201247229 六、發明說明: 【發明所屬之技術領域】 本發明係關於-種皮膚外用劑。更詳細而言,係關於 下皮膚外用劑,其係調配有擔載有銀離子之抗菌性沸石 •分末’且可減少或防止擔載有銀離子之抗菌性沸石粉末造 成之浮粉。 【先前技術】 抗菌性'弗石粉末係作為防腐劑或除臭劑而調配於化妝 料或準藥品等皮膚外用劑中。 例如’研製有調配有抗菌性彿石之抗菌性喷霧用組成 物(專利文獻1)或防臭化妝料(專利文獻2)。又,關於 改良了耐變色性之防臭化妝料,揭示有於抗菌性沸石中調 配聚矽氧之技術(專利文獻3 )。 以防臭或除臭為目的之抗菌性沸石大多係使用擔載有 銀離子之抗菌性滞石(專利文獻4、專利文獻5)。 方面調配有擔載有銀離子之抗菌性沸石之皮膚 ,用劑會產生擔載有銀離子之抗菌性沸石造成之浮粉問 題即,右使用調配有擔載有銀離子之抗菌性沸石之皮膚 外用劑,則存在於經塗佈之身體部位有浮粉明顯之問題。 為防止擔載有銀離子之抗菌性沸石造成之浮粉,於專 卜獻6中揭示有將一定量之乙醇與甘油加以調配之技 ’好」而其效果並不充分,且存在於高溫下產生變臭或 黑色異物之問題點。 於專利文獻7中揭示有藉由於調配有擔載有銀離 201247229 子之抗菌性沸石之止汗氣溶膠式化妝料中 特定之搭$ 烷衍生物而於使用後不易突顯白色之化妝料。然疋環氧 文獻7僅為氣浴膠式化妝料所特定之技術。又、;、、專和 溶膠式化妝料之液狀化妝料中組合擔載有銀離子於並非氣 沸石與特定之環氧烷衍生物之情形時,無法防止菌性 而,於專利讀7之止汗氣溶膠式化妝 之問題。 產生變臭 專利文獻1 專利文獻2 專利文獻3 專利文獻4 專利文獻5 專利文獻6 專利文獻7 【發明内容 本發明者等人繁於上述觀點,為了防止由擔載有銀離 子之抗菌性沸石粉末所引起之浮粉,針對調配有擔載有銀 離子之抗生沸石粉末之皮膚相劑進行潛心、研究,杜果 發現,若調配數量平均分子量為7GG〜4_ U丙二^ 聚丙二醇與聚丁二醇之共聚物、或聚丙二醇之衍生 可獲得塗佈後白色不明顯且能夠減少或防止浮粉之 用劑’從而完成了本發明。 本發明之目的在於提供一種皮膚外用劑,其係t周配有 擔載有銀離子之抗菌性彿石粉末者,且可減少或防止擔栽 曰本特開昭63-250325號公報 曰本特開平8-26956號公報 曰本特開平8-92051號公報 曰本特開2004-307375號公報 曰本特開2010-159214號公報 曰本特開2009-234995號公報 曰本特開2004-149434號公報 4 201247229 有銀離子粉末造成之浮粉。 即,本發明提供一種皮膚外用劑,含有: (A) 擔載有銀離子之抗菌性沸石、及 (B) 數量平均分子量為700〜4000之聚丙二醇、聚丙 一醇與聚丁二醇之共聚物、或聚丙二醇之衍生物之任一者。 又,本發明提供一種如上述之皮膚外用劑,其中,上 述(B)聚丙二醇之衍生物為數量平均分子量為7〇〇〜4〇〇〇 之聚氧丙烯甘油醚、聚氧丙烯山梨糖醇、聚氧丙烯丁醚之 任一者0 進而,本發明提供一種如上述之皮膚外用劑,其相對 於皮膚外用劑總量含有3〇質量%以上之乙醇。 又,本發明提供一種如上述之皮膚外用劑,其中,上 述皮膚外用劑為液狀化妝料,且該皮膚外用劑為填充於滚 塗式(r〇ll-on)容器中之防臭化妝料。 進而,本發明提供一種如上述之皮膚外用劑,其中, 上述皮膚外用劑為液狀化妝料,且該皮膚外用劑為填充於 氣溶膠式或分注式(dispenser)容器中之霧狀防臭化妝料。 又,本發明提供一種如上述之皮膚外用劑,其中,上 述皮膚外用劑為液狀化妝料’且該皮膚外用劑為含浸於片 材中之片狀防臭化妝料。 本發明之效果係就調配有擔載有銀離子之抗菌性沸石 粉末之皮膚外用劑而言,可減少或防止擔載有銀離子之打 菌性沸石粉末造成之浮粉。 ~ 【實施方式】 5 201247229 < (A )擔載有銀離子之抗菌性沸石> ,於本發明中用作(A)成分之擔載有銀離子之抗菌性沸 石係使用於沸石之可進行離子交換之部分保持有抗菌性銀 離子的彿石之粉末。即,為沸石之可進行離子交換之離子 之-部分或全部經抗菌性銀離子取代之沸石之粉末。擔載 有銀離子之抗菌性滞石可藉由常用方法由沸石較容易地製 造0 取 於本發明中,較佳為擔載有抗菌性 鋅離子與錄離子之沸叾μ & MU擔載有 弗石。於本發明中可传用古隹σ (CellaMedic Aji〇n: s 使用市售时 n miC股份有限公司)。 擔載有銀離子之抬站 抗菌性彿石之粉末之平均粒徑較佳A 10以m以下。進而較 τ仏敉佳為 該範圍之情形時,較佳為、二5心。又,於平均粒徑為 者為㈣以下。為於其粒度分佈中粒徑超過1 沸石可為天然彿石及合㈣石中之任 為具有三維骨架結構 者。'弗石通常 * AI2〇3 . YSi〇2 . Ζίί2〇 忭马通式,係以 ΧΜ2/η〇 離子交換之離子,通常為】。於該通式中,Μ表示可進行 離子之原子價。父及γ分尽或2價金屬離子。0為(金屬) 數,Ζ表示結晶水之數。;表不金屬氧化物' 二氧化石夕係 作為沸石之具體例,例如 石、Υ-型沸石、Τ-型沸石 '一。列舉·· Α-型沸石、X-型沸 向石夕;Ά ^ 方沸石、斜發沸石、菱沸石 那石、方鈉石、絲光沸石、 石、毛沸石等。該等沸石之離子 6 201247229 交換容量係Α·型沸;s 7 meq/g、χ—型沸石6 4叫/g、γ_型 彿石5meq/g、T』彿石3.4meq/g、方鈉石115咖心、絲 光彿石2.6 meq/g、方沸石5 meq/g、斜發彿石2 6叫/§、 菱彿石5meq/g、毛彿石3.8meq/g。該等於以抗菌性金屬離 子或銨離子進行離子交換時均具有充分之容量。 彿石中之可進行離子交換之離子例如為納離子、㈣ 子、卸離子、鎮離子、鐵離子等。又,該等離子所取代之 U性金屬離子例如有銀、銅、鋅、水銀、錫、鉛、鉍、 s鉻或知離子,但本發明係使用經銀離子交換者。 :抗菌性之觀點而言,抗菌性銀離子較佳為於沸石令 3有0.1〜1 5質量%。 例如,較佳為含有銀離子〇.〗〜 〜8質量。/。之抗菌性沸石。其一* 質量/〇及鋅離子0.1 中含右首 面,銨離子較佳為於沸石 而言,更佳為於沸石中含有。.5〜5二=變色之_ 石=量百:所謂ff%,係一乾燥基準之· 品。:ΓΓ LI;, ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ t p - t k方法’例如可以如下方々制供 :使’石與預先製備之含有銀離子: 溶液接觸,使沸石Φ夕1 〒雕于孚之混合水 進行取代。接觸可 為進行10〜24小時。t + 小時,較佳 再者,上述混合水溶液之PH值適合 201247229 調整為3〜1〇,較佳盔 马5〜7。藉由該調整,可防止銀之氧 化物等向沸石表面哎 4孔陳内之析出,故而較佳。又,混合 水溶液t之各離子參μ、_ , 通吊均以鹽之形式供給。例如,銀離子 係硕酸銀、硫酸銀、過氣酸銀、乙酸銀、二氨合銀硝酸鹽、 氨。銀&§文鹽等。鋅離子係硝酸鋅(II )、硫酸鋅、過氣 酸鋅、硫氰酸鋅、乙酸鋅等。 '弗石中之抗菌性銀離子之含量可藉由調整上述混合水 冷液中之各離子(鹽)濃度而適當控制。冑由將上述混合 水冷液中之銀離子濃度設S 0.002则〜0 15则,可適當地 獲得銀離子含量0·1〜5%之抗菌性沸石。又,於抗菌性沸石 it而含有鋅離子之情形時’ #由將上述混合水溶液中之辞 離子濃度設為G.l 5 M/1〜1.2 M/卜可適當地獲得鋅離子含量 〜8%之抗IH生沸石。抗菌性;弗石除上述混合水溶液以 外,亦可藉由使用單獨含有各離子之水溶液,使各水溶液 與彿石逐次接觸而進行離子交換。各水溶液中之各離子之 濃度可依據上述混合水溶液中之各離子濃度而確定。 離子交換結束後之沸石係於充分地清洗後進行乾燥。 乾燥較佳為以105。(:〜115。(:或於減壓(1〜3〇丁〇1^)下以 70〜90°C進行。 <利用MQ樹脂進行表面處理之擔載有銀離子之抗菌 性沸石> 於本發明中,擔載有銀離子之抗菌性沸石粉末較佳為 利用MQ樹脂藉由常用方法進行表面處理之疏水化處理粉 末。本發明中所使用之所謂MQ樹脂,係指由Si〇2單元(卩 8 201247229 單元)與R3Si〇l/2單元(M單元)所構成的局部交聯之八 知之有機聚碎氧樹脂(三甲基钱氧基料)。具有: ⑴所π之結構,且其M/Q莫耳比為〇 7〜。 ’ [化 1] ' (R3SiO"2)2 · nSi〇2 ( ι ) (式中,R為一價烴基,n為i〜5之數) MQ樹脂除先前作為防水劑等而單獨用作粉底、眼霜、 乳液、乳霜、防曬霜等化妝品之原料以外,亦可用作化妝 料用粉體之表面處理劑(日本專利第337859〇號等 又,本發明中所使用之MQ樹脂之分子量並無特別限 定,但較佳為於500〜10000之間。其原因在於,若分子量 未達500,Μ存在經處理之粉末容易;疑聚之缺點,若超過 10000’則存在MQ樹脂對於有機溶劑之溶解性降低而無法 均勻地被覆粉體表面之缺點。 MQ樹脂對擔載有銀離子之抗菌性沸石粉末之被覆方 法並無特別限定。例如可藉由一面利用亨舍爾混合機 (Henschel mixer)等攪拌抗菌性沸石一面添加混合溶解於 溶劑中之MQ樹脂後,將溶劑去除並進行乾燥而獲得。所 使用之溶劑為溶解MQ樹脂之揮發性有機溶劑,例如可例 示:十曱基環五矽氧烷、2-丙醇、正己烷、環己烷等。 MQ樹脂對於擔載有銀離子之抗菌性沸石之被覆量相 對於擔載有銀離子之抗菌性沸石以質量比計為〇 5質量。/〇以 上’就使用性之觀點而言’較佳為〇·5〜1〇質量%。進而較 佳為1〜3質量%。 201247229 < (A)擔載有銀離子之抗菌性沸石之綱配量> 擔載有銀離子之抗菌性沸石之調配量相對於皮膚外用 劑總量為0.1〜20質量。/〇,較佳為1〜10質量。/〇,進而較佳 為3〜7質量。/。。可根據製品形態而適當確定,從而調配適 宜量。 「(B)數量平均分子量為700〜4000之聚丙二醇、聚 丙二醇與聚丁二醇之共聚物、或聚丙二醇之衍生物」 於本發明中,為了減少或防止浮粉而調配之(B )成分 係如下所述。調配下述(丨)〜(3 )中之一種或兩種以上 之(B )成分。 (1) 數量平均分子量為700〜4000之聚丙二醇 (2) 數量平均分子量為7〇〇〜4〇〇〇之聚丙二醇與聚丁 二醇之共聚物 (3) 數量平均分子量為7〇〇〜4〇〇〇之聚丙二醇之衍生 物(具體而言,數量平均分子量為7〇〇〜4〇〇〇之聚氧丙烯 甘油醚、聚氧丙烯山梨糖醇、聚氧丙烯丁醚等) 於本發明中,數量平均分子量可利用化妝品原料基準 第一版註解I ( 1984年,藥事曰報社)之942頁中所 方法而求出》 上述(1 )〜(3 )之成分均可使用市售品。 作為(1)數量平均分子量為7〇〇〜4〇〇〇之聚丙二醇, 可較佳地使用數量平均分子量為職之Ne— ρρ ι_ (三洋化成工業股份有限公司)、數量平均分子量為膽 之NeWpol PP_2〇〇〇 (三洋化成工業股份有限公司)、數量平 10 201247229 均分子量為4000之Newpol PP-4000 (三洋化成工業股份有 限公司)等。 作為(2)數量平均分子量為700〜4000之聚丙二醇與 與聚丁二醇之共聚物’可較佳地使用數量平均分子量為700 之PBG/PPG-9/1共聚物(聚丁二醇與聚丙二醇為9M之共 聚物。UNIOL PB-700,日本油脂股份有限公司)。 作為(3)數量平均分子量為700〜4〇〇〇之聚丙二醇之 衍生物,可較佳地使用聚氧丙烯甘油醚、聚氧丙烯山梨糖 醇、聚氧丙缔丁喊。 作為聚氧丙烯甘油醚’可較佳地使用數量平均分子量 為1〇〇〇之>1^13〇1〇?-1〇〇〇(三洋化成工業股份有限公司)、 數里平均分子量為4000之Newpol GP-4000 (三洋化成工業 股份有限公司)。 又’作為聚氧丙烯山梨糖醇,可較佳地使用數量平均 分子量為700之Newp〇l SP-750 (三洋化成工業股份有限公 進而’作為聚氧丙烯丁醚,可較佳地使用數量平均分 子量為1200之Newpol LB-285 (三洋化成工業股份有限公 司)、平均分子量為1870 股份有限公司)。 1 870之Newpol LB-625 (三洋化成工業 上述(1 )〜(3 ) 保濕劑而調配之成分, 擔载有銀離子之抗菌性沸 浮粉降低防止劑而調配 之成分於皮膚外用劑中通常係作為 但於本發明中,係發揮減少或防止 沸石粉末造成之浮粉之效果且作為 之必需成分。 201247229 < (B)數量平均分子量為700〜4000之聚丙二醇、 聚丙二醇與聚丁二醇之共聚物、或聚丙二醇之衍生物之調 配量> 上述(B )成分之調配量相對於皮膚外用劑總量為〇 j 〜20質量。/〇,較佳為質量%,進而較佳為5〜2〇質量 %〇(B)成分之調配量可根據製品形態而適當確定,從而調 配適宜量。 本發明之皮膚外用劑除上述必需成分以外,於無損本 發明之效果之範圍内,亦可視需要適當調配通常化妝品或 准藥品等皮膚外用劑中所調配之其他成分,例如粉末成 分、液體油脂、固體油脂、蠟、烴油、高級脂肪酸、高級 醇、酯油、聚矽氧油、陰離子界面活性劑、陽離子界面活 性劑、兩性界面活性劑、非離子界面活性劑、㈣劑 '皮 膜劑、紫外線吸收劑、金屬離子螯合劑、低級醇、多元醇、 糖、胺基酸、有機胺、高分子乳膠、pH值調整劑、皮膚營 養劑、維生素、抗氧化劑、抗氧化助劑、香料、水等,根 據目標劑型藉由常用方法而製造。 再者,本發明之劑型並無限定,但較佳為分散有擔載 有銀離子之抗菌性沸石粉末之液狀皮膚外用劑。 、尤其是就提高B成分之溶解性或賦予清涼感或乾燥之 速度之觀點而t,較佳為相對於皮膚外用劑總量調配有至 :?質量%、較佳為3〇質量⑽質量%之乙醇的液狀皮 本發明之皮膚外用劑之製品形態並無特別限定。例 12 201247229 如’較佳為將分散有擔載有銀離子之抗菌性沸石粉末之液 狀化妝料⑴填充於滾塗式容器中之防臭化妝料、⑴填 f於氣溶膠式或分注式容器中之霧狀防臭化妝料、(3)含 浸於不織布等片材中之片狀防臭化妝料等製品形態,該等 製品係藉由常用方法製造。 除上述製品形態以外,粉型、粉餅型、膏型(stick type) 等防臭化妝料亦可作為本發明之皮膚外用劑藉由常用方法 而製造。 實施例 其次,列舉實施例進一步具體地說明本發明。本發明 並不限定於此。調配量只要無特別說明,則為相對於總量 之質量%。 利用「表1」所示之處方,藉由常用方法製造分散有擔 載有銀離子之抗菌性沸石之液狀化妝料,藉由下述評價方 法確認作為本發明之效果之塗佈後之浮粉。 又,針對黑色之產生,亦藉由下述評價方法確認。 再者,「表2」〜「表5」僅記載「表!」之調配於液狀 化妝料中之B成分(實施例)、或除B成分以外之各種保濕 劑(比較例)而表示調配該等之情形之評價。 「浮粉防止之評價」 利用微量吸管將「表L〜「表5」之皮膚外用劑於黑 色之人造皮膚上之1.5 cmxi.5 cm之範圍内塗佈1〇 "L。 以目視確認2小時後之浮粉,按照以下基準進行評價。 <評價基準> 13 201247229 ◎:完全未確認到浮粉β 〇:確認到少許浮粉,但與比較例1相比浮粉大幅度 減少,為所容許之範圍。 X :明確地確認到浮粉。 「黑色異物之評價」 將「表1」 1 表5」之皮膚外用劑於60°C之恆溫槽中 保存1週。針對於6〇。〇之 劑中是否…色異物存1週後之皮膚外用 進行評價。 、 硯進行觀察並按照以下基準 <評價基準> ο :未確認到黑色異物。 χ:確認到黑色異物。 14 201247229 [表i] 基本處方(質量% ) 乙醇 殘餘 水 5 羥丙基纖維素 0.2 經MQ樹脂處理之擔載有銀離子之抗菌性沸石” 5 對苯酚磺酸鋅鹽 0.35 麩胱甘肽 0.5 B成分或B成分以外之各種保濕劑 3〜10 合計 100 氺1 :擔載有銀離子之抗菌性沸石之mq樹脂處理係將 抗菌性沸石之粉末(擔載有銀離子、鋅離子、銨離子沸石 (CellaMedic AJION : Sinanen Zeomic 股份有限公司)5〇 g 放入小型粉碎機中,一面攪拌一面添加溶解於溶劑中之mq 樹脂處理劑。添加後,攪拌約3分鐘,將所獲得之粉末於 乾燥機中於120t下乾燥24小時。再者,所使用之MQ樹 脂係由Μ單元:(CH^SiO2"與Q單元:Si〇2所構成之三 曱基矽烷氧基矽酸。 「浮粉之減少、防止效果」 [表2] 浮粉之減 少 '防止 比較例1 比較例2 實施例1 實施例2 實施例3 實施例4 實施例5 聚丙二醇 200 聚丙二醇 400 聚丙二醇 1000 聚丙二醇 2000 聚丙二醇 4000 聚氧丙烯 甘油鰱 (數量平 均分子量 1000) 聚氧丙稀 甘油喊 (數量平 均分子量 4000) 3% X X ◎ ◎ ◎ 〇 ◎ 5% X X ◎ ◎ ◎ ◎ ◎ 10% X X ◎ ◎ ◎ ◎ ◎ 15 201247229201247229 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a skin external preparation. More specifically, the present invention relates to an external antibacterial agent which is prepared by mixing an antibacterial zeolite carrying silver ions, and which is capable of reducing or preventing floating powder of an antibacterial zeolite powder carrying silver ions. [Prior Art] The antibacterial 'Furstone powder is formulated as a preservative or deodorant in a skin external preparation such as a cosmetic or a quasi-drug. For example, a composition for antibacterial spray formulated with an antibacterial budstone (Patent Document 1) or a deodorant cosmetic (Patent Document 2) has been developed. Further, the odor-resistant cosmetic material having improved discoloration resistance has been disclosed, and a technique for blending polyoxanium with an antibacterial zeolite has been disclosed (Patent Document 3). In the antibacterial zeolite for the purpose of deodorizing or deodorizing, an antibacterial stagnation stone carrying silver ions is used (Patent Document 4, Patent Document 5). In the aspect of the invention, a skin containing an antibacterial zeolite carrying silver ions is prepared, and the agent causes a floating powder problem caused by an antibacterial zeolite carrying silver ions, that is, a skin external application using an antibacterial zeolite carrying silver ions on the right side. The agent is present in the body part of the coated body with the problem of floating powder. In order to prevent the floating powder caused by the antibacterial zeolite carrying silver ions, it is disclosed in the special 6 that the technique of blending a certain amount of ethanol and glycerin is not good, and the effect is insufficient at high temperature. The problem of stinky or black foreign objects. Patent Document 7 discloses a cosmetic material which is less likely to be white after use because it is formulated with a specific alkane derivative in an antiperspirant aerosol type cosmetic containing a silver-resistant antibacterial zeolite of 201247229. Epoxy Epoxy Document 7 is only a technique specific to air bath gel cosmetics. Moreover, when combined with a liquid cosmetic of a sol type cosmetic, silver ions are not contained in the case of a non-gas zeolite and a specific alkylene oxide derivative, and the bacterial property cannot be prevented. The problem of antiperspirant aerosol makeup. Patent document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 Patent Document 7 SUMMARY OF THE INVENTION The present inventors have exemplified the above viewpoints in order to prevent an antimicrobial zeolite powder supported by silver ions. The floating powder caused by the powder is prepared for the skin phase agent containing the anti-fermentation zeolite powder carrying silver ions. Duguo found that if the number average molecular weight is 7GG~4_ U-propane dipropylene glycol and polytetramethylene glycol The copolymer or the derivative of polypropylene glycol can be used to obtain an agent which is not white after coating and which can reduce or prevent the floating powder, thereby completing the present invention. An object of the present invention is to provide an external preparation for skin which is provided with an antibacterial buddha powder carrying silver ions at t weeks, and which can reduce or prevent the burden of sputum. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin 4 201247229 There is a floating powder caused by silver ion powder. That is, the present invention provides a skin external preparation comprising: (A) an antibacterial zeolite carrying silver ions, and (B) a polypropylene glycol having a number average molecular weight of 700 to 4000, a copolymerization of a polypropylene glycol and a polytetramethylene glycol; Any of the derivatives of the substance or polypropylene glycol. Further, the present invention provides the external preparation for skin according to the above aspect, wherein the derivative of the (B) polypropylene glycol is a polyoxypropylene glyceryl ether or a polyoxypropylene sorbitol having a number average molecular weight of 7 〇〇 to 4 Å. Further, the present invention provides a skin external preparation containing the ethanol in an amount of 3% by mass or more based on the total amount of the external preparation for skin. Furthermore, the present invention provides the external preparation for skin according to the above aspect, wherein the external preparation for skin is a liquid cosmetic, and the external preparation for skin is a deodorant cosmetic filled in a roll-type (r〇ll-on) container. Furthermore, the present invention provides the external preparation for skin according to the above aspect, wherein the external preparation for skin is a liquid cosmetic, and the external preparation for skin is a mist-like and deodorant makeup filled in an aerosol or dispenser container. material. Furthermore, the present invention provides the external preparation for skin according to the above aspect, wherein the external preparation for skin is a liquid cosmetic ‘ and the external preparation for skin is a flaky odor-resistant cosmetic immersed in a sheet. The skin effect of the present invention is that the skin external preparation containing the antibacterial zeolite powder carrying silver ions can reduce or prevent the floating powder caused by the silver-containing bacteriostatic zeolite powder. [Embodiment] 5 201247229 < (A) Antibacterial zeolite carrying silver ions> In the present invention, an antibacterial zeolite supporting silver ions used as the component (A) is used in zeolites. A part of the ion exchange is kept of a powder of Buddha stone having an antibacterial silver ion. Namely, it is a powder of a zeolite which is ion-exchanged and partially or completely substituted with an antibacterial silver ion. The antibacterial staghorn supported on the silver ion can be easily produced from the zeolite by a usual method. In the present invention, it is preferred to carry the antibacterial zinc ion and the ionized boiled μ & MU load. There is a stone. In the present invention, the ancient 隹σ can be used (CellaMedic Aji〇n: s is commercially available at n miC Co., Ltd.). The powder carrying the silver ions is preferably a particle having an average particle diameter of A 10 or less. Further, when it is better than τ, it is preferably two or five hearts. Further, the average particle diameter is (four) or less. In order to have a particle size distribution of more than 1 in the particle size distribution, the zeolite may have a three-dimensional skeleton structure among any of the natural Buddha stone and the (tetra) stone. 'Fostone usually * AI2〇3. YSi〇2 . Ζίί2〇 忭 horse-like, with ΧΜ2/η〇 ion-exchanged ions, usually]. In the formula, Μ indicates that the valence of the ion can be carried out. The parent and γ are separated or divalent metal ions. 0 is the number of (metal), and Ζ is the number of crystal water. The surface is not a metal oxide, 'the sulphur dioxide' is a specific example of the zeolite, for example, a stone, a cerium-type zeolite, or a cerium-type zeolite. Listed by: Α-type zeolite, X-type boiling to Shi Xi; Ά ^ analcite, clinoptilolite, chabazite, stone, sodalite, mordenite, stone, erionite, and the like. These zeolite ions 6 201247229 exchange capacity system Α · type boiling; s 7 meq / g, χ type zeolite 6 4 / g, γ _ type Buddha stone 5meq / g, T 』 Buddha stone 3.4meq / g, square Sodium stone 115 coffee heart, silk phoenix stone 2.6 meq / g, analcite 5 meq / g, oblique hair Buddha stone 2 6 called / §, Lingfo stone 5meq / g, Maofo stone 3.8meq / g. This is equivalent to having sufficient capacity for ion exchange with an antimicrobial metal ion or ammonium ion. The ions that can be ion-exchanged in the Buddha stone are, for example, nano ions, (tetra), unloading ions, town ions, iron ions, and the like. Further, the U-metal ion to be replaced by the plasma is, for example, silver, copper, zinc, mercury, tin, lead, antimony, s chromium or a known ion, but the present invention uses a silver ion exchanger. From the viewpoint of antibacterial property, the antibacterial silver ion is preferably 0.1 to 15% by mass based on the zeolite. For example, it is preferred to contain silver ions 〇. 〜 ~ 8 mass. /. Antibacterial zeolite. The *mass/germanium and zinc ion 0.1 have a right first side, and the ammonium ion is preferably contained in the zeolite, more preferably in the zeolite. .5~5 II=Discoloration_ Stone=Quantity: The so-called ff% is a dry basis. :ΓΓ LI;, ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ tp - tk method 'for example, can be made as follows: make 'stone and pre-prepared silver ion-containing solution to make the zeolite Φ 1 1 〒 于 于The mixed water is substituted. Contact can be carried out for 10 to 24 hours. t + hour, preferably, the pH of the mixed aqueous solution is suitable for 201247229 to be adjusted to 3~1〇, preferably to the helmet 5~7. By this adjustment, it is preferable to prevent the precipitation of silver oxide or the like into the pores of the zeolite. Further, each of the ion ions μ, _ of the mixed aqueous solution t is supplied in the form of a salt. For example, silver ions are silver silicate, silver sulfate, silver peroxyacid, silver acetate, diammine silver nitrate, and ammonia. Silver & § text salt and so on. Zinc ion is zinc (II) nitrate, zinc sulfate, zinc peroxylate, zinc thiocyanate, zinc acetate, and the like. The content of the antibacterial silver ion in the vermiculite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed water cooling liquid. The antibacterial zeolite having a silver ion content of 0.1 to 5% can be suitably obtained by setting the silver ion concentration in the mixed water-cooling liquid to S 0.002 to 〜15. Further, when the antibacterial zeolite is contained in the case of zinc ions, the resistance of the zinc ion content of 8% can be suitably obtained by setting the concentration of the ion in the mixed aqueous solution to Gl 5 M/1 to 1.2 M/b. IH raw zeolite. Antibacterial property; in addition to the above mixed aqueous solution, the ferrite may be subjected to ion exchange by successively contacting each aqueous solution with the fluorite by using an aqueous solution containing each ion alone. The concentration of each ion in each aqueous solution can be determined depending on the concentration of each ion in the above mixed aqueous solution. The zeolite after completion of the ion exchange is sufficiently washed and then dried. Drying is preferably at 105. (:~115. (: or under reduced pressure (1 to 3 〇 〇 1^) at 70 to 90 ° C. <Antibacterial zeolite loaded with silver ions by surface treatment with MQ resin> In the present invention, the antibacterial zeolite powder carrying silver ions is preferably a hydrophobized powder which is surface-treated by a conventional method using MQ resin. The so-called MQ resin used in the present invention is referred to as Si〇2. A partially-bonded organic polyoxygen resin (trimethyl hydroxy oxylate) composed of a unit (卩8 201247229 unit) and a R3Si〇l/2 unit (M unit). It has: (1) the structure of π, And the M/Q molar ratio is 〇7~. '[Chemical 1] ' (R3SiO"2)2 · nSi〇2 ( ι ) (wherein R is a monovalent hydrocarbon group, and n is the number of i~5) In addition to being used as a waterproofing agent or the like as a raw material for cosmetics such as foundations, eye creams, lotions, creams, and sunscreens, the MQ resin can also be used as a surface treatment agent for powders for cosmetics (Japanese Patent No. 337859, etc.) Further, the molecular weight of the MQ resin used in the present invention is not particularly limited, but is preferably between 500 and 10,000. If the molecular weight is less than 500, the treated powder is easy to be present; if it exceeds 10,000', there is a disadvantage that the solubility of the MQ resin in the organic solvent is lowered and the surface of the powder cannot be uniformly coated. The coating method of the antibacterial zeolite powder carrying the silver ion is not particularly limited. For example, the MQ resin can be added and dissolved in the solvent while stirring the antibacterial zeolite with a Henschel mixer or the like. The solvent is removed and dried to obtain a solvent. The solvent to be used is a volatile organic solvent in which the MQ resin is dissolved, and examples thereof include decamethylcyclopentaoxane, 2-propanol, n-hexane, cyclohexane, and the like. The amount of coating of the resin on the antibacterial zeolite carrying silver ions is 〇5 by mass based on the mass ratio of the antibacterial zeolite carrying silver ions. / 〇 or more 'in terms of usability' is preferably 〇 5 to 1% by mass, more preferably 1 to 3% by mass. 201247229 <(A) Formulation amount of antibacterial zeolite carrying silver ions> Preparation of antibacterial zeolite carrying silver ions Volume The total amount of the external preparation for skin is 0.1 to 20 mass%, preferably 1 to 10 mass%, more preferably 3 to 7 mass%, which may be appropriately determined according to the form of the product, thereby preparing a suitable amount. "(B) Polypropylene glycol having a number average molecular weight of 700 to 4000, a copolymer of polypropylene glycol and polytetramethylene glycol, or a derivative of polypropylene glycol". In the present invention, (B) is prepared for reducing or preventing floating powder. The components are as follows. One (2) or (3) of the following (B) components are formulated. (1) Polypropylene glycol having a number average molecular weight of 700 to 4000 (2) The number average molecular weight is 7 Copolymer of polypropylene glycol and polytetramethylene glycol of 〇〇~4〇〇〇(3) Derivative of polypropylene glycol having a number average molecular weight of 7〇〇~4〇〇〇 (specifically, the number average molecular weight is 7〇)聚~4〇〇〇 polyoxypropylene glyceryl ether, polyoxypropylene sorbitol, polyoxypropylene butyl ether, etc.) In the present invention, the number average molecular weight can be utilized in the first edition of the cosmetic raw material reference note I (1984, medicine According to the method in the 942 page of the newspaper, Commercially available products can be used as the components of the above (1) to (3). As the (1) polypropylene glycol having a number average molecular weight of 7 〇〇 to 4 Å, it is preferred to use a number average molecular weight of the content of Ne- ρρ ι_ (Sanyo Chemical Industry Co., Ltd.), and the number average molecular weight is biliary NeWpol PP_2〇〇〇 (Sanyo Chemical Industry Co., Ltd.), quantity flat 10 201247229 Newpol PP-4000 (Sanyo Chemical Industry Co., Ltd.) with an average molecular weight of 4,000. As the (2) a polypropylene having a number average molecular weight of 700 to 4000 and a copolymer with polytetramethylene glycol, a PBG/PPG-9/1 copolymer having a number average molecular weight of 700 (polybutylene glycol and Polypropylene glycol is a 9M copolymer. UNIOL PB-700, Nippon Oil & Fats Co., Ltd.). As the derivative of (3) a polypropylene glycol having a number average molecular weight of 700 to 4 Å, polyoxypropylene glyceryl ether, polyoxypropylene sorbitol, or polyoxypropylated can be preferably used. As the polyoxypropylene glyceryl ether, it is preferable to use a number average molecular weight of 1 & 1 1 13 〇 1 〇 1 -1 〇〇〇 (Sanyo Chemical Industry Co., Ltd.), and the average molecular weight is 4000. Newpol GP-4000 (Sanyo Chemical Industry Co., Ltd.). Further, as the polyoxypropylene sorbitol, Newp〇l SP-750 having a number average molecular weight of 700 (Sanyo Chemical Industry Co., Ltd.) can be preferably used as the polyoxypropylene butyl ether, and the number average can be preferably used. Newpol LB-285 (Sanyo Chemical Industry Co., Ltd.) with a molecular weight of 1200 and an average molecular weight of 1870 Co., Ltd.). 1 870 Newpol LB-625 (Sanyo Chemical Industry Co., Ltd. is a compound formulated with the above (1) to (3) humectant, and is formulated with an antibacterial boil-off powder reduction inhibitor containing silver ions. However, in the present invention, it is an essential component for reducing or preventing the floating powder caused by the zeolite powder. 201247229 < (B) Polypropylene glycol, polypropylene glycol and polytetramethylene glycol having a number average molecular weight of 700 to 4000 The amount of the copolymer or the derivative of the polypropylene glycol is less than or equal to the total amount of the external preparation for skin. The amount of the component (B) is preferably 质量j to 20% by mass. More preferably, it is preferably 5% by mass. ~2〇质量% The amount of the component (B) can be appropriately determined according to the form of the product, and the appropriate amount can be formulated. The skin external preparation of the present invention can be visually recognized in addition to the above-mentioned essential components without departing from the effects of the present invention. It is necessary to appropriately mix other ingredients formulated in external skin preparations such as general cosmetics or quasi-drugs, such as powder ingredients, liquid fats, solid fats, waxes, hydrocarbon oils, higher fatty acids, and advanced , ester oil, polyoxyxide oil, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, (four) agent' coating agent, ultraviolet absorber, metal ion chelating agent, lower alcohol, polyol , sugar, amino acid, organic amine, polymer latex, pH adjuster, skin nutrient, vitamins, antioxidants, antioxidants, perfumes, water, etc., are manufactured according to the target dosage form by common methods. The dosage form of the present invention is not limited, but is preferably a liquid external preparation for dispersing an antibacterial zeolite powder carrying silver ions. In particular, it improves the solubility of the component B or imparts a cooling sensation or a drying speed. In view of the above, it is preferable that the liquid skin of the skin external preparation of the present invention is prepared in an amount of up to 3% by mass, preferably 3 Å by mass (10% by mass) based on the total amount of the external preparation for skin. Example 12 201247229 If the liquid cosmetic (1) in which the antibacterial zeolite powder carrying silver ions is dispersed is preferably filled with a deodorant cosmetic in a roll-coated container, (1) A product such as a mist-like and deodorant cosmetic in a sol-type or dispensing container, and (3) a product such as a sheet-like deodorant cosmetic impregnated in a sheet such as a non-woven fabric, and the products are produced by a usual method. A deodorant cosmetic such as a powder type, a powder type, or a stick type can also be produced as a skin external preparation of the present invention by a usual method. EXAMPLES Next, the present invention will be specifically described by way of examples. The amount of the compound is not particularly limited, and is a mass % relative to the total amount unless otherwise specified. A liquid in which an antibacterial zeolite carrying silver ions is dispersed is produced by a usual method using the conditions shown in "Table 1". The coated cosmetic was confirmed to have a floating powder after application as an effect of the present invention by the following evaluation method. Further, the generation of black was also confirmed by the following evaluation method. In addition, "Table 2" to "Table 5" only describe the blending of the B component (Example) in the liquid cosmetic or the various moisturizing agents (Comparative Example) other than the B component. Evaluation of such circumstances. "Evaluation of the prevention of floating powder" Apply a skin external preparation of "L" to "Table 5" to a range of 1.5 cm × 5.5 cm on a black artificial skin using a micropipette. The floating powder after 2 hours was visually confirmed and evaluated according to the following criteria. <Evaluation Criteria> 13 201247229 ◎: The floating powder β 〇 was not confirmed at all: A little floating powder was confirmed, but the floating powder was drastically reduced as compared with Comparative Example 1, and the allowable range was obtained. X : Clearly confirm the floating powder. "Evaluation of black foreign matter" The skin external preparations of "Table 1" 1 Table 5" were stored in a thermostat at 60 ° C for 1 week. For 6〇. Whether or not the sputum agent was used for evaluation of the external use of the skin after 1 week.砚 Observe and follow the following criteria <Evaluation Criteria> ο : No black foreign matter is confirmed. χ: Confirmed black foreign matter. 14 201247229 [Table i] Basic prescription (% by mass) Ethanol residual water 5 Hydroxypropyl cellulose 0.2 Antibacterial zeolite loaded with silver ion treated with MQ resin 5 Pairs of zinc phenolsulfonate 0.35 Glutenin 0.5 Various humectants other than the B component or the B component 3 to 10 Total 100 氺1: The mq resin treatment of the antibacterial zeolite carrying the silver ion is a powder of the antibacterial zeolite (supporting silver ions, zinc ions, ammonium ions) 5 g of zeolite (CellaMedic AJION: Sinanen Zeomic Co., Ltd.) was placed in a small pulverizer, and mq resin treatment agent dissolved in a solvent was added while stirring. After the addition, the mixture was stirred for about 3 minutes, and the obtained powder was dried. The machine was dried at 120 t for 24 hours. Further, the MQ resin used was a ruthenium unit: (CH^SiO2" and Q unit: Si〇2 composed of trimethyl decyloxy decanoic acid. [Prevention effect] [Table 2] Reduction of floating powder 'Preventing Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Polypropylene glycol 200 Polypropylene glycol 400 Polypropylene glycol 1000 Polypropylene glycol 2000 Polypropylene glycol 4000 polyoxypropylene glycerin oxime (number average molecular weight 1000) polyoxypropylene glycerin shouting (number average molecular weight 4000) 3% XX ◎ ◎ ◎ 〇 ◎ 5% XX ◎ ◎ ◎ ◎ ◎ 10% XX ◎ ◎ ◎ ◎ ◎ 15 201247229
[表3] 浮粉之減 少、防止 實施例6 ----—" 赏施例7 實施例8 實施例9 比較例3 比較例4 聚氧丙 梨糖醇(數量 平均分子量 700) ^"""^7 丙稀 -J-滅(數量 f均分子 ti2〇〇)__ 聚氧丙稀 丁醚(數量 平均分子 量 1870) PBG/PPG-9 /1 (數量平 均分子量 700) POE (17) POP (4) 二甲醚 POE (55) POP ( 28) 二曱醚 3% δ ◎ 〇 X X 5% ◎ -^© ◎ ◎ X X 10% ◎ ◎ ◎ X X 「黑色異物之產生(60°C,1 w )」 [表4] 黑色異物 之產生 比較例1 比較例2 實施例1 實施例2 實施例3 實施例4 實施例5 聚丙二醇 200 聚丙二醇 400 聚丙二醇 1000 聚丙二醇 2000 聚丙二醇 4000 聚氧丙烯 甘油醚 (數量平 均分子量 1000) 聚氧丙烯 甘油喊 (數量平 均分子量 4000) 3% 〇 Π 〇 〇 卜〇 〇 Π 〇 〇 5% 〇 〇 卜〇 〇 〇 〇 〇 10% 〇 〇 〇 〇 〇 〇 〇 [表5][Table 3] Reduction of floating powder, prevention Example 6 -----" Appreciation Example 7 Example 8 Example 9 Comparative Example 3 Comparative Example 4 Polyoxypropylene sorbitol (number average molecular weight 700) ^"""^7 propylene-J-extin (quantity f-average ti2〇〇)__ polyoxypropylene butyl ether (quantitative average molecular weight 1870) PBG/PPG-9 /1 (quantitative average molecular weight 700) POE (17 POP (4) dimethyl ether POE (55) POP (28) Diterpenoid 3% δ ◎ 〇 XX 5% ◎ -^© ◎ ◎ XX 10% ◎ ◎ ◎ XX "The generation of black foreign matter (60 ° C, 1 w )" [Table 4] Production of black foreign matter Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Polypropylene glycol 200 Polypropylene glycol 400 Polypropylene glycol 1000 Polypropylene glycol 2000 Polypropylene glycol 4000 Polyoxyl Propylene glyceryl ether (quantitative average molecular weight 1000) Polyoxypropylene glycerin shouting (quantitative average molecular weight 4000) 3% 〇Π 〇〇 〇〇Π 〇〇 〇〇 5% 〇〇 〇〇〇〇〇 10% 〇〇〇〇〇〇 〇[Table 5]
黑色異物 之產生 實施例6 實施例7 實施例8 實施例9 比較例3 比較例4 聚氧丙烯山 梨糖醇(數量 平均分子量 700) 聚氧丙稀丁 蜮(數量爭 均分子量 1200) 聚氧丙烯 丁醚(數量 平均分子 量 1870) PBG/PPG-9/1 (數量平均 分子量700) P0E ( 17) POP (4)二 甲麵 P〇E(55) POP (28) 二曱醚 3% 〇 〇 〇 X X 5% 〇 〇 〇 X X 10% 〇 〇 r〇 X X 16 201247229 用作上述所使用之B成分、除B成分以外之各種保濕 劑之市售品係如下所述。 [表6] 比較例1 比較例2 實施例1 實施例2 實施例3 實施例4 實施例5 成分 聚丙二 醇200 聚丙二醇 400 聚丙二 醇 1000 聚丙二 醇 2000 聚丙二 醇 4000 聚氧丙烯 甘油醚(數 量平均分 子量1000) 聚氧丙烯 甘油醚(數 量平均分 子量4000) 商品名 Newpol PP-200 Newpol PP-400 Newpol PP-1000 Newpol PP-200 Newpol PP-400 Newpol PP-1000 Newpol PP-4000 製造商 三洋化 成工業 股份有 限公司 三洋化成 工業股份 有限公司 三洋化 成工業 股份有 限公司 三洋化 成工業 股份有 限公司 三洋化 成工業 股份有 限公司 三洋化成 工業股份 有限公司 三洋化成 工業股份 有限公司 [表7] 實施例6 實施例7 實施例8 實施例9 比較例3 比較例4 成分 聚氧丙稀山 梨糖醇(數量 平均分子量 700) 聚氧丙烯丁 醚(數量平均 分子量1200) 聚氧丙烯丁 醚(數量平均 分子量1870) PBG/PPG-9 /1 (數量平 均分子量 700) POE (17) POP (4) 二甲喊 POE (55) POP (28) 二甲喊 商品名 Newpol SP-750 Newpol LB-285 Newpol LB-625 UNIOL PB-700 Macbiobri de E-1075 Macbiobri de E-4060 製造商 三洋化成工 業股份有限 公司 三洋化成工 業股份有限 公司 三洋化成工 業股份有限 公司 日油股份 有限公司 日油股份 有限公司 日油股份 有限公司 根據上述「表2」〜「表5」之結果,本發明之實施例 於浮粉之防止效果優異之同時,針對黑色異物之產生亦具 有優異之效果。 與此相對,調配聚丙二醇200、聚丙二醇400、POE/POP 二甲醚等保濕劑代替本發明之(B )成分之比較例無浮粉之 17 201247229 防止效果’且存在產生黑色異物之情形。 以下’列舉本發明之皮膚外用劑之處方例。該等均為 ;浮私之減 >、防止效果優異之同時亦無黑色異物之產生 之化妝料。 厂 質量VO 殘餘 5 1 0.2 0.5 0.5 10 )_ 質量% 殘餘 5 10 0.2 0.5 0.5 10 處方例1 .適於滾塗式容器之化妝料(液狀化妝料) 調配成分 乙醇 水 擔載有銀離子之抗菌性沸石 羥丙基纖維素 麩胱甘肽 對苯盼續酸鋅鹽 聚丙二醇(數量平均分子量4000) 「處方例2 :適於滾塗式容器 ' 奋盗之化妝料(液狀化妝料 調配成分 乙醇 水 擔載有銀離子之抗菌性沸石 經丙基纖維素 麵胱甘肽 對苯酚磺酸鋅鹽 聚丙二醇(數量平均分子量 「處方例3 :填充於氣溶膠式 化妝料 或刀注式容器之霧狀防臭 18 201247229 調配成分 乙醇 水 擔載有銀離子之抗菌性沸石 質量% 殘餘 45 5 二氧化矽 麵胱甘肽 0.5 對苯酚磺酸鋅鹽 聚氧丙烯甘油醚(數量平均分子量1〇〇〇) 處方例4 ·含浸於片材中之片狀防臭化妝料 調配成分 乙醇 水 10 質量% 殘餘 40 擔載有銀離子之抗菌性沸石 滑石 麩胱甘肽 對笨盼續酸鋅鹽 聚氧丙烯丁醚(數量平均分子量1870) [產業上之可利用性] 3 0.5 0.5 5 根據本發明,可提供—種調配有擔載有銀離子之 I·生沸石粉末之皮膚外用齊丨,其可減少或防止擔載有銀 之抗菌性沸石粉末造成之浮粉。 菌 子 進而,本發明之皮膚外用 問題,SU匕可提供_卿4| 外用劑。 劑亦無黑色之異物之產生之 品無問題之新穎有用之皮膚 201247229 【圖式簡單說明】 無 【主要元件符號說明 無Production of black foreign matter Example 6 Example 7 Example 8 Example 9 Comparative Example 3 Comparative Example 4 Polyoxypropylene sorbitol (number average molecular weight 700) Polyoxypropylene butyl hydrazine (quantity average molecular weight 1200) Polyoxypropylene Butyl ether (quantitative molecular weight 1870) PBG/PPG-9/1 (quantitative average molecular weight 700) P0E (17) POP (4) Dimethyl P〇E (55) POP (28) Diterpenoid 3% 〇〇〇 XX 5% 〇〇〇 XX 10% 〇〇r〇 XX 16 201247229 A commercial product used as the above-mentioned component B and various moisturizing agents other than the component B is as follows. [Table 6] Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Ingredients Polypropylene glycol 200 Polypropylene glycol 400 Polypropylene glycol 1000 Polypropylene glycol 2000 Polypropylene glycol 4000 Polyoxypropylene glyceryl ether (Quantum average molecular weight 1000) Polyoxypropylene glyceryl ether (quantitative average molecular weight 4000) Trade name Newpol PP-200 Newpol PP-400 Newpol PP-1000 Newpol PP-200 Newpol PP-400 Newpol PP-1000 Newpol PP-4000 Manufacturer Sanyo Chemical Industry Co., Ltd. Sanyo Chemical Industry Co., Ltd. Sanyo Chemical Industry Co., Ltd. Sanyo Chemical Industry Co., Ltd. Sanyo Chemical Industry Co., Ltd. Sanyo Chemical Industry Co., Ltd. Sanyo Chemical Industry Co., Ltd. [Table 7] Example 6 Example 7 Example 8 Example 9 Comparative Example 3 Comparative Example 4 Component Polyoxypropylene sorbitol (number average molecular weight 700) Polyoxypropylene butyl ether (number average molecular weight 1200) Polyoxypropylene butyl ether (quantitative molecular weight 1870) PBG/PPG-9 /1 (quantitative average molecular weight 700) POE (17) POP (4) dimethyl shout POE (55) POP (28) dimethyl shark trade name Newpol SP-750 Newpol LB-285 Newpol LB-625 UNIOL PB-700 Macbiobri de E-1075 Macbiobri de E-4060 Manufacturer Sanyo Chemical Industry Co., Ltd. Sanyo Chemical Industry Co., Ltd. Ltd. Sanyo Chemical Industry Co., Ltd. Nippon Oil Co., Ltd. Nippon Oil Co., Ltd. Nippon Oil Co., Ltd. based on the results of the above "Table 2" to "Table 5", the embodiment of the present invention is excellent in the prevention effect of the floating powder. It also has an excellent effect on the generation of black foreign matter. On the other hand, a moisturizing agent such as polypropylene glycol 200, polypropylene glycol 400 or POE/POP dimethyl ether was blended in place of the comparative example of the component (B) of the present invention, which has no floating powder, and has a black foreign matter. The following is a list of examples of the external preparation for skin of the present invention. These are all; the reduction of the smuggling >, the cosmetic which is excellent in preventing the effect and having no black foreign matter. Plant quality VO Residue 5 1 0.2 0.5 0.5 10 ) _ mass % Residue 5 10 0.2 0.5 0.5 10 Formulation Example 1. Cosmetics suitable for roll-on containers (liquid cosmetics) Formulation ingredients Ethanol water loaded with silver ions Antibacterial zeolite hydroxypropyl cellulose glutathione p-benzophenone zinc salt polypropylene glycol (quantitative average molecular weight 4000) "Prescription Example 2: suitable for roll-on containers" Stretching cosmetics (liquid cosmetic blending) Inorganic ethanol water-loaded antibacterial zeolite with silver ion, propylcellulose, glutathione, zinc phenolsulfonate, polypropylene glycol (quantitative average molecular weight) Prescription Example 3: Filled with aerosol-type cosmetic or knife-injected container Haze-like deodorant 18 201247229 Formulation component Ethanol water Antibacterial zeolite with silver ion% by mass Residual 45 5 Ceria glucosinolate 0.5 Phenol sulfonate zinc oxide polyoxypropylene glyceryl ether (quantitative average molecular weight 1〇〇 〇) Formulation Example 4 - Sheet-like deodorant cosmetic immersed in sheet material Formulation component Ethanol water 10% by mass Residual 40 Antibacterial zeolite talc glutathione loaded with silver ions Oxypropylene butyl ether (quantitative average molecular weight: 1870) [Industrial availability] 3 0.5 0.5 5 According to the present invention, it is possible to provide a skin external application which is formulated with an I·raw zeolite powder carrying silver ions. It can reduce or prevent floating powder caused by silver-loaded antibacterial zeolite powder. Further, in the skin external use problem of the present invention, SU匕 can provide _Qing 4| external preparation. The agent also has no black foreign matter and has no problem. Novel and useful skin 201247229 [Simple description of the diagram] No [main component symbol description no