octyldodecyl Oleate))、油酸癸酯(:標示名(INCI: Decyl Oleate))、新戊二醇二辛酸酯(:標示名(INCI: Neopentyl Glycol Diethylhexanoate))、新戊二醇二癸酸酯(:標示名(INCI: Neopentyl Glycol Dicaprate))、二異硬脂醇蘋果酸酯(:標示名(INCI: Diisostearyl Malate))、檸檬酸三乙酯(:標示名(INCI: Triethyl Citrate))、二乙基己基琥珀酸酯(:標示名(INCI: Diethylhexyl Succinate))、乙酸戊酯(:標示名(INCI: Amyl Acetate))、乙酸乙酯(:標示名(INCI: Etyl Acetate))、乙酸丁酯(:標示名(INCI: Butyl Acetate))、異鯨蠟醇硬脂酸酯(:標示名(INCI: Isocetyl Stearate))、硬脂酸丁酯(:標示名(INCI: Butyl Stearate))、癸二酸二異丙酯(:標示名(INCI: Diisopropyl Sebacate))、癸二酸二乙基己酯(:標示名(INCI: Diethylhexyl Sebacate))、鯨蠟醇乳酸酯(:標示名(INCI: Cetyl Lactate))、肉豆蔻醇乳酸酯(:標示名(INCI: Myristyl Lactate))、異壬酸異壬酯(:標示名(INCI: Isononyl Isononanoate))、異十三烷醇異壬酸酯(:標示名(INCI: Isotridecyl Isononanoate))、棕櫚酸異丙醇酯(:標示名(INCI: Isopropyl Palmitate))、棕櫚酸乙基己酯(:標示名(INCI: Ethylhexyl Isopalmitate))、己基癸醇棕櫚酸酯(:標示名(INCI: Isocetyl Palmitate、Hexyldecyl Palmitate))等棕櫚酸酯、膽固醇羥基硬脂酸酯(:標示名(INCI: Cholesteryl Hydroxystearate))、肉豆蔻酸異丙脂(:標示名(INCI: Isopropyl Myristate))、辛基十二醇肉豆蔻酸酯(標示名(INCI: Octyldodecyl Myristate))、肉豆蔻醇肉豆蔻酸酯(:標示名(INCI: Myristyl Myristate))等肉荳蔻酸酯、月桂酸乙基己酯(:標示名(INCI: Ethylhexyl Laurate))、月桂酸己酯(:標示名(INCI: Hexyl Laurate))、二辛基十二烷醇月桂醯麩胺酸酯(:標示名(INCI: Dioctyldodecyl Lauroyl Glutamate))、月桂醯肌胺酸異丙酯(:標示名(INCI: Isopropyl Lauroyl Sarcosinate))、椰油醇-辛酸酯/癸酸酯(:標示名(INCI: Coco-Caprylate・Caprate))等。
又,於酯油中,作為甘油酯油,可列舉甘油三(乙基己酸)酯(INCI)、辛酸/癸酸甘油三酯(:標示名(INCI: Caprylic/Capric Triglyceride))、椰油酸甘油酯(INCI)、辛酸/癸酸/琥珀酸甘油三酯(:標示名(INCI: Caprylic/Capric/succinic Triglyceride))、辛酸/癸酸甘油酯(:標示名(INCI: Caprylic/Capric Glycerides))等。
·氟系油劑
作為氟系油劑,可列舉全氟萘烷(INCI)、全氟壬基二甲聚矽氧烷(INCI)、全氟甲基環戊烷(INCI)等。
·紫外線吸收劑
作為紫外線吸收劑,可列舉二苯酮-1(:標示名(INCI: Benzophenone-1))、二苯酮-2(:標示名(INCI: Benzophenone-2))、二苯酮-3(:標示名(INCI: Benzophenone-3))、二苯酮-4(:標示名(INCI: Benzophenone-4))、二苯酮-5(:標示名(INCI: Benzophenone-5))、二苯酮-6(:標示名(INCI: Benzophenone-6))、二苯酮-9(:標示名(INCI: Benzophenone-9))、胡莫柳酯(INCI)、奧克立林(INCI)、叔丁基甲氧基二苯甲醯基甲烷(:標示名(INCI: Butyl Methoxydibenzoylmethane))、水楊酸乙基己酯(:標示名(INCI: Ethylhexyl Salicylate))、二乙基氨基羥基苯甲醯苯甲酸己酯(:標示名(INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate))、聚矽氧烷-15(INCI)、二甲氧亞苄基二氧代咪唑烷基丙酸辛酯(:標示名(INCI: Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate))、對苯二亞甲基二樟腦磺酸(:標示名(INCI: Terephthalylidene Dicamphor Sulfonic Acid))、乙基己基三嗪酮(INCI)、異戊醇三甲氧基肉桂酸酯三矽氧烷(:標示名(INCI: Isopentyl Trimethoxycinnamate Trisiloxane))、甲酚曲唑三矽氧烷(INCI)、二甲基PABA乙基己酯(:標示名(INCI: Ethylhexyl Dimethyl PABA))、對甲氧基肉桂酸異丙酯(:標示名(INCI: Isopropyl Methoxycinnamate))、甲氧基肉桂酸乙基己酯(:標示名(INCI: Ethylhexyl Methoxycinnamate))、雙乙基己氧基苯酚甲氧基苯基三嗪(INCI)、苯基苯并咪唑磺酸(:標示名(INCI: Phenylbenzimidazole Sulfonic Acid))、亞甲基雙-苯并三唑基四甲基丁基酚(INCI)、甘油乙基己酸酯二甲氧基肉桂酸酯(:標示名(INCI: Glyceryl Ethylhexanoate Dimethoxycinnamate))、甘油PABA酯(INCI)、二異丙基肉桂酸甲酯(:標示名(INCI: Diisopropyl Methyl Cinnamate))、西諾沙酯(INCI)、二甲氧亞苄基二氧代咪唑烷基丙酸乙基己酯(:標示名(INCI: Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate))等。
(2)水性成分
水性成分只要為通常可調配至化粧料中之水性成分,便無特別限定。具體而言,可列舉水、乙醇(:標示名(INCI: Alcohol))、異丙醇(:標示名(INCI: Isopropyl Alcohol))等、碳原子數較佳為2~5的低級醇、山梨糖醇(INCI)、麥芽糖(INCI)、木糖醇(INCI)等糖醇。又,可列舉BG(:標示名(INCI: Butylene Glycol))、PG(:標示名(INCI: Propylene Glycol))、DPG(:標示名(INCI: Dipropylene Glycol))、戊二醇(INCI)、1,10-癸二醇(INCI)、辛二醇(INCI)、1,2-己二醇(INCI)、紅蘚醇(INCI)、甘油(INCI)、雙甘油(INCI)、聚乙二醇等多元醇;葡萄糖(INCI)、甘油葡糖苷(INCI)、甜菜鹼(INCI)、硫酸軟骨素鈉(:標示名(INCI: Sodium Chondroitin Sulfate))、PCA-Na(:標示名(INCI: Sodium PCA))、甲基葡糖醇聚醚10(INCI)、甲基葡糖醇聚醚20(INCI)、透明質酸、蛋黃卵磷脂、大豆卵磷脂、磷脂醯膽鹼、磷脂醯乙醇胺、磷脂酸絲胺酸、磷脂醯甘油、磷脂醯肌醇、鞘磷酯等保濕劑。
(3)界面活性劑
作為界面活性劑,有非離子性、陰離子性、陽離子性及兩性的活性劑,並無特別限制,只要為通常用於化粧料之活性劑,亦可使用任一種活性劑。該等界面活性劑中,選自非交聯型聚矽氧界面活性劑或交聯型聚矽氧界面活性劑中之一種或兩種以上由於能夠獲得穩定的化粧料,故較佳。於任一情況下,作為界面活性劑的調配量,均較佳為化粧料整體的0.1~20質量%。若為0.1%以上,則能夠充分發揮分散或乳化的機能;而若為20質量%以下,則無使用時感到化粧料黏連之虞,故較佳。界面活性劑的親水親油平衡值(Hydrophile Lipophile Balance, HLB)並無限定,就維持化粧料的耐水性之目的而言,較佳為2~14.5。
作為非交聯型聚矽氧界面活性劑,較佳為直鏈或分支狀的聚矽氧主鏈的部分甲基經聚乙二醇或聚甘油等的親水基團取代之活性劑,具體為直鏈或分支狀聚氧乙烯改性有機聚矽氧烷、直鏈或分支狀聚氧乙烯聚氧丙烯改性有機聚矽氧烷、直鏈或分支狀聚氧乙烯-烷基共改性有機聚矽氧烷、直鏈或分支狀聚氧乙烯聚氧丙烯-烷基共改性有機聚矽氧烷、直鏈或分支狀聚甘油改性有機聚矽氧烷、直鏈或分支狀聚甘油-烷基共改性有機聚矽氧烷、直鏈或分支狀吡咯啶酮改性有機聚矽氧烷。
可列舉PEG-11甲醚二甲聚矽氧烷(INCI)、PEG/PPG-20/22丁醚二甲聚矽氧烷(INCI)、PEG-3二甲聚矽氧烷(INCI)、PEG-10二甲聚矽氧烷(INCI)、PEG-9聚二甲基矽氧乙基二甲聚矽氧烷(INCI)、月桂醇PEG-9聚二甲基矽氧乙基二甲聚矽氧烷(INCI)、鯨蠟基PEG/PPG-10/1二甲聚矽氧烷(INCI)、聚甘油-3二矽氧烷二甲聚矽氧烷(INCI)、聚甘油-3聚二甲基矽氧乙基二甲聚矽氧烷(INCI)、月桂基聚甘油-3聚二甲基矽氧乙基二甲聚矽氧烷(INCI)等。
作為市售之非交聯型聚矽氧界面活性劑的示例,可列舉信越化學工業(股)製造之KF-6011、KF-6011P、KF-6012、KF-6015、KF-6017、KF-6043、KF-6028、KF-6038、KF-6048、KF-6100、KF-6104、KF-6106、KF-6105、KF-6115等。
作為交聯型聚矽氧界面活性劑,可列舉例如(二甲聚矽氧烷/(PEG-10/15))交聯聚合物(INCI)、(PEG-15/月桂基二甲聚矽氧烷)交聯聚合物(INCI)、(PEG-10/月桂基二甲聚矽氧烷)交聯聚合物(INCI)、(PEG-15/月桂基聚二甲基矽氧乙基二甲聚矽氧烷)交聯聚合物(INCI)、(二甲聚矽氧烷/聚甘油-3)交聯聚合物(INCI)、(月桂基二甲聚矽氧烷/聚甘油-3)交聯聚合物(INCI)、(聚甘油-3/月桂基聚二甲基矽氧乙基二甲聚矽氧烷)交聯聚合物(INCI)等。
又,當使用交聯型聚矽氧界面活性劑時,於由該交聯型聚矽氧界面活性劑及於室溫為液態之油劑組成之組成物中,交聯型聚矽氧界面活性劑較佳為相對於液態油包含自身重量以上的該液態油劑而膨潤。
作為該液態油劑,可使用抗氧化劑成分的(1)油劑中的液態的聚矽氧油、烴油、酯油、天然動植物油、半合成油等、氟系油,可列舉例如環戊矽氧烷(INCI)、二甲聚矽氧烷(INCI)、礦物油(INCI)、異十二烷(INCI)、異十六烷(INCI)、甘油三(乙基己酸)酯(INCI)、異十三烷醇異壬酸酯(:標示名(INCI: Isotridecyl Isononanoate))、鯊烷(INCI)等。
作為市售之交聯型聚矽氧界面活性劑包含液態油劑而膨潤之產品的示例,可列舉信越化學工業(股)製造之KSG-210、KSG-240、KSG-270、KSG-310、KSG-320、KSG-330、KSG-340、KSG-320Z、KSG-350Z、KSG-710、KSG-810、KSG-820、KSG-830、KSG-840、KSG-820Z、KSG-850Z等。
(4)粉體
作為粉體,可列舉著色顏料、無機粉體、金屬粉體、有機粉體、無機/有機複合粉體等。具體如下所述。
·著色顏料
作為著色顏料,通常只要為用於化粧料的著色目的之顏料,便無特別限定,可使用紅色的氧化鐵(:標示名(INCI: Iron Oxides))、黃色的氧化鐵(:標示名(INCI: Iron Oxides))、白色的二氧化鈦(:標示名(INCI: Titanium Dioxide))、黑色的氧化鐵(:標示名(INCI: Iron Oxides))、群藍(:標示名(INCI: Ultramarines))、亞鐵氰化鐵銨(:標示名(INCI: Ferric Ferrocyanide、Ferric Ammonium Ferrocyanide))、錳紫(:標示名(INCI: Manganese Violet))、氧化鈦鈷(:標示名(INCI: Cobalt Titanium Oxide))、氫氧化鉻綠(:標示名(INCI: Chromium Hydroxide Green))、氧化鉻綠(:標示名(INCI: Chromium Oxide Greens))、氧化鈷鋁(:標示名(INCI: Cobalt Aluminum Oxide))、氧化鈦鈷(:標示名(INCI: Cobalt Titanium Oxide))、(鈦/二氧化鈦)燒成物(:標示名(INCI: Titanium/Titanium Dioxide))、鈦酸鈷鋰(:標示名(INCI: Lithium Cobalt Titanate))、氧化鈦鈷(:標示名(INCI: Cobalt Titanium Oxide))、(氧化鐵/二氧化鈦)燒結物(:標示名)、氧化鐵摻雜二氧化鈦(:標示名(INCI: Iron Oxides, Titanium Dioxide))等摻雜有異種金屬之複合物、氮化鈦(:標示名(INCI: Titanium Nitride))、氫氧化亞鐵(:標示名(INCI: Iron Hydroxide))、γ-氧化鐵等無機褐色系顏料、黃土等無機黃色系顏料、焦油系色素經色澱化所得之顏料、天然色素經色澱化所得之顏料等有色顏料等中的任一種。
又,作為顏料的形狀,可為球狀、大致球狀、棒狀、紡錘狀、花瓣狀、短條狀、不定形狀等中的任一形狀,只要能夠對化粧料賦予顏色,其幾何學態樣便無特別限定。
·無機粉體
作為無機粉體,可列舉由氧化鋯(:標示名(INCI: Zirconium Dioxide))、氧化鋅(:標示名(INCI: Zinc Oxide))、氧化鈰(:標示名(INCI: Cerium Oxide))、氧化鎂(:標示名(INCI: Magnesium Oxide))、硫酸鋇(:標示名(INCI: Barium Sulfate))、硫酸鈣(:標示名(INCI: Calcium Carbonate))、硫酸鎂(:標示名(INCI: Magnesium Sulfate))、碳酸鈣(:標示名(INCI: Calcium Carbonate))、碳酸鎂(:標示名(INCI: Magnesium Carbnate))、滑石(INCI)、雲母(INCI)、高嶺土(INCI)、合成氟金雲母(:標示名(INCI: Synthetic Fluorphlogopite))、合成金雲母鐵(標示名)、黑雲母(:標示名(INCI: Biotite))、矽酸鉀(:標示名(INCI: Potassium Silicate))、二氧化矽(INCI)、矽酸鋁(:標示名(INCI: Aluminum Silicate))、矽酸鎂(:標示名(INCI: Magnesium Silicate))、矽酸鎂鋁(:標示名(INCI: Magnesium Aluminum Silicate))、矽酸鈣(:標示名(INCI: Calcium Silicate))、矽酸鋁鈣鈉(:標示名(INCI: Aluminum Calcium Sodium Silicate))、矽酸鈉鎂鋰(:標示名(INCI: Lithium Magnesium Sodium Silicate))、矽酸鎂鈉(:標示名(INCI: Sodium Magnesium Silicate))、硼矽酸鋁鈣(:標示名(INCI: Calcium Aluminum Borosilicate))、硼矽酸鈉鈣(:標示名(INCI: Calcium Sodium Borosilicate))、羥基磷灰石(INCI)、膨潤土(INCI)、蒙脫石(INCI)、水輝石(INCI)、沸石(INCI)、氧化鋁(INCI)、氫氧化鋁(:標示名(INCI: Aluminum Hydroxide))、氮化硼(:標示名(INCI: Boron Nitride))、玻璃(:標示名(INCI: Glass))等組成之微粒子。
又,作為無機著色珠光顏料,由二氧化鈦(:標示名(INCI: Titanium Dioxide))被覆之雲母(INCI)、由二氧化鈦(:標示名(INCI: Titanium Dioxide))被覆之合成氟金雲母(:標示名(INCI: Synthetic Fluorphlogopite))等珠光劑、由氯氧化鉍(:標示名(INCI: Bisniuth Oxychloride))、二氧化鈦(:標示名(INCI: Titanium Dioxide))被覆之氯氧化鉍(:標示名(INCI: Bismuth Oxychloride))、由二氧化鈦(:標示名(INCI: Titanium Dioxide))被覆之滑石(INCI)、由魚鱗箔(標示名)、二氧化鈦(:標示名(INCI: Titanium Dioxide))被覆之著色雲母等珠光顏料,亦可未經處理,亦可經過一般用於化粧品之周知的表面處理,並無特別限定。
·金屬粉體
作為金屬粉體,可列舉由Al(:標示名(INCI: Aluminum、Aluminum Powder))、銅(:標示名(INCI: Copper Powder))、銀(:標示名(INCI: Silver Powder))、金(:標示名(INCI: Gold))等組成之金屬微粒子。
·有機粉體
作為有機粉體,可列舉由聚矽氧、聚醯胺、聚丙烯酸-丙烯酸酯、聚酯、聚乙烯(INCI)、聚丙烯(INCI)、聚苯乙烯(INCI)、苯乙烯-丙烯酸共聚物、二乙烯苯-苯乙烯共聚物、聚胺基甲酸酯、乙烯樹脂、尿素樹脂、三聚氰胺樹脂、苯并胍胺、聚甲基苯并胍胺、四氟乙烯、聚甲基丙烯酸甲酯、纖維素(INCI)、絲(INCI)、尼龍(標示名)、酚樹脂、環氧樹脂、聚碳酸酯等組成之粉體。
尤其是作為聚矽氧,可列舉:矽酮樹脂粒子;聚甲基倍半矽氧烷(INCI)、矽酮橡膠粉末、由矽酮樹脂被覆之矽酮橡膠粉末;(乙烯基二甲聚矽氧烷/甲聚矽氧烷倍半矽氧烷)交聯聚合物(INCI)、(二苯基二甲聚矽氧烷/乙烯基二苯基二甲聚矽氧烷/倍半矽氧烷)交聯聚合物(INCI)、聚矽氧烷-1交聯聚合物(INCI)、聚矽氧烷-22(INCI)等。
作為市售之由聚矽氧組成之粉體的示例,可列舉信越化學工業(股)製造之KMP-590、KMP-591、KMP-592、KMP-597、KMP-598、KSP-100、KSP-101、KSP-102、KSP-105、KSP-300、KSP-411、KSP-441、KM-9729、KM-440等。
又,亦可列舉金屬皂等,作為具體例,亦可列舉由硬脂酸鋅(:標示名(INCI: Zinc Stearate))、硬脂酸鋁(:標示名(INCI: Aluminum Stearate))、硬脂酸鈣(:標示名(INCI: Calcium Stearate))、硬脂酸鎂(:標示名(INCI: Magnesium Stearate))、肉荳蔻酸鋅(:標示名(INCI: Zinc Myristate))、肉荳蔻酸鎂(:標示名(INCI: Magnesium Myristate))、鯨蠟醇磷酸酯鋅鈉(:標示名(INCI: Sodium Zinc Cetyl Phosphate))、鯨蠟醇磷酸酯鉀(:標示名(INCI: Potassium Cetyl Phosphate))等組成之粉體。
進而,亦可列舉有機系色素等,作為具體例,可列舉紅3、紅104(1)(:標示名(INCI: Red 28、Red 28 Lake))、紅106、紅201(:標示名(INCI: Red 6))、紅202(:標示名(INCI: Red 7))、紅204、紅205、紅220(:標示名(INCI: Red 34))、紅226(:標示名(INCI: Red 30))、紅227(:標示名(INCI: Red 33、RED 33 Lake;))、紅228(:標示名(INCI: Red 36))、紅230(1)(:標示名(INCI: Red 22、Red 22 Lake))、紅230(2)(標示名)、紅401(標示名)、紅505(標示名)、黃4(:標示名(INCI: Yellow 5))、黃5(:標示名(INCI: Yellow 6、Yellow 6 Lake))、黃202(1)(:標示名(INCI: Yellow 8))、黃203(:標示名(INCI: Yellow 10、Yellow 10 Lake))、黃204(:標示名(INCI: Yellow 11))、黃401、藍1(:標示名(INCI: Blue 1、Blue 1 Lake))、藍2、藍201、藍205(:標示名(INCI: Blue 4))、藍404(標示名)、綠3(:標示名(INCI: Green 3、Green 3 Lake))、綠201(:標示名(INCI: Green 5))、綠202(:標示名(INCI: Green 6))、綠204(:標示名(INCI: Green 8))、綠205(標示名)、橙201(:標示名(INCI: Orange 5))、橙203(:標示名(INCI: Pigment Orange 5))、橙204(標示名)、橙205(:標示名(INCI: Orange 4、Orange 4 Lake))、橙206(:標示名(INCI: Orange 10))、橙207(:標示名(INCI: Orange 11))等焦油色素、胭脂蟲紅(INCI)、紫膠酸(:標示名(INCI: Laccaic Acid))、紅花萃取物(:標示名(INCI: Carthamus Tinctorius (Safflower) Flower Extract))、白果紫草根萃取物(:標示名(INCI: Lithospermum Officinale Root Extract))、梔子黃(標示名)、梔子藍(:標示名(INCI: Hydrolyzed Gardenia Florida Extract))等天然色素。
·無機/有機複合粉體
作為無機/有機複合粉體,可列舉例如無機粉體表面藉由周知公用的方法由有機粉體被覆之複合粉體。
再者,上述粉體亦可使用對粒子表面進行處理後之粉體。又,就化粧料的耐水性之觀點而言,其表面處理劑較佳為能夠賦予疏水性,該賦予疏水性之處理劑並無特別限定,可列舉聚矽氧處理劑、蠟類、石蠟類、全氟烷基與磷酸鹽等有機氟化合物、界面活性劑、N-醯基麩胺酸等胺基酸、硬脂酸鋁、肉荳蔻酸鎂等金屬皂等處理劑。
更佳為聚矽氧處理劑,可列舉三乙氧基辛基矽烷(INCI)等矽烷類或矽化劑、二甲聚矽氧烷(INCI)、甲聚矽氧烷(INCI)、氫化二甲聚矽氧烷(INCI)、三乙氧基甲矽烷基乙基聚二甲基矽氧乙基二甲聚矽氧烷(INCI)、三乙氧基甲矽烷基乙基聚二甲基矽氧乙基己基二甲聚矽氧烷(INCI)、(丙烯酸(酯)類/十三醇丙烯酸酯/三乙氧基甲矽烷基丙醇甲基丙烯酸酯/二甲聚矽氧烷甲基丙烯酸酯)共聚物(:標示名(INCI: Acrylates/Tridecyl Acrylate/Triethoxysilylpropyl Methacrylate/Dimethicone Methacrylate Copolymer))等。
作為該等聚矽氧處理劑的具體例,可列舉信越化學工業(股)製造之AES-3083、KF-99P、KF-9901、KF-9908、KF-9909、KP-574、KP-541等。
進而,上述表面疏水化處理劑既可單獨使用一種,或組合使用兩種以上。
作為施以表面處理後之著色顏料的具體例,可列舉信越化學工業(股)製造之KTP-09系列,尤其是KTP-09W、09R、09Y、09B等。
(5)由交聯型有機聚矽氧烷及於室溫為液態之油劑組成之組成物
於由交聯型有機聚矽氧烷及於室溫為液態之油劑組成之組成物中,交聯型有機聚矽氧烷較佳為相對於液態油包含自身重量以上的該液態油劑而膨潤。作為該液態油劑,可使用任意成分的(1)油劑中的液態的聚矽氧油、烴油、酯油、天然動植物油、半合成油等、氟系油,可列舉例如環戊矽氧烷(INCI)、二甲聚矽氧烷(INCI)、礦物油(INCI)、異十二烷(INCI)、異十六烷(INCI)、甘油三(乙基己酸)酯(INCI)、異十三烷醇異壬酸酯(:標示名(INCI: Isotridecyl Isononanoate))、鯊烷(INCI)等。
(5)成分與前述(3)成分的交聯型聚矽氧界面活性劑不同,其是於分子結構中不具有聚醚或聚甘油結構之化合物,作為具體例,可列舉(二甲聚矽氧烷/乙烯基二甲聚矽氧烷)交聯聚合物(INCI)、(二甲聚矽氧烷/苯基乙烯基二甲聚矽氧烷)交聯聚合物(INCI)、(乙烯基二甲聚矽氧烷/月桂基二甲聚矽氧烷)交聯聚合物(INCI)、(月桂基聚二甲基矽氧乙基二甲聚矽氧烷/雙乙烯基二甲聚矽氧烷)交聯聚合物(INCI)等。
作為市售之由交聯型有機聚矽氧烷及於室溫為液態之油劑組成之組成物的示例,可列舉信越化學工業(股)製造之KSG-15、KSG-1510、KSG-16、KSG-1610、KSG-19、KSG-016F、KSG-18A、KSG-41A、KSG-42A、KSG-43、KSG-44、KSG-042Z、KSG-045Z、KSG-048Z等。
(6)成膜劑
成膜劑主要是為了進一步維持化粧料的效果持續性而調配。並無特別限定,就賦予撥水性之觀點而言,較佳為聚矽氧系組成物。具體而言,可使用三甲基矽烷氧基矽酸酯、丙烯酸-聚矽氧皮膜劑、聚矽氧改性降冰片烯、聚矽氧改性支鏈澱粉、聚矽氧改性聚乙烯醇等。
作為聚矽氧系組成物的成膜劑的示例,可列舉三甲基矽烷氧基矽酸酯(:標示名(INCI: Trimethylsiloxysilicate))、(丙烯酸(酯)類/二甲聚矽氧烷)共聚物(INCI)、(降冰片烯/三(三甲基矽烷氧基)甲矽烷基降冰片烯)共聚物(INCI)、三(三甲基矽烷氧基)甲矽烷基胺基甲醯支鏈澱粉(:標示名(INCI: Trimethylsiloxysilylcarbamoyl Pullulan))等。
該成膜劑亦可事先溶解在於室溫為液態之油劑中後調配至化粧料中。作為該液態油劑,可使用任意成分的(1)油劑中的液態的聚矽氧油、烴油、酯油、天然動植物油、半合成油等、氟系油。
作為市售之聚矽氧成膜劑的具體例,可列舉信越化學工業(股)製造之KF-7312J、KP-545、KP-549、KP-543、NBN-30-ID、TSPL-30-ID、TSPL-30-D5等。
(7)紫外線吸收散射劑
作為紫外線吸收散射劑,可列舉二氧化鈦微粒子、含鐵二氧化鈦微粒子、氧化鋅微粒子、氧化鈰微粒子及它們的複合物等吸收並散射紫外線之粒子,亦可使用使該等吸收並散射紫外線之粒子預先分散於油劑中所得之分散物。
作為該油劑,可使用任意成分的(1)油劑中的液態的聚矽氧油、烴油、酯油、天然動植物油、半合成油等、氟系油。
作為使吸收並散射紫外線之粒子預先分散於油劑中之分散物的具體例,可列舉信越化學工業(股)製造之SPD系列(商品名),尤其是SPD-T5、Z5、T6、Z6、T7等。
(8)其他添加劑
作為其他添加劑,可列舉油溶性凝膠化劑、防腐劑/殺菌劑、止汗劑、香料、鹽類、抗氧化劑、pH調節劑、螯合劑、清涼劑、抗發炎劑、美肌用成分(美白劑、細胞活化劑、皮膚粗糙改善劑、血液循環劑、皮膚收斂劑、抗脂溢劑等)、維生素類、胺基酸類、核酸、激素、包接化合物等。
·油溶性凝膠化劑
作為油溶性凝膠化劑,可列舉:硬脂酸鋁、硬脂酸鎂、肉荳蔻酸鋅等金屬皂;月桂醯麩胺酸(:標示名(INCI: Lauroyl Glutamic Acid))、α,γ-二-正丁胺等胺基酸衍生物;糊精棕櫚酸酯(:標示名(INCI: Dextrin Palmitate))、糊精異硬脂酸酯(:標示名(INCI: Dextrin Isostearate))、糊精肉豆蔻酸酯(:標示名(INCI: Dextrin Myristate))、硬脂醯菊粉(:標示名(INCI: Stearoyl Inulin))、糊精棕櫚酸酯/乙基己酸酯(:標示名(INCI: Dextrin Palmitate/Ethylhexanoate))等糊精脂肪酸酯;蔗糖棕櫚酸酯、蔗糖硬脂酸酯等蔗糖脂肪酸酯;寡果糖硬脂酸酯、寡果糖2-乙基己酸酯等寡果糖脂肪酸酯;單亞芐基山梨糖醇、二亞芐基山梨糖醇等山梨糖醇的亞芐基衍生物;二硬脂二甲銨水輝石(INCI)、司拉氯銨水輝石(INCI)、水輝石的有機改性黏土礦物;司拉氯銨膨潤土(INCI)等。
·防腐劑/殺菌劑
作為防腐劑/殺菌劑,可列舉對羥基苯甲酸烷基酯、苯甲酸、苯甲酸鈉、山梨酸、山梨酸鉀、苯氧乙醇、咪唑烷基脲、水楊酸、異丙基甲基酚、石炭酸、對氯間甲酚、六氯酚、苯紮氯銨、鹽酸氯己啶、三氯碳酸苯胺、碘代丙炔基胺基甲醯丁酯、聚離胺酸、感光素、銀、植物提取物等。
·止汗劑
作為止汗劑,可列舉氯化羥鋁等羥基鹵化鋁、氯化鋁等鹵化鋁、尿囊素鋁鹽、單寧酸、柿單寧、硫酸鋁鉀、氧化鋅、對苯酚磺酸鋅、燒明礬、四氯羥鋁鋯、三氯羥鋁鋯GLY配位化合物等。尤其是作為展現較高效果之成分,較佳為羥基鹵化鋁、鹵化鋁、以及它們與氧鹵化鋯及羥基鹵化鋯的錯合物或混合物(例如,四氯羥鋁鋯、三氯羥鋁鋯GLY配位化合物)等。
·香料
作為香料,有天然香料及合成香料。作為天然香料,有自花、葉、木材、果皮等分離出之植物性香料;麝香、靈貓香等動物性香料。作為合成香料,可列舉:單萜等烴類、脂肪族醇、芳香族醇等醇類;萜烯醛、芳香族醛等醛類;脂環式酮等酮類;萜烯系酯等酯類;內酯類;酚類;氧化物類;含氮化合物類;縮醛類等。
·鹽類
作為鹽類,可列舉無機鹽、有機酸鹽、胺鹽及胺基酸鹽。作為無機鹽,可列舉例如鹽酸、硫酸、碳酸、硝酸等無機酸的鈉鹽、鉀鹽、鎂鹽、鈣鹽、鋁鹽、鋯鹽、鋅鹽等;作為有機酸鹽,可列舉例如乙酸、去氫乙酸、檸檬酸、蘋果酸、琥珀酸、抗壞血酸、硬脂酸等有機酸類的鹽;作為胺鹽及胺基酸鹽,可列舉例如三乙醇胺等胺類的鹽、麩胺酸等胺基酸類的鹽等。又,另外,也可使用透明質酸、硫酸軟骨素等鹽、甘胺酸鋁鋯錯合物等、進而於化粧料配方中使用之酸鹼中和鹽等。
·抗氧化劑
作為抗氧化劑,並無特別限定,可列舉例如類胡蘿蔔素、抗壞血酸及其鹽、抗壞血酸硬脂酸酯、乙酸生育酚酯、生育酚、p-叔丁基苯酚、丁基羥基甲氧苯、二丁基羥基甲苯、植酸、阿魏酸、硫代牛磺酸、亞牛磺酸、亞硫酸鹽、異抗壞血酸及其鹽、綠原酸、表兒茶素、表沒食子兒茶素、表沒食子兒茶素沒食子酸酯、芹菜素、山奈酚、楊梅黃酮、槲皮酮等。抗氧化劑既可僅使用一種,亦可併用兩種以上。
·PH調節劑
作為pH調節劑,可列舉乳酸、檸檬酸、乙醇酸、琥珀酸、酒石酸、dl-蘋果酸、碳酸鉀、碳酸氫鈉、碳酸氫銨等。
·螯合劑
作為螯合劑,可列舉丙胺酸、依地酸鈉鹽、聚磷酸鈉、偏磷酸鈉、磷酸等。
·清涼劑
作為清涼劑,可列舉L-薄荷醇、樟腦、薄荷醇乳酸酯等。
·抗發炎劑
作為抗發炎劑,可列舉尿囊素、甘草酸及其鹽、甘草亭酸及硬脂醇甘草亭酸酯、傳明酸、甘菊藍等。
·美肌用成分
作為美肌用成分,可列舉:胎盤提取液、熊果苷、麩胱甘肽、虎耳草提取物等美白劑、蜂王漿、感光素、膽固醇衍生物、小牛血液提取液等細胞活化劑;皮膚粗糙改善劑、壬酸香草醯胺、煙酸苯甲酯、煙酸β-丁氧基乙酯、辣椒素、薑油酮、斑蝥酊、魚石脂、咖啡因、單寧酸、α-冰片、生育酚煙酸酯、六菸鹼酸肌醇、環扁桃酯、抗凝血劑拮抗劑(cinnarizine)、托拉佐林(tolazoline)、乙醯膽鹼、維拉帕米(verapamil)、頭花千金藤素(Cepharanthine)、γ-谷維素等血液循環劑、氧化鋅、單寧酸等皮膚收斂劑、硫磺、二甲噻蒽等抗脂溢劑等。
·維生素類
作為維生素類,可列舉維生素A油、視黃醇、視黃醇乙酸酯、視黃醇棕櫚酸酯等的維生素A類、核黃素、核黃素丁酸酯、黃素腺嘌呤核苷酸等維生素B2類、吡多素鹽酸鹽、吡多素二辛酸酯、吡多素三棕櫚酸酯等維生素B6類、維生素B12及其衍生物、維生素B15及其衍生物等維生素B類、L-抗壞血酸、L-抗壞血酸二棕櫚酸酯、L-抗壞血酸-2-硫酸鈉、L-抗壞血酸磷酸二酯二鉀等維生素C類、麥角鈣化醇、膽鈣化醇等維生素D類、α-生育酚、β-生育酚、γ-生育酚、dl-α-生育酚乙酸酯、d1-ct-生育酚煙酸酯、d1-α-生育酚琥珀酸酯等維生素E類、煙酸、煙酸苄酯、煙醯胺等煙酸類、維生素H、維生素P、泛酸鈣、D-泛醇、泛醇基乙基醚、乙醯基泛醇基乙基醚等泛酸類、生物素等。
·胺基酸類
作為胺基酸類,可列舉甘胺酸、纈胺酸、白胺酸、異白胺酸、絲胺酸、蘇胺酸、苯丙胺酸、精胺酸、離胺酸、天冬胺酸、麩胺酸、胱胺酸、半胱胺酸、甲硫胺酸、色胺酸等。
·核酸
作為核酸,可列舉去氧核糖核酸等。
·激素
作為激素,可列舉雌二醇、乙烯基雌二醇等。
·包接化合物
作為包接化合物,可列舉環糊精等。
[實施例]
以下,示出實施例及比較例對本發明更詳細地進行說明,本發明並不限於下述實施例。再者,於示例中,動黏度是於25℃利用毛細管黏度計所測得之值,表示濃度及含有率之「%」表示「質量%」。
[製造例1]
(矽酮橡膠粒子的水分散液的製造)
將由下式(11)所示之動黏度為55 mm
2/s的含乙烯基的二甲基聚矽氧烷(A1)344 g、由下式(12)所示之動黏度為30 mm
2/s的甲基氫聚矽氧烷(B1)56 g(相對於1個乙烯基,氫矽烷基為1.15個之調配量)、及d1-a-生育酚(抗氧化劑)0.1 g添加至容量為1升的玻璃燒杯中,利用均質攪拌機使其混合溶解。加入月桂醇聚氧乙烯醚(商品名:EMULGEN 109P、花王(股)(Kao Corporation)製造)30 g及水40 g,使用均質攪拌機攪拌,增黏至無法攪拌之狀態。利用均質分散機將增黏物混練15分鐘。接著,加入水528 g,利用均質攪拌機混合,獲得均勻的白色乳液。將該乳液轉移至帶有利用錨型攪拌翼實現之攪拌裝置之容量為1升的玻璃燒瓶中,將溫度調整至20~25℃後,於攪拌下添加鉑-含乙烯基二矽氧烷錯合物的異十二烷溶液(鉑含量0.5%)1 g、月桂醇聚氧乙烯醚(商品名:EMULGEN 109P、花王(股)製造)1 g的混合溶解物,於同一溫度攪拌24小時,獲得矽酮橡膠粒子的水分散液。
利用「雷射繞射/散射式粒度分佈測定裝置LA-960」((股)堀場製作所(HORIBA, Ltd.)製造)測定矽酮橡膠粒子的體積平均粒徑,結果為300 nm。
將由下式(11)所示之動黏度為55 mm
2/s的含乙烯基的二甲基聚矽氧烷(A1)、由下式(12)所示之動黏度為30 mm
2/s的甲基氫聚矽氧烷(B1)、及鉑-含乙烯基二矽氧烷錯合物的異十二烷溶液(鉑含量0.5%)按照上述調配比例混合,以厚度為10 mm之方式倒入鋁皿中,於25℃放置6小時後,進而於50℃的恒溫槽內加熱1小時。所獲得之硬化物為不黏的橡膠彈性體,利用日本JIS K6253所規定之A型硬度計測定硬度,結果為50。
(A1):含乙烯基的二甲基聚矽氧烷
(B1):甲基氫聚矽氧烷
[製造例2]
(矽酮橡膠粒子的水分散液的製造)
將由下式(13)所示之動黏度為5,060 mm
2/s的含乙烯基的二甲基聚矽氧烷(A2)393 g、由上式(12)所示之動黏度為30 mm
2/s的甲基氫聚矽氧烷7 g(相對於1個乙烯基,氫矽烷基為1.19個之調配量)、及d1-a-生育酚(抗氧化劑)0.1 g添加至容量為1升的玻璃燒杯中,利用均質攪拌機使其混合溶解。加入月桂醇聚氧乙烯醚(商品名:EMULGEN 109P、花王(股)製造)42 g及水35 g,利用均質攪拌機攪拌,增黏至無法攪拌之狀態。利用均質分散機將增黏物混練15分鐘。接著,加入水521 g,利用均質攪拌機混合,獲得均勻的白色乳液。將該乳液轉移至帶有利用錨型攪拌翼實現之攪拌裝置之容量為1升的玻璃燒瓶中,將溫度調整至20~25℃後,於攪拌下添加鉑-含乙烯基二矽氧烷錯合物的異十二烷溶液(鉑含量0.5%)0.6 g、月桂醇聚氧乙烯醚(商品名:EMULGEN 109P、花王(股)製造)1 g的混合溶解物,於同一溫度下攪拌24小時,獲得矽酮橡膠粒子的水分散液。
利用「雷射繞射/散射式粒度分佈測定裝置LA-960」((股)堀場製作所製造)測定矽酮橡膠粒子的體積平均粒徑,結果為300 nm。
將由下式(13)所示之動黏度為5,060 mm
2/s的含乙烯基的二甲基聚矽氧烷、由上式(12)所示之動黏度為30 mm
2/s的甲基氫聚矽氧烷、及鉑-含乙烯基二矽氧烷錯合物的異十二烷溶液(鉑含量0.5%)按照上述調配比例混合,以厚度為10 mm之方式倒入鋁皿中,於25℃放置6小時後,進而於50℃的恒溫槽內加熱1小時。所獲得之硬化物為不黏的橡膠彈性體,利用A型硬度計測定硬度,結果為20。
(A2):含乙烯基的二甲基聚矽氧烷
[實施例1]
向帶有利用錨型攪拌翼實現之攪拌裝置之容量為2升的玻璃燒瓶中添加纖維素粒子(商品名:CELLULOBEADS D5、大東化成工業(股)(DAITO KASEI KOGYO CO., LTD.)製造、形狀=球狀、體積平均粒徑=12 μm、電子顯微鏡照片:第4圖)150 g、於上述製造例1中獲得之矽酮橡膠粒子水分散液20 g(相對於纖維素粒子100質量份,矽酮橡膠粒子為5.3質量份之量)、30%月桂基三甲基氯化銨水溶液(商品名:CATION BB、日油(股)(NOF CORPORATION)製造)5.5 g(相對於水100質量份,月桂基三甲基氯化銨為0.2質量份之量)、40%二甲基二烯丙基氯化銨的聚合物水溶液(商品名:ME Polymer H40W、東邦化學工業(股)製造)0.62 g(相對於水100質量份,二甲基二烯丙基氯化銨的聚合物為0.03質量份之量)、2.8%氨水1.6 g、及水800 g。此時的液體的pH為10.8。將溫度調整至5~10℃後,花費20分鐘滴加四甲氧矽烷22 g(水解及縮合反應後的二氧化矽量為8.69g,相對於矽酮橡膠粒子100質量份,水解及縮合反應後的二氧化矽為109質量份之量),將此期間的液溫保持為5~10℃,再進行1小時攪拌。接著,加熱至75~80℃,於保持該溫度之狀態下進行1小時攪拌,結束四甲氧矽烷的水解及縮合反應。利用加壓過濾器將所獲得之懸濁液脫水。將脫水物轉移至帶有利用錨型攪拌翼實現之攪拌裝置之容量為2升的玻璃燒瓶中,添加水1,000 g,進行30分鐘攪拌後,利用加壓過濾器進行脫水。重複該操作兩次。於熱風流動乾燥機中以105℃的溫度乾燥所獲得之脫水物,利用噴射磨機將乾燥物壓碎,而獲得粒子。
利用電阻法粒度分佈測定裝置(Multisizer 3、貝克曼庫爾特有限公司(股)(Beckman Coulter Inc.)製造)測定所獲得之聚矽氧粒子的體積平均粒徑,結果為12 μm。
利用電子顯微鏡觀察所獲得之粒子,確認到大小約300 nm左右的球狀粒子無間隙地被覆附著於球狀的粒子表面,為使矽酮橡膠粒子附著於纖維素粒子表面而成之複合粒子。將電子顯微鏡照片示於第1圖。
向裝有溶解有1%月桂醇聚氧乙烯醚(商品名:EMULGEN 109P、花王(股)製造)之水溶液80 g之100 mL的燒杯中添加所獲得之粒子5 g,利用玻璃棒攪拌,使粒子分散於水溶液中。靜置24小時後,觀察粒子的起伏,結果,粒子全部沈降。矽酮橡膠粒子由於比重小於水,故上浮,根據該結果,判斷出矽酮橡膠粒子未自纖維素粒子表面脫落,二氧化矽為黏合劑,暗示矽酮橡膠粒子固著於纖維素粒子表面。
[實施例2]
向帶有利用錨型攪拌翼實現之攪拌裝置之容量為2升的玻璃燒瓶中添加纖維素粒子(商品名:CELLULOBEADS D5、大東化成工業(股)製造、形狀=球狀、體積平均粒徑=12 μm)150 g、於上述製造例2中獲得之矽酮橡膠粒子水分散液20 g(相對於纖維素粒子100質量份,矽酮橡膠粒子為5.3質量份之量)、30%月桂基三甲基氯化銨水溶液(商品名:CATION BB、日油(股)製造)5.5 g(相對於水100質量份,月桂基三甲基氯化銨為0.2質量份之量)、40%二甲基二烯丙基氯化銨的聚合物水溶液(商品名:ME Polymer H40W、東邦化學工業(股)(Toho Chemical Industry Co Ltd.)製造)0.62 g(相對於水100質量份,二甲基二烯丙基氯化銨的聚合物為0.03質量份之量)、2.8%氨水1.6 g、及水811 g。此時的液體的pH為10.8
。將溫度調整至5~10℃後,花費10分鐘滴加四甲氧矽烷11 g(水解及縮合反應後的二氧化矽量為4.34 g,相對於矽酮橡膠粒子100質量份,水解及縮合反應後的二氧化矽為54質量份之量),將此期間的液溫保持為5~10℃,再進行1小時攪拌。接著,加熱至75~80℃,於保持該溫度之狀態下進行1小時攪拌,結束四甲氧矽烷的水解及縮合反應。利用加壓過濾器將所獲得之懸濁液脫水。將脫水物轉移至帶有利用錨型攪拌翼實現之攪拌裝置之容量為2升的玻璃燒瓶中,添加水1,000 g,進行30分鐘攪拌後,利用加壓過濾器進行脫水。重複該操作兩次。於熱風流動乾燥機中以105℃的溫度乾燥所獲得之脫水物,利用噴射磨機將乾燥物壓碎,而獲得粒子。
利用電阻法粒度分佈測定裝置(Multisizer 3、貝克曼庫爾特有限公司(股)製造)測定所獲得之聚矽氧粒子的體積平均粒徑,結果為12 μm。
利用電子顯微鏡觀察所獲得之粒子,確認到大小約300 nm左右的球狀粒子及其凝聚體有8成至9成左右附著於球狀的粒子表面,為使矽酮橡膠粒子附著於纖維素粒子表面而成之複合粒子。將電子顯微鏡照片示於第2圖。
向裝有溶解有1%月桂醇聚氧乙烯醚(商品名:EMULGEN 109P、花王(股)製造)之水溶液80 g之100 mL的燒杯中添加所獲得之粒子5 g,利用玻璃棒攪拌,使粒子分散於水溶液中。靜置24小時後,觀察粒子的起伏,結果,粒子全部沈降。矽酮橡膠粒子由於比重小於水,故上浮,根據該結果,判斷出矽酮橡膠粒子未自纖維素粒子表面脫落,二氧化矽為黏合劑,暗示矽酮橡膠粒子固著於纖維素粒子表面。
[實施例3]
向帶有利用錨型攪拌翼實現之攪拌裝置之容量為2升的玻璃燒瓶中添加纖維素粒子(商品名:CELLULOBEADS D5、大東化成工業(股)製造、形狀=球狀、體積平均粒徑=12 μm)150 g、於上述製造例2中獲得之矽酮橡膠粒子水分散液3.5 g(相對於纖維素粒子100質量份,矽酮橡膠粒子為0.9質量份之量)、30%月桂基三甲基氯化銨水溶液(商品名:CATION BB、日油(股)製造)5.6 g(相對於水100質量份,月桂基三甲基氯化銨為0.2質量份之量)、40%二甲基二烯丙基氯化銨的聚合物水溶液(商品名:ME Polymer H40W、東邦化學工業(股)製造)0.63g(相對於水100質量份,二甲基二烯丙基氯化銨的聚合物為0.03質量份之量)、2.8%氨水1.6 g、及水828 g。此時的液體的pH為10.8。將溫度調整至5~10℃後,花費10分鐘滴加四甲氧矽烷11 g(水解及縮合反應後的二氧化矽量為4.34 g,相對於矽酮橡膠粒子100質量份,水解及縮合反應後的二氧化矽為310質量份之量),將此期間的液溫保持為5~10℃,再進行1小時攪拌。接著,加熱至75~80℃,於保持該溫度之狀態下進行1小時攪拌,結束四甲氧矽烷的水解及縮合反應。利用加壓過濾器將所獲得之懸濁液脫水。將脫水物轉移至帶有利用錨型攪拌翼實現之攪拌裝置之容量為2升的玻璃燒瓶中,添加水1,000 g,進行30分鐘攪拌後,利用加壓過濾器進行脫水。重複該操作兩次。於熱風流動乾燥機中以105℃的溫度乾燥所獲得之脫水物,利用噴射磨機將乾燥物壓碎,而獲得粒子。
利用電阻法粒度分佈測定裝置(Multisizer 3、貝克曼庫爾特有限公司(股)製造)測定所獲得之聚矽氧粒子的體積平均粒徑,結果為12 μm。
利用電子顯微鏡觀察所獲得之粒子,確認到大小約300 nm左右的球狀粒子稀疏地附著於球狀粒子表面,為使矽酮橡膠粒子附著於纖維素粒子表面而成之複合粒子。於未附著有矽酮橡膠粒子之表面可見100 nm以下的粒狀物的附著,判斷出其為二氧化矽。將電子顯微鏡照片示於第3圖。
向裝有溶解有1%月桂醇聚氧乙烯醚(商品名:EMULGEN 109P、花王(股)製造)之水溶液80 g之100 mL的燒杯中添加所獲得之粒子5 g,利用玻璃棒攪拌,使粒子分散於水溶液中。靜置24小時後,觀察粒子的起伏,結果,粒子全部沈降。矽酮橡膠粒子由於比重小於水,故上浮,根據該結果,判斷出矽酮橡膠粒子未自纖維素粒子表面脫落,二氧化矽為黏合劑,暗示矽酮橡膠粒子固著於纖維素粒子表面。
[比較例1]
向帶有利用錨型攪拌翼實現之攪拌裝置之容量為2升的玻璃燒瓶中添加纖維素粒子(商品名:CELLULOBEADS D5、大東化成工業(股)製造、形狀=球狀、體積平均粒徑=12 μm)150 g、於上述製造例1中獲得之矽酮橡膠粒子水分散液20 g(相對於纖維素粒子100質量份,矽酮橡膠粒子為5.3質量份之量)、2.8%氨水1.6 g、及水806 g。此時的液體的PH為10.8。將溫度調整至5~10℃後,花費20分鐘滴加四甲氧矽烷22 g(水解及縮合反應後的二氧化矽量為8.69g,相對於矽酮橡膠粒子100質量份,水解及縮合反應後的二氧化矽為109質量份之量),將此期間的液溫保持為5~10℃,再進行1小時攪拌。接著,加熱至75~80℃,於保持該溫度之狀態下進行1小時攪拌,結束四甲氧矽烷的水解及縮合反應。利用加壓過濾器將所獲得之懸濁液脫水。將脫水物轉移至帶有利用錨型攪拌翼實現之攪拌裝置之容量為2升的玻璃燒瓶中,添加水1,000 g,進行30分鐘攪拌後,利用加壓過濾器進行脫水。重複該操作兩次。於熱風流動乾燥機中以105℃的溫度乾燥所獲得之脫水物,利用噴射磨機將乾燥物壓碎,而獲得粒子。
利用電子顯微鏡觀察所獲得之粒子,於纖維素粒子表面未見粒子的附著。
於向將纖維素粒子、矽酮橡膠粒子、氨水及水調配而成之混合液中添加四烷氧矽烷,使其進行水解及縮合反應之步驟中,當未調配陽離子性物質(陽離子性界面活性劑及/或陽離子性水溶性高分子)時,矽酮橡膠粒子不附著於纖維素粒子表面。
[複合粒子的吸油量測定]
關於在上述實施例中製作之複合粒子及纖維素粒子(商品名:CELLULOBEADS D5、大東化成工業(股)製造、形狀=球狀、體積平均粒徑=12 μm),以日本JIS K 5101-13-1第13部:吸油量-第1節:精製亞麻仁油為參考,使用用於化粧品用途之油劑測定吸油量。將結果一併記入下述表1及第5圖中。
[表1]
(注1)信越化學工業(股)製造:25℃的動黏度為6 mm
2/s的二甲聚矽氧烷(INCI)
*比較例1中,橡膠粒子、二氧化矽未附著於有機樹脂粒子
項目 | 實施例1 | 實施例2 | 實施例3 | 比較例1* | 纖維素粒子 | ||
球狀有機樹脂粒子 | 有機樹脂 | 纖維素 | 纖維素 | 纖維素 | 纖維素 | 纖維素 | |
平均粒徑μm | 12 | 12 | 12 | 12 | 12 | ||
橡膠粒子 | 橡膠 | 矽酮橡膠 | 矽酮橡膠 | 矽酮橡膠 | 矽酮橡膠 | - | |
平均粒徑nm | 300 | 300 | 300 | 300 | - | ||
A型硬度計 | 50 | 20 | 20 | 50 | - | ||
有機樹脂粒子/橡膠粒子 重量比 | 100/5.3 | 100/5.3 | 100/0.9 | 100/5.3 | 100/0 | ||
橡膠粒子/二氧化矽 重量比 | 100/109 | 100/54 | 100/310 | 100/109 | - | ||
吸油量 g/100 g | KF-96A-6cs(注1) | 90 | 92 | 68 | - | 53 | |
鯊烷 | 69 | 68 | 60 | - | 48 | ||
根據上述表1及第5圖的結果可知,與纖維素粒子相比,實施例1~3對各種油劑之吸油性能較高。其中,可知於實施例3中,相對於有機樹脂粒子100質量份,矽酮橡膠粒子的量為1.0質量份以下,對各種油劑之吸油性能較高。
[實施例4~6、比較例2:複合粒子的使用性評價]
以下述方法製備下表3所示之配方的護膚化粧料,進行下述特性評價。
(1)使用性評價
針對調配有於上述實施例中製作之複合粒子及纖維素粒子(商品名:CELLULOBEADS D5、大東化成工業(股)製造、形狀=球狀、體積平均粒徑=12 μm)之護膚化粧料,評價塗抹時的使用性(抹開性、皮膚相容性)及塗抹後的使用性(不黏、遮瑕、順滑性)這些項目。關於使用性的程度,請十名專家討論小組成員進行評價。根據表2所示之評價基準來評價,基於十名成員的平均值,根據下述判斷基準對結果進行判定。將結果一併記入下述表3中。
[表2]
項目 | 使用性的程度 |
5分 | 良好 |
4分 | 基本良好 |
3分 | 一般 |
2分 | 略差 |
1分 | 差 |
(2)使用性的判定基準
◎:平均分為4.0分以上
〇:平均分為3.0分以上且不足4.0分
△:平均分為2.0分以上且不足3.0分
×:平均分不足2.0分
[表3]
(注1)信越化學工業(股)製造:(二甲聚矽氧烷70-80%+(二甲聚矽氧烷/(PEG-10/15))交聯聚合物20-30%)的混合物
(注2)信越化學工業(股)製造:(二甲聚矽氧烷80-90%+(二甲聚矽氧烷/乙烯基二甲聚矽氧烷)交聯聚合物10-20%)的混合物
(注3)信越化學工業(股)製造:PEG-10二甲聚矽氧烷
(注4)信越化學工業(股)製造:25℃的動黏度為6 mm
2/s的二甲聚矽氧烷
組成(%) | 實施例4 | 實施例5 | 實施例6 | 比較例2 | ||
KSG-210(注1) | 3.0 | 3.0 | 3.0 | 3.0 | ||
KSG-19(注2) | 1.0 | 1.0 | 1.0 | 1.0 | ||
KF-6017(注3) | 0.2 | 0.2 | 0.2 | 0.2 | ||
KF-96A-6cs(注4) | 12.0 | 12.0 | 12.0 | 12.0 | ||
於實施例1中獲得之複合粒子 | 5.0 | |||||
於實施例2中獲得之複合粒子 | 5.0 | |||||
於實施例3中獲得之複合粒子 | 5.0 | |||||
纖維素粒子 | 5.0 | |||||
甘油 | 8.0 | 8.0 | 8.0 | 8.0 | ||
BG | 4.0 | 4.0 | 4.0 | 4.0 | ||
苯氧乙醇 | 0.3 | 0.3 | 0.3 | 0.3 | ||
檸檬酸鈉 | 0.2 | 0.2 | 0.2 | 0.2 | ||
氯化鈉 | 0.5 | 0.5 | 0.5 | 0.5 | ||
水 | 65.8 | 65.8 | 65.8 | 65.8 | ||
合計 | 100.0 | 100.0 | 100.0 | 100.0 | ||
評價 | 塗抹時 使用性 | 抹開性 | 〇 | 〇 | 〇 | 〇 |
皮膚相容性 | ◎ | ◎ | 〇 | △ | ||
塗抹後 使用性 | 不黏 | ◎ | ◎ | 〇 | △ | |
遮瑕 | ◎ | ◎ | 〇 | △ | ||
順滑性 | ◎ | ◎ | 〇 | △ |
根據上述表3的結果,與纖維素粒子相比,實施例1~3的吸油性能較高,為於表面附著有矽酮橡膠粒子之複合粒子,結果,為含有實施例1~3之化粧料之實施例4~6中,塗抹時的皮膚相容性較佳,與比較例2相比,塗抹後的使用性結果為順滑且遮瑕的評價較高。
實施例7:油包水型面霜
(成分) (%)
1.KSG-310(注1) 3.0
2.KSG-44(注2) 1.0
3.KF-6048(注3) 0.2
4.鯊烷 10.8
5.於實施例3中獲得之複合粒子 1.0
6.BG 8.0
7.乙醇 5.0
8.硫酸鎂 0.2
9.氯化鈉 0.5
10.水 餘量
合計 100.0
(注1)信越化學工業(股)製造:(礦物油65-75%+(PEG-15/月桂基二甲聚矽氧烷)交聯聚合物25-35%)的混合物
(注2)信越化學工業(股)製造:(鯊烷65-75%+(乙烯基二甲聚矽氧烷/月桂基二甲聚矽氧烷)交聯聚合物25-35%)的混合物
(注3)信越化學工業(股)製造:鯨蠟基PEG/PPG-10/1二甲聚矽氧烷
(製造方法)
A:將成分1~5混合。
B:將成分6~10混合。
C:將於上述B步驟中獲得之混合物添加至於上述A步驟中獲得之混合物中,並混合均勻。
D:使於上述C步驟中獲得之混合物消泡後,填充至容器中,獲得油包水型面霜。
以如上方式獲得之本發明的油包水型面霜塗抹時的順滑性優異,不黏,延展也較輕,且服帖感優異,相稱度也較佳,具有油光得到抑制之自然的粧感。
實施例8:液態乳化粉底
(成分) (%)
1.KSG-710(注1) 4.0
2.KSG-15(注2) 2.0
3.KF-6105(注3) 3.0
4.KF-96A-6cs(注4) 12.0
5.二硬脂二甲銨水輝石 1.2
6.於實施例3中獲得之複合粒子 3.0
7.KF-7312J(注5) 5.0
8.異十三烷醇異壬酸酯 2.0
9.KF-6106(注6) 0.5
10.KTP-09W(注7) 8.5
11.KTP-09R(注7) 0.4
12.KTP-09Y(注7) 1.0
13.KTP-09B(注7) 0.1
14.香料 0.1
15.戊二醇 5.0
16.檸檬酸鈉 0.2
17.氯化鈉 0.5
18.水 餘量
合計 100.0
(注1)信越化學工業(股)製造:(二甲聚矽氧烷70-80%+(二甲聚矽氧烷/聚甘油-3)交聯聚合物20-30%)的混合物
(注2)信越化學工業(股)製造:(環戊矽氧烷90-96%+(二甲聚矽氧烷/乙烯基二甲聚矽氧烷)交聯聚合物4-10%)的混合物
(注3)信越化學工業(股)製造:月桂基聚甘油-3聚二甲基矽氧乙基二甲聚矽氧烷
(注4)信越化學工業(股)製造:25℃的動黏度為6 mm
2/s的二甲聚矽氧烷
(注5)信越化學工業(股)製造:三甲基矽烷氧基矽酸酯50%的環戊矽氧烷溶解品
(注6)信越化學工業(股)製造:聚甘油-3聚二甲基矽氧乙基二甲聚矽氧烷
(注7)信越化學工業(股)製造:三乙氧基甲矽烷基乙基聚二甲基矽氧乙基己基二甲聚矽氧烷處理後之著色無機顏料、W:白、R:紅、Y:黃、B:黑
(製造方法)
A:將成分1~7混合。
B:將成分8~13混合,並進行輥壓處理。
C:將於上述B步驟中獲得之混合物添加至於上述A步驟中獲得之混合物,並混合均勻。
D:將成分14~18混合。
E:將於上述D步驟中獲得之混合物添加至於上述C步驟中獲得之混合物,並混合均勻。
F:使於上述E中獲得之混合物消泡後,填充至容器中,獲得液態乳化粉底。
以如上方式獲得之本發明的液態乳化粉底塗抹時的順滑性及保濕性優異,不黏,延展也較輕,且服帖感優異,相稱度也較佳,具有油光得到抑制之自然的粧感。
實施例9:粉餅
(成分) (%)
1.新戊二醇二乙基己酸酯 4.0
2.礦物油 2.0
3.KF-56A(注1) 2.0
4.六(羥基硬脂酸/硬脂酸/松香酸)二季戊四醇酯 0.2
5.硬脂酸鋅 1.0
6.於實施例3中獲得之複合粒子 5.0
7.聚甲基倍半矽氧烷(注2) 3.0
8.氮化硼 3.0
9.KF-99P處理後之雲母(注3) 20.0
10.KF-99P處理後之滑石(注3) 餘量
11.AES-3083處理後之顏料級二氧化鈦(白)(注4) 8.0
12.AES-3083處理後之氧化鐵(紅)(注4) 0.4
13.AES-3083處理後之氧化鐵(黃)(注4) 1.3
14.AES-3083處理後之氧化鐵(黑)(注4) 0.3
合計 100.0
(注1)信越化學工業(股)製造:二苯基矽烷氧基苯基三甲聚矽氧烷
(注2)信越化學工業(股)製造:聚甲基倍半矽氧烷
(注3)信越化學工業(股)製造:甲聚矽氧烷處理
(注4)信越化學工業(股)製造:三乙氧基辛基矽烷處理
(製造方法)
A:將成分1~4混合均勻。
B:將成分5~14混合均勻。
C:將於上述A步驟中獲得之混合物添加至於上述B步驟中獲得之混合物,並混合。
D:將於上述C步驟中獲得之混合物過篩後,使用模具沖壓至金屬盤中,獲得粉餅。
以如上方式獲得之本發明的粉餅塗抹時的順滑性及附著性優異,粧效持久,具有良好的粧感。
實施例10:油包水型遮瑕膏
(成分) (%)
1.KSG-210(注1) 3.0
2.KSG-15(注2) 5.0
3.KF-6028(注3) 2.0
4.KF-96L-2cs(注4) 餘量
5.於實施例1中獲得之複合粒子 10.0
6.KP-545(注5) 3.0
7.棕櫚酸乙基己酯 2.0
8.KP-578(注6) 0.3
9.KTP-09W(注7) 7.0
10.KTP-09R(注7) 0.2
11.KTP-09Y(注7) 0.8
12.KTP-09B(注7) 0.2
13.BG 5.0
14.乙醇 8.0
15.檸檬酸鈉 0.2
16.氯化鈉 0.5
17.水 30.0
合計 100.0
(注1)信越化學工業(股)製造:(二甲聚矽氧烷70-80%+(二甲聚矽氧烷/(PEG-10/15))交聯聚合物20-30%)的混合物
(注2)信越化學工業(股)製造:(環戊矽氧烷90-96%+(二甲聚矽氧烷/乙烯基二甲聚矽氧烷)交聯聚合物4-10%)的混合物
(注3)信越化學工業(股)製造:PEG-9聚二甲基矽氧乙基二甲聚矽氧烷
(注4)信越化學工業(股)製造:25℃的動黏度為2 mm
2/s的二甲聚矽氧烷
(注5)信越化學工業(股)製造:(丙烯酸(酯)類/二甲聚矽氧烷)共聚物30%的環戊矽氧烷溶解品
(注6)信越化學工業(股)製造:(丙烯酸(酯)類/丙烯酸乙基己酯/二甲聚矽氧烷甲基丙烯酸酯)共聚物
(注7)信越化學工業(股)製造:三乙氧基甲矽烷基乙基聚二甲基矽氧乙基己基二甲聚矽氧烷處理後之著色無機顏料、W:白、R:紅、Y:黃、B:黑
(製造方法)
A:將成分1~6混合。
B:將成分7~12混合,並進行輥壓處理。
C:將於上述B步驟中獲得之混合物添加至於上述A步驟中獲得之混合物,並混合均勻。
D:將成分13~17混合。
E:將於上述D步驟中獲得之混合物添加至於上述C步驟中獲得之混合物,並混合均勻。
F:使於上述E中獲得之混合物消泡後,填充至容器中,獲得油包水型遮瑕膏。
以如上方式獲得之本發明的油包水型遮瑕膏塗抹時的順滑性優異,不黏,服帖性優異,油光得到抑制,粧效持久,具有良好的粧感。
實施例11:口紅
(成分) (%)
1.聚乙烯蠟 5.0
2.純地蠟 2.0
3.微晶蠟 3.0
4.堪地里拉蠟 1.0
5.二異硬脂醇蘋果酸酯 15.0
6.KP-561P(注1) 2.0
7.於實施例3中獲得之複合粒子 12.0
8.失水山梨醇倍半異硬脂酸酯 1.0
9.聚甘油-2三異硬脂酸酯 15.0
10.辛酸/癸酸甘油三酯 餘量
11.甘油三(乙基己酸)酯 3.0
12.KP-578(注2) 0.5
13.紅色202號 0.5
14.黃色4號鋁色澱 1.6
15.KP-574處理後之顏料級二氧化鈦(白)(注3) 4.0
16.KP-574處理後之氧化鐵(紅)(注3) 1.0
17.KP-574處理後之氧化鐵(黃)(注3) 0.3
18.KP-574處理後之氧化鐵(黑)(注3) 0.3
19.由二氧化鈦被覆之雲母珠光劑 3.0
合計 100.0
(注1)信越化學工業(股)製造:(丙烯酸(酯)類/硬脂醇丙烯酸酯/二甲聚矽氧烷甲基丙烯酸酯)共聚物
(注2)信越化學工業(股)製造:(丙烯酸(酯)類/丙烯酸乙基己酯/二甲聚矽氧烷甲基丙烯酸酯)共聚物
(注3)信越化學工業(股)製造:(丙烯酸(酯)類/十三醇丙烯酸酯/三乙氧基甲矽烷基丙醇甲基丙烯酸酯/二甲聚矽氧烷甲基丙烯酸酯)共聚物處理
(製造方法)
A:將成分1~10加熱溶解。
B:將成分11~18混合均勻,並進行輥壓處理。
C:將於上述B步驟中獲得之混合物與成分19添加至於上述A步驟中獲得之混合物中,並混合均勻。
D:使於上述C步驟中獲得之混合物消泡後,填充至容器中,獲得口紅。
以如上方式獲得之本發明的口紅塗抹時的順滑性優異,不黏,延展也較輕,且服帖感優異,相稱度也較佳,具有油光得到抑制之啞光粧感。
實施例12:水包油型底霜
(成分) (%)
1.水 餘量
2.甘油 3.0
3.微晶蠟 3.0
4.黃原膠 0.2
5.戊二醇 2.0
6.BG 5.0
7.蔗糖椰油酸酯 0.2
8.山梨醇硬脂酸酯 3.0
9.PEG-60甘油異硬脂酸酯 0.5
10.山萮醇 0.5
11.棕櫚酸乙基己酯 3.0
12.於實施例2中獲得之複合粒子 3.0
13.甘油三(乙基己酸)酯 6.0
14.聚羥基硬脂酸 0.5
15.金屬皂處理後之二氧化鈦微粒子 8.0
16.金屬皂處理後之顏料級二氧化鈦(白) 4.0
17.金屬皂處理後之氧化鐵(紅) 0.1
18.金屬皂處理後之氧化鐵(黃) 0.8
19.金屬皂處理後之氧化鐵(黑) 0.1
20.聚山梨醇酯60 0.3
21.丙烯酸羥乙酯/丙烯醯二甲基牛磺酸鈉共聚物 0.6
合計 100.0
(製造方法)
A:將成分1~6混合均勻。
B:將成分7~11加熱溶解,加入成分12使其均勻。
C:將成分13~19混合,並進行輥壓處理。
D:將於上述C步驟中獲得之混合物添加至於上述B步驟中獲得之混合物,並混合均勻。
E:將加熱後之於上述D步驟中獲得之混合物添加至加熱後之於上述A步驟中獲得之混合物中,並混合均勻。
F:將於上述E步驟中獲得之混合物冷卻至常溫後,添加成分20~21並混合均勻。
G:使於上述F步驟中獲得之混合物消泡後,填充至容器中,獲得水包油型底霜。
以如上方式獲得之本發明的水包油型底霜塗抹時的水潤性優異,不黏,延展也較輕,且服帖感優異,相稱度也較佳,具有油光得到抑制之啞光粧感。
實施例13:水性凝膠
(成分) (%)
1.於實施例3中獲得之複合粒子 5.0
2.KF-6100(注1) 0.5
3.乙醇 3.0
4.BG 4.0
5.甘油 2.0
6.(丙烯醯二甲基牛磺酸銨/VP)共聚物 0.2
7.黃原膠 0.2
8.精胺酸 0.5
9.苯氧乙醇 0.3
10.水 餘量
合計 100.0
(注1)信越化學工業(股)製造:聚甘油-3二矽氧烷二甲聚矽氧烷
(製造方法)
A:將成分1
~3混合均勻。
B:將成分4~10混合均勻。
C:將於上述A步驟中獲得之混合物添加至於上述B步驟中獲得之混合物中,並混合均勻。
D:使於上述C步驟中獲得之混合物消泡後,填充至容器中,獲得水性凝膠。
以如上方式獲得之本發明的水性凝膠塗抹時的水潤性優異,不黏,延展也較輕,且服帖感優異,相稱度也較佳,具有油光得到抑制之啞光粧感。
實施例14:油性凝膠
(成分) (%)
1.於實施例1中獲得之複合粒子 10.0
2.KSG-16(注1) 20.0
3.KSG-15(注2) 30.0
4.KF-56A(注3) 5.0
5.KF-995(注4) 餘量
合計 100.0
(注1)信越化學工業(股)製造:(二甲聚矽氧烷70-80%+(二甲聚矽氧烷/乙烯基二甲聚矽氧烷)交聯聚合物20-30%)的混合物
(注2)信越化學工業(股)製造:(環戊矽氧烷90-96%+(二甲聚矽氧烷/乙烯基二甲聚矽氧烷)交聯聚合物4-10%)的混合物
(注3)信越化學工業(股)製造:二苯基矽烷氧基苯基三甲聚矽氧烷
(注4)信越化學工業(股)製造:環戊矽氧烷
(製造方法)
A:將成分1~5混合均勻。
B:使於上述A步驟中獲得之混合物消泡後,填充至容器中,獲得油性凝膠。
以如上方式獲得之本發明的油性凝膠塗抹時的順滑性優異,不黏,延展也較輕,且服帖感優異,相稱度也較佳,具有油光得到抑制之啞光粧感。
實施例15:油性固形粉底
(成分) (%)
1.合成蠟 4.0
2.巴西棕櫚蠟 2.0
3.牛油樹油脂 0.5
4.辛酸/癸酸甘油三酯 3.0
5.KF-56A(注1) 5.0
6.甲氧基肉桂酸乙基己酯 7.0
7.雙乙基己氧基苯酚甲氧基苯基三嗪 0.5
8.KF-96L-2cs(注2) 5.0
9.異十三烷醇異壬酸酯 餘量
10.於實施例2中獲得之複合粒子 4.0
11.KMP-591(注3) 1.0
12.鯨蠟醇乙基己酸酯 3.0
13.KF-6115(注4) 1.0
14.KF-99P處理後之二氧化鈦微粒子(注5) 7.0
15.KTP-09W(注6) 9.0
16.KTP-09R(注6) 0.3
17.KTP-09Y(注6) 1.0
18.KTP-09B(注6) 0.2
合計 100.0
(注1)信越化學工業(股)製造:二苯基矽烷氧基苯基三甲聚矽氧烷
(注2)信越化學工業(股)製造:25℃的動黏度為2 mm
2/s的二甲聚矽氧烷
(注3)信越化學工業(股)製造:聚甲基倍半矽氧烷
(注4)信越化學工業(股)製造:月桂基聚甘油-3聚二甲基矽氧乙基二甲聚矽氧烷
(注5)信越化學工業(股)製造:甲聚矽氧烷處理
(注6)信越化學工業(股)製造:三乙氧基甲矽烷基乙基聚二甲基矽氧乙基己基二甲聚矽氧烷處理後之著色無機顏料、W:白、R:紅、Y:黃、B:黑
(製造方法)
A:將成分1~9加熱溶解。
B:將成分12~18混合均勻,並進行輥壓處理。
C:將於上述B步驟中獲得之混合物及成分10~11添加至加熱後之於上述A步驟中獲得之混合物中,並混合均勻。
D:於上述C步驟中獲得之混合物消泡後,於加熱後之狀態下填充至容器中,冷卻至室溫,獲得油性固形粉底。
以如上方式獲得之本發明的油性固形粉底延展擴散性輕盈,貼合肌膚,粧感滋潤,且獲得抑制油光且有張力之化粧膜,粧效持久,非常優異。
實施例16:油性粉底
(成分) (%)
1.KSG-42A(注1) 10.0
2.於實施例3中獲得之複合粒子 6.0
3.KF-6104(注2) 4.0
4.二硬脂二甲銨水輝石 1.5
5.矽化二氧化矽 1.0
6.TSPL-30-ID(注3) 2.0
7.KF-96A-6cs(注4) 5.0
8.乙醇 8.0
9.異十二烷 餘量
10.異十三烷醇異壬酸酯 10.0
11.KP-578(注5) 0.5
12.KF-9901處理後之二氧化鈦微粒子(注6) 8.0
13.KF-9901處理後之微粒子氧化鋅(注6) 5.0
14.AES-3083處理後之顏料級二氧化鈦(注7) 7.5
15.AES-3083處理後之氧化鐵(紅)(注7) 0.4
16.AES-3083處理後之氧化鐵(黃)(注7) 1.2
17.AES-3083處理後之氧化鐵(黑)(注7) 0.1
合計 100.0
(注1)信越化學工業(股)製造:(異十二烷75-85%+(乙烯基二甲聚矽氧烷/月桂基二甲聚矽氧烷)交聯聚合物15-25%)的混合物
(注2)信越化學工業(股)製造:聚甘油-3聚二甲基矽氧乙基二甲聚矽氧烷
(注3)信越化學工業(股)製造:三(三甲基矽烷氧基)甲矽烷基胺基甲醯支鏈澱粉30%的異十二烷溶解品
(注4)信越化學工業(股)製造:25℃的動黏度為6 mm
2/s的二甲聚矽氧烷
(注5)信越化學工業(股)製造:(丙烯酸(酯)類/丙烯酸乙基己酯/二甲聚矽氧烷甲基丙烯酸酯)共聚物
(注6)信越化學工業(股)製造:氫化二甲聚矽氧烷處理
(注7)信越化學工業(股)製造:三乙氧基辛基矽烷處理
(製造方法)
A:將成分1~9混合均勻。
B:將成分10~17混合均勻,並進行輥壓處理。
C:將於上述B步驟中獲得之混合物添加至於上述A步驟中獲得之混合物中,並混合均勻。
D:使於上述C步驟中獲得之混合物消泡後,填充至容器中,獲得油性粉底。
以如上方式獲得之本發明的油性粉底延展擴散性輕盈,貼合肌膚,粧感滋潤,且獲得抑制油光且有張力之化粧膜,粧效持久,非常優異。
實施例17:油性睫毛膏
(成分) (%)
1.石蠟 20.0
2.微晶蠟 8.0
3.聚乙烯蠟 3.0
4.硬脂醯菊粉 1.0
5.二硬脂二甲銨水輝石 2.0
6.KF-6028(注1) 1.0
7.NBN-30-ID(注2) 3.0
8.氫化聚異丁烯 餘量
9.於實施例3中獲得之複合粒子 2.0
10.新戊二醇二癸酸酯 5.0
11.KF-6115(注3) 1.0
12.KTP-09W(注4) 0.5
13.KTP-09B(注4) 6.0
合計 100.0
(注1)信越化學工業(股)製造:PEG-9聚二甲基矽氧乙基二甲聚矽氧烷
(注2)信越化學工業(股)製造:(降冰片烯/三(三甲基矽烷氧基)甲矽烷基降冰片烯)共聚物30%的異十二烷溶解品
(注3)信越化學工業(股)製造:月桂基聚甘油-3聚二甲基矽氧乙基二甲聚矽氧烷
(注4)信越化學工業(股)製造:三乙氧基甲矽烷基乙基聚二甲基矽氧乙基己基二甲聚矽氧烷處理後之著色無機顏料、W:白、B:黑
(製造方法)
A:將成分1~8加熱溶解。
B:將成分10~13混合均勻,並進行輥壓處理。
C:將於上述B步驟中獲得之混合物及成分9添加至加熱後之於上述A步驟中獲得之混合物中,並混合均勻。
D:使於上述C步驟中獲得之混合物消泡後,冷卻至室溫,之後,填充至容器中,獲得油性睫毛膏。
可知以如上方式獲得之本發明的油性睫毛膏塗抹時的順滑性優異,不黏,延展也較輕,且服帖感優異,具有相稱度也較佳且油光也得到抑制之粧感,不吃粧,粧效持久,非常優異。
實施例18:散粉
(成分) (%)
1.於實施例2中獲得之複合粒子 10.0
2.KF-9901處理後之合成氟金雲母(注1) 25.0
3.KF-9901處理後之滑石(注1) 餘量
4.月桂醯離胺酸 5.0
5.氮化硼 3.0
6.由二氧化鈦被覆之雲母珠光劑 3.0
7.AES-3083處理後之二氧化鈦(注2) 3.0
8.AES-3083處理後之紅氧化鐵(注2) 0.2
9.AES-3083處理後之黃氧化鐵(注2) 0.5
10.AES-3083處理後之黑氧化鐵(注2) 0.1
11.異壬酸異壬酯 2.0
12.乙基己基甘油 0.5
合計 100.0
(注1)信越化學工業(股)製造:氫化二甲聚矽氧烷處理
(注2)信越化學工業(股)製造:三乙氧基辛基矽烷處理
(製造方法)
A:將成分1~10混合均勻。
B:將成分11~12混合均勻。
C:將於上述B步驟中獲得之混合物添加至於上述A步驟中獲得之混合物中,並混合均勻。
D:將於上述C步驟中獲得之混合物過篩後,填充至容器中,獲得散粉。
可知以如上方式獲得之本發明的散粉塗抹時的順滑性優異,具有油光也得到抑制之粧感,粧效持久,非常優異。
實施例19:防曬乳液
(成分) (%)
1.KSG-270(注1) 3.0
2.KSG-18A(注2) 3.0
3.KF-6048(注3) 2.0
4.KF-56A(注4) 5.0
5.KF-4422(注5) 餘量
6.甲氧基肉桂酸乙基己酯 5.0
7.水楊酸乙基己酯 2.0
8.奧克立林 1.0
9.二乙基氨基羥基苯甲醯苯甲酸己酯 2.0
10.於實施例1中獲得之複合粒子 5.0
11.SPD-T5(注6) 10.0
12.SPD-Z5(注7) 10.0
13.BG 3.0
14.乙醇 5.0
15.檸檬酸鈉 0.2
16.氯化鈉 0.5
17.水 20.0
合計 100.0
(注1)信越化學工業(股)製造:(二苯基矽烷氧基苯基三甲聚矽氧烷75-85%+(二甲聚矽氧烷/(PEG-10/15))交聯聚合物15-25%)的混合物
(注2)信越化學工業(股)製造:(二苯基矽烷氧基苯基三甲聚矽氧烷80-90%+(二甲聚矽氧烷/苯基乙烯基二甲聚矽氧烷)交聯聚合物10-20%)的混合物
(注3)信越化學工業(股)製造:鯨蠟基PEG/PPG-10/1二甲聚矽氧烷
(注4)信越化學工業(股)製造:二苯基矽烷氧基苯基三甲聚矽氧烷
(注5)信越化學工業(股)製造:乙基三甲聚矽氧烷
(注6)信越化學工業(股)製造:二氧化鈦微粒子40%的環戊矽氧烷分散物
(注7)信越化學工業(股)製造:微粒子氧化鋅60%的環戊矽氧烷分散物
(製造方法)
A:將成分1~10混合均勻。
B:將成分13~17混合均勻。
C:將於上述B步驟中獲得之混合物添加至於上述A步驟中獲得之混合物中,並混合均勻。
D:向於上述C步驟中獲得之混合物中添加成分11~12,並混合均勻。
E:使於上述D步驟中獲得之混合物消泡後,填充至容器中,獲得防曬乳液。
可知以如上方式獲得之本發明的防曬乳液塗抹時的順滑性優異,具有油光也得到抑制之粧感,粧效持久,非常優異。
實施例20:防曬乳液
(成分) (%)
1.KSG-210(注1) 3.5
2.KSG-18A(注2) 3.0
3.KF-6038(注3) 0.5
4.KF-56A(注4) 5.0
5.甲氧基肉桂酸乙基己酯 7.5
6.KF-995(注5) 6.5
7.於實施例3中獲得之複合粒子 5.0
8.BG 5.5
9.檸檬酸鈉 0.2
10.氯化鈉 0.5
11.水 62.8
合計 100.0
(注1)信越化學工業(股)製造:(二甲聚矽氧烷70-80%+(二甲聚矽氧烷/(PEG-10/15))交聯聚合物20-30%)的混合物
(注2)信越化學工業(股)製造:(二苯基矽烷氧基苯基三甲聚矽氧烷80-90%+(二甲聚矽氧烷/苯基乙烯基二甲聚矽氧烷)交聯聚合物10-20%)的混合物
(注3)信越化學工業(股)製造:月桂基PEG-9聚二甲基矽氧乙基二甲聚矽氧烷
(注4)信越化學工業(股)製造:二苯基矽烷氧基苯基三甲聚矽氧烷
(注5)信越化學工業(股)製造:環戊矽氧烷
(製造方法)
A:將成分1~7混合均勻。
B:將成分8~11混合均勻。
C:將於上述B步驟中獲得之混合物添加至於上述A步驟中獲得之混合物中,並混合均勻。
D:使於上述C步驟中獲得之混合物消泡後,填充至容器中,獲得防曬乳液。
可知以如上方式獲得之本發明的防曬乳液塗抹時的順滑性優異,具有油光也得到抑制之粧感,粧效持久,非常優異。
實施例21:非水系除臭霜
(成分) (%)
1.三氯羥鋁鋯GLY配位化合物 19.0
2.KF-4422(注1) 30.0
3.KSG-15(注2) 21.5
4.於實施例3中獲得之複合粒子 10.0
5.新戊二醇二辛酸酯 9.68
6.香料 0.1
7.BHT 0.02
8.檸檬酸 0.1
9.苄醇 0.1
10.二甲基矽化二氧化矽 0.5
11.聚乙烯 3.0
12.純地蠟 6.0
合計 100.0
(注1)信越化學工業(股)製造:乙基三甲聚矽氧烷
(注2)信越化學工業(股)製造:(環戊矽氧烷90-96%+(二甲聚矽氧烷/乙烯基二甲聚矽氧烷)交聯聚合物4-10%)的混合物
(製造方法)
A:將成分2、3、5、7、9、11、12加熱,並混合均勻。
B:將成分10添加至於上述A步驟中獲得之混合物中,利用混合機均勻地分散混合。
C:將成分1、4、8加入至於上述B步驟中獲得之混合物,並混合均勻。
D:將成分6加入至於上述C步驟中獲得之混合物中,混合均勻後,填充至容器中。
以如上方式獲得之除臭霜能夠非常平滑地塗開,抹開性較佳,無過度的乾燥感或黏連感,防臭效果的持續性優異。
如上,根據本發明,可提供一種使橡膠粒子附著於有機樹脂粒子的表面而成之複合粒子及其製造方法、以及含有該複合粒子之化粧料,能夠賦予觸感柔軟或使用感順滑、具有延展性、且藉由光散射性而具有自然的粧感之效果。
本說明書包含以下發明。
[1]:一種複合粒子,其於球狀有機樹脂粒子的表面附著有橡膠粒子,其特徵在於,該橡膠粒子以二氧化矽為黏合劑而固著於該有機樹脂粒子。
[2]:如上述[1]所述之複合粒子,其中,相對於該有機樹脂粒子100質量份,該橡膠粒子的量為0.1~100質量份的範圍。
[3]:如上述[1]或[2]所述之複合粒子,其中,相對於該橡膠粒子100質量份,該二氧化矽的量為10~1,000質量份的範圍。
[4]:如上述[1]、上述[2]或上述[3]所述之複合粒子,其中,該橡膠粒子為矽酮橡膠粒子。
[5]:如上述[1]、上述[2]、上述[3]或上述[4]所述之複合粒子,其中,該有機樹脂粒子為纖維素粒子。
[6]:一種複合粒子的製造方法,其是如上述[1]、上述[2]、上述[3]、上述[4]或上述[5]所述之複合粒子的製造方法,其特徵在於,向將該有機樹脂粒子、該橡膠粒子、陽離子性物質、鹼性物質及水調配而成之混合液中添加四烷氧矽烷,使其進行水解及縮合反應,且,使該陽離子性物質為陽離子性界面活性劑及/或陽離子性水溶性高分子。
[7]:如上述[6]所述之複合粒子的製造方法,其中,使該陽離子性物質為陽離子性界面活性劑及陽離子性水溶性高分子。
[8]:如上述[6]或上述[7]所述之複合粒子的製造方法,其中,相對於該混合液中的水100質量份,使該陽離子性物質的調配量為0.0001~2.0質量份的範圍。
[9]:如上述[6]、上述[7]或上述[8]所述之複合粒子的製造方法,其中,相對於該混合液中的水100質量份,使該陽離子性界面活性劑的調配量為0.001~1.9質量份,且,相對於該混合液中的水100質量份,使該陽離子性水溶性高分子的調配量為0.0001~1.0質量份的範圍。
[10]:一種化粧料,其特徵在於,其含有上述[1]、上述[2]、上述[3]、上述[4]或上述[5]所述之複合粒子。
再者,本發明並不限於上述實施方式。上述實施方式為舉例,具有與本發明的申請專利範圍所記載之技術思想實質上相同的構成、且發揮相同作用效果之內容均包含在本發明的技術範圍內。
無
第1圖是於實施例1中獲得之複合粒子的電子顯微鏡照片。
第2圖是於實施例2中獲得之複合粒子的電子顯微鏡照片。
第3圖是於實施例3中獲得之複合粒子的電子顯微鏡照片。
第4圖是於實施例及比較例中使用之纖維素粒子的電子顯微鏡照片。
第5圖是實施例的複合粒子、及比較例的纖維素粒子的吸油量的測定結果。
國內寄存資訊(請依寄存機構、日期、號碼順序註記)
無
國外寄存資訊(請依寄存國家、機構、日期、號碼順序註記)
無
Claims (10)
- 一種複合粒子,其於球狀有機樹脂粒子的表面附著有橡膠粒子,其特徵在於,該橡膠粒子以二氧化矽為黏合劑而固著於該有機樹脂粒子。
- 如請求項1所述之複合粒子,其中,相對於該有機樹脂粒子100質量份,該橡膠粒子的量為0.1~100質量份的範圍。
- 如請求項1所述之複合粒子,其中,相對於該橡膠粒子100質量份,該二氧化矽的量為10~1,000質量份的範圍。
- 如請求項1所述之複合粒子,其中,該橡膠粒子為矽酮橡膠粒子。
- 如請求項1至請求項4中任一項所述之複合粒子,其中,該有機樹脂粒子為纖維素粒子。
- 一種複合粒子的製造方法,其是如請求項1所述之複合粒子的製造方法,其特徵在於,向將該有機樹脂粒子、該橡膠粒子、陽離子性物質、鹼性物質及水調配而成之混合液中添加四烷氧矽烷,使其進行水解及縮合反應,且, 使該陽離子性物質為陽離子性界面活性劑及/或陽離子性水溶性高分子。
- 如請求項6所述之複合粒子的製造方法,其中,使該陽離子性物質為陽離子性界面活性劑及陽離子性水溶性高分子。
- 如請求項6所述之複合粒子的製造方法,其中,相對於該混合液中的水100質量份,使該陽離子性物質的調配量為0.0001~2.0質量份的範圍。
- 如請求項6至請求項8中任一項所述之複合粒子的製造方法,其中,相對於該混合液中的水100質量份,使該陽離子性界面活性劑的調配量為0.001~1.9質量份,且,相對於該混合液中的水100質量份,使該陽離子性水溶性高分子的調配量為0.0001~1.0質量份的範圍。
- 一種化粧料,其特徵在於,其含有如請求項1至請求項4中任一項所述之複合粒子。
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