200423965 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種於肌膚優異感觸之除臭劑喷霧組成 物。 【先前技術】 作為防止因汗水而產生之黏腻感或異味之除臭劑製 品，配合有以消除汗水之黏腻感為目的之粉體的粉末喷霧 劑（ρ 〇 w d e r s p r a y )正廣泛地被使用。一般而言，含有粉 體之粉末噴霧劑係將粉體與其他成份混·合，並將分散之組 成物與喷射劑一起填充於喷霧容器内。若將該喷霧容器靜 置，粉體會沉降在容器底部，因此必須於使用前搖晃噴霧 容器，以使粉體進行再分散。 在粉體之分散性不佳之狀態下使用粉末喷霧劑時，具有 各成份無法均勻地喷射，以致除臭效果不足之問題。又， 亦有隨著粉體未均勾地噴射，粉體發生凝集等現象而於肌 膚上留有白色（白色殘留）之狀況。換言之，使粉體充分 地進行再分散，且再分散之粉體再次沉降之前喷射粉末喷 霧組成物，對為發現所希望之性能而言是重要的。尤其於 粉體為有機粉體之情況時，經再分散之粉體可保持良好分 散狀態之時間有縮短的傾向。 於是，為了提升粉末喷霧組成物中粉體之分散性，檢討 了各種方法。 例如，於日本專利特開平3 - 1 5 7 3 2 7號公·報中，揭示有 一種粉末氣膠（a i r - s ο 1 )組成物，其特徵為含有：滑石、 5 312/發明說明書(補件)/93-05/93106656 200423965 矽酸酐、高嶺土、氯化羥鋁等親水性無機粉體；含有液化 石油氣及甲醚中至少一者之噴射劑；非離子型界面活性劑 及矽酮油中之至少一者；以及乙醇。然而，該粉末氣膠組 成物中粉體之分散性並不充足。此外，該粉末氣膠組成物 於噴射時雖可抑制白色化狀態，但因油腻感強烈，無法使 肌膚感到粉體優異之清爽感觸。 於日本專利特開平6 - 4 8 9 1 9號公報中，記載有一種含粉 末之氣膠組成物，其特徵為含有液化石油氣與無機粉末， 並以特定量調配山梨糖醇酐脂肪酸酯及/或聚氧化烯烷基 醚。然而，該含粉末之氣膠組成物於粉體之分散性仍不算 充分，且並未考慮到有機粉體之分散性。 於日本專利特開平5 - 2 2 9 9 2 5號公報中，記載有一種液 狀制汗組成物，其中係調配有氯化羥鋁等制汗劑物質、與 醇類及聚醚改質矽酮。該制汗組成物係藉由聚醚改質矽酮 與醇類來防止組成物中之粉末結晶化，並抑制制汗鹽類之 白色殘留。然而，於該制汗組成物中調配有制汗劑以外之 粉體以提升清爽感等肌膚感觸時，無法獲得充分的白色殘 留之抑制效果。 於日本專利特開平8 - 1 2 5 4 5號公報中，記載有一種制汗 •消臭劑，其含有氣化經I呂（a 1 u m i n u ni h y d r ο X y c h 1 〇 r i d e ) 等收傲劑、玉潔新（t r i c 1 o s a n )等制菌或殺菌劑，並含有 特定的球狀矽酮橡膠粉末與液狀之油性成份。而作為可調 配使用之油性成份，則記載有包含聚氧化烯改質聚矽氧烷 之固形或液狀之矽酮油。然而，於該公報中，僅著眼於矽 6 312/發明說明書(補件)/93-05/93106656 200423965 酮橡膠粉體之感觸提升作用，完全未提及對於該球狀矽酮 粉末之分散性提升，對於白色殘留之抑制並不充足。 於曰本專利特開平1 1 - 3 3 5 2 5 4號公報中，記載有一種氣 膠組成物，其係於氣化羥鋁等無機粉體中，含有異種的有 機聚矽氧烷所構成之複合粉體、以及肉莖蔻酸異丙酯等液 狀油劑。然而，該氣膠組成物亦相同，雖具有清爽的使用 感，對於白色殘留的抑制卻不充足。 【發明内容】 本發明係藉由提升粉體成份之分散性，以提供一種優異 肌膚感觸之除臭劑喷霧組成物。 本發明者等發現，含有疏水性球狀粉體（a )及聚醚改 質矽酮（b )之除臭劑噴霧組成物可提升疏水性球狀粉體（a ) 之分散性及再分散性，可發現所希望的效果。 亦即，本發明係為含有：（a )疏水性球狀粉體；（b )聚 醚改質矽酮；（c )制汗鹽及/或殺菌劑；（d ) 2 5 °C下呈液狀 之油劑（但成份（b)除外）；以及（e )噴射劑之除臭劑喷霧 組成物。 (發明之詳細說明） 疏水性球狀粉體（a )係具有至少表面為疏水性之表面 特性的略球狀粉體，適用於肌膚上，具有抑制因汗水而產 生的黏腻感使提升肌膚感觸的清爽感之效果。相較於滑石 等習知為具有提升肌膚感觸之效果的親水性粉體，疏水性 球狀粉體（a )係使用疏水性大的球狀粉體。疏水性球狀粉 體（a )之形狀不需為嚴格的真球狀，例如斷面為橢圓形者 7 312/發明說明書(補件)/93-05/93106656 200423965 亦可，但以真球狀為佳。疏水性球狀粉體（a )之平均粒徑 以0 · 1〜3 0 // m為佳，較佳為1〜1 0 " m。藉由使其為0 . 1 // m 以上，可獲得較佳的滑順感觸，藉由使其為3 0 " m以下， 則可獲得無粗糙感之良好肌膚感觸。 疏水性球狀粉體（a )之疏水性基準以臨界表面張力在 5 0 m N / m以下為佳。臨界表面張力在5 0 m N / in以下之情況， 由於親水性小，粉體不會被汗水包覆，而可抑制黏腻感。 自該等之疏水性度及形狀之觀點而言，本發明之疏水性 球狀粉體（a )以有機聚合物粉體更優於無機粉體。 作為疏水性球狀粉體（a )，可具體列舉出尼龍樹脂、聚 苯乙稀系樹脂、聚乙稀樹脂、聚曱基丙烤酸甲酯系樹脂、 聚胺基甲酸酯系樹脂、酚系樹脂、矽酮樹脂等有機聚合物 粉體。 尤其係矽酮樹脂粉體，因其撥水性高，故較佳；可列舉 如曱基矽氧烷網狀聚合體，或複合矽酮粉體、將於單體末 端具有自由基聚合性基之聚矽氧烷化合物作為分散劑而於 溶劑中進行乙烯基單體之分散聚合所得之聚合物微粒子 (參照日本專利特開2 ◦ 0 2 - 3 0 8 9 0 9號公報）等。複合矽酮 粉體之中，於矽酮橡膠粉體之表面被覆矽酮樹脂之複合矽 酮粉體（交聯型矽酮、網狀型矽酮嵌段共聚合體），由於具 有高度的清爽感及長時間持續抑制白色殘留之效果，故特 佳。此種複合粉體被推測為可將後述之油劑吸藏於粉體内 部，且皮膚上會持續將其釋放出，因此可持續清爽的感觸 並可持續抑制白色殘留的效果。 8 312/發明說明書(補件)/93-05/93106656 200423965 使用於本發明之疏水性球狀粉體（a )為可買到之市售 品，可列舉如：S P - 5 0 0 (東麗製）等尼龍樹脂；梵帕魯（F i n e Pearl，住友化學工業製）、帖庫波里馬SB(TECHPOLYMER SB，積水化成品工業製）、梵帕烏達SGP(FinePowderSGP， 綜研化學製）等聚苯乙烯系樹脂；芙羅必茲（F L 0 - B E A D S，住 友精化製）等聚乙烯樹脂；松本微球體-M ( M A T S U Μ 0 T 0 Microsphere-M ?松本油脂製藥製）、帖庫波里馬 MB(TECHPOLYMERMB，積水化成品工業製）、梵帕烏達 Μ P ( F i n e P〇w d e r Μ P，綜研化學製）等聚曱基丙烯酸甲酯系 樹脂；Κ Μ Ρ - 5 9 0 (信越化學工業公司製）、托斯帕魯1 3 0 (Tospearl 1 3 0 )、托斯帕魯1 4 5、托斯帕魯2 0 0 0 B (以上 均為G E東芝矽利康製）等矽酮粉體。上述複合矽酮粉體（交 聯型矽酮、網狀型矽酮嵌段共聚合物）可特別列舉如 KSP-100、KSP-101 、KSP-102、KSP-1 05 (以上均為信越化 學工業公司製）等。 疏水性球狀粉體（a )之含有量，以設定為佔含喷射劑 之總量中之0 · 1〜3 0質量％為佳。尤其自抑制肌膚上之白色 殘留與獲得清爽感觸之觀點而言，粉體（a )之含有量以 0 . 3〜1 0質量％為佳。 聚醚改質矽酮（b )係於側鏈或末端處具有聚氧化烯基 之有機聚矽氧烷化合物，為糊狀且高黏度的液體。其具有 抑制疏水性球狀粉體（a )及制汗鹽及/或殺菌劑（c )所造 成之白色殘留的效果。聚醚改質矽酮可列舉如聚氧乙烯· 曱基聚矽氧烷共聚合體、聚（氧乙烯•氧丙烯）曱基聚矽 9 312/發明說明書(補件)/93-05/93106656 200423965 氧烷共聚合體。該等聚醚改質矽酮為垂懸型（P e n d e n t )改 質、單末端型改質、兩末端型改質均可。 聚醚改質矽酮（b )為可買到之市售品，可列舉如：矽 利康 KF-6011 、 KF-6013、 KF-6015、 KF-6017、 KF-6019、 K F - 6 0 2 8 (以上均為信越化學工業公司製）、S Η - 3 7 7 1、 5 Η - 3 7 7 5 (東麗·道康寧·矽利康製）等聚氧乙烯·甲基聚 矽氧烷共聚合體；K F - 6 0 1 2(信越化學工業公司製）等聚（氧 乙烯•氧丙烯）曱基聚矽氧烷共聚合體。 上述聚醚改質矽酮（b )中，H L Β為6以下、且於2 5 °C 下之黏度為5 0 0 m m2 / s以上者，具有適當的界面活性能，於 將疏水性球狀粉體（a )再分散於除臭劑喷霧組成物中時， 可產生均勻的分散狀態，並可使該良好的分散狀態長時間 持續。 藉由使用HLB6以下、較佳為HLB5以下之聚醚改質矽 酮，於將疏水性球狀粉體（a )再分散時，不會使其發生凝 集現象，可使其於組成物中均勻地分散。其中，HLB係指 親水親油平衡（H y d r 〇 p h i 1 e - L i ρ 〇 p h i 1 e - B a 1 a n c e )，係為由 葛利芬（G r i f f i n )公式算出之值： HLB - 20.- ~ ~~~聚醚改質矽酮之分子量~~ 又，藉由使用2 5 °C下黏度為5 0 0 in in2 / s以上、較佳為 6 0 0〜2 0 0 0 m m2 / s之聚醚改質矽酮，可使疏水性球狀粉體（a ) 之分散持續時間增長。其中，2 5 °C下之黏度可根據日本化 妝品原料基準第二版第1法（U型（U b b e 1 〇 h d e )毛細管黏 10 3丨2/發明說明書(補件)/93-05/93106656 200423965 度計）之方法測定。 HLB6以下、且於25°C下黏度為5 0 0 mm2/s以上之聚醚改 質矽酮，於上述市售品中，可列舉矽利康K F - 6 0 1 7 ( H L B 4 . 5， 黏度600mm2/s，信越化學工業公司製）、KF-6019(HLB4.5, 黏度8 5 0 mm2/s，信越化學工業公司製）、KF- 6 0 2 8 ( HLB4， 黏度900mm2/s，信越化學工業公司製）、SH-3775(HLB5, 黏度1 6 0 0 m m2 / s，東麗·道康寧·矽利康公司製）等。 為了使疏水性球狀粉體（a )之分散性有效地提升，並 發揮良好的白色殘留現象之抑制效果，聚醚改質矽酮（b ) 的使用量必須在某個程度以上，但為了使塗佈除臭劑喷霧 組成物時之肌膚感觸良好，以適量為宜。自此觀點而言， 除臭劑喷霧組成物中之聚醚改質矽酮（b )之含有量，包括 使用HLB6以下、且25°C下之黏度在500mm2/s以上者之情 況，於包含喷射劑之總量中為0 . 0 0 1〜5質量％為佳，較佳為 0 . 0 0 1〜3質量％，更佳為0 . (Π〜3質量％，特佳為0 . (Π〜1質 量％。 又，除臭劑噴霧組成物中之疏水性球狀粉體（a )與聚 醚改質矽酮（b )之質量比（（a ) : ( b))，自粉體成份之分 散性及塗佈除臭劑噴霧組成劑時之肌膚感觸之觀點而言， 以1 0 0 0 : 1〜5 : 1為佳，又以3 0 0 : 1〜1 0 : 1較佳，更以2 0 0 : 1〜1 0 : 1特佳。 於本發明之除臭劑噴霧組成物中，進一步使含有制汗鹽 及/或殺菌劑（c )。作為制汗鹽及/或殺菌劑（c )，可列舉 習知之一般使用於除臭劑者。例如，制汗鹽可列舉氯化經 11 312/發明說明書(補件)/93-05/93106656 200423965 鋁、鋁鍅複合鹽、氯化鋁等。又，殺菌劑可列舉如玉潔新、 異丙基甲基酚、苯曱酸、氣化苯二甲羥錢（b e n z a 1 k ο n i u m chloride)、三氯N -叛基苯胺等。亦可組合使用制汗鹽與 殺菌劑。本發明之除臭劑喷霧組成物中，於包含噴射劑之 總量中，含有0 . 0 1〜5質量％之制汗鹽、0 · 0 0 5〜0 · 1質量％之 殺菌劑為佳。 又，本發明之除臭劑噴霧組成物亦可含有成份（b )以 外的油劑（d )。尤以2 5 °C下為液狀之油劑為佳，藉此可獲 得更進一步抑制粉體成份於肌膚上之白色殘留的效果。 2 5 °C下為液狀之油劑（d )可列舉如：2 5 °C下黏度為 1 0 0 0 in m2 / s以下之二曱基矽酮、十曱基環戊矽氧烷、曱基 苯基矽酮等之矽酮油（但不包含與聚醚改質矽酮（b )相同之 成份）；鯊烷、流動石蠟等之烴類；甘油、1，3 - 丁二醇、1，4 -丁二醇等之多元醇類；分枝脂肪酸類；異丙醇、2 -乙基丁 醇等之分枝醇類；肉苴蔻酸肉莖蔻酯、肉菫蔻酸異丙酯、 棕櫚酸異丙酯、二葵酸新戊乙二酯等之脂肪酸酯類；肉莖 蔻酸異硬脂酸甘油等之甘油二酸酯；異硬脂酸甘油三酸 酯、椰子油脂肪酸甘油三酸酯等之甘油三酸酯等。 其中，自抑制白色殘留之效果較大之觀點而言，上述矽 酮油以及肉莖蔻酸異丙酯、棕櫚酸異丙酯、二葵酸新戊乙 二酯等之分枝酯油較佳，尤以組合使用矽酮油及分枝酯油 為佳。於組合使用矽酮油及分枝酯油之情況，其比例（矽 酮油：分枝酯油）係以質量比為5 : 1〜1 : 1 0為佳，又以1 : 1〜1 : 5特佳，可得到較好的白色殘留抑制效果。 12 312/發明說明書(補件)/93-05/93106656 200423965 該等油劑之含有量，係於包含噴射劑之總量中佔0 · 1〜2 0 質量％為佳，又以佔0 . 5〜1 5質量％更佳。藉由使其含有量在 0 . 1質量％以上，可發揮充分的白色殘留抑制效果，而藉由 使其含有量在2 0質量％以下，則可得到良好的肌膚感觸。 本發明之除臭劑噴霧組成物之噴射劑並無特別的限 定，可列舉如··佛利昂（F 1 ο η ) 1 3 4 a、佛利昂1 1 3等佛利 昂氣體；丙烷、異丁烷、異戊烷等烴系氣體；甲醚等液化 氣體；二氧化碳氣體及氮氣等。噴射劑之含有量，以於包 含伸噴射劑之總量中佔6 0〜9 9質量％左右為佳。 此外，本發明之除臭劑噴霧組成物可視需要，在不損及 本發明之效果的範圍内適當配合顏料、色素、香料、清涼 劑、消炎劑、濕潤劑、抗氧化劑、安定劑等。 本發明之除臭劑噴霧組成物可以一般方法製造，例如可 將喷射劑以外的成分均句混合，將所得之混合物裝入氣膠 容器中後，再填充噴射劑而製造。 如上所述，本發明之除臭劑噴霧組成物係藉由組合使用 疏水性球狀粉體（a )及聚醚改質矽酮（b )，使於搖晃喷霧 容器等將疏水性球狀粉體（a )於組成物中再分散時，分散 性優異且分散時間長。因此，可將疏水性球狀粉體（a )自 喷霧容器均勻地喷射出，而均勻地塗佈於肌膚上。故，由 於疏水性球狀粉體（a )之作用，本發明之組成物對於汗水 的黏膩感之抑制效果非常高，於抑制剛噴射後的黏腻感之 效果、持續清爽感良好的肌膚感觸之效果、以及抑制肌膚 上的白色殘留之效果均優異。 13 312/發明說明書(補件)/93-05/93106656 200423965 又，若提升疏水性球狀粉體（a )於喷霧容器内之再分 散性，則組成物中疏水性球狀粉體（a )以外的成份之再分 散性亦得以一併提高，因此，除臭劑組成物中之除臭成份 亦與疏水性球狀粉體（a )可一起自噴霧容器均勻地喷射 出。而可均勻地塗佈於肌膚上。因此，不僅具有抑制汗水 的黏腻感之效果，除臭效果亦提高。 此外，由於粉體之再分散性優異、分散時間亦長，將粉 體再分散之操作方式容易，僅要於最初的噴射前輕輕搖晃 容器即可均勻地再分散，且不需在連續喷射除臭劑喷霧組 成物之中途，再次重複搖晃等之再分散動作。 【實施方式】 (實施例） 以下，藉由實施例進一步說明本發明，並明確列示本發 明之實施態樣。 〈實施例A系列〉 (實施例A 1〜A 7及比較例A 1〜A 5 ) (製法） 將表1所示之LPG以外的成分均勻混合，將所得之混合 物裝入氣膠用耐壓玻璃容器後，填充LPG，以調製表1所 示組成之除臭劑噴霧組成物。又，組成係以質量％表示。 (評估方法） 於1 0名專門評估人員之上臂部均勻地適量塗佈噴霧組 成物，針對黏腻感之抑制、白色殘留之抑希彳、清爽感之持 續，根據以下基準進行官能評估。合計各評估人員之評價 14 3丨2/發明說明書(補件)/93-05/93106656 200423965 點數，並以平均評價點數予以分級。評估結果與組成併示 於表1。 〈評估基準〉 (1 )黏腻感之抑制（評估剛塗佈後之黏腻感的有無） 5 :完全不黏腻 4 :不黏腻 3 :普通 2 :稍微黏腻 1 :黏腻 (2 )清爽感之持績（評估塗佈1小時後之清爽感觸） 5 :有清爽感 4 :稍有清爽感 3 :普通 2 :不甚清爽 1 :完全不清爽 〈平均評價點數〉 ◎ : 4. 5 〜5· 0 〇：3· 5 〜4. 4 〇△ : 2· 5 〜3. 4 △ : 1 · 5 〜2· 4 X ·· 1 · 0 〜1 · 4 (3 )白色殘留（評估剛塗佈後之外觀變白程度） 4 :未變白 3 :不是變得很白 · 15 312/發明說明書(補件)/93-05/93106656 200423965 2 :稍微變白 1 :變白 〈平均評價點數〉 ◎ : 3. 5 〜4. 0 〇：2. 5 〜3. 4 △ : 1 . 5 〜2 . 4 X : 1. 0〜1· 4 312/發明說明書(補件)/93-05/93106656 200423965 (ί <) 二較例A LO CO 1 1 1 0· 05 1 r__< CZ) CD LO ◦ L〇 r 'Ή 1 1 C75 CD τ 1 X 〇 X 寸 1 1 1 CO 0. 05 τ < cz? LO C3> 1 1 1 寸 ς〇 ο ◦ r—Η 〇△ < 0 CO 1 CO 1 1 LO CZ5 r—< CD LO 〇> 1 1 1 寸 CO CJl ο 〇> r—Η < X JA CN1 1 1 1 CO 1 T—'< CD 〇> LO d? 1 LO r-^ 1 CD 寸· ◦ 〇> τ—Η 〇 X 〇△ 1 Η 1 CO I 1 1 CD CD LO CD 1 LO 1 "H 1 寸· CJi CD CD τ—Η 〇△ 1 X 卜 1 1 1 CO 0. 05 Ί < ◦ CD m CD 1 > 1 < LO o 寸 CD CD CD Ο Τ < ◎ ◎ ◎ CO 1 1 1 CO LO CD i 1 CD LO cz? 1 1 LO 呀 CD C7D CD CD ◎ 〇 ◎ LO 1 1 1 CO 0. 05 1 1 o LO CD 1 LO 1 寸 寸· ◦ τ—Η ◎ 〇 ◎ 呀 1 1 CO 1 LO CD 1 i CD LO 〇> 1 ，― LO ◦ 寸 ο CD r-H ◎ ◎ 〇 母Is CO 1 1 CO 1 LO CD 1—H CD LO CD 1 LO r—< 1 寸 CD 寸 〇> CZ) ◎ 〇 〇 οα 1 CO 1 1 LO 〇) 1 1 CD LO CD 1 LO r—1 1 寸 CH) 寸· CTD ο» !" < 〇 〇 γ··Η 1 CO 1 1 | 0· 05 I t—H o LO CD LO 1 1 ", 1 1 寸 CD 寸· cn> ◦ CD r"''< 〇△ 〇 〇△ 成分（質量« 滑石 聚苯乙烯樹脂*1 曱基矽氧烷網狀聚合體*2 交聯型矽酮·網狀型矽酮嵌段共聚合 體*3 聚氧乙烯·曱基聚矽氧烷共聚合體*4 異丙基甲基酚 氣化羥鋁*5 二甲基矽酮*6 棕櫚酸異丙酯 甲基苯基矽酮*7 LPG 合計 黏腻感 白色殘留 清爽感之持續 1 mi οα CQ LO CO 卜 oo at> ο V < r—Η cd 〇3 X) 〇 評估 ΐ 9关 LO关 寸关 ε关 00* ί r-1 t§<<_^^·蛛姆挪· i t 9LOLO-HS w<<#T^^^f了 330196-¾ im<<SI3H3HMsH3vg (s/smoLOTLO·寸 SH) t§<<#H^^^fT 9109-¾w<<麵 H^qY^fTLOoTds}!w<<f T^qf 潑 f了 osds 輕 τ^^^ϊτ dsoooooajsd 岂 Μ) “ψ^ 9S901 e6/s-e6/(涂3i)»rs_^^/n e 200423965 (實施例A 1〜A 7及比較例A 1〜A 5之結果） 經由該等結果可知，調配有疏水性球狀粉體（a )、聚醚 改質矽酮（b )、制汗鹽及/或殺菌劑（c )、以及於2 5 °C下 為液狀之油劑（d )(但聚醚改質矽酮除外）之本發明的除 臭劑噴霧組成物，於抑制白色殘留之效果、肌膚感觸及其 持續性均優。使用分枝酯油（棕櫚酸異丙酯）及甲基苯基 矽酮之組合作為油劑之實施例A 4，相較於僅使用棕櫚酸異 丙酯的實施例A 3，其白色殘留抑制效果提升，而相較於實 施例A 7與實施例A 6，亦可發現同樣的改善情況。又，使 用交聯型矽酮·網狀型矽酮嵌段共聚合體作為疏水性球狀 粉體之實施例A 5，相較於實施例A 2，其清爽感之持續性獲 得提升。同樣的改善情況於實施例A 7及實施例A 4亦可發 現。 另一方面，含有親水性粉體滑石而未含有疏水性球狀粉 體之比較例A 5，變成特別具黏膩感者。又，未含有聚醚改 質矽酮之比較例A 1及A 2，相較於實施例A 2及A 5，該等不 僅白色殘留現象顯著增加，且於清爽感等肌膚感觸亦不 佳，而使用交聯型矽酮·網狀型矽酮嵌段共聚合體作為疏 水性球狀粉體之情況（比較例A 2 )，甚至無法達到最高評 價。將含有疏水性球狀粉體但未含2 5 °C下為液狀的油劑之 比較例A 3及A 4與實施·例A 3及A 4比較，亦可發現同樣的 差別。 〈實施例B系列〉 (實施例B 1〜B 4及比較例B 1〜B 2 ) 18 312/發明說明書(補件)/93-05/93106656 200423965 (製法） 將表2所示之LPG以外的成分均勻混合，將所得之混合 物裝入氣膠用耐壓玻璃容器後，填充LPG，以調製表2所 示組成之除臭劑噴霧組成物。又，組成係以質量％表示。 (評估） 針對所得之除臭劑噴霧組成物之分散性、除臭效果、以 及抑制汗水的黏腻感之效果，以下述方法進行評估。評估 結果與組成併示於表2。 (1 )分散性 將除臭劑喷霧組成物填充於氣膠用耐壓玻璃容器中，予 以靜置並透過玻璃容器壁觀察内容物，待確認粉體已沉降 後，輕輕搖晃容器使粉體再分散，之後再次靜置，測定粉 體之分散時間。此處，分散時間係指輕輕搖晃容器後，自 靜置開始至2 ni m以上之分層形成為止的時間。 〈判定基準〉 〇：分散時間為1 5秒以上 △:分散時間未滿1 5秒 X :未再分散，保持凝集之狀態 (2 )除臭效果、汗水的黏腻感之抑制 將製得之除臭劑喷霧劑輕輕搖晃後，取0 . 5 g噴霧於1 0 名具有強烈狐臭問題之受驗者的腋下，經8小時後，針對 除臭效果及汗水的黏腻感之抑制，根據以下基準而進行評 估。合計各評價點數，並以平均評價點數予以分級。 〈評估基準〉 19 312/發明說明書(補件)/93-05/93106656 200423965 除臭效果（評估噴霧8小時後之除臭效果） 4 :防臭效果非常高 3 :防臭效果高 2 :防臭效果稍低 1 :防臭效果低 汗水的黏腻感之抑制（評估噴霧8小時後之黏膩感抑制效 果） 4 :極佳 3 :佳 2 :稍差 1 :差 〈平均評價點數〉 ◎ : 3. 5 〜4. 0 〇：2. 5 〜3· 4 △ : 1 · 5 〜2· 4 X ： 1.0-1.4 20 312/發明說明書(補件)/93-05/93106656 200423965 (表2) 實施例B 比較例B 1 2 3 4 1 2 a 尼龍粉末*1 3 — 3 — 3 — 交聯型矽酮·網狀型矽酮嵌段共聚體*2 — 3 — 3 — 3 b 聚氧乙烯·曱基聚矽氧烷共聚合體1 (聚醚改質矽酮1) *3 0. 1 0. 1 — — — 一 聚氧乙烯·曱基聚矽氧烷共聚合物2 (聚醚改質矽酮2) *4 聚氧乙烯·曱基聚矽氧烷共聚合體3 (聚醚改質矽酮3) *5 — — 0· 1 0. 1 — — c 氣化羥鋁*6 2 2 2 2 2 2 d 棕櫚酸異丙酯 2 2 2 2 2 2 十甲基環戊矽氧烷*7 10 10 10 10 10 10 LPG 82.9 82. 9 82. 9 82.9 83 83 合計 100.0 100.0 100.0 100.0 100.0 100.0 評 估 分散性 〇 〇 Δ Δ Δ Δ 除臭效果 〇 ◎ Δ 〇 Δ Δ 汗水的黏腻感之抑制 〇 ◎ 〇 〇 Δ △ *1 :尼龍粉末SP-500，東麗 *2 : KSP-105，信越化學工業公司 *3 : KF-6019，信越化學工業公司（HLB 4. 5，850_2/s) *4 : KF-6013，信越化學工業公司（HLB 10，400_2/s) * 5 : KF-6016，信越化學工業公司（HLB 4. 5，150imi2/s) 氺 6 : REACH 501，REHEIS 公司 *7 : SH-245，東麗·道康寧·矽利康公司 21 312/發明說明書(補件)/93-05/93106656 200423965 (實施例B 1〜B 4及比較例B 1〜B 2之結果） 由該等結果可知，當本發明之除臭劑喷霧組成物中含有 2 5 °C下黏度為5 0 0 m m2 / s以上之聚醚改質矽酮作為聚醚改 質矽酮（b )時，疏水性球狀粉體之分散性、除臭效果、汗 水的黏膩感之抑制效果均優。特別是使用於矽酮橡膠粉體 之表面被覆有矽酮樹脂之複合矽酮粉體（交聯型矽酮·網 狀型矽酮嵌段共聚合體）作為疏水性球狀粉體（a )之實施 例B 2，相較於使用尼龍粉末之實施例B 1，其除臭效果及汗 冰的黏腻感之抑制效果較佳。 含有於2 5 °C下之黏度值未滿5 0 0 ni m 2 / s之聚醚改質矽酮 3 ( H L B 4 . 5，黏度1 5 0 m m 2 / s )的實施例Β 3，其雖可抑制因 汗水所造成之黏腻感，但分散性及除臭效果均較不充足。 含有與實施例B3相同之聚醚改質矽酮，並含有上述矽 酮粉體（交聯型矽酮·網狀型矽酮嵌段共聚合體）作為疏 水性球狀粉體（a )之實施例B 4，相較於實施例B 3，其除 臭效果較佳。 另一方面，未含有聚醚改質矽酮之比較例B 1及比較例 B 2，不論疏水性球狀粉體（a )之種類為何，分散性均不充 足，而於除臭效果及汗水的黏腻感之抑制效果方面，亦較 實施例差。 (實施例B 5 ) 以下列配方（質量％ )製造粉末喷霧組成物。 尼龍粉末（Nylon Powder SP-500，東麗） 4·00 異丙基曱基酚 0.002 22 312/發明說明書(補件)/93-05/93106656 200423965 肉莖蔻酸異丙酯 1.50 聚氧乙烯•甲基聚矽氧烷共聚合體 〇.〇3 (S Η - 3 7 7 5，東麗·道康寧·矽利康公司，H L B 5，1 6 0 0 m丨]12 / s ) 香料 0.20 乙醇 4.268 LPG 90.00 (實施例B 6 ) 以下列配方（質量％ )製造粉末噴霧組成物。 交聯型矽酮·網狀型矽酮嵌段共聚合體 2.00 (KSP-105，信越化學工業公司） 氣化羥鋁 2.00 (洛克龍P，Hoechst AG公司） 聚氧乙烯·曱基聚矽氧烷共聚合體 0.05 (KF-6017，信越化學工業公司，HLB4.5， 600mm2/s) 異硬酯醇 0.50 香料 0.10 聚氧乙烯硬化蓖麻油 0.15 十曱基環戊矽氧烷 3.20 (SH-245，東麗·道康寧·矽利康公司） LPG 92.00 (實施例B 7 ) 以下列配方（質量％ )製造粉末噴霧組成物。 交聯型矽酮·網狀型矽酮嵌段共聚合體 2.00 (K S P - 1 0 0 ’信越化學工業公司） 23 312/發明說明書(補件)/93-05/93106656 200423965 氣化氫鋁 2.00 (REACH 101， REHEIS公司） 聚氧乙烯·曱基聚矽氧烷共聚合體 0.05 (S Η - 3 7 7 5，東麗·道康寧·矽利康公司，H L B 5，1 6 0 0 in m2 / s ) 肉菫蔻酸異丙酯 0.50 二甲基石夕S同（1 0 m m2 / s ) 0.10 香料 0.15 十甲基環戊矽氧烷 3.20 (S Η - 2 4 5，東麗·道康寧·矽利康公司） LPG 92.00 24 312/發明說明書(補件)/93-05/93106656200423965 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a deodorant spray composition having excellent skin feeling. [Prior art] As a deodorant product for preventing the sticky feeling or odor caused by sweat, powder sprays (ρ 〇wderspray) mixed with powder for the purpose of eliminating the sticky feeling of sweat are being widely used. use. Generally, powder sprays containing powders are powders mixed with other ingredients, and the dispersed components are filled in the spray container together with the propellant. If the spray container is left standing, the powder will settle on the bottom of the container, so the spray container must be shaken before use to re-disperse the powder. When the powder spray is used in a state where the dispersibility of the powder is not good, there is a problem that the components cannot be sprayed uniformly, so that the deodorizing effect is insufficient. In addition, as the powder is not sprayed uniformly, the powder may agglomerate and leave white (white residue) on the skin. In other words, it is important to spray the powder mist composition before the powder is sufficiently redispersed and the redispersed powder is allowed to settle again. Especially when the powder is an organic powder, the time during which the redispersed powder can maintain a good dispersion state tends to be shortened. In order to improve the dispersibility of the powder in the powder spray composition, various methods have been reviewed. For example, in Japanese Patent Laid-Open Publication No. 3-1 5 7 3 2 7, a powder aerosol (air-s ο 1) composition is disclosed, which is characterized by containing: talc, 5 312 / Invention Specification ( (Supplement) / 93-05 / 93106656 200423965 Hydrophilic inorganic powders such as silicic anhydride, kaolin, aluminum hydroxide, etc .; propellant containing at least one of liquefied petroleum gas and methyl ether; non-ionic surfactant and silicone At least one of the oils; and ethanol. However, the dispersibility of the powder in the powder aerosol composition is insufficient. In addition, although the powder aerosol composition can suppress the whitening state during spraying, it has a strong greasy feeling and cannot make the skin feel refreshing and excellent in powder. Japanese Patent Laid-Open No. 6-4 8 9 1 9 describes a powder-containing aerosol composition, which is characterized by containing liquefied petroleum gas and inorganic powder, and a sorbitan fatty acid ester is formulated in a specific amount. And / or polyoxyalkylene alkyl ether. However, the dispersibility of the powder-containing aerosol composition in the powder is still not sufficient, and the dispersibility of the organic powder is not considered. Japanese Patent Application Laid-Open No. 5-2 2 9 9 2 5 describes a liquid sweat-producing composition in which a sweat-producing substance such as hydroxyaluminum chloride and the like are modified with alcohols and polyethers. ketone. This sweat-producing composition uses polyether modified silicone and alcohols to prevent the powder from crystallizing in the composition and suppress the white residue of sweat-producing salts. However, when a powder other than a sweat-controlling agent is blended in the sweat-making composition to improve skin feeling such as refreshing feeling, a sufficient effect of suppressing white residue cannot be obtained. Japanese Patent Laid-Open No. 8-1 2 5 4 5 describes a sweat-making and deodorizing agent, which contains a proud agent such as a gasification meridian (a 1 uminu ni hydr ο X ych 1 〇ride). , Yujiexin (tric 1 osan) and other bacteriostatic or bactericidal agents, and contains specific spherical silicone rubber powder and liquid oily ingredients. As the oily component that can be used for adjustment, solid or liquid silicone oil containing polyoxyalkylene modified polysiloxane is described. However, in this bulletin, only the silicon 6 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 is used to improve the feel of the ketone rubber powder, and the dispersibility of the spherical silicone powder is not mentioned at all. Lifting, suppression of white residue is not sufficient. In Japanese Patent Laid-Open No. 1 1-3 3 5 2 5 4 there is described an aerosol composition which is composed of inorganic powders such as vaporized hydroxyaluminum, and contains heterogeneous organopolysiloxanes. Compound powder, and liquid oils such as isopropyl myristate. However, this aerosol composition is also the same. Although it has a refreshing feeling of use, the suppression of white residue is not sufficient. [Summary of the Invention] The present invention is to provide a deodorant spray composition with excellent skin feel by improving the dispersibility of powder components. The inventors have found that a deodorant spray composition containing a hydrophobic spherical powder (a) and a polyether modified silicone (b) can improve the dispersibility and redispersibility of the hydrophobic spherical powder (a) Sex, you can find the desired effect. That is, the present invention contains: (a) hydrophobic spherical powder; (b) polyether modified silicone; (c) sweat salts and / or fungicides; (d) at 25 ° C. Liquid oils (with the exception of component (b)); and (e) spray deodorant spray compositions. (Detailed description of the invention) Hydrophobic spherical powder (a) is a slightly spherical powder with surface characteristics that are at least hydrophobic on the surface. It is suitable for skin and has a sticky feeling caused by sweat to improve the skin. Feel the refreshing effect. In contrast to talc and the like, which are conventionally known as hydrophilic powders having the effect of enhancing skin feel, hydrophobic spherical powders (a) are spherical powders having high hydrophobicity. The shape of the hydrophobic spherical powder (a) does not need to be strictly true spherical, for example, the section is oval 7 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 It is also possible, but true spherical The shape is better. The average particle diameter of the hydrophobic spherical powder (a) is preferably from 0 · 1 to 3 0 // m, and more preferably from 1 to 1 0 " m. By setting it to above 0.1 // m, a better smooth feel can be obtained, and by making it below 3 0 " m, a good skin feel without roughness can be obtained. The hydrophobicity of the hydrophobic spherical powder (a) is preferably based on a critical surface tension of 50 m N / m or less. When the critical surface tension is below 50 m N / in, the powder is not covered with sweat due to its low hydrophilicity, and it can suppress the stickiness. From the viewpoint of the degree of hydrophobicity and shape of these, the hydrophobic spherical powder (a) of the present invention is superior to the inorganic powder in terms of the organic polymer powder. Specific examples of the hydrophobic spherical powder (a) include a nylon resin, a polystyrene resin, a polyethylene resin, a polymethyl methacrylate resin, a polyurethane resin, and the like. Organic polymer powder such as phenol resin and silicone resin. In particular, silicone resin powders are preferred because of their high water repellency; examples include fluorene-based siloxy network polymers, or composite silicone powders that have free-radical polymerizable groups at the ends of the monomers. Polymer fine particles obtained by dispersing and polymerizing a vinyl monomer in a solvent with a polysiloxane compound as a dispersant (see Japanese Patent Laid-Open No. 2 ◦ 0 2-3 0 8 9 0 9) and the like. Among the compounded silicone powders, the compounded silicone powders (cross-linked silicones, net-like silicone block copolymers) coated with silicone resin on the surface of the silicone rubber powders have a high refreshing feeling. And the effect of continuously suppressing white residue for a long time is particularly good. Such a composite powder is presumed to be able to absorb the oil agent described later inside the powder body and continue to release it on the skin. Therefore, the refreshing feeling can be sustained and the effect of white residues can be suppressed. 8 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 The hydrophobic spherical powder (a) used in the present invention is a commercially available product, and examples are: SP-5 0 0 (East Nylon resin, etc .; Van Paru (Fine Pearl (manufactured by Sumitomo Chemical Industries), The Techpolymer SB (manufactured by Sekisui Chemical Industry), Vanpa Uda SGP (FinePowderSGP, comprehensive research chemical system) Polystyrene resins such as Polystyrene (FL 0-BEADS, manufactured by Sumitomo Refining) and other polyethylene resins; Matsumoto Microspheres-M (MATSU Μ 0 T 0 Microsphere-M? Matsumoto Oils and Pharmaceuticals), The Library Polymarine MB (TECHPOLYMERMB, manufactured by Sekisui Chemical Industrial Co., Ltd.), Vanpa Uda MP (Fine Powder MP, manufactured by Kenken Chemicals), and other polymethyl acrylate resins; KM P-5 9 0 (Made by Shin-Etsu Chemical Industry Co., Ltd.), Tospearl 1 3 0 (Tospearl 1 3 0), Tosparu 1 4 5, Tosparu 2 0 0 0 B (The above are all made by GE Toshiba Silicon) Silicone powder. The above-mentioned composite silicone powder (cross-linked silicone, network-type silicone block copolymer) can be specifically exemplified as KSP-100, KSP-101, KSP-102, KSP-1 05 (the above are all Shin-Etsu Chemical Industrial company)). The content of the hydrophobic spherical powder (a) is preferably set to 0. 1 to 30% by mass based on the total amount of the propellant. In particular, from the viewpoint of suppressing white residue on the skin and obtaining a refreshing feeling, the content of the powder (a) is preferably 0.3 to 10% by mass. The polyether modified silicone (b) is an organic polysiloxane compound having a polyoxyalkylene group at a side chain or at an end, and is a paste-like and highly viscous liquid. It has the effect of suppressing the white residue caused by the hydrophobic spherical powder (a) and the sweat-making salt and / or bactericide (c). Examples of the polyether modified silicone include polyoxyethylene · fluorenyl polysiloxane copolymer, poly (oxyethylene • oxypropylene) fluorinated polysilicon 9 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 Oxane copolymer. These polyether modified silicones are pendant (Pendent) modified, single-ended modified, or both-ended modified. Polyether modified silicone (b) is a commercially available product, and examples include: Silicone KF-6011, KF-6013, KF-6015, KF-6017, KF-6019, KF-6 0 2 8 (The above are manufactured by Shin-Etsu Chemical Industry Co., Ltd.), S Η-3 7 7 1, 5, Η-3 7 7 5 (manufactured by Toray Dow Corning, Silicon), and other polyoxyethylene · methylpolysiloxane copolymers; KF-6 0 1 2 (manufactured by Shin-Etsu Chemical Co., Ltd.) and other poly (oxyethylene • oxypropylene) fluorenyl polysiloxane copolymers. In the above polyether modified silicone (b), HL Β is 6 or less, and the viscosity at 25 ° C is 500 m m 2 / s or more, which has proper interfacial activity and is suitable for the hydrophobic ball When the powder (a) is re-dispersed in the deodorant spray composition, a uniform dispersion state can be generated, and the good dispersion state can be maintained for a long time. By using polyether modified silicone with HLB6 or lower, preferably HLB5 or lower, when the hydrophobic spherical powder (a) is re-dispersed, it does not cause agglomeration, and it can be made uniform in the composition.地 scattered. Among them, HLB refers to the hydrophilic-lipophilic balance (Hydr 〇phi 1 e-L i ρ 〇phi 1 e-B a 1 ance), which is a value calculated from the Griffin formula: HLB-20.- ~ ~~~ Polyether modified silicone molecular weight ~~ Also, by using a viscosity at 25 ° C of 5 0 in in 2 / s or more, preferably 6 0 0 to 2 0 0 0 m m 2 / s Polyether modified silicone can increase the dispersion duration of the hydrophobic spherical powder (a). Among them, the viscosity at 25 ° C can be according to the first method of the second edition of the Japanese Cosmetics Raw Material Standard (U-shaped (U bbe 1 〇hde) capillary viscosity 10 3 丨 2 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 degree meter). Polyether modified silicones with a viscosity below HLB6 and a viscosity of 500 mm2 / s or more at 25 ° C. Among the above-mentioned commercially available products, Silicon KF-6 0 1 7 (HLB 4.5, viscosity 600mm2 / s, manufactured by Shin-Etsu Chemical Industry Co., Ltd., KF-6019 (HLB4.5, viscosity 8 50 mm2 / s, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), KF-6 0 2 8 (HLB4, viscosity 900 mm2 / s, Shin-Etsu Chemical Co., Ltd. Industrial company), SH-3775 (HLB5, viscosity 1600 m 2 / s, manufactured by Toray Dow Corning Silicon Silicon Co., Ltd.), etc. In order to effectively improve the dispersibility of the hydrophobic spherical powder (a) and exert a good effect of suppressing the white residual phenomenon, the amount of polyether modified silicone (b) must be used to a certain degree or more, but in order to When applying the deodorant spray composition, the skin feeling is good, and an appropriate amount is suitable. From this point of view, the content of the polyether modified silicone (b) in the deodorant spray composition includes the case where the HLB6 or lower and the viscosity at 25 ° C is 500mm2 / s or more. The total amount containing the propellant is preferably from 0.01 to 5% by mass, more preferably from 0.001 to 3% by mass, and even more preferably from 0. (Π to 3% by mass, particularly preferably 0. (Π ~ 1% by mass. In addition, the mass ratio of the hydrophobic spherical powder (a) and the polyether modified silicone (b) in the deodorant spray composition ((a): (b)), From the viewpoint of the dispersibility of the powder component and the skin feel when applying the deodorant spray composition, it is preferably 1 0 0 0: 1 to 5: 1 and 3 0 0: 1 to 1 0: 1 Preferably, it is particularly preferably 200: 1 to 10: 1. The deodorant spray composition of the present invention further contains a sweat-producing salt and / or a bactericide (c). As a sweat-producing salt and / Or bactericide (c), examples include those commonly used in deodorants. For example, sweat salts can be exemplified by chlorinated warp 11 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 Aluminum, aluminum tin Compound salts, aluminum chloride, etc. Examples of the fungicides include Yujiexin, isopropylmethylphenol, phenylarsinic acid, vaporized xylamine (benza 1 k ο nium chloride), trichloro N-benzylaniline, etc. It is also possible to use a combination of sweat salts and fungicides The deodorant spray composition of the present invention contains 0.01 to 5% by mass of sweat salt and 0. 0 to 5 to 0. 1% by mass of the total amount of the propellant. In addition, the deodorant spray composition of the present invention may also contain an oil agent (d) other than the component (b). Especially, an oil agent in a liquid state at 25 ° C is preferable, thereby obtaining more Further suppresses the effect of white residue on the skin of powder ingredients. Liquid oils (d) at 25 ° C can be exemplified as follows: the viscosity at 25 ° C is less than 1 0 0 0 in m2 / s Silicone oils such as fluorenyl silicone, decadecyl cyclopentasiloxane, fluorenyl phenyl silicone (but do not include the same ingredients as polyether modified silicone (b)); squalane, flowing paraffin, etc. Hydrocarbons; glycerol, 1,3-butanediol, 1,4-butanediol and other polyols; branched fatty acids; isopropanol and 2-ethylbutanol; branched alcohols; meat Myristic acid Fatty acid esters such as isopropyl myristate, isopropyl palmitate, neopentyl diacetate, etc .; diglycerides such as glyceryl isostearate, and glyceryl isostearate Triglycerides, triglycerides, etc. of coconut oil fatty acid triglycerides, etc. Among them, the silicone oil, isopropyl myristate, and palmitate are Branched ester oils such as propyl ester, neopentyl diacetate, and the like are preferred, and a silicone oil and a branched ester oil are preferably used in combination. In the case of using silicone oil and branched ester oil in combination, the ratio (silicone oil: branched ester oil) is preferably in a mass ratio of 5: 1 ~ 1: 1 0, and then 1: 1: 1 ~ 1: 5 is particularly good, can obtain better white residual suppression effect. 12 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 The content of these oil agents is preferably from 0.1 to 20% by mass of the total amount including the propellant, and 0. 5 to 15% by mass are more preferable. By setting the content to 0.1% by mass or more, a sufficient white residual suppression effect can be exhibited, and by setting the content to 20% by mass or less, a good skin feeling can be obtained. The propellant of the deodorant spray composition of the present invention is not particularly limited, and examples thereof include Freon (F 1 ο η) 1 3 4 a, Freon gas such as Freon 1 1 3; propane , Isobutane, isopentane and other hydrocarbon gases; liquefied gases such as methyl ether; carbon dioxide gas and nitrogen. The content of the propellant is preferably about 60 to 99% by mass based on the total amount of the propellant. In addition, the deodorant spray composition of the present invention may be appropriately blended with a pigment, a pigment, a fragrance, a cooling agent, an anti-inflammatory agent, a wetting agent, an antioxidant, a stabilizer, and the like within a range that does not impair the effects of the present invention, if necessary. The deodorant spray composition of the present invention can be produced by a general method. For example, ingredients other than the propellant can be mixed uniformly, and the resulting mixture can be filled into an aerosol container and then filled with the propellant. As described above, the deodorant spray composition of the present invention uses a hydrophobic spherical powder (a) and a polyether modified silicone (b) in combination to make the hydrophobic spherical shape shake in a spray container or the like. When the powder (a) is redispersed in the composition, the dispersibility is excellent and the dispersion time is long. Therefore, the hydrophobic spherical powder (a) can be uniformly sprayed from the spray container, and can be evenly applied to the skin. Therefore, due to the effect of the hydrophobic spherical powder (a), the composition of the present invention has a very high suppression effect on the sticky feeling of sweat, and has the effect of suppressing the sticky feeling immediately after spraying, and has good fresh skin. Both the effect of feeling and the effect of suppressing white residue on the skin are excellent. 13 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 In addition, if the redispersibility of the hydrophobic spherical powder (a) in the spray container is improved, the hydrophobic spherical powder in the composition ( The redispersibility of components other than a) can also be improved together. Therefore, the deodorizing component in the deodorant composition can be uniformly sprayed from the spray container together with the hydrophobic spherical powder (a). It can be evenly spread on the skin. Therefore, not only the effect of suppressing the stickiness of sweat, but also the deodorizing effect is improved. In addition, because the powder has excellent redispersibility and long dispersing time, the operation of redispersing the powder is easy. It can be evenly redispersed by shaking the container gently before the initial spraying, and there is no need to spray continuously During the deodorant spray composition, the redispersing operation such as shaking is repeated again. [Embodiments] (Examples) Hereinafter, the present invention will be further described by way of examples, and the implementation aspects of the present invention will be clearly listed. <Example A series> (Example A 1 to A 7 and Comparative Examples A 1 to A 5) (Manufacturing method) Components other than LPG shown in Table 1 were uniformly mixed, and the obtained mixture was charged into a pressure-resistant aerosol. After the glass container was filled with LPG, a deodorant spray composition having a composition shown in Table 1 was prepared. The composition is expressed by mass%. (Evaluation method) A spray applicator was uniformly coated with an appropriate amount on the arms of 10 specialized evaluators, and the sensory evaluation was performed based on the following criteria for the suppression of stickiness, the suppression of white residue, and the refreshing feeling. The evaluations of each evaluator are totaled 14 3 丨 2 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 points, and the average evaluation points are used for classification. The evaluation results and composition are shown in Table 1. <Evaluation Criteria> (1) Suppression of stickiness (evaluation of the presence of stickiness immediately after coating) 5: Not sticky at all 4: Not sticky 3: Normal 2: Slightly sticky 1: Sticky (2 ) Freshness (evaluation of freshness after 1 hour of application) 5: Refreshing feeling 4: Slightly refreshing feeling 3: Normal 2: Not very refreshing 1: Not refreshing at all <average evaluation points> ◎: 4 5 to 5. 0 〇: 3.5 to 4. 4 〇 △: 2 · 5 to 3.4 △: 1 · 5 to 2 · 4 X ·· 1 · 0 to 1 · 4 (3) White residue ( Assess the degree of whitening of the appearance immediately after coating) 4: Not whitened 3: Not very white · 15 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 2: Slightly whitened 1: Whitened < Average evaluation points> ◎: 3. 5 to 4. 0 〇: 2.5 to 3. 4 △: 1.5 to 2. 4 X: 1. 0 to 1.4 4 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 (ί <) Two comparative examples A LO CO 1 1 1 0 · 05 1 r __ < CZ) CD LO ◦ L〇r 'Ή 1 1 C75 CD τ 1 X 〇X inch 1 1 1 CO 0. 05 τ < cz? LO C3 > 1 1 1 inch ςοο ◦ r—Η 〇 △ < 0 CO 1 CO 1 1 LO CZ5 r— < CD LO 〇 > 1 1 1 inch CO CJl ο 〇 > r—Η < X JA CN1 1 1 1 CO 1 T — '< CD 〇 > LO d? 1 LO r- ^ 1 CD inch · ◦ 〇 > τ--Η 〇X 〇 △ 1 Η 1 CO I 1 1 CD CD LO CD 1 LO 1 " H 1 inch · CJi CD CD τ—Η 〇 △ 1 X 11 1 CO 0. 05 Ί < ◦ CD m CD 1 > 1 < LO o inch CD CD CD Ο Τ < ◎ ◎ ◎ CO 1 1 1 CO LO CD i 1 CD LO cz? 1 1 LO Ye CD C7D CD CD ◎ 〇 ◎ LO 1 1 1 CO 0. 05 1 1 o LO CD 1 LO 1 inch · ◦ τ—Η ◎ 〇 ◎ 1 1 CO 1 LO CD 1 i CD LO 〇 > 1, ― LO ◦ inch ο CD rH ◎ ◎ 〇 Mother Is CO 1 1 CO 1 LO CD 1—H CD LO CD 1 LO r— < 1 inch CD inch 〇 > CZ) ◎ 〇〇οα 1 CO 1 1 LO 〇) 1 1 CD LO CD 1 LO r—1 1 inch CH) inch · CTD ο »! &Quot; < 〇〇γ ·· Η 1 CO 1 1 | 0 · 05 I t—H o LO CD LO 1 1 ", 1 1 inch CD inch · cn > ◦ CD r " '' & lt 〇 △ 〇〇 △ Ingredients (mass «talc polystyrene resin * 1 fluorenylsiloxane network polymer * 2 crosslinked silicone · network type silicone block copolymer * 3 polyoxyethylene · 曱Polysiloxane copolymer * 4 Isopropylmethylphenol vaporized hydroxyaluminum * 5 Dimethylsilicone * 6 Isopropyl palmitate methylphenylsilicone * 7 LPG Total sticky feeling White residual refreshing feeling 1 mi οα CQ LO CO at oo at > ο V < r—Η cd 〇3 X) 〇Evaluate 关 9 levels Gomno it 9LOLO-HS w < &#; T # ^^^ f the 330196-¾ im < < SI3H3HMsH3vg (s / smoLOTLO · inch SH) t§ < <#H ^^^ fT 9109-¾w < < face H ^ qY ^ fTLOoTds}! w < < f T ^ qf osds light τ ^^^ ϊτ dsoooooajsd QM) "ψ ^ 9S901 e6 / s-e6 / (TU 3i)» rs_ ^ ^ / ne 200423965 (Results of Examples A 1 to A 7 and Comparative Examples A 1 to A 5) From these results, it can be seen that a hydrophobic spherical powder (a) and a polyether modified silicone (b) are prepared. , Deodorant spray composition of the present invention, sweat salt and / or fungicide (c), and oil (d) (except polyether modified silicone) which is liquid at 25 ° C, It is effective in suppressing white residue, skin feel and durability. Example A 4 using a combination of a branched ester oil (isopropyl palmitate) and methylphenyl silicone as an oil agent, compared with Example A 3 using only isopropyl palmitate, its white residue was suppressed. The effect is improved. Compared with Example A 7 and Example A 6, the same improvement can be found. In Example A 5 in which a crosslinked silicone / reticulated silicone block copolymer was used as the hydrophobic spherical powder, the refreshing feeling was improved compared to that in Example A 2. The same improvement can be found in Examples A 7 and A 4. On the other hand, Comparative Example A 5 containing hydrophilic powdered talc but not hydrophobic spherical powder became particularly sticky. In addition, in Comparative Examples A 1 and A 2 that did not contain polyether modified silicone, compared with Examples A 2 and A 5, these not only significantly increased the phenomenon of white residue, but also had poor skin feelings such as freshness. On the other hand, in the case of using a crosslinked silicone-reticulated silicone block copolymer as a hydrophobic spherical powder (Comparative Example A 2), the highest evaluation was not achieved. Comparing Comparative Examples A 3 and A 4 containing hydrophobic spherical powders but not containing a liquid oil at 25 ° C with Examples · A 3 and A 4 also revealed the same difference. <Example B Series> (Examples B 1 to B 4 and Comparative Examples B 1 to B 2) 18 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 (Manufacturing method) Except the LPG shown in Table 2 The ingredients were uniformly mixed, and the obtained mixture was charged into a pressure-resistant glass container for aerosol, and then filled with LPG to prepare a deodorant spray composition having a composition shown in Table 2. The composition is expressed by mass%. (Evaluation) The dispersibility of the obtained deodorant spray composition, the deodorizing effect, and the effect of suppressing the sticky feeling of sweat were evaluated by the following methods. The evaluation results and composition are shown in Table 2. (1) Dispersibility Fill the deodorant spray composition in a pressure-resistant glass container for aerosol, let it stand and observe the contents through the glass container wall. After confirming that the powder has settled, shake the container gently to make the powder. The powder was re-dispersed, and then left to stand again, and the dispersion time of the powder was measured. Here, the dispersion time means the time after the container is gently shaken, and the time from the start of standing to the formation of a layer of 2 nm or more. <Judgment criteria> 〇: Dispersion time is 15 seconds or more △: Dispersion time is less than 15 seconds X: Not redispersed and kept in a state of aggregation (2) Deodorizing effect and suppression of sweaty stickiness will be obtained After shaking the deodorant spray lightly, take 0.5 g of the spray to the underarms of 10 subjects with a strong body odor problem, and after 8 hours, suppress the deodorant effect and the sticky feeling of sweat The evaluation is based on the following benchmarks. The evaluation points are totaled and graded by the average evaluation points. <Evaluation Criteria> 19 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 Deodorizing effect (evaluating deodorizing effect after 8 hours of spraying) 4: Very high deodorizing effect 3: High deodorizing effect 2: Slightly deodorizing effect Low 1: Deodorizing effect Low suppression of sticky feeling of sweat (evaluation of sticky feeling suppression effect after 8 hours of spraying) 4: Excellent 3: Good 2: Slightly worse 1: Poor <average evaluation point> ◎: 3. 5 to 4. 0 〇: 2.5 to 3. 4 △: 1.5 to 2. 4 X: 1.0-1.4 20 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 (Table 2) Example B Comparative example B 1 2 3 4 1 2 a Nylon powder * 1 3 — 3 — 3 — Crosslinked silicone · reticulated silicone block copolymer * 2 — 3 — 3 — 3 b Polyoxyethylene · 曱Polysiloxane Modified Polymer 1 (Polyether Modified Silicone 1) * 3 0. 1 0. 1 — — — Monooxyethylene · fluorenyl polysiloxane copolymer 2 (Polyether Modified Silicone) 2) * 4 Polyoxyethylene · fluorenyl polysiloxane copolymer 3 (polyether modified silicone 3) * 5 — — 0 · 1 0. 1 — — c Gasified hydroxyaluminum * 6 2 2 2 2 2 2 d isopropyl palmitate 2 2 2 2 2 2 decamethylcyclopentasilyl Alkane * 7 10 10 10 10 10 10 LPG 82.9 82. 9 82. 9 82.9 83 83 Total 100.0 100.0 100.0 100.0 100.0 100.0 Assess dispersibility 〇〇Δ Δ Δ Δ Deodorizing effect 〇 ◎ Δ △ Δ Sweatiness of sweat Inhibition 〇 ◎ 〇〇Δ △ * 1: Nylon powder SP-500, Toray * 2: KSP-105, Shin-Etsu Chemical Industry Co., Ltd. * 3: KF-6019, Shin-Etsu Chemical Industry Co., Ltd. (HLB 4. 5,850_2 / s ) * 4: KF-6013, Shin-Etsu Chemical Industries (HLB 10, 400_2 / s) * 5: KF-6016, Shin-Etsu Chemical Industries (HLB 4.5, 150imi2 / s) 氺 6: REACH 501, REHEIS Corporation * 7: SH-245, Toray Dow Corning Silicone Company 21 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 (Results of Examples B 1 to B 4 and Comparative Examples B 1 to B 2) These results show that when the deodorant spray composition of the present invention contains polyether-modified silicone having a viscosity of more than 500 m m2 / s at 25 ° C as the polyether-modified silicone (b) At the same time, the dispersibility of the hydrophobic spherical powder, the deodorizing effect, and the effect of suppressing the sticky feeling of sweat are all excellent. In particular, it is used for the compound of the silicone rubber powder coated with silicone resin on the surface (crosslinked silicone · reticulated silicone block copolymer) as the hydrophobic spherical powder (a). Compared with Example B 1 using nylon powder, Example B 2 has better deodorizing effect and suppressing effect of sweaty sticky feeling. Example B 3 containing polyether modified silicone 3 (HLB 4.5, viscosity 150 mm 2 / s) with a viscosity value at less than 500 ni m 2 / s at 25 ° C, which Although the sticky feeling caused by sweat can be suppressed, the dispersibility and deodorizing effect are insufficient. Implementation of a hydrophobic spherical powder (a) containing the same polyether modified silicone as in Example B3 and containing the above-mentioned silicone powder (crosslinked silicone · reticulated silicone block copolymer) Compared with Example B 3, Example B 4 has a better deodorizing effect. On the other hand, in Comparative Examples B 1 and B 2 which do not contain polyether modified silicone, regardless of the type of the hydrophobic spherical powder (a), the dispersibility is insufficient, and the deodorizing effect and sweat are not sufficient. The effect of suppressing the sticky feeling is also inferior to the examples. (Example B 5) A powder spray composition was produced with the following formulation (% by mass). Nylon Powder SP-500, Toray 4.00 Isopropylpyrrolol 0.002 22 312 / Invention Note (Supplement) / 93-05 / 93106656 200423965 Isopropyl Myristate 1.50 Polyoxyethylene • Methylpolysiloxane copolymer 0.03 (S Η-3 7 75, Toray Dow Corning Silicone Company, HLB 5, 16 0 0 m)] 12 / s) perfume 0.20 ethanol 4.268 LPG 90.00 (Example B 6) A powder spray composition was produced with the following formulation (mass%). Crosslinked silicone / reticulated silicone block copolymer 2.00 (KSP-105, Shin-Etsu Chemical Co., Ltd.) Gasified hydroxyaluminum 2.00 (Rockron P, Hoechst AG) Polyoxyethylene / fluorenyl polysiloxane Copolymer 0.05 (KF-6017, Shin-Etsu Chemical Industry Co., Ltd., HLB4.5, 600mm2 / s) Isostearyl alcohol 0.50 Fragrance 0.10 Polyoxyethylene hardened castor oil 0.15 Decadecylcyclopentasiloxane 3.20 (SH-245, East Rei Dow Corning Silicon Silicone Co., Ltd.) LPG 92.00 (Example B 7) A powder spray composition was produced with the following formulation (% by mass). Crosslinked silicone / reticulated silicone block copolymer 2.00 (KSP-1 0 0 'Shin-Etsu Chemical Industry Co., Ltd.') 23 312 / Invention Specification (Supplement) / 93-05 / 93106656 200423965 Aluminum Hydrogenated Gas 2.00 ( REACH 101, REHEIS) Polyoxyethylene · fluorenyl polysiloxane copolymer 0.05 (S Η-3 7 7 5, Toray Dow Corning · Silicone, HLB 5, 16 0 0 in m2 / s) Meat Isopropyl myristate 0.50 Dimethyl sulphate S (1 0 m m2 / s) 0.10 Fragrance 0.15 Decamethylcyclopentasiloxane 3.20 (S Η-2 4 5 by Toray Dow Corning Silicone Company ) LPG 92.00 24 312 / Invention Specification (Supplement) / 93-05 / 93106656