TW419484B - Amphoteric porous particulate comprising a basic polysaccharide and a polymer of an organic acid or a salt thereof, process for producing the same, deodorant composition of a chitosan particulate and a deodorant composition of a polysiloxane - Google Patents

Abstract

An amphoteric porous particulate comprising a basic polysaccharide and a polymer of an organic acid containing a reactive vinyl group or a salt thereof and having an average particle size of 50 mu m or less, which is capable of adsorbing a large amount of an acid or a base that is stronger than the acid or basic groups thereof and which is useful as a deodorant, a cosmetic or the like. The amphoteric porous particulate is obtained by emulsifying or suspending an aqueous solution containing a basic polysaccharide and an organic acid having a reactive vinyl group in a hydrophobic solvent and thereafter effecting polymerization thereof. A deodorant comprising a chitosan particulate having an average particle size of 0.01 to 50 mu m as a deodorant. A chitosan particulate having an available amino group content of 1.0 x 10<-7> to 1.0 x 10<-2> mol/g and a specific surface area of 10 to 300 m<2>/g is particularly useful. A polysiloxane having long-chain alky1 groups and a melting point of 20 DEG C or above is useful as an oil component of a deodorant.

Description

經濟部中央標準局負工消費合作社印製 Α7 Β7 五、發明説明（1 ) 〔產業上之利用領域] 本發明係有關一種可用於皮庙化粧品（制汗劑、除臭劑 、潤虜劑、保濕劑）、毛髮化粧品、醫藥品、纖維處理劑 '紙加工劑、水泥添加劑、被覆材料、殺菌/淨菌劑、農 業等之多孔性微粒子D 〔晋知之技術〕 一般，以乳化或懸浮法等所得到之陰雛子/陽離子的兩 性微粒子像可依如下方法得到：主要具有胺基之單體與具 有酸基之單體進行共聚合；或，彤成陰離子或陽離子性粒 子之後，藉修飾反應等使反應基之一部分轉移至陽離子基 或陰離子基上；或藉複合使陽離子性或陰離子性之物質混 合在一起。 例如 &gt; 使兩性微粒子生成之方法有：藉由含有胺基的軍 體與（甲基）丙烯酸之乳化共聚合的方法；使笨乙烯/丙 烯醯胺共聚合體所構成之微粒子進行霍夫曼反應的方法〔 J. App!· Polya. Sci.， 26， 2015(1981)]、藉由從甲基 丙烯酸/丙烯醯胺/ p-硝基苯基丙烯酸酯/亞甲基雙丙稀 醯胺之沈澱聚合乙二胺之後反應的方法〔有關微粒子、分 散糸之特別討論會演講要旨集，P. 23, (1 993)]等。但， K此等方法無法得到多孔性之微粒子，每一與強酸/強驗 反應之粒子的鹼/酸基之量非常少。 又*蓮用天然材料之微粒子的製造法有：K具有1趿胺 基之聚甲殼糖為基劑》而使聚甲殼糖溶解於酸之後，將此 溶液滴入鹼凝固疲中之方法（特開昭59-30722號公報、特 本紙張尺度適用中國國家標準（CNS ) Α4規格（2丨0 X 297公釐） ---- - - BJ^^^1 ^^^1 ^—^^1 ^^^1 ^^^1 一ΰί -I- (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 ί 41 948 4 、 Μ _____ Β7 五、發明説明（2 ) 開昭（52-62827號公報、特開昭62-7040 1號公報、特開昭 62-79201號公報等）；機械性處理聚甲殼糖或聚甲設糖分 散液之方法（特開昭6 3 - 2 0 3 0 2號公報、特開昭S 3 Μ. 7 9 0 2號 公報、特開昭6 3 - 2 0 1 0 1號公報）等。但，任一者之粒子亦 為陽離子性的微粒子，且，只能得到數+ μ m〜數百《 πιΜ 上之粒徑的粒子》又，製作以鹼性多糖為基劑之兩性粒子 的方法，乃於水溶癍中聚甲殼糖存在下使具有反應性乙烯 基之有機酸（共）聚合，以合成一由聚甲殼糖與有機酸聚 合體之錯合所構成的粒狀髏〔高分子論文得* V 〇 1 . 37 , Ν 〇 . 3 , 1 3 5 (1 9 8 0 )〕。但，以此等方法所製成之聚甲殼糖 微粒子，其粒徑分布廣•且只能得到含有5 0 « ε以上之粒 子的非球形粒子*多孔度亦低。 如此，無法得到一為兩性之微粒子且可大量吸附比其酸 基或鹼基邐強之酸或鹼的平均粒徑為50«m Κ下之多孔性 微粒子。 又，若無法得到可大量吸附如此之強酸或鹼的多孔性微 粒子*亦可利用其吸附性而使用於除臭劑等。 腋臭、足臭、汗臭等之體臭為不悅的臭氣，對於染有此 之人而言乃相當煩惱。體臭成分為由發臭之汗、老廢物、 腐敗物質等受皮慮常在菌作用而放出之代謝物質。因此* 所分泌之汗等其本身雖無很強臭味，®因存在皮膚上之菌 的作用產生低级羧酸或揮發性物質，成為不悅臭味物質的 原因。臭味物質已知有醋酸、酪酸、丙酸、異吉草酸等之 低級羧酸類、類画醇類等各種東西。 本紙張尺度適用中國國家標準（CNS ) A4規格（2IOX297公釐） ^^^1 ^^^1 in —II ί - - 1 士衣 ^^1 ^^1 In 11 - 1-— ! - - (請先閲讀背面之注項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 4 194 8 4 A7 ________B7_ 五、發明説明（5 ) 抑制此等體臭之方法可舉例①使用金饜氧化物（氧化詳 、氧化鎂' 氧化钛、氧化鋁等）之方法（特公平1_49372 號公報）、②利用活性碳等多孔性物質之物理吸附的方法 、③使用姐可抑制皮旖常在菌繁殖之抗菌劑（三克勞酸 卜5/夕口寸^)、異丙基甲基酚、殺藻胺、鹽酸氯亥斯丁 (chiorexfdine)葡萄糖酸氯亥斯丁（chlorhexidine.)、齒 卡幫（c h a 1 〇 ca r b a η )等）之方法、④具有很強收斂作用之 藥劑（對酚磺酸鋅、檸檬酸、鋁鹽、锆鹽）之方法⑤以香 料遮蔽等。 但’ Κ使用活性碳等之物理除臭法，其低級脂肪酸類之 吸附容量不充分，且在使用感、捋鑛性之面亦有問題。以 香料遮蔽等之感覺性除臭雖可藉香料使臭味物質的質改變 *但因很臭物質依然殘存在替，故除臭效果有限度。另外 ，使用氧化鋅、氧化鎂、氧化鈦、氧化鋁等之金屬氧化物 之方法，因此等金豳氧化物只在表面與酸反應，故形成在 提高表面積上下各種工夫，但，即使提高表面積，與臭味 物質即酸之反應亦會進行凝膠化，故用Κ長斯性捕捉所產 生之酸則能力匮乏，且無法充分滿足。 至今，有關聚甲殷糖之水溶性酸鹽可發揮防臭防菌效果 之化粧品已揭示於特開昭6 3 - 2 9 0 8 0 8號公報*但可諝幾乎 無防臭效栗。又，有關聚甲殼糖微粒子於特開昭62-190110號、特開平4-235006號公報中雖已記載可調配於粉 底、眼影等化粧品且可提高使用感、完成感、安定性、成 形性，但*對於應用在·除臭劑上則完全未記載。 本紙張尺度適用中國國家標準（CNS ) Α4規格（2Ι0Χ297公釐） I 士民| 1 丁._ I. 7·^-5 (請先閱讀背面之注意事項再填寫本頁) ί A1 948 4 Α7 __Β7_ 五、發明説明（4 ) 除奥劑當以塗布等方法適用於皮逋時，會於皮瓛上形成 多多少少的被膜，此皮庸上所影成之被膜乃擔任防止有效 成分揮發的角色。 但，至今之除臭劑因主成分為水、醇、油等，故昜受汗 或皮脂流動’觸感亦粘滯且易擴散，故無充分之被膜形成 效果，且大多缺乏使除臭劑中之有效成分持績性滞留在皮 庙上的效果。 又，石蠟、凡士林等在常溫下為画體或半固體之化合物 雖可用來作為被膜形成劑，但，此等被瞑形成效果很高， 有效成分之持續性亦高，但，會防礙皮晡呼吸、水蒸氣之 散發，尤其在夏季等之高溫時對皮庸有不良影響。 另外，矽醑油最近被使用來作為一將除臭劑等塗布於皮 旖之油劑。此之主要理由係可提高由分子間力極低所產生 滑溜感的觸感。 又，因砂_油有很高之氣體或水蒸氣的透過性，故認為 . 不會引起上述蠘類所產生之防止皮虜呼吸、水蒸氣揮散的 問題。然而 &gt; 矽嗣油因表面張力很低，易在皮虜上擴散* 不能形成一有效成分具有持續性的膜。矽氧烷之使用則掲 示於待開平5 - 2 5 5 0 5 6號、特開平5 - 2 6 2 6 1 6號中。 經濟部中央棵準局貝工消費合作社印装 I II ------- 装-II - 訂 - (請先閱讀背面之注意事項再填寫本頁) 可於皮虜上形成被膜之基材，在恃開平5 - 1 9 4 1 8 3號、特 開平6 - 9 3 6 7號公報等揭示一使用具有長鏈烷基之聚矽氧烷 而應用於護庙劑上《此等係利用烷基之結晶性►於特開平 5 - 1 9 4 1 8 3號公報中係使用複數之聚矽氧烷的混合物*特開 平6 - 9 3 6 7號公報中係以在兩末端具有烷基之聚砂氧烷單獨 -7- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ί 419 4 8 ,4 Α7 Β7 五、發明説明（5 ) 發揮抑制來自乾燥皮廣之水分的蒸發，但，使用於本發明 之聚砂氧烷則與此作用相反，係充分利用矽酮之高水蒸氣 透過性►具有使有效成分持續性滞留於皮旖上之性質，但 *卻不阻止水分的蒸發。亦即，本發明之除臭劑持別是在 夏季易流汗之時期使用時很有效f若將上述習知公報記載 之聚矽氧烷使用於如此之時期所採用的除臭劑，融點很低 、在體溫附近呈油狀、觸感亦粘滯，高溫時之被膜持續性 很匮乏。 〔本發明之掲示] 因此，本發明之目的在於提供一種為兩性的粒子，且可 大量吸附比其酸性基或鹸性基遢強之酸或鹼，其且平均粒 徑為50vm Μ下之多孔性微粒子。 進而本發明之目的在於提供一種除臭效果高、且速效性 、持績性優異之除臭劑等的化粧品。 因此，本發明之課題在於：當適用於皮朦時*可以不妨 礙皮旖呼吸、水蒸氣的蒸發*且形成一具有使有效成分持 Μ地滯留於皮庙上之性質的被膜，並防止有效成分之飛散 、流失，除臭效果的持續性優異之除臭劑。 經濟部t夬標準局員工消費合作社印农 ^^^1 ^^^^1 nil— 11 t (請先閣讀背面之注意事項再填寫本頁) 於是，本發明人等累積銳意研究，結果*發現一種天然 材料即鹼性多糖為基底之兩性多孔性微粒子，且具有陰離 子及陽離子之兩性，並於非極性及極性溶劑中，每一與強 酸/強鹼反應之粒子的鹼與酸性基之量會比習知微粒子還 壓倒性多的多孔性微粒子；進而亦發現若依此兩性之多孔 性微粒子，酸捕捉性能極高*且可顯現長期之酸物質捕捉 -8- 本紙張尺度適用中國國家揉準（CNS ) Α4規格（210X297公釐） ! 41948 4 at 4 B7 五、發明説明（6 ) 性能不降低的除臭性能；終完成本發明。 本發明係提供一種具有除臭性能之多孔性微粒子、其製 造方法、含有其之化粧品姐成物、含有聚甲殼糖微粒子作 為除臭劑之化粧品組成物，含有聚矽氧矽烷作為油劑之化 粧品、持別是以提供除臭劑姐成物為主。 詳而言之，首先係一種由鹼性多糖、與具有反應性乙烯 基之有機酸或其鹽之聚合體所構成的，且平均粒徑為50ti m以下*並為兩性之多孔性微粒子。較佳係多孔性微粒子 之形狀為球狀•比表面積為10〜300 iu2/s ·鹼性多_為聚 甲殼糖，或具有反應性乙烯基之有機酸或其鹽為甲基丙烯 酸或其鹽。 此微粒子可依如下製造，即使一含有具鹼性多糖與反應 性乙烯基之有機酸的水溶液於疏水性溶劑中乳化或懸浮&gt; 然後*使其聚合。較佳係聚合终了後，於含有鹼之有機溶 劑中滴下或全部添加聚合反應疲*K使多孔性微粒子析出 。每一鹼性多糖之單糖單元亦可使用有機酸0.1〜500倍。 較佳係以含有此多孔性微粒子0 . 1〜7 0重量JK之化粧品 姐成物作為除臭劑。 經濟部中央標準局貝工消費合作社印製 ^^1 n —^^1 ^^1 ^^1 m Λ ^^1 ^^1 HI 1^1 5 ,v* - (請先閱讀背面之注意事項再填寫本頁) 化粧品姐成物可含有化粧品配方所常用之成分，例如、 油劑。 本發明中*亦含有一由鹼性多糖與具有反應性乙烯基之 有機酸的聚合體所構成的*且平均粒徑為以下，並 為兩性之多孔性球狀微粒子。 進而，本發明係提供一 K平均粒徑為0.01〜50wm之聚 -9- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） Γ 419484 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（7 ) 甲殼糖微粒子作為除臭劑，旦提供一含有其之除臭等的化 粧品姐成物、使用其之脫臭方法。 較佳係聚甲殼糖微粒子之比表面積為1〇〜300ni2/&amp; , 聚甲殻糖微粒子之有效胺基量為1.0Χ丨〇_7〜l.〇x moi/s*且聚甲殷糖微粒子之形狀為球狀。 提供一具有融點20 t:以上之長鍵烷基的聚矽氧烷作為化 粧品，尤其是作為除臭劑中之油劑u 亦提供一含有此聚矽氧烷0.01〜99重量SK ，且含有敵性 物質、鹼性多糖、或上述之多孔性微粒子或聚甲殷糖作為 除臭劑之組成物。 此聚矽氧烷宜為融點60〜140 Ό ，且分子兩末端具有長 鍵烷基，或具有長鏈烷基之聚矽氧烷中之長踺烷基部分的 比率合計為0 , 5〜4 0重量％。 以下 &gt; 詳細說明本發明。 本發明之兩性的多孔性微粒子可依如下製得，即，使一 具有驗性多糖與反應性乙烯基之有機酸的水溶液於疏水性 溶劑中乳化或懸浮後*再使其聚合。 本發明中所使用之鹼性多糖為一擁有具1级或2級胺基 之耻哺糖_似醚鏈結合之構造的化合物，洌如相當於聚葡 萄糖胺之聚甲殻糖、其乙醯化物之幾丁質、聚胺基半轧糖 及其乙醯化物等。但，一般，存在於天然之幾丁質因會變 成乙醯胺基之一部份未被乙醢化的胺基，故，本發明所使 甩之幾丁質表示脫乙醯化度為30¾以下者*聚甲殻糖係表 不脫乙醯化度為30%以上者。此等鹼性多糖係亦含有其— -10- 本紙張尺度適用中國國家標準（CNS &gt; A4規格（210X297公爱） - I - — - I— I - -IP - - - I*^-- I - - n - TV (請先閱讀背面之注意事項再填寫本頁) I 41 948 4 A7 B7 五、發明説明（8 ) 部分被以醱化、醚化、醅化等反應所修飾者。又，本發明 中從形成多孔性構造為特徵’尤以使用聚甲殼糖為佳。本 發明中，鹼性多糖之分子量並無特別限定，可使用的1萬 〜10 0萬左右者。 又，具有本發明中所使用之反應性乙烯基的有機酸，係 可溶解鹼性多糖並形成水溶液者，可使用分子内具有1橱 以上之反應性乙烯基且1個以上之酸性基之水溶性有機酸 。具體上可舉例丙烯酸、甲基丙烯酸、巴豆酸、分解鳥頭 酸、馬來酸等之不飽和羧酸s體、或、苯乙烯磺酸、乙-丙烯醯胺-乙-甲基丙烯磺酸、3 -磺基丙基（甲基）丙烯 酸酯、雙（3 -磺基丙基）分解鳥頭酸酯等之不飽和磺酸單 體、或乙烯基磷酸、乙烯基磷酸酯、雙（甲基丙烯醯氧乙 基）磷酸酿、二苯基-2 -丙烯醢氧乙基磷酸酯、二苯基 -2 -甲基丙烯醢氧乙基磷酸酯、二丁基-2 -丙烯酿氧乙基磷 酸酯、二丁基-2 -甲基丙烯醯氧乙基隣酸酯，二辛基-2 -( 甲基）丙烯醸氧乙基磷酸酯等不胞和磷酸單體等 &gt; 此等可 Μ 1種單獨使用，亦可2種Μ上合併使用。又*其中，以 酸性度比較低的不飽和羧酸單體為佳，尤其以聚合物之酸 性度低的甲基丙烯酸最佳。有機酸之使用比率，為得到兩 性之多孔性微粒子，換算成每一鹼性多糖之單糖單元為 0.1〜500倍莫耳的範圍&gt; Κ0.5〜10倍莫耳範圍為佳，就 運用各別聚合體之恃激的意義上，Κ1.0〜5倍萁耳最佳。 又，亦可任意潟合具有此等反應性乙烯基之有機酸κ及 各種的酸。此時，所潖合之酸的種類可舉Μ諸酸、硫酸、 本紙張尺度適用中國國家標準（CNS ) A4現格（210X297公釐） .1. ml I - u I - I -I I I --1 I In -- (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 I 41 94 8 d A7 _____B7 五、發明説明（9 ) 鱗酸等之無機酸、键酸、醋酸、乳酸、檸樣酸、酒石酸、 琥珀酸、蘋果酸、草酸、乙二酸、二氣醋酸.、三氟醋酸等 之有機酸。 又’亦可使一可與具有反應性乙烯基之有機酸共聚合之 其他單體共聚合。其他單體可舉例如不飽和酸酯、有機酸 乙烯酯類、芳香族系乙烯基單體等。尤其，較佳係可以 W/0型聚合所合成之水溶性單體，例如2_羥基乙基（甲基 )丙婦酸酯、2 -徑.基丙基（甲基）丙烯酸酯、乙二醇二（ 甲基）丙歸酸酯、二乙二酵二（甲基）丙烯酸酯、三乙二 醇一（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯等 之不飽和酸酯類、乙酸乙烯醋、丙酸乙烯酯等之有機酸乙 烯醅類、乙烯基吡啶等之芳香族糸乙烯基類等。又，只要 為具有反應性基之化合物，旦可與具有反應性乙烯基之有 機酸的酸基反應的化合物，亦可併用。又，亦可使鏈移動 劑、停止劑等共存。 經濟部中夬標隼局員4消費合作社印裝 n^i- ^^^^1 H ^^^^1 ^^^^1 I. 一 i * 』 {請先閲讀背面之注$項再填寫本頁) 本發明之乳化或懸浮聚合係可在界面活性劑之存在下或 不存在下進行，但，κ在界面活性劑之存在下進行為佳。 本發明中所使用之界面活性劑可使用陰離子型、非離子型 、陽離子型及兩性之一般界面活性劑。例如，十二烷基硫 酸鹽、十二烷基苯磺酸鹽、聚氧乙烯基壬基苯基辭之硫酸 鹽等的陰離子界面活性劑；氯化十八烷基三甲基銨等之陽 離子性界面活性劑；聚氣乙烯十二烷基醚、聚氧乙烯十六 烷基醚、聚氧乙烯壬基笨基醚、山梨聚糖單硬脂酸酯、山 梨聚糖單油酸醅山梨聚糖單月桂酸醅、聚氧乙烯山梨聚糖 -12· 本紙浪尺度適用中國國家標準（CNS ) A4规格（2丨0X297公釐} 經濟部中央標準局員工消費合作社印製 I 419 4 8 4 A7 丨_ B7 五、發明説明（1〇) 翬硬脂酸酯、聚氧乙烯山梨聚糖單油酸醋、聚氧乙烯山梨 聚糖單月桂酸酯等之非離子界面活性劑；烷基二甲基胺基 醋酸甜菜鹼、烷基醯胺二甲基胺基醋酸甜菜鹼、2-烷基 -N -羧基-N -羥基咪唑甜菜鹼等之兩性界面活性劑。但， 粒子内存在兩性離子，若考慮粒子之安定性等，K非離子 界面活性劑為佳。此等界面活性劑亦可單獨使用，亦可潖 合2種以上使用。 本發明之反應中所使用之疏水性溶劑，具體上 &gt; 可舉例 如戊烷、己烷、庚烷、辛烷、壬烷、癸烷、環己烷等之烴 類、甲笨、苯等之芳香族類、石油醚、二乙基醚等之醚類 、氯仿、四氫化碳等之鹵化烴、丙酮、甲乙嗣、二乙嗣、 等之酮類、己酵、庚醇等之長鏈醇等。本發明中|較佳係 於此等之疏水性溶劑使上述界面活性劑溶解而進行反應。 於此疏水性溶劑中所含有之界面活性劑濃度適宜在0 . 1〜 10.0重量％的範圍 &gt; 以0.5〜5.0重量S5為佳。 _進而*本發明中•亦可使用羥乙基纖維素’、聚乙烯醇、 導入4級鹼之陽離子性聚乙烯醇、導入羧酸基或磺酸基之 陰離子性聚乙烯酵、溅粉、導入4级鹼之陽離子性澱粉等 、作為乳化劑或保護膠體而具有粒子安定性效果之水溶性 高分子。 於本發明中所使用之聚合開始劑*係在熱或遝原性物質 之存在下進行自由基分解而使單體之加成聚合開始者，一 般可使用水溶性或油溶性之過氧化二硫酸鹽、過氧化物、 偶氮雙化合物等。例如過硫酸鉀、過硫酸按、過氧化氫、 -13- 本紙張尺度適用中國國家標準（CNS ) A4規格（2IOX297公釐） ——^ϋ 1. — ^^1 1^1 ^^^1 (請先閲讀背面之注意事項再填寫本頁) ! 41948 4 at B7 五、發明説明（11 ) 第三丁基Μ過氧化物等之過氧化哟；2,2'-偶氮雙-2-胖基 丙烷鹽類（V-50)、4,4'-偶氮雙-4-氰基戊嗣酸等之偶氮化 合物。依需要亦可與堪原劑姐合，而使用來作為氧化堪原 系開始劑。此等聚合開始劑可單獨或合併2種以上使用之 。此等聚合開始劑亦可添加於鹼性多糖之有機酸酸性水溶 液中，亦可直接添加於乳化液糸中，對有機酸之重要化可 使用0.05〜10.0¾的範圍。 進而 &gt; 於本發明之聚合法中*除上述之單體、界面活性 劑、聚合開始劑之外，依需要亦可使用硫醇化合物等之鏈 移動劑、碳酸納等之出緩衝劑。 本發明之方法中，首先，使鹸性多楗之有機酸酸性水溶 液與加有界面活性劑之疏水性溶劑混合，使用乳化裝置而 藉機械播拌進行乳化以調製W/0乳液。乳化裝置可使用均 質機、高壓均質機、調和機、均混機、超音波乳化裝置、 奈米化糸統、玻瑀膜乳化裝置等。 又，從鹼性多糖之有機酸酸性水溶液與加有界面活性劑 之疏水性溶劑，使用一般之逆相懸浮法而製作出W/0懸浮 液*亦可直接進行聚合反應。 經涛部中夬標準局員工消费合作社印製 ---------装-- *~ (请先閲讀背面之注意事項再填寫表頁) 又，轧化/懸浮時之鹼性多糖的有機酸酸性水溶液/疏 水性溶劑之混合比率*就容積比可在70/30〜0. 1/99. 9之 範爾自由選擇。 本發明中，於上述般調製之鹼性多糖的W/0乳液或懸浮 液中加人聚合開始劑，可在2 0 °C〜8 0 T：之範圍進行聚合。 聚合0 . 1小時至2 4小時之間終了，冷卻後，滴人或全部添 ^14- 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0 X 297公釐） 經濟部中央標準局貝工消費合作社印製 Γ 4194 8 4 Α7 ____Β7_ 五、發明説明（12 ) 加於有機溶劑中等，而使多孔性微粒子析出。 所得到之微粒子係藉過溏、離心分離等處理進行固鞔分 離，再以醇等反複洗淨後，進行乾燥處理而得到微粒子粉 末。 此等所使用之有機溶劑較佳係使用甲醇、乙醇、丙醇、 異丙醇、丁醇、己醇、庚酵、辛醇等之醇類、或、丙_、 乙腈、四氬呋喃、二噁烷、醋酸乙酷等之極性溶劑、環己 烷、己烷、庚烷、辛烷等之非極性溶劑等。 又，於此溶劑中，宜添加銨、甲胺、乙胺、丙胺、丁胺 、異丁胺、己胺、辛胺、胺基變性砂酮、乙二胺、丙二胺 、丁二胺等之胺類、氫氧化納、氫氧化鉀、氫氧化钙、碳 酸納、烷氧基納、烷氧基鉀等之鹼性物質作為鹼。鹼之添 加量相對於微粒子中之有機酸聚合體宜為03〜2.0莫耳J； ，尤以0.8〜1.2莫耳為佳。 又，於多孔性微粒子中亦可內包ZnO、Ms 0等之無機物質 、精氨酸等之鹼性物質、環狀矽嗣、甘油三酸酯、醇蠘婦 等之親油性物質、香料等。 本發明之兩性多孔性微粒子其平均粒徑為SO E以下者 ’通常為O.Oltfm以上，較佳係0.1〜30tfiu者。平均粒徑 比5Gwm邐大者，每一與強酸/強鹼反應之粒子的驗/酸 性基的量會變少*吸附效果變差。 此處，平均粒徑係藉雷射繞射型粒徑分布測定裝置（ U-100、H〇mBA裝）於室溫下測定聚合體微粒子之1重量 %乙醇溶液而求得者。 -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） —^1 ^^^1 ----- - - ί ^—^1 1 - l^i 1^1 ^^^1 HI r* (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消費合作社印製 4194 8 4 A7 _ B7 五、發明説明（13) 本發明之兩性多孔性微粒子的形狀並無特別限定，但》 Μ球狀體為佳*因皮旖塗布時之觸感良好。 又*本發明之兩性多孔性微粒子的比表面積為10〜300 ，於得到酸/鹼之充分吸附效果•宜為20〜200 m2/g，尤 K 25〜150ra2/g為佳。 此處，比表面積係使用流動式比表面積自動測定装置（ 流動吸附2300型、SHIMAZU製），Μ BET1點法求得。又* 比表面大者意指該微粒子為多孔者。 本發明中所使用之聚甲殺糖微粒子可舉例：使蝦、蟹、 昆虫類等之甲餃類外皮的構成物質即幾丁質於30〜50重量 %之鹼性水溶液中加熱至上的溫度，而進行脫*** 化所得到的，且Μ —定之方法使聚甲殻糖進行微粒子化者 〇 聚甲殼糖微粒子之製造方法可舉例①使用噴嘴將聚甲殼 糖酸性水溶液滴入鹼性水溶疲的方法②形成聚甲設糖酸性 水溶液，嗔耢於高溫氣氛中進行乾燥的方法、③混合聚甲 殼楗酸性水溶莜與疏水性溶劑並進行乳化&gt; Κ形成乳液， 再注人鹼或有機溶劑中使之凝固的方法（乳化法）等。其 中③之方法較佳 &gt; 因具有高有效胺基量、高比表面積*且 可得到形狀被控制之聚甲殻糖微粒子。 聚甲殼糖微粒子之形狀可舉例球狀、不‘定形、非球狀定 形等，但以球狀體為佳，因皮嗛塗布時之觸感良好。此胃 *所謌非球狀定形謂具有球進行收縮變形而得到之定形上 的凹凸構造之形狀，钶如雖不是紅血球狀、帽子狀、高爾 -16- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^^^1 ^—^1 ^^^^1 flt—ν ίϋ^ϋ —IJI ^^^^1*2^ 1—ϋ ^^^^1 nn pn^i J 1 ^^^^1 (A ¢. 言 (請先閲讀背面之注意事項再填寫本頁) Γ 419484 Α7 Β7 五、發明説明（14 ) 夫球狀等所示之球狀，但指合乎一定要求的形態。 帽子狀者可藉由中空的球在一軸上、一方向上收縮變形 而得；又*紅血球狀者可藉由在一軸上、二方向上收縮而 得；藉由在多袖上、多方向上收縮變形可得到從3方向進 行凹凸者或高爾夫球狀者。 因此，以下說明藉上述③之乳化法得到球狀或非球狀定 形之聚甲殻糖微粒子的方法。 經濟部中央標準局負工消費合作社印装 (請先閱讀背面之注意事項再填寫本頁) 調製聚甲殼糖酸性水溶液時*使用來作為酸性水溶液之 酸可擧钶鹽酸、硫酸、磷酸等之無機酸、蟻酸、醋酸、乳 酸、檸攆酸、酒石酸、琥珀酸、蘋果酸、草酸、乙二酸、 二氯醋酸、三氟醋酸等之有機酸，但從溶解性/安定性/ 臭味等之觀點而言，K酒石酸、琥珀酸、蘋果酸、乙二酸 為佳。又，亦可舉例分子内具有反應性乙烯基之水溶性有 機酸，可使用分子内具有1個以上反應性乙烯基之水溶性 有機酸。具體上 &gt; 可舉例丙烯酸、甲基丙烯酸、巴豆酸、 分解鳥頭酸、馬來酸等之不飽和羧酸單體、或、苯乙烯磺 酸、2 -丙烯醢胺-2-甲基丙烷磺酸、3 -磺基丙基（甲基） 丙烯酸、雙-(3-磺基丙基）-分解鳥頭酸等之不飽和磺酸單 體、或、乙烯基磷酸、乙烯基磷酸酷、雙（甲基丙烯醯氧 乙基）磷酸酯、二苯基-2 -丙烯醢氧乙基磷酸酯、二苯基 -2 -甲基丙烯酿氧乙基磷酸酯、二丁基-2-丙烯醢氧乙基磷 酸醏、二丁基-2 -甲基丙烯醯氧乙基瞵酸酯，二辛基-2-( 甲基）丙烯醯氧乙基磷酸酯等之不飽和瞵酸單體等，此等 亦可1種單獨使用，亦可2種以上合併使用。尤其Μ聚合 ™17' 本紙張尺度適用中國國家標準（CNS) Α4規格（210Χ297公釐） 41 948 4 A7 B7 五、發明説明（15 ) 物之酸性度低的甲基丙烯酸為佳。 聚甲殼糖酸性水溶液之調製法-般係於加熱至5 〇〜7 0它 之上述酸的酸性水溶液中一面攪伴一®媛慢添加聚甲殼糖 並使之溶解的方法。此時之酸的澹度只要可溶解聚甲殼糖 即可，無待別限制。又’聚甲殻糖之濃度亦無特別限制’ 但粘度上宜為1〜10重量％。 本調製法中，乳化時所使用之乳化劑宜為山梨聚糖單硬 脂酸酯.、山梨聚糖單油酸醏、山梨聚糖月桂酸醋、聚氧乙 烯山梨聚糖單硬脂酸酯、聚氧乙烯山梨聚糖單油酸醅、聚 氧乙烯軍月桂酸酯、聚氧乙烯月桂基酵醚、聚氧乙烯醢基 醇醚等之非離子性界面活性劑。此等乳化劑亦可簞獨使用 ，亦可混合2種類以上使用。 用以溶解此種乳化劑之疏水性溶劑，具體上，可舉例己 烷、環己烷等之烴類、甲苯、苯等之芳香族類、石油醚、 二乙基醚等之醚類、氮仿、四氯化碳等之鹵化烴類等。此 疏水性溶劑中所含有之乳化劑濃度以0.1〜10,0重量5K之 範圍為適宜*較佳係0.5〜5.0重量56。 本調製法中之聚甲殼糖酸性水溶液的W/0乳液係嵌如下 調製，即，於聚甲殼糖酸性水溶液中加入含有乳化劑疏水 性溶劑，使用乳化裝置並K機械揀伴進行乳化α乳化裝置 可舉例均質機、高歷均質機、調和機、均混機.、接觸混合 機、超音波乳化裝置、奈米化***、玻璃_乳化装置等。 又，乳化時之聚甲殼糖酸性水溶液/含乳化劑疏水性溶 劑之混合比率就容量比以9 / 1〜1 / 9的範圍為佳，以7 / 3〜 -18- 本紙張尺度適用中國國家標準（CNS &gt; A4規格（2ίΟΧ297公釐） 7 —^υ ^^^^1 nl· ^^^^1 ]4^i ^^^^1 t mu m ^^^^1 一^ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消費合作社印製 1 41948 4 A7 A / ______B7 五、發明説明（π ) 3/7尤佳。 本調製法中，為得到球狀聚甲殼糖微粒子係將上述所調 製之聚甲殼糖酸性水溶疲的W/0乳液注人於有機溶劑或含 有鹼之有機溶劑中，直接維持球狀而凝画析出。 使聚甲殼糖乳鞔凝固析出之凝固液，有櫬溶劑單獨時， 較佳係使用甲醇、乙醇、丙醇.、異丙醇、丁醇.、辛醇等之 醇類或丙嗣、乙腈、四氫咲喃、二噁烷、乙酸乙酯等之極 性溶劑、環己烷·、己烷等之非極性溶劑等。 凝画液含有鹼之有機溶劑時t有機溶劑可使用甲酵、乙 醇、丙醇、異丙醇、丁醇等之酵類.、或丙嗣、乙腈、四氫 呋喃、二噁烷、醋酸乙醅等之極性溶劑、環己烷、己烷等 之非極性溶劑等，尤其K碳數4 Μ下之醇類、丙酮、乙腈 、四氫呋喃、二噁烷、醋酸乙酯等之極性溶劑為佳。鹼可 舉例氨、甲胺、乙胺、丙胺、丁胺、異丁胺、己胺、辛胲 、胺基變性矽SI、乙二胺、丙二胺、丁二胺等之胺等之肢 類、氫氧化納、氫氧化鉀、氫氧化鈣等之鹼性物質，以氫 氧化納、氫氧化鉀、丁胺、己胺、辛胺為佳，進而可舉出 丁胺、己胺、辛胺得到更真球狀之聚甲殼糖微粒子，並成 為更佳者。 經濟部中央標準局負工消費合作社印聚 -li— ^^1 tn n^i 1^1 (請先閲讀背面之注意事項再填寫本f ) 此時之凝固液的量依凝固液之種類而異，但通常對於乳 液為2〜50容量倍。 於如此之凝固液中一面滴下含有聚甲殼糖之W/0乳液一 面播拌，則聚甲設糖會凝固析出而成為球狀體。Κ過滹或 離心分離等捕捉此聚甲殻糖球狀體，並Μ醇等充分洗淨’ -*19- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ! 419 4 6 . ι ' A7 ___B7 五、發明説明（17) 進而藉由乾燦處理可得到球狀微粒子。 又，於本調製法中‘為得到非球狀定形之聚甲殼糖微粒 子係使用胺與醇之混合液液作為上述凝固液》胺可擧例氨 、具碳數1〜12左右之烷基鏈長的1级胺、二乙胺、二異 丁胺、二輿丙胺等之2級胺、三乙胺、三-正辛胺等之3 級胺、乙二胺、丙二胺、丁二胺等之二胺、單乙醇胺、二 乙醇胺、三乙醇胺等之胺基酵類、吡啶、吡咯等雑環式胺 及聚乙烯亞胺、胺基變性丙烯基聚合物、胺基變性砂酮等 〇 此等胺之中，較佳係在通常之處理溫度中與水完全不相 溶之微水溶性的胺，可使用具有碳數2〜1 2之烷基的胺、 更佳係烷基之碳數為4〜1 2之單烷基胺的1級胺、烷基之 碳數為3〜10的2級胺、烷基之碳數為2〜8的3级胺或胺 基變性矽_，尤其K胺基變性矽酮更佳。 本調製法中所使用之醇可舉例具有碳數1〜20左右之烷 基鏈長的單醇等*但K 丁醇、異丁醇、己醇、庚酵 '辛醇 等之碳数為4〜12的單醇為佳。 又，胺為使用胺基變性矽_時，尤以異丁醇、丁醇為佳 。使用正丁醇等之1級胺時*尤以碳數6〜12之單醇為佳 經濟部中央標準局貝工消費合作社印製 i^i ^^1 m ^^1 - in ^^^1 I )^1 ^^1 m ttt ^^1 -¾ 、va {請先閲讀背面之注意事項再填寫本頁) Ο 於本調製法中，胺與醇之混合溶液的胺/醇混合比率並 無特別限定，但，胺為使用胺基變性矽醒時，胺/醇混合 比率就容積比K 2/3〜8/2為佳。若此容積比超過8.2 ，所 得到之微粒子形狀變成非球狀定形微粒子的凝集物，不能 -20- 本紙張尺度適用中國i( CNS ) Mim- { 210X297/&gt;# } 經濟部中夬標準局員工消費合作杜印製 1 4194 8 1 A7 B7 五、發明説明（18) 得到分散粒子。另外，容積比不足2 /3 ’則雖可得到分散 微粒子，但變成球狀，不能得到非球狀定形微粒子n 本調製法中，有關凝固溫度像只要在凝固液及乳液中之 疏水性溶劑或水等的沸點Μ下即可，而無特別限制’但* 可藉凝固溫度使粒子形狀變化。雖依胺&amp;醇之混合溶蔽的 種類而異*但一般凝固溫度為20〜50t：時，會從3方向形 成已凹凸化之定脬粒子，若在50ΉΚ上，刖會形成紅血球 狀或帽子狀的定形粒子。凝固液量依凝固液之種類等而異 ，但通常對於乳液為2〜50容量倍。 若於如此之凝固液中一面滴入聚甲殼糖酸性水溶液的 W/0乳蔌一面攪伴，則聚甲殼糖會凝固析出成為非球狀定 形體。以過滤或離心分離等之公知方法分離此聚甲殼糖非 球狀定形體，再K醇等充分洗淨處理，進而進行乾燥處理 ，可得到平均粒徑為5 0 « in K下之非球狀定形聚甲殼糖微 粒子。 進而，聚甲殻糖微粒子亦可包含：經實施部分乙豳化等 之化學修飾的聚甲殼糖微粒子、以環氧基等進行交聯之聚 甲殼糖微粒子、藉由以聚甲設糖作為保護膠體之乳化聚合 等所得到的聚甲榖糖被覆微粒子、進而有機或無機粉之複 合聚甲殼糖微粒子、藉逆相懸浮聚合所得到之聚甲殻糖/ 乙烯基聚合物複合微粒子等。 本發明中所使用之聚甲殼糖微粒子的粒徑*其平均粒徑 為0 ‘ 0 1〜5 0 W Π1 *較佳像0 . 1〜3 . 0 w ，進而更佳係1〜 30«ια 。若平均粒徑超過50um ，皮腐上塗布時會產生參 -21 - 本紙張尺度適用中國國家揉準（〇奶）八4規/格（210乂297公釐） —---------装-- - (請先閲讀背面之注意事項再填寫本頁) -β 經濟部中央標準局貝工消費合作社印裝 Γ 41948 4 Α7 Β7五、發明説明（19 ) 差不齊且觸惑不佳。又，若平均粒徑Κ下，調 配有時會產生困難，皮膚上塗布時因會產生粗滯感而不佳 。此處，平均粒徑係Κ雷射繞射型粒徑分布测定裝置（ U -1 0 0 .、Η 0 R I Β Α裝置）在室溫下測定聚甲殼糖微粒子的1 重量Si乙醇溶液而求得者。 本發明中所使用之聚甲殷糖微粒子的有效胺基量宜為 l，〇x 10-7〜l.ox 10_2mol/g ，更佳為 1.0X 1〇_θ〜1.0X 1 0 - 2 mo 1 /s，但Κ可得到充分之防臭效果為佳。此處所諝 聚甲殼糖徵粒子之有效胺基量（m〇l/s)係於聚甲殼糖微粒 子單位重量中可胗成羧酸與鹽之胺基的莫數，且、由在聚 甲殼糖微粒子中添加4 -苯基酪酸之2xl0_4mol /升瓌己烷 或乙醇溶莜後&gt; Μ濾膜Uembrane f i 1 te「）過滹，UV測定 (λ « H x = 2 1 0 n iu)濾液而求得者。 本發明中所使用之聚甲殼糖微粒子的比表面稹宜為1〇〜 300m2/s ，更宜為 30 〜300ra2/s ，尤宜為 50 〜300ra2/g * 但，Μ可得到充分之防臭效果為佳。此處，比表面積係使 用流動式比表面積自動測定裝置（流動吸附2300型， SHIMAZU製）並以BET 1點法求得，又，比表面稹高者乃 指此微粒子為多ft。 本發明中所使用之聚甲殼糖微粒子的分子量若考慮微粒 子的強度，重蠆平均分量宜為IX 1〇3〜IX 1〇β。此處，重 量平均分子量係使用GPC ，且Μ0.5Μ醋酸媛衝液（0.5Μ醋 酸+ 0 , 5 Μ醏酸鈉）作為溶離疲*使用水糸管柱而求得。又 &gt;分子量係經P E G換算而計算出。 (請先閲讀背面之注意事項再填寫本頁) -22- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 41948 A7 B7 五、發明説明（2〇 又 &gt; 本 為可得到 膠體'滴定 甲殼糖醋 使用8 -苯 劑複合體 本發明 烷基者* 或分子童 時 &gt; 會因 殘存於皮 上0 又，在 平均碳數 於本發 ，且於分 示之構造 發明中所使用之聚甲殻糖微粒子的脫乙醯化度宜 充分防臭效果之8 0 %以上。此處*脫乙醯化度係 以甲苯胺藍作為指示劑而Μ聚乙烯硫酸鉀滴定聚 酸水溶液而求得。又，亦可以如下方法：指示劑 胺基-1 -亞蔡基磺酸酯，以形成聚甲殻糖-指示 而進行螢光測定。 中所使用$聚矽氧烷係於側鏈或兩末端具有長鏈 且融點只要在20 以上即可*而於烷基鏈之碳敵 上無特別規定。若融點在20 t：以下，塗布於皮虜 皮旖溫而溶解*成為油狀，易流落、粘滯、很難 Γ#上，無法使除臭劑的有效成分持續留滯於皮麂 本發明中，長鏈烷基乃指平均碳數1 6以上者；K 30以上者為佳*平均碳數40〜70者更佳。 明所使用之聚砂氧烷中較佳者像融點6 0〜1 4 0 t 子兩末端具有長鏈烷基者，尤以具有下式（I )所 的聚矽氧烷為佳。 CH3Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives A7 B7 V. Description of the invention (1) [Industrial applications] The present invention relates to a kind of cosmetics (sweat-making agent, deodorant, emollient, Moisturizing agent), hair cosmetics, pharmaceuticals, fiber treatment agents, paper processing agents, cement additives, coating materials, bactericidal / bactericidal agents, agricultural fine particles D [Jin Zhi Technology] Generally, emulsification or suspension method, etc. The obtained amphoteric / cationic amphoteric microparticle images can be obtained as follows: a monomer mainly having an amine group and a monomer having an acid group are copolymerized; or, after anion or cationic particles are formed, modification reactions are performed, etc. Part of the reactive group is transferred to a cationic or anionic group; or a cationic or anionic substance is mixed together by compounding. For example, a method for generating amphoteric microparticles includes: a method of emulsifying copolymerization of a military body containing an amine group and (meth) acrylic acid; and performing a Huffman reaction on microparticles composed of a stupid ethylene / acrylamide copolymer Method [J.  App! Poly.  Sci. 26, 2015 (1981)], Method for reacting by polymerizing ethylenediamine by precipitation from methacrylic acid / acrylamide / p-nitrophenylacrylate / methylenebispropylamine 、 Summarization of Lectures in the Special Symposium  23, (1 993)] and so on. However, these methods cannot obtain porous fine particles, and the amount of alkali / acid groups per particle that reacts with strong acid / strong test is very small. Also, the manufacturing method of fine particles of natural materials for lotus is: K has a chitosan with a 1 amino group as the base agent, and after the chitosan is dissolved in an acid, the solution is dripped into an alkali to solidify the fatigue. Kaizhao No. 59-30722 and the special paper size apply the Chinese National Standard (CNS) A4 specification (2 丨 0 X 297 mm) ------BJ ^^^ 1 ^^^ 1 ^-^^ 1 ^^^ 1 ^^^ 1 一 ΰί -I- (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 41 948 4 Μ _____ Β7 V. Description of the Invention (2 ) Kaizhao (Japanese Patent Publication No. 52-62827, Japanese Patent Laid-Open Publication No. 62-7040, Japanese Patent Laid-Open Publication No. 62-79201, etc.); a method for mechanically treating a polychitosan or a polymethylose dispersion (Japanese Patent Laying-Open No. 6 3-2 0 3 02, JP S 3 M.  7 9 0 2 and JP 6 3-2 0 1 101). However, any one of the particles is also a cationic fine particle, and only a few + μm to several hundred "particles with a particle size of πM" can be obtained, and a method for producing an amphoteric particle based on a basic polysaccharide , In the presence of polychitosan in water-soluble tincture, the organic acid with a reactive vinyl group is (co) polymerized to synthesize a granular cross-body composed of the combination of polychitosan and an organic acid polymer [Polymer Paper Get * V 〇1.  37, Ν 〇.  3, 1 3 5 (1 9 8 0)]. However, the chitosan microparticles produced by these methods have a wide particle size distribution and can only obtain non-spherical particles containing particles of 50 «ε or more * Porosity is also low. In this way, amphoteric fine particles cannot be obtained and can absorb a large amount of porous fine particles having an average particle diameter of 50 «m K that is stronger than acids or bases which are stronger than their acid groups or bases. In addition, if porous microparticles * capable of adsorbing such a strong acid or alkali in a large amount cannot be obtained, they can also be used in a deodorant or the like due to their adsorption properties. Underarm odor, foot odor, sweat odor, and other body odors are unpleasant odors, which are quite annoying to those who suffer from them. Body odor components are metabolites released by dermatological effects such as stinky sweat, old waste, and spoilage. Therefore, although the perspiration and other secreted substances do not have a strong odor, ® is caused by the presence of bacteria on the skin to produce lower carboxylic acids or volatile substances, which is a cause of unpleasant odor substances. Various odorous substances are known, such as lower carboxylic acids such as acetic acid, butyric acid, propionic acid, isochrylic acid, and the like. This paper size applies to China National Standard (CNS) A4 (2IOX297 mm) ^^^ 1 ^^^ 1 in —II ί--1 士 衣 ^^ 1 ^^ 1 In 11-1 ---!--( Please read the note on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 194 8 4 A7 ________B7_ V. Description of the Invention (5) Examples of methods for suppressing these body odors ① Use of gold oxide (Oxidation details, magnesium oxide, titanium oxide, aluminum oxide, etc.) (JP 1-49372), ② physical adsorption of porous materials such as activated carbon, ③ the use of sisters can inhibit the growth of pupa Antibacterial agents (Mr. Claurate 5 / Xiakou ^), isopropyl methylphenol, alzacil, chiorexfdine chlorhexidine gluconate (chlorhexidine. ), Tooth clamping (c h a 1 〇 ca r b a η), etc.), ④ a method with strong astringent effect (for zinc phenol sulfonate, citric acid, aluminum salt, zirconium salt) method ⑤ masking with perfume and so on. However, a physical deodorization method using activated carbon or the like for 'K' has insufficient adsorption capacity of lower fatty acids, and has problems in terms of feeling of use and mineralization. Sensitive deodorization with fragrance masking can change the quality of the odorous substance through fragrance * However, because very stinky substances still remain, the deodorizing effect is limited. In addition, the method of using metal oxides such as zinc oxide, magnesium oxide, titanium oxide, and aluminum oxide, so that the gold oxide only reacts with the acid on the surface, so various efforts are made to increase the surface area. However, even if the surface area is increased, The reaction with the odorous substance, ie, the acid, also gels, so the ability to capture the acid produced by CK Changs is lacking, and cannot be fully satisfied. So far, cosmetics concerning the water-soluble acid salt of polymethylinose exhibiting anti-odor and anti-bacteria effects have been disclosed in JP-A-6 3-2 0 98 0 *. However, almost no deodorant effect is available. In addition, the chitosan fine particles are disclosed in JP-A-Sho 62-190110 and JP-A 4-235006, which can be formulated into cosmetics such as foundations and eye shadows, and can improve the feeling of use, finish, stability, and moldability. However, * is not described at all for application to deodorants. This paper size applies the Chinese National Standard (CNS) Α4 specification (2Ι0 × 297 mm) I Shimin | 1 Ding. _ I.  7 · ^ -5 (Please read the precautions on the back before filling this page) ί A1 948 4 Α7 __Β7_ V. Description of the invention (4) When the Austrian agent is applied to the skin by coating or other methods, it will be on the skin Forming more or less coatings, the coatings shadowed on Pi Yong play the role of preventing the volatilization of active ingredients. However, since the main components of the deodorant are water, alcohol, oil, etc., the sweat or sebum flow is also sticky and easy to diffuse, so there is no sufficient film formation effect, and most of them lack deodorant. The effect of the active ingredients in the Pi Temple. In addition, although paraffin, vaseline, and other compounds that are paintings or semi-solids at room temperature can be used as film-forming agents, the effects of these formations are very high, and the persistence of active ingredients is also high, but it will hinder skin晡 Respiration and the emission of water vapor, especially in summer, have a bad effect on Pi Yong. Silicone oil has recently been used as an oil agent for applying deodorant and the like to the skin. The main reason for this is to improve the feel of slippery feel caused by extremely low intermolecular forces. In addition, because sand _ oil has a high permeability of gas or water vapor, it is considered.  It does not cause the problems caused by the above tadpoles to prevent the skin from breathing and water vapor. However, &gt; Silicone oil is easy to spread on the skin due to its low surface tension. * It cannot form a continuous film with active ingredients. The use of siloxane is shown in No. 5-2 5 5 0 5 6 and No. 5-2 6 2 6 1 6 in Kaikai. Printed I II by Shellfish Consumer Cooperative of the Central Kezhun Bureau of the Ministry of Economic Affairs ------- Pack -II-Order-(Please read the precautions on the back before filling this page) Substrate that can form a film on the skin In Japanese Kaikaihei 5-1 9 4 1 8 3, Japanese Patent Laid-Open No. 6-9 3 6 7 and the like, a polysiloxane with a long-chain alkyl group and its application to a temple protector are disclosed. Crystallinity of Alkyl ►In Japanese Patent Application Laid-Open No. 5-1 9 4 1 8 3, a mixture of plural polysiloxanes is used. * Japanese Patent Application No. 6-9 3 6 7 uses alkyl groups at both ends. Zhishaxane alone -7- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) ί 419 4 8, 4 Α7 Β7 V. Description of the invention (5) Play to suppress the moisture from the dry skin. Evaporation, however, the polyoxaxane used in the present invention has the opposite effect, making full use of the high water vapor permeability of silicone ►It has the property of keeping the active ingredients on the skin, but it does not prevent it Evaporation of water. That is, the deodorant of the present invention is very effective when used in the period when sweating is easy in summer. If the polysiloxane described in the above-mentioned conventional publication is used in such a period, the melting point Very low, oily near body temperature, sticky to the touch, and persistent film at high temperatures. [Indication of the Present Invention] Therefore, an object of the present invention is to provide amphoteric particles which can absorb a large amount of acids or bases which are stronger than their acidic or alkaline groups, and have an average particle diameter of 50 vm. Sex particles. Furthermore, an object of the present invention is to provide a cosmetic, such as a deodorant, which has a high deodorizing effect and is fast-acting and excellent in performance. Therefore, the problem of the present invention is that when applied to the skin, it is possible to prevent the skin from breathing and evaporate the water vapor, and to form a film having the property of retaining the active ingredients on the skin temple, and to prevent the skin from being effective. A deodorant that scatters and loses its ingredients and has a long-lasting deodorizing effect. Ministry of Economic Affairs t 夬 Standards Bureau Employee Consumption Cooperative India Nong ^^^ 1 ^^^^ 1 nil— 11 t (please read the precautions on the back before filling out this page). Therefore, the inventors and other accumulated intensive research, results * A natural material, namely, amphoteric porous microparticles based on basic polysaccharides, having anionic and cationic amphoteric properties, and the amount of alkali and acid groups of each particle that reacts with a strong acid / strong base in a non-polar and polar solvent It is more overwhelmingly porous than conventional particles; it has also been found that if the amphoteric porous particles are used, the acid capture performance is very high * and long-term acid capture can be achieved. Standard (CNS) Α4 specification (210X297 mm)! 41948 4 at 4 B7 V. Description of the invention (6) Deodorizing performance without reducing performance; the present invention is finally completed. The present invention provides a porous fine particle having deodorizing performance, a manufacturing method thereof, a cosmetic product containing the same, a cosmetic composition containing polychitosan fine particles as a deodorant, and a cosmetic containing polysiloxane as an oil agent. The main reason is to provide a deodorant product. Specifically, first, it is an amphoteric porous fine particle composed of a polymer of a basic polysaccharide and an organic acid or a salt thereof having a reactive vinyl group and having an average particle size of 50 tm or less *. Preferably, the shape of the porous fine particles is spherical. • The specific surface area is 10 to 300 iu2 / s. • The polybasic is polychitosan, or the organic acid or its salt having a reactive vinyl group is methacrylic acid or its salt. . The microparticles can be produced as follows, even if an aqueous solution containing an organic acid having a basic polysaccharide and a reactive vinyl group is emulsified or suspended in a hydrophobic solvent and then polymerized. It is preferred that after the polymerization is completed, the organic solvent containing an alkali is dropped or all added to the polymerization reaction to form porous fine particles. Organic acids can also be used for the monosaccharide unit of each basic polysaccharide. 1 to 500 times. Preferably, the porous fine particles are contained.  1 ~ 70 weight of JK cosmetics The finished product is used as a deodorant. Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^^ 1 n — ^^ 1 ^^ 1 ^^ 1 m Λ ^^ 1 ^^ 1 HI 1 ^ 1 5, v *-(Please read the notes on the back first (Fill in this page again) Cosmetic products can contain ingredients commonly used in cosmetic formulations, such as oils. The present invention * also contains an amphoteric porous spherical fine particle composed of a polymer of a basic polysaccharide and an organic acid having a reactive vinyl group and having an average particle size of the following or less. Further, the present invention provides a K average particle diameter of 0. 01 ~ 50wm of poly-9- This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) Γ 419484 Printed by A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) As a deodorant, a cosmetic product containing deodorant and the like is provided, and a deodorizing method using the same is provided. Preferably, the specific surface area of the polychitosan fine particles is 10 to 300 ni2 / &amp;, and the effective amount of the amine group of the polychitosan fine particles is 1. 0Χ 丨 〇_7 ~ l. 〇x moi / s * and the shape of the polymethyin fine particles is spherical. Provide a polysiloxane having a melting point of 20 t: a long-bond alkyl group or more as a cosmetic product, especially as an oil agent in a deodorant, and also provide a polysiloxane containing the polysiloxane. 01 to 99 weight SK, and contains a hostile substance, basic polysaccharide, or the above-mentioned porous fine particles or polymethylene sugar as a deodorant composition. The polysiloxane preferably has a melting point of 60 to 140 Ό, and has a long bond alkyl group at both ends of the molecule, or a ratio of the long fluorene alkyl moiety in the polysiloxane having a long chain alkyl group, totaling 0, 5 to 40% by weight. The following &gt; describes the present invention in detail. The amphoteric porous microparticles of the present invention can be prepared by emulsifying or suspending an aqueous solution of an organic acid having an authentic polysaccharide and a reactive vinyl group in a hydrophobic solvent, and then polymerizing them. The basic polysaccharide used in the present invention is a compound having a structure with a class 1 or class 2 amine group-like ether chain binding structure, such as polychitosan equivalent to polyglucosamine, and its acetonate Chitin, polyamines and their acetonates. However, in general, the chitin existing in nature will become a part of acetamido which is not acetylated. Therefore, the chitin produced by the present invention indicates a degree of deacetylation of 30¾. The following * chitosans are those whose deacetylation degree is above 30%. These basic polysaccharides also contain them — -10- This paper size applies to Chinese national standards (CNS &gt; A4 specifications (210X297 public love)-I-—-I — I--IP---I * ^- I--n-TV (Please read the notes on the back before filling out this page) I 41 948 4 A7 B7 V. Description of the invention (8) Part modified by reactions such as tritiation, etherification, tritiation, etc. In the present invention, the formation of a porous structure is characterized by the use of chitosan. In the present invention, the molecular weight of the basic polysaccharide is not particularly limited, and it may be about 10,000 to 100,000. It also has The reactive vinyl organic acid used in the present invention is one that can dissolve basic polysaccharides and form an aqueous solution. A water-soluble organic acid having at least one cabinet of reactive vinyl and one or more acidic groups in the molecule can be used. Specific examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, decomposing ornithic acid, and maleic acid, or styrene sulfonic acid, ethyl-acrylamide-ethyl-methacrylic acid Acid, 3-sulfopropyl (meth) acrylate, bis (3-sulfopropyl) decomposition bird Unsaturated sulfonic acid monomers such as acid esters, or vinyl phosphoric acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-propenyloxyethyl phosphate, diphenyl 2-methyl methacryloxyethyl phosphate, dibutyl-2-propenyl oxyethyl phosphate, dibutyl-2 -methacryl oxyethyl orthoester, dioctyl-2 -(Meth) acrylic acid oxyethyl phosphate and other monomers and phosphate monomers &gt; These can be used alone or in combination of two kinds. Also, among them, the acidity is relatively low. Unsaturated carboxylic acid monomers are preferred, especially methacrylic acid with a low acidity of the polymer. The ratio of organic acids used in order to obtain amphoteric porous microparticles, converted to the monosaccharide unit of each basic polysaccharide is 0. 1 to 500 times the mole range> K0. 5 to 10 times the molar range is better, in the sense of using the stimulation of the respective polymer, Κ1. 0 to 5 times the ear is best. In addition, organic acids κ and various acids having these reactive vinyl groups may be arbitrarily combined. At this time, the types of acids to be mixed can be exemplified by various acids, sulfuric acid, and this paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm). 1.  ml I-u I-I -III --1 I In-(Please read the notes on the back before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shelley Consumer Cooperative I 41 94 8 d A7 _____B7 V. Invention (9) Inorganic acids such as phosphonic acid, bond acids, acetic acid, lactic acid, citric acid, tartaric acid, succinic acid, malic acid, oxalic acid, oxalic acid, and diacetic acid. , Trifluoroacetic acid and other organic acids. It is also possible to copolymerize another monomer copolymerizable with an organic acid having a reactive vinyl group. Examples of other monomers include unsaturated acid esters, organic acid vinyl esters, and aromatic vinyl monomers. In particular, it is preferably a water-soluble monomer that can be synthesized by W / 0 type polymerization, such as 2-hydroxyethyl (methyl) propionate, 2-diameter. Propyl (meth) acrylate, ethylene glycol di (meth) propionate, diethylene glycol di (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol Unsaturated acid esters such as alcohol di (meth) acrylates, organic acid vinyl acetates such as vinyl acetate, vinyl propionate, and aromatic pyrene vinyls such as vinyl pyridine. Further, as long as it is a compound having a reactive group, a compound which can react with an acid group of an organic acid having a reactive vinyl group can be used in combination. In addition, a chain-moving agent, a stopping agent, and the like may be coexisted. Member of the Ministry of Economic Affairs of the Ministry of Economic Affairs 4 Consumer Cooperatives printed n ^ i- ^^^^ 1 H ^^^^ 1 ^^^^ 1 I.  一 i * "{Please read the note on the back before filling in this page) The emulsification or suspension polymerization of the present invention can be performed in the presence or absence of a surfactant, but κ is in the presence of a surfactant Better to proceed. The surfactants used in the present invention can be general anionic, non-ionic, cationic and amphoteric surfactants. For example, anionic surfactants such as dodecyl sulfate, dodecylbenzenesulfonate, polyoxyvinyl nonylphenyl sulfate, and cations such as stearyl trimethylammonium chloride Surfactant; Polyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene nonyl benzyl ether, sorbitan monostearate, sorbitan monooleate Sugar monolaurate, polyoxyethylene sorbitan-12 · The size of this paper is applicable to the Chinese National Standard (CNS) A4 (2 丨 0X297mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs I 419 4 8 4 A7丨 _ B7 V. Description of the invention (10) 翚 Nonionic surfactants such as stearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monolaurate, etc .; alkyldimethyl Amphoteric surfactants such as aminoaminobetaine, alkylamidodimethylaminobetaine, 2-alkyl-N-carboxy-N-hydroxyimidazole betaine, etc. However, there are zwitterions in the particles, If the stability of the particles is taken into consideration, K nonionic surfactant is preferred. The agent can be used alone or in combination of two or more kinds. The hydrophobic solvent used in the reaction of the present invention, specifically &gt; Examples include pentane, hexane, heptane, octane, nonane, decane Hydrocarbons such as alkane, cyclohexane, aromatics such as methylbenzene, benzene, ethers such as petroleum ether, diethyl ether, halogenated hydrocarbons such as chloroform, tetrahydrocarbon, acetone, methyl ethyl hydrazone, diethyl fluorene Ketones, etc., long-chain alcohols such as hexanoate, heptanol, etc. In the present invention, it is preferred that these hydrophobic solvents dissolve and react with the above-mentioned surfactants. The hydrophobic solvent contains The surfactant concentration is preferably at 0.  1 to 10. 0% by weight &gt; range from 0. 5 ~ 5. 0 weight S5 is preferred. _Furthermore, in the present invention, hydroxyethyl cellulose ', polyvinyl alcohol, cationic polyvinyl alcohol introduced with a 4th-level alkali, anionic polyethylene yeast introduced with carboxylic acid group or sulfonic acid group, splash powder, It is a water-soluble polymer that introduces cationic starch such as 4th grade alkali, and has particle stabilization effect as emulsifier or protective colloid. The polymerization initiating agent used in the present invention * is a monomer that initiates the addition polymerization of monomers by performing radical decomposition in the presence of heat or luteogens. Generally, water-soluble or oil-soluble peroxodisulfuric acid can be used. Salts, peroxides, azobis compounds, etc. For example, potassium persulfate, persulfate, hydrogen peroxide, -13- This paper size is applicable to China National Standard (CNS) A4 (2IOX297 mm) —— ϋ ϋ 1.    — ^^ 1 1 ^ 1 ^^^ 1 (Please read the notes on the back before filling this page)! 41948 4 at B7 V. Description of the invention (11) Peroxide of the third butyl M peroxide; Azo compounds such as 2,2'-azobis-2-fatylpropane salts (V-50) and 4,4'-azobis-4-cyanopentanoic acid. If necessary, it can also be used as a starting agent for oxidized Kanyuan system. These polymerization initiators may be used alone or in combination of two or more. These polymerization initiators can also be added to the organic acidic acidic aqueous solution of basic polysaccharides, or can be added directly to the emulsion 糸. For the importance of organic acids, 0. 05 ~ 10. 0¾ range. Further &gt; In the polymerization method of the present invention *, in addition to the above-mentioned monomers, surfactants, and polymerization initiators, chain shifting agents such as thiol compounds and buffering agents such as sodium carbonate may be used as required. In the method of the present invention, first, a polybasic organic acidic acidic aqueous solution is mixed with a hydrophobic solvent added with a surfactant, and emulsified by mechanical sowing using an emulsifying device to prepare a W / 0 emulsion. As the emulsification device, a homogenizer, a high-pressure homogenizer, a blender, a homomixer, an ultrasonic emulsification device, a nano-chemical system, and a glass film emulsification device can be used. In addition, a W / 0 suspension can be prepared from an organic acidic acidic aqueous solution of a basic polysaccharide and a hydrophobic solvent to which a surfactant is added, using a general inverse-phase suspension method *, or a polymerization reaction can be directly performed. Printed by the Consumers' Cooperatives of the Zhongli Standards Bureau of the Ministry of Economic Affairs ------------------- (Please read the precautions on the back before filling in the form page) Also, alkaline polysaccharides when rolling / suspending The mixing ratio of organic acid and acid aqueous solution / hydrophobic solvent * can be 70/30 ~ 0 in volume ratio.  1/99.  9 of Vail is free to choose. In the present invention, a polymerization initiator can be added to the W / 0 emulsion or suspension of the basic polysaccharide prepared as described above, and the polymerization can be performed in a range of 20 ° C to 80 ° T. Aggregation 0.  After the end of 1 hour to 24 hours, after cooling down, add or add all of them ^ 14- This paper size applies to China National Standard (CNS) A4 specifications (2 丨 0 X 297 mm) Printed by the cooperative Γ 4194 8 4 Α7 ____ Β7_ 5. Description of the invention (12) It is added to organic solvents, etc., so that the porous fine particles are precipitated. The obtained fine particles are subjected to solid separation through treatment such as centrifugation and centrifugation, and then repeatedly washed with alcohol or the like, and then subjected to drying treatment to obtain fine particle powder. The organic solvents used in these are preferably alcohols such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, heptyl alcohol, octanol, or the like, propane, acetonitrile, tetrahydrofuran, dioxane Polar solvents such as oxane and ethyl acetate, non-polar solvents such as cyclohexane, hexane, heptane, and octane. In this solvent, ammonium, methylamine, ethylamine, propylamine, butylamine, isobutylamine, hexylamine, octylamine, amino-modified denatured ketone, ethylenediamine, propylenediamine, butanediamine, etc. Basic substances such as amines, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium alkoxide, potassium alkoxylate are used as bases. The addition amount of alkali is preferably 03 ~ 2 relative to the organic acid polymer in the fine particles. 0 Mor J;, especially 0. 8 ~ 1. 2 moles is better. In addition, the porous fine particles may contain inorganic substances such as ZnO and Ms 0, alkaline substances such as arginine, cyclic silicic acid, triglycerides, alcohol-soluble substances such as alcohol, and perfumes. . The amphoteric porous fine particles of the present invention whose average particle diameter is less than SO E ′ are usually O. Above Oltfm, preferably 0. 1 ~ 30tfiu. If the average particle size is larger than 5Gwm, the amount of test / acid groups per particle that reacts with strong acid / strong base will be reduced * adsorption effect will be worsened. Here, the average particle diameter is obtained by measuring a 1% by weight ethanol solution of polymer fine particles at a room temperature using a laser diffraction type particle size distribution measuring device (for U-100, HOBA). -15- This paper size applies to China National Standard (CNS) A4 (210X297 mm) — ^ 1 ^^^ 1 -------ί ^ — ^ 1 1-l ^ i 1 ^ 1 ^^^ 1 HI r * (Please read the precautions on the back before filling out this page) Printed by the Central Laboratories of the Ministry of Economic Affairs and printed by the Consumer Cooperatives 4194 8 4 A7 _ B7 V. Description of the invention (13) Shape of the amphoteric porous fine particles of the present invention There is no particular limitation, but ″ M spheroids are preferred. * The touch is good when the skin is coated. * The specific surface area of the amphoteric porous fine particles of the present invention is 10 to 300, which is sufficient to obtain an acid / base adsorption effect. It is preferably 20 to 200 m2 / g, especially K 25 to 150ra2 / g. Here, the specific surface area was obtained using a flow-type specific surface area automatic measuring device (fluid adsorption 2300 type, manufactured by SHIMAZU) and the BET 1 point method. Also, * larger than the surface means that the particles are porous. Examples of the polymethicillin fine particles used in the present invention include: chitin, which is a constituent material of shrimp dumplings, crabs, insects, and other shells, is heated to a temperature of 30-50% by weight in an alkaline aqueous solution. Those obtained by de-etherification and the method of M-micronizing polychitosan. The manufacturing method of polychitosan microparticles can be exemplified by the method of using a nozzle to drip an acidic aqueous solution of polychitosan into alkaline water and dissolving it. A method for forming an acidic aqueous solution of polymethoxide and drying it in a high-temperature atmosphere; ③ mixing polychitin (acidic water-soluble) with a hydrophobic solvent and emulsifying it> K to form an emulsion, and then injecting it into an alkaline or organic solvent to make Methods of solidification (emulsification method), etc. Among them, the method of ③ is preferred &gt; Because it has a high effective amine group amount, a high specific surface area *, and a chitosan fine particle having a controlled shape can be obtained. Examples of the shape of the polychitosan particles include spheres, irregular shapes, non-spherical shapes, and the like, but spheroids are preferred because they have a good touch when applied to the skin. The non-spherical shape of this stomach * refers to the shape of the concave-convex structure on the shape obtained by shrinking and deforming the ball. If it is not red blood cells, hat-shaped, or Gol-16-This paper applies Chinese national standards (CNS ) A4 size (210X297mm) ^^^ 1 ^ — ^ 1 ^^^^ 1 flt—ν ίϋ ^ ϋ —IJI ^^^^ 1 * 2 ^ 1—ϋ ^^^^ 1 nn pn ^ i J 1 ^^^^ 1 (A ¢.  (Please read the precautions on the back before filling out this page) Γ 419484 Α7 Β7 V. Description of the invention (14) The spherical shape shown by the spherical shape, etc., but refers to a form that meets certain requirements. A hat-shaped person can be obtained by shrinking and deforming a hollow ball on one axis and one side; and a red blood cell can be obtained by contracting on one axis and two directions; by contracting on multiple sleeves and in multiple directions Deformation can be obtained from three directions of unevenness or golf. Therefore, a method for obtaining spherical or non-spherical shaped polychitosan fine particles by the above-mentioned emulsification method will be described below. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) When preparing polychitosan acid aqueous solution Organic acids such as acids, formic acid, acetic acid, lactic acid, citric acid, tartaric acid, succinic acid, malic acid, oxalic acid, oxalic acid, dichloroacetic acid, trifluoroacetic acid, etc., but from the solubility / stability / odor, etc. From a viewpoint, K tartaric acid, succinic acid, malic acid, and oxalic acid are preferred. In addition, a water-soluble organic acid having a reactive vinyl group in the molecule may be exemplified, and a water-soluble organic acid having one or more reactive vinyl groups in the molecule may be used. Specifically &gt; Examples thereof include unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, decomposing ornithic acid, and maleic acid, or styrene sulfonic acid and 2-propenylamine-2-methylpropane. Unsaturated sulfonic acid monomers such as sulfonic acid, 3-sulfopropyl (meth) acrylic acid, bis- (3-sulfopropyl) -decomposed ornidic acid, or vinyl phosphoric acid, vinyl phosphoric acid, Bis (methacryloxyethyl) phosphate, diphenyl-2-propenyloxyethyl phosphate, diphenyl-2-methacryloxyethyl phosphate, dibutyl-2-propene Unsaturated ethyl acetate monomers, such as phosphonoethylphosphonium phosphate, dibutyl-2-methacrylic acid oxyethylphosphonate, dioctyl-2- (meth) propylene, oxyethylphosphonate, etc. These can be used alone or in combination of two or more. Especially M polymer ™ 17 'This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 × 297 mm) 41 948 4 A7 B7 5. Invention description (15) Methacrylic acid with low acidity is preferred. Polychitosan acid aqueous solution preparation method-generally based on the acidic aqueous solution heated to 50 ~ 70 it while mixing with one ® Yuan slowly add and dissolve polychitosan. The acidity of the acid at this time is only required to dissolve the polychitinose, and it is not limited. There is no particular limitation on the concentration of the polychitosan, but the viscosity is preferably 1 to 10% by weight. In this preparation method, the emulsifier used in emulsification is preferably sorbitan monostearate. , Sorbitan monooleate, sorbitan laurate vinegar, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene army laurate, polyoxyethylene Nonionic surfactants such as lauryl ferment ether, polyoxyethylene fluorenyl alcohol ether, etc. These emulsifiers can be used alone or in combination of two or more kinds. The hydrophobic solvent used to dissolve this emulsifier. Specific examples include hydrocarbons such as hexane and cyclohexane, aromatics such as toluene and benzene, ethers such as petroleum ether and diethyl ether, and nitrogen. Halogenated hydrocarbons such as imitation and carbon tetrachloride. The concentration of the emulsifier contained in this hydrophobic solvent is 0. The range of 1 ~ 10,0 weight 5K is suitable * preferably 0. 5 ~ 5. 0 重量 56。 0 weight 56. The W / 0 emulsion of the polychitosan acidic aqueous solution in this preparation method is prepared by adding a hydrophobic solvent containing an emulsifier to the polychitosan acidic aqueous solution, and using an emulsification device and K mechanical pick-up to perform an emulsification α emulsification device Examples include homogenizers, calendar homogenizers, blenders, and mixers. , Contact mixer, ultrasonic emulsification device, nanometer system, glass_emulsification device, etc. In addition, the mixing ratio of the chitosan acidic aqueous solution / emulsifier-containing hydrophobic solvent at the time of emulsification is preferably in the range of 9/1 to 1/9, and 7/3 to -18. This paper size is applicable to China Standard (CNS &gt; A4 size (2ί〇 × 297 mm) 7 — ^ υ ^^^^ 1 nl · ^^^^ 1] 4 ^ i ^^^^ 1 t mu m ^^^^ 1 1 ^ (please Read the notes on the back and fill in this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 1 41948 4 A7 A / ______B7 V. Invention Description (π) 3/7 is particularly good. In this modulation method, the spherical shape is obtained. The polychitosan fine particles are injected into the organic / solvent-containing organic solvent W / 0 emulsion prepared in the aforementioned chitos acidic water-soluble W / 0 emulsion, and directly maintain the spherical shape and precipitate. Precipitated coagulation liquid, when there is a solvent of rhenium alone, it is preferable to use methanol, ethanol, propanol. , Isopropanol, butanol. Alcohols such as octanol, polar solvents such as propane, acetonitrile, tetrahydrofuran, dioxane, ethyl acetate, and non-polar solvents such as cyclohexane and hexane. When the paint contains an organic solvent containing an alkali, the organic solvents can be fermented with formic acid, ethanol, propanol, isopropanol, butanol, etc. Or polar solvents such as propionate, acetonitrile, tetrahydrofuran, dioxane, acetamidine acetate, non-polar solvents such as cyclohexane, hexane, etc., especially alcohols, acetone, acetonitrile, tetrahydrofuran at a carbon number of 4 M , Dioxane, ethyl acetate and other polar solvents are preferred. Examples of the base include limbs such as ammonia, methylamine, ethylamine, propylamine, butylamine, isobutylamine, hexylamine, octylamine, amino modified silicon SI, ethylenediamine, propylenediamine, butylenediamine, and the like Alkaline substances such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and the like are preferably sodium hydroxide, potassium hydroxide, butylamine, hexylamine, and octylamine. Further examples include butylamine, hexylamine, and octylamine. Get more spherical spherical chitosan particles and become better. Yinju-li— ^^ 1 tn n ^ i 1 ^ 1 (Please read the precautions on the back before filling in this f) The amount of coagulation liquid at this time depends on the type of coagulation liquid Different, but usually 2 to 50 capacity times for emulsions. When the W / 0 emulsion containing polychitosan is dropped into such a coagulating solution and stirred, the polymethylose will solidify and precipitate into a spheroid. Capture this polychitosan spheroid by κ or centrifugation, and wash it thoroughly with M alcohol and so on ’-* 19- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)! 419 4 6.  ι 'A7 ___B7 V. Description of the invention (17) Furthermore, spherical particles can be obtained through dry-can treatment. In addition, in this preparation method, in order to obtain non-spherical shaped chitosan fine particles, a mixed liquid of amine and alcohol is used as the coagulation liquid. Examples of the amine include ammonia and an alkyl chain having about 1 to 12 carbon atoms. Long primary amines, secondary amines such as diethylamine, diisobutylamine, and dipropylamine, tertiary amines such as triethylamine, tri-n-octylamine, ethylenediamine, propylenediamine, butanediamine Diamine, monoethanolamine, diethanolamine, triethanolamine and other amine-based enzymes, pyridine, pyrrole and other cyclic amines and polyethyleneimine, amine-modified acrylic polymer, amine-modified sandone, etc. Among other amines, it is preferably a slightly water-soluble amine that is completely incompatible with water at ordinary processing temperatures. An amine having an alkyl group having 2 to 12 carbons, more preferably an alkyl group having a carbon number Primary amines of monoalkylamines of 4 to 12, secondary amines of alkyl groups of 3 to 10 carbon atoms, tertiary amines of alkyl groups of 2 to 8 carbons, or modified amino amines, especially K amino modified silicone is more preferred. Examples of the alcohol used in the preparation method include monoalcohols having an alkyl chain length of about 1 to about 20 carbon atoms, but the number of carbons of K butanol, isobutanol, hexanol, and heptyl alcohol is 4 A monoalcohol of ~ 12 is preferred. When amines are modified with amine-modified silicon, isobutanol and butanol are particularly preferred. When using first-grade amines such as n-butanol * Mono-alcohols with 6 to 12 carbon atoms are preferred. Printed by Shellfish Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs i ^ i ^^ 1 m ^^ 1-in ^^^ 1 I) ^ 1 ^^ 1 m ttt ^^ 1 -¾, va {Please read the notes on the back before filling out this page) 〇 In this preparation method, the amine / alcohol mixing ratio of the mixed solution of amine and alcohol is not It is particularly limited. However, when the amine is amine-modified denatured silica, the volume ratio of the amine / alcohol mixture is preferably K 2/3 to 8/2. If this volume ratio exceeds 8. 2. The shape of the obtained microparticles becomes agglomerates of non-spherical shaped microparticles, which cannot be -20- This paper size applies to China i (CNS) Mim- {210X297 / &gt;#} Consumption cooperation by employees of the China Standards Bureau of the Ministry of Economic Affairs Preparation 1 4194 8 1 A7 B7 V. Description of the invention (18) The dispersed particles are obtained. In addition, if the volume ratio is less than 2/3 ', dispersed fine particles can be obtained, but they become spherical and non-spherical shaped fine particles cannot be obtained. In this preparation method, the coagulation temperature image only needs to be a hydrophobic solvent in the coagulation solution or emulsion or There is no particular limitation on the boiling point M of water and the like, but * the particle shape can be changed by the solidification temperature. Although it varies depending on the type of amine & alcohol mixed dissolving *, generally when the coagulation temperature is 20 ~ 50t :, it will form the fixed particles with unevenness from 3 directions. If it is 50 ° K, it will form red blood cells or Hat-shaped shaped particles. The amount of coagulation fluid varies depending on the type of coagulation fluid, etc., but it is usually 2 to 50 times the volume of the emulsion. If the W / 0 milk of the chitosan acid aqueous solution is dripped into the coagulation solution, the chitosan will solidify and precipitate into a non-spherical shape. The polychitosan non-spherical shaped body is separated by a known method such as filtration or centrifugation, and then sufficiently washed with K alcohol and the like, and then dried to obtain a non-spherical shape with an average particle diameter of 50 «in K. Shaped polychitosan particles. Further, the chitosan fine particles may include: chemically modified polychitosan fine particles, partially chitosanized, polychitosan fine particles crosslinked with epoxy groups, etc. For example, the polymethylmethacrylate-coated microparticles obtained by emulsion polymerization, etc., and the composite polychitosan particles of organic or inorganic powder, and the polychitosan / vinyl polymer composite microparticles obtained by reverse-phase suspension polymerization, etc. The particle size of the chitosan fine particles used in the present invention * has an average particle size of 0 ′ 0 1 to 50 W Π1 * preferably like 0.  1 ~ 3.  0 w, and more preferably 1 ~ 30 «ια. If the average particle size exceeds 50um, it will produce -21 when coated on the skin rot-This paper size is applicable to the Chinese national standard (〇 奶) 8.4 regulations / block (210 乂 297 mm) —------- --Installation--(Please read the notes on the back before filling this page) -β Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Γ 41948 4 Α7 Β7 V. Description of the invention (19) Vary and confused Not good. In addition, if the average particle size is lower than K, it will be difficult to prepare the product, and it will be unfavorable because of a rough feeling when applied to the skin. Here, the average particle diameter is a K-laser diffraction type particle size distribution measuring device (U -1 0 0. (Η 0 R I Β Α device), obtained by measuring a 1 weight Si ethanol solution of polychitosan fine particles at room temperature. The effective amount of amine groups of the polymethylin fine particles used in the present invention is preferably 1.0 × 10-7 ~ l. ox 10_2mol / g, more preferably 1. 0X 1〇_θ ~ 1. 0X 1 0-2 mo 1 / s, but it is better to obtain sufficient deodorant effect. The effective amount of amine groups (mol / s) of the polychitosan particles here is based on the number of amine groups of the carboxylic acid and salt in the unit weight of the microchitosan particles. After adding 2 × 10 to 4 mol of 4-phenylbutyric acid per liter of hexane or ethanol to dissolve the microparticles, the filter membrane Uembrane fi 1 te ") was filtered, and the filtrate was measured by UV measurement (λ« H x = 2 1 0 n iu). The specific surface area of the chitosan particles used in the present invention is preferably 10 to 300m2 / s, more preferably 30 to 300ra2 / s, and particularly preferably 50 to 300ra2 / g. However, M can be obtained A sufficient deodorizing effect is better. Here, the specific surface area is obtained by using a flow-type specific surface area automatic measurement device (flow adsorption 2300 type, manufactured by Shimazu) by the BET 1-point method, and the higher specific surface area means the fine particles. It is multi-ft. If the molecular weight of the chitosan microparticles used in the present invention takes into account the strength of the microparticles, the average weight of the weight is preferably IX 103 to IX 10 β. Here, GPC is used as the weight average molecular weight, and M0 . 5M acetic acid solution (0. 5M acetic acid + 0, 5M sodium sulfonate) was used as the dissociation solution. The &gt; molecular weight is calculated by P E G conversion. (Please read the precautions on the back before filling in this page) -22- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297mm) 41948 A7 B7 V. Description of the invention (2〇 又 &gt; This is available Colloidal titration of crustose and vinegar using an 8-benzene agent complex. The alkyl group of the present invention * or molecular childhood> will remain on the skin because it remains on the skin. Also, the average carbon number is in the hair, and it is shown in the invention of the structure. The degree of deacetylation of the polychitosan particles used should be more than 80% of the sufficient deodorizing effect. Here * the degree of deacetylation is based on the use of toluidine blue as an indicator and the titration of the polyacrylic acid aqueous solution with potassium polysulfate. It can also be determined by the following method: the indicator amine-1-acelidene sulfonate to form a chitosan-indicator for fluorescence measurement. The $ polysiloxane used in the side chain or Both ends have a long chain and the melting point is only required to be above 20 *, but there is no special requirement on the carbon enemy of the alkyl chain. If the melting point is below 20 t: or less, it will be melted when applied to the skin temperature of Pippi * to become oily , Easy to flow, sticky, difficult to Γ #, can not make the deodorant effective In the present invention, the long-chain alkyl group refers to those with an average carbon number of 16 or more; those with an average carbon number of K 30 or more are preferred. * Average carbon numbers are more preferably from 40 to 70. The polyoxaxane used The better ones are those with a melting point of 60 to 1 4 0 t, which have long-chain alkyl groups at both ends, especially polysiloxanes having the formula (I) below. CH3

CH (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製CH (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Si — (CH2)„ —CH3 (I CH3-(CH2)n——Si-0 卜 Si —I V Ich3 xch3 (式中*n為長鏈烷基之平均碳數、亦即U + l)為30以上 之數目，m為0以上之數目，無特別限定，但，宜為10 0 〜5 0 0 0。何故，若m為1 0 0 Μ上，被膜之透濕性、柔軟性 23 本紙張尺度適用中國國家標準（CNS ) Α4規格（2丨0 X 297公釐） &lt; 41 948 4 A7 B7 經濟部中央標準局員Η消費合作.杜印製 五、發明説明（21 ) 會更良好。又，化合物粘度而引起的調配性亦在5000以下 為佳。同理，更佳為200〜5000)。 本發明所使用之聚矽氧烷像在白金等之觸媒存在下使 1 -烯烴與具有矽一氫鍵之聚二甲基矽氧烷反應而製得。但 ，若以此合成法合成於上述通式（I )所表示之兩末端具有 長鏈烷基之聚矽氧烷*很難得到高融點之長鏈垸基變性聚 二甲基眇氧烷。亦即*於上述通式（I )所示之兩末端具有 長鏈烷基的聚矽氧烷*係以一於分子兩末端具有氫原子之 聚矽氧烷作為原料 &gt; 且於白金等觸媒存在下，使卜烯烴反 應而得，但因作為原料之1-烯烴的分子量受到限制，例如 很難得到融點6 0 t: Μ上之髙融點的長鍵皖基變性聚二甲基 矽氧烷。又*若使用高分子量1-烯烴，因要除去殘存之 卜烯烴、觸媒很困難，故上述之合成方法不佳。因此*於 上述通式（I )所示之兩末端具有長鍵烷基的聚矽氧烷 &gt; 本 發明人等已發捤且宜依已申請專利之牡特願平6- 6 9478號 .說明書記載的長鏈烷基變性聚矽氧烷的合成法進行合成。 亦即*於乙烯之活性聚合後所得到的活性聚乙烯與環狀矽 氧烷反應，進而》使環狀聚二甲基矽氧烷、末端具有矽烷 基之鏈狀聚二甲基矽氧烷或此等之混合物在觸媒存在下進 行聚合*可再現性能地合成兩末端具有長鏈烷基之聚二甲 基矽氧烷。 如此所合成之兩末端具有長鏈烷基之聚矽氧烷 &gt; 因於兩 末端具有融點高的结晶性烷基，可承受高氣溫時期之流落 ，且可使除臭劑之有效成分長時間定著於皮虜上。又’因 (請先閲讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） J 419484 A7 經濟部中央榇準局貝Μ消費合作社印製 _B7_____五、發明説明（22 ) 只在兩末端具有長鏈烷基，可將氣體或水蒸氣透過性高之 砂氧烷部分以高比率保持於分子中，亦具有不阻礙皮虜呼 吸、皮虜乾燦之特徵u因此，於本發明中’尤宜為在如此 之兩末端具有長鏈烷基之聚矽氧烷。 本發明之化粧料係含有以上述之方法所得到的兩性多孔 性徽粒子。本發明之化粧料中的兩性多孔性微粒子的含量 ，若考慮除臭效果及調配安定性，宜為0·〗〜70重量％ ， 尤以10〜60重量％為佳。 於本發明中*化粧料可舉例制汗劑、除臭劑、潤旖劑、 保濕劑等之皮慮化粧料或毛髮化粧料，但*尤以使用來作 為除臭劑為佳。 使用本發明之化粧料作為除臭劑時，可調配从注公知之 任意成分。此任意成分可舉例如氧化鉾、氧化鎂等之金屬 氧化物、鋁氫氧氣化物、磺酸基碳酸鋅等之制汗收斂劑、 異丙基甲基酚、三氯二苯腺、桑后卓（sanizol)等之殺菌 劑、滑石‘、阿米赫普（了 ί水-歹）、耐隆粉末等之板狀、 球狀粉體、凡士林+、白地蠘、高鈒脂肪酸、高級醇等之固 態、半固態油劑、角鯊烯、酯油、二甘油酯、矽酮油等之 流動油劑、聚丙烯酸納、聚乙烯醇、甲基纖維素等之水溶 性聚合物、乳酸、琥珀酸等之有機酸、甘油、山梨糖醇等 之保濕劑、甘油基抑細胞素酸二評、尿囊素等之濟炎劑、 其他、增粘劑、界面活性劑、色素、香料、冷感劑等，在 無損於本發明目的之範圍均可調配。尤其 &gt; 宜含有可分散 兩性多孔性微粒子之油劑，油劑之含量宜在除臭劑中為 - - I- I - nn I - —I 1 H^I I I ^^^1 (^^1 - - I^OJ » I (請先閲讀背面之注意事項再填寫本頁) -25- 本紙張尺度逋用中國國家標隼（CNS ) A4現格（210X 297公釐} (419484 A 7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（23 ) 10〜90重蠆％。 本發明之化粧料的使用形態無特別限定*可舉例化粧水 、飛沫劑、粉末、軟费·、乳霜、濶膚、肥皂、洗髮精等之 形態。 本發明'除臭劑中之聚甲殻糖微粒子的調配蠆*若考慮除 臭效果及調配安定性，宜為0.1〜50重量3：，更佳為1〇〜 50重量％ ，尤宜為20〜50重量3：。 本發明之除臭劑中，進一步可調配習知公知的任意成分 。此成分可舉洌如氧化鋅、氧化銕等之金屬氧化物、鋁氫 氧氯化物、丹寧酸等之制汗劑、三氯羥基二苯基醚（三克 勞酸）、異丙基甲基酚、三氯二笨脲、桑尼卓（sa n i zo 1 ) 等之殺菌劑或香料等之遮蔽劑等。2 ，油劑可舉Μ如二甲 基矽氧烷、揮發性環狀矽等之矽酹油、高鈒脂肪酸酯、 蠟、硬脂醇等之高級醇等；保濕劑舉例如甘油、山梨糖醇 等；界面活性劑可舉钶如硬脂酸納等之金屬皂、山梨聚糖 脂肪酸酯等之非離子活性劑等·，防腐劑可舉例如甲基對控 苯甲酸、丁基對羥苯甲酸、丙基對羥苯甲酸等；粉體可舉 例如耐隆粉末、滑石等；消炎劑可舉例如甘油基抑细胞素 酸二鉀、尿囊素、癒創舆等；增粘劑可舉例如聚丙烯酸納 、聚乙烯醇、甲基纖維素、膨土、水輝石等；色素可擧例 如綠色3號、藍色1號、黃色4號、黃色5號；其他如收 斂劑等。 本發明之除臭劑的使用形態並無特限定，可舉例化粧水 、飛沫劑、粉末、軟甭、乳霜等的形態。 -26- 本紙張尺度適用中國國家標準（CNS &gt; A4規格（2丨〇&gt;&lt;297公釐） (請先閲讀背面之注意事項再填寫本頁) .丨表· 經濟部t央榡準局員工消費合作社印製 (4194 8 /1 ΑΊ Β7 五、發明説明（2斗） 本發明中所使用之具有融點2〇 υ以上長鍵烷基的聚矽氧 烷中長鏈烷基部分之比率，合計宜為0.5〜40重量$ ，更 宜為1〜40重量：《 。此比率超過40重童％時，被膜之透濕 性、柔軟性會惡化•若在0 . 5重量％ Κ下*特別是高溫時 因皮脂等而易流落、粘滞、殘存於皮_上。 本發明之除臭劑中具有融點2 ο υ κ上長鏈烷基的聚矽氧 烷之調配量會因使用形態、調配形態而異》但為〇. 〇 1〜 99重量％的範圍，Ml〜70重量％的範圍為佳。此調配量 不足0 . 0 1重量3ί時，除臭劑中所含有之有效成分無法持績 滯留於皮臏上，且不能得到除輿效果之持續性，若超過 99重量；S *有效成分之調配量會變少，很難得到除臭效果 〇 本發明之除臭劑甩調配公知之任意成分 &gt; 各別之成分可 持續滯留於皮樓上 &gt; 高溫時•即使於發汗時等之苛酷條件 下 &gt; 經過長時間亦可持續除臭效果。調配成分之具體例可 擧例鋁氫氧氯化物、酚磺酸鋅等之收斂劑、異丙基甲基般 、三氮二苯脲、桑尼卓（sa n i ζο 1 )等之殺菌劑、滑石、阿 米赫普7)、耐隆粉末等之粉體。 又，本發明之除臭劑因含有鹼性物質而可於被腹中捕捉 造成體臭原因之有機酸，能得到高除臭效果。鹼性物質之 例可舉例如氧化鋅、氧化鎂等之金屬氧化物等的無抗物、 具有聚甲殼糖等之胺基的有機化合物等。本發明除臭劑中 的鹼性物質調配量，若考if除臭效果及調配安定性，Κ 0 . 1〜70重量％為佳。 -27- 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先聞讀背面之注意事項再填寫本頁) 装· 訂 i 419484 ΑΊ Β7 經 濟 部 中 央 榡 準 扁 Ά X ί 合 作 社 印 % 五、發明説明（25 ) 又，於本發明之除臭劑中調 述鹼性物質，可使高除臭效果 構雖不很明確，但，於一形成 基的變性聚矽氧烷之柔軟且疏 子會分散*油性即有機酸會擴 性微粒子捕捉。此疏水性被膜 很強、透濕度亦高，故顯示出 溫多濕環境部位之使用、夏季 優異之除臭效果。 此兩性多孔性微粒子可依如 使一具有以聚甲殼糖為首之胺 甲基丙烯酸為首之反應性乙烯 行乳化或懸浮聚合。 本發明除臭劑中之兩性多孔 除臭效果及調配安定性，宜為 本發明之除臭劑其他的成分 、其他油性原料等。但調配量 明效果。 本發明之除臭劑係可將具有 基的聚矽氧烷及其他成分混合 亦須加熱溶解。 本發明之除臭劑可以軟赍、 之形態來使用。 〔發明之效果] 配前述多孔性微粒子作為上 捋縝極長時間，故佳。此機 具有融點20 &quot;C Κ上之長鏈烷 水性被膜中兩性多孔性微粒 散於被膜中，並被兩性多孔 因對於本自汗、外部的水分 對腋、足、頸、胸等經常高 游泳、蓮動時之使用具特別 下得到，即在疏水性溶劑中 基的鹼性多糖、與一具有以 基的有機酸單體之水溶液進 性微粒子的調配嗇 &gt; 若考慮 0.1〜70重量％。 可調配界面活性劑、醇、水 、調配方法係須無損於本發 前述融點20 t:以上之長鍵烷 、攪拌而得到，但依情況而 飛沫、噴霧、乳箱、乳液等 -28 本紙張尺度適用中國國家標準（CNS &gt; A4規格（21〇Χ297公釐） 經濟部中央樣準局貝工消費合作社印製 ! 4194 8 4 A? _______________B7_五、發明説明（％ ) 本發明之多孔性微粒子為弱酸與弱鹼之兩性微粒子，此 微粒子為一M酸性高分子使鹼性多糖内部交聯之多孔性微 粒子’且，在非極性及極性溶劑中，可與強鹼或強酸進行 簡單反應，興有於内部可捕捉此等物質之能力。又，在不 同極性之各種溶劑中，不可進行溶化，並能保持粒子形狀 。進而，K天然材料為基材之本發明多孔性微粒子*因不 使用交聯劑，故具安全性，當然可用於皮潘化粧品（制汗 劑、除臭劑、潤虜劑、保濕劑）、毛髮化粧品等之化粧品 /香粧品的領域*亦可使用於凿療品。進而，亦可用於纖 維處理劑、紙加工劑、水泥添加劑、被覆材料、殺菌/靜 菌劑、農藥等。 [圖面之簡單說明〕 圖1條用以計算合成例1所得到之聚甲殼糖微粒子的有 妷胺基量，為4 -苯基酪酸殘留率（Y)對每一聚甲殼糖微粒 子1 s之4 -苯基酪酸添加量（X)的對數表。 〔實施例〕 其次*嵌兩性多孔性微粒子之製造實施例、及其除臭劑 配方例進一步詳细說明本發明 &gt; 担本發明不限於下述之實 施例及配方例。 又，例中，只要無特別記載乃為重量基準。 實施例1 於市售之聚甲設糖〔甲陽化學（股）製S Κ - 10 、脫乙醯 化度35〜88¾ 、重量平均分子量130000] 80s中加人水Μ 成為900g&gt;再加人甲基丙烯酸34.5g(相對聚甲殼糖之單糖 1 1 n ^^^1 - -. - - I*^, I ma nn ^^^1 V* 牙-5 » * (請先閱讀背面之注意事項再填寫本頁) -29- 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） 經濟部中央標準局貝工消費合作社印製 ’4194 8 4 a7 ______^--- 五、發明説明（27 ) 單元為等箅量），在s 〇 t：下一面禊拌一面溶解，以調製聚 甲設糖/甲基丙烯酸水溶疲。於其中，加入一'使過硫酸狎 3 s溶於離子交換水1 0 〇 s而形成者，在常溫下伴數分鐘° 以5/5之比率（容積比）混合聚甲設糖經液與山梨聚糖 單月桂酸酯之1.0重量％環己烷溶液·再从均質機進行高 速播拌（15000 rpra)，俾形成W/0乳液° 其次，在70 下進行聚合反應2小時後’冷卻至常溫’ —面播拌一面滴入5倍莫耳蜃（容稹）之乙醇中’搜梓 30分鐘後，Μ傾析除去凝集物，再於乙醇中浸潰/搜泮後 ，進行努氏過溏之步驟重複3次，藉真空乾燥得到微粒子 。所得到之微粒子的粒徑/形態等歸納於表1中。 實施例2 於實施例1中 &gt; 使甩6 9 . 3 s之甲_丙®酸（相對聚甲殼 糖之單糖單元為2倍箅耳量）取代甲基丙婦酸34·6κ &gt;且 同於實施例1之製法而得到微粒子。所得到微粒子之粒徑 /形態等歸納於表1中。 實腌例3 於實施例1中，使用5 1 · 9 g之甲基丙烯酸（相對聚甲殼 糖之簞糖單元為1.5倍莫耳量）取代甲基丙稀酸34&gt;6s * 旦同於實施例1之製法而得到微粒子。所得到微粒子之粒 徑/形態等歸納於表1中。 實施例4 於實施例1中*使甩26.0g之甲基丙烯酸（相對聚甲殼 糖之單糖單元為0.75倍莫耳量）取代甲基丙婦酸34.6s ， -30- 本紙張尺度適用中國國家標準(〉Μ規^ ( 210'χ：297公釐） u ak^i m I i I - — - Hi ^^^1 Hr 一ei *k (請先閲讀背面之注意事項再填寫本頁) 經濟·部中央標準局負工消费合作社印製 f 4194 6 4 Α7 ___Β7_______ 五、發明説明（28) 且同於實施例1之製法而得到微粒子。所得到微粒子之粒 徑/彤態等歸納於表1中。 實施例5 於簧施例1中，使用2 S . 0 s之甲基丙烯酸（相對聚甲殻 糖之單糖簞元為〇·75倍莫耳量）與6g之醋酸（相對聚甲殼 糖之單糖單元為0.25倍莫耳量）取代甲基丙烯酸34.6s ， 且同於實腌例1之製法而得到微粒子。所得到微粒子之粒 徑/形態等歸納於表1中。Si — (CH2)… —CH3 (I CH3- (CH2) n—Si-0 and Si—IV Ich3 xch3 (where * n is the average carbon number of the long-chain alkyl group, that is, U + l) is 30 The above number, m is a number of 0 or more, but it is not particularly limited, but it is preferably 10 0 to 5 0 0. Why, if m is 100 M, the moisture permeability and softness of the film are 23 paper standards Applicable to China National Standard (CNS) Α4 specification (2 丨 0 X 297 mm) &lt; 41 948 4 A7 B7 Member of the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperation. Du printed 5. The invention description (21) will be better. Also, The compounding property caused by the viscosity of the compound is also preferably below 5000. Similarly, it is more preferably 200 to 5000). The polysiloxane used in the present invention, in the presence of a catalyst such as platinum, makes 1-olefin and silicon It is produced by the reaction of one hydrogen-bonded polydimethylsiloxane. However, it is difficult to obtain a polysiloxane having a long-chain alkyl group at both ends represented by the general formula (I). High melting point long-chain fluorenyl-denatured polydimethyl oxane. That is, a polysiloxane having a long-chain alkyl group at both ends shown in the general formula (I) above. Polysiloxane with a hydrogen atom at the end as a raw material> It is obtained by reacting olefin in the presence of a catalyst such as platinum, but the molecular weight of 1-olefin as a raw material is limited, for example, it is difficult to obtain a melting point of 60 t: Long bond Wan-based denatured polydimethylsiloxane with melting point on M. Also, if high molecular weight 1-olefin is used, it is difficult to remove the remaining olefin and catalyst, so the above synthesis method Not good. Therefore * Polysiloxane having long-bond alkyl groups at both ends represented by the above general formula (I) &gt; The present inventors and others have already issued and should apply according to patent application No. 6-6 No. 9478. Synthesis of the long-chain alkyl-denatured polysiloxane described in the specification. That is, the living polyethylene obtained after the living polymerization of ethylene reacts with the cyclic siloxane, and the cyclic polysiloxane is further polymerized. Dimethylsiloxane, chain polydimethylsiloxane with silane groups at the end, or a mixture of these are polymerized in the presence of a catalyst. * Reproducible synthesis of polydimethyl methoxides with long chain alkyl groups at both ends Polysiloxane with long-chain alkyl groups at both ends &gt; Because both ends have crystalline alkyl groups with a high melting point, they can withstand the high temperature period, and the active ingredients of the deodorant can be fixed on the skin for a long time. And '因 (Please read the back first Note: Please fill in this page again.) The size of the paper is applicable to China National Standards (CNS) A4 (210X297mm) J 419484 A7. Printed by the Central Bureau of Standards, the Ministry of Economic Affairs, and the BM Consumer Cooperative. 22) It has long-chain alkyl groups only at both ends, which can keep the oxaxane portion with high gas or water vapor permeability in the molecule at a high ratio. It also has the characteristics that it does not hinder the breathing of the skin and the skin is dry. In the present invention, 'particularly, it is a polysiloxane having a long-chain alkyl group at both ends. The cosmetic material of the present invention contains amphoteric porous emblem particles obtained by the above-mentioned method. The content of the amphoteric porous fine particles in the cosmetic of the present invention is preferably from 0 to 70% by weight, and more preferably from 10 to 60% by weight, in consideration of deodorizing effect and stability of formulation. In the present invention, * cosmetics can be exemplified by skin care cosmetics such as sweats, deodorants, emollients, humectants, or hair cosmetics, but it is particularly preferred to use them as deodorants. When the cosmetic of the present invention is used as a deodorant, any of the known ingredients can be formulated. Examples of such optional components include metal oxides such as hafnium oxide, magnesium oxide, aluminum hydroxides, sulfonic acid zinc carbonate, and the like, acrylamide, isopropyl methylphenol, trichlorodiphenyl gland, and sangzhuozhu. (Sanizol) and other fungicides, talc ', Ami Hep (Li water- 歹), plate-like powder, spherical powder, petroleum jelly +, white ground tincture, high fat fatty acid, higher alcohol, etc. Solid, semi-solid oils, mobile oils such as squalene, ester oils, diglycerides, silicone oils, water-soluble polymers such as sodium polyacrylate, polyvinyl alcohol, methyl cellulose, lactic acid, succinic acid Organic acids, glycerin, sorbitol, etc., humectants, glyceryl cytosolic acid second evaluation, allantoin, etc., inflammation inhibitors, others, thickeners, surfactants, pigments, flavors, cold sensation agents Etc., can be adjusted within a range not detrimental to the purpose of the present invention. Especially &gt; An oil agent containing dispersible amphoteric porous fine particles should be contained, and the content of the oil agent should be--I- I-nn I--I 1 H ^ III ^^^ 1 (^^ 1- -I ^ OJ »I (Please read the notes on the back before filling out this page) -25- This paper size uses Chinese National Standard (CNS) A4 now (210X 297 mm) (419484 A 7 B7 Ministry of Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 5. Description of the invention (23) 10 to 90% by weight. There is no particular limitation on the form of use of the cosmetic material of the present invention. * Examples include lotions, sprays, powders, soft charges, creams. , Skin, soap, shampoo, etc. The formulation of the "chitosan fine particles in the deodorant" of the present invention * If considering the deodorizing effect and the stability of the formulation, it is preferably 0.1 to 50 weight 3: better It is 10 to 50% by weight, and particularly preferably 20 to 50% by weight. 3: The deodorant of the present invention may further be equipped with any conventionally known and well-known ingredients. The ingredients may include metals such as zinc oxide, hafnium oxide, and the like. Sweat-making agents such as oxides, aluminum hydroxide chloride, tannin, trichlorohydroxydiphenyl ether (tri-claurate), isopropyl Methyl phenol, trichlorobenzyl urea, sa ni zo 1 and other fungicides or masking agents for perfumes, etc. 2, oil agents such as dimethyl siloxane, volatile cyclic Silicone oils such as silicon, higher alcohol fatty acid esters, waxes, and higher alcohols such as stearyl alcohol; humectants such as glycerin, sorbitol, etc .; surfactants such as metal soaps such as sodium stearate , Sorbitan fatty acid esters and other non-ionic active agents, etc., preservatives such as methyl para-benzoic acid, butyl para-hydroxybenzoic acid, propyl para-hydroxybenzoic acid, etc .; powders such as Nalon Powder, talc, etc .; anti-inflammatory agents can be, for example, dipotassium glycerostatin, allantoin, guaiacine, etc .; thickeners can be, for example, sodium polyacrylate, polyvinyl alcohol, methyl cellulose, bentonite, Gypsum and the like; pigments can be, for example, green No. 3, blue No. 1, yellow No. 4, yellow No. 5; others such as astringent, etc. The use form of the deodorant of the present invention is not particularly limited, and examples include lotions, Forms of droplets, powders, soft creams, creams, etc. -26- This paper size applies to Chinese national standards (CNS & g t; A4 specifications (2 丨 〇 &gt; &lt; 297 mm) (Please read the precautions on the back before filling out this page). Tables · Printed by the Ministry of Economic Affairs t Central Government Procurement Bureau Employee Consumption Cooperative (4194 8/1 ΑΊ Β7 V. Description of the invention (2 buckets) The ratio of the long-chain alkyl moiety in the polysiloxane having a long-bond alkyl group having a melting point of 20 ° or more used in the present invention is preferably 0.5 to 40% by weight, More preferably from 1 to 40 weight: ". When this ratio exceeds 40 weight percent, the moisture permeability and softness of the film will deteriorate. If it is 0.5% by weight, it is easy to flow off due to sebum, etc., especially at high temperatures. , Sticky, remaining on the skin. In the deodorant of the present invention, the blending amount of the polysiloxane having a long-chain alkyl group on the melting point of 2 ο υ κ will vary depending on the use form and the blending form, but it is in the range of 0.01 to 99% by weight, A range of M1 to 70% by weight is preferred. When this blending amount is less than 0.01 weight 3 liters, the effective ingredients contained in the deodorant cannot be retained on the skin for a long time, and the continuity of the deodorizing effect cannot be obtained, if it exceeds 99 weight; S * the effective ingredient The blending amount will be reduced, and it is difficult to obtain a deodorizing effect. The deodorant of the present invention is blended with any of the well-known ingredients &gt; The individual ingredients can remain on the leather floor &gt; at high temperatures and even under severe sweating Under conditions &gt; The deodorizing effect can be sustained over a long period of time. Specific examples of the compounding ingredients include astringents such as aluminum hydroxide chloride, zinc phenolsulfonate, isopropylmethyl, triazodiphenyl urea, bactericides such as sa ni ζο 1, Powders of talc, Ami Hep 7), Nylon powder, etc. In addition, the deodorant of the present invention can capture an organic acid that causes body odor in the abdomen because it contains an alkaline substance, and can obtain a high deodorizing effect. Examples of the basic substance include non-resistant substances such as metal oxides such as zinc oxide and magnesium oxide, and organic compounds having an amine group such as polychitosan. The blending amount of the alkaline substance in the deodorant of the present invention, if considering the deodorizing effect and the stability of blending, K 0. 1 to 70% by weight is preferred. -27- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page) Binding and binding i 419484 ΑΊ Β7 Central Ministry of Economy X ί Cooperative seal% V. Description of the invention (25) In addition, the basic substance is described in the deodorant of the present invention, although the structure of the high deodorizing effect is not very clear, but the modified polysilicon formed in a base Oxygen is soft and sparse, and it disperses. * Oily, that is, organic acid will expand and capture fine particles. This hydrophobic coating is very strong and has a high moisture permeability, so it shows excellent deodorizing effects in the use in warm and humid environments. The amphoteric porous fine particles can be subjected to emulsification or suspension polymerization, such as reactive ethylene having amine methacrylic acid such as polychitosan. The amphoteric porous deodorizing effect and stability of the deodorant of the present invention are preferably other components of the deodorant of the present invention, other oily raw materials, and the like. However, the amount of blending has obvious effects. The deodorant of the present invention can be mixed with a polysiloxane having a base and other components, and must be dissolved by heating. The deodorant of the present invention can be used in the form of soft scabs. [Effects of the Invention] It is preferable to mix the porous fine particles as the upper particles for a long time. This machine has a melting point of 20 &quot; C KK, long-chain alkanes in the aqueous coating film. The amphoteric porous particles are scattered in the coating, and the amphoteric porous layer is often used for the self-sweat and external moisture on the armpits, feet, neck, chest, etc. The use of high swimming and lotus movement is particularly obtained, that is, the preparation of basic polysaccharides in a hydrophobic solvent and the advancing microparticles of an aqueous solution containing an organic acid monomer based on a base. If we consider 0.1 to 70 weight%. Adjustable surfactants, alcohols, water, and the preparation method must not damage the aforementioned melting point of the hair 20 t: long bond or more obtained by stirring, but depending on the situation, droplets, sprays, milk boxes, emulsions, etc. Paper size applies to Chinese national standards (CNS &gt; A4 size (21 × 297 mm) Printed by the Shell Cooperative Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs! 4194 8 4 A? _______________B7_V. Description of the invention (%) Porosity of the invention Sexual microparticles are amphoteric microparticles of weak acid and alkali. The microparticles are porous microparticles of an M acidic macromolecule that internally cross-links basic polysaccharides. In addition, in non-polar and polar solvents, it can simply react with strong bases or strong acids. It has the ability to capture these substances in the interior. In addition, it cannot be dissolved in various solvents of different polarities and can maintain the shape of the particles. Furthermore, the porous particles of the present invention with K natural materials as the base material * Cross-linking agent is used for safety, of course, it can be used in the field of cosmetics / cosmetics such as Pippan cosmetics (perspirants, deodorants, emollients, moisturizers), hair cosmetics, etc. * It can also be used for chisel healing products. Furthermore, it can also be used for fiber treatment agents, paper processing agents, cement additives, coating materials, bactericidal / sterilizers, pesticides, etc. [Simplified description of the drawing] Figure 1 is used to calculate the synthesis The amount of amido groups of the polychitosan microparticles obtained in Example 1 is a logarithmic table of the 4-phenylphenyl butyric acid residual rate (Y) for the amount of 4-phenylphenyl butyric acid (X) added per 1 chitosan microparticles [Examples] Next, the production examples of the amphoteric porous fine particles and the deodorant formulation examples will be described in detail. The present invention is not limited to the following examples and formulation examples. As long as there is no special record, it is based on weight. Example 1 Add commercially available polymethionose [S K-10 by Koyo Chemical Co., Ltd., deacetylation degree 35 ~ 88¾, weight average molecular weight 130000] 80s Human water M becomes 900 g &gt; and 34.5 g of human methacrylic acid (relative to the monosaccharide of chitosan 1 1 n ^^^ 1--.--I * ^, I ma nn ^^^ 1 V * 牙 -5 »* (Please read the notes on the back before filling out this page) -29- This paper size applies to China National Standard (CNS) A4 Specifications (210X297 mm) “4194 8 4 a7 ______ ^-” printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (27) The unit is the same amount), at s 0t: the next side Dissolve on one side to adjust the water solubility of polymethoxide / methacrylic acid. To this, add a 'sodium persulfate 3 s dissolved in ion-exchanged water for 10 s to form, with a few minutes at room temperature ° 5 The ratio of / 5 (volume ratio) was mixed with a 1.0% by weight cyclohexane solution of polymethoxide menstrual fluid and sorbitan monolaurate, and then mixed at high speed (15000 rpra) from a homogenizer to form W / 0. Emulsion ° Secondly, polymerization was carried out at 70 ° C for 2 hours and then 'cooled down to normal temperature'-noodles were dropped and dropped into 5 times more molasses (volume) in ethanol. After searching for 30 minutes, M was decanted to remove aggregates. After being immersed / searched in ethanol, the process of Knooping is repeated 3 times, and fine particles are obtained by vacuum drying. The particle size, morphology, and the like of the obtained fine particles are summarized in Table 1. Example 2 In Example 1 &gt; Substitute 6-9. 3 s of formazan-propionic acid (2 times the amount of monosaccharide units relative to the chitosan monosaccharide unit) to replace methylpropionic acid 34 · 6κ &gt; The same method as in Example 1 was used to obtain fine particles. The particle size / morphology and the like of the obtained fine particles are summarized in Table 1. Actual pickling example 3 In Example 1, 5 1 · 9 g of methacrylic acid (1.5 times the molar amount of polysaccharide unit of chitosan) was used in place of methyl acrylic acid 34 &gt; 6s. Fine particles were obtained by the method of Example 1. The particle diameter / morphology and the like of the obtained fine particles are summarized in Table 1. Example 4 In Example 1 * 26.0g of methacrylic acid (0.75 times moles relative to the monosaccharide unit of polychitosan) was substituted for 34.6s of methacrylic acid, -30- This paper size applies to China National Standard (> M Regulation ^ (210'χ: 297 mm) u ak ^ im I i I---Hi ^^^ 1 Hr ei * k (Please read the precautions on the back before filling this page) Economy · Printed by the Ministry of Standards and Technology ’s Consumer Cooperatives f 4194 6 4 Α7 ___ Β7 _______ V. Description of Invention (28) The same method as in Example 1 was used to obtain the microparticles. The particle diameters and states of the microparticles are summarized in Table 1. Example 5 In the spring example 1, 2 S. 0 s of methacrylic acid (with respect to the monosaccharide unit of polychitosan is 0.75 times the molar amount) and 6 g of acetic acid (relative to polychitosan The monosaccharide unit is 0.25 times the molar amount) in place of 34.6s of methacrylic acid, and fine particles are obtained in the same manner as in Production Example 1. The particle size / morphology of the obtained fine particles are summarized in Table 1.

實施例S 於實施例1中，使用肢基半乳糖（重童平均分子蠆20萬 )8 0 s取代聚甲殼糖’且同於實施例1之製法而得到微粒 子。所得到微粒子之粒徑/形態等歸納於表1中。 實施Μ 7 於實施例〗中’使用山梨聚糖單月桂酸_之5.0重量龙 環己烷溶疲取代山梨聚糖單月桂酸醋之1重量％環己烷溶 液，且同於實施例1之製法而得到微粒子。所得到微粒子 之粒徑/形態等歸納於表1中。 實腌例8 於實_例1中，使用丙烯酸（相對於聚甲殻糖之單糖單 元等舅耳量）取代甲基丙烯酸’且同於實施例1之製法而 得到微粒子。所得到微粒子之粒徑/形態等歸納於表、1中 0 實施例9 於實施例4中，在7 0 C下進行聚合反應3小時後，冷卻 -3卜 本紙張尺度適用中國國家標準（CNS ) Α4規格（2!〇X297公董) -UK i= I n^i I - - I I ^^1 - - . 1^1 - - . I -« {請先閲讀背面之注意事項再填寫本頁) 419484 A7 經濟部中央橾準局員工消费合作社印製 ______B7_五、發明説明（29 ) 至常溫，K 0 ‘ 〇 5 N (當量）H a Ο Η水/異丙醇（1 / 5 V ο 1 / V ο 1) 溶液進行中和反應，使出9 . 0為終點。以異丙醇反複洗淨 /過溏3次，進行真空乾燥*得到微粒子。所得到之微粒 子的粒徑/形態等歸納於表1中。 比較例1 於市售之聚甲殼糖〔甲陽化學（股）製SK-10 、脫乙_ 化度85〜88¾ 、重量平均分子量1 30 0〇〇〕δ(^中加人水Κ 成為900s，再加人甲基丙烯酸34.Ss(相對聚甲殼糖之簞糖 單元為等舅量） &gt; 在60t：下一面攫拌一面溶解，K調製聚 甲骹糖/甲基丙烯酸水溶液。 於此聚甲殼糖溶疲125g中加人離子交換水435g*再加人 山梨聚糖犟月桂酸酷之5.0重量S：並潖合之，添加聚合開 始蜊之過硫酸鉀〇 · 7 3 g &gt;在7 0 π下進行聚合反應5小時後 ，冷卻至常溫，一面播拌一面滴入5倍莫耳（容積）之乙 醇中.播拌30分鐘後，以傾析除去凝集物*再於乙醇中浸 漬/攪拌後，進行努氐過濾之步驟重複3次*藉真空乾燥 得到粒體。所得到之粒體的粒徑/形態等歸納於表1中^ 比較例2 於此較例1中*除使用丙烯酸（相對於聚甲殼糖之_糖 單元為等Μ耳量）取代甲基丙烯酸以外，其餘同於比較例 1而得到粒體。所得到之粒體的粒徑/形態等歸納於表1 中〇 - - PH n I l n^i nn I I In、)··&quot; 1 1 (請先閲讀背面之注意事項再填寫本頁) -32- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公嫠） 經濟部中央標準局員工消費合作社印製 ί 41 948 4 Α7 __Β7 五、發明説明（5〇) N3 — CO 〇〇 -vj cn CO ro 1—* 聚甲殼糖 聚甲殼糖 m •a 薇 聚甲骰糖 聚甲骹糖 :聚胺基 i半乳糖 i 聚甲殻糖 聚甲殼糖 聚甲殼糖 聚甲殻糖 聚甲骹糖 鹼性多槌 寒 碎 丙烯酸 甲基 丙烯醃 甲基 丙烯酸' 丙烯酸 ai书 mm 漭 甲基 丙烯酸 甲基 丨丙烯酸 甲基 丙烯酸 甲基 丙烯酸 甲基 丙晞酸 田甚 丙烯酸 5¾ © | 1倍莫耳 1倍箅耳 0.75 倍莫耳 1倍莫耳 1倍莫耳 1倍莫耳 0.75 倍轉耳 0. 75 倍«耳 L5 倍莫珲 2倍莫耳 1倍莫耳 調配最u 醋酸 槌類 -其他之混合酞 0. 25 掊箅耳 調配贵η 水溶液 水溶液 ____ _______ 環己烷 . 環己烷 . ____ |環己烷 環己烷 環己烷 環己烷 .1 環己烷 _____1 環己烷 環己烷 疏水性 山梨聚糖單 月桂酸醋 {ί梨聚糖單 月桂酸酯 山梨聚糖羅 月桂酸酯 裳缴 m 山梨聚糖麗| 月桂酸醋 山梨聚糖簞 月桂酸酯 山梨聚糖單1 月桂醃酯 ..............1 山梨聚糖康_ 月桂酸酯 山梨聚糖單 月桂酸酷 山梨聚糖單 月桂酸酷 山梨聚糖簞 月桂Sf醋 活性劑 〇 〇 〇 〇 〇 〇 〇 CD on 〇 〇 〇 ro ◦ 〇 〇 CZ5 〇 〇 〇 &lt;3&gt; 活性劑 mis: (90 不定形 不定形 真球状 1 Μ球状 真球状 真球状 Μ球状 W球状 真球状 ........... 真球状 寘球状 u 〇 〇 〇 〇 CO οο 〇〇 〇〇 〇 二 ΓΟ c筠书 to — ro Ln ο ο 02 Co ΟΪ Ο -ο tSD C75 CO CJ1 ΟΠ 〇 比-¾ 而桢 (mVf；) 水泣液 St合 金1液 逆相懸浮 Φ箱処理 ir浮 靈2懸浮 m賴 n&gt;a ir浮 ir浮 賽r浮 〇t&gt;'S hH -33_ ---------衣—-----訂 - 1 (請先聞讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（2iOX297公釐） 419484 A7 B7 ----- 經濟部中央標準局貝工消費合作社印製 五、發明説明（51 ) 註） *1:每一鹼性多糖之單糖簞元I的莫耳量 其次表示含有本發明兩性多孔性球狀微粒子之除臭劑$ 配方例。 又，於Μ下之配方例中*除臭試驗係Κ如下所示之方法 實施。 〈除臭試驗方法〉 從健康男性（20〜40歲）選取腋及腳很臭的人並依專門 評定小姐4人的官能評價進行評價。首先，上班後（約 9:00左右）依專門評定小姐4人進行官能評價，評價後Κ 各配方例所調製之除臭劑逋量塗布於軍側之腋及腳。進行 塗布後之臭味評價*傍晚回家前（約16:00左右）的臭味 評價。另一側之腋及腳作為對照而絲毫不塗布。評價係使 用下述之6階段評價，有關腋之臭味將專門評定小姐4人 之平均表示於配方例1〜5，而有翮腳之臭味方面則表示於 配方例6中。又，不採用本發明之兩性多孔性球狀的粒子 ，而Μ有關氧化鋅（比表面積50ra2/g)配方之評價結果作 為比較配方例。 評價基準 0 :不臭 1 :微臭 2 臭味弱 3 :明顯臭味 -34- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐} — I— I In I— I— I— I 1 n i - ^ (请先聞讀背面之注意事項再填寫本頁) 訂 ^ 41948 4 Α7 Β7 五、發明説明〇2 ) 4 :臭味很強 5 :臭味非常強 配方例1 除臭化粧水（己醇型） 調製下述姐成之除臭化粧水，將此化粧水塗布於腋下&gt; 進行除臭試驗。結果表示於表2。 &lt;姐成〉 兩性多孔性球狀微粒子（實施例9 ) 8 . 0% 兩性多孔性球狀微粒子（實施钶2 ) 2.0¾ 甘油 5.0¾ 水 10.0¾ 乙醇___7 5.0% 合計 100.0¾ 表2 _ I. I— -I In I - I - - - -i 1^1 ii ! 牙 i (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 P f f I 维布前 猞布後 冏家節 9 : 00左右 1 R ： 00 # ί； 本發明品 未塗布部 (對照） R B Η 塗布 3 比較品 (氬彳h鋅） 未塗布部 (對昭） 5 fi S 塗布部 4 4 配方例2 除臭化粧水（揮發性矽酮型） -35- 本紙張尺度適用中國國家榇準（CNS ) A4規格（210X297公嫠） 41948 4 A7 B7 五、發明説明（乃） 調製下述姐成之除臭化粧水，將此化粧水塗布於腋下， 進行除臭試驗。結果表示於表3 。 &lt;姐成&gt; 兩性多孔性球狀微粒子（實腌例9 ) 50.0% 異丙基肉豆蔻酸酯 5.0¾ 二甲基矽_ 5.0¾ 甲某聚砘氬糕_ 40.0¾ 合計 100.0% 表 3 (I fl 9 途布前 途布谤 间家前 9 : 00左右 16 : 00左右 本發明品 未塗布部 (對照） 5 5 飧布部 5 1 .·? 比較品 未塗布部 (對照） R 5 檢布部 5 _4 4 配方例3 除臭粉末飛沫（液狀飛沫型） 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 調製下述組成之除臭粉末飛沭，將此粉末飛沫塗布於腋 下，進行除臭試驗。結果表示於表4 。 &lt;姐成&gt; •原液 -36 - 本紙張尺度適用中國國家標準{ CNS ) A4規格（2丨OX297公釐） t 419484 A7 B7 五、發明説明（M ) 兩性多孔性球狀微粒子（實施例9) 40.0¾ 甘油 5.0¾ 異丙基肉豆蔻酸酯 5.0¾ 水 5.0¾ 7,輯___4 5.0% 合計 100.0¾ •充填 上述原液 35 . 0% LPG 氣體_fi Fi . 0 % 合計 100.0¾ 表 4 S__ 習 途布前 途布後 同家前 9 : 00左右 1fi : 00弁右 本發明品 未塗布.部 (對照） FS 5 维布邬 1 :i 比較品 未塗布部 (對照） Fi S E (氬彳h鋅） 淦布部 _^ 4 經濟部中央標準局員工消費合作社印製 ^^^1 ^^^^1 ^^^^1 ^^^^1 ^^^^1 ^^^^1 I 1 Ί &gt; 1 {請先閲讀背面之注意事項再填寫本頁) 配方.例4 除臭凝膠 調製下述姐成之除臭凝膠，將此凝膠塗布於腋下，進行 除臭試驗。結果表示於表5 。 -37- 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） ί 41948 4 Α7 Β7 五、發明説明（55 ) &lt;組成&gt; 兩性多孔性球狀微粒子（實施例9 ) 40.0¾ 羥乙基聚合物 1.0¾ 丙二醇 10.0¾ 三乙醇胺 1.0¾ 乙醇 30.0¾ 7k_18.0¾ 合計 100.0% 表 5 評 _ I 途布前 淦布總 冋家前 Q : 0 0左右 18 : 00左右 本發明品 未塗布部 淦布部 Β 2 比較品 未塗布部 (對摒） 5 Η 塗布部 4 _4_, ---------^丨_ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作衽印製 配方例5 除臭乳霜 調製下述姐成之除臭乳霜，將此乳霜塗布於腋下，進行 除臭試驗。結果表示於表6 。 &lt;姐成&gt; 兩性多孔性球狀微粒子（實施例9 ) 10.0¾ -38 - 本紙張尺度適用中國國家標隼（CNS ) 格（210X297公釐） &gt; 419484 A7 B7五、發明説明（56 )Example S In Example 1, fine particles were obtained by using extremity galactose (average molecular weight of heavy children: 200,000) for 80 s instead of polychitosan, and the same method as in Example 1. The particle size, morphology, and the like of the obtained fine particles are summarized in Table 1. Implementation of M 7 In the examples, 'using sorbitan monolauric acid 5.0% by weight of cyclic cyclohexane to dissolve 1% by weight cyclohexane solution of sorbitan monolauric acid vinegar, and the same as in Example 1 Manufacturing method to obtain fine particles. The particle size / morphology and the like of the obtained fine particles are summarized in Table 1. Practical Example 8 In Practical Example 1, fine particles were obtained by using acrylic acid (relative to the amount of monosaccharide unit of polychitosan, etc.) in place of methacrylic acid 'and the same method as in Example 1. The particle size / morphology of the obtained microparticles are summarized in the table, 1 in 0. Example 9 In Example 4, after polymerization was performed at 70 ° C for 3 hours, it was cooled down. The size of the paper was adapted to Chinese national standards (CNS ) Α4 Specification (2! 〇X297 公 董) -UK i = I n ^ i I--II ^^ 1--. 1 ^ 1--. I-«{Please read the notes on the back before filling this page ) 419484 A7 Printed by the Consumer Cooperatives of the Central Bureau of Quasi-Staff of the Ministry of Economic Affairs ______ B7_ V. Description of the invention (29) to normal temperature, K 0 '〇5 N (equivalent) H a 〇 water / isopropanol (1/5 V ο 1 / V ο 1) The solution undergoes a neutralization reaction so that 9.0 is the end point. Wash repeatedly with isopropanol 3 times and dry under vacuum * to obtain fine particles. The particle size / morphology and the like of the obtained fine particles are summarized in Table 1. Comparative Example 1 Commercially available polychitosan [SK-10 manufactured by Koyo Chemical Co., Ltd., degree of deacetylation 85 to 88¾, weight average molecular weight 1 300,000] δ (^ Zhongjia human water K becomes 900s, Add 34.Ss of human methacrylic acid (equivalent to carbohydrate units of polychitosan) &gt; At 60t: the next side is mixed and dissolved, and K is used to prepare a polymethylose / methacrylic acid aqueous solution. 125g of chitosan is dissolved, 435g of human ion-exchanged water is added, and then sorbitan, lauric acid is 5.0 weight S: and combined, potassium persulfate of clams at the beginning of polymerization is added. 7 3 g &gt; at 7 After the polymerization reaction at 0 π for 5 hours, cool to normal temperature, and drop into 5 times the mole (volume) of ethanol while sowing. After soaking for 30 minutes, remove the agglomerates by decantation * and immerse in ethanol / After stirring, the steps of filtering are repeated 3 times * granules are obtained by vacuum drying. The particle size / morphology of the obtained granules are summarized in Table 1 ^ Comparative Example 2 In this Comparative Example 1 * Except using acrylic acid (The sugar unit of polychitoose is equal to the amount of M ears) Except for the substitution of methacrylic acid, the rest are the same as those of Comparative Example 1 The granules were obtained. The particle size and morphology of the obtained granules are summarized in Table 1. 0--PH n I ln ^ i nn II In,) ... &quot; 1 1 (Please read the precautions on the back before filling (This page) -32- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297). Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 41,948 4 Α7 __Β7 V. Description of Invention (5〇) N3 — CO 〇〇-vj cn CO ro 1— * polychitosan polychitosan m • a victoria polychitosan polymethylose: polyamino i galactose i polychitosan polychitosan polychitosan polychitosan polychitosan骹 sugar alkaline multi-hammer cold broken acrylic methacrylic acid pickled methacrylic acid 'acrylic ai book mm 漭 methacrylic acid 丨 acrylic methacrylic acid methacrylic acid methacrylic acid field very acrylic acid 5¾ © | 1 time Mor 1x Molar 0.75x Molar 1x Molar 1x Molar 1x Molar 0.75x Rotary 0.75x «Ear L5 Double Mox 2x Molar 1x Molar Mix Most Acetic Acid Hammers-Other Mixed phthalate 0. 25 掊 箅 ear preparation of expensive η aqueous solution _ ___ _______ cyclohexane. Cyclohexane. ____ | cyclohexane cyclohexane cyclohexane cyclohexane. 1 cyclohexane _____1 cyclohexane cyclohexane hydrophobic sorbitan monolaurate {ί 梨 聚Sugar monolaurate sorbitan Luo laurate shangmi m sorbitan Li | laurate vinegar sorbitan laurate sorbitan sorbitan mono 1 laurate pickled ester ............ ..1 Sorbitan Kang_ Laurate Sorbitan Monolaurate Cool Sorbitan Monolaurate Cool Sorbitan 箪 Laurel Sf Vinegar Active Agent 〇〇〇〇〇〇〇CD on 〇〇〇〇ro ◦ 〇〇〇〇 CZ5 〇〇〇 &lt; 3 &gt; Active agent mis: (90 Amorphous Unshaped true spherical 1 M spherical true spherical Spherical true spherical M spherical W spherical true spherical ......... True spherical shaped spherical u 〇 〇〇〇CO οο 〇〇〇〇〇〇two ΓΟ c 筠 shu to — ro Ln ο ο 02 Co 〇Ϊ 〇 -ο tSD C75 CO CJ1 〇Π-¾ and 桢 (mVf;) Phase suspension Φ box processing ir floating spirit 2 suspension m lai n> a ir floating ir floating race r floating 〇t> 'S hH -33_ --------- yi —----- order-1 ( Please read first Please fill in this page again if you need to pay attention to this page) This paper size is applicable to Chinese National Standard (CNS) Α4 specification (2iOX297mm) 419484 A7 B7 ----- Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 51) Note) * 1: Molar amount of monosaccharide unit I of each basic polysaccharide is the second example of a deodorant formulation containing amphiphilic porous spherical fine particles of the present invention. In addition, in the formulation example under M, the * deodorization test was performed as follows. 〈Deodorization test method〉 From healthy males (20 to 40 years old), those with bad armpits and feet were selected and evaluated based on the sensory evaluation of four specially-assigned young ladies. First of all, after work (about 9:00), the sensory evaluation was performed by four specially evaluated young ladies. After the evaluation, the amount of deodorant prepared in each formula was applied to the axilla and feet of the military side. Evaluation of odor after coating * Evaluation of odor before returning home (about 16:00) in the evening. The armpits and feet on the other side served as controls without coating. The evaluation was carried out using the following 6-stage evaluation. The average of 4 people who were specially evaluated for the axillary odor was shown in Formulas 1 to 5, and the bad odor was shown in Formula 6. In addition, instead of using the amphoteric porous spherical particles of the present invention, the evaluation results of the formula concerning zinc oxide (specific surface area: 50ra2 / g) were used as comparative formulation examples. Evaluation Criteria 0: Not smelly 1: Slightly smelly 2 Weak smelly 3: Significantly smelly -34- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) — I— I In I— I— I— I 1 ni-^ (Please read the precautions on the back before filling this page) Order ^ 41948 4 Α7 Β7 V. Description of the invention 〇 2) 4: Strong odor 5: Very strong odor Formula 1 Deodorant makeup Water (hexanol type) The following deodorizing lotion was prepared, and this lotion was applied to the armpits to conduct a deodorizing test. The results are shown in Table 2. &lt; Seoul> Amphoteric porous spherical microparticles (Example 9) 8. 0% Amphoteric porous spherical microparticles (Implementation 2) 2.0¾ Glycerin 5.0¾ Water 10.0¾ Ethanol ___7 5.0% Total 100.0¾ Table 2 _ I. I— -I In I-I----i 1 ^ 1 ii! Tooth i (Please read the notes on the back before filling this page) Printed by P ff I Front cloth front cloth back home festival around 9: 00 1 R: 00 # ί; uncoated part of the product of the present invention (control) RB Η coated 3 comparative product (argon 彳 h zinc) uncoated part (to Zhao) 5 fi S Coating section 4 4 Formulation example 2 Deodorant lotion (volatile silicone type) -35- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 male) 41948 4 A7 B7 5. Description of the invention (is) The following deodorizing lotion was prepared, and this lotion was applied to the armpit to perform a deodorizing test. The results are shown in Table 3. &lt; Seisen &gt; Amphoteric porous spherical fine particles (Solid pickling example 9) 50.0% Isopropyl myristate 5.0¾ Dimethylsilicone_ 5.0¾ A certain polypyridine cake_ 40.0¾ Total 100.0% Table 3 (I fl 9 Toubu Toubuu Touuu Touya House 9: 00 to 16:00: Uncoated part of the product of the present invention (control) 5 5 Uncoated part of the product 5 1. ·? Comparative product uncoated (control) R 5 Inspection Cloth Department 5 _4 4 Formulation Example 3 Deodorizing powder droplets (liquid droplet type) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Prepare the deodorizing powder with the following composition Alas, this powder droplet was applied to the underarms to perform a deodorization test. The results are shown in Table 4. &lt; 姐 成 &gt; • Stock solution -36-This paper size is in accordance with the Chinese National Standard {CNS) A4 specification (2 丨 OX297) T) 419484 A7 B7 V. Description of the invention (M) Amphoteric porous spherical fine particles (Example 9) 40.0¾ Glycerin 5.0¾ Isopropyl myristate 5.0¾ Water 5.0¾ 7, ___4 5.0% Total 100.0 ¾ • Fill the above stock solution 35.0% LPG gas _fi Fi. 0% total 100.0¾ Table 4 S__ Xi The front of the cloth The front of the same house around 9: 00 1fi: 00 弁 Right This product of the present invention is not coated. Section (control) FS 5 Weibu 邬 1: i Comparative product uncoated section (control) Fi SE (argon 彳 h zinc ） 淦 布 部 _ ^ 4 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^^^ 1 ^^^^ 1 ^^^^ 1 ^^^^ 1 ^^^^ 1 ^^^^ 1 I 1 Ί &gt; 1 (Please read the precautions on the back before filling this page) Formula. Example 4 Deodorizing gel Prepare the following deodorizing gel, apply this gel to the armpit, and perform a deodorizing test. The results are shown in Table 5. -37- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ί 41948 4 Α7 Β7 V. Description of the invention (55) &lt; Composition &gt; Amphoteric porous spherical microparticles (Example 9) 40.0¾ Hydroxyethyl polymer 1.0¾ Propylene glycol 10.0¾ Triethanolamine 1.0¾ Ethanol 30.0¾ 7k_18.0¾ Total 100.0% Table 5 Comment _ I Tubuqianqian cloth total front Q: 0 0 about 18: 00 or so Coating section 淦 Cloth section B 2 Comparative product uncoated section (opposite) 5 Η Coating section 4 _4_, --------- ^ 丨 _ (Please read the precautions on the back before filling this page) Ministry of Economy Consumers of the Central Bureau of Standards printed the formulation example 5 Deodorant Cream The following deodorant cream was prepared, and this cream was applied to the underarms to perform a deodorization test. The results are shown in Table 6. &lt; Jiecheng &gt; Amphoteric porous spherical microparticles (Example 9) 10.0¾ -38-This paper size applies to the Chinese National Standard (CNS) grid (210X297 mm) &gt; 419484 A7 B7 V. Description of the invention (56 )

兩性多孔性球狀微粒子（實施例2 ) 5.0¾ 乳酸 1.0¾ 乳酸納 1.5% 鯨蠟醇 8.0¾ 硬脂醇 7.0¾ 凡士林 6.0% 流動石鱲 5.0% 聚氧乙烯（20莫耳加成物） 山梨聚糖硬脂酸酯 3.0% jii__m % 合計 100.0¾ 表 S {請先聞讀背面之注意事項再填寫本頁) 装 -5 經濟部中央標準局員工消費合作社印裝 m f 菅 猞祐前 同家節 9 : 00左右 1R : 00左右 本發明品 未塗布部 〔對照） 5 5 塗布部 fi 1 2 比較品 (氬化鋅） 未塗布部 (對照） 5 5 5 塗布部 5 4 4 配方例S 除臭粉末飛沫（粉末飛沫型） 調製下述組成之除臭粉末飛沫，將此粉末飛沫塗布於腳 -39- 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） Ί 4194 8 4 Α7 Β7 五、發明説明（57 ) 下 進 行 除 臭 試 驗 〇 結 果 表 示 於 表 7 ° &lt; 姐 成 &gt; 原 液 兩 性 多 孔 性 球 狀 微 粒 子 ( 實 施 例 9) 20 _ 0% 兩 性 多 孔 性 球 狀 微 粒 子 ( Μ 施 例 2) 10 . ,0¾ 滑 石 20 4 0¾ 鋁 氫 氧 氛 化 物 2 . .0¾ 異 丙 基 肉 豆 蔻 酸 酯 3 , 0¾ 鯨 蠟 醇 15 . ,0¾ 二 甲 華 1 矽 氧 烷 .*?0 . Q% 合計 100.0¾ •充填 上述原疲 8.0% 1, P fi氩鵲 Ώ . 0 % !-.—. 1 ~1. 装 I 1 ί ^ (請先鬩讀背面之注意事項再填寫本頁) 經濟部中央樣準局員工消費合作社印製 合計 100.0¾ 表 7 ^_Μ 途布前 淦布谧 P家前 9 : 0 0左右 1 fi : 0 0左右 本發明品 未塗布部 (對照） B 5 5 维布部 B 1 2 比較品 未塗布部 (對照） F； 5 5 (氬化鉍） 雄布部 5 4 4 本紙張尺度適用中國國冢標準{ CNS ) Α4規格（21ΟΧ297公釐） I 41948 4 A7 B7 五、發明説明（58 ) K下*舉出聚甲殻楗微粒子之合成例及調配系的實施例 ，更進一步詳龃說明本發明’但’本發明不限於此等。又 ►合成例、實腌例及比較例中之％只要無特別記載均為重 量％。 本實胞例中有效肢基量係依以下方法算出°又，本實施 例之除臭試驗，有關腋臭及腳臭係依以下之試驗方法實施 〇 &lt;有效胺基量之算出方法&gt; 於10m〗燒杯中以表8所示之量秤量聚甲殼糖微粒子*再 加人4-苯基酪酸之2X l〇_4mol /升環己烷溶液（標準溶液 )後，5分鐘後，K據膜進行過濾，測定濾液之UV吸收， 求得吸光度Aebs2 。從此值及聚甲殼糖微粒子接觸前之 4 -苯基酪_溶液的吸光度A &amp; ^ ^依下式泶取4 -苯基酪酸殘 存率。 4 -苯基酪酸殘存率（％)=Aebs2/Aabslx 100Amphoteric porous spherical microparticles (Example 2) 5.0¾ Lactic acid 1.0¾ Sodium lactate 1.5% Cetyl alcohol 8.0¾ Stearyl alcohol 7.0¾ Vaseline 6.0% Flowing stone concrete 5.0% Polyoxyethylene (20 mol adduct) Yamanashi Polysaccharide stearate 3.0% jii__m% Total 100.0¾ Form S (Please read the precautions on the back before filling out this page) Pack-5-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs mf 9: 00 or so 1R: 00 or so Uncoated part of the product of the present invention [control] 5 5 Coated part fi 1 2 Comparative product (zinc argon) Uncoated part (control) 5 5 5 Coated part 5 4 4 Formulation example S Deodorization Powder droplets (powder droplet type) Prepare deodorizing powder droplets with the following composition and apply this powder droplets to the feet -39- This paper size applies Chinese National Standard (CNS) A4 (2 丨 0X297 mm) Ί 4194 8 4 Α7 Β7 5. Deodorization test under the description of the invention (57) 〇 The results are shown in Table 7 ° &lt; Sister &gt; stock solution amphoteric porous spherical fine particles (Example 9) 20 _ 0% Porous spherical microparticles (M Example 2) 10., 0¾ Talc 20 4 0¾ Aluminohydroxide 2.. 0¾ Isopropyl myristate 3, 0¾ Cetyl alcohol 15. 0, Dimethylhua 1 Siloxane . *? 0. Q% Total 100.0¾ • Fill the original fatigue 8.0% 1, P fi argon. 0%! -.—. 1 ~ 1. Install I 1 ί ^ (Please read the precautions on the back first (Fill in this page again.) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs, totaling 100.0¾. Table 7 ^ _Μ Tubu Qianbu cloth P in front of the house 9: 0 0 1 fi: 0 0 or so (Control) B 5 5 Weave cloth section B 1 2 Comparative product uncoated section (Control) F; 5 5 (Bismuth argon) Male cloth section 5 4 4 This paper size is applicable to the Chinese National Takazaki Standard {CNS) A4 specification (21〇 × 297) (%) I 41948 4 A7 B7 V. Description of the invention (58) Under K *, examples of synthesis and preparation of polychitinol fine particles are given, and the present invention is further described in detail, but the present invention is not limited to these. ►% in the synthesis examples, actual pickling examples, and comparative examples are weight percentages unless otherwise specified. In this case, the effective limb base amount is calculated according to the following method. The deodorization test of this example is performed according to the following test methods. &Lt; Calculation method of effective amine base amount &gt; 10m〗 Measure the polychitosan particles in the beaker with the amount shown in Table 8 and add 2X 10-4mol / L cyclohexane solution (standard solution) of human 4-phenylbutyric acid. After 5 minutes, After filtering, the UV absorption of the filtrate was measured, and the absorbance Aebs2 was obtained. From this value and the absorbance A of the 4-phenylbutyrate solution before the chitosan fine particles were contacted, the residual rate of 4-phenylbutyric acid was obtained according to the following formula. 4-Phenylbutyric Acid Residue (%) = Aebs2 / Aabslx 100

Asbsl ：聚甲殼糖微粒子接觸前之4-苯基酩酸溶液的 吸光度 ：聚甲縠糖微粒子接觸後之4 -苯基酷酸溶液的 吸光度 (請先聞讀背面之注意事項再填寫本頁) 裟. 訂 經濟部中央橾準局員工消费合作社印製 &quot;41_ 本紙張尺度適用中國國家標準（CMS ) A4規格{ 210X297公釐） 41948 4 A7 B7 五、發明説明（39〉 表 8 微粒子量 f 1Γ ) 標準溶液量β 1 (fB 1 ) -.. 苯基酪酸添加蠆 f ιπ 〇 1 / ) 0.005 10 4 x 1 0 ~ Λ 0.01 5 IX 1 0 ~ 4 0.01 10 2 X 10 — Λ 0,1 5 1 χ 1 0 - β _..... 10 — ?. X 1 0 - 5 註） 幸1: 4-苯基酪酸之環己烷溶液（2xl〇-4mol/l) *2:每聚甲設糖Is之4 -苯基酪酸量 所得到之4 -苯基酪酸殘存率（？）對每聚甲殼糖微粒子 U之4 -苯基酪酸添加蠆（X)，至少3點以上製成對數表，依 下述式使用最小二乘法進行處理，以決定常數M 0 +、M1。 Y = M〇 + MiX l〇g(X) 使此數表與函數Y = 0之交點值（X切片）喾作微粒子可 全部捕捉溶液中之酸的濃度（酸之殘存率為0丨之點），並 當作微粒子之有效胺基量（nto Ι/s)。 經濟部中央榇準局員工消費合作社印製 &lt;除臭試驗方法&gt; 從健康男性（20〜40歲）選取腋及腳很臭的人並依專鬥 評定小姐4人的官能評價進行評價。首先*上班後（約 9 : 0 0左右）依專門評定小姐4人進行官能評價，評價後Μ 各實腌例所調製之除臭劑通量塗布於單側之腋及腳。進行 -42- 本紙張尺度適用中國國家標準（CNS ) Α4規格（2〖0X297公釐） 經濟部中央榇準局員工消費合作杜印製 4194 8 4 A7 B7 五、發明説明（4〇) 塗布後之奥味評價。另一側之腋及腳作為對照而絲毫不塗 布。評價係使用下述之6階段評價’有關臟之臭味將專門 抨定小姐4人之平均表示於實施例10〜1 3 ’而有關腳之臭 味方面則表示於實施例1 9〜20。又，不採兩本發明之聚甲 餃糖微粒子，而Μ有關氧化鋅調配之評價結果作為比較例 〇 評價基準 0 :不臭 1 :微臭 2 :臭味弱 3 :明顯臭味 4 :臭味很強 5 :臭味非常強 &lt;使用聚甲設糖微粒子合成例&gt; 合成例1 使市售之聚甲殼糖（甲陽化學（股）製，SK：_10 ’脫乙 豳化度85〜88¾ ，重量平均分子量1 30000) 分散於水 中，加入酒石酸50g ，在60t：下一面攪拌一面溶解’以調 製7.8¾聚甲殼糖/酒石酸水溶疲。 以1 /1之比率（容量比）混合此聚甲殼糖酸性水溶液與 山梨聚糖簞月桂酸酯之2.0¾甲苯溶液，再以均質機進行高 速攫拌（1 0 0 0 0 r p m)而形成W / 0乳液。 其次，將所得到之乳液20 m 1滴人1 / 1 0 N 丁胺/乙醇溶液 1 〇 〇 m 1中並搁拌之，進行凝画處理 &gt; 以不銹鋼製金髑網過 -43™ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先聞讀背面之注意事項再填寫本頁) 装. 經濟部中央標準局員工消費合作社印製 419484 A7 B7 _ 五、發明説明（41 ) 濾凝固物及反複乙醇洗淨，回收後’進行真空乾燥’得到 聚甲殼糖微粒子。所得到之聚甲殼糖微粒子的形狀為真球 狀，平均粒徑為lOwia。 為算出所得到之聚甲般糖微粒子的有效胺基量，逋出 4 -苯基酪酸殘存率（Y)對每聚甲設糖微粒子lg之4 -笨基酪 酸添加量（X)的對數表’表示圖1中。又將所得到之聚甲 殼糖微粒子的有效胺基童、其他之物性表示於表9中。 合成例2 使市售之聚甲殼糖（合成例1所使用之SK-10) 80s分散 於水中，加入酒石酸50g ，在60 t：下一面槻拌一面溶解， 以調製8.0¾聚甲殻糖/酒石酸水溶液。 K 1 /1之比率（容量比）混合此聚甲殼糖酸性水溶液與 山梨聚糖單月桂酸醏之5.0¾環己烷溶液，再以均質機進行 高速搁拌（15000「pm)而形成W/0乳液。 其次，將所得到之乳液2 0 nt 1於室溫下滴入胺基變性砂萌 〔信越矽_ (股）製、兩末端胺基變f生矽嗣X - 2 2 - 1 6 1 B ) 5 0 m丨、丁醇5 0 ra 1之混合溶液中同時並攞拌，進行凝固處理 ，以不銹鋼製金屬網過濾凝固物及反複乙醇洗淨，回收後 ，進行真空乾燥*得到聚甲殼糖微粒子。所得到之聚甲殼 糖微粒子的形狀為至少從3方向彤成凹凸化之非球狀形II ，且平均粒徑為20 « ra。 將所得到之聚甲殼糖微粒子的有效胺基量，其他之物性 表示於表9中。 合成Μ 3 -4 4 - 本紙張XJt適用中國國家標準（CNSI A4規格（210X297公釐） II - -I - 1_ ^^1 I - I « 1^1 H 11 In - ^T (請先閲讀背面之注意事項再填寫本頁) Γ 419 4 8 4 a? Β7 五、發明説明（4·2 ) 使市售之聚甲設糖（合成例1所使用之SK-iO)78s分散 於水中，加入酒石酸5 0 g並於6 0 X〕下攢拌並溶解之，以調 製7.8Γ聚甲殻糖/酒石酸水溶液。另外，將氧化鋁0.2g ( 對聚甲殺糖5«)分散於水5ml中&gt; Μ使此氧化鋁分散菘分 散於聚甲殼糖酸性水溶液5 0 m 1中。 K5/5之比率（容虽比）混合此聚甲殼糖酸性水溶液與 山梨聚糖單硬腊酸酯之2.0¾環己烷溶疲，再以均質機進行 高速攪拌（ 1 5000γ*ρπι)而形成W/0乳液。 其次，將所得到之乳液20ml滴入丁胺/乙醇50ml、丁 醇5 0 m 1中並攪拌之*進行凝固處理，K不銹鋼製金屬網過 漶凝固物及反複乙醇洗淨，回收後，進行真空乾燥，得到 聚甲殼糖微粒子°所得到之聚甲殻糖微粒子的形狀為真球 狀，平均粒徑為2 Ο μ m。 將所得到之聚甲殼楗微粒子的有效胺基量 '其他之物性 表示於表9中。 合成例4 經濟部中央標準局貝工消費合作社印製 ϋ -- ! - I. -1 1 1ϋ , f - If — i - i n T (請先閲讀背面之注意事項再填寫本頁) 將合成例1所得到之聚甲殼糖微粒子1 〇 S分散於乙醇 5 0 m 1中，添加二乙二醇二縮水甘油基醚（長瀨化成製、迪 那柯E X - S 1 0 ) 10 S ，在6 0 下攪拌一夜，Μ對微粒子表面 進行交聯處理。此微粒子以不銹鋼製金屬網過濾之後’反 複乙醇洗淨，回收後，進行.真空乾燥，得到交聯聚甲殼糖 微粒子。所得到之聚甲設糖微粒子的形狀為真球狀’平均 粒徑為1 0 m。 將所得到之聚甲殼楗微粒子的有效胺基量、其他之物性 -45 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210X^97公釐} / 419484 A7 B7 五、發明説明（43 ) 表示於表9中。 合成例5 將合成例1所得到之聚甲殼糎微粒子1 〇 s分散於甲醇 200ml中，一面攪拌一面添加吡啶200ml 、無水醋酸63g . ，在室溫攪拌一夜後，以不銹鋼製金屬網過滹及反複乙醇 洗淨，回收後，進行真空乾燥*得到部分乙醯化聚甲殼糖 微粒子。所得到之羿甲殼糖微粒子的彤狀為真球狀，平均 粒徑為1 0 y m。 將所得到之聚甲殼糖微粒子的有效胺基量、其他之物性 表示於表9中。 表 9 H^J tK nn -1 ^^^^1 ' —ii 一OJ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央梯準局員工消費合作社印製 合 iS 例 Να 合成 方法 原料聚甲骰糖 微粒子形態 酸捕捉能 脱乙醱’ 化度 C%) 重量平均 分子量 形態 平均 泣徑 (Jim) 比表 而積 (m2/g) 有効 胺基量 (raol/g) 1 乳化 凝固 85 〜88 130,000 真球状 10 63. 0 2 X icr5 2 乳化 凝固 85 〜88 1 30, 000 非球状 定形体 20 50. 0 2 χ 10 -5 3 乳化 凝固 85 〜88 130, 000 真球状 20 64. 0 1 X10&quot;5 4 乳化 凝固 85 〜88 130,000 真球状 10 50. 0 2 χ 1〇-5 5 乳化 凝固 85 〜88 130,000 真球状 10 50. 0 1 X l〇-s -46- 本紙張尺度適用中國國家標準（CNS ) A4規格（21 Ox：297公釐） ! 4194 8 4 A7B7 五、發明説明（44 賁施例1 0 除臭化粧水（乙醇型） 製造下述姐成之除臭化粧水，進行有關腋臭之除臭試驗 。结果表示於表1 0中。 &lt;除臭化粧水姐成&gt; 聚甲殼糖微粒子（合成例1平均粒徑1 0 m) 10.0% 甘油 5.0¾ 水 10.0¾ 乙醇__75.0% 合計 100.0¾ ---------装-- (請先閱讀背面之注意事項再填寫本頁) 表 10 評 m 調配物 塗布前 9 . 00左右 塗布後 未绝布（對膊） 5 本發明品 聚甲設糖微粒子 (合成例1平询粒揮1 hz m ) 5 2 比較品 去净布（對照） Β F, Μ化繂 5_ 經濟部中央標準局員工消費合作社印製 實施例11 除臭化粧水（揮發性矽酮型） 製造下述姐成之除臭化粧水，進行有關腋臭之除臭試驗 〇結果表示於表11中。 &lt;除臭化粧水組成&gt; 聚甲殼糖微粒子（合成例2平均粒徑2 0 m) 50. 0¾ -47 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） 419484 A7 B7 五、發明説明) 二甲基矽_ 甲某聚頊砂氬烷 10.0¾ 4 0.0¾ 合計 100.0¾ 表 11 評 僧 調配物 塗布前 9 . 00左右 塗布後 未绝布（對照） 5 5 本發明品 聚甲殼糖微粒子 (合成例2平均》俾？. 0 w m ) 5 1 比較品 未域布（對照1 5 氯化鋅 5 3 (請先閱讀背面之注意事項再填寫本頁) 經濟中央標準局員工消費合作社印製 實施例1 2 髮齑狀除臭蜊 製造下述姐成之髮裔狀除臭劑，進行有關腋臭之除臭試 驗。結果表示於表1 2。 &lt;髮裔狀除臭劑姐成&gt; 聚甲殼糖微粒子（合成例1平均粒徑10 y m) 20.0¾ 硬脂醇 60.0¾ 滑石_______20.0¾ 合計 100.0¾ 48- 本紙張尺度適用中國國家標準（CNS ) A4規格（2ωχ297公釐〉 t 4194 8 4 A7 B7 五、發明説明（46 ) 表 12 調配物 抨 價 塗布前 塗布接 9.00* ίί 未塗布（對照} 5 F5 本發明品 聚甲殻糖微粒子 5 1 ί合成Μ 1平均»禪2 0 ^ m 1 比較品 未 '換布（對脬） R S 氬ih鋅 5 ^ 實施例13 液狀飛沫型除臭劑 製造下述姐成之液狀飛沫型除臭劑，進行有關腋臭之除 臭試驗。結果表示於表13。 &lt;液狀飛沫型除臭劑姐成&gt; 原液 I ^r— mi - i 1^1 -- 1— J^i —III I ) &gt; «s.-e (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 聚 甲 殻 魅 ra 微 粒 子 (合成例4 平均粒徑1 0 m) 12, ,5¾ 異 丙 基 肉 豆 蔻 酸 酯 5 . ,0% 甘 油 5 . ,0¾ 水 5 . ,0¾ 7, 醇 7?.. . 合 計 100 , .0% -49- 本纸張尺度適用中國國家樓準（CNS ) A4規格（210X297公釐） 1 419484 A7 B7 五、發明説明（47 ) 充填 上述原液 35.0% l,Pf]氣賴_______β 5 . 0 % 合計 100.0% 表 13 (請先閱讀背面之注意事項再填寫本頁) 實施例1 4 粉末飛沬型除臭劑 製造下述姐成之粉末飛沫型除臭劑，進行有關腋臭之除 經濟部中央標準局員工消費合作杜印製 臭 試 驗 結 果 表 示 於表].4中。 &lt; 粉 末 飛 沫 型 除 臭 劑姐成&gt; 原 液 聚 甲 殼 糖 微 粒 子 (合成例1平均粒徑1 0 « m) 5,5% 滑 石 46.5% 肉 SL 蔻 酸 酷 25.0¾ __ 甲 基 矽 m 5.0% -50- 調配物 評 m 塗布前 9 . 0 0左右 塗布後 本發明品 去績布ί對照） 5 聚甲殻糖微粒子 (合成例4平抱粒禪1 0 i/ m ) 5 2 比較品 未绝布（對照） 5 5 氬化铃 B 3 本紙張尺度適用中國國家橾準（CMS &gt; Α4規格（210Χ297公釐） A7 4194 8 4 B7 五、發明説明（48 ) 甲某聚擐碑氬梡 18.5¾ 合計 100.0¾ 充填 上述原液 8.0¾ i,pg« m 9 2.0¾ 合計 100.0¾ 表 14 評 m 調配物 塗布前 9 . 0 0左右 塗布後 未途布ί對照） 5 5 本發明品 聚甲設糖微粒子 (合成例〗平齿粒撺1 0 〃 m ) 5 1 比較品 未途布（對照） 5 B 5_ 2 實施例、5 凝膠狀型除臭劑 (請先閱讀背面之注意事項再填寫本頁) 裝 -5 經濟部中央標隼局員工消費合作社印製 製造下述姐成之凝膠狀型除臭劑，進行有關腋臭之除臭 試驗。結果表示於表15中。 &lt;凝膠狀型除臭劑姐成&gt; 聚甲殼糖微粒子（合成例5平均粒徑1 0 w ra ) 40 .0¾ 羧乙烯基聚合物 1.0¾ 丙二醇 10.0¾ 三乙醇胺 1.0¾ -51 - 本紙張尺度適用中國國家標準（CNS &gt; A4規格（2IOX297公釐） Α7 ί 419484 Β7 五、發明説明（49 ) 乙醇 30,0¾ 水________18.0¾ 合計 100.0¾ 表 15 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 實施例1 6 乳霜狀型（0 / W乳霜）除臭劑 製 造 下 述 姐 成 之 0/W乳霜 狀型除臭劑， 進行 有關腋臭 臭 試 0 结 果 表 示於表1 6 中〇 乳 ft 狀 型 除 臭 萷 姐成&gt; 聚 甲 殼 糖 微 粒 子 (合成例3 平均粒徑2 0 u m) 10.0¾ 鯨 蠟 醇 9.0¾ 硬 脂 醇 8.0% 凡 士 林 7,0% 流 動 石 蠘 7.0¾ 聚 氧 乙 烯 ( 20 莫 耳加成物 ) 山 梨 聚 糖 硬 脂 酸酯 3.0¾ -52- 調配物 —W_____Μ 塗布前 9 . 0 0弁右 塗布後 本發明品 去猞布ί對照） 5 5 聚甲殼糖微粒子 (合成例5平炮粒禪1 0 Η m ) 5 2 比較品 未塗布（對照） 5 氬化繂 Ε 3 本紙張尺度適用中國國家標準（CNS ) A4規格（2 f 0 X四7公嫠} 419484 λ7 Β7五、發明説明（5〇 ) 水__________5 6.0¾ 合計 100.0¾ 表 16 Γ 1 評 價 調配物 塗布前 9 . 0 0 _左右 塗布後 未檢布（對賻） 5 ί 本發明品 聚甲殻糖微粒子 (合成例：?平fe粒撣？. 0 m ) 5 2 比較品 未塗布（對昭） 5 氬化銓 5 3 實施例17 乳霜狀型（0/W乳霜）除臭劑 製造下述組成之0/W乳霜狀型除臭劑，進行有翮腋臭之 除臭試驗。結果表示於表1 7中。 &lt;乳霜狀型除臭劑姐成&gt; 1^1 ^—^1 &gt; i f J m^l ί^— ί - 1 —J 0¾ (請先閱^背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作杜印製 聚 甲 殼 糖 微 粒 子 (合成例4平均粒徑20 w m) 1 0 , ,0¾ 蜜 蠘 10 . .0¾ 鯨 m 醇 5 , .0¾ 甘 油 基 單 硬 脂 酸 醋 2 . .0¾ 聚 氧 乙 烯 c 20 莫 珲加成物） 山 梨 聚 独 糖 硬 脂 酸酯 2. ,0¾ 水 81 . .0¾ -53- 本紙張尺度適用中國國家標準（CNS &gt; A4規格（210X297公釐） i 41 94 8 4 A7 B7 五、發明説明（51 ) -角鲨烯__10.0% 合計 100.0¾ 表 17 評 m 調配物 塗布前 9 . 00方右 塗布後 来殮布f對昭） 5 本發明品 聚甲穀糖微粒子 f合成例4平询粒徑1 Ou τη ) 5 2 比較品 未檢布（對照） 5 5 5 3 實施例1S 乳霜狀型（0/W乳霜）除臭劑 製造下述組成之0/W乳霜狀型除臭劑，進行有關腋臭之 除臭試驗。結果表示於表1 8中。 &lt;乳霜狀型除臭劑姐成&gt; 聚甲殻糖微粒子（合成例5平均粒徑20 u m) 40.0¾ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 固態石蠟 8.0¾ 蜜蠟 8.0¾ 凡士林 12.0¾ 聚氧乙烯（20莫耳加成物） 山梨聚糖硬脂酸酯 4.0% 流動石蠟 10.0% -54- 本纸張尺度適用中國國家標準（CNS ) A4規格（210XW7公釐） f 41948 4 A7 B7五、發明説明（52 ) Μ.___________18.0¾ 合計 100.0¾ 表 18 評 僧 調配物 塗布前 塗布後 9 . 00左右 夫檢布（對照） S 5 本發明品 聚甲殼糖微粒子 5 2 (合成例5平均粒揮1 0 w m 1 比較品 去檢布（對照） 5 氬化t辛 5 3 實施例1 9 莜狀飛沫型除臭劑 製造下述組成之疲狀飛沫型除臭劑，進行有闞腳臭之除 臭試驗。結果表示於表1 9中。 &lt;液狀飛沫型除臭劑姐成&gt; 原液 1· ^^^1 - - .^^1 «^^1 n -1 «. ' «^^1 n^i «i I -- ^^^1 ^¾. 、va &gt; (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 聚 甲 殼 糖 微 粒 子 (合成例1平均粒徑10 w m) 12 . 5% 異 丙 基 肉 豆 m 酸 酯 5 · 0¾ 甘 油 5 . 0% 水 5 . 0¾ 酵 Ί2, 5% 合 計 100. 0¾ -55- 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X 297公釐） 經濟部中央橾準局員工消費合作社印掣 419484五、發明説明（55 ) 充填 上述原液 LPGM §§ A7 B7 35.0¾ 6 5.0¾ 合計 100.0¾ 表 19 評 價 調配物 塗布前 塗布後 9 . 0 0左右 夫塗布（對賻1 5 S 本發明品 聚甲殼糖微粒子 5 1 ί合成Μ 1平抝粒徑1 0 m ) 比較品 未塗布（對照） B 氬化鋅 5 1 實腌例2 0 粉末飛沫魁除臭劑 製造下述组成之粉末飛沫型除臭劑，進行有關腳臭之除 臭試驗。結果表示於表20中。 &lt;粉末飛沬型除臭劑組成&gt; 原液 聚甲殼糖微粒子（合成例2平均粒徑20 μ m) 5.0% 滑石 46.5¾ 肉豆蔻酸酯 25.0¾ 二甲基矽_ 5.0¾ -56 本纸張尺度適用中國國家標準（CNS } A4規格（210 X 297公嫠） (請先閱讀背面之注意事項再填寫本頁) 4 A7 B7 五、發明説明（54 ) 甲某聚瑱砘氬烷 18.5% 合計 充填 上述原液 L P G氣鵲 100.0¾ 8.0% 9 2.0¾ 合計 1 00 . 03ί 表 20 m 檲 調配物 塗布前 9 . 00左右 塗布後 未驗布ί對照） B 5 本發明品 聚甲殼糖微粒子 (会成例2平担I粒揮20 &quot; m 1 5 . 1 比較品 未猞布f對照） fi S 氬化鋅 _5 3 (請先閎讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 實腌例2 1 將綿墊裝著於狐臭被驗者的腋下1日，採取臭味。接者 ，以甲醇浸潰約20人分的綿，回收臭味（約2升）。濃縮 至約6〇1111&gt;以此為狐臭試樣。 · 於300ml燒杯底裝入直徑70πιηι之濟紙 &gt; 於其上添加 0 . 3 5 s之上述狐臭試樣而使之滲人。於室溫下放置3分鐘 後，撒上下述姐成之除臭劑0 . 2s。於室溫下放置2分鐘後 ，以未添加除臭劑者作為對照而依專門評定小姐4人進行 57 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） 1 4194 8 4 at Β7 五、發明説明（55 ) 相同於實施例1 0〜20之6階段評價。又，有關氧化鋅作為 比較品亦同樣地評價。結果表示於21中。 &lt;除臭劑組成&gt; 聚甲殻糖微粒子 2.0¾ 乙醇 20 % 矽嗣SH245 [東電道矽酹（股）製〕 均衡 表21 装-- (請先閲讀背面之注意事項再填寫本頁) 以下舉出聚矽氧烷之實施例而更詳®說明本發明，但本 發明不因此等實施例而受到任何限制。 經濟部中央標準局員工消費合作社印策 合成例0 (兩末端長鏈烷基變性聚矽氧烷之合成例） 於經氮置換之1升高壓鍋中饋入乾燥環己烷400ml 、四 甲基乙二胺 3mi、正 丁基鋰（l.Smoi/升）12.5ml(0.02!tt〇l) ，使反應系之溫度保持於30 t:、乙烯氣體導入壓力保捋於 2ks/cm2 ，乙烯氣體導人8 . 2升。然後，除去乙烯氣體， 進行氮置換。預先，於1升燒瓶中準八甲基環四矽氧烷 11.8s 、乾燦環己烷10ml溶液，氮氣流下滴入前述之聚合 混合物。滴入終了後，於30它下反應1小時後，將反應混 合物投入2升之甲醇中。槻拌1小時後，以減壓過瀘，收 -58&quot; [:匕較品 躲珥躲艄微粒平 調配物 無添加 氧化梓 異形 球形 (合戚例2) 〔合成剜1 ) 評僭鈷第 1 1〜？. 本紙張尺度遥用中國國家標準（CNS &gt; Α4規格（2丨0X297公釐） A7 419484 _____ _ B7 _ 五、發明説明（56 ) —--------裝------訂 Γ請先閱讀背面之沒意事項再填寫本頁} 集所生成之固體。在5〇 t；之高溫爐、真空下乾燦24小時， 得到白色蠘狀固體。生成物之產量為分析（ Waters社製 '鄰二氯苯、135υ 、聚乙烯標準試樣校疋） 之結果，數目平均分子量為61〇 ，分子量分布為Log。 HMR 分析（Bruker社製、200MHz、氯仿-d、50f、操 準使甩〗WS)之結果。在- 〇.〇5ΡΡίη (單峰）為鏈結在甲砂院 基上之甲基，在〇，4 p p m (三峰）為鍵結在甲矽烷基上之伸 乙蹄基、在0 . 3 P p m (三峰）為開始末端甲基、在丨.2 p p ^附 近為主鏈之亞甲基之訊號。從各別訊號之積分比，可知末 端矽烷基導入荜99¾ 。又 &gt; 矽氧烷單元之導入率係每2歸 末端為1 . 4個。 其次，於安裝有冷凝器之一升可分離燒瓶中，置入經合 成之末端矽焼基聚乙輝12_.0g八甲基環四砂氧焼88g 、甲 苯100ml ，在油浴上加熱直至甲苯進行迴流。全部原料均 經濟部中央標準局員工消費合作杜印製 -溶解時點*加入氫氧化鉀〇.〇1ε ，再繼績迴流48小時。 然後*加人1 Ν酵性鹽酸溶液〇 . 1 8 ra 1，充分進行播拌。加人 水*確認pH為7 ，取出因水所生成之無機鹽。加熱後，再 進行三次水洗*安裝汀史達克管以取代冷凝器，進行甲笨 迴流直至完全脫水。餾去甲苯*得到橡膝狀之白色蠘。生 成物之產量為96g。 GPG分析（Waters社製、鄰二氯苯、135T：、換算聚苯 乙烯）之結果 &gt; 重量平均分子量為1 8 6 0 〇 、分子量分布為 2.03° UMR 分析（Brisker社製、200MHz、氯仿-d、50¾、標 -59- 本紙張尺度適用中國國家梯準（CNS ) A4規格（210 X 297公釐&gt; 1 41948 4 Α7 __- ___Β7五、發明説明（5了） 經濟部中央標隼局員工消費合作杜印製 準乃使用T M S )之結果。在-〇 , 〇 5 p p ^ (單峰）為鍵結在甲砂 综基上之甲基，〇 . 4 p p m (三峰）為鍵結在甲矽烷基之亞甲 基、〇. 8ppra (三峰）為開始末端甲基、u 2ppra附近為聚乙 稀鏈之亞甲基的訊號。從各別之訊號的積分比 &gt; 可知聚乙 婦部分與砂氧烷部分之重量比為1〇 : 9()。 從DSC之昇溫测定*融點（吸熱譜峰之頂點）為92t:。 合成例7 (側鏈烷基變性聚矽氧烷之合成例） 於安装有冷凝器之1升可分離的熗瓶中，蝕入甲基氫變 性聚砂氧烷(股）製PS12() Mw = 227〇) 79s與載亞 連18(三菱化成（股）製、1-十八烯）2〇s 、甲苯：00^1 ’以白金換算加人氯化鉑酸].Q〇PPia，於g〇t：下反應24小時 β使用乙醇之再沈澱精製進行2次後，得到略裼色之柔軟 蠘。產量為99s *融點為23°C。UMR分析、IR分析之結 果、末端氫殘存率為0¾，烯烴之殘存率為U。 合成例8 (兩末端烷基變性聚矽氧烷之合成例） 安裝冷凝器之1升可分雛燒瓶中，蝕入末端氫變性聚矽 氧烷（千 7(股）製 PS537、Mw = 440) 38gM 上之《-蹄 烴混合物）7 4 s、甲苯1 0 0 m 1，以白金換算加人氯化鉑酸 1 0 0 P m，在3 0 t下反應24小時。再沈澱精製後，得到略褐 色之柔軟蠟。產量為98g ，融點為42Ό。iH-NMR.、IR分析 之結果、末端氫殘存率為1¾，烯烴之殘存率為8¾。 試驗例1 使用上述合成例6〜8所得到之變性聚矽氧烷、或作為比 較之石蠟（融點68 1C、日本精製蠟）作為蠟成分，依表 60- 本紙張尺度適用中國國家操準（CMS &gt; Α4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝. -* ί 41948 4 Α7 Β7 五、發明説明（邓） 22之姐成調製懸浮液狀姐成物。將此等之懸浮液狀組成物 塗布於熟皮草上，觀察在3 7 t：下Κ熟皮草摩擦表面時之殘 存率的測定與表面之狀態。又，塗布於玻璃膜之上，测定 透濕度（單位為g / m 2 - 2 4 h r / 1 9 y in)、使用氯化縛作為吸濕 ，劑，在25¾、6 5¾ RH下測定）。將結果表示於表22中。 表 22 本發明品 比較品 I 2 3 4 調 配 組 成 r—% 重 量 % 'W 兩末端長鏈烷基變性聚矽氧烷 (合成例1 ) 10 一 — — 側_烷基變性聚矽氣烷 (合成例2 ) ~ 10 兩末端烷基變性聚矽氧烷 (合成例3) -- — 10 — 石峨 (融点68°C,曰本精蠟製） 一— 一 — 10 八甲基四環矽氧烷. (東芝矽嗣· TSF404) 30 30 30 30 異戊烷 50 50 50 50 乙醇 10 10 10 10 試 驗 項 巨 被膜殘存率 C重量％) 78 13 23 了 9 表面観察 搬狀 油狀 油狀 蠟狀 透濕度 (g/m2 - 24hr/10 ^ m ) 790 14 121 2 &quot;•61*· 經濟部中央標準局員工消費合作社印聚 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標隼（CNS}A4現格（210X297公釐） I 4194 84 A7 經濟部中央標準局負工消費合作社印聚 B7 ___ ____ __ _五、發明説明（59) 合成例9(兩性多孔性微粒子之合成Μ) 於市售之聚甲殻糖[甲陽化學（股）製SK-10 、脫乙酿 化度85〜88¾ 、簠量平均分子量130000〕80ίί中加人水而 形成900g，再加人甲基丙烯酸34.6g(相對於聚甲毅糖之單 糖犟元為等莫耳量）…在6 ο υ下一面攒拌一面使之溶解’ Μ調製聚甲殼糖/甲基丙烯酸水溶液。再於其中加入—將 過硫酸鉀3g溶於離子交換水100s中而形成者，在常溫下搜 拌數分鐘。 K 5 / 5之比例（容積比）混合該聚甲殼糖溶液與山梨聚 糖單月桂酸醋之1.0重量％瓌己烷溶液，以均質機進行高 速攪拌U 5000rpni)，形成W/0乳液。 其次，在7 0 t：下進行聚合反應2小時後，冷卻至常 '溫， —面滴入5倍奠耳量（容積）之乙酵溶液中—面進行擬样 ，携拌30分後，以傾析除去凝集物，於乙醇中浸漬/播拌 之後，反複進行3次努氏過濾之步驟，藉真空乾燥得到徵 粒子。所得到之微粒子的平均粒徑為1 2 ^ ra *形態為真球 狀，比表面積為50^/容。 實施例22 使用合成例6所合成之兩末端長鍵烷基變性聚矽氧烷' 合成例9所合成之兩多孔性微粒子，而依表2 3之姐成調製 除臭軟箭。 本紙張尺度適用中國國家標隼（CNS &gt; A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁} 裝- -5 419484 A7 B7五、發明説明（6〇 )Asbsl: Absorbance of 4-phenylarsinic acid solution before contact with polychitosan particles: Absorbance of 4-phenylarsinic acid solution after contact with microchitosan particles (please read the precautions on the back before filling this page)裟. Order printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs &quot; 41_ This paper size applies to China National Standard (CMS) A4 specifications {210X297 mm) 41948 4 A7 B7 V. Description of the invention (39> Table 8 Microparticles f 1Γ) Standard solution amount β 1 (fB 1)-.. phenylbutyric acid addition 虿 f ιπ 〇1 /) 0.005 10 4 x 1 0 ~ Λ 0.01 5 IX 1 0 ~ 4 0.01 10 2 X 10 — Λ 0,1 5 1 χ 1 0-β _..... 10 —?. X 1 0-5 Note) Fortunately, 1: 4-phenylbutyric acid in cyclohexane solution (2xl0-4mol / l) * 2: per polymer The 4-phenyl phenyl butyric acid residual rate (?) Obtained from the amount of 4-phenyl butyric acid of forsketose Is is added to the 4-phenyl phenyl butyric acid per polychitosan fine particles U, and at least 3 points are made into a logarithm. The table is processed using the least square method according to the following formula to determine the constants M 0 + and M1. Y = M〇 + MiX l〇g (X) Make the intersection of this table and the function Y = 0 (X slice), and use it as a microparticle to capture all the acid concentration in the solution. ), And regarded as the effective amount of amine groups (nto Ι / s) of the fine particles. Printed by the Consumers' Cooperative of the Central Government Office of the Ministry of Economic Affairs &lt; Deodorization test method &gt; From healthy males (20 to 40 years old), those with bad armpits and feet were selected and evaluated based on the sensory evaluations of four judges. Firstly * After work (about 9: 00), the sensory evaluation was performed by 4 specially evaluated young ladies. After the evaluation, the flux of deodorant prepared by each of the pickled examples was applied to the axillary and feet on one side. Continued -42- This paper size applies to Chinese National Standard (CNS) A4 specification (2 〖0X297mm） Staff consumption cooperation of the Central Bureau of Standards of the Ministry of Economy 4194 8 4 A7 B7 V. Description of the invention (4〇) After coating The mysterious evaluation. The armpits and feet on the other side were used as controls without coating. The evaluation was performed using the following six-stage evaluation. The average odor of four people was specifically determined in Examples 10 to 1 3, and the odor of the feet was shown in Examples 19 to 20. In addition, instead of collecting the two sesame sugar microparticles of the present invention, the evaluation results of M regarding zinc oxide preparation were used as a comparative example. Evaluation criteria 0: Not smelly 1: Slightly smelly 2: Weak smell 3: Weak smell 4: Stink Very strong taste 5: Very strong odor &lt; Synthesis example using polymethionine fine particles &gt; Synthesis example 1 A commercially available polychitosan (made by Koyo Chemical Co., Ltd., SK: _10 'Deacetylation degree 85 ~ 88¾, weight average molecular weight 1 30000) dispersed in water, add 50g of tartaric acid, and at 60t: stir while dissolving 'to prepare 7.8¾ polychitosan / tartaric acid. Mix this polychitosan acidic aqueous solution with sorbitan laurate in 2.0¾ toluene solution at a ratio of 1/1 (capacity ratio), and then perform high-speed mixing (100 000 rpm) with a homogenizer to form W / 0 lotion. Next, 20 m of the obtained emulsion was dropped into a 1/1/10 N butylamine / ethanol solution of 1000 m 1 and left to stand for painting. &Gt; Made of stainless steel with gold mesh-43 ™ Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page). Packing. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 419484 A7 B7 _ V. Description of the invention (41) The coagulum is filtered and repeatedly washed with ethanol, and after being recovered, it is vacuum-dried to obtain polychitosan fine particles. The obtained chitosan fine particles had a true spherical shape and an average particle size of 10wia. In order to calculate the effective amount of amine groups of the obtained polymethionose microparticles, a logarithmic table of the residual ratio of 4-phenylbutyric acid (Y) to the addition amount of 4-benzylbutyric acid (x) per polymethylose microparticles was derived. 'Represents in FIG. 1. Table 9 shows the effective amine groups and other physical properties of the obtained chitosan fine particles. Synthesis Example 2 Disperse 80s of commercially available chitosan (SK-10 used in Synthesis Example 1) in water, add 50 g of tartaric acid, and dissolve at 60 t: mix on the next side to prepare 8.0¾chitosan / tartaric acid Aqueous solution. The ratio of K 1/1 (capacity ratio) is to mix this polychitosan acid aqueous solution with sorbitan monolaurate 5.0 ¾ cyclohexane solution, and then perform high-speed stand mixing (15000 "pm) with a homogenizer to form W / 0 lotion. Next, the obtained lotion 20 nt 1 was dropped into amine-modified denatured sand at room temperature [made by Shin-Etsu Silicon Co., Ltd., both ends of the amine group were changed to raw silicon 嗣 X-2 2-1 6 1 B) 5 0 m 丨, butanol 50 0 ra 1 in a mixed solution at the same time and mixed together, and subjected to coagulation treatment, the coagulum was filtered with a stainless steel metal mesh and repeatedly washed with ethanol. After recovery, vacuum drying was performed to obtain a polymer. Chitosan microparticles. The shape of the obtained chitosan microparticles is a non-spherical shape II that is convex and concave from at least 3 directions, and the average particle diameter is 20 «ra. The effective amine group of the obtained chitosan microparticles The amount and other physical properties are shown in Table 9. Synthetic M 3 -4 4-This paper XJt applies the Chinese national standard (CNSI A4 specification (210X297 mm) II--I-1_ ^^ 1 I-I «1 ^ 1 H 11 In-^ T (Please read the notes on the back before filling this page) Γ 419 4 8 4 a? Β7 V. Description of the invention (4 · 2) Disperse 78s of commercially available polymethionose (SK-iO used in Synthesis Example 1) in water, add 50 g of tartaric acid, mix and dissolve it at 60x] to prepare 7.8Γ polychitin An aqueous sugar / tartaric acid solution. In addition, 0.2 g of alumina (p-methicose 5 «) was dispersed in 5 ml of water. The aluminum oxide was dispersed and dispersed in an aqueous solution of polychitosan acid 50 m 1. K5 / The ratio of 5 (capacity ratio) is mixed with the polychitosan acid aqueous solution and sorbitan monostearate of 2.0¾ cyclohexane to dissolve, and then high-speed stirring (1 5000γ * ρπι) with a homogenizer to form W / 0 lotion. Next, 20 ml of the obtained lotion was dropped into 50 ml of butylamine / ethanol and 50 ml of butanol and stirred to perform a coagulation treatment. The stainless steel metal mesh was subjected to coagulation and repeatedly washed with ethanol and recovered. Then, vacuum drying was performed to obtain polychitosan fine particles. The shape of the obtained chitosan fine particles was true spherical and the average particle diameter was 20 μm. The effective amount of amine groups of the obtained chitosan fine particles was 'others' The physical properties are shown in Table 9. Synthesis Example 4 Shellfisher Consumer Cooperation of the Central Standards Bureau of the Ministry of Economic Affairs Printed ϋ-!-I. -1 1 1ϋ, f-If — i-in T (Please read the precautions on the back before filling this page) Disperse the chitosan fine particles 1 〇S obtained in Synthesis Example 1 In ethanol 50 m 1, diethylene glycol diglycidyl ether (Nagase Kasei, Dinako EX-S 1 0) 10 S was added, and the mixture was stirred overnight at 60 to crosslink the microparticle surface. deal with. The fine particles were filtered through a stainless steel metal mesh, washed with ethanol, and then recovered, and then vacuum-dried to obtain cross-linked polychitosan fine particles. The shape of the obtained polymethoxide fine particles was true spherical and the average particle diameter was 10 m. The effective amount of amine groups and other physical properties of the obtained micro-shell crustacean particles are -45-This paper size is applicable to China National Standard (CNS) A4 (210X ^ 97 mm) / 419484 A7 B7 V. Description of the invention (43 ) Is shown in Table 9. Synthesis Example 5 The chitosan fine particles 10s obtained in Synthesis Example 1 were dispersed in 200 ml of methanol, and 200 ml of pyridine and 63 g of anhydrous acetic acid were added while stirring. After stirring overnight at room temperature, The metal mesh made of stainless steel was washed and repeatedly washed with ethanol. After recovery, vacuum drying was performed * to obtain a part of the ethylated chitosan fine particles. The obtained chitin fine particles had a true spherical shape and an average particle size of 10 ym. The effective amine group content and other physical properties of the obtained chitosan fine particles are shown in Table 9. Table 9 H ^ J tK nn -1 ^^^^ 1 '—ii-OJ (Please read the back Please fill in this page again) Printed iS by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs. Example Nα Synthesis Method Raw Material Micose Microparticles Forms Acid Capture Deacetylation Degree C%) Weight Average Molecular Weight Form Average Crypt Path (Jim) than Surface product (m2 / g) Effective amine group amount (raol / g) 1 Emulsified solidified 85 ~ 88 130,000 True spherical 10 63. 0 2 X icr5 2 Emulsified solidified 85 ~ 88 1 30, 000 Non-spherical shaped body 20 50. 0 2 χ 10 -5 3 emulsion coagulation 85 ~ 88 130,000 true spherical 20 64. 0 1 X10 &quot; 5 4 emulsion coagulation 85 ～ 88 130,000 true spherical 10 50. 0 2 χ 1〇-5 5 emulsion coagulation 85 ～ 88 130,000 True Spherical 10 50. 0 1 X l0-s -46- This paper size applies Chinese National Standard (CNS) A4 (21 Ox: 297 mm)! 4194 8 4 A7B7 V. Description of the invention (44 贲 例10 Deodorant lotion (ethanol type) The following deodorant lotion was produced, and a deodorization test was performed for underarm odor. The results are shown in Table 10. &lt; Deodorant lotion sister &gt; Micro-particles (average particle size of 1 m in Synthesis Example 1) 10.0% glycerol 5.0¾ water 10.0¾ ethanol __75.0% total 100.0¾ --------- install-(Please read the precautions on the back first (Fill in this page) Table 10 Comment m. Preparations are applied around 9.00 before coating. The cloth is not covered after coating. (1 hz m) 5 2 Comparative products to clean cloth (control) Β F, Μ 繂 繂 5_ Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs Example 11 Deodorant lotion (volatile silicone type) The resulting deodorizing lotion was subjected to a deodorization test for underarm odor. The results are shown in Table 11. &lt; Composition of deodorant lotion &gt; Polychitosan fine particles (average particle size of Synthetic Example 2 20 m) 50. 0¾ -47 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 419484 A7 B7 V. Description of the invention) Dimethylsilicone _ A certain poly-arsenic argon 10.0¾ 4 0.0¾ Total 100.0¾ Table 11 Appraisal of monk preparations About 9.00 before coating Not coated (coated) 5 5 The product of the invention Polychitosan microparticles (average of synthesis example 2 俾?. 0 wm) 5 1 Comparative product without control cloth (control 1 5 zinc chloride 5 3 (Please read the precautions on the back before filling out this page) Employees of the Central Bureau of Economic Standards Example 12 printed by a consumer cooperative Co., Ltd. 2 Hair-shaped deodorant clams The following hair-like deodorant was produced and tested for underarm odor. The results are shown in Table 12. 2 &lt; Hair-like deodorant Sister &gt; Polychitosan fine particles (average particle size of 10 ym in Synthesis Example 1) 20.0¾ Stearyl alcohol 60.0¾ Talc _______ 20.0¾ Total 100.0¾ 48- This paper size applies to China National Standard (CNS) A4 specification (2ωχ297mm) %> T 4194 8 4 A7 B7 V. Description of the invention (46) Table 12 Tune Coating before coating 9.00 * ί Uncoated (control) 5 F5 Polychitosan fine particles 5 1 of the present invention Synthetic M 1 Average »Zen 2 0 ^ m 1 Comparative product has not been changed (opposite) RS Ar ih Zinc 5 ^ Example 13 Liquid droplet type deodorant The following liquid droplet type deodorant was produced and tested for underarm odor. The results are shown in Table 13. &lt; Liquid droplet type deodorant Agents &gt; Stock Solution I ^ r— mi-i 1 ^ 1-1— J ^ i —III I) &gt; «s.-e (Please read the precautions on the back before filling this page) Central Ministry of Economic Affairs Standard Bureau staff consumer cooperatives printed poly-crust charm ra microparticles (Synthesis Example 4 average particle size 10 m) 12, 5, 5¾ isopropyl myristate 5. 0% glycerol 5. 0, water 5., 0¾ 7 , Alcohol 7? .. Total 100, .0% -49- This paper size is applicable to China National Building Standard (CNS) A4 (210X297 mm) 1 419484 A7 B7 V. Description of the invention (47) Filling the above stock solution 35.0 % l, Pf] Qi Lai _______ β 5. 0% Total 100.0% Table 13 (Please read the precautions on the back before filling in this ) Example 1 4 The powdered fly-catcher type deodorant was manufactured as the following powder spray-type deodorant, and the underarm odor-related deodorization test was performed in accordance with the consumption cooperation of employees of the Central Standards Bureau of the Ministry of Economic Affairs. in. &lt; Powder spray type deodorant sister &gt; Raw liquid polychitosan fine particles (Synthesis example 1 average particle size 1 0 «m) 5,5% talc 46.5% meat SL myristic acid 25.0¾ __ methyl silicon m 5.0% -50- Preparations Evaluation m. Before coating about 9. 0 0 After coating, the product of the present invention is compared. 5 Chitosan fine particles (synthesis example 4 flat clinging grain Zen 1 0 i / m) 5 2 Comparative products are not yet available. Cloth (control) 5 5 argon bell B 3 This paper size is applicable to China National Standard (CMS &gt; A4 size (210 × 297 mm) A7 4194 8 4 B7 V. Description of the invention (48) A certain poly-stone stele 18.5 ¾ Total 100.0¾ Fill the above stock solution 8.0¾ i, pg «m 9 2.0¾ Total 100.0¾ Table 14 Comment m Preparation before coating is about 9. 0 0 and not spread after comparison) 5 5 Polymethylose Microparticles (Synthesis example) Flat tooth granules 撺 1 0 〃 m) 5 1 Comparative products are not distributed (control) 5 B 5_ 2 Examples, 5 Gel-type deodorants (Please read the precautions on the back before filling in this Page) Zhuang-5 Employee Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Following production of the sister made to gel deodorant, the deodorization trials of underarm odor. The results are shown in Table 15. &lt; Gel-like deodorant sister &gt; Polychitosan fine particles (Synthesis Example 5 average particle size 10 w ra) 40 .0¾ Carboxyvinyl polymer 1.0¾ Propylene glycol 10.0¾ Triethanolamine 1.0¾ -51-This Paper size applies to Chinese national standard (CNS &gt; A4 size (2IOX297 mm) Α7 ί 419484 Β7 V. Description of the invention (49) Ethanol 30,0¾ Water ________ 18.0¾ Total 100.0¾ Table 15 (Please read the notes on the back first (Fill in this page again.) Printed in Example 16 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Cream-type (0 / W cream) deodorant Manufacture of the following sister-type 0 / W cream-type deodorant. The results of the underarm odor test were performed. The results are shown in Table 16. The milk ft-like deodorizing agent was formed.> Chitosan fine particles (Synthesis Example 3, average particle size 2 0 um) 10.0¾ Cetyl alcohol 9.0¾ Stearyl alcohol 8.0% petroleum jelly 7,0% mobile stone 7.07.0 polyoxyethylene (20 mol adduct) sorbitan stearate 3.0¾ -52- formulation—W _____ M before coating 9. 0 0 弁 right after coating invention Product comparison: 5 5 Chitosan microparticles (Synthetic Example 5 Flat Cannonball Zen 1 0 Η m) 5 2 Comparative product is uncoated (control) 5 Argonized 繂 3 This paper applies Chinese national standard (CNS) ) A4 specification (2 f 0 X four 7 males) 419484 λ7 B7 V. Description of the invention (5〇) Water __________5 6.0¾ Total 100.0¾ Table 16 Γ 1 Evaluation of the formulation before coating 9. 0 0 _ left and right after coating Cloth inspection (countermeasure) 5 ί The chitosan fine particles of the present invention (synthetic example:? Flat fe granules ?. 0 m) 5 2 Comparative product uncoated (opposite) 5 argon halide 5 3 Example 17 Cream Shape (0 / W Cream) Deodorant A 0 / W cream-type deodorant having the following composition was produced, and a deodorization test was carried out with an underarm odor. The results are shown in Table 17. 7 Type deodorant sister> 1 ^ 1 ^ — ^ 1 &gt; if J m ^ l ί ^ — ί-1 —J 0¾ (Please read the notes on the back of ^ before filling this page) Central Ministry of Economic Affairs Bureau's consumer cooperation with Du printed polychitosan microparticles (average particle size of 20 wm in Synthesis Example 4) 1 0, 0¾ Melamine 10. .0¾ Cetyl alcohol 5, .0¾ Glycerin Base monostearate vinegar 2. .0¾ polyoxyethylene c 20 molybdenum adduct) sorbitan monostearate 2., 0¾ water 81. .0¾ -53- This paper size applies to Chinese national standards (CNS &gt; A4 specifications (210X297 mm) i 41 94 8 4 A7 B7 V. Description of the invention (51)-Squalene__10.0% Total 100.0¾ Table 17 Comment m. 9.00 right before coating Lai Fu cloth f Zhao Zhao 5 Synthetic example 4 of the present invention polymethotose fine particles f Inquiry particle size 1 Ou τη) 5 2 Comparative product without inspection cloth (control) 5 5 5 3 Example 1S Creamy type ( 0 / W cream) Deodorant A 0 / W cream-type deodorant having the following composition was produced, and a deodorization test was performed for underarm odor. The results are shown in Table 18. &lt; Cream-type deodorant sister Cheng &gt; Polychitosan fine particles (Synthetic Example 5 average particle size 20 um) 40.0¾ (Please read the precautions on the back before filling out this page) Employees' Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Printing solid paraffin 8.0¾ beeswax 8.0¾ petrolatum 12.0¾ polyoxyethylene (20 mol adduct) sorbitan stearate 4.0% mobile paraffin 10.0% -54- This paper size applies to Chinese national standards (CNS ) A4 specifications (210XW7 mm) f 41948 4 A7 B7 V. Description of the invention (52) M .___________ 18.0¾ Total 100.0¾ Table 18 Appraisal of monk preparations before coating After coating around 9.00, check the cloth (control) S 5 The chitosan fine particles of the present invention 5 2 (Synthesis Example 5 Average particle size 10 wm 1 Comparative test cloth (control) 5 Argon t octane 5 3 Example 1 9 The following composition is produced by a spheroidal spray type deodorant The tired droplet-type deodorant was subjected to a deodorization test with lame odor. The results are shown in Table 19. &lt; Liquid droplet-type deodorant &gt; Original solution 1 ^^^ 1--. ^^ 1 «^^ 1 n -1«. '«^^ 1 n ^ i« i I-^^^ 1 ^ ¾., Va &gt; (Please read first Note on the back, please fill in this page again.) Polychitosan microparticles printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (average particle size 10 wm) 1. 5% isopropyl myristate 5 · 0¾ glycerin 5 0% water 5. 0¾ leaven 2, 5% total 100. 0¾ -55- This paper size is applicable to China National Standard (CNS) A4 (210X 297mm) Central Government Bureau of the Ministry of Economic Affairs Consumer Cooperatives Seal 419484 V. Description of the invention (55) Filling the above-mentioned stock solution LPGM §§ A7 B7 35.0¾ 6 5.0¾ Total 100.0¾ Table 19 Evaluation of coating before coating 9.0 coating after coating (vs. 1 5 S polycarat of the present invention) Sugar particles 5 1 ί Synthetic Μ 1 Flat particle size 10 m) Comparative product uncoated (control) B Zinc argon 5 1 Actual pickling example 2 0 Powder droplet deodorant Manufacture of powder droplet type deodorant with the following composition The deodorant test was performed on the foot odor. The results are shown in Table 20. &lt; Composition of powdered fly 沬 type deodorant &gt; raw liquid polychitosan fine particles (Synthesis Example 2 average particle diameter 20 μm) 5.0% Talc 46 .5¾ Myristate 25.0¾ Dimethicone_ 5.0¾ -56 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 cm) (Please read the precautions on the back before filling this page) 4 A7 B7 V. Description of the invention (54) 18.5% of a certain polypyrazine is filled with the above-mentioned stock solution LPG gas 100.0¾ 8.0% 9 2.0¾ total 1 00. 03ί Table 20 m 檲 preparations around 9.00 before coating The cloth was not inspected after coating. 对照 Control) B 5 The chitosan microparticles of the present invention (will be taken as Example 2 and the weight is 1 capsule and 20 quotations; m 1 5. 1 Comparative product is not cloth control.) Fi S Zinc argon_5 3 (Please read the precautions on the reverse side before filling out this page) Example of printing and marinating in the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 2 1 Put a cotton pad under the armpit of the body odor test subject for 1 day, and take the odor. Then, the cotton was soaked with methanol for about 20 people, and the odor was recovered (about 2 liters). Concentrated to about 601111> This was used as a body odor sample. · A 300ml beaker was filled with a paper of 70 μm in diameter &gt; The above-mentioned odor sample of 0.35 s was added to the bottom to make it penetrate. After standing at room temperature for 3 minutes, sprinkle the following deodorant 0.2s. After standing at room temperature for 2 minutes, the test was performed with 4 persons who were not qualified as deodorants as controls. 57 paper sizes are applicable to China National Standard (CNS) A4 (210X297 mm) 1 4194 8 4 at Β7 5. Description of the invention (55) The same as the 6-stage evaluation of Example 1 0-20. The zinc oxide was evaluated similarly as a comparative product. The results are shown in 21. &lt; Composition of deodorant &gt; Chitosan fine particles 2.0¾ Ethanol 20% Silicone SH245 [manufactured by Toden Road Silicone Co., Ltd.] Balance sheet 21 Pack-(Please read the precautions on the back before filling this page) The following The present invention will be described in more detail by giving examples of polysiloxanes, but the present invention is not limited in any way by these examples. Synthetic Example 0 of the Consumer Cooperative Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Synthesis Example of Modified Polysiloxanes with Long-chain Alkyl at Both Ends) In a 1-liter autoclave replaced with nitrogen, 400 ml of dry cyclohexane and tetramethyl ethyl were fed. Diamine 3mi, n-butyllithium (l.Smoi / liter) 12.5ml (0.02! Tt〇l), keep the temperature of the reaction system at 30 t :, ethylene gas introduction pressure is maintained at 2ks / cm2, ethylene gas conduction People 8.2 liters. Then, the ethylene gas was removed, and nitrogen substitution was performed. In advance, in a 1 liter flask, a solution of quasi-octamethylcyclotetrasiloxane 11.8 s and 10 ml of dry brilliant cyclohexane was added dropwise to the aforementioned polymerization mixture under a stream of nitrogen. After the dropwise addition was completed, after reacting at 30 ° C for 1 hour, the reaction mixture was poured into 2 liters of methanol. After mixing for 1 hour, decompression was performed to reduce the pressure to -58 &quot; [: dagger comparison product 珥 珥 珥 艄 艄 艄 艄 艄 艄 梓 梓 平 艄 艄 艄 艄 添加 添加 添加 添加 添加 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 例 剜 2 剜 Synthetic 剜 1 僭1 1 ~? . This paper uses the Chinese national standard (CNS &gt; A4 specification (2 丨 0X297mm) A7 419484 _____ _ B7 _ V. Description of the invention (56) —-------- Installation ----- -Order Γ, please read the unintentional matter on the back before filling in this page} The solids generated by the collection. Dry in a high temperature furnace under vacuum at 50t for 24 hours to obtain a white solid. The yield of the product is analyzed ('O-dichlorobenzene, 135υ, polyethylene standard sample calibration made by Waters) As a result, the number average molecular weight was 61 and the molecular weight distribution was Log. HMR analysis (Bruker, 200MHz, chloroform-d, 50f, The result is WS). At-〇.05ΡΡίη (single peak) is the methyl group linked to the base of methyl sand, and at 0.4 ppm (trimodal) is the bond to the silyl group Ethyl chloride, at 0.3 P pm (three peaks) as the starting terminal methyl group, and the main chain methylene group signal near 丨 2 pp ^. From the integral ratio of each signal, it can be seen that the terminal silyl group is introduced荜 99¾. And &gt; The introduction rate of the siloxane unit is 1.4 per 2 ends. Second, it can be divided into 1 liter with a condenser installed. Into the flask, put synthetic terminal silylate-based polyethene 12_.0g octamethylcyclotetrasandoxan 88g and toluene 100ml, and heat on an oil bath until the toluene is refluxed. All raw materials are employees of the Central Standards Bureau of the Ministry of Economic Affairs Consumption cooperation Du-printing-dissolution time * potassium hydroxide 0.001ε was added, and then refluxed for 48 hours. Then * 1 NH fermented hydrochloric acid solution 0.1 8 ra 1 was added, and thoroughly stirred. Add water * Make sure the pH is 7. Take out the inorganic salt generated by water. After heating, wash it three more times. * Install a Ting Stark tube instead of the condenser and carry out the reflux of methylbenzine until it is completely dehydrated. Distill the toluene off to get a rubber knee shape. The white tincture. The yield of the product was 96 g. Results of GPG analysis (manufactured by Waters, o-dichlorobenzene, 135T :, converted polystyrene) &gt; The weight-average molecular weight was 1866, and the molecular weight distribution was 2.03 ° UMR analysis (made by Brisker, 200MHz, chloroform-d, 50¾, standard -59- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm &gt; 1 41948 4 Α7 __- ___ Β7 Explanation (5) Member of the Central Bureau of Standards, Ministry of Economic Affairs Consumption cooperation Du printed standard is the result of the use of TMS). At -〇, 〇5 pp ^ (single peak) is methyl group bonded to methyl sand complex, 0.4 ppm (three peaks) is bonded to methyl a The signal of the methylene group of the silane group and 0.8 ppra (tri-peak) is a start terminal methyl group, and the methylene group of the polyethylene chain is near the u 2 ppra. From the integral ratios of the respective signals &gt;, it can be seen that the weight ratio of the polyethylene portion to the oxasane portion is 10: 9 (). The DSC temperature rise measurement * melting point (peak of the endothermic peak) is 92t :. Synthesis Example 7 (Synthesis Example of Side Chain Alkyl Modified Polysiloxane) In a 1-liter separable tin bottle equipped with a condenser, PS12 () Mw made of methyl hydrogen denatured polyoxaxane (strand) was etched = 227〇) 79s and Zialian 18 (Mitsubishi Chemical Co., Ltd., 1-octadecene) 20s, toluene: 00 ^ 1 'Add platinum chloride in platinum conversion]. Q〇PPia, in Got: The reaction was continued for 24 hours, and β was re-precipitated and purified using ethanol twice, to obtain a slightly dark-colored soft cream. Yield is 99s * Melting point is 23 ° C. As a result of UMR analysis and IR analysis, the terminal hydrogen residual ratio was 0¾, and the olefin residual ratio was U. Synthesis Example 8 (Synthesis example of both-terminal alkyl-denatured polysiloxane) In a 1-liter separable young flask equipped with a condenser, a terminal hydrogen-denatured polysiloxane (PS537, manufactured by Chinose 7 Co., Ltd., Mw = 440) ) "-Hydrocarbon mixture" on 38gM for 7 4 s, toluene 100 m 1, add platinum chloride manganese platinic acid 100 P m in platinum conversion, and react at 30 t for 24 hours. After reprecipitation and purification, a slightly brown soft wax was obtained. The yield is 98g and the melting point is 42Ό. As a result of iH-NMR. and IR analysis, the terminal hydrogen residual ratio was 1¾, and the olefin residual ratio was 8¾. Test Example 1 The denatured polysiloxanes obtained in Synthesis Examples 6 to 8 above, or the paraffin wax (melting point 68 1C, Japanese refined wax) as a comparison, were used as the wax composition according to Table 60. This paper is in accordance with China's national standards. (CMS &gt; Α4 specification (210X297mm) (Please read the precautions on the back before filling out this page) Pack.-* Ί 41948 4 Α7 Β7 V. Description of the invention (Deng) 22 Sisters into a suspension-like sister These suspension-like compositions were coated on the mature fur, and the measurement of the residual rate and the state of the surface when the surface was rubbed at 37 ° C were observed. The coating was coated on a glass film and measured. Moisture permeability (unit: g / m 2-2 4 hr / 19 y in), using chlorinated bond as moisture absorption agent, measured at 25¾, 6 5¾ RH). The results are shown in Table 22. Table 22 Comparative product of the present invention I 2 3 4 Formulation composition r—% by weight% 'W Long-chain alkyl-denatured polysiloxane at both ends (Synthesis Example 1) 10 One-side-alkyl-denatured polysiloxane ( Synthesis Example 2) ~ 10 Two-terminal alkyl-denatured polysiloxanes (Synthesis Example 3)-10-Shiga (melting point 68 ° C, made from refined wax) One-one-10 octamethyltetracyclic silicon (Toshiba TSF404) 30 30 30 30 Isopentane 50 50 50 50 Ethanol 10 10 10 10 Test item Residual rate of giant film C% by weight) 78 13 23 9 Surface inspection oily oily wax Moisture Permeability (g / m2-24hr / 10 ^ m) 790 14 121 2 &quot; • 61 * · Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Applicable to Chinese National Standard (CNS) A4 (210X297mm) I 4194 84 A7 Yinju B7, Consumer Work Cooperative, Central Standards Bureau, Ministry of Economic Affairs ___ ____ __ _ V. Description of the invention (59) Synthesis example 9 (amphoteric porosity Synthesis of microparticles M) Commercially available polychitosan [SK-10 manufactured by Jiayang Chemical Co., Ltd., degree of deethylation 85 ~ 88¾ (Mean weight average molecular weight 130000) 80 liters, adding 900 g of human water to form 900 g, and then adding 34.6 g of methacrylic acid (compared with the equivalent amount of the monosaccharide unit of polymethylose) ... Stir at 6 ο υ While dissolving it, it will prepare a polychitosan / methacrylic acid aqueous solution. Then add it—a solution formed by dissolving 3 g of potassium persulfate in 100s of ion-exchanged water, and search for several minutes at room temperature. K 5/5 of A ratio (volume ratio) of the chitosan solution and a 1.0% by weight hexane solution of sorbitan monolaurate vinegar was mixed in a high-speed homogenizer (U 5000 rpni) to form a W / 0 emulsion. Secondly, the polymerization reaction was performed at 70 t for 2 hours, and then cooled to normal temperature, the surface was dropped into an acetic acid solution with a volume 5 times the volume (volume), and the surface was sampled. After mixing for 30 minutes, Agglutinate was removed by decantation, and after soaking / sowing in ethanol, the Knoop filtration process was repeated three times, and the particles were obtained by vacuum drying. The average particle size of the obtained fine particles was 1 2 ^ ra * The shape was true spherical and the specific surface area was 50 ^ / vol. Example 22 Two-terminal long-bond alkyl-denatured polysiloxanes synthesized in Synthesis Example 6 were used. Two porous microparticles synthesized in Synthesis Example 9 were used to prepare a deodorizing soft arrow according to the sister of Table 23. This paper size applies to Chinese national standard (CNS &gt; A4 size (210X297 mm) (Please read the precautions on the back before filling out this page}) -5-419484 A7 B7 V. Description of the invention (60)

表 23 辋配 成分 辋配量（雷s %) 兩末端長鏈烷基變性聚矽氧烷 20 (舍戚M 兩务礼件微粒芊r合成俐91 10 二申某趵蒯 10 八申某四頊肿氬烷 .10 毐丙某棕櫊酸醅 20 磾脂_ B m « 合計 ^IJLQ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 實施例2 3、2 4 K相同量使用合成例7所合成之側鏈烷基變性聚矽氧烷 、合成例8所合成之兩末端烷基變性聚矽氧烷K取代合成 例S所合成之兩末端長鏈烷基變性聚矽氧烷*並依實例 2 2之製法，調製除臭軟齋。 實腌例25 Μ相同童使用混成氧化梓以取代合成例9所合成之兩性 多孔性微粒子，並依實施例22之製法，調製除臭軟#。 比較例3 Μ相同量使用石蠟（融點1 6 8 I〕，日本精製蠘）Κ取代 合成例6所合成之兩末端長鏈烷基變性矽氧烷，並依實施 例22之製法*調製除臭軟膏。 -6 3- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ! 41948 4 A7 B7五、發明説明（61 ) 試驗例2 有關K實施例22〜25及比較例3所調製之除臭軟豪，依 下述之方法進行除臭效果的試驗。结果表示於表2 4中。 &lt;試驗方法&gt; 從健康之男性（2 Q〜4 0歲）選取腳很臭的人並依專門評 定小姐4人的評價進行試驗。早上9點依評定小姐4人進 行官能評價，評價後以各例所調製之除臭軟齎適量塗布於 左右腳的局部位，塗布後1小時、8小時後進行評價。又 ，為了比較，有關合成例9所合成之兩性多孔性微粒子及 混成氧化鋅亦同樣地進行評價。評價係使用下述之6階段 評價*由專門評定小姐4人實施。又，8小時後進行塗布 面外觀之觀察。 評價基準： 0 :不臭 1 :微臭 2 :臭味弱 3 :明顯臭味 4 :臭味很強 5 :臭味非常強 IF I t I f I I --1 —i I I -1 - : I I ΪΓ 一aJ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印黎 -64- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） Α7 ί' 41948 4 _Β7 五、發明説明（62 ) 表 24 塗布 前 塗布 後 1小時 狻 8小時 塗布面 外親 實施例2 2 5 0 ! 1 8 平滑、很難 知谙有猞布 實施例2 3 5 1 ! 3 3 僅殘存少許 油狀物 實施例24 ' 5 1 0 1 1 2 如塗布油般 姑滯 實腌例2 5 5 0 3 3 平滑、有殘 白 hh m m .*? 0 4 白色，龜II 去途布 5 5 兩性多孔 性微粒子 1 ί合成剜Q) 5 0 4 4 幾乎未殘留 遐成Μ化繂 5 0 4 Β 幾平未溥留 實施例2 6 --I I- 1 I -- - - - HH ^^1 - I - —1 _ ^~ί 二=u (請先閏讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作杜印製 使用合成例6所合成之兩末端長鐽烷基變性聚矽氧烷、 合成例9所合成之兩多孔性微粒子、K調製Μ下表2 5之組 成原液，並使用此原硖1 0重量_、LPG氣體90重量％而充 填至飛沫罐中，Κ調製除臭飛沫。 -65* 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 419454五、發明説明（63 Μ Β7 表 2 5 調 配 成 份 ί κ # (mm%) 兩 末 端 長 鍵 基 變性聚S夕氧烷 25 ( 合 例 兩 劣 孔 件 微 料 子 (合戚俐in 10 滑 石 1 0 異 丙 華 肉 W 转 醉 酷 5 —. m 概 里 1 5 _Δ_ 甲 華 四 環 氧 烷 ί Η 二 甲 華 Μ 嗣 10 j計 1 00 實施例2 7、2 8 經濟部中央標準局員工消費合作社印製 以相冏量使用合成例7所合成之側键烷基變性聚矽氧烧 、合成例8所合成之兩末端烷基變性聚矽氧烷K取代合成 例6所合成之兩末端長鍵烷基變性聚矽氧焼，並依實施例 26之製法，調製除臭飛沫。 實施例29 以相同量使用混成氧化鋅以取代合成例9所合成之兩性 多孔性微粒子*並依實施例2 6之製法•調製除臭飛沫。 比較例4 K枏同量使用石蠟（融點6 3 1D、日本精製蠟）以取代合 成例6所合成之兩末端長鏈烷基變性矽氧烷，並依實施例 26之製法，調製除臭飛床。 -66- --------^------1Τ------^.械 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標隼（CNS } Α4規格U10X297公釐） f 41948 4 A7 B7五、發明説明（64 ) 試驗例3 有關實施例26〜29及比較例2所調製之除臭飛沫而進行 除臭效果之試驗。試驗方法係同於試綠例2 。將試驗結果 表示於表26中。 表 28 經濟部中央標準局員工消費合作社印製 塗布 前 塗布 後 1小時 後 8小時 塗布面 外觀 實跑例26 5 0 0 1 很難知道 塗布 實施例2? 5 1 3 4 僅殘存少許 油狀物 實施例28 5 0 1 3 僅殘存少計 油狀物 官施例？.9 5 0 3 3 赂總留ft诗， hh齩例4 5 .*? 4 4 如_ h粉末 来域布 5 5 5 兩性多孔 性微粒子 (合成例9) 5 0 4 4 幾乎不殘留 渴成酸化 5 ί 1 0 1 4 5 幾乎不殘留 -67- 本紙伕適用中國國家標準（CNS ) A4規格（2:0X297公釐） (諳先閱讀背面之注意事項再填寫本頁)Table 23 Wing formulation ingredients Wing formulation (Rays%) Long-chain alkyl denatured polysiloxanes 20 at both ends (Mr. M. Bi-service gift microparticles 合成 r Synthetic 91 10 Two application 10 10 application four Bloated argane. 10 Acrylic brown palmitic acid 20 Acetate _ B m «Total ^ IJLQ (Please read the precautions on the back before filling this page) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 2 3 The same amount of 2 4 K was used as the side chain alkyl-denatured polysiloxane synthesized in Synthesis Example 7, and the two-terminal alkyl-denatured polysiloxane synthesized in Synthesis Example 8 was used instead of the two-terminal long chain synthesized in Synthesis Example S. Alkyl-denatured polysiloxanes were prepared in accordance with the method of Example 2 2 to prepare deodorant soft fast. Example 25: The same child used mixed oxidized cataleps instead of the amphoteric porous microparticles synthesized in Synthesis Example 9, and according to the examples 22 的 制 法 ， 制作 除臭 柔 #. Comparative Example 3 The same amount of paraffin wax (melting point 1 6 8 I], Japanese refined 蠘) was used in place of the two-terminal long chain alkyl denatured siloxane synthesized in Synthesis Example 6, And prepare the deodorant ointment according to the manufacturing method of Example 22. -6 3- This paper size is applicable to China Standard (CNS) A4 specification (210X297 mm)! 41948 4 A7 B7 V. Description of the invention (61) Test example 2 For the deodorant softeners prepared in Examples 22 to 25 of K and Comparative Example 3, follow the method below The deodorizing effect was tested. The results are shown in Table 24. &lt; Test method &gt; From healthy males (2Q ~ 40 years old), people with bad-smelling feet were selected and tested according to the evaluation of 4 women who were specially rated The sensory evaluation was performed at 4 o'clock in the morning according to the evaluation of the four women. After the evaluation, an appropriate amount of the deodorant soft palate prepared in each case was applied to the local positions of the left and right feet, and the evaluation was performed 1 hour and 8 hours after the application. For comparison, The amphoteric porous fine particles and the mixed zinc oxide synthesized in Synthesis Example 9 were also evaluated in the same manner. The evaluation was performed by 4 people using the following 6-stage evaluation *, and the appearance of the coated surface was observed after 8 hours. Evaluation criteria: 0: no odor 1: slight odor 2: weak odor 3: obvious odor 4: very strong odor 5: very strong odor IF I t I f II --1 —i II -1-: II ΪΓ aJ (Please read the notes on the back before filling out this page) Ministry of Economy Employees 'Cooperative of the Central Bureau of Standards, Yinli-64- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) Α7 ί' 41948 4 _Β7 V. Description of the invention (62) Table 24 1 hour after coating 涂布8 hours of coating the outer face Example 2 2 50 0! 1 8 Smooth, hard to know if there is a cloth Example 2 3 5 1! 3 3 Only a little oil remains Example 24 '5 1 0 1 1 2 Such as Oil-like stagnation case 2 5 5 0 3 3 Smooth, whitish hh mm. *? 0 4 white, turtle II Totubu 5 5 amphoteric porous fine particles 1 剜 synthetic 剜 Q) 5 0 4 4 almost There is no residual chemical compound 5 0 4 Β Jiping did not retain Example 2 6 --I I- 1 I----HH ^^ 1-I-—1 _ ^ ~ ί two = u (Please (Read the precautions on the back before filling out this page.) Consumption cooperation with employees of the Central Bureau of Standards of the Ministry of Economic Affairs. Du printed the two-terminal long alkyl alkyl modified polysiloxane synthesized in Synthesis Example 6, and the two porous materials synthesized in Synthesis Example 9. The microparticles and K are prepared in the following composition liquids of the following Table 5 and filled into the spray cans using this raw material: 10% by weight and 90% by weight of LPG gas. Deodorant droplets. -65 * This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 419454 V. Description of the invention (63 Μ7) Table 2 5 Formulation ingredients κ # (mm%) Long-end bond group denatured polystyrene at both ends Oxygen 25 (common example two small holes in the micro-material (He Qili in 10 talc 1 0 isopropyl Chinese meat W Zhuzuo cool 5 —. M 里 里 1 5 _Δ_ 甲 华 四氢 氢 ί Η dimethyl hua M嗣 10 j counts 1 00 Example 2 7, 2 8 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, using side-bonded alkyl denatured polysiloxanes synthesized in Synthesis Example 7, synthesized in Synthesis Example 8 The two-terminal alkyl-denatured polysiloxanes K were substituted for the two-terminal long-bond alkyl-denatured polysiloxanes synthesized in Synthesis Example 6, and the deodorizing droplets were prepared according to the method of Example 26. Example 29 The same amount was used and mixed Zinc oxide was used in place of the amphoteric porous fine particles * synthesized in Synthesis Example 9 and the deodorizing droplets were prepared according to the manufacturing method of Example 26. Comparative Example 4 Paraffin (melting point 6 3 1D, Japanese refined wax) was used in the same amount as Substituted for Synthesis Example 6 The two end long-chain alkyl denatured siloxanes were prepared in accordance with the method of Example 26 to prepare a deodorizing flying bed. -66- -------- ^ ------ 1Τ ----- -^. MACHINE (Please read the precautions on the back before filling out this page) This paper size is applicable to Chinese national standard (CNS} Α4 size U10X297 mm) f 41948 4 A7 B7 V. Description of the invention (64) Test example 3 Related The deodorizing effect of Examples 26 to 29 and Comparative Example 2 was used to test the deodorizing effect. The test method is the same as that of Test Green Example 2. The test results are shown in Table 26. Table 28 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Consumption Cooperative Printed before coating 1 hour and 8 hours after coating Example of coating surface running example 26 5 0 0 1 It is difficult to know the coating example 2? 5 1 3 4 Only a little oily material is left Example 28 5 0 1 3 Only Example of remaining oily matter ?. 9 5 0 3 3 Total ft poem, hh Example 4 5. *? 4 4 Such as _ h powder to cloth 5 5 5 Amphoteric porous fine particles (Synthesis Example 9 ) 5 0 4 4 Almost no residual thirsty acidification 5 ί 1 0 1 4 5 Almost no residual -67- This paper sheet applies Chinese National Standard (CNS) A4 specification (2: 0X297 mm (Read the notes come to know first and then fill in the back of this page)

Claims (1)

A8 B8 心專利範圍 一種兩性多孔性微粒子*係由驗性多糖、與具有反應性 乙烯基之有機酸或其鹽之聚合體所構成，平均粒徑為 以下·其中鹼性多糖為聚甲殼耱或聚半乳糖胺· 而具有反應性乙烯基之有櫬酸為甲基丙烯酸或丙烯酸。 3. 5 . 經济部令央糅準局負工消费合作社印装 8. 根據申 粒子係 根據申 面積為 根據申 性多糖 根據申 反應性 一棰如 ，係使 溶液· 而每一 酸*其 愿性乙 根據申 其中在 添加聚 多糖之 一棰除 或2項 讁專利範圍第 圼球狀a 讀專利範圍第 10〜300m2/g c 請專利範匾第 為聚甲殼糖。 請專利範匾第 乙烯基之有機 申請專利範匾 含有《性多糖 於疏水性溶劑 «性多糖之單 中鹼性多糖為 烯基之有機酸 諸專利範圍第 聚合終了後， 合反應液，以 單糖單元使用 臭劑姐成物· 中之多孔性徽 1項之多孔性微粒子•其多孔性微 1或2項之多孔性微粒子 &gt; 其比表 1或2項之多孔性微粒子 &gt; 其中鹼 1或2項之多孔性微粒子，其中具有 酸或其鹽為甲基丙稀酸或其》。 第1項之多孔性微粒子之製造方法 與具有反應性乙烯基之有櫥酸的水 中轧化或懸浮|然後再使其聚合· 糖單元使用0.1〜500倍莫耳之有櫬 聚甲毅糖或聚半乳糖胺*而具有反 為甲基丙烯酸或丙烯酸。 6項之多孔性微粒子的製造方法* 於含有鹼之有機溶劑中滴人或一次 使多孔性微粒子析出，而每一《(性 0. 1〜500倍II耳之有機酸。 其待戡在於含有申謅專利範圃第1 粒子0.1〜70重量K及其他之任 (請先閨讀背面之注意事項再填寫本頁) 本紙法尺度適用中國國家揲準（CNS) Α4洗格（210&gt;&lt;297公釐） 41 948 4 Α8 Β8 C8 D8 六、申請專利範圍 9 . 10 11 12 13 14 15 意化 根據 任意 根據 融點 根據 糖為 根據 鏈烷 具有 根據 鐽烷 40重 根據 物霣 根據 垸係 粧品成 申請專 化粧品 申請專 20 t：以 申講專 聚甲殼 申講專 基之聚 長鐽烷 申請專 基之聚 申謫專 份 0 . 01 利範圍 成份係 利範圓 上之具 利範圍耱。 利範圔 矽氧烷 基。 利範園 矽氧烷 〜9 9重量3!。 第3項之除奥劑姐成物，其中其他之 油劑。 第9項之除臭m姐成物，其中油劑係 長鏈烷基之聚矽氣烷。 第8項之除臬劑姐成物，其中麯性多 第10項之除臭_姐成物•其中具有長 其融點為60〜140 1C ，且分子兩末斓 第10項之除臭劑姐成物，其中具有長 中的長Μ烷基部分之總比率為0.5〜 利範圃第10項之除舆劑姐成物，其含有驗性 申請專利範匾第10項之除奥劑姐成物，其中聚矽氧 如式（I )所定義， (請先Μ讀背面之注意事項存填寫本頁) 經濟部中央榣率局員工消费合作社印東 C ΗI — ( C Κ 2) CH： ' /CHi 丨.ί 1 '1S i - 0 t— S i -i V ί CHa xCH3 CH：i - (OH：) „ — CHi CH, ί ) (式中· r&gt;為長鍵烷基之平均碳数*亦即U + l)為30以 上之數目，Η為0 Μ上之數目）° 16.根據申譆專利範圍第項之除奥劑姐成物’其中β之值 本紙張尺度逋用中國«家梂準（仁邮）八4規&gt;格（210&gt;&lt;297公釐&gt; ^ 419484 I D8六、申請專利範圍為 100 至 5000 。 ---------农-- {請先Μ讀背面之注意事項再填寫本頁) ΪΤ 經濟部中央楳率局工消费合作社印装 本纸張尺度適用中國國家播準（CNS } Α4規格（210X297公釐）A8 B8 Heart Patent Scope Amphoteric porous microparticles * are composed of polymer of test polysaccharide and organic acid or salt with reactive vinyl group, the average particle size is below. Polygalactosamine. The reactive vinylic acid is methacrylic acid or acrylic acid. 3.5. Order printed by the Ministry of Economic Affairs, Central Bureau of quasi-bureau, Consumer Cooperatives 8. According to Shen particles, according to Shen area, according to Shen polysaccharide, according to Shen reactivity, such as solution, and each acid * its wish According to the application, one or two of the polysaccharides are added. The scope of the patent is the spherical one. The scope of the patent is 10 ~ 300m2 / gc. The patent plaque is the polychitin. Please apply for the patent application. The organic application patent application for vinyl group contains "sex polysaccharides in hydrophobic solvents." The polysaccharides in the list of basic polysaccharides are alkenyl organic acids. After the scope of the patents is polymerized, the reaction solution is combined. The sugar unit uses odorant products. Porous microparticles in item 1 of the porous emblem. • Porous microparticles in which the porosity is 1 or 2 &gt; It is more than the porous microparticles in table 1 or 2 &gt; where alkali The porous fine particles according to item 1 or 2, wherein the acid or the salt thereof is methyl acrylic acid or》. The method for producing porous fine particles of the first item and rolling or suspending in water with a reactive vinyl acid having cabinet acid | and then polymerizing it. Use a sugar unit of 0.1 to 500 times the molar polymethylmethacrylate or Polygalactosamine * instead has methacrylic acid or acrylic acid. Method for producing porous fine particles according to item 6 * Dropping a person in an organic solvent containing an alkali or precipitating the porous fine particles at a time, and each of the organic acids of (0.1 to 500 times II ears. It is to be contained in that Shenyang Patent Fanpu No. 1 particle 0.1 ~ 70 weight K and others (please read the precautions on the back before filling out this page) The paper method scale is applicable to China National Standards (CNS) Α4 wash grid (210 &gt; &lt; 297 mm) 41 948 4 Α8 Β8 C8 D8 VI. Application for patent scope 9. 10 11 12 13 14 15 Proprietary according to any melting point based on sugar based on paraffinic based on pristane based on 40 weight based on physical properties Successful application for cosmetic application for 20 t: application of poly-cryptoxane for application of poly-crust, application for application of polymer-specific application for application of the application for the application of the application for the application of the application for the application of the application for the application of the application for the application of the application for the application of the application for the application of the patent (01)圔 Silyoxyalkyl. Lifanyuan Siloxane ~ 9 9 Weight 3 !. The deodorant product of item 3, among other oils. The deodorant product of item 9, where oil is long Polysiloxane of alkyl group. Divide by item 8 Deodorant product, which has the deodorant of the 10th item_Older product • Among them, it has a long melting point of 60 ~ 140 1C, and the molecule has the deodorant product of the 10th product, which has The total ratio of the long M alkyl moiety in the long middle is 0.5 to 10. The product of the herbicide remover of Lifanpu Item 10, which contains the product of the herbicide remover of the 10th patent test plaque, of which polysiloxane As defined by formula (I), (please read the precautions on the back and fill in this page) Yindong C ΗI — (C Κ 2) CH: '/ CHi 丨 .ί 1 '1S i-0 t— S i -i V ί CHa xCH3 CH: i-(OH :) „— CHi CH, ί) (where r &gt; is the average carbon number of the long-bond alkyl group *, that is, U + l) is a number of 30 or more, Η is a number on 0 M) ° 16. According to the Shenhe patent scope of the Olympics in addition to the product 'of the value of β in this paper size, the use of Chinese «家 梂 准 （仁Post) Rule 4 &gt; Grid (210 &gt; &lt; 297 mm &gt; ^ 419484 I D8 6. The scope of patent application is 100 to 5000. --------- 农-{Please read the back first (Notes on this page, please fill out this page) Printed by the Industrial and Consumer Cooperatives of the Central Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China The paper size is applicable to China National Broadcasting Standard (CNS) Α4 size (210X297 mm)