TW470653B - O/W/O type multiple emulsion contains orgarnphilic clay mineral in outer oil phase and method of preparing the same - Google Patents

Abstract

In an oil-in-water-in-oil type multiple emulsion in which an oil-in-water emulsion is dispersed in a continuous outer oil phase, the outer oil phase contains an organophilic clay mineral. Since the addition of the organophilic clay mineral in the outer oil phase can prevent the inner oil phase combining with the outer oil phase, the excellent stability of the oil-in-water-in-oil type multiple emulsion over time can be obtained. Further, upon the using an oil-soluble compound, which can be easily oxidized, in the inner oil phase, this multiple emulsion system can prevent the compound from oxidation, and the excellent stability of the compound will be obtained. Also, since the coalescence between the inner oil phase and the outer oil phase is prevented and oils can be selected from quite wide range as an oil phase, it is possible to keep two kinds of oil components which have different properties independently from each other in one emulsion system stably. For example, when an oil-soluble material which is hard to dissolve in one special oil and an oil to which the material is soluble are added in one oil phase, whereas the special oil is added in the other oil phase, the material can be prevented from depositing crystals or separation while these components are made to coexist stably in one emulsion system.

Description

470653 修正 本年月 補充ea 6.14 A7 B7 經濟部智慧財產局員工消費合作社印製 五、 發明説明 '1 ) 1 1 技 術 Μ. 域 1 [ 本 發 明 為 有 關 於 —11 種 油 包 水 包 油 (0/W/0)型多重乳液 1 1 及 其 製 造 方 法 9 尤 其 是 其 内 油 相 與 外 油 相 混合 之 防 止 及 配 /—\ 請 | 先 1 合 於 内 油 相 中 脂 溶 性 藥 劑 安 定 性 之 改 良 〇 閱 讀 背 1 i 抟 術 面 I 之 1 注 1 將 水 包 油 型 (M下稱之為0/W/0型 )乳液進- -步予Μ乳 意 富 I 化 Ψ 項 I 分 散 於 油 相 中 而 成 之 油 包 水 包 油 型 (K下稱之為0/W/0 型 再 填 1 )乳化組成物又稱為多重乳液或複乳液Uu 1 t i p 1 e 寫 本 頁 1 e m u 1 si on), 在化粧品 、食品 、醫藥品等各種工業上有重 1 I 要 之 用 途 〇 具 體 之 > 通 常 W/0型乳液僅有水相分散於油 1 I 相 中 9 而 多 重 乳 液 之 粒 子 構 造 則 有 如 ΓΒΠ _ 1 中所 示 之 構 造 9 1 1 訂 外 油 相 10 中 分 散 之 水 相 12 中 又 有 內 油 相 14分散 著 〇 因 此 1 可 Μ 預 期 其 具 有 單 純 之 0/W型或W/0 型 乳 液 所無 之 特 殊 使 用 1 1 感 或 效 果 〇 1 1 例 如 内 油 相 14 由 於 水 相 12及 外 油 相 10遮蔽 其 與 外 界 空 1 氣 之 接 觸 ， 內 油 相 1 4中 若 含 有 易 氧 化 性 脂 溶性 藥 劑 則 可 1 I Μ 期 待 其 氧 化 安 定 性 能 較 在 0/W型或W/0 型 乳液 之 油 相 中 為 1 1 佳 0 1 1 此 外 > 近 年 來 為 要 求 延 展 性 佳 有 清 爽感 、 不 粘 腻 等 1 1 良 好 之 使 用 性 及 優 良 之 耐 水 性 耐 油 性 9 不易 因 流 汗 水 1 1 份 而 脫 落 等 功 能 9 皮 霜 外 用 劑 及 化 粧 用 品 主劑 廣 泛 使 用 二 1 1 甲 基 聚 矽 氧 综 等 聚 矽 氧 系 為 主 劑 〇 特 別 是 防晒 用 化 粧 品 因 1 | 為 在 夏 天 廣 泛 使 用 9 多 要 求 要 具 有 清 爽 之 使用 蹢 且 不 容 易 1 I 因 汗 水 、 皮 脂 、 淋 浴 等 而 脫 落 > 因 而 增 加 了使 用 此 類 聚 矽 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 3 (修正頁 385 1 4 470653 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（2 ) 1 1 氧 条 為 主 劑 之 頻 數 0 1 I 然 而 配 合 於 —- 般 化 粧 用 品 或 皮 膚 外 用 劑 之 脂 溶 性 藥 劑 1 1 中 有 不 少 為 矽 院 % 油 分 難 溶 性 0 例 如 配 合 於 護 虜 用 化 粧 用 /—S 请 1 1 1 品 中 之 油 溶 性 紫 外 線 吸 收 劑 > 其 中 甚 多 對 矽 氧 % 主 劑 之 溶 先 閱 讀 1 1 解 度 明 顯 偏 低 者 0 因 此 1 含 大 量 矽 氧 主 劑 之 化 粧 用 品 中 1 背 面 1 1 | 若 配 合 此 類 紫 外 線 吸 收 劑 發 生 紫 外 線 吸 收劑長期間後析 注 意 事 項 再 填 1 1 1 出 結 晶 之 問 題 點 0 1 因 此 ， 為 防 止 此 類 結 晶 析 出 9 必 須 限 制 其 中 矽 氣 条 油 寫 本 頁 衣 I 分 難 溶 性 脂 溶 m 劑 之 使 用 量 或 者 併 用 大 量 該 藥 劑 之 高 溶 ·—✓ 1 1 I 解 性 極 性 油 等 油 分 0 然 而 9 藥 劑 之 效 果 通 常 取 決 於 其 添 加 1 1 I 量 t 限 制 使 用 量 將 使 藥 劑 無 法 得 到 充 份 之 效 果 0 此 外 * 大 1 1 量 使 用 極 性 油 等 非 矽氣糸油時 » 例 如 乳 化 組 成 物 中 由 於 製 訂 1 劑 上 之 問 題 必 須 限 制 矽 氣 % 油 之 配 合 量 9 因 此 在 無 法 配 1 1 大 量 之 聚 矽 氣 % 油 時 » 將 難 以 獲 得 充 份 之 使 用 感 或 耐 水 性 1 I 耐 油 性 0 1 此 外 » 由 於 聚 矽 氣 % 油 與 其 他 極 性 油 及 非 極 性 油 構 造 Ί I 及 性 質 全 然 不 同 » 在W/0型或0/W型乳液之油相 中 矽 氣 % 油 1 1 分 同 時 配 合 非 聚 矽 氣 % 油 分 之 場 合 » 難 以 選 擇 乳 化 劑 及 乳 1 1 化 條 件 等 因 此 欲 得 到 一 般 具 有 良 好 乳 化 安 定 性 之 乳 化 組 1 1 成 物 非 常 困 難 0 1 1 因 此 之 故 為 解 決 上 述 問 題 點 亦 有 人 考 慮 應 用 1 1 (0/W/0)多重乳液加以解決c ，具體言之， 即在0/W/0型多 重 1 I 乳 液 中 内 油 相 14與外油相 10偽 由 水 相 12所隔離 因 此 理 1 1 | 論 上 二 種 具 不 同 性 質 之 油 如 聚 矽 氣 % 油 與 非 聚 矽 氣 % 油 之 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0'乂297公釐） 4 3 8 5 1 4 470653 A7 經濟部中央標準局員工消費合作社印製 B7五、發明説明（3 ) 類性質上迴然不同的油分可以使其在一乳液中獨立地存在 。具體之例如在一油相中為矽氣条油分難溶性之脂溶性藥 劑與溶解該蕖劑之非矽氣条油分，另一油相中則為矽氣条 油分，分別配合時可以使其安定地共存於一乳液中，且可 防止該麵劑析出。 已往公知之多重乳液之製法為將利用親水性界面活性 劑16調製的油包水型乳液，再乳化於親油性界面活性劑18 所溶解之外油相中，即所謂之二段乳化法。然而，以此方 法調製之多重乳液，其乳化安定性極差，在長期間後内油 相14會與外油相10融合或與水相12合一，終至油成份與水 成份分離。因此，由於此類多重乳液本身之乳化安定性極 差，無法充份得到前述0/W/0型多重乳液所具有之預期效 果。 為改善此類問題已有各種組合。具體之例如日本特公 昭5 5 -33294號公報中所載，以乳蛋白質併用蔗糖脂肪酸酯 之方法；日本特公平3 - 54709號公報中所載，於外相油中 配合聚甘油脂肪酸酷之方法。又如日本特開昭63 - 30405號 公報中所載，分別以特定之皂土配合於水相中，以糊精脂 肪酸酯配合於外相中之方法。 然而，以上述已往方法調製之0 / W / 0型多重乳液仍然 有内相油與外相油融合，或内相油之殘餘量長期間後減少 之傾向，亦即内油相14與外油相10夾箸水相12及界面活性 劑1 6，1 8之親水基而相對，兩油相1 0 , 1 4融合之間隔極小。 另一方面，由於期望内油相14存在，因此其物理性質或在 H - - - -I- I I I I - II I I . —ϋ ,1τ (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準（CNS ) Α4規格（210Χ297公釐〉 5 3 8 5 1 4 470653 A7 B7五、發明説明（4 )製造時即難以縮小水相1 2之粒徑，其不安定化之因素明顯 比較一般之0 / W型或W / ϋ型乳液為大。因此，以上述方法調 經濟部中央標準局員工消費合作杜印製 。劑 低油 .。期少成型 調中如 此劑 果抑 點化ItL性内 者長滅油油 ·合份 因藥 結地 缺氧),定善 定經量或包 性場成 ，及 之箸 的抗44安改 安劑留劑水 定此定 題性 討顯 性及18化法 性藥殘藥包 安。安 課定 檢可 特劑10乳無 期性之之油 之 Η 不 之安 意， 理收7-其仍 長溶相中到 液加熱 上化 刻時 物吸 平於此 到油油相得 乳化， 術乳 ，在 之線開由因。得之内油份 善塑備 技之 的存 液外特 ，，性以含使内充 改可設 往一 目物 乳紫本法壊定難所致此法 為冷之 已合 述礦 重合日方破安中中而因無 C,急殊 述相 前土 多配 < 之會化液相合，生題中之特 前油。成拈 現有Lil往態氧乳油融一發問法繼有 於外液達質 表告？ 已狀性重内生合會的方後須 。 鑑與乳為改 份報重為化期多，發相即果往工必難 有相重等機 充近!^法乳長之時相油，效已加但困 為油多人有 法最0¾方其的往製油外中期述熱不亦 的内的明有 無 -«/造間劑已調外與相預上加工加 目制高發中 有面0/製期藥在在與相油之在括加添 之抑均之相 會方之之存之 ，如相油外物 ，包冷之一i 明可性明油 品一.相液 保合此例油内 至成外 中急等 i 發一定發外 製另油乳期配因 ，内致動組此驟 、素 1 本供安本 ’ 的 内重長中 此後終移化 步熱生 1 提期 現 製於多 ，相 因間 ，分乳 製加維 d 欲長 發 (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準（CNS ) A4規格（210X297公釐） 6 385 1 4 470653 修正 本年月 丨?1充Qq·心ί 4 曰 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、 發明説明 :5 ) 1 | 制 内 油 相 與 外 油 相 之 合 一 1 所 得 的 0/W/0型多重乳液之乳 1 I 化 安 定 性 及 內 油 相 中 配 合 的 脂 溶 性 藥 劑 之 槩 劑 安 定 性 非 常 1 1 高 而 完 成 本 發 明 0 y—V 請 1 1 具 體 -5— 之 9 本 發 明 之 多 重 乳 液 為 外 油 相 中 分 散 0/W/0 先 閱 1 I 讀 I 型 乳 液 之 0/W/0型多重乳液， 其特徵為前述外油相中含有 月 1 I 之 1 有 機 改 質 粘 土 礦 物 〇 注 意 1 | 事 1 本 發 明 之 多 重 乳 液 中 之 有 機 改 質 粘 土 礦 物 水 膨 潤 性 項 再 1 % 粘 土 礦 物 經 第 四 級 銨 型 陽 離 子 界 面 活 性 劑 及 非 離 子 性 界 面 寫· 本 艮 頁 1 活 性 劑 處 理 者 為 佳 〇 1 1 本 發 明 之 多 重 乳 液 中 之 0/W型乳液與外油相之配合比 1 1 1 例 Μ 重 量 比 2 ： 3〜1 9 ： 1為佳 ) 1 1 本 發 明 之 多 重 乳 液 Μ 油 相 中 含 有 矽 氧 系 油 分 者 為 佳 〇 訂 1 前 逑 之 矽 氧 糸 油 分 對 多 重 乳 液 之 配 合 >λ 全 量 重 量 百 分 1 1 比 之 5〜6 0 %為佳c > 1 | 前 述 之 矽 氧 系 油 分 >λ 沸 點 200 ΌΜ下之低沸點矽氧油 1 為 佳 〇 ! I 本 發 明 中 之 多 重 乳 液 Λ 內 相 油 中 含 脂 溶 性 藥 劑 者 為 1 1 佳 0 1 本 發 明 之 多 重 乳 液 内 油 相 中 配 合 的 脂 溶 性 藥 劑 矽 1 烧 系 油 分 難 溶 性 藥 劑 9 且 外 油 相 配 合 矽 氧 系 油 分 為 佳 0 1 本 發 明 之 多 重 乳 液 9 内 油 相 中 配 合 之 脂 溶 性 藥 劑 易 1 I 氧 化 性 之 脂 溶 性 維 生 素 、 油 溶 性 紫 外 線 吸 收 劑 不 飽 和 脂 1 1 1 肪 酸 及 其 衍 生 物 中 選 擇 之 1 種 或 2 種 Μ 上 者 為 佳 〇 I 1 I 本 發 明 之 多 重 乳 液 Μ 水 相 含 親 水 性 高 分 子 為 佳 〇 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (修正頁） 385 1 4 470653 經濟部智慧財產局員工消費合作社印製 修正 本年月曰補充 89, 6, 14 A7 B7 五、發明説明（6 )前述之親水性高分子以裼藻酸納、鹿角菜膠、黃素樹 糖 蘭 得 卡 ' 膠 明、 脂 Γ υ 醣 聚 露 甘 糖 萄 葡 ' 菜 洋 糖 葡 聚 質 角 Λ 酸 質 明 透、 粉 澱470653 Amend this month to add ea 6.14 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Invention Description '1) 1 1 Technology M. Domain 1 [The present invention relates to -11 types of oil-in-water-in-oil (0 / W / 0) type multiple emulsion 1 1 and its manufacturing method 9 Especially for the prevention and formulation of mixing of the internal oil phase and the external oil phase / — \ Please | First 1 Improve the stability of the fat-soluble agent in the internal oil phase 〇Reading the back 1 i 面 operative surface I 1 Note 1 Into the oil-in-water type (hereinafter referred to as 0 / W / 0 type) emulsion--step to M milk Yifu I chemical Ψ item I dispersed in the oil phase The middle-formed oil-in-water-in-oil type (hereinafter referred to as 0 / W / 0 type and refill 1) emulsified composition is also called multiple emulsion or multiple emulsion Uu 1 tip 1 e write this page 1 emu 1 si on ), In cosmetics, food, medical Various industries such as pharmaceuticals have important 1 I applications. Specific > Generally, W / 0 emulsions only have the water phase dispersed in the oil 1 I phase 9 and the particle structure of multiple emulsions is as shown in ΓΒΠ _ 1 Structure 9 1 1 The outer oil phase 10 is dispersed in the water phase 12 and the inner oil phase 14 is dispersed. Therefore, 1 can be expected to have a special use that is not found in pure 0 / W or W / 0 emulsions 1 1 Feeling or effect 〇1 1 For example, the internal oil phase 14 is because the water phase 12 and the external oil phase 10 shield its contact with the outside air. The internal oil phase 1 4 can contain 1 I M if it contains easily oxidizable fat-soluble agents. It is expected that its oxidative stability is 1 1 better than 0 / W or W / 0 emulsion oil phase 1 1 0 1 1 In addition > In recent years, it has been required to have good ductility, refreshing, non-sticky, etc. 1 1 Good Usability and excellent water and oil resistance 9 Sweat 1 1 part and other functions 9 Skin cream topical and cosmetic products are widely used. 1 1 Polysiloxane based agents such as methyl polysiloxane etc. Especially for sunscreen cosmetics 1 | It is widely used in summer Use more than 9 requirements to have a refreshing use 蹢 and not easy 1 I fall off due to sweat, sebum, shower, etc. > so the use of such polysilicon is increased 1 1 This paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 (Mm) 3 (Revised page 385 1 4 470653 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) 1 1 The frequency of oxygen strips as the main agent 0 1 I Or the skin-soluble fat-removing agents 1 1 1 Many of them are silica gels% Oil content is poorly soluble 0 For example, it is used for cosmetic and / or S cosmetic preparations 1- 1 Oil-soluble UV absorbers in products > Many of them Oxygen% Master Read about the dissolution of the agent 1 1 Those with a significantly lower resolution 0 Therefore 1 In cosmetic products containing a large amount of silica-based main agent 1 Back 1 1 | If a UV absorber is used for a long period of time after the UV absorber is combined with this type of UV absorber, the precautions should be filled again 1 1 1 Problems with crystallization 0 1 Therefore, in order to prevent such crystallization, 9 it is necessary to limit the amount of hardly soluble fat-soluble agent in which the silicon gas stripe oil is written on the cover of the coating or the high solubility of a large amount of the agent. —✓ 1 1 I Decomposable polar oil and other oils 0 However, the effect of the medicine usually depends on its addition 1 1 I Amount t Limiting the amount of use will prevent the medicine from getting a full effect 0 In addition * Large 1 1 Use polar oil, etc. In the case of non-silicon gas oils »For example, in the emulsified composition, due to the formulation of 1 agent, the amount of silicon gas% oil must be limited to 9. Therefore, when it is impossible to mix 1 1 with a large amount of polysilicon gas oil, it will be difficult to obtain a charge. Part of the feeling of use or water resistance 1 I Oil resistance 0 1 In addition »Because of the polysilicon gas% oil and other polar and non-polar oil structure Ί I and properties are completely different» Oil in W / 0 or 0 / W emulsion In the case of silicon gas% oil 1 1% and non-polysilicon gas% oil content at the same time »It is difficult to choose emulsifiers and milk 1 1 chemical conditions, so it is very difficult to obtain an emulsified group 1 1 with good emulsification stability. 0 1 1 Therefore, in order to solve the above problems, some people also consider applying 1 1 (0 / W / 0) multiple emulsion to solve c, specifically, that is, the internal oil phase in the 0 / W / 0 multiple 1 I emulsion 14 It is separated from the external oil phase 10 by the water phase 12. Therefore, the above two types of oils with different properties, such as polysilicon gas% oil and non-polysilicon gas% oil 1 1 CNS) A4 size (2 丨 0 '乂 297mm) 4 3 8 5 1 4 470653 A7 Ministry of Economic Affairs Bureau of Standards consumer cooperative printed B7 five employees described invention (3) back to the totally different nature of the type of oil that it can exist independently in a emulsion. Specifically, for example, in one oil phase, a silicon gas strip oil is insoluble fat-soluble agent and a non-silicon gas strip oil component which dissolves the tincture, and in another oil phase, it is a silicon gas strip oil component, which can be stabilized when combined. Coexist in an emulsion, and can prevent the facial agent from precipitating. A conventionally known multiple emulsion manufacturing method is a so-called two-stage emulsification method in which a water-in-oil emulsion prepared by using a hydrophilic surfactant 16 is re-emulsified in an oil phase in which the lipophilic surfactant 18 is dissolved. However, the multiple emulsions prepared in this way have extremely poor emulsification stability. After a long period of time, the internal oil phase 14 will merge with the external oil phase 10 or become integrated with the water phase 12 until the oil and water components are separated. Therefore, due to the poor emulsification stability of such multiple emulsions, the expected effects of the aforementioned 0 / W / 0 multiple emulsions cannot be fully obtained. Various combinations have been developed to improve such problems. For example, the method described in Japanese Patent Publication No. 5 5-33294 using milk protein in combination with a sucrose fatty acid ester; the method described in Japanese Patent Publication No. 3-54709 containing polyglycerol fatty acid in an external oil . As disclosed in Japanese Patent Application Laid-Open No. 63-30405, a method in which a specific bentonite is added to the aqueous phase and a dextrin fatty acid ester is added to the external phase is used. However, the 0 / W / 0 type multiple emulsion prepared by the previous method still has the tendency to fuse the internal phase oil with the external phase oil, or the residual amount of the internal phase oil tends to decrease after a long period of time, that is, the internal oil phase 14 and the external oil phase 10 sandwiches the aqueous phase 12 and the surfactants 16 and 18 with hydrophilic groups opposite to each other, and the interval between the two oil phases 10, 14 is extremely small. On the other hand, because the internal oil phase 14 is expected to exist, its physical properties may be in H----I- IIII -II II. —Ϋ, 1τ (Please read the precautions on the back before filling this page) Applicable to China National Standard (CNS) A4 specification (210 × 297 mm> 5 3 8 5 1 4 470653 A7 B7 V. Description of the invention (4) It is difficult to reduce the particle size of the water phase 12 during manufacture, and the factors of instability are obvious. The general 0 / W type or W / / type emulsion is large. Therefore, the above method is used to adjust the consumption cooperation of employees of the Central Standards Bureau of the Ministry of Economic Affairs to print. The agent is low in oil. ItL sex insider can kill oil and oil due to lack of oxygen due to drug binding), determine the amount of menstruation, or include the field, and the anti-44 anti-analeptic agent retention agent water. Sexual and 18-chemistry French medicine residual medicine Baoan. Anke's regular inspection of the special oil of 10 emulsions of volatile oils is uneasy. Take care of 7- it is still in the long-term solution phase to liquid heating and engraving. When the oil is absorbed, the oil and oil phase are emulsified. Surgical milk, open cause on the line. The content of the oil is well-prepared and the liquid storage is special. The nature of the method is to make the filling can be set to a single point. This method is difficult to determine. This method is cold. Because there is no C in the middle of the break, it is urgent to describe the combination of the former soils and the combination of the liquid phase and the special oil in the question. Cheng Cheng's existing Lil-oriented oxygen emulsification method is followed by the quality of the external liquid. The party who has already undergone a re-endogenetic meeting shall be required to do so. Jian and milk are changed to report weight for more time, it is difficult to have phase reconciliation when the phase is released! ^ French milk is long-term phase oil, the effect has been increased, but it ’s difficult for many people. Fang Qi's oil production is not clear in the mid-terms and the heat is not clear-«/ intermediate agent has been adjusted externally and pre-processed plus high-preparation system to produce high-quality products 0 / in-phase drugs in the In addition, the existence of the party that meets the balance, such as the foreign matter of the oil, including the cold one. The clear oil product. The liquid phase keeps this example. Out of the oil and milk phase, the internal actuation group, the internal actuation group at this stage, the original weight for Aben's, the internal weight of the long-term middle, and then the final step of the heat generation 1 The promotion period is now based on multiple, inter-phase, milk division Make Jiawei d For long hair (please read the notes on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 6 385 1 4 470653 Amend this month Qq · 心 ί 4 Said Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention description: 5) 1 | The combination of internal oil phase and external oil phase 1 The obtained milk of the 0 / W / 0 multiple emulsion 1 The stability of the liniment and the stability of the elixir of the fat-soluble agent mixed in the internal oil phase are very high 1 1 to complete the present invention 0 y-V Please 1 1 Specific- 5-9 of the multiple emulsion of the present invention is dispersed in the external oil phase 0 / W / 0 Read 1 I Read Type I emulsion of 0 / W / 0 multiple emulsion, characterized in that the external oil phase contains month 1 I No. 1 Organically Modified Clay Minerals 0 Note 1 | Matter 1 The water-swellability term of the organically modified clay minerals in the multiple emulsion of the present invention is 1%. The clay minerals are written with a fourth-order ammonium-type cationic surfactant and non-ionic interface. · Bengen Page 1 The active agent treatment is better. 0 1 1 The mixing ratio of the 0 / W type emulsion and the external oil phase in the multiple emulsion of the present invention is 1 1 1 case M weight Ratio 2: 3 ~ 1 9: 1 is preferred) 1 1 The multiple emulsion M of the present invention is preferably one containing silicone oil in the oil phase. Order 1 The combination of the silicone oil in the front and the multiple emulsion > λ A weight percentage of 1 1 is better than 5 to 60%. C > 1 | The aforementioned silicone oil > λ low boiling point silicone oil 1 at a boiling point of 200 μM is better. I. Multiple emulsions in the present invention Λ Fatty-soluble agents in the internal phase oil are 1 1 Good 0 1 The fat-soluble agents in the oil phase of the multiple emulsion of the present invention are formulated with silicone 1 0 1 Multiple emulsions of the present invention 9 Fat-soluble agents easy to mix in the internal oil phase 1 I Oxidative fat-soluble vitamins, oil-soluble ultraviolet absorbers unsaturated fats 1 1 1 Choice of fatty acids and their derivatives 1 Or 2 kinds of M is better. The multiple emulsion M of the present invention is preferably water-containing hydrophilic polymer in the water phase. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ( (Revised page) 385 1 4 470653 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and amended to add 89, 6, 14 A7 B7 this month. 5. Description of the invention (6) The aforementioned hydrophilic polymer is sodium alginate, antlers Vegetable gum, flavin tree sugar Landecka 'gelatin, fat Γ υ sugar mannose grape glucose', caramel sugar glucose angle Λ acid clear, powder lake

a C 藻 生 原 膠 醣 多 菇 蘑 Λ η 創 癒 ' 粉 澱 rtj 0 素 維 纖 基 乙 ' 素 維 纖 基 甲 ' 素 維 I 嫌 f 醣 多 布 昆 r 醣 聚 萄 葡 羧 ' 禮 合 聚 烯 乙 羧、 醇 烯 乙 聚 ' 膠 伯 拉 阿 r 素 維 纖 化 硝 膠 蕃 黃 、 醇二 乙 聚、 素 維 纖 基 乙 羥 r 素 維 纖 基 甲 聚 乳 半 糖膠 膠 果 、 膠 樹 槐 剌 膠 豆 槐 剌 膠 樹 拉 瓜 子 桴 白 蛋 賂 ' 原 膠、 糖 三 芽 麥 聚 ' 糖 聚 葡、 酸 根 草 甘 藻白 素 fc= 铺 纖 基 丙 羥 基 甲 、 粉 0 基 丙 羥 基 甲 r 粉 澱 基 甲 羧 ' 白 蛋 聚烯 共乙 、 烷聚 酯丙 、 醇氧胺 二環醯 丙聚烯 酸烷丙 藻乙聚 裼氧、 、 環 塩 素聚基 維 、 纖酮 基烷 丙咯 羥吡 、 烯 納乙 酸聚 硫 、 素醚 維基 纖甲 、 烯 攪 βα^ 乙 酸 烯 丙 聚 納 酸 烯 丙 聚 佳 為 者 上 1 種 2 或 種 IX 之 擇 選 中 胺 亞 (請先閱讀背面之注意事項再填寫本頁) 乙 聚 包 為 徵 特 其 法 方 造 製 之 液 乳 重 多 型 ο / W / ο 之 明 發 本 於驟 再步 , 製 劑調 性之 活液 面乳 界型 子油 離中 非劑 性溶 水性 親溶 加水 添之 中份 劑成 溶相 性油 溶内 水加 在添 : 中 括其 之含 份於 成化 相乳 水散 型分 油液 加乳 添型 3 W 中 / U 液 乳 型 油 中 劑 溶 性 溶 水 述 前 在 及 述 前 將 及 驟 步 製 調 之 液 乳 型 矽 W 合 。 配 驟之 步分 化成 重相 多油 之 ， 中法 分方 成造 相製 油之 外液 之乳 衫 8 礦多 土之 粒明 質發 改本 機 有 合 配 之 〇 分 佳成 為相 中油 分内 成 ， 相中 油法 外方 於造 合製 配之 Μ 液 分乳 油重 。糸多 佳氧之 為矽明 分述發 油前本 糸 氧 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） 8 (修正頁） 385 1 4 五、發明説明b ) 以脂溶性藥劑為佳。 本發明之多重乳液之製造方法中，内油相中配合之脂 經濟部智慧財產局員工消費合作社印製 油 述吸上 油性分有前 為與 脹子 種 外 前線以 π 内溶成含加 膨離 一 之 之外種 加水相於添 液LW水非 之 合合紫 25:添該水 散及。 乳纟 將及 造 配 配性或,ί再於之分.，佳 重 一 。係劑 構。 包 將 其 中溶種S!， 及子 散驟為 多 成般性 層示 且 相油 1 4 中.，分分步驟 為 而述活 三表 法 後 ， 油、之 ， 劑驟高液化步。稱 g 化上面 有 I 劑 内素擇 y 溶步性乳重化容單“乳如界 具式 藥 中生選 Η 性製水型多膠內下S?合物子 為學 之 法維中 U 溶調親/W之凝術以««混礦雛 物化 性 方性物 纟水液及Μ中相技Μ0/相土陽 礦述 難佳製脂衍 加型含 Μ 成劑明 ^製外質塩 粘 Μ 分為 之之其 Μ 添油包¾相 化發 調 之改銨。性般 油分液性及 劑中加 I 油膠本 劑物機級得潤一 系油乳化酸0¾性劑添 Μ 外凝明0¾性礦有 四而膨 丨 氧糸重氧肪V/活溶中 r 之之說W/活 土之第 理水鋁 矽氧多易脂0/面性液!ϊ物子细0/面粘用經處之酸 對矽之 Μ 和 之 界溶乳 Ρ 礦分 詳之界質所物劑用矽 ΜΚ明劑飽 明 子水型 U 土高 即明性 改明礦性使水 劑分發藥不。發 離之油S3^粘性 上發水機發土 活此含 藥成本性、佳本 非分中 S 質水K本親 有本粘 面在性 性中 溶劑為 性成劑0/改親 將加 性界 膠 溶相 脂收者 水相溶 之機述 由添 潤性 凝 (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準（CNS ) A4規格（210X2.97公釐） 9 (修正頁） 385 1 4 470653a C algal raw gum sugar mushroom Λ η Chuangyu 'powder lake rtj 0 Suwei fiber base B' Suwei fiber base A 'Suwei I suspicion f sugar dobuqun r sugar polyglucose glucocarboxylate' Ethyl Carboxylic Acid, Alkyl Ethylene Polyethylene Glycol, Gumbera r Suvir Fiber Fibrillated Nitragon, Diol, Alcohol Diethyl Glycol, Ethyl Hydroxyl R Hydroxyl Cellulose Gum Papaya, Gum Tree Sophora japonicus bean Sophora japonicus Laguna seed white egg brie 'original gum, sugar saccharin polysaccharides, sugar polyglucose, phytoplankton fc = stilbyl propyl hydroxymethyl, powder 0 propyl hydroxymethyl r Fendo-based methylcarboxy 'white egg polyene copolymer, alkane polyester propylene, alkoxyamine dicyclo methacrylic acid alkaloid polyethylenoxide, cyclamyl polyvinyl alcohol, cellulosin alkylpropanol Pyridine, enoacetic acid polysulfide, acetic acid succinic acid fiber, enolactone βα ^ Allyl acetate acetic acid polyacrylic acid acrylic acid polyacrylic acid is the best choice of 1 or 2 or IX (please read the note on the back first) (Please fill in this page for matters) The liquid milk weight type made by the French method ο / W / ο is made in a quick step. The liquid-emulsion-type milky-type oil of the preparation is toned, non-agent-soluble, water-soluble, and water-soluble. Additive-soluble phase oil-soluble internal water is added to Tim: include the content of Chenghua-phase emulsion-water-dispersed oil-separated liquid-added emulsion-type 3 W medium / U liquid emulsion-type oil. As mentioned before, the liquid emulsion silicon W combined with and adjusted step by step. The step of differentiation is divided into heavy phase and oil, and the Chinese and French formulas are made into oil-free outerwear. 8 mineral and earthy grains. The hair quality is changed. This machine has a match of 0 points. The weight of the M liquid emulsifiable concentrate prepared by the external parties in the synthetic method is heavy. The best oxygen is Si Ming. The paper size before the oil is oxidized. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 8 (correction page) 385 1 4 V. Description of invention b) Fat-soluble agents are preferred. In the method for manufacturing the multiple emulsion of the present invention, the oil phase printed in the internal oil phase is printed by the employee of the Intellectual Property Bureau of the Ministry of Economics and Intellectual Property Bureau, and the oil is absorbed into the oil front. Add a water phase to the liquid LW Shui Fei He Zi Zi 25: add the water to disperse.纟 纟 will match with or match, or better, one better. Department of agent structure. Including the solubilizing seeds S !, and the sub-dispersion step is shown as a multi-layered phase, and the phase oil 14 is divided into steps. After the three-table method is described, the oil, the oil, and the agent suddenly increase the liquefaction step. We call the formula “I” with endolysin and y, and the step-by-step milk-reducing capacity list, “Such as a milk-like medicine, a drug-selective drug, and a water-soluble poly-in-and-inner compound.” Dissolving and adjusting the affinity / W's coagulation technique with «« mixed minerals, physical and chemical properties, square water, liquid solution, and medium phase technology, M0 / phase of Tuyang mine. It is divided into its M oil package and ammonium chloride. The oil is liquid-separating and the agent is added with I oil glue. This agent is a machine-grade oil-emulsifying acid. Ningming 0¾ mineral ore has four swells: oxygen, heavy oxygen, fat V, active r, W / active earth, hydrous aluminum, siloxane, and easy-to-fat 0 / facial fluid! Ϊ 物 子 细 0 / The surface of the surface is treated with the acidic acid of the silicon and the boundary of the soluble milk. The mineral substance is detailed. The agent of the material is silicon MK. The brightener is saturated with water. The soil is clear and the minerality is changed to make the liquid medicine. No. The oil S3 is released from the viscous water dispenser. This medicine is cost-effective, and the quality is not good. The quality of the water is K. The parent has the sticky surface. The solvent is a sexual agent. The mechanism of water-miscibility in the additive-peptide-soluble fat collector (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X2.97 mm) 9 (correction page) 385 1 4 470653

A7 B7五、發明説明（8 ) (X,Y)A(Si,Al)4〇t〇(OH)2ZB* nH2〇.........化學式 I 1 在此，X = A1 , Fe η I， Mn i η，Cr u IA7 B7 V. Description of the invention (8) (X, Y) A (Si, Al) 4〇t〇 (OH) 2ZB * nH2〇 ... Chemical formula I 1 Here, X = A1, Fe η I, Mn i η, Cr u I

Θ FΘ F

• I L• I L

Z kZ k

d C 表 A 又d C Table A again

表 B 石 脱 蒙 如 例 之 體 具 ( 如 成 品 合 商 或 售 然市 /IX 天 等 石 脱 蒙 鋰代 、 取 石所 皂氟 、 為 基 羥 之 中 式 中 合 場 此 在 群 土 脱 蒙 等 多 耐 布母 勒 雲 、 成 亞 合 比之 尼 母 可 雲 、 帶 亞鋰 比為 尼稱 可名 、 俗 膠 或 毫 ΛΜ 、身 0 : 母 雲 鈉 酸 矽 及 如 品 商 售 市 (請先閱讀背面之注意事項再填寫本頁) 股 等 式 學 化 列 下 用 使 可 劑 性 活 面 等界 多 子 耐離 莫陽 德型 之塩 司銨 公级 丨四 第 業 Η 者 示 所Table B Stone demensions as examples of body tools (such as finished product manufacturers or sale of market / IX days and other stone demensing lithium generation, taking stone Soap Fluorine, as the basic hydroxyl in the Chinese formula in the compound field demulsification, etc. Nyblomer cloud, Nimbi cloud which has a ratio of Asia, Lithium bimium is called Nickel name, vulcanizate or milliM, body 0: mica-silicic acid and other products sold on the market (please read first Note on the back, please fill in this page again.) The stock equation is used in the column of chemical equivalence.

R +R +

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R 經濟部中央標準局員工消費合作社印製 數 子 原 硪 表 R 中 Τ Ι 式 學 化 數 子 原 磺 或 基 甲 表 基 烷 羥 或 基 烷 之 基 甲 ，苯 或 基 烷 之 數 C 子 基 原 塩 碳酸 表硫 R4基 及甲 R3或 , 子 基原 烷素 之鹵 22表 甲化甲 三 氣二 基 、基 四銨四 + 基 + 化甲化 氣 三 氣 .、基 、 銨八銨 基十基 甲化甲 三 氣三 基 、基 二 銨 二 十基十 化 甲 二 氛 三 化 : 基氣 如六 、 例十銨 之化基 體氣甲 具 、三一 銨基 基烷 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 10 3 8 5 1 4 470653 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（9 ) 基乙基銨、氣化十六基二甲基乙基銨、氣化十八基二甲基 乙基銨、氣化烷基二甲基乙基銨、氯化二十二基二甲基乙 基銨、氛化十四基二乙基甲基銨、氯化十六基二乙基甲基 銨、氣化十八基二乙基甲基銨、氣化烷基二乙基甲基銨、 氣化二十二基二乙基甲基銨、氣化苯甲基二甲基十四基銨 、氱化苯甲基二甲基十六基銨、氣化苯甲基二甲基十八基 銨、氛化苯甲基二甲基二十二基銨、氣化苯甲基甲乙基十 六基銨、氣化苯甲基甲乙基十八基銨、氛化二二十二基二 羥乙基銨及相當之溴化物等，以及甲基硫酸一二一十六烷 基丙基乙基銨等。 本發明中可任意選擇此類物質之1種或2種以上。 其次說明本發明中之前述第四级銨塩型陽離子界面活 性劑及同時在處理水膨潤性粘土礦物中使用之非離子界面 活性劑。 本發明中處理拈土礦物所使用之非離子界面活性劑以 H LB值存在範圍為2〜16者為佳，3〜12者更佳。 此處之H LB值為以下述之川上計算式計算之值。 HLB = 7 + 11.7 · log (Mw/Ho) 在此Hw分別表示親水性基部份之分子量，Mo表示親油 性基部份之分子量。 具體之例如：2〜30莫耳聚環氣乙烷加成{以下略稱 P0D(2-30)}之十八醚、P0E(2〜35)之十八碳烯醚、P0E(2 〜20)之十二醚、P0E(1〜20)之烷基苯基醚、P0E(6〜18) 之二十二醚、P〇E(5〜25)之2 -癸基十五基醚、P0E(3〜20) 11 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 3 8 5 1 4 (請先閲讀背面之注意事項再填寫本頁) 470653 A7 B7 五' 發明説明（10 ) 2 -癸基十四基醚、p〇E(3〜20)之2 -癸基十四基醚、P〇E( 8〜U)之2 -辛基癸基醚等之醚型活性劑，及P0E(4〜60)之 硬化箆麻油、P0E(3〜14)之脂肪酸單酯、P〇E(6〜30)之脂 肪酸雙_、P〇E(5〜20)之山梨糖醇酐脂肪酸_等之酷型活 性劑，或P0E(2〜30)之丙三基單異硬脂酸酯、p〇E(10〜60 )之丙三基三異硬脂酸酯、P〇E(7〜50)之硬化箆麻油單異 硬脂酸酯、P〇E(12〜60)之硬化箆麻油三異硬脂酸酯等之 賊酷型活性劑等之琛氣乙烷加成型界面活性劑，及十一_ 丙三基-四-油酸酯、六-丙三基-三·異硬脂酸酯、四-丙二 基'•二-異硬脂酸酷、二-丙三基-二-異硬脂酸_等之聚丙 三醇脂防酸酯，丙三基-單-異硬脂酸酷、丙三基一單一油 酸_等之丙三醇脂肪酸酯等之多元醇胞肪酸酯型界面活性 劑，例如下述化學式ΙΙΪ所示之二甲基_聚砂氣院一聚氣嫌 烴羥烯烴共聚體等非離子改質矽氣活性劑等。 CH3 /CH3\ /ch3\ CH3 之R Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. The number of formulas in Table R is shown in the formula Τ Ⅰ. Orthopyrene episulfide R4 group and methyl R3 or halogen of protonyl alkanes form methyl triazine diyl group, tetramethylammonium tetra + group + methyl trimethylammonium group. Decamethyl methyl triazine triyl, dimethyl diammonium icosyl decamethanyl trioxane: base gases such as hexadecyl, for example, deca-ammonium base gas, triammonium-based alkanes, paper size applicable to China National Standard (CNS) A4 Specification (210X297 mm) 10 3 8 5 1 4 470653 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (9) Ethylethylammonium, Cetylhexamethyl Ethylammonium, octadecyldimethylethylammonium, gasified alkyldimethylethylammonium, behenyldimethylethylammonium chloride, tetradecyldiethylmethyl Ammonium chloride, cetyl diethylmethylammonium chloride, gasified octadecyldiethylmethylammonium, gasified alkyl Ethylmethylammonium, vaporized behenyldiethylmethylammonium, vaporized benzyldimethyltetradecylammonium, halogenated benzyldimethylhexadecylammonium, vaporized benzyl Dimethyl octadecyl ammonium, Benzyl dimethyl behenyl ammonium, Benzyl methyl ethyl hexadecyl ammonium, Benzyl methyl ethyl octadecyl ammonium Dodecyldihydroxyethylammonium and equivalent bromide, etc., and 1,2hexadecylpropylethylammonium methyl sulfate. In the present invention, one kind or two or more kinds of these substances can be arbitrarily selected. Next, the aforementioned fourth-order ammonium sulfonium type cationic surfactant in the present invention and the non-ionic surfactant used in the treatment of water-swellable clay minerals will be described. The non-ionic surfactant used in the treatment of ocher minerals in the present invention has a H LB value in the range of 2-16, more preferably 3-12. The H LB value here is a value calculated by the following Kawakami calculation formula. HLB = 7 + 11.7 · log (Mw / Ho) Here Hw represents the molecular weight of the hydrophilic group portion, and Mo represents the molecular weight of the lipophilic group portion. Specific examples are: 2 ~ 30 mole polycyclic gas ethane addition {hereinafter referred to as POD (2-30)} octadecyl ether, P0E (2 ~ 35) octadecyl ether, P0E (2 ～ 20 ) Dodecyl ether, P0E (1 ~ 20) alkyl phenyl ether, P0E (6 ~ 18) 22 ether, P0E (5 ~ 25) 2-decyl pentadecyl ether, P0E (3 ~ 20) 11 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 3 8 5 1 4 (Please read the precautions on the back before filling out this page) 470653 A7 B7 Five 'Invention Description (10 ) 2-Decyltetradecyl ether, 2-decyltetradecyl ether of POE (3-20), ether type active agents such as 2-decyltetradecyl ether of POE (8 ~ U), 2-octyldecyl ether , And hardened ramie oil of P0E (4 ~ 60), fatty acid monoester of P0E (3 ~ 14), fatty acid di_ of POE (6 ~ 30), sorbitan anhydride of P0E (5 ~ 20) Fatty acid and other cool active agents, or glyceryl monoisostearate of POE (2 ~ 30), glyceryl triisostearate of POE (10 ~ 60), POE ( (7 ~ 50) hardened ramie oil monoisostearate, POE (12 ~ 60) hardened ramie oil triisostearate, etc., thief-type active agent, etc. Agent, Undecyl_glyceryl-tetra-oleate, hexa-glyceryl-tri-isostearate, tetra-glycyl'-di-isostearate, di-glyceryl-di- Polyglycerol fatty acid esters such as isostearic acid, polyglycerol fatty acids such as glyceryl-mono-isostearate, glycerol-monooleic acid, etc. The ester-type surfactant is, for example, a non-ionic modified silica gas active agent such as a dimethyl-polysand gas station monopoly hydrocarbon olefin copolymer as shown in the following chemical formula III. CH3 / CH3 \ / ch3 \ CH3

CH3/m -Sio -Si—CH3 ---.--η-----^-------ΙΤ (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CH3 / m -Sio -Si—CH3 ---.-- η ----- ^ ------- ΙΤ (Please read the notes on the back before filling out this page) Staff Consumption of the Central Bureau of Standards, Ministry of Economic Affairs Printed by a cooperative

n CH3 …化學式111(CH2)a 0(C2H4〇)b(C3H6〇)cR (式中a為1〜5 , b為7〜1 5，C為〇〜4，BI為2 0〜1 0 〇 , η為1〜5之各整數，R為氫原子或破數1〜5之院基。） 此化合物中尤以使用十一丙三基一四一油酸酯、六_ 四三基—三-異硬脂酸、四-丙三基-二-異硬脂酸等二縮二 丙三醇以上之二縮三丙三醇脂肪酸、Ρ0Ε(2〜12)之十八砍 烯基醚、Ρ0Ε(3〜12)之硬脂基酸、Ρ0Ε(2〜1 0 )之十一院基 本紙張尺度適用中國國家標準（CNS ) Α4規格（2丨〇><297公瘦） 12 3851 4 經濟部中央橾準局員工消費合作社印製 A7 B7 五、發明説明（11 ) 、P〇E(2〜10)之壬基苯基醚、賊、P〇E(6〜15)之二十二烷 基p〇E(5〜20)之2-癸基-十五烷基醚、P0E(5〜17)之2 '癸基-十四烷基醚、P0E(8〜16)之2-辛基-癸基醚等之Ρ0Ε 加成ϋ型活性劑，及P0E(10〜20)之硬化篦麻油、P0E(5〜 14)之油酸單酯、P〇E(6〜20)之油酸雙酯、P0E(5〜10)之 111梨糖醇酐油酸酯等之Ρ0Ε加成酯型活性劑，P0E(3〜15) 之丙三基-單-異硬脂酸酯、P0E(10〜40)之丙三基-三-異 $脂酸酸等之Ρ0Ε加成醚酯型活性劑等之環氣乙烷加成型 &離子性界面活性劑，前述化學式ΠΙ所示之二甲基-聚矽 氧烷-聚氣烯烴共聚體等之非離子改質矽氣活性劑為佳。 於本發明中，可自此等非離子性界面活性劑之中任意 瓖擇一種或二種以上。 本發明中使用之有機改質拈土礦物，其處理方法之例 可以在水、丙酮或低级醇等低沸點溶劑中將水膨潤性拈土 礦物與第四级銨塩型陽離子界面活性剤及非離子性界面活 ft劑分散攪拌處理，或預先將水膨潤性粘土礦物與第四级 $塩型陽離子界面活性劑在低沸點溶劑中處理，所得的陽 @子改質粘土礦物再以非離子性界面活性劑處理，再去除 低沸點溶劑邸得。 以下說明上述方法調製之有機改質粘土礦物。粘土確 物如屬蒙脱石（smecfite)族而有水膨潤性之Ha型蒙脱土（ mentmoril Ionite),以第四級鞍塩型有機陽離子交換其陽 離子後即成為疏水性之有機改質蒙脱土。接著再以非離子 界面活性劑包合即生成包合化合物（複合體），在油中膨潤 (請先閱讀背面之注意事項再填寫本頁) •装· 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 13 385 1 4 470653 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（12 ) 後即生成粘稠性之油性凝膠。非離子界面活性劑者應是促 使陽離子交換反應無關之蒙脫石層間（矽酸塩層）之極性側 包合，使該層間生成油性凝膠，再由油侵入而膨潤，凝膠 化（油化學第40卷，第6號491〜496頁，1991)。 所得有機改質粘土礦物之構造，由於水膨潤性粘土礦 物層間由第四级銨塩型陽離子界面活性劑與非離子界面活 性劑所介入，因此形成層間隔變大之狀態。因此由X射線 繞射測定長面間隔即可確認有無吸附第四级銨塩型陽離子 界面活性劑與非離子界面活性劑。 此外，所得的有機改質粘土礦物利用氣仿、***等以 索可勒萃取器萃取時可以流洗出層間物理性吸附之界面活 性劑，因此將該萃取液以氣相層析儀分析，測定熱分解溫 度或熱分解量（DTA-TG測定）等即可以確定物理性吸附的界 面活性劑之存在量。 本發明中使用之有機改質粘土礦物中之第四級銨塩型 陽離子界面活性劑之含量並無待別之限制，但以相對於 100s水膨潤性粘土礦物60〜140毫當量（以下略稱meq)為佳 。有機改質粘土礦物中非離子界面活性劑之含量以相對於 100g水膨潤性粘土礦物在5〜100g為佳，15〜50g更佳。 此有機改質粘土礦物已知以例如日本特公平2-32015 等所示之方法可有效調製得安定之W/0型乳液。然而多重 乳液之安定化，待別是有效防止其内油相與外油相合一之 點仍未完全明瞭C· 0 / W / 0型多重乳液中，外油相中含有此類有機改質粘 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ，』 0 c , 14 38514 (請先閲讀背面之注意事項再填寫本頁) 470653 A7 B7 經濟部中央標準局員工消費合作社印製 五、 發明説明（]3 ) 1 | 土 礦 物 即 可 抑 制 内 油 相 與 外 油 相 之 合 一 » 得 到 長 期 安 定 性 1 I 極 高 之 0 / W / 0型多重乳液。 此夕 卜， 此種条在内油相中配合 1 1 | 脂 溶 性 藥 劑 之 場 合 9 可 以 防 止 該 脂 溶 性 藥 劑 氣 化 » 因 此 藥 /-—\ 請 1 1 1 劑 安 定 性 佳 C 先 閲 讀 背 ιέ 之 1 1 I 有 機 改 質 粘 土 礦 物 之 使 用 量 9 以 相 對 於 多 重 乳 液 組 成 1 1 物 之 〇. 1〜5 重量？· ;為佳， 0.5 3 重 量 % 更 佳 0 少 於 0 . 1 ’/王 意 事 1 1 重 量 % 之 場 合 I 無 法 得 到 添 加 有 機 改 質 粘 土 礦 物 應 有 之 效 項 再 填 1 ! ά I 果 1 無 法 有 安 定 之 多 重 乳 液 0 具 體 言 之 » 經 長 時 期 後 内 油 寫 本 頁 相 會 消 失 而 無 法 保 持 多 重 乳 液 0 又 t 超 過 5 重 量 % 時 調 製 1 1 1 之 乳 液 粘 度 變 高 1 因 此 實 際 使 用 上 會 産 生 延 展 性 變 差 無 1 1 I 光 澤 、 不 透 明 等 問 題 0 1 1 訂 1 本 發 明 中 由 於 外 油 相 中 配 合 前 述 所 得 之 有 機 改 質 粘 土 磧 物 » 油 相 可 以 使 用 之 範 圍 廣 泛 t 白 極 性 油 至 非 極 性 油 均 1 1 可 0 可 使 用 之 油 例 如 液 體 石 蠘 、 三 十 硪 院 Λ 異 院 烴 枝 鐽 1 | 低 级 石 蠟 等 m fey m 化 合 物 油 * 異 丙 基 十 四 碩 烷 酸 酯 十 基 1 異 辛 酸 酯 丙 三 基 三 辛 酸 m 等 酷 油 » 矽 氣 % 油 分 等 0 Γ I 使 用 矽 氣 % 油 分 之 場 合 > 乳 液 可 有 良 好 之 耐 油 性 Λ 耐 1 1 水 性 及 使 用 感 0 本 發 明 中 使 用 之 聚 矽 氣 % 油 可 以 使 用 範 圍 1 1 廣 泛 之 矽 氣 油 > 但 若 以 使 用 感 及 製 劑 上 之 觀 點 則 以 常 壓 下 1 1 沸點2 0 0它1 认下者為佳。 具體之例如二甲基聚矽氣烷、 甲 1 I 基 苯 基 聚 矽 氣 烷 Λ 甲 基 氫 烯 聚 矽 氧 烷 等 鏈 狀 聚 矽 氣 院 八 1 I 甲 基 一 璟 四 矽 氣 院 Λ 十 甲 基 璟 五 矽 氣 烷 十 二 甲 基 環 * - 矽 1 1 I 氧 烷 、 四 甲 基 一 四 氫 二 烯 環 四 矽 氣 烷 等 之 環 聚 矽 氣 烷 等 0 1 1 其 中 使 用 低 聚 合 度 之 二 甲 基 聚 矽 烷 (聚合度2 7 )等 之 揮 發 1 1 15 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 38 5 1 4 470653 A7 B7 經濟部中央標準局員工消費合作社印製 五、 發明説明（14 ) 1 I 性 鐽 狀 聚 矽 氧 烷 及 十 甲 基 環 五 矽 氣 院 八 甲 基 環 四 矽 氣 烷 1 I 等 揮 發 性 環 聚 矽 氧 院 等 之 揮 發 性 矽 氧 油 之 場 合 9 塗 抹 皮 虜 1 1 I 上 時 油 殘 留 感 tb 較 — 般 之 矽 氣 油 為 少 » 在 要 求 清 爽 使 用 請 1 I 感 之 場 合 尤 其 適 宜 0 先 閱 讀 背 之 1 I 本 發 明 之 多 重 乳 液 中 矽 氣 % 油 分 之 配 合 量 可 以 適 當 地 1 1 選 擇 i 但 以 相 對 於 多 重 乳 液 全 量 之 5 ^ -60%重量％為佳， 注 意 事 1 1 尤 以 5〜40重量％更佳， 1 5〜40重量％時又更佳。 矽氧条 項 再 填 1 ! 1 油 分 之 配 合 量 少 之 場 合 $ 無 法 得 到 充 份 之 耐 水 性 及 耐 油 性 烏 本 頁 % 使 用 感 等 0 矽 氣 % 油 分 多 之 場 合 » m 有 乳 液 難 以 安 定 化 1 1 1 之 情 形 C 1 1 I 本 發 明 中 矽 氧 % 油 分 視 場 合 亦 可 配 合 於 内 油 相 中 ， 但 1 1 訂 1 以 配 合 於 外 油 相 中 為 佳 0 矽 氣 % 油 分 配 合 於 外 油 相 之 場 合 1 矽 氣 % 油 分 相 對 於 外 油 柑 之 配 合 量 可 依 外 油 相 在 多 重 乳 1 1 液 中 之 比 例 在 8〜100重 量 % 範 圍 中 選 擇 % 但 以60重 量 % 以 1 | 上 更 佳 > 90重量 % 以 上 更 佳 〇 1 本 發 明 中 含 矽 氣 % 油分之0/W/0型多重乳液， 其最佳 1 1 形 態 之 一 為 内 油 相 分 為 非 矽 氣 % 油 分 » 而 外 油 相 油 分 為 矽 1 氣 % 油 分 C 或 者 内 油 相 油 分 為 非 矽 氣 % 油 分 而 外 油 相 油 分 1 1 為 矽 氣 系 油 分 與 非 矽 氣 % 油 分 之 U 合 物 之 形 態 亦 佳 0 1 1 本 發 明 中 之 親 水 性 高 分 子 可 藉 由 增 加 水 相 之 粘 度 1 因 1 1 此 可 以 抑 制 内 相 油 之 合 一 及 向 外 相 油 之 移 動 0 在 使 用 時 > 1 I 由 於 可 促 使 水 相 之 親 水 性 高 分 子 凝 膠 化 9 因 此 内 相 油 中 溶 1 I 解 之 藥 物 可 具 有 緩 釋 性 0 具 體 —a— 之 9 由 於 緩 衝 性 取 決 於 水 1 1 1 相 之 粘 度 凝 _ 之 硬 度 » 因 此 控 制 高 分 子 之 種 類 '孤 m 度 即 1 1 16 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 385 1 4 470653 經濟部中央標準局員工消費合作杜印製 A7 B7五、發明説明Q5 ) 可自由地調整緩釋之速度。可使用之親水性高分子之例如 :褐藻酸納、鹿角菜膠、黃素樹脂、明膠、卡得蘭糖、洋 菜、葡萄糖甘露聚_、澱粉、透明質酸、角質聚葡糖、原 生藻膠、蘑菇多糖、副澱粉、癒創《萄聚_、昆布多_、 纖維素、甲基潘維素、乙基纖維素、硝化雜維素、*** 膠、聚乙烯醇、羧乙烯聚合體、羧甲基纖維素、羥乙基纖 維素、聚乙二醇、黃蕃膠、半乳聚糖、瓜拉樹膠、剌槐豆 膠、剌槐樹膠、果膠、椹桴子、藻膠、甘草根酸、葡聚醏 、聚麥芽三糖、_原、酪原白、白蛋白、羧甲基澱粉、甲 基羥丙基澱粉、甲基羥丙基纖雄素、纖維素硫酸納、羥丙 基潘維素、褐藻酸丙二醇酯、聚乙烯基甲基醚、聚乙烯吡 咯烷酮、聚環氧乙烷聚環氧丙烷共聚物、聚丙烯酸鈉、聚 丙烯酸乙酯、聚丙烯醋胺、聚乙烯亞胺等。實施本發明時 ，可選擇其中之一種或二種以上。 本發明中使用親水性界面活性劑之0/W型乳液之調製 法並無恃別限定，只要是可以得到安定之乳液的方法均可 ，調製方法可以例如於第1階段中將親水性非離子界面活 性劑添加入水溶性溶劑中，再將油相成分添加入其中製造 水溶性溶劑中油型乳液，第2階段則將水相成分添加入該 溶液中（日本待公昭5 7 - 2 9 2 1 3號等）。以此乳化法調製之 0/W型乳液，其内相油之配合撤油且安定，待別適於本發 明多重乳液之調製。 此乳化法中水溶性溶劑中溶解親水性非離子界面活性 劑，因此與其後添加之油相定向之界面效率效果良好，可 (請先閲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 ) A4規格（210X297公釐） 17 3 8 5 1 4 經濟部智慧財產局員工消費合作社印製 470653 Hfi ，本年月曰 |補充 89. 5. -4 五、發明說明（16) 自低級一元醇類、低級多元醇類、酮類、醛類、醚類、胺 類、低級脂肪酸類、其他凡親水性可溶解非離子性界面活 性劑之範圍廣泛的物質中選擇。具體之例可如日本特公昭 57-292〗3之中記載之水溶性溶劑。 親水性非離子界定活性劑K環氧乙烷及/或環氧丙烷加 成物為宜，具體之例如日本特公昭57-29213記載中所示之 親水性非離子界面活性劑。 其次再將所得之0/W型乳液在上述含有機改質粘土礦 物之外油相中一面攪拌一面混合、乳化即得目的之油包水 包油型多重乳液。在此使用之乳化機並無特別限定，但以 使用分散機（TK HOMD DISPER;特殊機械工業股份有限公 司製造）等為佳。 在此，0/W型乳液與含有機改質粘土礦物之外油相的 比例K重量比2:3至19:1為佳，1:1至4:1更佳。0/W型乳液 之混合比低於2:3時，調製之多重乳液粘度變低，長期間 後乳化安定性亦將變差。而在0/W型乳液之混合比高於 19:1時，搅拌乳化中相轉變而無法形成多重乳液。 K上形成之多重乳液，如第2圖所示，水相12與外油相 10之界面中由有機改質粘土礦物20定向，内油相14與外油 相10在構造上，物理上由有機改質粘土礦物所隔離。因此 ，其结果可有效防止内油相14與外油相10之合一，而可得 優良的乳化安定性。本發明所得之乳液内相油中配合的脂 溶性藥劑，其氧化安定性之改良效果可因此種機構在調製 時內油相中所含之脂溶性蕖劑不致移動至外油相中，因此 — — — — — — — 111 — —. . I i — — I — I^dJ— — — — — — — — — (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準（CNS)A4規格（210 X 297公釐） 1 8 (修正頁） 38 5 1 4 470653 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 ) 藥劑與外油相及外界空氣直接接觸之概率即小。製程中並 無特別需要加熱，因此調製中之熱分解極少，熱安定性差 成份之配合亦完全可能。 此外，例如内油相中以對聚矽氧条油難溶性之脂溶性 藥劑與該藥劑溶劑性高之極性油配合，而外油柑中若以矽 氣系油分配合，兩者可在同一乳液条中安定共存，因此可 防止該藥劑之結晶析出。此外，其使用感及延展性佳，亦 不粘腻，與含矽氣系油分之單純W/0型乳液相比非常良好 0 本發明中使用之脂溶性藥劑可視目的選擇，凡一般化 粧品或翳藥品中使用者均可，並無特別限定，但脂溶性維 生素或油溶性紫外線吸收劑、不飽和脂肪酸及其衍生物等 亦可以。特別在脂溶性藥劑為易於受氣化分解之易氧化性 藥劑之場合，配合在内油相中時可以有效提高其氣化安定 性。 至於脂溶性維生素，可列舉維生素A有視黃醇、3 -脱 氫視黃醇、視黃醛、3-脱氫視黃醛、視黃酸、3-脱氫視黃 酸、維生素A乙酯、維生素A十六碩烷酸酯等酯類外，而 前維生素A有：《、々-7胡籮荀素、y8-玉米黃質、海臛 烯酮等類胡蘿葡素或窠黃素等。維生素D有：維生素〇2至 等。維生素E有：α-、 /8-、 7-5-生育齡、〇t-、召- 、7-、 生育三烯酚或維生素E乙酯、菸鹸酸維生素E 等酯類。維生素{(則有：維生素K 1至K 3等。 _紫外線吸收劑之例有：2,4 -二羥二苯基酮、2,2’-二 本纸張尺度適用中國國家標準（CNS ) A4規格（210'〆297公釐） 19 38514 (請先閲讀背面之注意事項再填寫本頁) 470653 A7 B7 經濟部中央標準局員工消費合作社印製 五、 發明説明（18 ) 1 I 羥 -4 -甲氣基二苯基酮、 2 ,2 f ^ 二 羥 -4 ,4 二 甲 氣 基 二 苯 基 1 I 酮 2 , 2 ' ,4 ,4 » — 四 羥 二 苯 基 酮 Λ 2- 羥 -4 -甲 氧基二苯基酮 1 1 I S 2- 羥 -4 -甲氣基- 4 ' -甲基二苯基_等二苯基酮条紫夕 卜線 /·-\ 1 | 請 Λ. I 吸 收 劑 3 - (4 1 _ 甲 基 苯 亞 甲 基 )-d , ]- 樟 腦 、 3 - 苯 亞 甲 基 - 无 閱 1 % 1 I d , 1 - 樟 腦 4- 甲 氧 基 -4 t _ 第 三 -丁基二苯甲醯甲烷等。 η 1 之 1 不 飽 和 脂 肪 酸 之 例 有 ； 油 酸 > 亞 油 酸 S α -亞麻油酸 注 意 事 1 1 7 -亞麻油酸、 二同- 7 -亞麻油酸、 花生四烯酸、 二十 項 再 1 填 I m 五 烯 酸 > 二 十 二 m —L* 烯 酸 等 〇 其 衍 生 物 則 有 • • 甲 基 酯 、 本 頁 1 乙 基 酯 丙 基 酯 等 醇 酯 類 Λ 早 甘 油 酯 雙 甘 油 酯 、 三 甘 油 '—^ 1 I 酯 等 甘 油 酯 磷 脂 醯 膽 m 磷 脂 醯 乙 醇 胺 神 經 鞘 髓 磷 脂 1 1 I 等 脂 質 葡 萄 糖 基 神 經 醯 胺 等 糖 脂 質 Λ 神 經 m 胺 峨 ·> 1 1 訂 1 膽 固 醇 酯 等 0 本 發 明 中 此 類 不 飽 和 脂 肪 酸 即 使 其 不 飽 和 度 高 者 > 如 一 分 子 中 含 3 儲 以 上 不 飽 和 鍵 結 之 類 不 飽 和 脂 肪 丨 酸 亦 可 以 得 到 非 常 高 之 藥 劑 安 定 性 0 1 | 此 外 > 對 矽 氧 条 油 分 難 溶 性 之 脂 溶 性 藥 劑 » 可 如 刖 述 1 般 將 該 藥 劑 配 合 於 矽 氣 % 油 分 油 相 之 外 配 合 的 其 他 油 相 中 1 | » 可 以 防 止 結 晶 析 出 或 液 態 之 分 離 9 因 此 為 適 於 本 發 明 之 1 1 脂 溶 性 藥 劑 0 1 1 對 矽 氣 油 分 難 溶 性 之 脂 溶 性 藥 劑 除 刖 述 油 溶 性 紫 外 1 1 線 吸 收 劑 外 其 他 如 防 晒 劑 之 成 膜 劑 安 得 龍 (聚乙烯吡咯烷 1 1 酮 院 基 共 聚 物 )或三烯醇、 3 -辛醇、 1 -辛烯- 3- 醇 9- 癸 烯 1 I 醇 沈 香 醇 、 香 m 醇 等 » 極 性 較 高 » 對 矽 氣 % 油 互 溶 性 低 1 1 I 之 液 體 香 料 等 亦 可 0 1 1 1 本 發 明 中 之 多 重 乳 液 * 因 其 乳 化 安 定 性 或 藥 劑 安 定 性 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 20 3 8 5 1 4 470653 修正 .、本年月曰補充 89, 6, ! 4 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（19 ) 佳，可Μ期待將其應用在各種範_上，尤其是乳液、乳賫 、粉底之類化粧用品，在皮庙外用劑上更為有用。其他之 洗髮精、潤絲精等毛髮化粧用品等亦可。 此外，本發明之多重乳液中在不損及本發明功效之範 圍内可Μ配合一般在化粧用品或皮嫌外用劑中配合之成份 。其例如醇類、保濕劑、美白劑、紫外線吸收劑、防腐劑 、蝥合劑、香料、色素、顔料、染料、界面活性劑及其他 之藥劑。 [圖式之簡單說明] 第1圖為一般0/W/0型多重乳液之概念圖。 第2圖為本發明之0/W/0型多重乳液之概念圖。 [實施例] Μ下Μ具體例詳细說明本發明，但本發明並不限定於 各例。又，Μ下所示之各配合量除特別出者外均為重量％ 〇 有機改皙粘+磕物夕錮郸 首先詳细說明本發明中使用之有機改質粘土礦物之調 製法及其確認法。 讕靱例1 將45g之氯化苯甲基二甲基硬脂醢銨（約相當於1〇 On eq )及30g之P0E(6)十二醚於50t：中溶解，於500ml水溶液中 添加100s之水膨潤性粘土礦物蜂膠（Beegun)(美國 Vanderbi It公司商品名），Μ分散機充份分散混合約30分 鐘。其次取過滤器除去其中水份，再乾燥約一畫夜即得目 (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準（CNS ) A4規格（2〖0X297公釐） 2 1 (修正頁） 385 1 4 470653 修正 本年月日 捕充叫.5. -4 A7 B7 五、發明說明（2G) 的之有機改質粘土礦物。有無吸附氯化苯甲基二甲基硬脂 酿銨{略稱（A)}及P0E(6)十二醚{略稱（B)}可以KX射線繞 射及DTA-TG法測定界面活性劑之熱分解量，再與水膨潤性 粘土礦物（蜂膠）比較後判定。 结果不於表1 ° 表 1 測 定 處理前之水膨潤性 調製1之有機 巨 粘土碾物（蜂膠） 改質粘土礦物 線繞射之 1 3 . 之層間隔值 (A ) 40 . 1(A ) K DTA-TG法 測定之界面 活性劑熱分 解量s (A) (B) 1 0 1 m e q 2 9 g n I •^i n n n tt i I, · n n D n n 1 d ^ 01 I n n n n n i^i n I J (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 s表為對lOOg水膨潤性粘土礦物之量。 由表1顯示，調製例1之有機改質粘土礦物比處理前 之水膨潤性粘土碾物其層間隔明顯增大。由DTA-TG測定之 结果可知此為（A)氯化笨甲基二甲基硬脂醢銨與（B)之Ρ0Ε (6) +二醚结合之结果。 讕靱例 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 2 2 (修正頁） 3 8 5 1 4 470653n CH3… chemical formula 111 (CH2) a 0 (C2H4〇) b (C3H6〇) cR (where a is 1 ~ 5, b is 7 ~ 15, C is 0 ~ 4, BI is 2 0 ~ 1 0 〇 , η is an integer of 1 to 5, R is a hydrogen atom or a radical of 1 to 5.) In this compound, eleven glyceryl-tetrayl oleate, hexa-tetratriyl-triyl -Diisostearic acid, tetra-glyceryl-di-isostearic acid, and other triglycerol fatty acids, such as octadecenyl ethers of POE (2-12), POE (3 ~ 12) of stearic acid, POE (2 ~ 1 0), the basic paper size of the Eleventh House applies to the Chinese National Standard (CNS) A4 specification (2 丨 〇 > < 297 male thin) 12 3851 4 Economy A7 B7 printed by the Consumers' Cooperative of the Ministry of Health, Central and Central Bureau of the People's Republic of China 5. Description of the Invention (11), Nonylphenyl Ether of POE (2 ~ 10), Thieves, Pecosane of POE (6 ~ 15) 2-decyl-pentadecyl ether of p0E (5-20), 2'decyl-tetradecyl ether of POE (5-17), 2-octyl of POE (8-16) -POE addition addition type active agent such as decyl ether, and hardened ramie oil of POE (10 ~ 20), oleic acid monoester of POE (5 ~ 14), oleic acid double ester of POE (6 ~ 20) Esters, P0E (5 ~ 10) of 11 1 POE addition ester-type active agents such as sorbitan oleate, glyceryl-mono-isostearate of POE (3 ~ 15), glyceryl-tri- of POE (10 ~ 40) Cycloethane addition molding & ionic surfactant such as POE addition ether ester type active agent such as iso fatty acid, dimethyl-polysiloxane-polygas olefin copolymerized as shown in the aforementioned chemical formula II Non-ionic modified silica gas active agent is preferred. In the present invention, one or two or more of these nonionic surfactants can be arbitrarily selected. Examples of treatment methods for the organic modified ocherite minerals used in the present invention can be water-swellable ocherite minerals and a fourth-order ammonium phosphonium-type cation interface active phosphonium and non-aqueous in a low boiling point solvent such as water, acetone or a lower alcohol. The ionic interfacial active agent is dispersed and stirred, or the water-swellable clay mineral and the fourth-grade $ 塩 -type cationic interfacial agent are treated in a low boiling point solvent in advance. Surfactant treatment, and then remove the low boiling point solvent. The organic modified clay mineral prepared by the above method will be described below. The clay material, such as mentmoril Ionite, which belongs to the smecfite family and has water swelling property, is a hydrophobic organic modified Mongolia after exchanging its cation with a fourth-order saddle-type organic cation. Take off the soil. Then encapsulation with non-ionic surfactants will generate inclusion compounds (complexes), which swell in oil (please read the precautions on the back before filling this page) • The size of the paper is bound to the Chinese national standard (CNS ) A4 size (210X297 mm) 13 385 1 4 470653 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (12) A viscous oily gel is formed. Non-ionic surfactants should promote the inclusion of the polar side of the montmorillonite layer (the phosphonium silicate layer) unrelated to the cation exchange reaction, so that an oily gel is formed in the layer, which is swelled by the invasion of oil, and gelled (oil Chemistry Vol. 40, No. 6 491 ~ 496, 1991). The structure of the obtained organic modified clay mineral is formed in a state where the interlaminar interval becomes large because the water-swellable clay mineral layer is interposed by a fourth-order ammonium sulfonium type cationic surfactant and a nonionic surfactant. Therefore, it is possible to confirm the presence or absence of adsorption of a fourth-order ammonium phosphonium-type cation surfactant and a non-ionic surfactant by measuring the long-surface interval by X-ray diffraction. In addition, the obtained organic modified clay minerals can be washed out of the interlayer physical adsorption surfactant when they are extracted with a Soxhlet extractor using aerosol, ether, etc., so the extract is analyzed by gas chromatography and measured. Thermal decomposition temperature or thermal decomposition amount (DTA-TG measurement) can determine the amount of physically adsorbed surfactant. The content of the fourth-order ammonium sulfonium type cationic surfactant in the organic modified clay mineral used in the present invention is not subject to any other restrictions, but it is 60 to 140 milliequivalents (hereinafter abbreviated as "100%") relative to 100s of water-swellable clay mineral. meq) is better. The content of the non-ionic surfactant in the organic modified clay mineral is preferably 5 to 100 g, more preferably 15 to 50 g, relative to 100 g of the water-swellable clay mineral. It is known that this organically modified clay mineral can effectively prepare a stable W / 0 type emulsion by a method shown in, for example, Japanese Patent Publication No. 2-32015. However, the stabilization of multiple emulsions is not fully understood until the point of effectively preventing the internal oil phase from integrating with the external oil phase. In C · 0 / W / 0 multiple emulsions, the external oil phase contains such organic modified viscosity This paper size applies to China National Standard (CNS) A4 specification (210X297 mm), "0 c, 14 38514 (Please read the precautions on the back before filling out this page) 470653 A7 B7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Explanation of the invention (] 3) 1 | Soil mineral can inhibit the integration of the internal oil phase and the external oil phase »to obtain long-term stability 1 I 0 / W / 0 type multiple emulsion. Now, when this kind of oil is used in the internal oil phase, 1 1 | Fat-soluble agent 9 can prevent the gasification of the fat-soluble agent »Therefore medicine / -— \ Please 1 1 1 agent with good stability C Read it first 1 1 I The amount of organic modified clay minerals used is 9 to 0.1 to 5 by weight relative to the composition of the multiple emulsion. · Is better, 0.5 3% by weight is better 0 is less than 0.1 1 '/ Wang Yishi 1 1% by weight I I can not get the effect that the organic modified clay minerals should have, then fill 1! Ά I Fruit 1 No stable multi-emulsion 0. Specifically »After a long period of time, the internal oil phase will disappear and the multiple-emulsion will not be maintained. When t exceeds 5% by weight, the viscosity of the emulsion will become higher. Poor ductility degradation No 1 1 I Luster, opacity, etc. 0 1 1 Order 1 In the present invention, the organically modified clays obtained in combination with the aforementioned in the external oil phase »Oil phase can be used in a wide range t white polar oil Up to non-polar oils 1 1 Available 0 Oils that can be used, such as liquid stone ash, thirty-thousand gardens Λ different garden hydrocarbon branches 1 | lower paraffin, etc. m fey m compound oils * isopropyltetrasodium decanoate tenyl 1 isooctanoate Cool oils such as acid m »Silicone gas% Oil content 0 Γ I Where silicon gas% Oil content is used > Emulsion can have good oil resistance Λ Resistant to 1 1 Water and feel 0 Silicone gas oil used in the present invention can Application range 1 1 Wide range of silicon gas oil> From the point of view of use and formulation, it is better to recognize 1 1 at normal pressure, boiling point 2 0 0 and 1. Specifically, for example, dimethyl polysilazane, methyl 1 I phenyl polysilazane Λ methylhydroene polysiloxane, etc. chain polysilicon gas VIII 1 I methyl monosilicon gas Λ 10 Methylphosphonium pentasilane dodecyl methyl ring *-Silicon 1 1 I Oxane, tetramethyl-tetrahydrodiene cyclotetrasilane, etc. Cyclosilane etc. 0 1 1 Where a low degree of polymerization is used Volatilization of dimethyl polysilane (degree of polymerization 2 7), etc. 1 1 15 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 38 5 1 4 470653 A7 B7 Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printed 5. Description of the invention (14) 1 I Volatile silicones such as decyl-type polysiloxanes and decamethylcyclopentasilyl octamethylcyclotetrasilane 1 I Occasion of oxygen oil 9 When the skin is applied, 1 1 I has less residual oil tb when compared to-Silicone oil in general »It is especially suitable for applications where 1 I is required for refreshing use Should be 0 read first 1 I The silicon gas% oil content in the multiple emulsion of the present invention can be appropriately 1 1 Choose i but it is preferably 5 ^ -60% by weight relative to the total amount of the multiple emulsion. Note 1 1 It is more preferably 5 to 40% by weight, and even more preferably 15 to 40% by weight. Fill silicone item 1 again! 1 When the amount of oil content is small $ Ca n’t get sufficient water resistance and oil resistance. Ubiquitous %% Feeling of use, etc. 0 Silicon gas% When oil content is large »m It is difficult to stabilize with emulsion 1 1 Case 1 C 1 1 I In the present invention, the silicon oxygen% oil content can also be blended in the internal oil phase, but it is better to order 1 1 to blend in the external oil phase. 0 Silicon gas% oil distribution in the external oil phase Occasion 1 The amount of silicon gas% oil content relative to the outer tangerine can be selected from 8 to 100% by weight based on the ratio of the external oil phase in the multiple emulsion 1 1 liquid, but 60% by weight and 1 | better are better 90% by weight or more is better. 01 In the present invention, the silicon / gas /% / oil type multiple emulsion of 0 / W / 0 type is one of the best 1 1 forms in which the internal oil phase is divided into non-silicon gas% oil and the external oil. Phase oil is divided into silicon 1 gas% oil content C or internal oil phase oil is divided into non-silicon gas% oil content The oil phase oil component 1 1 is a form of the U-composition of silicon oil and non-silicon gas% oil. 0 1 1 The hydrophilic polymer in the present invention can be increased by increasing the viscosity of the water phase 1 because 1 1 Integration of internal phase oil and migration of external phase oil 0 When in use> 1 I Promote gelation of hydrophilic polymer in aqueous phase 9 Soluble in internal phase oil 1 I Drugs with slow release properties 0 Specific —a— of 9 Because the buffering depends on the water 1 1 1 phase viscosity _ hardness »Therefore, the type of polymer 'solitary m degree is 1 1 16 This paper size applies Chinese National Standard (CNS) A4 specifications (210X297mm) 385 1 4 470653 Consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs, printed by A7 B7 5. Invention Description Q5) The speed of slow release can be adjusted freely. Examples of the hydrophilic polymers that can be used are: sodium alginate, carrageenan, xanthophyll resin, gelatin, cardanol, amaranth, glucomannan, starch, hyaluronic acid, keratin polyglucose, protozoa Gum, mushroom polysaccharides, para starch, guaiac, grapes, kumbutol, cellulose, methyl pavidin, ethylcellulose, nitroazuridine, gum arabic, polyvinyl alcohol, carboxyvinyl polymer, carboxymethyl Cellulose, hydroxyethyl cellulose, polyethylene glycol, xanthan gum, galactan, guar gum, locust bean gum, locust gum, pectin, gardenia, algin, glycyrrhizic acid , Glucosinolate, polymaltotriose, _pro, casein white, albumin, carboxymethyl starch, methyl hydroxypropyl starch, methyl hydroxypropyl cellulose, sodium cellulose sulfate, hydroxypropyl Paclitaxel, propylene glycol alginate, polyvinyl methyl ether, polyvinyl pyrrolidone, polyethylene oxide polypropylene oxide copolymer, sodium polyacrylate, polyethylene acrylate, polypropylene acetate, polyethyleneimine, and the like. In carrying out the present invention, one kind or two or more kinds can be selected. The method for preparing a 0 / W type emulsion using a hydrophilic surfactant in the present invention is not particularly limited, as long as it is a method capable of obtaining a stable emulsion, the preparation method may be, for example, in a first stage, a hydrophilic nonionic The surfactant is added to the water-soluble solvent, and then the oil phase component is added to make the oil-based emulsion in the water-soluble solvent. In the second stage, the water phase component is added to the solution (Japanese to be published 5 7-2 9 2 1 3 Number, etc.). The 0 / W type emulsion prepared by this emulsification method has a combination of internal phase oil withdrawing oil and is stable, which is suitable for the preparation of multiple emulsions of the present invention. This emulsification method dissolves the hydrophilic nonionic surfactant in the water-soluble solvent, so the interface efficiency with the oil phase added after it is good. (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 Specification (210X297 mm) 17 3 8 5 1 4 Printed 470653 Hfi by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, said this month | Supplement 89. 5. -4 V. Description of Invention (16) Choose from a wide range of lower monohydric alcohols, lower polyalcohols, ketones, aldehydes, ethers, amines, lower fatty acids, and other hydrophilic soluble nonionic surfactants. A specific example is the water-soluble solvent described in Japanese Patent Publication No. 57-292〗 3. The hydrophilic nonionic defined active agent K ethylene oxide and / or propylene oxide adduct is suitable, and specific examples thereof include the hydrophilic nonionic surfactant shown in Japanese Patent Publication No. 57-29213. Next, the obtained 0 / W type emulsion is mixed in the oil phase other than the organic modified clay mineral while stirring and emulsified to obtain the desired oil-in-water multiple emulsion. The emulsifier used here is not particularly limited, but a disperser (TK HOMD DISPER; manufactured by Special Machinery Industry Co., Ltd.) is preferred. Here, the ratio K by weight of the 0 / W emulsion to the oil phase other than the organic modified clay mineral is preferably 2: 3 to 19: 1, and more preferably 1: 1 to 4: 1. When the mixing ratio of the 0 / W type emulsion is less than 2: 3, the viscosity of the prepared multiple emulsions becomes low, and the emulsification stability after a long period of time will also deteriorate. When the mixing ratio of the 0 / W type emulsion is higher than 19: 1, the phase transition cannot be formed during stirring and emulsification. In the multiple emulsion formed on K, as shown in FIG. 2, the interface between the water phase 12 and the outer oil phase 10 is oriented by the organic modified clay mineral 20, and the inner oil phase 14 and the outer oil phase 10 are structurally and physically Organic modified clay minerals isolated. Therefore, as a result, the unity of the inner oil phase 14 and the outer oil phase 10 can be effectively prevented, and excellent emulsification stability can be obtained. The effect of improving the oxidation stability of the fat-soluble agent formulated in the emulsion internal phase oil obtained by the present invention can prevent the fat-soluble tincture contained in the internal oil phase from moving to the external oil phase during the preparation of such a mechanism, therefore— — — — — — — 111 — —.. I i — — I — I ^ dJ — — — — — — — — — (Please read the notes on the back before filling out this page) This paper size applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) 1 8 (revised page) 38 5 1 4 470653 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (〖7) Pharmaceutical and external oil phase and external air The probability of direct contact is small. No special heating is required in the manufacturing process, so there is very little thermal decomposition during the preparation, and the combination of components with poor thermal stability is also completely possible. In addition, for example, in the internal oil phase, a fat-soluble agent that is poorly soluble in polysiloxane oil is mixed with a polar oil with high solvent property of the agent, and if the outer tangerine is partitioned and combined with a silicone gas oil, the two can be in the same emulsion. The stability and coexistence of the bar can prevent the crystallization of the drug. In addition, it has a good feeling of use and ductility, and it is not sticky. Compared with a simple W / 0 emulsion containing a silicon-based oil, the fat-soluble agent used in the present invention can be selected according to the purpose. The medicine can be used by any user, and is not particularly limited, but fat-soluble vitamins or oil-soluble ultraviolet absorbers, unsaturated fatty acids, and derivatives thereof may also be used. Particularly in the case where the fat-soluble agent is an easily oxidizable agent which is susceptible to gasification and decomposition, it can effectively improve the gasification stability when it is mixed with the internal oil phase. As for fat-soluble vitamins, vitamin A includes retinol, 3-dehydroretinol, retinal, 3-dehydroretinaldehyde, retinoic acid, 3-dehydroretinoic acid, and vitamin A ethyl ester. In addition to esters such as vitamin A, hexadecanoate, and pre-vitamin A, there are: carotenoids or lutein like carotenoids, lutein-7, eugenin, y8-zeaxanthin, norenone, etc. Wait. Vitamin D is: Vitamins 02 to etc. Vitamin E includes: α-, / 8-, 7-5-bearing age, 0t-, zhao-, 7-, tocotrienol or tocopherol ethyl ester, nicotinic acid tocopherol and other esters. Vitamin {(There are: Vitamins K 1 to K 3, etc. _ Examples of UV absorbers are: 2,4-dihydroxydiphenyl ketone, 2,2'-two paper standards applicable to Chinese National Standards (CNS) A4 specification (210'〆297 mm) 19 38514 (Please read the notes on the back before filling out this page) 470653 A7 B7 Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (18) 1 I Hydroxy-4 -Methylamino diphenyl ketone, 2,2 f ^ dihydroxy-4,4 dimethylamino diphenyl 1 I ketone 2, 2 ', 4, 4 »-tetrahydroxydiphenyl ketone Λ 2-hydroxy -4 -Methoxydiphenyl ketone 1 1 IS 2-Hydroxy-4 -methylamino-4'-methyldiphenyl_isodiphenyl ketone purple silk line / ·-\ 1 | Please Λ I Absorbent 3-(4 1 _methylbenzylidene) -d,]-camphor, 3-phenylmethylene-none 1% 1 I d, 1-camphor 4-methoxy-4 t _ Tertiary-butyldibenzomethane, etc. Examples of η 1 to 1 unsaturated fatty acids are: oleic acid > linoleic acid S α-Linolenic acid Note 1 1 7-Linolenic acid, Diiso-7-linolenic acid, arachidonic acid, Twenty-one term again 1 Fill in I m Pentaenoic acid > Twenty-two m —L * ene Acids and other derivatives include: • Alcohol esters such as methyl esters and ethyl propyl esters on this page Λ early glycerides diglycerides, triglycerides'-^ 1 I esters, etc. Phospholipids, ethanolamines, sphingomyelin, 1 and other lipids, glycosyl lipids, such as glucosylceramide, and nerve lipids, amines, and amines. ≫ 1 1 Order 1 cholesterol esters, etc. 0 Such unsaturated fatty acids in the present invention are highly unsaturated Or > if one molecule contains 3 or more unsaturated bonds such as unsaturated bonds, acid can also get very high pharmaceutical stability 0 1 | In addition > fat-soluble drugs that are insoluble in silicone oil » Introduction 1 It can be used in other oil phases other than the silicon gas% oil phase and oil phase 1 | »It can prevent crystal precipitation or liquid separation 9 Therefore, it is suitable for the present invention 1 1 Fat-soluble agent 0 1 1 Insoluble lipid for silicon gas oil Soluble agents In addition to the oil-soluble UV 1 1 rays absorbers described, other film-forming agents such as sunscreens, anderone (polyvinylpyrrolidine 1 1 ketone-based copolymer) or trienol, 3-octanol, 1- Octene- 3-ol 9-decene 1 I Alcohol, mellow alcohol, etc. »High polarity» To silicon gas% Oil miscibility 1 1 I Liquid perfume, etc. 0 1 1 1 Multi-emulsion * Because of its emulsification stability or pharmaceutical stability 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 20 3 8 5 1 4 470653 Amendment. 4 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (19) To be used in a variety _ range, especially an emulsion, milk Ji, cosmetic foundation or the like, more useful in the skin with the agent outside the temple. Other hair cosmetics such as shampoo and conditioner are also available. In addition, the multiple emulsions of the present invention can be formulated with ingredients generally used in cosmetics or external skin preparations within a range that does not impair the efficacy of the present invention. They include, for example, alcohols, humectants, whitening agents, ultraviolet absorbers, preservatives, couplers, perfumes, pigments, pigments, dyes, surfactants, and other agents. [Brief description of the diagram] Figure 1 is a conceptual diagram of a general 0 / W / 0 multiple emulsion. Figure 2 is a conceptual diagram of the 0 / W / 0 multiple emulsion of the present invention. [Examples] Specific examples of M and M will explain the present invention in detail, but the present invention is not limited to the examples. In addition, each of the blending amounts shown below is a weight% except for those that are specifically mentioned. 〇Organic modification + sticky substance 锢 锢 锢 First, the preparation method and confirmation of the organic modified clay mineral used in the present invention will be described in detail. law. Example 1 45 g of benzyl dimethyl stearyl ammonium chloride (approximately 10 On eq) and 30 g of POE (6) dodecyl ether were dissolved in 50 t: and added to 500 ml of aqueous solution for 100 s. The water-swellable clay mineral propolis (Beegun) (trade name of Vanderbi It Company, USA) was fully dispersed and mixed for about 30 minutes. Then take the filter to remove the water, and then dry it for about one painting night (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (2 〖0X297mm） 2 1 (Amendment page) 385 1 4 470653 Amendments to the current month, day, and month. 5. -4 A7 B7 V. Organic modified clay minerals of the invention description (2G). With or without adsorption of benzyl dimethyl stearyl ammonium chloride {abbreviated (A)} and POE (6) dodecyl ether {abbreviated (B)} can be determined by KX-ray diffraction and DTA-TG method The amount of thermal decomposition is determined by comparing with the water-swellable clay mineral (propolis). The results are not in Table 1 ° Table 1 Determination of the water swelling properties before the treatment of the organic giant clay mill 1 (propolis) Modified clay mineral line diffraction 1 3. Interlayer value (A) 40.1 (A) K DTA-TG method for thermal decomposition of surfactant s (A) (B) 1 0 1 meq 2 9 gn I • ^ innn tt i I, · nn D nn 1 d ^ 01 I nnnnni ^ in IJ (Please (Please read the notes on the back before filling out this page) The s sheet printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is the amount of 100g of water-swellable clay minerals. As shown in Table 1, the organic modified clay mineral of Preparation Example 1 has a significantly larger interlayer interval than the water-swellable clay mill before the treatment. From the results of DTA-TG measurement, it is known that this is the result of the combination of (A) benzyldimethyldimethylstearate and (B) POE (6) + diether. Example This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 2 2 (corrected page) 3 8 5 1 4 470653

A7 B7 1 五、發明説明（2 將100s之陽離子改質粘土礦物膨潤土（Bent〇ne)-38加 入溶解有20gP0E(15)2-辛基癸基醚（略稱（C)}之50ml乙醇 中，Μ均質機充份分散混合。膨潤土 -38為M lOOmeq氯化 二硬脂醯二甲基銨（Μ下略稱（D))處理100g之水膨潤性粘 土礦物之陽離子改質粘土礦物，為美國National Red公司 製造之商品名。 其次K蒸發器去除乙醇後，於50t：下乾燥一晝夜即得 目的之有機改粘土礦物。與調製例1同樣地，改質之有無 可MX射線繞射及由氯仿Μ索司勒萃取液中之界面活性劑 量（K DTA-TG法測定）評估。 結果不於表2。 表 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 測 定 B e n t ο n e -38 調製2 之有機 項 改質粘 土礦物 X 線 繞 射 之 26.8 36 . 8 層 間 隔 值 (A ) (A ) DTA- TG 測 定 (D) (C) (D) (c) 之 界 面 活 性 1 2 m e q 0 1 2 m e q 20g 熱 分 解 量 *同表1。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） 23 (修正頁） 385 1 4 470653 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（ 22 ) 1 1 由 表 2 可 知 (D )之層間隔即使使用預先从 1第四级銨 1 | 型 陽 離 子 界 面 活 性 劑 處 理 之 陽 離 子 改 質 粘 土 礦 物 (Ben tone 1 I -3 8 )亦 tb 由 非 離 子 性 界 面 活 性 劑 處 理 之 (C)更大。 推測此 請 1 1 與 調 製 例 1 同 樣 偽 由 於 非 離 子 性 界 面 活 性 劑 之 結 合所 致。 先 閱 讀 1 1 以 索 司 勒 萃 取 液 萃 取 之 第 四 級 銨 塩 型 陽 離 子 界 面 活性 劑之 背 面 之 注 意 事 項 再 填 1 1 量 為 由 陽 離 子 交 換 反 應 物 理 性 地 吸 附 於 陽 離 子 界 面活 性劑 1 I 的 量 (化學性吸附者無法萃取） 0 如 調 製 例 1 所 示 DTA- TG法 1 1 可 以 定 量 所 有 物 理 性 及 化 學 性 吸 附 之 第 四 级 銨 塩 型陽 離子 寫 本 頁 装 1 界 面 活 性 劑 之 量 0 1 I 軍 乳 液 乳 化 定 件 評 估 方 法 1 1 以 下 之 實 施 例 中 使 用 之 多 重 乳 液 9 其 乳 化 安 定性 的評 1 1 估 方 法 如 下 ： 訂 1 ① 形 態 觀 察 1 1 調 製 之 乳 液 於 常 溫 (RT)下保存6 櫥 月 » 或在50 t之 1 1 恒 溫 槽 内 保 存 1 値 月 後 以 光 學 顯 檝 鏡 及 肉 眼 進 行形 態觀 1 察 〇 全 無 異 常 之 場 合 (乳化狀態及粒子均勻）為 良好 (0 ) 1 I » 以 顯 微 鏡 觀 察 時 粒 子 略 有 不 均 勻 * 但 肉 眼 判 定無 異常 1 1 I 之 場 合 為 (0 ), 有 異 常 之 場 合 (水或油分離， 粒子變粗 1 1 大 之 場 合 等 )為不良&lt; X )C 1 1 ② 内 油 相 殘 餘 率 1 1 以 試 驗 為 顯 示 内 油 相 不 為 外 油 相 所 吸 收 之 點。 1 1 (1) 定 性 試 驗 ： 調製0/W/0型多重乳液後在顯徹鏡下觀察 1 I 長 時 期 之 形 態 變 化 〇 安 定 性 不 良 之 % &gt; 長 期 間後 内油 1 I 相 消 失 $ 終 變 成 単 純 之 W/0型乳液c 欲加速試驗可 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 24 3 8 5 1 4 470653 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（ 23 ) 1 1 於5〇υ 之 高 溫 下 進 行 〇 1 I ⑵ 定 量 試 驗 ： 於 内 油 相 中 溶 解 油 溶 性 標 識 物質 (苯二甲 1 | 酸 二 酯 )， 調製0/W/0型 多 重 乳 液 〇 其 次 將乳 液 離 心 分 /-—V 請 1 1 離 i 強 制 分 離 外 油 相 油 分 0 定 量 外 油 相 中所 含 標 識 物 先 閱 讀 1 1 之 濃 度 I 再 由 全 體 之 濃 度 中 扣 除 後 即 可 計算 出 内 油 相 背 面 % 事 項 -S- 填 1 1 中 標 識 物 之 濃 度 〇 長 期 間 操 作 則 可 觀 察 移動 至 外 油 相 1 | 中 之 狀 態 » 並 計 算 出 内 油 相 中 之 殘 餘 率 〇 1 1 藥.劑安定性之評估方法 寫 本 頁 裝 1 ①笔 劑 殘 餘 率 1 I 將 樣 品於5 0 t 之 恒 溫 箱 内 保 存 1 個 月 後， 以HPLC法 1 1 I 定 量 各 樣 品 中 之 藥 劑 濃 度 i 再 對 照 各 藥 劑 之加 入 量 計 算 1 1 殘 餘 率 0 依 據 殘 餘 率 如 下 表 示 藥 劑 之 安 定 性。 訂 1 ◎ … 對 加 入 量 藥 劑 殘 餘 率 在90 % 以 上 者 1 1 〇 … 對 加 入 量 藥劑殘餘率在8 0 % 以 上 不滿90 % 者 1 1 Δ … 對 加 入 量 藥劑殘餘率在60 % 以 上 不 滿 80 * 者 1 X … 對 加 入 量 藥劑殘餘率不滿60 % 者 1 I ②結 晶 析 出 1 1 | 樣 品於5 0 ΐ： 之 恒 溫 箱 内 保 存 1 値 月 後 ,以 光 學 顯 徹 1 1 鏡 觀 察 有 無 藥 劑 析 出 〇 1 1 0 … 無 結 晶 析 出 者 (無) 1 1 △ … 有 少 許 結 晶 析 出 者 (徹） 1 1 X … 有 明 顯 之 結 晶 析 出 者 (有） 1 | 俥用 感 評 估 方 法 1 由 10名 專 門 品 評 員 以 調 製 之 樣 品 實 際 塗 抹皮 虜 進 行 官 1 1 本紙張尺度適用中國國家標準（叫Μ規格⑺οχ 297_ 3 8 5 1 4 470653 A7 B7 五、發明説明（24 ) 能試驗。品評之結果如下表示。 Θ: 10名中有8名以上回答無粘腻感者 0: 10名中有6〜7名回答無粘腻感者 △ : 10名中有4〜5名回答無粘腻感者 X 10名中有3名以下回答無粘腻感者 奮旃例1 本發明者等先取各種界面活性劑依表3〜5之配方以各 種常法調製0/W型乳液、W/0型乳液、油包水包油型乳液後 評估其乳化安定性。 表 3 : 0/W型乳液 經濟部中央標準局員工消費合作社印製 組 成成分 實施例 1-1 (a)界面活性劑 1，3-丁二醇 21 純 水 2 Ρ0Ε (60)硬化篦麻油 2 (b)油相 液體石蠟 33 (c)水相 純水 42 乳化安定性（形態觀察） 室溫 0 50 1C 〇 ^ϋ. -- m. —i 1^1 .....-- —I n HI ----- - - -i ml ------ ! -: -&quot;TeJ (請先閱讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 26 3 8 5 1 4 470653 A7 B7 五、發明説明（25 ) 表4: W/0型乳液 組成成分 1-2 1-3 實 1-4 施例 1-5 1-6 1-7 (a)界面活性劑 P0E(3)十八醚 1 - - - - - P0E(2)十八醚 - 5 - - - - 山梨糖醇單硬脂酸酯 - - 1 - - - 山梨糖醇單硬脂酸酯 - - - 5 - - P0E(10)硬化蓖麻油 - - - - 10 - P0E(10)硬化蓖麻油 - - - - - 5 (b)油相 液體石蠟 39 35 39 35 30 35 (C)水相 離子交換水 60 60 60 60 60 60 乳化安定性（形態觀察） 室溫 〇 〇 0 〇 〇 〇 50它 〇 0 0 〇 〇 〇 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 〈調製方法〉 將表3中記載之（a)成分溶解混合均勻，與（b)成分一 面攪拌一面混合、乳化後，將（c)成分加入混合即得0/W型 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 27 3 8 5 1 4 470653 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（26 ) 乳液。 〈調製方法〉 將上述U)成分與（b)成分混合。再與（C)成分一面攪 拌一面混合乳化，卽得目的之W/0型乳液。 表5:油包水包油型乳液 ----------------訂 (請先閱讀背面之注意事項再填寫本頁) 實 施例 組成成分 1-8 1-9 1-10 1-11 1-12 1-13 u)om 目 實施例1-1之0/VI型乳液 70 70 70 70 70 70 (b)外油相 液體石蟠 29 25 29 25 20 25 (C)親油性界面活性劑 P0E(3)十八醚 1 - - - - - P0E(2)十八醚 - 5 - - - - 山梨糖醇單硬脂酸酯 - - 1 师 - - 山梨糖醇單硬脂酸酯 - - - 5 - - P0E(10)硬化蓖麻油 - - - - 10 - P0E(10)硬化Μ麻油 - - - - - 5 乳化安定性 形態觀察（室溫） X X X X X X (50。。） X X X X X X 内油相殘餘率（50t8週後） &lt;5 &lt;5 &lt;5 &lt;5 &lt;5 &lt;5 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 2 8 38 5 1 4 470653A7 B7 1 V. Description of the invention (2 100s of cationic modified clay mineral bentonite (Bentone) -38 is added to 50 ml of ethanol in which 20 g of POE (15) 2-octyldecyl ether (abbreviated as (C)) is dissolved) The homogenizer is fully dispersed and mixed. Bentonite-38 is a 100 cationic modified clay mineral treated with 100 g of water-swellable clay mineral treated by M 100meq distearyl dimethyl ammonium chloride (hereinafter abbreviated as (D)). Trade name manufactured by National Red, USA. Secondly, the K evaporator removes ethanol and then dry it at 50t for one day and night to obtain the target organic modified clay mineral. As in Modification Example 1, whether the modification has MX diffraction and It was evaluated by the interfacial active dose (determined by the K DTA-TG method) in the chloroform M Sossler extract. The results are not in Table 2. Table (Please read the precautions on the back before filling this page) Employees ’Intellectual Property Bureau of the Ministry of Economy Consumption Co-operative printed measurement of Bent ent ne-38 Modulation 2 of organic modified clay mineral X-ray diffraction 26.8 36.8 Interlayer value (A) (A) DTA-TG measurement (D) (C) (D) (c) interfacial activity 1 2 meq 0 1 2 meq 20g heat Decomposition amount * Same as table 1. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 23 (revised page) 385 1 4 470653 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Explanation (22) 1 1 According to Table 2, we can see that the interval of (D) is tb even if the cationic modified clay mineral (Ben tone 1 I -3 8) treated with 1 ~ 4th ammonium 1 | type cationic surfactant is treated in advance. (C) is larger when treated with nonionic surfactants. It is speculated that this is due to the combination of nonionic surfactants as in Preparation Example 1. Read 1 1 Note on the back of the fourth-grade ammonium phosphonium-type cationic surfactant 1 1 The amount is the amount of 1 I physically adsorbed on the cationic surfactant by the cation exchange reaction (the chemical adsorber cannot extract it) 0 Such as the preparation example The DTA-TG method shown in 1 1 1 can quantify all physical properties and Chemically-adsorbed fourth-order ammonium sulfonium-type cations written on this page 1 Amount of surfactant 0 1 I Evaluation method of military emulsion emulsified parts 1 1 Multiple emulsions used in the following examples 9 Evaluation of emulsification stability 1 1 The estimation method is as follows: Order 1 ① Morphological observation 1 1 The prepared emulsion is stored at room temperature (RT) for 6 months »or stored in a 50 t 1 1 thermostat for 1 month. The appearance is performed with an optical microscope and the naked eye. Observation 1 Observation 〇 All abnormal conditions (emulsified state and uniform particles) are good (0) 1 I »Particles are slightly non-uniform when observed under a microscope *, but visually judged that there is no abnormality 1 1 I is (0), yes Abnormal occasions (water or oil separation, coarse particles 1 1 large, etc.) are bad &lt; X) C 1 1 ② Internal oil phase residual ratio 1 1 The test shows that the internal oil phase is not the external oil phase The points absorbed. 1 1 (1) Qualitative test: Observe 1 I long-term morphological changes after preparing a 0 / W / 0 multiple emulsion under a clear microscope.% Of poor stability &gt; Phase I of internal oil 1 disappears after a long period. It becomes a pure W / 0 emulsion c. For accelerated testing, 1 1 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 24 3 8 5 1 4 470653 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation 5. Description of the invention (23) 1 1 Perform 〇1 I 〇 Quantitative test at a high temperature of 5〇υ: Dissolve an oil-soluble labeling substance (xylylene-1 | acid diester) in the internal oil phase, and adjust 0 / W / 0 multiple emulsion 〇Second centrifugation of the emulsion / -V Please 1 1 to force separation of the external oil phase oil fraction 0 Quantify the markers contained in the external oil phase First read the concentration of 1 1 and then subtract it from the overall concentration After that, the back% of the internal oil phase can be calculated. Matter-S- Fill the concentration of the marker in 1 1 〇 Long-term operation You can observe the state of moving to the outer oil phase 1 | and calculate the residual rate in the inner oil phase. 〇1 1 The method for evaluating the stability of the drug. Dose is written on this page 1 ① Residual rate of pen 1 I Put the sample in 5 After being stored in a 0 t incubator for 1 month, the HPLC method 1 1 I was used to quantify the concentration of the drug in each sample i and then calculated based on the amount of each drug added. 1 1 Residual rate 0 According to the residual rate, the stability of the drug is shown below. Order 1 ◎… for the dosage of the residual drug rate of 90% or more 1 1 〇… for the dosage of the drug residual rate of 80% or more and less than 90% 1 1 Δ… for the dosage of drug residual rate of 60% or more and less than 80 * For 1 X… the remaining ratio of the dosage is less than 60%. For 1 I ② Crystal precipitation 1 1 | The sample is stored in a 50 ° C incubator for 1 month, then it is optically cleared 1 1 to observe the presence or absence of pharmaceutical precipitation 〇1 1 0… without crystal precipitation (none) 1 1 △… with slight crystal precipitation (complete) 1 1 X… with obvious crystal precipitation (yes) 1 | evaluation of usability 1 by 10 experts The actual application of the prepared sample to the skin was performed by the officer. 1 This paper size is in accordance with the Chinese national standard (called M specifications ⑺οχ 297_ 3 8 5 1 4 470653 A7 B7. 5. Description of the invention (24)) The test can be performed as shown below. Θ: 10 people 8 or more people answered non-sticky 0: 6 to 7 of them answered non-sticky △: 4 to 5 of 10 answered non-sticky X 3 or less of 10 Answers to those who do not feel sticky Example 1 The inventors first took various surfactants according to the formulas in Tables 3 to 5 to prepare 0 / W type emulsions, W / 0 type emulsions, and oil-in-water-type emulsions by various conventional methods. The emulsification stability was evaluated afterwards. Table 3: Composition of components printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of 0 / W emulsion Example 1-1 (a) Surfactant 1,3-butanediol 21 Pure water 2 POE (60) Hardened ramie oil 2 (b) Oil phase liquid paraffin 33 (c) Water phase pure water 42 Emulsion stability (morphological observation) Room temperature 0 50 1C 〇 ^.-M. —I 1 ^ 1 .. ...-- --I n HI --------i ml ------!-:-&Quot; TeJ (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) A4 specification (210X297 mm) 26 3 8 5 1 4 470653 A7 B7 V. Description of the invention (25) Table 4: W / 0 emulsion composition 1-2 1-3 Examples 1-4 Example 1-5 1-6 1-7 (a) Surfactant POE (3) stearyl ether 1-----P0E (2) Octadecyl ether-5----Sorbitol monostearate--1---Sorbitol monostearate---5--P0E (10 ) Hardened castor oil----10-P0E (10) Hardened castor oil-----5 (b) Oil phase liquid paraffin 39 35 39 35 30 35 (C) Water phase ion exchanged water 60 60 60 60 60 60 Emulsification stability (morphological observation) Room temperature 0 0 0 0 0 0 0 5 0 0 0 0 0 0 0 0 It is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) <Modulation method> The components (a) described in Table 3 are dissolved and mixed uniformly, and the components (b) are mixed while being emulsified, and then the component (c) is added to the mixture to obtain a 0 / W type. This paper size is applicable to Chinese National Standards (CNS) A4 specification (210X297 mm) 27 3 8 5 1 4 470653 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (26) Emulsion. <Preparation method> The said U) component and (b) component are mixed. It is then mixed with component (C) and emulsified while mixing to obtain the desired W / 0 type emulsion. Table 5: Oil-in-water-oil-in-water emulsion --- Order (please read the precautions on the back before filling this page) Example composition 1-8 1-9 1-10 1-11 1-12 1-13 u) om Emulsion 0 / VI of Example 1-1 70 70 70 70 70 70 (b) External oil phase liquid ballast 29 25 29 25 20 25 (C ) Lipophilic surfactant P0E (3) octadecyl ether 1-----P0E (2) octadecyl ether-5----sorbitol monostearate--1 division--sorbitol mono Stearate---5--P0E (10) hardened castor oil----10-P0E (10) hardened sesame oil-----5 Emulsification stability observation (room temperature) XXXXXX (50 ... ) XXXXXX Residual oil phase (after 50t8 weeks) &lt; 5 &lt; 5 &lt; 5 &lt; 5 &lt; 5 &lt; 5 5 1 4 470653

A7 B7 五、發明説明（27 ) 〈調製方法〉 將（b)成分與（c)成分混合，再將實施例1-1中之0/W型 乳液（a) —面攪拌一面與（b) + (c)成分混合、乳化，即得目 的之0/W/0型多重乳液。 參考前述表3及表4選擇各0/W型乳液及W/0型乳液之適 當界面活性劑，即可得到相當高之安定性。另一方面，亦 可知將如表5中安定之O/tf型乳液分散於油相或0/W/0油型 乳液之場合，乳化安定性將大為降低，特別是内油相會渗 出於外相油中。 因此，本發明之發明者等如下檢討有機改質粘土礦物 對多重乳液之安定化，特別是防止内油相與外油相合一之 效果。 表6:油包水包油型乳液 ----------产—— (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 組成成分 1-14 1-15 實施 1-16 例 1-17 1-18 (a)0/W相 實施例1-1之0/W型乳液 70 70 70 70 70 (b)外油相 液體石蠘 28 28 28 28 28 (C)外油相中之界面活性劑 有機改質粘土礦物（調製例1) 2 - - 一 - 未改質粘土礦物（蜂膠） - 2 - - - 氯化苯甲基二甲基十八醯銨 - - 2 - P0E(6)十八醚 - - - 2 - 氛化苯甲基二甲基十八醯銨 + P0E(6)十八醚 - - - - 2 乳化安定性 形態觀察（室溫） 〇 X X X X (50它） 〇 X X X X 内油相殘餘率（經50108週後） 98 &lt;5 &lt;5 &lt;5 &lt;5 本紙張尺度適用中國國家標準（CNS ) Α4規格（21 ΟΧ297公釐） 29 (修正頁）38514A7 B7 V. Description of the invention (27) <Preparation method> The components (b) and (c) are mixed, and then the 0 / W type emulsion (a) in Example 1-1 (a) is stirred and (b) + (c) The components are mixed and emulsified to obtain the desired 0 / W / 0 type multiple emulsion. With reference to the aforementioned Tables 3 and 4, selecting a suitable surfactant for each of the 0 / W type emulsion and the W / 0 type emulsion can obtain a relatively high stability. On the other hand, it can also be seen that when the stable O / tf type emulsion as shown in Table 5 is dispersed in the oil phase or 0 / W / 0 oil type emulsion, the emulsification stability will be greatly reduced, especially the internal oil phase will ooze out. In external oil. Therefore, the inventors of the present invention reviewed the stabilization effect of the organic modified clay mineral on multiple emulsions, and particularly the effect of preventing the internal oil phase from being integrated with the external oil phase as follows. Table 6: Oil-in-water-in-oil emulsion ---------- Production-(Please read the precautions on the back before filling out this page) Printed Compositions of Employees' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 1 14 1-15 Implementation 1-16 Example 1-17 1-18 (a) 0 / W phase 0 / W emulsion of Example 1-1 70 70 70 70 70 (b) External oil phase liquid ballast 28 28 28 28 28 (C) Surfactant organically modified clay mineral in external oil phase (Preparation Example 1) 2----Unmodified clay mineral (propolis)-2---Chlorobenzyl dimethyl deca Octamonium Ammonium--2-P0E (6) Octadecyl Ether---2-Amorphous benzyldimethyl octadecyl ammonium + P0E (6) Octadecyl Ether----2 Room temperature) 〇XXXX (50 it) 〇XXXX Oil phase residual rate (after 50108 weeks) 98 &lt; 5 &lt; 5 &lt; 5 &lt; 5 This paper size applies Chinese National Standard (CNS) Α4 specification (21 〇 × 297 Mm) 29 (revision page) 38514

,1T 470653 A7 B7五、發明説明（28 ) 〈調製方法〉 依據前述表5以表6之配方調製0 / W / 0油型乳液。 由上述表6可知，將有機改質拈土礦物配合於外油相 中之場合，乳化型態、内油相殘餘率均極佳，主要構成該 有機改質粘土礦物之未改質粘土礦物、氣化苯甲基二甲基 硬脂醯銨、P0E(6)十二醚單獨或組合使用均無法得到如配 合有機改質粘土礦物場合之高乳化安定性。 單以安定之0/W型乳液取代安定之W/0型乳液之水相， 仍無法得到安定之多重乳液，因此可以了解到有機改質粘 土礦物對多重乳液之安定化作用極為特別。 窖旃例2 其次檢討本發明之多重乳液之適當組成。 (1 )組成 表7 :油包水型乳液之組成 -- --- - !-1- - - ml ==· - i— — I- n 二— - - --- ..... I I! 1-- - 、一-eJ (請先閱讀背面之注意事項再填寫本頁) 組成成分 含量 經濟部中央標準局員工消費合作社印製 (a )界面活性劑相 1 , 3-丁二醇 21 純水 2 P 0 E ( 6 0 )硬化1麻油 2 (b)内油相 液體石蟠 33 (c)水相 純水 42 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） +0 470653 A7 B7五、發明説明（29 ) 表8 :外油相之組成 組成成分 含量 (d)界面活性劑 有機改質粘土礦物（調製例υ 7 (e )外油相油 液體石蟠 93 經濟部中央標準局員工消費合作社印製 表9 : 油包 水包油型乳液之 構成比例 實施 例 0/W型乳液量 外油相量 (重量比） (重量比） 實施例2-1 50 50 實施例2 -2 60 40 實施例2 -3 7 0 30 實施例2 -4 80 20 實施例2 -5 3 5 65 實施例2 -6 97 3 (2)諝製方法 先將上述表7中所記載之（a)成分溶解混合均勻，再與 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 31 385 1 4 -----1— - - H! - - -- -...... . II 1 - - - - I I - — I -、ISJ (請先閱讀背面之注意事項再填寫本頁) 470653 修正 本年月曰|補充 89,6, 14 Α7 Β7 五、發明説明（1 0 ) (b)成分一面授拌一面混合乳化，再將（(：）成分加入混合， 即得0/1ί型乳液。 將表8之外油相成分混合，再將上述調製之0/W型乳液 —面攪拌一面與外油相混合乳化，即得目的之多重乳液， 0/W型乳液與外油相之比例依上述表9之比例變化即為實施 例 2-1 至 2-6。 (3)结果 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 表10:乳液特性之評估 實施例 乳液之形態 (調製後瞬間） 乳化安定性乳化安定性 (RT) (50¾) 内油相殘餘率 (50Ό，1 個月） 實施例2-1 0/W/0 〇 〇 93.0¾ 實施例2-2 0/W/0 ◎ 〇 95.5 實施例2-3 0/Μ/0 〇 ◎ 98.6 實施例2-4 0/W/0 ◎ 〇 92.8 實施例2-5 0/W/0 X X - 實施例2-6 0/W/0+0/W X X - 如上述表10之評估所示，實施例 2 -5中0/W型乳液與油 相之比超過2:3時油相量 過多，因此乳化後形成之0/W/0型 乳液乳化安定性比實施例2-1至2-4差 ，室溫保存、50t：保 存均有浮油產生。此外， 如實施例2- 6所示， 0/W型乳液與 油相比超過19:1時，0/W型乳液過多， 在乳化 分散中會有 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） 32 (修正頁） ,ιτ 1 8 5 1 4 470653 A7 B7 五、發明説明（3 1) 相轉變，調製之乳液可確認出混雜有0/W/0型及0/«型。 因此，0/W型乳液與外油相之配合比以重量比2 : 3〜 19 : 1範圍為佳。 JLL 比較例1.-1至1-6以下述表U組成之外油相調製。各外 油相中使用已往調製W/0型乳液時廣泛使用之親油性界面 活性劑。 又，0/W型乳液同實施例2之表7調製，再與下述表11 中各比較例之外油相以7 : 3重量比混合乳化。 調製乳液之乳化安定性評估如表1 2所示。 表1 1 :外油相之組成 1 I n I - - - I I - I I I I I (請先閲讀背面之注意事項再填寫本頁) 外油相 親油性活性劑（重量比） 油（重量比） 經濟部中央標準局員工消費合作社印製 比較例1 -1 比較例1 - 2 比較例1 - 3 比較例1 - 4 比較例1 - 5 比較例1 - 6 P 0 E ( 3 )十八醚（1 ) P 0 E ( 3 )十 Λ 醚（5 ) 液體石蟠（99) 液體石锄（95) 山梨糖醇單硬脂酸酯（1) 液體石蟠（99) 山梨糖醇單硬脂酸酯（5 ) 液體石蟠（9 5 ) Ρ0Ε(10)硬化蓖麻油（10) 液體石蟠（90) Ρ0Ε (10)硬化Μ麻油（5) 液體石蟠（95) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 33 38 5 1 4 470653 A7 B7 五、發明説明（32 表12:乳液特性之評定 外油相 乳化形態 (調製後瞬間） 乳化安定性 乳化安定性 (RT) (50Ϊ：)1T 470653 A7 B7 V. Description of the invention (28) <Preparation method> Prepare 0 / W / 0 oil-based emulsion according to the aforementioned Table 5 and Table 6 formula. As can be seen from Table 6 above, when the organic modified vermiculite mineral is blended in the external oil phase, the emulsified form and the residual ratio of the internal oil phase are excellent. The unmodified clay mineral, Gasified benzyl dimethyl stearyl ammonium and POE (6) dodecyl ether alone or in combination can not obtain high emulsification stability as in the case of organic modified clay minerals. It is not possible to obtain stable multiple emulsions by simply replacing the aqueous phase of stable W / 0 emulsions with stable 0 / W emulsions. Therefore, it can be understood that the stability of multiple emulsions by organic modified clay minerals is extremely special. Example 2 Next, the proper composition of the multiple emulsion of the present invention is reviewed. (1) Composition Table 7: Composition of water-in-oil emulsion-----! -1---ml == ·-i- — I- n two —----- ..... II ! 1---、 e-eJ (Please read the precautions on the back before filling this page) Composition Content Printed by (a) Surfactant Phase 1, 3-Butanediol 21, Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Pure water 2 P 0 E (6 0) hardened 1 sesame oil 2 (b) Internal oil phase liquid stone 蟠 33 (c) Water phase pure water 42 This paper size applies to Chinese National Standard (CNS) Λ4 specification (210X297 mm) + 0 470653 A7 B7 V. Description of the invention (29) Table 8: Composition of the external oil phase Composition content (d) Surfactant organically modified clay mineral (Modification example υ 7 (e) External oil phase oil liquid stone 蟠 93 Economy Printed by the Ministry of Standards and Staff's Consumer Cooperatives Table 9: Composition ratio of oil-in-water-in-oil emulsion Example 0 / W type Emulsion amount External oil phase (weight ratio) (weight ratio) Example 2-1 50 50 Implementation Example 2-2 60 40 Example 2-3 7 0 30 Example 2-4 80 20 Example 2-5 3 5 65 Example 2 -6 97 3 (2) Method of making Firstly record in Table 7 above (A) component Dissolve it evenly, and apply the Chinese National Standard (CNS) A4 specification (210X 297 mm) to this paper size 31 385 1 4 ----- 1—--H!----...... II 1----II-— I-, ISJ (Please read the notes on the back before filling this page) 470653 Amendment this month | Supplement 89,6, 14 Α7 Β7 V. Description of the invention (1 0) (b) Ingredients are mixed and emulsified while mixing, and ((:) ingredients are added and mixed to obtain 0/1 ί emulsion. Mix the oil phase ingredients other than those in Table 8 and then mix the 0 / W emulsion prepared above— Mix and emulsify while mixing with the external oil phase to obtain the desired multiple emulsion. The ratio of the 0 / W type emulsion to the external oil phase changes according to the ratio in Table 9 above, which is Examples 2-1 to 2-6. (3) Results (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Cooperation, Du Printed Table 10: Evaluation of Emulsion Properties ) (50¾) Internal oil phase residual rate (50Ό, 1 month) Example 2-1 0 / W / 0 〇093.0¾ Example 2-2 0 / W / 0 ◎ 〇95.5 Implementation 2-3 0 / M / 0 〇 98.6 Example 2-4 0 / W / 0 ◎ 〇 92.8 Example 2-5 0 / W / 0 XX-Example 2-6 0 / W / 0 + 0 / WXX -As shown in the evaluation of Table 10 above, when the ratio of the 0 / W type emulsion to the oil phase in Example 2-5 exceeds 2: 3, the amount of the oil phase is too much, so the 0 / W / 0 type emulsion formed after emulsification is stable. The performance is inferior to that of Examples 2-1 to 2-4. When stored at room temperature and 50t, oil slicks are generated. In addition, as shown in Examples 2-6, when the 0 / W type emulsion is more than 19: 1 compared with the oil, the 0 / W type emulsion is too much, and the paper size will be applicable to the Chinese National Standard (CNS) Α4 in the emulsion dispersion. Specifications (210 X 297 mm) 32 (correction page), ιτ 1 8 5 1 4 470653 A7 B7 V. Description of the invention (3 1) Phase transition, the emulsion prepared can be confirmed to be mixed with 0 / W / 0 type and 0 /"type. Therefore, the mixing ratio of the 0 / W type emulsion to the external oil phase is preferably in a range of 2: 3 to 19: 1 by weight. JLL Comparative Examples 1.-1 to 1-6 were prepared with an oil phase other than the composition shown in Table U below. For each external oil phase, a lipophilic surfactant that has been widely used in the preparation of W / 0 emulsions is used. The 0 / W emulsion was prepared in the same manner as in Table 7 of Example 2 and mixed with the oil phase other than the comparative examples in Table 11 below to emulsify at a weight ratio of 7: 3. The emulsification stability evaluation of the prepared emulsion is shown in Table 12. Table 1 1: Composition of external oil phase 1 I n I---II-IIIII (Please read the notes on the back before filling out this page) External oil phase lipophilic active agent (weight ratio) Oil (weight ratio) Central Ministry of Economic Affairs Standard Bureau employee consumer cooperative prints Comparative Example 1 -1 Comparative Example 1-2 Comparative Example 1-3 Comparative Example 1-4 Comparative Example 1-5 Comparative Example 1-6 P 0 E (3) Octadecyl Ether (1) P 0 E (3) Deca-ether (5) Liquid Rock Fructus (99) Liquid Rock Fructus (95) Sorbitol Monostearate (1) Liquid Rock Fructus (99) Sorbitol Monostearate (5 ) Liquid stone mortar (9 5) PO0 (10) hardened castor oil (10) Liquid stone mortar (90) PO0 (10) Hardened sesame oil (5) Liquid stone mortar (95) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 33 38 5 1 4 470653 A7 B7 V. Description of the invention (32 Table 12: Evaluation of emulsion characteristics External oil phase emulsification form (instantaneous after preparation) Emulsification stability Emulsification stability (RT) (50Ϊ: )

比 較 例 1 - 1 0/W/0 X X 比 較 例 1-2 0/W/0+0/W X X tb 較 例 1-3 0/W/0 X X tb 較 例 1-4 0/W/0 X X tb 較 例 1-5 0/W/0+0/W X X tb 較 例 1-6 0/W/0+0/W X X (請先閱讀背面之注意事項再填寫本頁)Comparative Example 1-1 0 / W / 0 XX Comparative Example 1-2 0 / W / 0 + 0 / WXX tb Comparative Example 1-3 0 / W / 0 XX tb Comparative Example 1-4 0 / W / 0 XX tb Comparative example 1-5 0 / W / 0 + 0 / WXX tb Comparative example 1-6 0 / W / 0 + 0 / WXX (Please read the precautions on the back before filling this page)

、1T 比較表1 0及表1 2之評估可知，與比較例1 - 1至1 - 6相比 本發明之實施例2-1〜2-4乳化安定性較佳。 經濟部中央標準局員工消費合作杜印製 其次測定内油相中配合脂溶性藥劑之乳液的乳化安定 性及藥劑殘餘率。在此脂溶性藥劑使用視黃醇，而表13〜 16乳液之調製方法則參照前述表3-6。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 34 3 8 5 1 4 470653 A7 B7 五、發明説明（3 3 ) 表1 3 : 0 / W型乳液 經濟部中央標準局員工消費合作社印製 組成成分 實施例 3-1 (a )界面活性劑相 1，3-丁二醇 21 純水 2 P 0 E (6 0 )硬化蓖麻油 2 (b )油相 液體石蠟 32 視黃醇 1 (c )水相 純水 42 乳化安定性（形態觀察）It can be seen from Table 1 and Table 12 that 1T is compared with Comparative Examples 1-1 to 1-6 and the emulsification stability of Examples 2-1 to 2-4 of the present invention is better. Consumption cooperation by employees of the Central Bureau of Standards, Ministry of Economic Affairs, Du printed. Secondly, determine the emulsification stability and the residual rate of the emulsion with fat-soluble agents in the internal oil phase. Retinol is used as the fat-soluble agent, and the preparation methods of the emulsions in Tables 13 to 16 are referred to the aforementioned Tables 3-6. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 34 3 8 5 1 4 470653 A7 B7 V. Description of invention (3 3) Table 1 3: 0 / W type emulsion Ministry of Economics Central Standards Bureau staff consumption Cooperative printed composition Example 3-1 (a) Surfactant phase 1,3-butanediol 21 Pure water 2 P 0 E (60) Hardened castor oil 2 (b) Oil phase liquid paraffin 32 Retinol 1 (c) Emulsion stability of pure water in aqueous phase 42 (morphological observation)

室溫 〇 50 t： 〇 劑殘餘率 X 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 35 3 8 5 1 4 1 I- - 1 I I I !批衣— — I I —— I 訂 (請先閱讀背面之注意事項再填寫本頁) 470653 A7 B7 五、發明説明（34) 表14: W/0型乳液 組成成分 3-2 3-3 實 3-4 施例 3-5 3-6 3-7 (a)界面活性劑 P0E(3)十八醚 1 - - - - - POE(2)十八醚 - 5 - - - - 山梨糖醇單硬脂酸酯 - - 1 - - - 山梨糖醇單硬脂酸酯 - - - 5 - - POE(IO)硬化蓖麻油 - - - - 10 - P0E(10)硬化蓖麻油 - - - - - 5 (b)油相 液體石蟠 38 34 38 34 29 34 視黃醇 1 1 1 1 1 1 (C)水相 離子交換水 60 60 60 60 60 60 ^1- nn .^ϋ m mV I ml -- - . n i m^l n^— --SJ (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Room temperature 〇50 t: 〇Residue ratio X This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 35 3 8 5 1 4 1 I--1 III! Approval — — II — I order (Please read the precautions on the back before filling out this page) 470653 A7 B7 V. Description of the invention (34) Table 14: W / 0 emulsion composition 3-2 3-3 Example 3-4 Example 3-5 3- 6 3-7 (a) Surfactant POE (3) Octadecyl ether 1-----POE (2) Octadecyl ether-5----Sorbitol monostearate--1--- Sorbitol monostearate---5--POE (IO) hardened castor oil----10-P0E (10) hardened castor oil-----5 (b) oil phase liquid stone concrete 38 34 38 34 29 34 Retinol 1 1 1 1 1 1 (C) Aqueous ion-exchanged water 60 60 60 60 60 60 ^ 1- nn. ^ Ϋ m mV I ml--. Nim ^ ln ^---SJ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

乳化安定性（形態觀察） 室溫 0 . 〇 〇 〇 〇 〇 ' 501C 〇 〇 〇 〇 〇 〇 藥劑殘餘率 X X X X X X 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨OX297公釐） 36 38514 470653 A7 B7 五、發明説明（35 ) 表15:油包水包油型乳液 經濟部中央標準局員工消費合作社印製Emulsification stability (morphological observation) Room temperature 0. 〇〇〇〇〇〇〇 '501C 〇 〇 〇 〇 00 〇 Residue ratio of XXXXXX This paper size applies Chinese National Standard (CNS) A4 specifications (2 丨 OX297 mm) 36 38514 470653 A7 B7 V. Description of Invention (35) Table 15: Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

組成成分 3-8 3-9 實施例 3-10 3-11 3-12 3-13 (a)油包水相[油相中含視黃醇] 實施例3-1之0/W型乳液 70 70 70 70 70 70 (b)外油相 液體石_ 29 25 29 25 20 25 (C)親油性界面活性劑 P0E(3)十八醚 1 - - - - - P0E(2)十八醚 - 5 - - - - 山梨糖醇單硬脂酸酯 - - 1 - - - 山梨糖醇單硬脂酸酯 - - - 5 - - P0E(10)硬化蓖麻油 - - - - 10 - POE(IO)硬化Μ麻油 - - - - - 5 乳化安定性（形態觀察） 室溫 X X X X X X 501、 X X X X X X 内油相殘存率（50C8週後） &lt;5 &lt;5 &lt;5 &lt;5 &lt;5 &lt;5 藥劑殘餘率 X X X X X X (請先閲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 ) Λ4規格（210X297公釐） 37 38514 470653 A7 B7 經濟部智慧財產局員工消費合作社印製 修正 本年月 補充紙5 · - 4 五、發明說明（36 ) 表16:油包水包油型乳液3-8 3-9 Example 3-10 3-11 3-12 3-13 (a) Water-in-oil phase [Retinol in oil phase] 0 / W emulsion 70 of Example 3-1 70 70 70 70 70 (b) External oil phase liquid stone _ 29 25 29 25 20 25 (C) Lipophilic surfactant P0E (3) octadecyl ether 1-----P0E (2) octadecyl ether-5 ----Sorbitol monostearate--1---Sorbitol monostearate---5--P0E (10) hardened castor oil----10-POE (IO) hardened Μ sesame oil-----5 Emulsification stability (morphological observation) Room temperature XXXXXX 501, XXXXXX oil phase residual rate (after 50C8 weeks) &lt; 5 &lt; 5 &lt; 5 &lt; 5 &lt; 5 &lt; 5 Pharmacy Residual rate XXXXXX (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 37 38514 470653 A7 B7 Printed and revised copy of the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Year and month supplementary paper 5 ·-4 V. Description of the invention (36) Table 16: Oil-in-water-in-oil emulsion

組成成分 3-14 3-15 實施 3-16 例 3-17 3-18 (a)油包水相[油相中含視黃醇] 實施例3-1之0/W型乳疲 70 70 70 70 70 (b)外油相 液體石蠟 28 28 28 28 28 (C)外油相中之界面活性劑 有機改質粘土礦物（調製例1) 2 - - - - 未改質粘土礦物（蜂膠） - 2 - - - 氯化笨甲基二甲基十八醯銨 - - 2 一 - P0E(6)十二 _ - - - 2 - 氯化苯甲基二甲基十八醯銨 + P0E(6)十二醚 - - - - 2 乳化安定性 形態觀察（室溫） 〇 X X X X (50t ) 〇 X X X X 内油相殘存率（50t 8週後） 98 &lt;5 &lt;5 &lt;5 &lt;5 藥劑殘餘率 0 X X X X ----I--------* i ------. I I------ (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準（CNS)A4規格（210 x 297公釐） 38(修正頁） 38514Composition 3-14 3-15 Implementation 3-16 Example 3-17 3-18 (a) Water-in-oil phase [Retinol in oil phase] 0 / W milk fatigue of Example 3-1 70 70 70 70 70 (b) Liquid paraffin in external oil phase 28 28 28 28 28 (C) Surfactant organic modified clay mineral in external oil phase (Preparation Example 1) 2----Unmodified clay mineral (propolis)- 2---Benzyl dimethyl octadecyl ammonium chloride--2--P0E (6) Dodecyl----2-Benzyl dimethyl octadecyl ammonium chloride + P0E (6) Dodecyl ether----2 Observation of emulsification stability morphology (room temperature) ○ XXXXXX (50t) 〇XXXXXX oil phase residual rate (50t after 8 weeks) 98 &lt; 5 &lt; 5 &lt; 5 &lt; 5 pharmaceutical residue Rate 0 XXXX ---- I -------- * i ------. I I ------ (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) A4 Specification (210 x 297 mm) 38 (correction page) 38514

470653 A7 B7 經濟部智慧財產局員工消費合作社印製 五、 發明説明 (3 7 ) 1 ] 參 考 刖 述 表 13及 表 1 4 * 在 0/W型乳液及W/0 型 乳 液 中 油 1 1 相 配 合 脂 溶 性 藥 劑 之 場 合 t 若 各 選 擇 適 當 之 界 面 活 性 劑 9 1 1 仍 可 得 到 相 當 高 之 乳 化 安 定 性 * 但 藥 劑 殘 餘 率 則 非 常 差 〇 ^—S 請 I 1 因 此 ， 為 求 改 善 藥 劑 之 安 定 性 如 表 15在 安 定 之 0/W型乳液 閱 讀 1 1 中 將 其 分 .散 成 油 包 水 包 油 型 乳 液 9 但 所 得 之 0/W/0型乳液 背 1 I 之 1 | 之 乳 化 安 定 性 大 為 降 低 9 内 相 油 會 滲 出 於 外 相 油 中 〇 因 此 注 意 1 I 事 1 9 内 油 相 中 配 合 之 視 黃 醇 會 滲 出 於 外 油 相 中 t 無 法 得 到 期 項 再 1 導 望 之 安 定 化 效 果 0 為· 本 本 頁 1 相 對 地 9 如 上 述 表 16在 外 油 相 中 配 合 有 ijSgk m 改 質 粘 土 礦 SW&quot; 1 | 物 之 場 合 ， 可 得 到 乳 化 形 態 Λ 内 油 相 殘 餘 率 均 極 佳 之 乳 液 1 1 1 且 內 油 相 中 配 合 之 視 黃 醇 之 藥 劑 安 定 性 大 幅 提 高 〇 1 1 另 訂 — 方 面 9 該 有 m 改 質 粘 土 礦 物 主 要 構 成 之 未 改 質 粘 1 土 礦 物 、 氯 化 苯 甲 基 二 甲 基 嫂 脂 醒 銨 Ρ0Ε (6) 十 二 醚 若 單 1 1 獨 或 組 合 使 用 * 則 無 法 得 到 如 配 合 有 機 改 質 粘 土 礦 物 之 場 1 I 合 的 高 乳 化 安 定 性 或 藥 劑 安 定 性 0 1 因 此 9 單 將 安 定 之 0/W型乳液取代成安定之W/0 型 乳 液 1 1 中 之 水 相 仍 hrf m 法 提 高 多 重 乳 液 之 乳 化 安 定 性 及 內 油 相 中 藥 1 1 劑 之 安 定 性 0 該 效 果 惟 有 外 油 相 中 配 合 有 機 改 質 粘 土 礦 物 1 1 之 場 合 極 特 別 地 可 Η 獲 得 〇 1 1 實 例 4 1 | Μ 下 檢 討 内 油 相 中 配 合 脂 溶 性 藥 劑 之 場 合 之 適 當 組 成 1 1 1 (1)組成 1 1 1 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 39 (修正頁） 385 1 4 470653 A7 B7 五、發明説明（38 ) 表17: 0/W型乳液之組成 經濟部中央標準局員工消費合作社印製 組成成分 含量 (a )界面活性劑相 1 , 3-丁二醇 21 純水 2 P 0 E ( 6 0 )硬化1麻油 2 (b )内油相 液體石蟠 32 視黃醇 1 (c )水相 純水 42 表1 8 :外油相之組成 組成成分 含量 (d )界面活性劑 有機改質粘土礦物（調製例1) 7 (e )外油相 液體石撤 93 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 40 3 8 5 1 4 (請先閲讀背面之注意事項再填寫本頁) 470653 A7 B7 五、發明説明（39 ) 表1 9 :油包水包油型多重乳液之組成比 實施例 0 / W型乳液量 外油相量 實施例4-1 50 50 實施例4-2 60 40 實施例4-3 70 30 實施例4-4 80 20 實施例4-5 35 65 實施例4-6 97 3 (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 (2 )調製方法 同前述實施例2進行。具體言之，即先將上述表17中 所載之（a)成分均勻地溶解混合，再一面攪拌一面與（b)成 分混合、乳化，之後將（c)成分加入混合卽得0/W型乳液。 將表18之外油相成分混合，再一面攪拌一面將上述調 製之0 / W型乳液混合、乳化在外油相中，即得目的之0 / W / 0 型多重乳液。將0/W型乳液與外油相之比例依上述表1 9變 化，所得之0/W/0型乳液各為實施例4-1至4-6。 (3)結果 本纸張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 41 3 8 5 1 4 470653 A7 B7 五、發明説明（4〇 ) 表20:乳液特性之評估470653 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3 7) 1] Refer to the descriptions in Tables 13 and 1 4 * In the 0 / W type emulsion and the W / 0 type emulsion oil 1 1 match In the case of fat-soluble medicaments, if a suitable surfactant 9 1 1 is selected, a relatively high emulsification stability can still be obtained *, but the residual rate of the medicament is very poor. ^ -S Please I 1 Therefore, in order to improve the stability of the medicament As shown in Table 15, it is divided into the stable 0 / W type emulsion reading 1 1. It is dispersed into an oil-in-water-in-oil type emulsion 9 but the obtained 0 / W / 0 type emulsion back 1 I 1 | The emulsion stability is large In order to reduce 9 the internal phase oil will seep out of the external phase oil. Therefore, pay attention to 1 I. 1 9 The retinol blended in the internal oil phase will seep out of the external oil phase. T The phase term cannot be obtained again. For Page 1 Relatively 9 As shown in Table 16 above, when the ijSgk m modified clay ore SW &quot; 1 | is blended in the outer oil phase, an emulsion 1 1 1 with excellent internal oil phase residual ratio and an inner oil can be obtained. The stability of the retinol drug in the phase has been greatly improved. 01 1 Separately-Aspect 9 The unmodified clay mainly composed of modified clay minerals. 1 Earth mineral, benzyl chloride Ammonium P0E (6) Dodecyl ether alone 1 1 alone or in combination * will not give you the high emulsification stability or pharmaceutical stability of 1 I combined with organic modified clay minerals 0 1 Therefore 9 single stability of 0 / W type emulsion is replaced by stable W / 0 type emulsion 1 1 The aqueous phase is still hrf m method to improve the emulsion stability of multiple emulsions and the stability of internal oil phase Chinese medicine 1 1 The stability of the agent 0 This effect is only compatible with the external oil phaseIn the case of mechanically modified clay mineral 1 1, it is extremely special to obtain 0 1 1 Example 4 1 | The appropriate composition of the case where the fat-soluble agent is blended in the internal oil phase is reviewed 1 1 1 (1) Composition 1 1 1 1 1 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 39 (revised page) 385 1 4 470653 A7 B7 V. Description of the invention (38) Table 17: Composition of 0 / W emulsion Printed by Consumer Consumption Cooperatives (a) Surfactant phase 1, 3-butanediol 21 Pure water 2 P 0 E (60) Hardened 1 Sesame oil 2 (b) Internal oil phase Liquid stone concrete 32 Retinol 1 (c) Water-phase pure water 42 Table 1 8: Composition of the outer oil phase (d) Surfactant organically modified clay mineral (Modification Example 1) 7 (e) Liquid oil phase of the outer oil phase 93 papers Standards apply to Chinese National Standards (CNS) Λ4 specifications (210X297 mm) 40 3 8 5 1 4 (Please read the precautions on the back before filling this page) 470653 A7 B7 V. Description of the invention (39 ) Table 19: Composition ratio of oil-in-water-in-water multiple emulsions Example 0 / W-type emulsion amount External oil phase amount Example 4-1 50 50 Example 4-2 60 40 Example 4-3 70 30 Implementation Example 4-4 80 20 Example 4-5 35 65 Example 4-6 97 3 (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (2) The modulation method is the same as above Example 2 was carried out. Specifically, firstly, the component (a) contained in the above Table 17 is uniformly dissolved and mixed, and then mixed with the component (b) and emulsified while stirring, and then the component (c) is added to the mixture to obtain a 0 / W type. Emulsion. The oil phase components other than those shown in Table 18 are mixed, and the 0 / W type emulsion prepared above is mixed and emulsified in the external oil phase while stirring, to obtain the desired 0 / W / 0 type multiple emulsion. The ratio of the 0 / W type emulsion to the external oil phase was changed according to Table 19 above, and the obtained 0 / W / 0 type emulsions were Examples 4-1 to 4-6, respectively. (3) Results This paper size is in accordance with the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 41 3 8 5 1 4 470653 A7 B7 V. Description of the invention (40) Table 20: Evaluation of emulsion characteristics

• '. 乳液之形態 (調製後瞬間） 乳化安定性 RT 50t： 内油相* 殘餘率 藥劑 殘餘率 實施例4-1 0/W/0 〇 〇 93 % ◎ 實施例4-2 0/W/0 〇 〇 96 ◎ 實施例4-3 0/W/0 0 ◎ 99 ◎ 實施例4-4 0/W/0 〇 〇 93 〇 實施例4-5 0/W/0 X X - X 實施例4-6 0/W/0+0/W X X - X 1 n II I II - n n -- n - I - I n (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 =?内油相殘餘率為5 ο η , 1値月後測定者。 如上述表20所示，0/W型乳液與外油相比在2:3〜19:1 之範圍外時即無法得到安定之多重乳液，而且内油相中配 合之藥劑（視黃醇）之安定性極差。相對地可以理解，0/W 型乳液與外油相之比在2 : 3〜1 9 : 1之範圍内之場合，糸之 乳化安定性佳且内油相中配合之藥劑安定性待別增高。 奮施例5 依前述實施例4之調製方法以如下述表21及表22所示 之配方，變化各成分之配合量調製成0/V/0型多重乳液， 条之乳化安定性及蕖劑安定性如同前述表20所示之情形， 〇 / W型乳液與外油相之比在2 : 3〜1 9 : 1之範圍内時良好。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 42 3 8 5 1 4 470653 年. y8s.本正充 修補 5 月 4 0• '. Emulsion form (instantaneous after preparation) Emulsification stability RT 50t: Internal oil phase * Residual ratio Residual ratio Example 4-1 0 / W / 0 〇〇93% ◎ Example 4-2 0 / W / 0 〇〇96 ◎ Example 4-3 0 / W / 0 0 ◎ 99 ◎ Example 4-4 0 / W / 0 〇〇93 〇 Example 4-5 0 / W / 0 XX-X Example 4- 6 0 / W / 0 + 0 / WXX-X 1 n II I II-nn-n-I-I n (Please read the precautions 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 =? The internal oil phase residual rate is 5 ο η, measured after 1 month. As shown in Table 20 above, when the 0 / W emulsion is outside the range of 2: 3 to 19: 1 compared with the external oil, a stable multiple emulsion cannot be obtained, and the drug (retinol) mixed in the internal oil phase The stability is extremely poor. It can be relatively understood that when the ratio of 0 / W emulsion to the external oil phase is in the range of 2: 3 ~ 19: 1, the emulsification stability of osmium is good and the stability of the drug compounded in the internal oil phase will be increased . Fenshi Example 5 According to the preparation method of the foregoing Example 4, the formula shown in the following Table 21 and Table 22 was used to change the blending amount of each component to prepare a 0 / V / 0 multiple emulsion, emulsion stability and tincture. The stability is the same as that shown in Table 20 above, and the ratio of the 0 / W type emulsion to the external oil phase is good when it is in the range of 2: 3 to 19: 1. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 42 3 8 5 1 4 470653 years.

7 7 A B 五、發明說明（41) 表21:組成比之檢討 經濟部智慧財產局員工消費合作社印製 實施例 組成成分 5-1 5-2 5-3 5-4 5-5 (a)界面活性劑相 1,3-丁二醇 3 4 3 2 3 甘油 5 6 5 4 5 P0E(60)硬化篦麻油 1 1.2 1 0.8 1 對羥基苯甲酸甲酯 0.15 0.15 0.15 0.15 0.15 (b)內油相 三十碳烷 5 5 5 5 5 三-2-乙基己酸甘油酯 5 10 5 2.5 5 維生素A十六烷酸酯 1 2 1 0.5 17 7 AB V. Description of invention (41) Table 21: Review of composition ratio Composition of printed examples of employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5-1 5-2 5-3 5-4 5-5 (a) Interface Active agent phase 1,3-butanediol 3 4 3 2 3 Glycerol 5 6 5 4 5 POE (60) hardened ramie oil 1 1.2 1 0.8 1 methyl parahydroxybenzoate 0.15 0.15 0.15 0.15 0.15 (b) internal oil phase Tricosane 5 5 5 5 5 Glyceryl tri-2-ethylhexanoate 5 10 5 2.5 5 Vitamin A hexadecanoate 1 2 1 0.5 1

(c)水相 纯水 73.35 55.15 46.85 35.55 13.85 (d)外油相 三十碳烷 3 15 30 45 60 陽離子改質粘土礦物（Bentone-38) 0.5 0.5 1 1.5 2 P0E(6)十八醚 1 1 2 3 4 油包水乳液：外油相（重量比） 21:1 5:1 2:1 1:1 0.5:1 乳化安定性（形態觀察） 501C X 〇 ◎ 〇 X 藥劑殘餘率 X 〇 ◎ 0 X (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準（CNS)A4規格（210 X 297公釐） 36514 470653 丨修正本… |補充撒5. -4 Α7 Β7 五、發明説明（42 ) 表22:組成比之檢討 實施 例 組成成分 5-6 5-7 5-8 5-9 5-10 (a)界面活性劑相 1,3-丁二醇 3 4 3 2 3 甘油 5 6 5 4 5 P0E(60)硬化蓖麻油 1 1.2 1 0.8 1 對羥基苯甲酸甲酯 0.15 0.15 0.15 0.15 0.15 (b)内油相 甲氧基肉桂酸辛基酯 5 5 5 5 5 三-2-乙基己酸甘油酯 5 10 5 2.5 5 辛基二甲基對氨苯甲酸 1 2 1 0.5 1 (C)水相 純水 73.35 55.15 46.85 35.55 13.85 (d)外油相 液體石獵 1.5 7.5 15 22.5 30 異烷烴 1.5 7.5 15 22.5 30 陽離子改質粘土碾物（Bentone-38) 0.5 0.5 1 1.5 2 經 濟 部 P0E(10)山梨糖醇脂肪酸酯 1 1 2 3 4 智 慧 財 產 0/W乳液：外油相（重量比） 21:1 5:1 2:1 1:1 0.5:1 局 員 工 乳化安定性（形態觀察〉 消 費 50t： X .〇 ◎ 〇 X 合 社 藥劑殘餘率 Δ ◎ 0 ◎ Δ 印 製 請 先 閲 讀 背 面 意 事 項 再 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 互4(修止貝） 38514 470653 A7 B7 五、發明説明（43 ) 液 藥 W/性 0/溶 製脂 調同 方不 配之 之合 示配 所中 23相 表油 依内 ，定 次測 其再 型 或 液 劑 藥 之 劑 fu t£ 5性 型定 成 組 表 組成·成分 實施例6 (0/W/0) 比較例2 (W/0) 比較例3 (0/W/0) (a)界面活性劑相 1,3-丁二醇 5 5 5 P0E(60)硬化蓖麻油 1 - - 皂土 / - 0.5 對羥基苯甲酸甲酯 0.1 0.1 0.1 (b)内油相 三十磺烷 5 - 5 四-2-乙基己酸季戊四醇 5 -' 5 十六醇 - - 3 Ρ0Ε (20)山梨糖醇三硬脂酸酯 - - 1 油酸單甘油酯 - - 2 脂溶性維生素（表24參照） 1 - 1 ----------------訂 (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 (c)水相 純水 49.9 50.9 37.4 (d)外油相 液體石蟠 30 30 30 有機改質粘土礦物（調製例1) 1 1 1 P0E(6)十八醚 2 2 - 三十磺烷 - 5 - 四-2-乙基己酸季戊四醇 -糊精十六酸酯 -十六醇 - 5 1 3 蜜蠘 - - 2 山梨糖醇倍半油酸酯 - - 3 山梨糖醇單硬脂酸酯 -脂溶性維生素（表24參照） - 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 45 3 8 5 1 4 470653 修正 本年月日 A7補充网，6. 14 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（4 4 ) (2 )調製方法 窗倫例fi 將（a)各成分溶解混合均勻，再一面搅拌一面與（b)成 分混合、分散、乳化，得到界面活性劑相中油型乳化組成 物，再將（c)成份加人混合即得0/W型乳液。其次將此0/W 型乳液一面攪拌一面與預先混合分散之（d)成分混合、乳 化即得目的之0/W/0型多重乳液。 比—較例2 將（a)成分溶解混合均勻後，將（a)成分與（c)成分混 合。再一面撹拌一面與（d)成分及（a) + (c)成分混合、乳化 ，即得目的之W/0型乳液。 卜上龄例3 將（a) + (c)成分與（b)成分在70t：下分別加熱溶解後， —面攪拌一面將（a) + (c)成分與（b)成分混合、分散、乳化 ，即得0/W型乳液。其次，將此0/W型乳液一面攪拌一面與 預先Μ 80=0加熱溶解之（d)成分混合，再持續攪拌冷却至 30Ό即得目的之0/W/0型多重乳液。 (3)評估方法 對此方法調製之乳液&gt;i前述方法評估其乳化安定性及 藥劑殘餘率。於501C恒溫槽內保存1個月後判定變色、變 臭之情形，再依下述標準評估。 锻色（目視判宝） ◎:全無變色 〇：稍有變色 (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準（CNS ) A4規格（210 X 297公釐） 46 (修正頁）385 1 4 470653 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（45 ) △:變色多 X :明顯變色 螢臭 ◎:全無變化 0 :幾乎無變化 △:稍有異臭 X :有明顯異臭 (4)結果 表24:各乳液之特性評估 請 先 閱 讀 背 面 之 注 意 事 1 1 1 1 1 1 1 1 1 1 1 1 項 1 脂溶性維生素 乳化安定性 藥劑殘存率 再 填 I 變色 變臭形態觀察 (% ) 寫 本 裝 頁 | 實施例6-1 視黃醇 ◎ ◎ 0 90.5 '--- 1 I (0/W/0) 2 維生素A+八酸酯 0 ◎ 〇 98.1 1 1 3 維生素A乙酸酯 ◎ ◎ 〇 97.8 1 4 α -生育酚 ◎ ◎ 〇 97.2 1 5 維生素Ε乙酸酯 ◎ 0 〇 100.2 1 丁 I 6 維生素D2 0 ◎ 〇 99.5 1 I 7 /3 -胡籮荀素 ◎ ◎ 〇 96.5 1 I 比較例2-1 視黃醇 X X 0 65.0 1 1 1 (y/〇) 2 維生素Α十八酸酯 Δ Δ 〇 70.1 1 3 維生素A乙酸酯 Δ Δ 〇 74.9 1 4 α -生育酚 Δ 〇 〇 69.9 1 5 維生素Ε乙酸酯 0 0 〇 80.1 1 6 維生素D2 Δ 〇 〇 83.8 1 7 /3-胡蘿葡素 Δ 〇 〇 79.8 1 1 l:b較例3-1 視黃醇 X X X 17.2 1 1 (0/W/0) 2 維生素Α十八酸酯 X X X 36.6 1 3 維生素A乙酸酷 X X X 40.8 1 4 α -生育齡 △ △ X 66.7 1 I 5 維生素Ε乙酸酯 △ Δ X 78,9 1 | 6 雒生素D2 △ △ X 80.7 1 7 /9 -胡蘿葡素 Δ 〇 Δ 77.7 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 47 88514 470653 A7 B7五、發明説明（46 ) 由表24可知，外油相中配合有機改質粘土礦物之0/W/ 0型乳液（實施例6-1〜6-7)中其油分等無分離或變色、變 臭情形，因此乳化安定性佳，藥劑殘餘率極高。 相對地，比較例2 - 1〜2 - 7之W / ϋ型中無油相之分離等， 可得安定之乳化狀態，但因外油相中有藥劑（脂溶性維生 素）配合，藥劑之殘餘量因氧化分解而明顯減少。比較例 3 - 1〜3 - 7之類依已往方法之0 / W / 0型多重乳液之場合，乳 化安定性差而容易分離，且在調製製程中伴有加熱，因此 内油相中配合之藥劑分解明顯，變色及變臭之程度亦大。 啻旃例7好屮龄例4 以表2 5所示之配方在内油相中配合各種油溶性紫外線 吸收劑，配製成0 / W / 0型乳液或W / 0型乳液，再測定其乳化 安定性。 (1 )組成 表25 組成成分 實施例7 (0/W/0) 比較例 (W/0) n. - - I -i I 1 - - - ......- 1'( --- I- —i -- -- - —I - (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 a )界面活性劑相 1，3-丁二 醇 5 5 P 0 E ( 6 0 )硬化1麻油 1 - 對羥基苯 甲 酸 甲酯 0.1 0.1 (b)内油相 三十碩烷 5 - 四-2-乙基己酸季戊 四 醇 5 - 紫外線吸 收 劑 (表26 參 照 ) 2 - (c )水相 純水 48 . 9 59.9 (d)外油相 液體石蟠 30 30 有機改質 粘 土 礦物（ 調 製 例U 1 1 Ρ0Ε (6)十 八 碩 烯醚 2 2 紫外線吸 收 劑 (表26 參 照 ) - 2 本紙張尺度適用中國國家標準（CNS ) A4規格（210&gt;&lt; 297公釐） 48 3 8 5 1 4 470653 A7 B7 五、發明説明（4 7 ) (2 )調製方法 窖旃例7 依照前述實施例6。 卜上較例4 依照前述比較例2。 (3.)評.估方法 表25之乳液以前述方法觀察形態，檢査其粒徑之變化 或分離、變色等乳化狀態之變化，評估其乳化安定性。保 存期間則為2 5勺6個月或5 0 t： 2個月。 (4)結果 表26:乳化安定性(c) Water phase pure water 73.35 55.15 46.85 35.55 13.85 (d) External oil phase triacarbon 3 15 30 45 60 Cationic modified clay mineral (Bentone-38) 0.5 0.5 1 1.5 2 P0E (6) octadecyl ether 1 1 2 3 4 Water-in-oil emulsion: External oil phase (weight ratio) 21: 1 5: 1 2: 1 1: 1 0.5: 1 Emulsification stability (morphological observation) 501C X 〇 ◎ 〇X Residue ratio X 〇 ◎ 0 X (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 36514 470653 丨 revised version ... | Supplementary 5. -4 Α7 Β7 Five Explanation of the invention (42) Table 22: Examination of composition ratio Composition Example 5-6 5-7 5-8 5-9 5-10 (a) Surfactant phase 1,3-butanediol 3 4 3 2 3 Glycerin 5 6 5 4 5 POE (60) hardened castor oil 1 1.2 1 0.8 1 methyl parahydroxybenzoate 0.15 0.15 0.15 0.15 0.15 (b) internal oil phase methoxy octyl cinnamate 5 5 5 5 5 tri- 2-Ethylhexanoic acid glyceride 5 10 5 2.5 5 Octyldimethyl p-aminobenzoic acid 1 2 1 0.5 1 (C) Water phase pure water 73.35 55.15 46.85 35.55 13.85 ( d) External oil phase liquid stone hunting 1.5 7.5 15 22.5 30 Isoalkane 1.5 7.5 15 22.5 30 Cationic modified clay mill (Bentone-38) 0.5 0.5 1 1.5 2 Ministry of Economic Affairs POE (10) sorbitol fatty acid ester 1 1 2 3 4 Intellectual property 0 / W emulsion: external oil phase (weight ratio) 21: 1 5: 1 2: 1 1: 1 0.5: 1 Emulsion stability of staff (morphological observation> Consumption 50t: X .〇 ◎ 〇X Cooperative Pharmacy Residual Ratio Δ ◎ 0 ◎ Δ Please read the notice on the back before printing. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). Mutual 4 (repair only) 38514 470653 A7 B7 V. Invention Explanation (43) Liquid medicine W / sex 0 / solubilizing fat blending formula does not match the 23-phase table oil in accordance with the internal display, according to the order of its remodeling or liquid medicine fu t £ 5 Group Table Composition / Composition Example 6 (0 / W / 0) Comparative Example 2 (W / 0) Comparative Example 3 (0 / W / 0) (a) Surfactant Phase 1,3-butanediol 5 5 5 P0E (60) hardened castor oil 1--bentonite /-0.5 methyl parahydroxybenzoate 0.1 0.1 0.1 (b) internal oil phase triclosane 5-5 tetra-2-ethyl Pentaerythritol caproate 5-'5 Cetyl alcohol--3 POE (20) Sorbitol tristearate--1 Monoglyceryl oleate--2 Fat-soluble vitamins (refer to Table 24) 1-1 --- ------------- Order (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (c) Water-phase pure water 49.9 50.9 37.4 (d) External oil phase liquid stone 30 30 30 Organic modified clay minerals (preparation example 1) 1 1 1 P0E (6) octadecyl ether 2 2-tridecasulfane-5-tetra-2-ethylhexanoic acid pentaerythritol-paste Hexadecanoate-hexadecanol-5 1 3 Melamine--2 Sorbitol sesquioleate--3 Sorbitol monostearate-fat-soluble vitamins (refer to Table 24)-1 1 Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 45 3 8 5 1 4 470653 Amendment A7 supplementary website, 6. 14 B7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs (4 4) (2) Modulation method Window example fi Dissolve and mix (a) each component uniformly, and then mix, disperse, and emulsify with (b) component while stirring to obtain interfacial activity Oil emulsion agent phase composition, and then (c) addition of ingredients mixed to obtain the 0 / W emulsion. Next, this 0 / W type emulsion is mixed with the component (d) previously mixed and emulsified while stirring to obtain the desired 0 / W / 0 type multiple emulsion. Ratio—Comparative Example 2 After component (a) is dissolved and mixed uniformly, component (a) and component (c) are mixed. Mix and emulsify with component (d) and component (a) + (c) while mixing, and obtain the desired W / 0 emulsion. Bu Shangling Example 3 After the components (a) + (c) and (b) are heated and dissolved at 70 t, the components (a) + (c) and (b) are mixed, dispersed, and emulsified while stirring. That is, a 0 / W type emulsion was obtained. Next, the 0 / W emulsion was mixed with the component (d) heated and dissolved in advance at 80 ° M while stirring, and then continuously stirred and cooled to 30 ° C to obtain the desired 0 / W / 0 multiple emulsion. (3) Evaluation method The emulsion prepared by this method &gt; i was evaluated for its emulsification stability and drug residue rate. After being stored in a 501C thermostatic bath for one month, the discoloration and odor were judged, and then evaluated according to the following standards. Forged color (visual judgement) ◎: No change in color 〇: Slight change in color (please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 46 (Revised page) 385 1 4 470653 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (45) △: Many changes in color X: Significant changes in color fluorescein ◎: No change at all 0: Almost no change △: Slightly Stinky X: Significantly stink (4) Results Table 24: Evaluation of the characteristics of each emulsion Please read the notes on the back 1 1 1 1 1 1 1 1 1 1 1 1 Item 1 Residual rate of fat-soluble vitamin emulsification stabilizers Filling I Observation of discoloration and discoloration (%) Written book | Example 6-1 Retinol ◎ ◎ 0 90.5 '--- 1 I (0 / W / 0) 2 Vitamin A + octaate 0 ◎ 〇98.1 1 1 3 Vitamin A acetate ◎ ◎ 〇97.8 1 4 α-Tocopherol ◎ ◎ 〇97.2 1 5 Vitamin E acetate ◎ 0 〇100.2 1 Butan I 6 Vitamin D2 0 ◎ 〇99.5 1 I 7/3 -Hu Zhi Element ◎ ◎ 〇 96.5 1 I Comparative Example 2-1 Retinol XX 0 65.0 1 1 1 (y / 〇) 2 Vitamin A stearyl acetate Δ Δ 〇70.1 1 3 Vitamin A acetate Δ Δ 〇74.9 1 4 α-tocopherol Δ 〇〇69.9 1 5 Vitamin E acetate 0 0 〇80.1 1 6 Vitamin D2 Δ 〇〇83.8 1 7 / 3-Jululose Δ 〇〇79.8 1 1 l: b Comparative Example 3-1 Retinol XXX 17.2 1 1 (0 / W / 0) 2 Vitamin A 18 Ester XXX 36.6 1 3 Vitamin A Acetic Acid XXX 40.8 1 4 α-Reproductive age △ △ X 66.7 1 I 5 Vitamin E acetate △ Δ X 78,9 1 | 6 Biotin D2 △ △ X 80.7 1 7 / 9-Carrot glucoside Δ 〇Δ 77.7 1 1 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 47 88514 470653 A7 B7 V. Description of the invention (46) As can be seen from Table 24, in the outer oil phase The 0 / W / 0 type emulsion of organic modified clay minerals (Examples 6-1 to 6-7) has no separation or discoloration or odor, so it has good emulsification stability and extremely high residual rate of the drug. On the other hand, in the W / ϋ type of Comparative Examples 2-1 to 2-7, there is no separation of the oil phase, etc., and a stable emulsified state can be obtained. However, the drug (fat-soluble vitamin) in the outer oil phase is combined, and the residue of the drug is left. The amount is significantly reduced due to oxidative decomposition. Comparative Examples 3-1 to 3-7 In the case of 0 / W / 0 type multiple emulsions according to the previous method, the emulsification stability is poor and it is easy to separate, and it is accompanied by heating during the preparation process. Therefore, the pharmaceutical compounded in the internal oil phase The decomposition is obvious, and the degree of discoloration and odor is also large.啻 旃 Example 7 Good age example 4 The formulations shown in Table 2 and 5 were used to mix various oil-soluble ultraviolet absorbers in the internal oil phase to prepare 0 / W / 0 emulsion or W / 0 emulsion, and then measured Emulsification stability. (1) Composition Table 25 Composition Example 7 (0 / W / 0) Comparative Example (W / 0) n.--I -i I 1---...-1 '(--- I- —i---—I-(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs) Surfactant phase 1,3-butanediol 5 5 P 0 E (6 0) hardened 1 sesame oil 1-methyl parahydroxybenzoate 0.1 0.1 (b) internal oil phase triclosan 5-tetra-2-ethylhexanoic acid pentaerythritol 5-ultraviolet absorber (refer to Table 26 ) 2-(c) Water-phase pure water 48. 9 59.9 (d) External oil-phase liquid ballast 30 30 Organic modified clay mineral (Modification example U 1 1 POL0 (6) Octadexenyl ether 2 2 Ultraviolet absorbent (Refer to Table 26)-2 This paper size applies the Chinese National Standard (CNS) A4 specification (210 &gt; &lt; 297 mm) 48 3 8 5 1 4 470653 A7 B7 V. Explanation of the invention (4 7) (2) Modulation method Example 7 is in accordance with the foregoing Example 6. Comparative Example 4 is in accordance with the foregoing Comparative Example 2. (3.) Evaluation and Evaluation Method The emulsion of Table 25 is observed in the aforementioned manner. Check the changes in particle size or changes in emulsification status such as separation and discoloration, and evaluate its emulsification stability. The storage period is 25 scoops for 6 months or 50 t: 2 months. (4) Results Table 26: Emulsification stability Sex

紫外線吸收劑 乳化安定性 實施例7-1 2,4-二羥基二苯基_ ◎ (0/W/0) 2 2,2’-二羥基-4-甲氣基二苯基酮 ◎ 3 2,2’-二羥-4,4'-二甲氧基二苯基酮 ◎ 4 2,2’，4,4’-四羥基二苯基酮 ◎ 5 2-羥基-4-甲氣基二苯基酮 0 6 2-羥基-4-甲氧基-4’-甲基二苯基酮 ◎ 7 3-(4’-甲基苯亞甲基）-d,卜樟腦 0 8 3-苯亞甲基-d,卜樟腦 0 9 4-甲氣基-4’-第三-丁基二苯甲醯甲烷 ◎ 比較例4-1 2,4-二羥基二苯基酮 X (W/0) 2 2,2’-二羥基-4-甲氣基二苯基酮 X 3 2,2’-二羥-4,4’-二甲氧基二苯基酮 X 4 2,2’，4,4'-四羥基二苯基酮 X 5 2-羥基-4-甲氣基二苯基酮 X 6 2-羥基-4-甲氧基-4’-甲基二苯基酮 X 7 3-(4’-甲基苯亞甲基）-d,卜樟腦 X 8 3-苯亞甲基-d,卜樟腦 X 9 4-甲氣基-4’-第三-丁基二苯甲醯甲烷 X 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210Χ 297公釐） 經濟部中央標準局員工消費合作社印製 4 9 (請先閱讀背面之注意事項再填寫本頁) 3 8 5 1 4 470653 A7 B7 五、發明説明（48 ) 由表26可知，比較例之W/0型乳液中紫外線吸收劑因 經濟部中央標準局員工消費合作社印製 存在於直接與空氣接觸之 外油相中 ，而有變色 或油分離等 情形，但相對地實施例中 無論在何 種場合乳化 安定性均佳 0 因此，本發明之油包 水包油型 乳液可用以 調製乳化安 定性優良之防晒用化粧用 品。 奮旃例8好K*.較例5〜β 其次，以表2 7所示之配方改變 内油相中配 合之不飽和 脂肪酸類調製0/W/0型乳液或W/0及0/W型乳液， 測定其藥 劑安定性。 (1 )組成 表27 組成成分 實施例8 比較例5 比較例6 (0/W/0) (W/0) (0/W) U)界面活性劑相 1,3-丁二醇 10 10 10 Ρ0Ε(60)硬化蓖麻油 1 - 1 對羥基苯甲酸甲酯 0.1 0.1 0.1 (b)内油相 液體石蠟 5 - 5 四-2-乙基己酸季戊四醇 5 - 5 十六烷醇 - - 2 不飽和脂肪酸類（表28參照） 1 - 1 (C)水相 純水 46.9 57.9 75.9 (d)外油相 液體石蠟 10 10 - 異構鏈石蟠 10 10 - 三十磺烷 10 10 - 有機改質粘土礦物（調製例1) 1 1 不飽和脂肪酸類（表28參照） - 1 - (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準（CNS ) Λ4規格（210X297公釐） 50 3 8 5 1 4 470653 本年月曰 補充侧，6. 4 五、發明説明（4 9 ) (2) 調製方法 啻确例8 依照前述實_例6調製。 比龄例5Ultraviolet absorbent emulsification stability example 7-1 2,4-dihydroxydiphenyl_ ◎ (0 / W / 0) 2 2,2'-dihydroxy-4-methylaminodiphenyl ketone ◎ 3 2 , 2'-Dihydroxy-4,4'-dimethoxydiphenyl ketone ◎ 4 2,2 ', 4,4'-tetrahydroxydiphenyl ketone ◎ 5 2-hydroxy-4-methylaminodiphenyl Phenyl ketone 0 6 2-hydroxy-4-methoxy-4'-methyldiphenyl ketone ◎ 7 3- (4'-methylbenzylidene) -d, camphor 0 8 3-phenylene Methyl-d, camphor 0 9 4-methylamino-4'-tertiary-butyldibenzoylmethane ◎ Comparative Example 4-1 2,4-dihydroxydiphenyl ketone X (W / 0) 2 2,2'-dihydroxy-4-methoxydiphenyl ketone X 3 2,2'-dihydroxy-4,4'-dimethoxydiphenyl ketone X 4 2,2 ', 4, 4'-tetrahydroxydiphenyl ketone X 5 2-hydroxy-4-methylamino diphenyl ketone X 6 2-hydroxy-4-methoxy-4'-methyldiphenyl ketone X 7 3- ( 4'-methylbenzylidene) -d, bucamole X 8 3-benzylidene-d, bucamole X 9 4-methylamino-4'-tertiary-butyldiphenylmethane X This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm). Employees' Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs System 4 9 (Please read the precautions on the back before filling this page) 3 8 5 1 4 470653 A7 B7 V. Description of the invention (48) As can be seen from Table 26, the UV absorber in the W / 0 emulsion of the comparative example is economical because of its economy. Printed by the Consumers' Cooperative of the Ministry of Standards of the People's Republic of China exists in the oil phase directly in contact with air, and there are cases of discoloration or oil separation. However, the emulsification stability is relatively good in any case in the examples. The oil-in-water-in-oil emulsion of the invention can be used for the preparation of sunscreen cosmetics with excellent emulsification stability. Example 8 is good K *. Comparative example 5 ~ β Secondly, the formula shown in Table 2 7 is used to change the unsaturated fatty acids in the internal oil phase to prepare 0 / W / 0 emulsion or W / 0 and 0 / W. Type emulsion, and its drug stability was measured. (1) Composition Table 27 Composition Example 8 Comparative Example 5 Comparative Example 6 (0 / W / 0) (W / 0) (0 / W) U) Surfactant phase 1,3-butanediol 10 10 10 POE (60) hardened castor oil 1-1 methyl parahydroxybenzoate 0.1 0.1 0.1 (b) internal oil phase liquid paraffin 5-5 tetra-2-ethylhexanoic acid pentaerythritol 5-5 cetyl alcohol--2 no Saturated fatty acids (refer to Table 28) 1-1 (C) Pure water in the aqueous phase 46.9 57.9 75.9 (d) Liquid paraffin in the outer oil phase 10 10-Heterophosphine 10 10-Trisulcan 10 10-Organic modification Clay minerals (Example 1) 1 1 Unsaturated fatty acids (refer to Table 28)-1-(Please read the precautions on the back before filling this page) The paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) ) 50 3 8 5 1 4 470653 This month, the supplementary side, 6. 4 V. Description of the invention (4 9) (2) Modulation method 啻 Confirmation Example 8 Modulation is performed according to the foregoing example _ Example 6. Specific age example 5

依照前述比較例2調製。 hh龄例R 將（a)成分溶解混合均勻，再一面攪拌一面與加熱溶 解之（b)成分混合、分散、乳化成界面活性劑相中油型乳 化組成物，再將（c)成分加入混合即得0/W型乳液。 (3) 評估方法 依照前述實施例6。 (4) 結果 表28:各種乳液之特性評定 不飽和脂肪酸類 乳化安定性 藥劑殘餘率 變色 變臭 形態観察 (% ) 實施例8— 1 γ -亞麻油酸 ◎ ◎ 〇 98.1 (0/W/0) 2 花生四烯酸 ◎ 0 ◎ 94.5 3 二十碳五烯酸 ◎ 〇 〇 92.1 4 二十二碳六烯酸 ◎ 〇 〇 90.2 5 二十二碳六烯酸甲酯 ◎ 〇 0 97.8 6 二十二碳六烯酸乙酯 ◎ 〇 ◎ 99.2 比較例5 - 1 7 -亞麻油酸 〇 Δ ◎ 60.9 (W/0) 2 花生四烯酸 Δ Δ 〇 52.5 3 二十碳五烯酸 X X 〇 48.8 4 二十二碳六烯酸 X X 〇 45.2 5 二十二碳六烯酸甲酯 X X 〇 58.4 6 二十二碳六烯酸乙酯 X X ◎ 63.3 比較例6— 1 7 -亞麻油酸 〇 Δ ◎ 52.1 (0/W) 2 花生四烯酸 △ X ◎ 42.3 3 二十碳五烯酸 Δ X 〇 40.6 4 二十二碳六烯酸 X X 〇 32.7 5 二十二碳六烯酸甲酯 X X 〇 68.4 6 二十二碳六烯酸乙酯 Δ X 〇 65.7 本紙張尺度適用中國國家標準（CNS )八4規格（21〇'〆297公釐） 經濟部智慧財產局員工消費合作社印製 1 - I---I n 1 衣-I - I - I ^ (請先閱讀背面之注意事項再填寫本頁) 51 (修正頁）38514 470653 A7 B7五、發明説明（50 ) 由表2 8可知，外油相中配合有機改質拈土礦物之0 / W / 0型乳液（實施例8 - 1〜8 - 6 )中油分等均無分離或變色、變 臭情形，因此乳化安定性佳，藥劑殘餘率極高。 相對地，比較例5 - 1〜5 - 6之W / 0型中，雖然無油相分 離而有安定之乳化狀態，但因外油相中配合藥劑（不飽和 脂肪#類），藥劑之殘餘量明顯因氣化分解減少，變色或 變臭亦顯箸。 此外，在ϋ較例6 - 1〜6 - 6之類0 / W乳液之場合，乳化 狀態安定但藥劑安定性差，變色、變臭亦顯著。 奮旃例9 其次，亦檢討油相中配合矽氧糸油分之場合。以處下 述表29〜32之乳液各依照前述表3-6之方法調製。 表29 : 0/W型乳液 經濟部中央標準局員工消費合作社印製Modulation was performed according to the aforementioned Comparative Example 2. hh age example R Dissolve and mix the component (a) uniformly, and mix, disperse, and emulsify with the component (b) dissolved by heating while stirring to form an oil-based emulsified composition in the surfactant phase, and then add the component (c) to the mixture to mix. A 0 / W type emulsion was obtained. (3) Evaluation method According to the foregoing Example 6. (4) Results Table 28: Evaluation of the characteristics of various emulsions Unsaturated fatty acid emulsion stabilizers Residual rate change discoloration and odor observation (%) Example 8-1 γ-Linolenic acid ◎ 98.1 (0 / W / 0 ) 2 Arachidonic acid ◎ 0 ◎ 94.5 3 Eicosapentaenoic acid ◎ 〇092.1 4 Docosahexaenoic acid ◎ 0090.2 0.2 5 Methyl docosahexaenoic acid ◎ 0 97.8 6 Twenty Ethyl dihexaenoate ◎ 〇 ◎ 99.2 Comparative Example 5-1 7-Linoleic acid 〇Δ ◎ 60.9 (W / 0) 2 Arachidonic acid Δ Δ 〇52.5 3 Eicosapentaenoic acid XX 〇48.8 4 Docosahexaenoic acid XX 〇45.2 5 Methyl docosahexaenoate XX 〇58.4 6 Ethyl docosahexaenoate XX 63.3 Comparative Example 6-17-Linoleic acid 〇Δ ◎ 52.1 (0 / W) 2 Arachidonic acid △ X ◎ 42.3 3 Eicosapentaenoic acid Δ X 〇40.6 4 Docosahexaenoic acid XX 〇32.7 5 Methyl docosaenoate XX 〇68.4 6 Ethyl docosahexaenoate Δ X 〇 65.7 This paper size is applicable to China National Standard (CNS) 84 (21 ° '297 mm) Printed by the Consumer Cooperative of the Property Bureau 1-I --- I n 1 Yi-I-I-I ^ (Please read the precautions on the back before filling out this page) 51 (Revised page) 38514 470653 A7 B7 V. Description of the invention (50) As can be seen from Table 2-8, there is no separation or discoloration or odor in the oil content of the 0 / W / 0 type emulsion (Examples 8-1 to 8-6) in which the organic modified vermiculite mineral is mixed in the outer oil phase. In this case, the emulsification stability is good, and the drug residue rate is extremely high. On the other hand, in the W / 0 type of Comparative Examples 5-1 to 5-6, although there is no oily phase separation and a stable emulsified state, the remaining oil due to the addition of a pharmaceutical agent (unsaturated fat #) in the external oil phase The amount is obviously reduced due to gasification and decomposition, and the discoloration or odor is also noticeable. In addition, in the case of 0 / W emulsions such as Comparative Examples 6-1 to 6-6, the emulsified state is stable but the stability of the drug is poor, and the discoloration and odor are also significant. Fendi Example 9 Secondly, the occasion where the siloxane oil is mixed in the oil phase is also reviewed. The emulsions in Tables 29 to 32 described below are each prepared according to the methods of Tables 3-6. Table 29: 0 / W type emulsion Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

組成成分 實施例9 -1 (a )界面活性劑相 1 , 3-丁二醇 2 1 純水 2 P 0 E ( 6 0 )硬化1麻油 2 (b)油相 液體石蟠 33 (c)水相 純水 42 乳化安定性（形態觀察） 室溫 〇 50 ^ 〇 使用感 X ---------- ------訂 (請先閲讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 5 2 3 8 5 1 4 470653 A7 B7 五、發明説明（51 ) 表30: W/0型乳液 經濟部中央標準局員工消費合作社印製 組成成分 9-2 9-3 實 9-4 施例 9-5 9-6 9-7 (a)界面活性劑 Ρ0Ε甲基聚矽氧烷共聚體〃 1 5 10 - - - Ρ0Ε甲基聚矽氧烷共聚體 (b)油相 — — _ 1 5 10 十甲基-環五矽氣烷 39 35 30 - - - 八甲基-環四矽氣烷 (C)水相 ~ — — 39 35 30 離子交換水 60 60 60 60 60 60 乳化安定性（形態觀察） 室溫 〇 〇 〇 〇 〇 〇 50Ό 〇 0 〇 〇 〇 0 使用感 〇 〇 〇 〇 0 〇 *1:商品名矽氣SC9450N(信越化學工業（股）製） *2:商品名矽氧KP6015(信越化學工業（股）製） 本紙張尺度適用中國國家標準（CNS ) Α4規格（210'乂297公釐） 53 38514 (請先閱讀背面之注意事項再填寫本頁) 470653 A7 B7 五、發明説明（52 ) 表31:油包水包油型乳液 組成成分 9-8 9-9 實 9-10 施例 9-11 9-12 9-13 (a)0/W相 實施例9-1之0/W型乳液 70 70 70 70 70 70 (b)外油相 十甲基-環五矽氣烷 29 25 20 - - - 八甲基-環四矽氧烷 - - - 29 25 20 (C)親油性界面活性劑 Ρ0Ε甲基聚矽氧烷共聚體η 1 5 10 - - - POE甲基聚矽氧烷共聚體2:2 - - - 1 5 10 (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 乳化安定性 形態觀察（室溫） X X X X X X (50^) X X X X X X 内油相殘餘率（50=08週後） &lt;5 &lt;5 &lt;5 &lt;5 &lt;5 &lt;5 使用感 Δ Δ Δ Δ △ Δ *1〜2:同表30。 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X2·97公釐） 54 38514 470653 A7 B7 五、發明説明（53 ) 表32:油包水包油型乳液 經濟部中央標準局員工消費合作社印製 構成成分 9-14 9-15 實施例 9-16 9-17 9-18 (a)0/W相 實施例9-1之0/W型乳液 70 70 70 70 70 (b)外油相 十甲基-環五矽氣烷 28 28 28 28 28 (C)外油相中之界面活性劑 有機改質粘土礦物* 2 - - - - 未改質粘土礦物（美膠） - 2 - - - 氨化苯甲基二甲基十八醯銨 - - 2 - - Ρ0Ε甲基聚矽氣烷共聚體《 - - - 2 - 氣化苯甲基二甲基十八醯銨 +Ρ0Ε甲基聚矽氧烷共聚體料 - - - - 2 乳化安定性 形態觀察（室溫） 〇 X X X X (50¾) 0 X X X X 内油相殘餘率（50108週後） 98 &lt;5 &lt;5 &lt;5 &lt;5 使用感 ◎ 〇 0 〇 〇 *調製例〗中有機改質粘土礦物以Ρ0Ε甲基聚矽氧烷共聚體（矽氣SC9450N,信 越化學工業（股）製）取代Ρ0Ε(6)十二醚調製。 *矽氣SC9450N(信越化學工業（股）製）。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 55 38514 (請先閱讀背面之注意事項再填寫本頁) 470653 修正 本年月Θ補充8a 6. ί 4Composition Example 9 -1 (a) Surfactant phase 1, 3-butanediol 2 1 Pure water 2 P 0 E (60) Hardened 1 sesame oil 2 (b) Oil phase liquid stone concrete 33 (c) Water Phase pure water 42 Emulsification stability (morphological observation) Room temperature 〇50 ^ 〇 Feel of use X ---------- ------ Order (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 5 2 3 8 5 1 4 470653 A7 B7 V. Description of the invention (51) Table 30: W / 0 type emulsion Ministry of Economics Central Standards Bureau staff consumption Cooperative printed composition 9-2 9-3 Example 9-4 Example 9-5 9-6 9-7 (a) Surfactant PO 0E methyl polysiloxane copolymer 〃 1 5 10---POE E Polysiloxane compound (b) oil phase — _ 1 5 10 Decamethyl-cyclopentasilane 39 35 30---Octamethyl-cyclotetrasiloxane (C) water phase ~ — — 39 35 30 Ion-exchanged water 60 60 60 60 60 60 Emulsification stability (morphological observation) Room temperature 〇 〇〇〇〇〇〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 * 1: Trade name silicon gas SC9450N (Shin-Etsu Chemical Industry Co., Ltd. System) * 2: Trade name Silicon Oxide KP6015 (Shin-Etsu Chemical Industry Co., Ltd.) This paper size is applicable to China National Standard (CNS) A4 specification (210 '乂 297 mm) 53 38514 (Please read the precautions on the back before (Fill in this page) 470653 A7 B7 V. Description of the invention (52) Table 31: Composition of oil-in-water-in-oil emulsion 9-8 9-9 Example 9-10 Example 9-11 9-12 9-13 (a) 0 / W phase 0 / W emulsion of Example 9-1 70 70 70 70 70 70 (b) Decamethyl-cyclopentasilane 29 25 20---Octamethyl-cyclotetrasiloxane Alkane---29 25 20 (C) Lipophilic surfactant POE methyl polysiloxane copolymer η 1 5 10---POE methyl polysiloxane copolymer 2: 2---1 5 10 ( Please read the notes on the back before filling in this page) Observation of the emulsion stability morphology printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (room temperature) XXXXXX (50 ^) XXXXXX Oil phase residual rate (after 50 = 08 weeks) &lt; 5 &lt; 5 &lt; 5 &lt; 5 &lt; 5 &lt; 5 Usability Δ Δ Δ Δ Δ Δ Δ * 1 ~ 2: Same as Table 30. This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X2 · 97 mm) 54 38514 470653 A7 B7 V. Description of the invention (53) Table 32: Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation component 9-14 9-15 Example 9-16 9-17 9-18 (a) 0 / W phase Example 9-1 0 / W type emulsion 70 70 70 70 70 (b) External oil phase Methyl-cyclopentasilane 28 28 28 28 28 (C) Surfactant in the external oil phase Organically modified clay minerals * 2----Unmodified clay minerals (beauty)-2---Ammonia Benzyl dimethyl octadecyl ammonium--2--POE methyl polysilazane interpolymer "---2-vaporized benzyl dimethyl octadecylammonium + POE methyl polysiloxane Alkane copolymer----2 Observation of emulsification stability (room temperature) XXXXXX (50¾) 0 XXXX Oil phase residual rate (after 50108 weeks) 98 &lt; 5 &lt; 5 &lt; 5 &lt; 5 feeling of use ◎ 〇0 〇〇 ＊ Preparation example: In the organic modified clay mineral, POE methyl polysiloxane copolymer (silicon gas SC9450N, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) is used to replace POE (6) Diether modulation. * Silicon gas SC9450N (made by Shin-Etsu Chemical Industry Co., Ltd.). This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 55 38514 (Please read the precautions on the back before filling out this page) 470653 Amendment This month Θ Supplement 8a 6. ί 4

7 7 A B 經濟部智慧財產局員工消費合作社印製 五' 發明説明（5 4 ) 1 1 參 考 前 述表29及 表 30可 知 無論0/W型乳液或W/0型乳 1 1 液 » 若 選 擇 適 當 之 界 面 活性 劑 即 可 得 相 當 高 之 乳 化安 定 性 1 〇 然 而 將 此 安 定 之 0 / W型乳液分散| 今含矽氧油分之外油相 /·—S 請 1 先 1 中 成 油 包 水 包 油 型 乳 液 之場 合 9 則 如 表 3 1所示乳化安定性 閱 讀 1 背 1 大 為 減 低 9 特 別 是 内 油 相會 滲 出 於 外 油 相 中 0 之 1 注 1 相 件t 對 地 &gt; 如 上 逑 表 32所示 t 於 含 矽 氧 系 油 分 之油 包 水 意 事 1 項 I 包 油 型 乳 液 中 若 外 油 相中 配 合 有 機 改 質 粘 土 礦 物， 則 其 再 填 1 乳 化 安 定 性 之 形 態 觀 察 及內 油 相 殘 餘 率 均 極 佳 可得 到 良 寫 本 頁 1 好 之 乳 化 安 定 性 〇 1 | 此 外 9 於 實 施 例 9- 1 4中 t 含 矽 氧 糸 油 分 且 外 相中 配 合 1 I 有 機 機 改 質 粘 土 礦 物 之 多 重乳 液 9 在 塗 抹 皮 虜 時 使 用感 延 1 1 訂 展 性 極 佳 清 爽 Λ 不 粘 腻， 與表30中其油成份為矽氧 系 油 1 之 W/0型乳液或表31中之多重乳液比較， 其使用感極為良 1 1 好 〇 1 1 表32中 使 用 八 甲 基 環六 矽 氧 烧 取 代 十 甲 基 環 五矽 氧 烷 1 之 場 合 亦 有 同 樣 之 结 果 0 1 | 因 此 如 上 述 般 f 單將安定之0/W型乳液取代成安定之 1 I W/0型乳液中之水相時仍無法得到安定之含矽氧条油分多 1 1 1 重 乳 液 9 調 製 時 矽 氧 糸 油分 與 非 矽 氧 % 油 分 分 別 配合 在 各 1 1 油 相 中 時 亦 m 法 保 持 其 安定 〇 相 對 地 9 外 油 相 中 配合 有 機 1 1 改 質 粘 土 礦 物 時 可 抑 制 內油 相 與 外 油 相 之 合 一 &gt; 因此 可 得 1 1 到 安 定 之 含 矽 氧 系 油 分 多重 乳 液 ， 調 製 時 矽 氧 糸 油分 與 非 1 I 矽 氧 系 油 分 分 別 配 合 在 各油 相 中 時 9 可 使 其 安 定 地獨 立 保 1 I 持 在 一 乳 液 中 〇 此 外 9 其使 用 感 與 含 矽 氧 系 油 分 之W/0型 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ，…卞试、 0 „ r , „ 56 (修正頁） 38514 470653 A7 B7 五、發明説明（5 5 ) 乳液比較極為良好。 實施110 其次，以一種紫外線吸收劑4 -第三-丁基- 4’-甲氧基 二苯甲醯甲烷為矽氧糸油分難溶性脂溶性藥劑檢討此多重 乳救中防止其結晶析出之效果。同時亦檢討其使用感。下 述表3 3 - 3 6乳液之調製方法則依照前述表3 - 6之方法。 表3 3 : 0 / VI型乳液 組成成分 實施例1 0 - 1 (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 (a )界面活性劑相 1 , 3-丁二醇 21 純水 2 P 0 E ( 6 0 )硬化Μ麻油 2 (b )油相 琥珀酸二辛酯 31 4-第三-丁基- 4’-甲氧基二苯甲醯甲烷 2 (c )水相 純水 427 7 AB Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 'Invention Description (5 4) 1 1 Refer to the aforementioned Table 29 and Table 30 to know whether the 0 / W type emulsion or W / 0 type milk 1 1 liquid» if appropriate Surfactant can obtain quite high emulsification stability 1 〇 However, this stable 0 / W type emulsion dispersion | today's oil-containing oily phase / · —S please 1 first 1 into oil-in-water package For oil-based emulsions, 9 is shown in Table 3. Emulsification stability is shown in Table 1. 1 Back 1 is greatly reduced. 9 In particular, the internal oil phase will leak out of the external oil phase. 0 1 Note 1 Phase t to the ground &gt; as above. Table 32 shows the water-in-oil content of silicon-containing oils. Item I I oil-in-oil emulsion If the external oil phase is mixed with organic modified clay minerals, then it is filled again. 1 Emulsification stability and morphological observation Excellent oil phase residual ratio is available Write this page 1 Good emulsification stability 〇1 | In addition 9 in Example 9- 1 4 t Contains siloxane oils and blends with 1 in external phase 1 I Multiple emulsions of organically modified clay minerals 9 Use when applying pimple Feeling 1 1 Excellent ordering and refreshing Λ non-sticky, compared with the W / 0 emulsion in Table 30 whose oil content is silicone oil 1 or the multiple emulsion in Table 31, the use feeling is very good 1 1 Good 〇1 1 In Table 32, the same result is obtained when octamethylcyclohexasiloxane is used instead of decylcyclopentasiloxane. 0 1 | Therefore, as above, f will stabilize the 0 / W emulsion. When the water phase in the stable 1 IW / 0 emulsion is replaced, the stable silicon oil containing oil is still not available. 1 1 1 Heavy emulsion 9 The silicon oil and the non-silicone oil content are mixed in each 1 1 In the oil phase, the method is also used to maintain its stability. Relatively 9 In the outer oil phase, organic 1 1 is used to improve the viscosity. When mineral is used, the combination of the internal oil phase and the external oil phase can be suppressed. Therefore, a multiple emulsion containing 1 1 to stable silicone-containing oil can be obtained. When it is in the oil phase, 9 can make it stable and independent. 1 I keep it in an emulsion. In addition, 9 its feeling of use and W / 0 type containing silicone oil. 1 This paper size applies the Chinese National Standard (CNS) A4 specification ( 210X297 mm), ... test, 0 „r,„ 56 (revised page) 38514 470653 A7 B7 V. Description of the invention (5 5) The emulsion is very good. Implementation 110 Secondly, a UV absorber 4-tert-butyl-4'-methoxydibenzoylmethane is used as a silicone oil. The oil-soluble and fat-soluble agent is reviewed for the effect of preventing the crystallization of the multiple milk during the rescue. . It also reviews its sense of use. The preparation method of the emulsions in Tables 3 to 3 6 described below follows the method in Tables 3 to 6 described above. Table 3 3: Composition of Type 0 / VI Emulsion Example 1 0-1 (Please read the precautions on the back before filling out this page) Printed by (a) Surfactant Phases 1, 3 from Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs -Butanediol 21 Pure water 2 P 0 E (60) Hardened sesame oil 2 (b) Oil phase dioctyl succinate 31 4-Third-butyl-4'-methoxydibenzomethane 2 (c) Pure water 42

乳化安定性（形態觀察） 室溫 〇 5 0 Ό 〇 結晶析出 Ο (無） 使用感 X 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 470653 A7 B7 五、發明説明（5 6 ) 表3 4 : W / 0型乳液 經濟部中央標準局員工消費合作社印製 組成成 分 實施 10-2 例 10-3 U)界面活性 劑 Ρ0Ε甲基聚矽 氧烷共 聚體=!= 5 5 (b)油相 十甲基-環五 矽氧烷 33 - 八甲基-環四 矽氣烷 - 33 4-第三-丁基 -4，-甲 氣 基二苯甲醯甲烷 2 2 (c )水相 離子交換水 60 60 乳化安定性| (形態觀 察） 室溫 0 〇 50 t： 〇 〇 結晶析出 X (有） X (有） 使用感 0 0 *矽氧S C 9 4 5 0 N (信越化學工業（股）製） (請先閲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 ) A4規格（210X297公釐） 5 8 3 8 5 1 4 470653 經濟部中央標準局員工消費合作社印製 Α7 Β7 五、發明説明（57 ) 表3 5 :油包水包油 型乳液 實施 例 組成成分 10-4 10-5 (a ) 0 / W相[内油相含4 -第三-丁基-4 ’ -甲氣基二 苯甲醯甲烷] 實施例1 0 - 1之0 / W型乳液 70 70 (b)外油相 十甲基-環五矽氣烷 25 一 八甲基-環四矽氧烷 - 25 (C)親油性界面活性劑 Ρ0Ε甲基聚矽氧烷共聚體* 5 5 乳化安定性 形態觀察（室溫） X X (501C ) X X 内油相殘餘率（50t： 8週間後） &lt;5 &lt;5 結晶析出 X (有） X (有） 使用感 Δ Δ *矽氣SC9 450 M信越化學工業（股）製） 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 59 385 1 4Emulsification stability (morphological observation) Room temperature 0 5 0 Ό 〇 Crystal precipitation 0 (None) Feeling of use X This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 470653 A7 B7 V. Description of the invention ( 5 6) Table 3 4: W / 0 emulsion, printed by the Central Standards Bureau of the Ministry of Economic Affairs, employee consumer cooperatives, print out the composition 10-2 Example 10-3 U) Surfactant POE methyl polysiloxane copolymer =! = 5 5 (b) Decamethyl-cyclopentasiloxane 33-octamethyl-cyclotetrasilazane-33 4-tertiary-butyl-4, -methyldibenzoylmethane 2 2 ( c) Aqueous ion-exchanged water 60 60 Emulsification stability | (morphological observation) room temperature 0 〇50 t: 〇〇 crystal precipitation X (yes) X (yes) feel 0 0 * silicon oxygen SC 9 4 5 0 N ( Shin-Etsu Chemical Industry Co., Ltd. (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 5 8 3 8 5 1 4 470653 Central Standard of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives A7 B7 V. Description of Invention (57) Table 3 5 : Example of oil-in-water-in-oil emulsion Composition 10-4 10-5 (a) 0 / W phase [internal oil phase contains 4 -third-butyl-4'-methylaminodibenzoylmethane] Example 1 0-1 of 0 / W type emulsion 70 70 (b) Decamethyl-cyclopentasilane 25-octamethyl-cyclotetrasiloxane- 25 (C) lipophilic surfactant POL0 methyl polysiloxane copolymer * 5 5 Emulsification stability morphology observation (room temperature) XX (501C) XX internal oil phase residual rate (50t: after 8 weeks) &lt; 5 &lt; 5 crystal precipitation X (yes) X (Yes) Feeling Δ Δ * Silicon gas SC9 450 M manufactured by Shin-Etsu Chemical Industry Co., Ltd. The paper size is applicable to China National Standard (CNS) Α4 specification (210X297 mm) 59 385 1 4

----------^------1T (請先閲讀背面之注意事項再填寫本頁) 470653 A7 B7 五、發明説明（58 ) 表36: 0/W/0型乳液 組成成分 實 10-6 施例 10-7 (a)0/W相[内油相中含4-第三 -丁基-4’-甲氧基二苯甲醯甲烷] 實施例10-1之0/W型乳液 70 70 (b&gt;外油相 十甲基-環五矽氣烷 28 - 八甲基-環四矽氣烷 - 28 (C)外油相中之界面活性劑 有機改質粘土礦物 2 2 (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 乳化安定性 形態觀察（室溫） 〇 〇 (50^ ) 〇 〇 内油相殘餘率（50t：8週間後） 98 98 結晶析出 〇（無） 〇（無） 使用感 ◎ ◎ *同表32中使用者。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 60 38514 470653 修正 本年月曰 A7 補充 89。6. 14 B7 五、發明説明（5 9) 由前述表33及表34可知，即使在油相中配合脂溶性藥 劑（4 -第三-丁基-4’-甲氧基二苯甲醸甲烷）之場合，仍可 得到高乳化安定性之o/y型乳液及W/0型乳液，但未配合矽 氧系油分之場合，藥劑不析出但使用感差，而配合矽氧系 油分時使用感可以改善，但長期間後藥劑會析出。 因此，為求能有矽氧系油分之使用感及防止藥劑结晶 析出之效果，將表33中之安定0/W型乳液分散於含矽氧系 油分之油相中，調製0/W/0型乳液，如表35之情形，其乳 化安定性大為降低，由於內油相滲出於外油相中，無法得 到預期之防止结晶析出的效果。此外，使用感亦有變差之 趨勢。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 機殘之 丁 線好 質抑 油一糸 有相相__外良 改可内在氧 合油油I-&amp; 紫常 機亦而如矽 第 油 配內外 ， ％ 止非 有 ，因例非 中、與(4C 防感 有時。而之 氧 相.態相劑 效腻 因分性 ，劑 油形油藥 有粘 中油定中藥 外化内性 可無 相糸安糸該 ，乳中溶 此亦 油氧 化一解 形與液 難 因上 外矽 乳同溶 情性乳之一 ，感 其份高於與 之 定重合 W 中用 ，成 到在劑 中安多 配 } 相使 液油 得存藥 36化該中 烷油其 乳有 ，立性 表乳 ，相 甲外 ， 重合一獨溶 述 ，此油醢至外 多配合地難 上 合因內 甲動此 之使 之定分 在場。 ，苯移。 明即 相安油 如之好制 二不出 發 ，油 以系 ，物良抑基亦析 本在 外可氧 地礦為到氧 ，晶 ，存與相矽 對 土極受 甲少结 此 物相油 K 相粘均可'極劑 因礦油外中 質率 1-4觸收 土 內與相 改餘合基 接吸。 粘 制相油 61 (修正頁） 385 1 4 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 470653 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（60 ) 油分配合，另一油相中則配合矽氧条油分時，所得的乳液 中彼此可在一糸中安定地共存，可防止該藥劑析出，而且 使用感極為良好。 奮施例11 其次檢討矽氧条油分難溶性藥劑與含矽氧糸油分之多 重乳液的適當組成比。 (1)組成 表3 7 : 0 / W型乳液之組成 ----------裝------訂------ (請先閱讀背面之注意事項再填寫本頁) 組成成分 含有量 (a )界面活性劑相 1 , 3 - 丁二醇 21 純水 2 P 0 E ( 6 0 )硬化里麻油 2 (b )内油相 琥珀酸二辛酯 3 1 4-第三-丁基- 4’-甲氣基二苯甲醯甲烷 2 (c )水相 純水 42 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 6 2 3 8 5 1 4 470653 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（61 ) 表3 8 :外油相之組成 組成成分 含 有量 (d )界面活性劑 有機改質拈土礦物（調製例1) 7 (e )外油相 十甲基-環五 δ夕氧烷 93 表39 : 0 / W / 0型乳液之組成 比 實施例 0/W型乳液量 外油相 量 實施例U -1 50 50 實施例U - 2 60 40 實施例U -3 70 30 實施例U - 4 80 20 實施例11 - 5 35 65 實施例U -6 97 3 (2 )調製方法 依照前述實施例2調製。具體言之，即將上述表37中 記載之U)成分溶解混合均勻後一面擬拌一面將（b)成分加 ----------.裝------訂-------\ (請先閲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 ) A4規格（210X297公釐） 63 38 5 1 4 470653 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（62 ) 入混合乳化，再將（C )成分加入混合即得0 / W乳液。 將表38之外油相成分混合，再一面攪拌一面將上述調 製之0 / W型乳液加入外油相中混合、乳化，即得目的之0 / W/0型多重乳液。此外，將0/W型乳液與外油相之比例如上 述表39變化，所得的0/W/0型乳液各為實施例11-1至U-6。 (3)結果 表40:乳液待性評估 實施例 乳液形態 (調製後瞬間） 乳化安定性 RT 50¾ 内油相1 殘餘率 結晶 析出 實施例11-1 ϋ/νι/ο 〇 0 92 % 0 (無） 實施例11-2 0/W/0 ◎ 0 93 〇（無） 實施例11-3 0/W/0 ◎ ◎ 98 0 (無） 實施例11-4 0/V/0 0 〇 93 0 (無） 實施例11-5 0/W/0 X X - X (有） 實施例11-6 0/W/0+0/W X X .- X (有） ------------裝------訂------^ (請先閱讀背面之注意事項再填寫本頁) 1 内油相殘存率偽於5 0 , 1個月後測定者。 由上述表4 0可知，0 / W型乳液與外油相比在2 : 3〜1 9 : 1 之範圍外時無法得到安定之多重乳液，内油相中配合之藥 劑（4 -第三-丁基- 4’-甲氧基二苯甲醯甲烷）會結晶析出。 相對地，如實施例1 1 - 1〜U - 4 ,可知0 / W型乳液與外油相 比例在2:3〜19:1之範圍内之場合，条之乳化安定性良好， 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 6 4 3 8 5 14 470653 A7 B7 五、發明説明（63 ) 且可防止内油相中配合之藥劑結晶析出。 奮旃例1 2及hh較例7〜8 其次，依照表4 1所示之配方，調製各種配合有矽氣系 油分難溶性紫外線吸收劑之0 / W / 0型乳液或W / 0型乳液，測 (請先閲讀背面之注意事項再填寫本頁) 定防止在其内油相中配 (1 )組成 合之脂溶性藥劑結晶析出之效果 表41 組成成分 實施例12 比較例7 比較例8 (O/W/O) (W/0) (W/0) (a)界面活性劑相 1,3-丁二醇 5 5 5 P0E(60)硬化蓖麻油 1 - - 對羥基苯甲酸甲酯 0.1 0.1 0.1 (b)内油相 三十碩烷 5 - - 四-2-乙基己酸季戊四醇 5 - - 紫外線吸收劑（表42參照） 2 - - (C)水相 純水 48.9 59.9 59.9 經濟部中央標準局員工消費合作社印製 (d)外油相 琥珀酸二辛酯 9 9 30 二甲基聚矽氧烷 10 10 - 十甲基-環五矽氣烷 10 10 - 聚矽氧橡膠 1 1 - 有機改質粘土礦物（調製例1) 1 1 1 P〇E(6)硬脂醚 1 1 1 Ρ0Ε甲基聚矽氧烷共聚體* 1 1 1 紫外線吸收劑（表42參照） - 2 2 *矽氧SC9450JU信越化學工業（股）製） 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2丨OX 297公釐） 65 3 8 5 1 4 470653 A7 B7 五、發明説明（64 ) (2 )調製方法 實.施例12 依照前述實施例6。 卜卜.較例7及卜h較例8 依照前述比較例2。 (3 )評估方法 先以前述方法對表4 1之乳液觀察其形態，測定粒徑之 變化及分離等乳化狀態之變化，評估其乳化安定性。再於 保存期間2 5 t： 6値月或5 0 1C 2個月後再以前述方法評估防止 結晶析出之效果及使用感。 (4)結果 I--------裝------訂------^ (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 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） 66 3 8 5 1 4 470653 A7 B7 五、發明説明（65 ) 表42:乳液特性評估 經濟部中央標準局員工消費合作社印製 紫外線吸收劑 乳化安定性 結晶析出 使用感 實施例(0/W/0) 12-1 2,4-二羥基二苯基酮 ◎ 0 (無） ◎ 2 2; 2’-二羥基-4-甲氣基二苯基酮 ◎ 〇（無） ◎ 3 2,2’-二羥基-4,4'-二甲氧基二苯基酮 0 0 (無） ◎ 4 2,2’，4,4’-四羥二苯基酮 ◎ 0 (無） 0 5 2-羥基-4-甲氧基二苯基酮 ◎ 〇 (無） ◎ 6 2-羥基-4-甲氣基-4’-甲基二苯基酮 ◎ 〇 (無） ◎ 7 3-(4’-甲基苯亞甲基）-d，l-樟腦 ◎ 〇 (無） ◎ 8 3-苯亞甲基-d,l-樟腦 ◎ 〇 (無） ◎ 9 4-甲氣基-4’-第三-丁基二苯甲醯甲烷 ◎ 〇 (無） 0 比較例（W/0油型：含矽氣条油分） 7-1 2,4-二羥基二苯基酮 X X (有） 〇 2 2,2'-二羥基-4-甲氧基二苯基酮 X X (有） 〇 3 2,2^二羥基-4,4’-二甲氧基二苯基酮 X X (有） 〇 4 2,2',4,4’-四羥二苯基酮 X X (有） 〇 5 2-羥基-4-甲氧基二苯基酮 X X (有） 〇 6 2-羥基-4-甲氧基-4’-甲基二苯基酮 X X (有） 〇 7 3-(4’-甲基苯亞甲基）-d,卜樟腦 X X (有） 〇 8 3-苯亞甲基-d,l-樟腦 X X (有） 〇 9 4-甲氣基-4’-第三-丁基二苯甲醯甲烷 X X (有） 〇 比較例（W/0型：無矽氧糸油分配合） 8-1 2,4-二羥基二苯基酮 X 〇 (無） X 2 2,2’-二羥基-4-甲氣基二苯基酮 X 〇 (無） X 3 2,2’-二羥基-4,4’-二甲氧基二苯基酮 X 〇 (無） X 4 2,2’，4,4·-四羥二苯基酮 X 〇 (無） X 5 2-羥基-4-甲氣基二苯基酮 X 〇 (無） X 6 2-羥基-4-甲氧基-4’-甲基二苯基酮 X 〇 (無） X 7 3-(4’-甲基苯亞甲基樟腦 X 〇 (無） X 8 3-苯亞甲基-d,l-樟腦 X 〇(無） X 9 4-甲氣基-4’-第三-丁基二苯甲醯甲烷 X 0 (無） X 本紙張尺度適用中國國家標準（CNS ) A4規格（210'乂297公釐） 67 (請先閱讀背面之注意事項再填寫本頁) 38514 470653 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（66 ) 如表42所示，在比較例7中其外油相中含紫外線吸收 劑並配合矽氧油之W / 0型乳液，其粘腻感之點均較良好。 但紫外線吸收劑與其低溶解性之矽氧糸油分配合於同一油 相中時，保存中紫外線吸收劑會析出。 另一方面，如比較例8 ,在外油相中不配合矽氧油而 使用紫外線吸收劑溶解性高之極性油取代之W/0型乳液之 場合，長期間後雖無紫外線吸收劑析出，但卻有粘腻感， 使用感不佳。 相對地，本發明之0 / W / 0型乳液（實施例1 2 - 1〜9中無 結晶析出，乳化安定性亦佳。此外，其使用感清爽無粘腻 感，與比較例5乳液相較，所得之乳裔使用感佳。 由上述情形可知，在本發明之多重乳液中令矽氧糸油 分難溶性藥劑、非矽氧糸油分、矽氧糸油分之所謂低互溶 性成份並存於同一乳液糸中，所得的乳液可以防止該藥劑 結晶析出，乳化安定性及使用感極為良好，因此可以調製 成使用性及安定性良好之防曬化粧用品。 窨旃例1 3 於含矽氧糸油分之0 / W / 0型多重乳液中脂溶性藥劑使 用易氧化性之脂溶性維生素（維生素A十六烷酸酯）或易氧 化性之油溶性紫外線吸收劑（辛基二甲基對氨基苯甲酸酯） 以下述表43及表44配方中所示之各種成份變化其配合量， 調製0 / W / 0型多重乳液。調製方法則依照前述實施例6。 結果含矽氣糸油分之0 / W / 0型多重乳液中，0 / W型乳液 與外油相之l:b在2 : 3〜1 9 : 1之範圍内時，顯示糸之乳化安 定性及藥劑之氣化安定性良好。 H. --- - - I -- - - - j I t , m I i ---- ; I ---、waJ (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率（CNS ) A4規格（210X297公釐） 68 3 8 5 1 4 κΰ . 經濟部智慧財產局員工消費合作社印製 6 ο 7 4 3 修正 本年月曰 補充 89。5. - 4 A7 B7 五、發明説明（67 ) 表43: 組成比之檢討 實施例 組成成分 13-1 13-2 13-3 13-4 13-5 U)界面活性劑相 1,3-丁二酵 5 5 5 5 5 甘油 2 2 2 2 2 Ρ0Ε(60)硬化蓖麻油 1 1 1 1 1 對羥基苯甲酸甲酯 0.1 0.1 0.1 0.1 0.1 (b)内油相 三十碳烷 5 5 5 5 5 維生素A十六碳烷酸酯 0.2 0.2 0.2 0.2 0.2 (C)水相 純水 82.2 76.7 56.7 36.7 16.7 (d)外油相 八甲基-環四矽氧烷 2.1 7,6 27.6 47.6 67.6 陽離子改質粘土礦物（Bentone-38) 2 2 2 2 2 POE甲基聚矽氧烷共聚體* 0.4 0.4 0.4 0.4 0.4 油包水乳液：外油相（重量比） 21:1 9:1 7:3 5:5 3:7 乳化安定性（形態觀察） 501： X 〇 ◎ 〇 X 藥劑殘餘率 X 0 0 0 X *矽氧SC9450N (信越化學工業（股）製） (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準（CNS) A4規格（210X297公釐）69(修正頁） 38514 -裝. 訂 泉 5 6 ο 7 4 I修正 1 本年月曰 i補充 89. 5.-4 五、發明説明（⑽） 表44:組成比之檢討 經濟部智慧財產局員工消費合作社印製 實施例 組成成分 13-6 13-7 13-8 13-9 13-10 (a)界面活性劑相 1,3-丁二醇 5 5 5 5 5 甘油 2 2 2 2 2 P0E(60)硬化蓖麻油 1 1 1 1 1 對羥基苯甲酸甲酯 0.1 0.1 0.1 0.1 0.1 (b)内油相 甲氧基肉桂酸辛基酯 5 5 5 5 5 三-2-乙基己酸甘油酯 10 10 10 10 10 辛基二甲基對氨基苯甲酸酯 1 1 1 1 1 (C)水相 純水 70.75 65.3 45.3 25.3 5.3 (d)外油相 液體石蠘 0.65 2.6 9.2 16.0 22.6 十一甲基-環五矽氧烷 1.5 5.0 18.4 31.6 45.0 陽離子改質粘土礦物（Bentone-38) 1 1 1 1 1 POE (10)山梨糖醇脂肪酸酯 1 1 1 1 1 Ρ0Ε甲基聚矽氧烷共聚體* 1 1 1 1 1 油包水乳液：外油相（重量比） 21:1 9:1 7:3 5:5 3:7 乳化安定性（形態観察） 50¾ X 〇 ◎ 〇 X 槩劑殘餘率 Δ ◎ ◎ ◎ △ *矽氧SC9450N(信越化學工業（股）製) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 70(修正頁） 38514 ----------裝------訂------線 (請先閱讀背面之注意事項再填寫本頁) 470653 A7 B7 五、發明説明（69 ) 經濟部中央標準局員工消費合作社印製 窖掄例1 4及吐較例9〜1 0 其次，在含矽氧条油分 各種脂溶性維生素易氣化性 劑之藥劑殘餘率。 之多重乳 劑之場合 表45 液中，内油 ，測定該易 相中配合 氧化性藥 組成成分 實施例14 比較例9 比較例10 (0/W/0) (W/0) (0/W/0) (a)界面活性劑相 1, 3 - 丁二醇 5 5 5 P0E(60)硬化蓖麻油 1 - - 皂土 - - 0.5 對羥基苯甲酸甲酯 0. 1 0.1 0.1 (b)内油相 三十碩烷 5 - 5 四-2-乙基己酸季戊四醇 5 - 5 十六烷醇 - - 3 P0E(20)山梨糖醇三硬脂酸酯 - - 1 單油酸甘油酯 - - 2 脂溶性雒生素（表46參照） 1 - 1 (C)水相 純水 51.9 52.9 37.4 (d)外油相 液體石蟠 10 10 10 二甲基聚矽氧烷 10 10 10 十甲基-環五矽氣烷 10 10 10 有機改質粘土礦物（調製例1) 1 1 1 三十磺烷 - 5 - 四-2-乙基己酸季戊四醇 - 5 - 糊精十六酸酯 - - 1 十六烷醇 - - 3 蜜蠘 - - 2 山梨糖醇倍半油酸酯 - - 3 山梨糖醇單硬脂酸醋 - - 1 脂溶性維生素（表46參照） - 1 - (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準（CNS ) A4規格（210X297公釐） 7 1 3 8 5 1 4 470653 A7 B7五、發明説明（70 ) (2 )調製方法 窖旃例1 4 依照前述實施例6 ^ 比..較例 依照前述比較例2。 比..較.例.li 依照前述比較例3。 (3 )評估方法 依照前述方法評估形態觀察及藥劑殘餘率。此外，於 恒溫槽内保存1個月後仍同樣依照前述實施例6評估其變色 、變'臭。 (4)結果 ----------裝 訂 (請先閱讀背面之注意事項再填寫本貢) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2丨0'乂 297公釐） 72 3 8 5 1 4 470653 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（Ή ) 1 I 表46:各乳液待性之評估 1 1 1 .脂溶性維生素 乳化安定性 藥劑殘餘率 1 1 變色 變臭 形態觀察 (%) 請 先 閱 讀 1 1 I 1 1 實施例14-1 視黃醇 ◎ ◎ 〇 90.1 背 1¾ 1 | 之 1 (0/W/0) 2 維生素Α十六碩烷酸酯 ◎ ◎ 〇 97,5 意 1 3 維生素A乙酸酯 ◎ ◎ 〇 95.1 項 1 1 4 α -生育酚 ◎ ◎ 0 92.2 再 ύ 1 5 雒生素E乙酸酯 ◎ ◎ 〇 99.8 寫 本 頁 裝 1 6 維生素D2 ◎ ◎ 〇 93.2 1 7 /3-胡蘿®素 ◎ ◎ 〇 99.1 1 1 I 比較例9- -1 視黃醇 X X 〇 48.9 1 1 訂 (W/0) 2 維生素A十六磺烷酸酯 Δ Δ 〇 67.5 1 I 3 維生素A乙酸酯 Δ △ 〇 50.8 1 1 4 α -生育酚 Δ 0 〇 63,2 1 I 5 維生素Ε乙酸酯 〇 〇 0 70.4 1 6 維生素D2 Δ 〇 〇 83.3 、‘求 I 7 卢-胡籮葡素 Δ 〇 〇 87.1 1 1 | 比較例10 -1 視黃醇 X X X 12.1 1 1 (0/V/0) 2 維生素Α十六碳烷酸酯 X X X 22.3 1 I 3 維生素A乙酸酯 X X X 30.6 1 1 4 ot -生育酚 Δ Δ X 63.7 1 I 5 維生素E乙酸酯 Δ △ X 72.4 1 1 6 維生素1)2 Δ △ X 77,7 1 I 7 /9-胡籮萄素 Δ 〇 Δ 69.6 1 1 1 1 本纸張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 38514 η 470653 A7 B7五、發明説明（72 ) 由表46可知，與比較例9、 10比較，顯示本發明之多 重乳液（實施例】4-1〜14-7)為無油分離或變色、變臭，乳 化安定性佳，藥劑殘餘率亦極高之乳液。 實…施—例..1 5_ 其次檢討本發明之水相中配合親水性高分子之場合的 多重乳液C 表4 7 : 0 / W型乳液 經濟部中央標準局員工消費合作社印製 組成成分 實施例1 5 - 1 (a )界面活性劑相 1 , 3-丁二醇 21 純水 2 P 0 E ( 6 0 )硬化蓖麻油 2 (b )油相 液體石蠛 33 (c )水相 純水 39 褐藻酸鈉 3 乳化安定性（形態觀察） 室溫 〇 50V 〇 裝 訂 I π (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 ) Λ4規格（2ΙΟΧ297公釐） 7 4 3 8 5 1 4 470653 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 3 ) 〈調製方法〉 依照前述實施例1表3中之調製方法調製0 / W型乳液， 再對每1 0 0 g之乳液添加〗g之1 0 %氣化鈣水溶液使褐藻酸鈉 凝_化。 表48: W/0型乳液 組成成分 15-2 15-3 實施 15-4 例 15-5 15-6 15-7 (a)界面活性劑相 P0E(3)十八醚 1 - - - - - P0E(2)十八醚 - 5 - - - - 山梨糖醇單 - - 1 - - - 硬脂酸酯 - - - 5 - - P0E(10)硬化Μ麻油 - - - - 10 - Ρ0Ε(10)硬化蓖麻油 (b)油相 — _ _ — 5 液體石锄 (C)水相 39 35 39 35 30 35 離子交換水 57 57 57 57 57 57 褐藻酸鈉 3 3 3 3 3 3 乳化安定性（形態觀察） 室溫 〇 〇 0 〇 〇 〇 50它 〇 〇 〇 〇 〇 〇 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210Χ297公釐）_ ----------裝 訂^·· (請先閱讀背面之注意事項再填寫本頁) 470653 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 4 ) 〈調製方法〉 依照前述實施例1表4中之調製方法調製W / 0型乳液， 再對每1 0 0 g之乳液添加]g之1 0 %氣化鈣水溶液使褐藻酸納 凝膠化。 . 表49: 0/W/0型乳液 ----------裝 訂 « π (請先閱讀背面之注意事項再填寫本頁) 組成成分 15-8 15-9 實 15-10 施例 15-11 15-12 15-13 (a)0/W相[水相中含褐藻酸鈉] 實施例15-1之0/W型乳液 70 70 70 70 70 70 (b)外油相 液體石蟠 29 25 29 25 20 25 (C)親油性界面活性劑 P0E(3)十八醚 1 - - - - - P0E(2)十八醚 - 5 - - - - 山梨糖醇單硬脂酸酯 - - 1 - - - 山梨糖醇單硬脂酸酯 - - - 5 - - P0E(10)硬化蓖麻油 - - - - 10 - P0E(10)硬化蓖麻油 - - - - 5 乳化安定性 形態觀察（室溫） X X X X X X (5010) X X X X X X 内油相殘餘率（5018週後） &lt;5 &lt;5 &lt;5 &lt;5 &lt;5 &lt;5 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 7 6 3 8 5 1 4 r V 5 6 ο 7 4 丨修正 I 本年月θ I補充 8a 5.-4 五、發明説明（75 ) 〈調製方法〉 依照前述實腌例1之表5調製油包水包油型多重乳液， 再對每100g所得之乳液添加lg之10%氯化鈣水溶液，使褐 藻酸納凝膠化。 表50: 0/W/0型乳液 經濟部智慧財產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) 組成成分 15-14 15-15 實施 15-16 例 15-17 15-18 (a)0/W相[水相中含裼藻酸納] 實施例15-1之油包水型乳液 70 70 70 70 70 (b)外油相 液體石蠘 28 28 28 28 28 (C)外油相中之界面活性劑 有機改質粘土礦物（調製例1) 2 一 一 — 一 未改質粘土礦物（蜂膠） 一 2 - - - 氯化笨甲基甲乙基十八醯銨 - - 2 - - P0E(6)十二醚 氯化苯甲基甲乙基十八醢銨 +P0E(6)十二醚 - - - 2 2 乳化安定性 形態観察（室溫） 〇 X X X X (50¾) 〇 X X X X 内油相殘餘率（50TC8週後） 98 &lt;5 &lt;5 &lt;5 &lt;5 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 77(修正頁） 38514 5 . 經濟部智慧財產局員工消費合作社印製 6 ο 7 4 3 修正 本年月曰補充 89. 6. 1 4 A7 B7 五、發明説明（7 6 ) 〈調製方法〉 依照前述實施例1之表6調製0/W/0型多重乳液，再對 每100s所得之乳液添加lg之10%氯化鈣水溶液，使褐藻酸 納凝膠化。 由參考前述表47及表48可知，0/W型乳液及W/0型乳液 在選擇適當之界面活性劑時可得到相當高之安定性。然而 ，以安定之0/W型乳液分散於油相中之〇/1ί/〇型乳液之場合 ，其保存安定性大為降低，尤其内油相會滲出至外油相中 此外，如表49所示，一般對乳化安定有效之親水性高 分子（裼藻酸納）在添加於0/W/0型多重乳液之場合，可大 幅提高其安定性。 相對地，如上述表50之情形，水相中配合親水性高分 子之場合，在外油相中配合有機改質粘土礦物時，其乳化 安定性在形態觀察、內油相中之殘餘率等均極佳，因此有 良好之乳化安定作用。 因此，單將安定之0/W型乳液取代成安定之W/0型乳液 中之水相，例如在水相中配合親水性高分子將其凝膠化時 ，仍無法得到安定之多重乳液，因此配合有機改質粘土礦 物可得特別的多重乳液安定作用。 奮倫例1 fi 以下檢討水相中配合親水性高分子場合適當之組成。 (1)組成 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） 78 (修正頁）3 85 1 4 (請先閲讀背面之注意事項再填寫本頁) 470653 A7 經濟部中央標準局員工消費合作社印製 B7 、發明説明（77 ) 表5 1 : 0 / W型乳液之組成 組成成分 含有量 (a) 界面活性劑相 1 , 3 - 丁二醇 21 純水 2 P 0 E (6 0 )硬化蓖麻油 2 (b) 内油相 液體石蠟 33 (c) 水相 純水 39 褐藻酸鈉 3 表5 2 :外油相之組成 組成成分 含有量 (d) 界面活性劑 有機改質粘土礦物（調製例υ 7 (e) 外油相 液體石蠟 9 3 ---------二衣------、1T-------J (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準（CNS ) A4規格（210X297公釐） 7 9 385 1 4 470653 A7 B7 .五、發明説明（78 ) 表53: 0/W/0型乳液之組成比 實施 例 0 / W / 0型乳液量 (重量比） 外油相量 (重量比） 賁施例 16-1 50 50 實施例 16-2 60 40 實施例 16-3 70 30 實施例 16-4 80 20 實施例 16-5 35 65 實施例 16-6 97 3 (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 (2) 調製方法 先將上述表51中記載之（a)成分溶解混合均勻，再一 面攪拌一面與（b)成分混合-乳化，其次將（c)成分加入混 合卽得0/W型乳液。 將表52之外油相成分混合，再一面攪拌一面將上述調 妥的0/W型乳液混合-乳化於各外油相中，再對每〗OOg乳化 物加入1 g之1 0 %氮化鈣水溶液使褐藻酸納凝膠化，即得目 的之多重乳液。0/W型乳液與外油相之比例以上述表53之 比例變化即為實施例16-1至16-6。 (3) 結果 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 80 38 5 1 4 470653 A7 B7五、發明説明（7 9 ) 表54:乳液待性之評估 實施例 乳液之形態 (調製後瞬間） 乳化安定性 (RT) 乳化安定性 (5〇r) 内油相殘餘率 (50t, 1個月） 實施例16-1 0/W/0 〇 〇 93.0 實施例16-2 0/W/0 ◎ 〇 95.5 實施例16-3 0/W/0 ◎ ◎ 98.6 實施例16-4 0/W/0 ◎ 〇 92.8 實施例16-5 0/W/0 X X - 實施例16-6 0/W/0+0/W X X - 由上 述表54可知 ，在本發明 之多重乳液 中，水相中配 (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 合親水性高分子使其凝膠化之場合，0 / W型乳液與油相之 適當組成比例為重量比2:3〜19:1範圍。 比較例11 將外油相依下述表5 5之組成混合調製，即成Irb較例11 -1至1 1 - 6。各傾外油相中使用已往調製W / 0型乳液時，廣 泛使用之親油性界面活性劑。 此外，以實施例1 6表5 1中之0 / W型乳液與下述表5 5之 外油相以7 : 3比例混合乳化，再對每1 0 0 g此乳化物添加U 之1 0 %氣化鈣水溶液使褐藻酸鈉凝膠化即得目的之ϋ / W / 0 型多重乳液。 調製之多重乳液之乳化安定性如表5 6所示。 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210 X 297公釐） 8 j 3 8 5 1 4 470653 A7 B7 五、發明説明（80) 表5 5 :外油相之組成 經濟部中央標準局員X消費合作社印製---------- ^ ------ 1T (Please read the notes on the back before filling this page) 470653 A7 B7 V. Description of the invention (58) Table 36: 0 / W / 0 type Composition of emulsion 10-6 Example 10-7 (a) 0 / W phase [containing 4-third-butyl-4'-methoxydibenzomethane in internal oil phase] Example 10-1 0 / W type emulsion 70 70 (b &gt; outer oil phase decamethyl-cyclopentasilane 28-octamethyl-cyclotetrasilazane-28 (C) organic modification of surfactant in outer oil phase Clay mineral 2 2 (Please read the notes on the back before filling this page) Observation of emulsification stability morphology printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (room temperature) 〇〇 (50 ^) 〇 50t: after 8 weeks) 98 98 Crystal precipitation 〇 (none) 〇 (none) Feeling of use ◎ ◎ * Same as the user in Table 32. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 60 38514 470653 Revised the month of this year A7 supplement 89. 6. 14 B7 V. Description of the invention (5 9) As can be seen from the above-mentioned Tables 33 and 34, even if a fat-soluble agent (4- tertiary-butyl-4 'is added to the oil phase -Methoxydiphenyl In the case of formazan), o / y type emulsion and W / 0 type emulsion with high emulsifying stability can still be obtained, but in the case where the silicone oil is not mixed, the agent does not precipitate but the use feeling is poor. The feeling of using oil can be improved, but the medicament will precipitate after a long period of time. Therefore, in order to have the effect of silicone oil and prevent the crystallization of the medicament, the stable 0 / W emulsion in Table 33 is dispersed in In the oil phase of the silicone oil, a 0 / W / 0 type emulsion is prepared. As shown in Table 35, the emulsification stability is greatly reduced. Since the internal oil phase penetrates into the external oil phase, the expected prevention of crystal precipitation cannot be obtained. In addition, the feeling of use also tends to deteriorate. (Please read the precautions on the back before filling out this page.) The Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperative Co., Ltd. Printing Machine Residues Ding Line is good quality and oil suppression. __The external good change can be the internal oxygenated oil I- &amp; purple regular machine, as the silicon oil is equipped with internal and external, ％ only non-existent, due to non-normal, and (4C anti-sense sometimes. And the oxygen phase. The effect of the state phase agent is greasy, and the oil is in the form of oil. The internalization of the drug can be phase-free, so it should be safe and stable. It can be dissolved in milk and also oxidized and disintegrated. The liquid silicon is also one of the soluble milk, and its content is higher than its fixed weight. Into the agent, a multi-matching phase is used to make the liquid oil available for storage. The medium oil has its milk, standing surface milk, phase-A, and superposition. It is difficult to match this oil to the outside. The Shanghai Co-op was present because of the move by the Najia. , Benzene shift. In the Ming dynasty, the oil is not as good as the second one. The oil is based on the material, and the good and stable base is also analyzed. Oxygen, minerals, crystals, deposits, and phases are very affected by soil. The phase can be sticky, because the mineral oil outside the medium-mass ratio of 1-4 touches the soil and the phase change Yu Heji. Viscosity phase oil 61 (revised page) 385 1 4 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 470653 Printed by A7 B7, Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (60) Oil content When the other oil phase is mixed with silicone oil, the obtained emulsion can coexist with each other in a stable manner, which can prevent the drug from precipitating, and the use feeling is very good. Example 11 Secondly, review the appropriate composition ratio of the silicone emulsion oil-insoluble agent and the silicone emulsion containing the heavy oil emulsion. (1) Composition Table 3 7: Composition of 0 / W type emulsion ---------- equipment ------ order ------ (Please read the precautions on the back before filling in this Page) Composition Contents (a) Surfactant Phase 1, 3-Butanediol 21 Pure Water 2 P 0 E (60) Hardened Linseed Oil 2 (b) Internal Oil Phase Dioctyl Succinate 3 1 4- Tertiary-butyl-4'-methylaminodibenzoylmethane 2 (c) Aqueous phase pure water 42 This paper is sized to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 6 2 3 8 5 1 4 470653 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (61) Table 3 8: Composition of the external oil phase Composition content (d) Surfactant organically modified vermiculite mineral (Modification Example 1) 7 (e) Decamethyl-cyclopentaδoxane in external oil phase 93 Table 39: Composition ratio of 0 / W / 0 type emulsion Example 0 / W type emulsion amount External oil phase amount Example U-1 50 50 Example U-2 60 40 Example U-3 70 30 Example U-4 80 20 Example 11-5 35 65 Example U-6 97 3 (2) The modulation method is modulated according to the foregoing Example 2. Specifically, that is, after the components (U) described in Table 37 above are dissolved and mixed uniformly, the components (b) are added while the mixture is intended to be mixed. ---- \ (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 63 38 5 1 4 470653 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation of A7 B7 V. Description of the invention (62) Mix and emulsify, then add component (C) to mix to obtain 0 / W emulsion. The oil phase components other than those shown in Table 38 are mixed, and the 0 / W type emulsion prepared as described above is added to the external oil phase while mixing, and emulsified to obtain the desired 0 / W / 0 type multiple emulsion. In addition, the ratio of the 0 / W type emulsion to the external oil phase was changed, for example, in Table 39 described above, and the obtained 0 / W / 0 type emulsions were Examples 11-1 to U-6, respectively. (3) Results Table 40: Example of emulsion stability evaluation Example Emulsion morphology (instantaneous after preparation) Emulsification stability RT 50¾ Internal oil phase 1 Residual ratio crystal precipitation Example 11-1 ϋ / νι / ο 〇0 92% 0 (None ) Example 11-2 0 / W / 0 ◎ 0 93 〇 (None) Example 11-3 0 / W / 0 ◎ ◎ 98 0 (None) Example 11-4 0 / V / 0 0 〇93 0 ( None) Example 11-5 0 / W / 0 XX-X (Yes) Example 11-6 0 / W / 0 + 0 / WXX .- X (Yes) ------------ Install ------ order ------ ^ (Please read the precautions on the back before filling out this page) 1 The residual rate of the internal oil phase is faked to 50, and the test will be performed after 1 month. It can be seen from the above Table 4 that when the 0 / W type emulsion is outside the range of 2: 3 to 19: 1 compared with the external oil, a stable multiple emulsion cannot be obtained, and the drug (4 -third- Butyl-4'-methoxydibenzoylmethane) will crystallize out. In contrast, as in Example 1 1-1 to U-4, it can be seen that when the ratio of the 0 / W emulsion to the external oil is in the range of 2: 3 to 19: 1, the emulsification stability of the strip is good. Applicable to Chinese National Standard (CNS) Λ4 specification (210X297 mm) 6 4 3 8 5 14 470653 A7 B7 V. Description of the invention (63) It can prevent the crystallization of the pharmaceutical compounded in the internal oil phase. Fenxi example 12 and hh comparative examples 7 ~ 8 Secondly, according to the formula shown in Table 41 1, various 0 / W / 0 type emulsions or W / 0 type emulsions mixed with a silicon gas-based oil-insoluble ultraviolet absorber were prepared. (Please read the precautions on the back before filling this page) The effect of preventing the crystallization of the fat-soluble pharmaceutical compound (1) in the oil phase is determined. Table 41 Composition Example 12 Comparative Example 7 Comparative Example 8 (O / W / O) (W / 0) (W / 0) (a) Surfactant phase 1,3-butanediol 5 5 5 P0E (60) Hardened castor oil 1--methyl parahydroxybenzoate 0.1 0.1 0.1 (b) Inner oil phase triclosan 5--Tetra-2-ethylhexanoic acid pentaerythritol 5--Ultraviolet absorbent (refer to Table 42) 2--(C) Water phase pure water 48.9 59.9 59.9 Economic Printed by the Consumer Standards Cooperative of the Ministry of Standards, China (d) Dioctyl succinate in external oil phase 9 9 30 Dimethylpolysiloxane 10 10-Decamethyl-cyclopentasilane 10 10-Polysiloxane 1 1-Organic modified clay minerals (Preparation Example 1) 1 1 1 POE (6) stearyl ether 1 1 1 POE methyl polysiloxane copolymer * 1 1 1 UV absorber (refer to Table 42)-2 2 * Silicone SC9450J U Shin-Etsu Chemical Industry Co., Ltd. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 OX 297 mm) 65 3 8 5 1 4 470653 A7 B7 V. Description of the invention (64) (2) Modulation method Example 12 According to the foregoing Example 6. [Bub. Comparative Example 7 and Buh Comparative Example 8] According to the aforementioned Comparative Example 2. (3) Evaluation method First, observe the morphology of the emulsion in Table 41 according to the method described above, measure the change in particle size and changes in the emulsified state such as separation, and evaluate its emulsion stability. After the storage period of 2 5 t: 6 months or 50 1 C, the effect of preventing the precipitation of crystals and the feeling of use were evaluated by the methods described above. (4) Result I -------- install ------ order ------ ^ (Please read the precautions on the back before filling out this page) The paper size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) 66 3 8 5 1 4 470653 A7 B7 V. Description of the invention (65) Preparation of UV-absorbing agent for emulsification and stable crystal precipitation Example of use (0 / W / 0) 12-1 2,4-dihydroxydiphenyl ketone ◎ 0 (none) ◎ 2 2; 2'-dihydroxy-4- Methanyl diphenyl ketone ◎ 〇 (none) ◎ 3 2,2'-dihydroxy-4,4'-dimethoxydiphenyl ketone 0 0 (none) ◎ 4 2,2 ', 4,4 '-Tetrahydroxydiphenyl ketone ◎ 0 (none) 0 5 2-hydroxy-4-methoxydiphenyl ketone ◎ 〇 (none) ◎ 6 2-hydroxy-4-methylamino-4'-methyl Diphenyl ketone ◎ 〇 (none) ◎ 7 3- (4'-methylbenzylidene) -d, l-camphor ◎ ○ (none) ◎ 8 3-benzylidene-d, l-camphor ◎ 〇 (none) ◎ 9 4-methylamino-4'-tertiary-butyldibenzofluorene methane ◎ (none) 0 Comparative example (W / 0 oil type: containing silicon Oil content) 7-1 2,4-dihydroxydiphenyl ketone XX (Yes) 〇2 2,2'-dihydroxy-4-methoxydiphenyl ketone XX (Yes) 〇3 2,2 ^ Di Hydroxy-4,4'-dimethoxydiphenyl ketone XX (yes) 〇4 2,2 ', 4,4'-tetrahydroxydiphenyl ketone XX (yes) 〇5 2-hydroxy-4-methyl Oxydiphenylketone XX (Yes) 〇6 2-hydroxy-4-methoxy-4'-methyldiphenylketone XX (Yes) 〇7 3- (4'-methylbenzylidene) -d, camphor XX (yes) 〇 8 3-benzylidene-d, l-camphor XX (yes) 〇 9 4-methylamino-4'-tertiary-butyldibenzomethane XX ( Yes) 〇 Comparative example (W / 0 type: non-silicone oil distribution combination) 8-1 2,4-dihydroxydiphenyl ketone X 〇 (No) X 2 2,2'-dihydroxy-4-methyl gas Diphenyl ketone X 〇 (no) X 3 2,2'-dihydroxy-4,4'-dimethoxydiphenyl ketone X 〇 (no) X 4 2,2 ', 4,4 ·- Tetrahydroxydiphenyl ketone X 〇 (no) X 5 2-hydroxy-4-methylamino diphenyl ketone X 〇 (no) X 6 2-hydroxy-4-methoxy-4'-methyldiphenyl Ketone X 〇 (no) X 7 3- (4'-methylbenzylidene camphor X 〇 (no) X 8 3-benzylidene-d, l-camphor X (None) X 9 4-methylamino-4'-tertiary-butyldibenzoylmethane X 0 (None) X This paper size applies to Chinese National Standard (CNS) A4 specification (210 '乂 297 mm) 67 (Please read the precautions on the back before filling out this page) 38514 470653 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (66) As shown in Table 42, the external oil phase in Comparative Example 7 The W / 0 emulsion containing UV absorber and silicone oil has good stickiness. However, when the UV absorber and the low-solubility siloxane oil are combined in the same oil phase, the UV absorber may precipitate during storage. On the other hand, as in Comparative Example 8, when a W / 0 type emulsion in which a polar oil with high UV absorbent solubility is used instead of a silicone oil in the external oil phase is substituted, no UV absorbent will be precipitated after a long period of time, but However, it has a sticky feeling and a poor use feeling. In contrast, the 0 / W / 0 emulsion of the present invention (Examples 1 to 2 to 1-9 had no crystal precipitation, and the emulsification stability was also good. In addition, the use feeling is refreshing and non-sticky, which is similar to the emulsion of Comparative Example 5 From the above situation, it can be known that in the multiple emulsion of the present invention, the so-called low-miscibility ingredients of the silicone oil, the non-silicone oil, and the silicone oil are co-existing in the same emulsion. In emulsion emulsion, the obtained emulsion can prevent the crystallization of the drug, and has excellent emulsification stability and use feeling, so it can be prepared into a sunscreen cosmetic with good usability and stability. 窨 旃 Example 1 3 Fat-soluble agents in type 0 / W / 0 multiple emulsions use easily oxidizable fat-soluble vitamins (vitamin A hexadecanoate) or easily-oxidizable oil-soluble ultraviolet absorbers (octyldimethyl paraaminobenzoic acid) Esters) The various ingredients shown in the following Table 43 and Table 44 were used to change the blending amount to prepare a 0 / W / 0 type multiple emulsion. The preparation method was as described in Example 6 above. Results 0 / W of silicon gas-containing oil / Type 0 Multiple In the liquid, l / b of 0 / W type emulsion and external oil phase is in the range of 2: 3 ~ 19: 1, showing good emulsification stability of rhenium and good gasification stability of pharmaceuticals. H. --- --I----j I t, m I i ----; I ---, waJ (Please read the notes on the back before filling out this page) This paper standard is applicable to China National Standards (CNS) A4 specifications (210X297 mm) 68 3 8 5 1 4 κΰ. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 6 ο 7 4 3 Amendments to this month and supplement 89. 5.-4 A7 B7 V. Description of the invention (67 ) Table 43: Examination of composition ratio Examples Composition 13-1 13-2 13-3 13-4 13-5 U) Surfactant phase 1,3-butanediase 5 5 5 5 5 Glycerol 2 2 2 2 2 POE (60) hardened castor oil 1 1 1 1 1 methyl parahydroxybenzoate 0.1 0.1 0.1 0.1 0.1 (b) internal oil phase triacontane 5 5 5 5 5 vitamin A hexadecanoate 0.2 0.2 0.2 0.2 0.2 (C) Pure water in the water phase 82.2 76.7 56.7 36.7 16.7 (d) Octamethyl-cyclotetrasiloxane in the outer oil phase 2.1 7,6 27.6 47.6 67.6 Cationic modified clay mineral (Bentone-38) 2 2 2 2 2 POE methyl polysiloxane copolymer * 0.4 0.4 0.4 0.4 0.4 Water-in-oil emulsion: external oil phase (weight ratio) 21: 1 9: 1 7: 3 5: 5 3: 7 emulsification stability (morphological observation) 501 ： X 〇 ◎ 〇X Residual ratio of drug X 0 0 0 X * Silica SC9450N (made by Shin-Etsu Chemical Industry Co., Ltd.) (Please read the precautions on the back before filling in this page) This paper applies Chinese National Standard (CNS) A4 specifications (210X297 mm) 69 (correction page) 38514-installed. Shochu 5 6 ο 7 4 I correction 1 This month, I added 89. 5.-4 V. Description of the invention (⑽) Table 44: Composition ratio Review of the examples printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 13-6 13-7 13-8 13-9 13-10 (a) Surfactant phase 1,3-butanediol 5 5 5 5 5 Glycerin 2 2 2 2 2 POE (60) hardened castor oil 1 1 1 1 1 methyl parahydroxybenzoate 0.1 0.1 0.1 0.1 0.1 (b) internal oil phase methoxy cinnamate octyl 5 5 5 5 5 tri-2 -Glyceryl ethylhexanoate 10 10 10 10 10 Octyldimethyl para-aminobenzoate 1 1 1 1 1 (C) Pure water in water phase 70.75 65.3 45.3 25.3 5.3 (d) Liquid oil in outer oil phase 0.65 2. 6 9.2 16.0 22.6 Undecylmethyl-cyclopentasiloxane 1.5 5.0 18.4 31.6 45.0 Cationic modified clay mineral (Bentone-38) 1 1 1 1 1 POE (10) Sorbitol fatty acid ester 1 1 1 1 1 POE Methylpolysiloxane copolymer * 1 1 1 1 1 Water-in-oil emulsion: External oil phase (weight ratio) 21: 1 9: 1 7: 3 5: 5 3: 7 Emulsification stability (morphological inspection) 50¾ X 〇 ◎ 〇X Tincture Residue Δ ◎ ◎ ◎ △ * Silicone SC9450N (Shin-Etsu Chemical Industry Co., Ltd.) This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 70 (correction page) 38514- --------- Install ------ Order ------ line (please read the precautions on the back before filling this page) 470653 A7 B7 V. Description of Invention (69) Central of the Ministry of Economic Affairs Standard Bureau staff consumer cooperatives printed cellar example 14 and comparative examples 9 to 10 Second, the residual rate of various fat-soluble vitamins and easy-gasifying agents in silicon oil strips. In the case of multiple emulsions, Table 45 is the internal oil in the liquid, and the composition of the oxidizing drug in the easy phase is determined. Example 14 Comparative Example 9 Comparative Example 10 (0 / W / 0) (W / 0) (0 / W / 0) (a) Surfactant phase 1, 3-butanediol 5 5 5 P0E (60) hardened castor oil 1--bentonite--0.5 methyl parahydroxybenzoate 0.1 1 0.1 0.1 (b) internal oil Phase Thirstane 5-5 Tetra-2-ethylhexanoate pentaerythritol 5-5 Cetyl alcohol--3 POE (20) Sorbitol tristearate--1 Glyceryl monooleate--2 Fat-soluble biotin (refer to Table 46) 1-1 (C) Pure water in water phase 51.9 52.9 37.4 (d) Liquid oil in outer oil phase 10 10 10 Dimethylpolysiloxane 10 10 10 Decamethyl-cyclo Pentasilazane 10 10 10 Organically Modified Clay Minerals (Preparation Example 1) 1 1 1 Tricosane-5-tetra-2-ethylhexanoate pentaerythritol-5-dextrin hexadecanoate--1 16 Alkanol--3 Melamine--2 Sorbitol sesquioleate--3 Sorbitol monostearate--1 Fat-soluble vitamins (refer to Table 46)-1-(Please read the notes on the back first Please fill in this page for the matters) National National Standard (CNS) A4 specification (210X297 mm) 7 1 3 8 5 1 4 470653 A7 B7 V. Description of the invention (70) (2) Modulation method Example 1 4 According to the previous embodiment 6 Examples are in accordance with the aforementioned Comparative Example 2. Than .. compare. Example. Li According to the aforementioned Comparative Example 3. (3) Evaluation method The morphological observation and the drug residue rate were evaluated according to the aforementioned method. In addition, after storage in the thermostatic bath for one month, the discoloration and odor were evaluated in accordance with Example 6 described above. (4) Result ------- binding (please read the notes on the back before filling in this tribute) The paper size printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) Λ4 specification (2 丨 0 '乂 297 mm) 72 3 8 5 1 4 470653 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (Ή) 1 I Table 46: Evaluation of the properties of each emulsion 1 1 1 Residual rate of fat-soluble vitamin emulsifying stabilizer 1 1 Observation of discoloration and odor (%) Please read 1 1 I 1 1 Example 14-1 Retinol ◎ ◎ 〇90.1 Back 1¾ 1 | of 1 (0 / W / 0) 2 Vitamin A hexadecanoate ◎ ◎ 〇97,5 meaning 1 3 Vitamin A acetate ◎ ◎ 1095.1 Item 1 1 4 α-tocopherol ◎ ◎ 0 92.2 Zai 1 5 雒 生 素 E Acetate ◎ ◎ 〇99.8 Written on this page 16 Vitamin D2 ◎ ◎ 〇93.2 1 7 / 3-Carrot® ◎ ◎ 〇99.1 1 1 I Comparative Example 9- -1 Retinol XX 〇48.9 1 1 Order (W / 0) 2 Vitamin A hexadecanoate Δ Δ 〇 67.5 1 I 3 Vitamin A acetate Δ △ 50.8 1 1 4 α-tocopherol Δ 0 〇63, 2 1 I 5 Vitamin E acetate 〇007 70.4 1 6 Vitamin D2 Δ 〇〇3.3. 1 | Comparative Example 10 -1 Retinol XXX 12.1 1 1 (0 / V / 0) 2 Vitamin A hexadecanoate XXX 22.3 1 I 3 Vitamin A acetate XXX 30.6 1 1 4 ot-tocopherol Δ Δ X 63.7 1 I 5 Vitamin E acetate Δ △ X 72.4 1 1 6 Vitamin 1) 2 Δ △ X 77,7 1 I 7 / 9-Huagen Δ 〇Δ 69.6 1 1 1 1 paper size Applicable to Chinese National Standard (CNS) Λ4 specification (210X297 mm) 38514 η 470653 A7 B7 V. Description of the invention (72) As can be seen from Table 46, compared with Comparative Examples 9 and 10, the multiple emulsion of the present invention is shown (Example) 4 -1 ~ 14-7) is an emulsion with no oil separation or discoloration, odor, good emulsification stability, and extremely high drug residue rate. Implementation ... Implementation. 1 5_ Secondly review the multiple emulsion C where the hydrophilic phase is mixed with the hydrophilic polymer in the water phase of the present invention. Example 1 5-1 (a) Surfactant phase 1, 3-butanediol 21 Pure water 2 P 0 E (60) Hardened castor oil 2 (b) Oil phase Liquid stone concrete 33 (c) Water phase pure water 39 Sodium alginate 3 Emulsification stability (morphological observation) Room temperature 〇50V 〇Binding I π (Please read the precautions on the back before filling in this page) This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (2ΙΟ × 297 mm) ) 7 4 3 8 5 1 4 470653 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (7 3) <Modulation method> The 0 / W type emulsion was prepared according to the preparation method in Table 3 of Example 1 above. Then, for each 100 g of emulsion, add 10 g of a 10% aqueous solution of calcium carbonate to make sodium alginate coagulate. Table 48: W / 0 emulsion composition 15-2 15-3 Implementation 15-4 Example 15-5 15-6 15-7 (a) Surfactant phase POE (3) stearyl ether 1----- P0E (2) Octadecyl ether-5----Sorbitol mono--1---Stearate---5--P0E (10) Hardened sesame oil----10-Ρ0Ε (10) Hardened castor oil (b) oil phase — _ _ — 5 liquid rockwort (C) water phase 39 35 39 35 30 35 ion-exchanged water 57 57 57 57 57 57 sodium alginate 3 3 3 3 3 3 emulsification stability (morphology Observation) Room temperature 0000 50,000 0000 0000 This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) _ ---------- binding ^ ... (Please read the notes on the back before filling out this page) 470653 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (7 4) <Modulation method> Modulation according to the modulation method in Table 4 of Example 1 above For W / 0 type emulsion, add 10g of 10% aqueous solution of calcium gas to each 100g of emulsion to gelate the alginate. Table 49: Type 0 / W / 0 Emulsion ---------- Staple «π (Please read the precautions on the back before filling out this page) Composition 15-8 15-9 实 15-10 施Example 15-11 15-12 15-13 (a) 0 / W phase [sodium alginate in water phase] The 0 / W emulsion of Example 15-1 70 70 70 70 70 70 (b) External oil phase liquid Rockwell 29 25 29 25 20 25 (C) Lipophilic surfactant P0E (3) octadecyl ether 1-----P0E (2) octadecyl ether-5----sorbitol monostearate --1---Sorbitol monostearate---5--P0E (10) hardened castor oil----10-P0E (10) hardened castor oil----5 Emulsification stability observation (Room temperature) XXXXXX (5010) XXXXXX Oil phase residual rate (after 5018 weeks) &lt; 5 &lt; 5 &lt; 5 &lt; 5 &lt; 5 &lt; 5 This paper size applies Chinese National Standard (CNS) Λ4 specifications ( 210X297 mm) 7 6 3 8 5 1 4 r V 5 6 ο 7 4 丨 Correction I Month this year θ I Supplement 8a 5.-4 5. Description of the invention (75) <Modulation method> According to the above example 1 Table 5: Oil-in-water-in-water multiple emulsions were prepared, and 10% of lg was added to each 100 g of the emulsion. An aqueous solution of calcium gels sodium alginate. Table 50: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of 0 / W / 0 Emulsion Economy Department (please read the precautions on the back before filling this page) Composition 15-14 15-15 Implementation 15-16 Example 15-17 15 -18 (a) 0 / W phase [sodium alginate in the water phase] The water-in-oil emulsion of Example 15-1 70 70 70 70 70 (b) External oil phase liquid stone 28 28 28 28 28 ( C) Surfactant organically modified clay mineral in external oil phase (Modification Example 1) 2-1-An unmodified clay mineral (propolis)-2---Benzylmethyl ethyl stearylamine- -2--P0E (6) dodecyl benzylmethyl ethyl stearylamine + P0E (6) dodecyl ether---2 2 Emulsification and stability morphological observation (room temperature) 〇 XXXX (50¾) 〇 XXXX internal oil phase residual rate (after 50TC8 weeks) 98 &lt; 5 &lt; 5 &lt; 5 &lt; 5 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 77 (correction page) 38514 5. Economy Printed by the Ministry of Intellectual Property Bureau ’s Consumer Cooperatives 6 ο 7 4 3 Amendments to this month ’s supplement 89. 6. 1 4 A7 B7 V. Description of the invention (7 6) <Modulation method> Adjust according to Table 6 of Example 1 above A 0 / W / 0 type multiple emulsion was prepared, and 10% calcium chloride aqueous solution of lg was added to the emulsion obtained every 100 s to gelate the alginate. As can be seen by referring to the aforementioned Tables 47 and 48, the 0 / W type emulsion and the W / 0 type emulsion can obtain relatively high stability when selecting an appropriate surfactant. However, when the 0 / W emulsion of the stable 0 / W emulsion is dispersed in the oil phase, the storage stability is greatly reduced, especially the internal oil phase will ooze into the external oil phase. In addition, as shown in Table 49 As shown, when a hydrophilic polymer (sodium alginate) generally effective for emulsification and stabilization is added to a 0 / W / 0 multiple emulsion, its stability can be greatly improved. In contrast, as in the case of Table 50 above, when a hydrophilic polymer is blended in the water phase and an organic modified clay mineral is blended in the outer oil phase, its emulsification stability is observed in the morphology and the residual rate in the inner oil phase, etc Excellent, so it has good emulsification and stability. Therefore, when the stable 0 / W emulsion is simply replaced with the stable aqueous phase in the stable W / 0 emulsion, for example, when a hydrophilic polymer is mixed in the aqueous phase to gelate it, a stable multiple emulsion cannot be obtained. Therefore, combined with the organic modified clay mineral, a special multiple emulsion stabilization effect can be obtained. Fenlun case 1 fi The following review the appropriate composition in the case of hydrophilic polymers in the water phase. (1) The composition of this paper applies the Chinese National Standard (CNS) A4 (210X297 mm) 78 (correction page) 3 85 1 4 (Please read the precautions on the back before filling this page) 470653 A7 Central Standard of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau B7, Description of Invention (77) Table 5 1: Composition of 0 / W type emulsion (a) Surfactant phase 1, 3-butanediol 21 Pure water 2 P 0 E ( 6 0) Hardened castor oil 2 (b) Internal oil phase liquid paraffin 33 (c) Water phase pure water 39 Sodium alginate 3 Table 5 2: Composition of the external oil phase (d) Surfactant organic modification Clay minerals (Preparation example υ 7 (e) External oil phase liquid paraffin 9 3 --------- 二 衣 ------ 、 1T ------- J (Please read the back Note: Please fill in this page again.) This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 7 9 385 1 4 470653 A7 B7. 5. Description of the invention (78) Table 53: 0 / W / 0 type emulsion Composition ratio Example 0 / W / 0 type emulsion amount (weight ratio) External oil phase amount (weight ratio) 贲 Example 16-1 50 50 Example 16-2 60 40 Example 16-3 70 30 Example 16-4 80 20 Example 16-5 35 65 Example 16-6 97 3 (Please read the precautions on the back before filling out this page) Preparation (2) Preparation method: Dissolve and mix the component (a) described in Table 51 above, mix and emulsify with the component (b) while stirring, and then add the component (c) to the mixture to obtain a 0 / W emulsion. Mix the oil phase ingredients other than those in Table 52, and while stirring, mix and emulsify the adjusted 0 / W type emulsion in each external oil phase, and then add 1 g of 10% nitrogen to each OO g of the emulsion. The calcium alginate solution gels the sodium alginate to obtain the desired multiple emulsion. The ratio of the 0 / W type emulsion to the external oil phase is changed by the ratio in Table 53 above to give Examples 16-1 to 16-6. (3 ) Results This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 80 38 5 1 4 470653 A7 B7 V. Description of invention (7 9) Table 54: Evaluation of emulsion properties After the instant) Emulsification stability (RT) Emulsification stability (50r) Internal oil phase residual rate (50t, 1 month) Example 16-1 0 / W / 0 〇〇3.0 3.0 Example 16-2 0 / W / 0 ◎ 95.5 Example 16-3 0 / W / 0 ◎ ◎ 98.6 Example 16-4 0 / W / 0 ◎ 〇92.8 Example 16-5 0 / W / 0 XX-Example 16-6 0 / W / 0 + 0 / WXX-As can be seen from Table 54 above, in the multiple emulsion of the present invention, the (Please read the notes on the back and fill in this page again.) When a hydrophilic polymer is printed and gelled by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, the appropriate composition ratio of 0 / W emulsion and oil phase is 2 by weight: 3 ~ 19: 1 range. Comparative Example 11 The external oil phase was mixed and prepared according to the composition of Table 5 5 below to obtain Irb Comparative Examples 11 -1 to 1 1-6. A widely used lipophilic surfactant when using conventionally prepared W / 0 emulsions in each oil phase. In addition, the emulsion of 0 / W type in Table 1 of Example 16 and Table 5 and the oil phase other than Table 5 below was mixed and emulsified at a ratio of 7: 3, and then U of 10 was added to each 100 g of this emulsion. The gelled sodium alginate solution with a gasified aqueous solution of %% calcium alginate yields the desired ϋ / W / 0 multiple emulsion. The emulsification stability of the prepared multiple emulsion is shown in Table 56. This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) 8 j 3 8 5 1 4 470653 A7 B7 V. Description of invention (80) Printed by X Consumer Cooperative

活性劑（重量比） 油 (重量比） 比較例U - 1 P 0 E ( 3 )十八醚 (1) 液 體石蠟 (99) 比較例1 ] - 2 Ρ0Ε (3)十八醚 (5) 液 體石蠟 (95) 比較例11 - 3 山梨糖醇單硬 脂酸酯u) 液 體石蠟 (99) 比較例]1 - 4 山梨糖醇單硬 脂酸酯（5 ) 液 體石蠟 (95) 比較例U - 5 P 0 E (1 0 )硬化蓖麻油（1 0 ) 液 體石蟠 (90) 比較例U - 6 P 0 E (1 0 )硬化Μ麻油（5 ) 液 體石蠟 (95) 表5 6 :乳液 待性之評估 乳化形態 乳化安定性 1化安定性 (RT) (50¾ ) 比較例11 - 1 o/y/o X X 比較例U - 2 0/W/0+0/W X X 比較例11 - 3 0/V/0 X X 比較例U - 4 0/W/0 X X 比較例1卜5 0/W/0+0/W X X 比較例U - 6 o/y/o+o/w X X -.— — — ——II '私衣 I I I I '1T (請先閲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 ) Λ4規格（210X297公釐） 82 38 5 1 4 470653 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（81 ) tb較表54及表56之評估可知，本發明之實施例16-1〜 1 6 - 4乳化安定性比比較例1 1 - 1至U - 6為佳。 奮旆例1 7及hh較例1 2 以下對配合親水性高分子之多重乳液，由藥物對皮膚 之剌激性、效果之持纊性評估其應用於外皮之適用性。 具體言之，水相中添加親水性高分子對組成物有安定 化之效果，特別是對内相油中藥效成分有緩釋性效果，此 缓釋性可防止藥物對皮慮有激烈作用，旦使該藥物效果持 纊。 具體地即將下述表57中之組成樣品塗抹在男女各25名 之品評員上手臂上，以塗抹後30分鐘内剌痛感之剌激性及 3小時後效果之持續性評估之。各評估之標準如下。 皮庸刺激忡 0: 50人中有0〜5人之皮虜有剌痛感 0: 50人中有6〜20人之皮虜有剌痛感 △ : 50人中有21〜35人之皮慮有剌痛感 X: 50人中有36〜50人之皮慮有剌痛感 效果持餹件 0 : 50人中有36〜50人感覺效果持鑛 0:50人中有21〜35人感覺效果持續 △ : 50人中有6〜20人感覺效果持續 X : 50人中有0〜5人感覺效果持缅 (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準（CNS ) A4規格（210X 297公釐） 83 3 8 5 1 4 470653Active agent (weight ratio) Oil (weight ratio) Comparative Example U-1 P 0 E (3) Octadecyl ether (1) Liquid paraffin (99) Comparative Example 1]-2 POL0 (3) Octadecyl ether (5) Liquid Paraffin (95) Comparative Example 11-3 Sorbitol Monostearate u) Liquid Paraffin (99) Comparative Example] 1-4 Sorbitol Monostearate (5) Liquid Paraffin (95) Comparative Example U- 5 P 0 E (1 0) hardened castor oil (1 0) liquid litter (90) Comparative Example U-6 P 0 E (1 0) hardened sesame oil (5) liquid paraffin (95) Table 5 6: Emulsion Evaluation of Emulsification Form Emulsion Stability 1st Stability (RT) (50¾) Comparative Example 11-1 o / y / o XX Comparative Example U-2 0 / W / 0 + 0 / WXX Comparative Example 11-3 0 / V / 0 XX Comparative Example U-4 0 / W / 0 XX Comparative Example 1 5 0 / W / 0 + 0 / WXX Comparative Example U-6 o / y / o + o / w XX-. — — — — —II 'Private clothes IIII' 1T (Please read the notes on the back before filling this page) This paper size applies to Chinese National Standard (CNS) Λ4 specification (210X297 mm) 82 38 5 1 4 470653 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperative A7 B7 V. Description of Invention (81) tb 54 and Table 56 Evaluation of the apparent, embodiments of the present invention 16-1~ 16--4 emulsion stability than Comparative Example 11--1 to U - 6 is preferred. Fendi Example 17 and hh are compared to Example 1 2 For multiple emulsions mixed with hydrophilic polymers, the applicability of the drug to the skin is evaluated by its irritability and effect on the skin. Specifically, the addition of a hydrophilic polymer to the water phase has a stabilizing effect on the composition, especially a slow-release effect on the medicinal ingredients in the internal phase oil. This slow-release property can prevent the drug from having a drastic effect on skin concerns. Once the effect of the drug is persistent. Specifically, the composition samples in Table 57 below were smeared on the upper arms of 25 male and female judges to evaluate the excitement of pain within 30 minutes after application and the effect of continuous evaluation after 3 hours. The evaluation criteria are as follows. Pi Yong stimulates: 0: 0 to 5 out of 50 people have pain in the skin 0: 6 to 20 out of 50 people have pain in skin △: 21 to 35 out of 50 people have skin pain剌 Pain X: 36 ~ 50 of 50 people have sorrow and pain effects. 餹 0: 36 ~ 50 of 50 people feel the effect. 0:50 of 21 ~ 35 people feel the effect. △ : 6 to 20 out of 50 people feel the effect lasts X: 0 to 5 out of 50 people feel the effect lasting (please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 Specifications (210X 297 mm) 83 3 8 5 1 4 470653

7 7 A B 五、發明説明（82 ) 表57 實施 例 比較例 17-1 17-2 12-1 12-2 12-3 乳化形態 0/W/0 0/V/0 0/W W/0 0/W/0 (a) 1,3-丁二醇 10.5 - 10.5 10.5 純水 1 - 1 - POE (60)硬化蓖麻油 1 - 1 - P0E(25)十六醚 3 單硬脂酸甘油酯 - 2 - - Ί油土 (a甘皂 5 5 0 (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 液體石蟠 15.4 9 28.9 26.9 14.4 P0E(20)山梨糖醇三硬脂酸酯 - - - - 1 三辛酸甘油酯 - 3 - - - 橄欖油 十八醇 - 2 -0.5 - - - (C) 壬酸-4-羥基-[3]-甲氧基苯甲醯胺 1 1 1 1 1 (d) 純水 TO 100 (e) 有機改質粘土礦物（調製例2) 2 2 - 2 - (e，） 糊精硬脂酸酯 - - - - 1 (f) 液體石蟠 28 28 - - 29 (g) 卡得蘭糖 1 1 - - 一 ⑹ 黃素樹膠（Keltrol) - - 1 - - (i) IN-NaOH 0.2 0.2 ~ - - (j) 1N-HC1 0.2 0.2 - - - 皮膚剌激（剌痛感） ◎ 〇 Δ X 〇 持绩性 ◎ 0 X X Δ 本紙張尺度適用中國國家標率（CNS ) A4規格（210X297公釐） 84 38514 經濟部智慧財產局員工消費合作社印製 470653 ^-- ] 本年月曰7 7 AB V. Description of the invention (82) Table 57 Examples Comparative Examples 17-1 17-2 12-1 12-2 12-3 Emulsified form 0 / W / 0 0 / V / 0 0 / WW / 0 0 / W / 0 (a) 1,3-butanediol 10.5-10.5 10.5 Pure water 1-1-POE (60) Hardened castor oil 1-1-P0E (25) cetyl ether 3 Glyceryl monostearate-2 --Ίoil soil (a sugar soap 5 5 0 (please read the precautions on the back before filling this page) printed liquid stone concrete by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 15.4 9 28.9 26.9 14.4 P0E (20) sorbitol Tristearate----1 Glyceryl tricaprylate-3---Stearyl alcohol in olive oil-2 -0.5---(C) Nonanoic acid 4-hydroxy- [3] -methoxybenzoyl Phenamine 1 1 1 1 1 (d) Pure water TO 100 (e) Organic modified clay mineral (Preparation example 2) 2 2-2-(e,) Dextrin stearate----1 (f) Liquid stone maggot 28 28--29 (g) Catalan 1 1--One lutein Keltrol--1--(i) IN-NaOH 0.2 0.2 ~--(j) 1N-HC1 0.2 0.2---Skin irritation (pain sensation) ◎ △ △ X 〇 Persistence ◎ 0 XX Δ This paper size is applicable to China National Standard (CNS) A4 specification (210 X297 mm) 84 38514 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 470653 ^-]

丨補充8认6。U 五、發明說明（8 3) 由上述表57可知，本發明之0/W/0型多重乳液與其他 之單純乳化系比較，對皮慮之剌激性低亦有持績性。Μ比 較例12-3調製之0/W/0型乳液，因其水相中不含高分子， 在藥物之緩釋性之點上無法發揮充份之效果。 各組成物之調製方法如下。 啻濂例1 7 - 1 將（a)，（b) + (c)成分分別溶解均匀後，一面攪拌一面 將（b) + (c)成分加入（a)成分中混合、乳化•再加入（d) + (g ) + (i)成分，調製成0/W型乳液。再一面攪拌一面將預先混 合之（e) + (f)成分加入上述得到之0/W型乳液中混合乳化， 再將（J)成分加人攪拌，即得目的之0/W/0型乳液。 當油？例1 7 - 2 將（a ) + ( b ) + (c )、（ a ' ) + ( d )成分分別混合溶解均勻後 一面攪拌一面將（a) + (b) + (c)成分與（a’）+ (d)成分中混合 乳化，即Μ所謂之相轉變乳化法而得0/W型乳液。再將（i )成分加入Μ少量純水分散之（g)成分中溶解之，即得0/W 型乳液。再一面攪拌一面將該添加卡得蘭糖之0/W型乳液 加入預先混合之（e) + (f)成分中混合乳化，再將（i)加入攪 拌即得目的之0/W/0型乳液。 fch龄例1 2 - 1 將（a)成分溶解混合均勻後一面攪拌一面將（b) + (c)成 分混合乳化，再將（d)及（h)成分加入混合，即得0/W型乳 液0 bh龄例1 2 - 2 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 85 (修正頁）38514 -----------^--------訂---------^ &lt;請先閱讀背面之注意事項再填寫本頁) 470653 I修正 本年月曰補充 89· 6. 14 A7 B7 五、發明説明（ 84 將（b) + (C) + (e)成分攪拌混合均勻後，一面搅拌一面 加入U) + (d)成分混合乳化，即得W/0型乳液。 l:h 齩例 1 2 3 將（a’）+ (d)，（b) + (c)成分分別加熱溶解，再一面攪 拌一面將（b) + (c)成分加入此（a’）+ (d)成分中混合，即得 分散乳化之0/¥型乳液。其次將此乳液一面攪拌一面加入 預先M80t：加熱混合之（e’）+ (f)成分中混合，再持續搅拌 使其冷卻至3010後即得0/W/0型乳液。 啻淪例〗8及hh龄俐1 3 其次藥物以水楊酸甲酯取代壬酸香草基醯胺後同前述 表57之例調製再加Μ評估。結果如次表58所示。 表58 請 先 閣 讀 背 δ 之 注 意 事 項 再 填 寫丨 本 頁 經濟部智慧財產局員工消費合作社印製 實施例 比較例 18-1 18-2 13-1 13-2 13-3 皮成 剌激（剌痛感） 〇 〇 Δ Δ Δ 持續 性 ◎ 〇 X X Δ 由上述表58可知，與前述表57同樣，本發明之多重乳 液可得良好之皮成剌激減低效果及效果持續性。 由Κ上之說明可知，本實施例之多重乳液及此製法可 Η (1)得到安定且均匀之多重乳液，且不須特殊之轧化機或· 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 86 (修正頁）3 85 1 4 470653 A7 B7 五、發明説明（85 ) 加熱急冷步驟，常溫下即可簡單地調製，因此製造費 低廉。 液 乳 多 到 得 地 單 簡 可 下 溫 常 驟 步 冷 急 熱 須 不 合 配 地 定 安 以 可 分 成 定 安 不 熱 此 因 之 勻 均 定 安 到 得 可 中 相 油 内 此 因 液 乳 重 多 型 性 定 安 劑 藥 的 好 良 得 可 合 場 之 劑 藥 性 溶 脂 合 Π-3 酉 _ 凝 子 分 高 性 水 親 以 中 相 水 於 由 之 解 容 •7— 中 相 油 内 有 果 效 物 藥 使 並 性 激 剌 低 減 可 此 因 化 釋 緩 以 可 物 藥 性 持 (請先閱讀背面之注意事項再填寫本頁) '裝- 訂 iΛ 經濟部中央橾準局員工消費合作社印製 本纸張尺度適用中國國家標準（CNS ) Α4規格（21〇'乂 297公釐） 87 38 5 1 4丨 Added 8 recognition 6. U 5. Description of the invention (8 3) As can be seen from the above Table 57, the 0 / W / 0 multiple emulsion of the present invention has lower irritation to skin anxiety than other simple emulsified systems. M ratio The 0 / W / 0 emulsion prepared in Comparative Example 12-3, because the water phase does not contain a polymer, so it cannot exert a sufficient effect in terms of the slow-release properties of the drug. The preparation method of each composition is as follows. Example 1 7-1 After the components (a) and (b) + (c) are dissolved uniformly, the components (b) + (c) are added to the component (a) while mixing, emulsifying and then adding ( d) + (g) + (i) component to prepare a 0 / W type emulsion. Add the (e) + (f) components mixed in advance to the 0 / W type emulsion obtained above while stirring, and then add the (J) component and stir to obtain the intended 0 / W / 0 type emulsion. . When oil? Example 1 7-2 Mix the components (a) + (b) + (c), (a ') + (d) and dissolve them, and stir (a) + (b) + (c) and ( a ') + (d) components are mixed and emulsified, which is the so-called phase transition emulsification method to obtain 0 / W type emulsion. Then, the component (i) is added to a small amount of pure water and the component (g) is dissolved to obtain a 0 / W type emulsion. While stirring, add the 0 / W type emulsion with added cardanolose to the (e) + (f) component mixed in advance and emulsify, and then add (i) to the mixture to obtain the desired 0 / W / 0 Emulsion. Fch age example 1 2-1 After dissolving and mixing the component (a), mix and emulsify the components (b) + (c) while stirring, and then add the components (d) and (h) to the mixture to obtain 0 / W type Emulsion 0 bh age example 1 2-2 The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 85 (correction page) 38514 ----------- ^ ---- ---- Order --------- ^ &lt; Please read the notes on the back before filling this page) 470653 I amended this month and added 89 · 6. 14 A7 B7 V. Description of the invention (84 After the components (b) + (C) + (e) are stirred and mixed uniformly, the components U) + (d) are added while mixing and emulsified to obtain a W / 0 type emulsion. l: h Example 1 2 3 Heat and dissolve (a ') + (d), (b) + (c) respectively, and add (b) + (c) to this (a') + while stirring (d) The components are mixed to obtain a dispersed emulsified 0 / ¥ type emulsion. Next, add this emulsion while stirring, and mix it with the component (e ') + (f) of M80t: heating and mixing, and continue to stir to cool to 3010 to obtain 0 / W / 0 emulsion. Example 8 and hh age Li 1 3 Secondly, the drug was replaced with methyl salicylate to vanillyl nonanoate, and was prepared in the same manner as in the example in Table 57 before evaluation. The results are shown in Table 58 below. Table 58 Please read the notes of δ before filling in. 丨 Printed on the page of the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Comparative Example 18-1 18-2 13-1 13-2 13-3 (Pain sensation) 〇〇Δ Δ Δ Persistence ◎ XX Δ As can be seen from the above-mentioned Table 58, similar to the above-mentioned Table 57, the multiple emulsion of the present invention can obtain a good skin formation reduction effect and effect persistence. From the description on K, it can be known that the multiple emulsions of this embodiment and the manufacturing method can (1) obtain stable and uniform multiple emulsions, and do not require a special rolling machine or · This paper size applies Chinese National Standard (CNS) Α4 Specifications (210 × 297 mm) 86 (correction page) 3 85 1 4 470653 A7 B7 V. Description of the invention (85) The heating and cooling steps can be easily adjusted at room temperature, so the manufacturing cost is low. The liquid milk is too high to be simple, the temperature can be lowered, the temperature can be stepped, and the cold and hot must be set properly. It can be divided into stable and not hot. The medicine is good and good. The medicine is soluble in fat. Π-3 酉 _ The coagulant is divided into high-quality water and medium-phase water to dissolve it. • 7— There are fruit drugs in the medium-phase oil to make the skin irritating.剌 The reduction can be due to the slow release of the drug. (Please read the precautions on the back before filling this page) (CNS) Α4 specification (21〇'297 mm) 87 38 5 1 4

Claims (1)

470653 H3 附 件 經濟部中央標準局員工福利委員會印製 第8 5 1 1 3 6 5 0號專利申請案 申請專利範圍修正本 (89年6月1 4日） 1. 一種多重乳液，其特徵為該多重乳液為外油相中分散 0/W(水包油）型乳液之油包水包油（0/Ϊ//0)型多重乳液 ，前述外油相中含有有機改質粘土礦物，該有機改質 粘土礦物係水膨潤性枯土礦物經第四级銨型陽離子界 面活性劑及非離子性界面活性劑處理而得者，其含量 為總組成物之0.1至5重量：!；，且前述0/W(水包油）型 乳液與外油相之配合比例為重量比2:3〜19:1者。 2. 如申請專利範圍第1項之多重乳液，其特徵為該多重乳 液為油相中含矽氧系油分者。 3. 如申請專利範圍第2項之多重乳液，其特徵為該多重 乳液為外油相中配合有矽氧系油分者。 4. 如申請專利範圍第2項或第3項之多重乳液，其特徵為 該多重乳液中配合之矽氧糸油分對該多重乳液全量為5 〜60重量％者。 5. 如申請專利範圍第2項之多重乳疲，其特徵為該多重乳 液中之矽氧系油分為沸點2001CM下之低沸點矽氧糸油 分者。 6. 如申請專利範圍第1項之多重乳液，其特激為該多重乳 液為内油相中含脂溶性藥劑者。 7. 如申請專利範圍第6項之多重乳液，其特徵為該多重 乳液之内油相中配合之脂溶性藥劑為對矽氧系油分難 溶者，且其矽氧系油分配合於外油相中者。470653 H3 Attachment Printed by the Employees Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs No. 8 5 1 1 3 6 50 Patent Application Amendment to the Patent Scope (June 14th, 89) 1. A multiple emulsion, characterized by The multiple emulsion is an oil-in-water (0 / Ϊ // 0) multiple emulsion in which a 0 / W (oil-in-water) type emulsion is dispersed in an external oil phase. The external oil phase contains an organic modified clay mineral. The organic The modified clay mineral water-swellable subsoil mineral is obtained by treating a fourth-grade ammonium cationic surfactant and a nonionic surfactant, and the content is 0.1 to 5 weight of the total composition:!;, And the foregoing The mixing ratio of 0 / W (oil-in-water) type emulsion to the external oil phase is one with a weight ratio of 2: 3 to 19: 1. 2. The multiple emulsion according to item 1 of the patent application, characterized in that the multiple emulsion is a silicone oil in the oil phase. 3. If the multiple emulsion of item 2 of the patent application is applied, it is characterized in that the multiple emulsion is a compound containing a silicone oil in the outer oil phase. 4. If the multiple emulsion of item 2 or 3 of the scope of patent application is applied, it is characterized in that the total amount of the silicone emulsion in the multiple emulsion is 5 to 60% by weight of the multiple emulsion. 5. If the multiple milk fatigue in item 2 of the patent application scope is characterized in that the silicone oil in the multiple emulsion is divided into low boiling point silicone oil at the boiling point of 2001CM. 6. For the multiple emulsion of item 1 of the patent application scope, the special emulsion is that the multiple emulsion is a fat-soluble drug in the internal oil phase. 7. The multiple emulsion of item 6 of the patent application, characterized in that the fat-soluble agent compounded in the internal oil phase of the multiple emulsion is hardly soluble in silicone oil, and the silicone oil is distributed in the external oil phase. In the middle. 本紙張尺度適用中國國家標準（CNS )A4規格（210 X 297公爱) 1 3 8 5 1 4 470653 _H3_ 8. 如申請專利範圍第6項或第7項之多重乳液，其特徵為 該多重乳液之内油相中配合之脂溶性藥劑為易氧化性 ，為自脂溶性維生素、油溶性紫外線吸收劑、不飽和 脂肪酸及其衍生物中選擇之1種或2種Μ上者。 9. 如申請專利範圍第1項之多重乳液，其特徵為該多重 乳液為水相中含親水性高分子者。 經濟部中央標準局員工福利委員會印製 重素澱、纖烯、膠聚澱硫甲聚乙 該溶溶溶 多黃、醣基 乙素豆 葡基素基共聚 為 水性水 該、醣多甲 聚維槐、甲維 烯烷、 徵 入溶包 為膠聚菇、 、纖剌酸羧纖乙丙胺 特加水油 徼 菜露蘑 素膠基、根、 、聚 氧醯 其 劑包述 特角甘 、維 伯乙膠 草白素 、環烯 ， 性油前 其鹿糖膠纖拉羥樹甘蛋維酯聚丙 法活之入 , 、萄藻、阿、拉、白纖醇烷聚 方面中加 液納葡生醣-素瓜膠、基 二乙、 。造界其分 乳酸 、原 多素維、藻白 丙丙氧 酯者製 子入成 重藻菜、布維纖糖、蛋羥酸環 乙上之離加相 多裼洋糖昆纖基聚子胳基藻聚酸 Κ 液非分水 之為、葡 、化 甲乳桴 、 甲褐 、烯種乳 性成將 項子糖聚醣硝羧半 原、 、酮丙 U 重水相及 9 分蘭質聚、 、 、 、膠粉 素烷聚 i 多親油 ， 第高得 角萄素 體膠膠、澱維咯 、1 型 將内驟 圍性卡、葡維合蕃果糖基纖吡納之油含將步 範水、酸創纖聚黃、三 丙基烯酸擇包包再製 利親膠質癒基烯、膠 ί牙羥丙乙烯選水係，調 專之明明、乙乙醇樹麥基羥聚丙中包法中液 請中、透粉、羧 二槐 聚甲、 、聚胺油方劑乳 申液膠、澱素、乙剌、 、納醚、亞種造溶型 如乳樹粉副維醇聚 、_粉酸基體稀 一 製性劑 3 8 5 1 4 本紙張尺度適用中國國家標準（CNS)A4規格（210X297公给 470653 _H3_ 性溶劑型乳液中之ο/w(水包油）型乳液調製步驟，及 將前述0/W(水包油）型乳液加入含有機改質粘土礦物 之外油相成分中分散乳化之多重化步驟而成者。 12. 如申請專利範圍第11項之油包水包油型多重乳液之製 造方法，其特徴為該多重乳液之製造方法中配合之油 相成分為矽氧系油分者。 13. 如申請專利範圍第12項之油包水包油型多重乳液之製 造方法，其特徵為該多重乳液之製造方法中配合之外 油相成分為矽氧系油分者。 14. 如申請專利範圍第11至13項任一項之油包水包油型多 重乳液之製造方法，其特徵為該多重乳液之製造方法 經濟部中央標準局員工福利委員會印製 製方溶 製 中生物 製 親中， 之造難 之 相維生 之將其驟 液製分。液 油性衍 液 含於步 乳之 油者乳内溶其 乳 包再製 重液 系分重 中脂及 重為，調 多乳 氧油多 法自酸 多 法中液 型重矽糸 型方為肪 型方劑乳 。 油多對 氧油造，脂 油 造溶型 者包 型為矽 包 製性和 包 製性劑 劑水油劑合水 之化飽 水 之溶溶 藥包包藥配包 液氧不 包液水性 性油水 性中油 乳易、 。油乳入溶 溶之 包溶分 之重為 劑者之 重加水 脂項 油脂成 項多劑 收上項多劑包 合14該之相14該藥吸ΚΠ該性油 配第 為合油 第為性 線種第 為活之 中圍徵配外圍 徵溶外^2圍徵面分 分範特 中且範 特脂紫13範特界成 成利其相，利 其述性 1 利其子相 相專，油劑專，前 溶之專，離油 油請 法内藥 請法之 油擇請 法非内 内申 方中之 申方合 、 選申 方性入 為如 造法性 如造配 素中如 造水加 本紙張尺度適用中國國家標準（CNS )A4規格（210X 297公董) 3 3 8 5 1 4 470653 H3 及將含水及親水性高分子之水相成分加入該油包水溶 性溶劑型乳液之0/W (水包油）型乳液調製步驟，及將 前述0/W(水包油）型乳液分散乳化於含有機改質粘土 礦物之外油相成分中之多重化步驟，及加入前述親水 性高分子之凝膠化劑之水相凝膠化步驟而成者。 經濟部中央標準局員工福利委員會印製 本紙張尺度適用中國國家標準（CNS)A4規格（210X297公董) 4 3 8 5 1 4This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public love) 1 3 8 5 1 4 470653 _H3_ 8. If the multiple emulsion of the scope of patent application item 6 or 7 is applied, it is characterized by the multiple emulsion The fat-soluble agent incorporated in the internal oil phase is easily oxidizable, and is one or two selected from fat-soluble vitamins, oil-soluble ultraviolet absorbers, unsaturated fatty acids, and derivatives thereof. 9. The multiple emulsion according to item 1 of the application, characterized in that the multiple emulsion is a hydrophilic polymer in the aqueous phase. The Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs printed heavy cellulose, cellulose, and polyethylenic acid. Sophora, vinyl alkane, and leaching solution are gelatin mushrooms, cellulose acetate, carboxycellulose, ethylpropylamine, water, oil, amaranth, gelatin, roots, and polyoxygenin. Glycogenin, cycloolefin, sucralose fiber, hydroxyglycerin, vitamin E, and polypropylene are added before the sex oil, and sodium gluconate is added to the alkaloid polymerization of phytoplankton, alga, ala, and leucoalcohol. Raw sugar-sugar guar, diethyl, Created from lactic acid, protoporphyrin, and phycoerythroxypropionate, it was made into heavy algae, cloth dextrose, and methacrylic acid. The non-water-separating solution of phytoplankton polyacrylic acid, glucose, methyl lactate, methyl brown, and olefinic milky ingredients are polysaccharide nitroglycans, ketopropyl U heavy water phase, and 9-cyanine polymer. ,,,,, Colloidin, polyalkylene, and more lipophilic, the first high-quality glucosamine gelatin, Dianwei slightly, type 1 will be the inner card, the vitamin and the fructose-based cellulose Pina Bufan water, acid wound fiber yellow, tripropyl enoic acid select bag and then make the colloidal guaiacene and gum hydroxypropyl ethylene water selection system, adjust the special Mingming, Ethanol tree McGy French liquid, please use medium, penetrating powder, carbodiacrylic acid, polyamine oil formula emulsion emulsion glue, diansu, acetamidine, sodium ether, subspecies solubilizing type such as milk powder, paravinyl alcohol, _ Powder acid base diluent 3 8 5 1 4 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 to 470653 _H3_ ο / w (oil-in-water) type emulsion in solvent-based emulsion The preparation step and the multiple step of adding the aforementioned 0 / W (oil-in-water) emulsion to the dispersion and emulsification of oil phase components other than organic modified clay minerals. 12. For example, the oil in the scope of patent application No. 11 The manufacturing method of the water-in-oil-in-water multiple emulsion is characterized in that the oil phase component in the manufacturing method of the multiple-emulsion is a silicone oil component. 13. For example, the oil-in-water-in-oil multiple in the application scope of the patent No. 12 A method for manufacturing an emulsion, characterized in that the oil phase component outside the blending method in the method for manufacturing the multiple emulsion is a silicone oil component. 14. For example, the oil-in-water-in-water type multiple of any one of claims 11 to 13 The manufacturing method of the emulsion is characterized in that the manufacturing method of the multiple emulsion is printed by the employee welfare committee of the Central Standards Bureau of the Ministry of Economic Affairs. The oily extract is contained in the milk of the step milk, and the milk is dissolved in the milk bag, and the heavy liquid system is divided into heavy fat and heavy fat. Formula milk. Oil-based, fatty-oil-soluble type package type is silicon-encapsulating and encapsulating agent agent, water-oil agent, and water-saturated water-soluble solution. 、. The weight of the oil emulsion into the soluble solvent is the weight of the agent, and the water and fat are added. The multi-agent is received. The multi-agent is included in the above. The 14 is the phase. 14 The drug is sucked. The oil is the first. The sex line is the first to be enlivened and the outer is to be dissolved. 2 The encirclement is divided into the Fante and the Fantezhi 13. The Fante boundary becomes a favorable phase. Relative special, oil special, pre-dissolving special, oil-free oil, internal medicine, legal method, oil selection method, non-internal application party, the application party is selected as the law, such as the formulation The paper size of Zhongru water is added to the Chinese National Standard (CNS) A4 specification (210X 297 public directors) 3 3 8 5 1 4 470653 H3 and the water phase components of water-containing and hydrophilic polymers are added to the oil-in-water-soluble solvent 0 / W (oil-in-water) type emulsion preparation steps, and disperse and emulsify the aforementioned 0 / W (oil-in-water) type emulsion in Oil phase component of the multi-step addition of clay minerals, water was added and the hydrophilic polymer gelling agent of the phase formed by the gelation step. Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210X297 public directors) 4 3 8 5 1 4