1248377 玖、發明說明 【發明所屬之技術領域】 本發明是有關於一種具相變化材料 法，且特別是有關於一種適用於織品上之 膠囊的製造方法。 【先前技術】BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a method of phase change material, and more particularly to a method of making a capsule suitable for use on a fabric. [Prior Art]
Materials, PCMS)為一種在特定溫度襄 由固相變化至液相，或由液相變化至固 很多物質可以在某一溫度範圍下作為相 水-冰就可以在攝氏〇度左右作為相變# 對於相變化材料的選用有兩個考量 材料適用的溫度範圍，第二是相變化材 潛熱的吸收或釋放的大小。基本上係視 選擇適當溫度範圍之相變化材料。再者 大潛熱值的相變化材料來進行應用，較 相變化時可以吸收，釋放更多的熱量，而 範圍内維持較長的時間，而得到較佳的 通常相變化材料在加熱過程中所造 ，到達熔點後會消失。在整個相轉變過 材料及週圍m境的溫度可維持一定p 熱，其溫度會持續上昇。 又 改膠囊的製造方 具相變化材料微 (Phase-Change 内，其物理態可 的物質。當然， 化材料》例如， 料使用。 ，第一是相變化 在相變化時伴隨 境溫度的需要來 也會選擇具有較 的潛熱值代表在 以在相變化溫度 的溫度上昇現象 完成後，相變化 再對此類材料加 5 1248377 當冷卻至相變化材料結晶溫度時，潛熱將被釋放出 來。在液相轉為固相時，相變化材料的溫度維持不變。當 相變化完成後，若對此類材料持續降溫，其溫度會持續降 低。 由於相變化材料在實際應用時會在於固態及液態間進 行轉變，當相變化材料為液態時，若無任何包覆層的包覆， 將會發生逸失的情形，因此，一種將相變化材料利用微膠 囊包覆而避免液態相變化材料逸失的技術已被運用於相變 化材料的應用領域之内。 微膠囊的合成方法包括化學合成方法、物理化學合成 方法及物理機械合成方法，在化學合成方法中，又包括界 面聚合法、原位聚合法及銳孔-凝固浴法。其中，界面聚合 法具有相當多的優點，例如反應速率快、反應條件溫和、 對反應單體純度要求不高、對兩種反應單體的原料配比要 求不嚴等等，故廣為業界所採用，一般而言，微膠囊的壁 材係為一聚合物。 界面聚合法包括了水相及有機相，水相的溶劑為水而 有機相的溶劑可以為二氯甲烷、三氯曱烷、三氯乙烷、四 氯二氟乙烷、四氯化碳、苯、曱苯、二甲苯、二硫化碳、 戊烧、環己烧、礦物油或上述幾種溶劑的混合物。相變化 材料及用於形成微膠囊壁材的至少一單體會溶於有機相之 中，而形成微膠囊壁材的至少一單體會溶於水相中，水相 另外必須包括一界面活性劑。 6 1248377 界面活性劑在界面聚合法中扮演一個非常重要的角 色，界面活性劑能將有機相形成微胞（M i c e I丨e)後帶入水相 中，在微胞的界面上，有機相中的單體和水相中的單體發 生聚合反應而生成微膠囊的外殼（Shell)，而將原存在於 微胞中之相變化材料包覆於其中。適用於界面聚合法的界 面活性劑可以為例如聚乙烯醇、明膠、甲基纖維素及或其 他界面活性劑等等。 另外，在習知形成包覆相變化材料的微膠囊的界面聚 合法中，由於相變化材料主要係使用烷基或芳香基的碳氫 化物類之低極性物質，而一般溶於有機相的單體多為具有 極性或高極性的物質，例如苯乙烯、異氰酸鹽等等，因此， 需要有機溶劑來溶解相變化材料及單體。 以界面聚合法中形成微膠囊，有機相中的有機溶劑有 可能會被包覆在其中。在相變化材料微膠囊中，這種情形 會改變微膠囊適用的溫度範圍，而影響到微膠囊的品質。 雖然現有微膠囊界面聚合法的製程中，會利用溫度來去除 有機溶劑，但有機溶劑仍可能有不低的殘留。再者，由於 習知形成的微膠囊係具有疏水性的外殼，因此微膠囊係存 在於有機相中。微膠囊塗佈在織品上的方法必需將微膠囊 分散於水相中，因此，在完成微膠囊的製造之後，需除去 有機溶劑，在去除有機溶劑的過程中，高溫常會損傷微膠 囊的外殼，雖然這不會造成立即的相變化材料外逸，但仍 會造成微膠囊在後續使用上容易發生外殼破損，而造成相 7 1248377 變化材料外逸的情形發生。 【發明内容】 就習知形成微膠囊的界面聚合法中，可以暸解關鍵點 係出現在有機相中的有機溶劑，若能避免使用有機溶劑， 則可避免習知之問題。但是，在習知形成微膠囊的界面聚 合法中若不使用有機溶劑，原溶於有機溶劑中的單體無法 分散於有機相中，根本上製程完全不能進行。另外，即令 形成了微膠囊，微膠囊亦無法適當的分散於有機溶劑中。 有鑑於此，本發明的目的就是在提供一種適用於界面 聚合法形成微膠囊的組成，可以不需要外加有機溶劑，即 可有效的製造微膠囊。 本發明的另一目的就是在提供一種適用於界面聚合法 形成微膠囊的組成，形成的微膠囊具有親水性的外殼，可 分散於水相中，而得以在製造過程中排除有機溶劑的使用。 本發明的又一目的就是在提供一種適用於界面聚合法 形成微膠囊的組成，使用具有極性的相變化材料作為有機 相，而可以排除有機溶劑的使用。 本發明的再一目的就是在提供一種適用於界面聚合法 形成微膠嚢的組成，無須使用界面活性劑，即可完成微膠 囊的製造。 本發明所揭露之適用於界面聚合法形成微膠囊的組成 包括水相及有機相兩相。在水相中使用水當溶劑，其中至 少包括水性聚胺酯，例如水性聚胺基曱酸酯（W a t e r b 〇 r n e 1248377Materials, PCMS) is a phase change from a solid phase to a liquid phase at a specific temperature, or from a liquid phase to a solid matter. It can be used as a phase change in a certain temperature range as a phase water-ice. For the choice of phase change material, there are two temperature ranges for the material to be considered, and the second is the absorption or release of the latent heat of the phase change material. Basically, the phase change material of the appropriate temperature range is selected. Furthermore, the phase change material with large latent heat value can be applied, and can absorb more when the phase changes, and release more heat, while maintaining a longer period in the range, and obtaining a better normal phase change material in the heating process. , will disappear after reaching the melting point. The temperature of the material and the surrounding environment can maintain a certain p-heat and the temperature will continue to rise. Also, the capsule is manufactured with a phase change material micro (Phase-Change, the physical state of the material. Of course, the chemical material), for example, is used. First, the phase change is accompanied by the need for temperature in the phase change. The latent heat value is also selected to represent that after the temperature rise phenomenon at the phase change temperature is completed, the phase change is added to the material 5 1248377. When cooled to the crystallization temperature of the phase change material, the latent heat will be released. When the phase is changed to the solid phase, the temperature of the phase change material remains unchanged. When the phase change is completed, if the material is continuously cooled, the temperature will continue to decrease. Since the phase change material will be in the solid state and the liquid state in practical application. When the phase change material is in a liquid state, if there is no coating of any coating layer, the escape will occur. Therefore, a technique for coating the phase change material with the microcapsule to avoid the liquid phase change material is lost. It is used in the field of application of phase change materials. The synthesis methods of microcapsules include chemical synthesis methods, physical and chemical synthesis methods, and physical machines. The synthesis method includes, in the chemical synthesis method, an interfacial polymerization method, an in-situ polymerization method and an orifice-coagulation bath method. Among them, the interfacial polymerization method has considerable advantages, such as a fast reaction rate, a mild reaction condition, and a reaction sheet. The purity of the body is not high, and the raw material ratio of the two reaction monomers is not strict, so it is widely used in the industry. Generally, the wall material of the microcapsule is a polymer. The interfacial polymerization method includes water. The organic phase, the solvent of the aqueous phase is water and the solvent of the organic phase may be dichloromethane, trichloromethane, trichloroethane, tetrachlorodifluoroethane, carbon tetrachloride, benzene, toluene, and Toluene, carbon disulfide, pentane, cyclohexane, mineral oil or a mixture of the above solvents. The phase change material and at least one monomer used to form the microcapsule wall material are dissolved in the organic phase to form a microcapsule wall. At least one monomer of the material will dissolve in the aqueous phase, and the aqueous phase must additionally include a surfactant. 6 1248377 The surfactant plays a very important role in the interfacial polymerization process, and the surfactant can form the organic phase. (M ice I丨e) is carried into the aqueous phase. At the interface of the micelles, the monomer in the organic phase and the monomer in the aqueous phase are polymerized to form a shell of the microcapsule, and the original The phase change material present in the micelle is coated therein. The surfactant suitable for the interfacial polymerization method may be, for example, polyvinyl alcohol, gelatin, methyl cellulose, or other surfactants, etc. In the interfacial polymerization method for forming microcapsules coated with a phase change material, since the phase change material mainly uses a low polarity substance of an alkyl group or an aromatic hydrocarbon group, the monomer generally dissolved in the organic phase is mostly polar. Or a highly polar substance such as styrene, isocyanate, etc., therefore, an organic solvent is required to dissolve the phase change material and the monomer. The microcapsules are formed in the interfacial polymerization method, and the organic solvent in the organic phase may be Wrapped in it. In phase change material microcapsules, this situation changes the temperature range applicable to the microcapsules and affects the quality of the microcapsules. Although the existing microcapsule interfacial polymerization process uses temperature to remove the organic solvent, the organic solvent may still have a low residual. Further, since the microcapsules which are conventionally formed have a hydrophobic outer shell, the microcapsules are present in the organic phase. The method of coating the microcapsules on the fabric must disperse the microcapsules in the aqueous phase. Therefore, after the completion of the manufacture of the microcapsules, the organic solvent needs to be removed, and in the process of removing the organic solvent, the high temperature often damages the outer shell of the microcapsules. Although this does not cause immediate phase change material escaping, it still causes the microcapsule to be easily damaged in subsequent use, which causes the material to escape from the phase change. SUMMARY OF THE INVENTION In the conventional interfacial polymerization method for forming microcapsules, it is possible to understand an organic solvent which is present in the organic phase at a critical point, and if the organic solvent is avoided, the conventional problem can be avoided. However, in the conventional interfacial polymerization method for forming microcapsules, if an organic solvent is not used, the monomer originally dissolved in the organic solvent cannot be dispersed in the organic phase, and the process cannot be carried out at all. Further, even if microcapsules are formed, the microcapsules are not properly dispersed in the organic solvent. In view of the above, an object of the present invention is to provide a composition suitable for forming a microcapsule by an interfacial polymerization method, which can efficiently produce a microcapsule without an external organic solvent. Another object of the present invention is to provide a composition suitable for interfacial polymerization to form microcapsules which are formed into a hydrophilic outer shell which can be dispersed in an aqueous phase to eliminate the use of organic solvents in the manufacturing process. A further object of the present invention is to provide a composition suitable for the formation of microcapsules by interfacial polymerization, using a phase change material having polarity as an organic phase, and the use of an organic solvent can be excluded. A further object of the present invention is to provide a composition suitable for the formation of microcapsules by interfacial polymerization, and the manufacture of microcapsules can be accomplished without the use of surfactants. The composition of the present invention for forming microcapsules by interfacial polymerization comprises two phases of an aqueous phase and an organic phase. Water is used as the solvent in the aqueous phase, including at least aqueous polyurethanes such as aqueous polyamino phthalates (W a t e r b 〇 r n e 1248377
Polyurethane)、2，2 -雙（經曱基）丙酸或其三乙基 含磺酸鹽的二胺（此處與D r_林確認過）及其任意 組成之族群。水性聚胺酯的重量百分率濃度約介於 40%之間，而較佳的重量百分率濃度約介於1 5% 3 之間。 有機相中至少包括相變化材料，油相單體及 (S ο I i d W a X )。其中，相變化材料係為羧酸酯，以 取代習用烷基或芳香基的碳氫化物的目的在於提供 極性來溶解油相單體，其中，羧酸酯之羧酸基係選 酸基、乙酸基及丙酸基所組成之族群，而羧酸酯之 為碳數介於1 〇至1 8的飽和烷醇。此一羧酸酯相變 適用的溫度範圍約介於攝氏負20度至攝氏40度之 然，選用更長的醇基碳鏈可以適用於更高的溫度範 如，選用20至28個碳的直鏈醇基的羧酸酯即可適 氏45至80度的範圍。 油相單體係在界面聚合製程中和水性聚胺酯發 反應以形成微膠囊的外殼。油相單體可以為三聚氰 異氰酸鹽，油相單體相對於相變化材料的重量百分 約介於3 %至1 2 %之間，較佳的重量百分率濃度約 %至1 0 %之間。另外，所使用的油相單體與水性聚 重量比約介於2 5 %至5 0 %之間，較佳的重量比約： %至4 5 %之間。在形成微膠囊之後，固體蠟和相變 會被聚合後的水性聚胺酯外殼包覆，固體蠟的熔點 相變化材料的熔點，其用途在於相變化材料在相變 胺鹽、 組和所 5%至 L 35% 固體臘 羧酸酯 較高的 自於曱 醇基係 化材料 間，當 圍，例 用到攝 生聚合 醯胺或 率濃度 介於5 胺酯的 介於30 化材料 遠南於 化時作 9 1248377 為晶種之用。 將水相及有機相至於反應容器中，以均質機高速 並進行加熱，其中均質機授拌的速度約介於每分鐘 轉至9 0 0 0轉之間做乳化攪拌2分鐘至5分鐘；而加 溫度約介於攝氏20度至90度之間進行一梯度升溫製 梯度升溫製程係將升溫過程區分成至少兩個階段，在 階段均維持一固定的溫度1小時至5小時，然後升溫 下一個階段，例如升溫至一第一溫度，第一溫度係介 氏2 0度至4 0度之間，維持第一溫度2小時至5小時 著，升温至一第二溫度，第二溫度約介於攝氏40度 度之間1小時至3小時，最後升溫至一第三溫度，第 度約介於攝氏6 0度至9 0度之間，維持3 0分鐘至2 總加熱的時間約介於3.5小時至1 0小時之間，即可形 覆相變化材料的微膠囊。 在界面聚合製程中，水性聚胺酯不只作為聚合反 單體，也可作為界面活性劑之用。水性聚胺酯將有機 成微胞後帶入水相中，在微胞的界面上，有機相中的 和水相中的單體發生聚合反應而生成微膠囊的 (Shell)，而將原存在於微胞中之相變化材料包覆 中。所以，運用本發明所提供之適用於界面聚合法形 膠囊的組成無須另外加入界面活性劑。無須另外添加 活性劑，不僅可節省製造成本，亦可避免廢液中界面 劑對環境造成的衝擊。 乳化 4000 熱的 .程。 每一 進入 於攝 ，接 至60 三溫 、時。 成包 應的 相形 單體 外殼 於其 成微 界面 活性 10 1248377 λλ , ⑺叫承令沄形成微牒春 的、、且成可以排除使用有機溶劑，即使 4 機溶劑並無礙於利用本 ’ 加入有 卽— 本^明k供的組成來形成微膠囊。介 在具有有機溶劑的情形下， ’、 〗、/产P 4〜听所知供的組成亦π 在"、、須另外添加界面活性劑的情形下， σ 材料的微膠嚢的製程。 〃目變化 【實施方式】 為了讓本發明所提供之適用於界面聚合法 的組成及製造方、、共# + 、主姑& S ’货I囊 成及h方法更加清楚起見，下文特舉數個較 例’來詳細說明如何運用本發明所揭露之組成及製造： 法，並進一步由實施例之揭露來瞭解本發明之優點。k 實施例一 將水性聚胺基曱酸酯6 9克、水3 0 〇克、彳，6 一六亞甲 基二異氰酸之異三聚氰酸鹽（丨s〇cyanurate 〇f 1’6-Hexamethylene Diisocyanate) 克、甲酸十六碳酯 (Hexadecanyl Formate) 207克及固體蠟u克置於反應 槽中’其中’水相中包括水性聚胺基曱酸酯和水，而有機 相中包括上述之異三聚氰酸鹽、曱酸十六碳酯及固體纖。 以每分鐘7000轉的轉速做乳化攪拌3分鐘後，以攝 氏40度加熱彳小時，之後，每隔1小時再升溫1 〇度至攝 氏90度維持一小時。最後，加入7.7克的十二碳烷基磺酸 11 1248377 鈉（Natriumdodecylsulfate)做為安定劑。最後得到具有3〇 %固型物之水溶液。其中’微膠囊的粒徑約介於1微米至 2微米之間。相變化溫度約為攝氏2 8度。 實施例二 將水性聚胺基甲酸酯9 1克、水3 0 0克、1 ,6 —六亞甲 基一'異亂酸之異二聚亂酸鹽 （Isocyanurate of 1,6-Hexamethylene Diisocyanate) 15 克、乙酸十八碳酉旨 (Octadecanyl Acetate ) 1 95克及固體蠟1 〇克置於反應 槽中，其中，水相中包括水性聚胺基曱酸酯和水，而有機 相中包括上述之異三聚氰酸鹽、乙酸十八碳酯及固體壤。 以每分鐘6 5 0 0轉的轉速做乳化攪拌3分鐘後，以攝 氏6 0度加熱3小時後，再升溫至攝氏8 0度維持3小時。 最後，加入4克的十二碳烧基續酸鈉做為安定劑。最後得 到具有4 0 %固型物之水溶液。其中，微膠囊的粒徑約介於 1 _ 5微米至2 _ 5微米之間。相變化溫度約為攝氏3 0度。 實施例三 將水性聚胺基甲酸酯1 1 5克、水3 0 0克、1，6 —六亞 曱基二異氰酸之異二聚氰酸鹽（Isocyanurate of 1,6-Hexamethylene Diisocyanate) 18 克、乙酸十六碳酯 (Hexadecanyl Acetate) 182克及固體蠟克置於反應 12 1248377 槽中，其中，水相中包括水性聚胺基甲酸酯和水，而有機 相中包括上述之異三聚氰酸鹽、乙酸十六碳酯及固體蠟。 以每分鐘5000轉的轉速做乳化攪拌4分鐘後，以攝 氏40度加熱3小時後，升溫至攝氏60度加熱2小時，之 後，再升溫至攝氏8 0度維持一小時。最後，加入6 4克的 十二碳烷基磺酸鈉做為安定劑。最後得到具有4 5 %固型物 之水溶液。其中，微膠囊的粒徑約介於2微米至3 · 5微米 之間。相變化溫度約為攝氏24度。 實施例四 將水性聚胺基甲酸酯8 3克、水3 0 0克、1，6 —六亞曱 基二異氰酸之異三聚氰酸鹽 （Isocyanurate of 1,6-Hexamethylene Diisocyanate) 13 克、乙酉曼十八石炭酉旨 (Octadecanyl Acetate)與甲西复十六碳 SI ( Hexadecanyl Formate )以1 : 1混和共200克及固體蠟11克置於反應 槽中，其中，水相中包括水性聚胺基曱酸酯和水，而有機 相中包括上述之異三聚氰酸鹽、乙酸十八碳S旨、曱酸十六 碳酯及固體蠟。 以每分鐘6000轉的轉速做乳化攪拌3分鐘後，以攝 氏4 5度加熱3小時後，升溫至攝氏6 5度加熱2小時，之 後，再升溫至攝氏8 5度維持一小時。最後，加入6克的 十二碳烷基磺酸鈉做為安定劑。最後得到具有3 5 %固型物 之水溶液。其中，微膠囊的粒徑約介於1 .5微米至2.5微 13 1248377 米之間。相變化溫度約為攝氏2 8度。 實施例五 將水性聚胺基甲酸酯124克、水300克、1，6—六亞 甲基二異氰酸之異三聚氰酸鹽 （Isocyanurate 〇f 1,6-Hexamethylene Diisocyanate)20 克、乙酸十八碳I旨、 丙酸十八石炭酯 （H e X a d e c a n y丨P r 〇 p i ο n a t e ) 以1 :1混合共 178克及固體蠟9克置於反應槽中，其中，水相中包括水 性聚胺基曱酸酯和水，而有機相中包括上述之異三聚氰酸 鹽、乙酸十八碳酯、丙酸十八碳酯及固體蠟。 以每分鐘7 5 0 0轉的轉速做乳化攪拌2 _ 5分鐘後，以 攝氏4 5度加熱3小時後，升溫至攝氏6 0度加熱1小時， 至攝氏7 5度加熱1小時，之後，再升溫至攝氏90度維持 一小時。最後，加入6 · 4克的十二碳烷基磺酸鈉做為安定 劑。最後得到具有4 5 %固型物之水溶液。其中，微膠囊的 粒徑約介於〇 _ 5微米至1 5微米之間。相變化溫度約為攝 氏29度。 實施例六 將水性聚胺基曱酸酯1 1 〇克、水300克、1，6_六亞 甲基二異氰酸之異三聚氰酸鹽（Isocyanurate of 1 ,6-Hexamethylene Diisocyanate) 16 克、丙酸十八碳醋 14 1248377 (Hexadecanyl Propionate)185 克及固體堪 10 克置於反 應槽中，其中，水相中包括水性聚胺基曱酸S旨和水，而有 機相中包括上述之異三聚氰酸鹽、丙酸十八碳酯及固體蠟。 以每分鐘8 0 0 0轉的轉速做乳化攪拌2分鐘後，以攝 氏4 0度加熱1小時，之後，每隔1小時再升溫1 0度至攝 氏9 0度維持一小時。最後，加入3克的山梨糖醇甘油酸 單酯（S 〇 r b i t a η Μ ο η ο ο丨e a t e )做為安定劑。最後得到具有 4 5 %固型物之水溶液。其中，微膠囊的粒徑約介於0.5微 米至1 .5微米之間。相變化溫度約為攝氏2 7度。 實施例七 將水性聚胺基甲酸酯8 5克、水3 0 0克、1，6 —六亞甲 基二異氰酸之異三聚氰酸鹽 （Isocyanurate of 1 ,6-Hexamethylene Diisocyanate ) 13 克、乙西曼十石炭酯 (Octyl Acetate) 200克及固體蠟11克置於反應槽中， 其中，水相中包括水性聚胺基曱酸酯和水，而有機相中包 括上述之異三聚氰酸鹽、乙酸十碳酯及固體蠟。 以每分鐘6 0 0 0轉的轉速做乳化攪拌3分鐘後，以攝 氏4 5度加熱3小時後，升溫至攝氏6 5度加熱2小時，之 後，再升溫至攝氏8 5度維持一小時。最後，加入6克的 十二碳烷基磺酸鈉做為安定劑。最後得到具有3 8 %固型物 之水溶液。其中，微膠囊的粒徑約介於1 . 5微米至2.5微 米之間。相變化溫度約為攝氏負1 3度。 15 1248377 由上述之實施例可知，利用本發明所揭露之適用於界 面聚合法形成微膠囊的組成及微膠囊的製造方法，確實可 以將具有曱酸基、乙酸基或丙酸基之羧酸酯的相變化材 料，包覆於水性聚胺酯所形成的外殼中而形成微膠囊，其 中，相變化材料羧酸酯之醇基係為碳數介於1〇至1 8的飽 和烷醇。由於相變化材料可以溶解油相單體，因此無須加 入有機溶劑，而水性聚胺酯單體或預聚物具有界面活性劑 的功效，因此無須再加入界面活性劑。而最後形成的具親 水性外殼之微膠囊，直接分散於水中，而避免了為去除有 機溶劑所做之加熱步驟造成對微膠囊的傷害。 接著下兩個實施例中，係為在有機相中加入有機溶 劑。此二實施例的目的在於顯示即使具有有機溶劑的情形 下，本發明所揭露的之適用於界面聚合法形成微膠囊的組 成依然能用於微膠囊的製造，且進一步凸顯組成中以水性 聚胺酯取代習知製程中水溶性單體的功效。水性聚胺酯不 僅只當作水溶性單體或預聚合物（P r e - ρ ο I y m e r)使用，也 可作為界面活性劑之用，因此，無須額外加入界面活性劑。 實施例八 將水性聚胺基曱酸酯48克、水300克、1，6 —六亞曱 基二異氰酸之異三聚氰酸鹽 （Isocyanurate of 1,6-Hexamethylene Diisocyanate)7 克、乙酉变乙酯（Ethyl Acetate) 120 克、曱酸十八碳酯（Octadecanyl Formate ) 16 1248377 217克及固體蠟17克置於反應槽中’其中，水相中包括水 性聚胺基甲酸酯和水，而有機相中包括乙酸乙酯、上述之 異三聚氰酸鹽、曱酸十八破酯及固體蝶。 以每分鐘7 0 〇 〇轉的轉速做乳化攪拌3分鐘後，以攝 氏4 0度加熱3小時後，升温至攝氏6 0度加熱2小時，之 後，再升溫至攝氏80度加熱一小時。最後，加入2.6克的 十二碳烧基續酸納（Natriumdodecylsulfate)做為安定劑。 最後得到具有2 0 %固型物之水溶液。其中，微膠囊的粒徑 約介於1微米至2微米之間。相變化溫度約為攝氏3 7度。 實施例九 將水性聚胺基甲酸酯1 4 3克、水3 0 0克、1，6 —六亞 甲基二異氰酸之異三聚氰酸鹽（Isocyanurate of 1,6-Hexamethylene Diisocyanate )21 克、乙酸乙酉旨（Ethyl Acetate ) 120 克、乙酸十八碳醋（Octadecanyl Acetate) 169克及固體蠟13克置於反應槽中，其中，水相中包括水 性聚胺基曱酸酯和水，而有機相中包括乙酸乙酯、上述之 異三聚氰酸鹽、乙酸十八碳酯及固體蠟。 以每分鐘6 5 0 0轉的轉速做乳化攪拌3分鐘後，以攝 氏6 0度加熱3小時後，再升溫至攝氏8 0度維持3小時。 最後’加入 5 克的十二碳烷基磺酸鈉 (Natriumdodecylsulfate)做為安定劑。最後得到具有25% 固型物之水溶液。其中，微膠囊的粒徑約介於1.5微米至 17 1248377 2.5微米之間。相變化溫度約為攝氏3 0度。 由以上兩實施例可知，即使在有機溶劑的存在之下， 本發明所揭露的之適用於界面聚合法形成微膠囊的組成依 然能用於微膠囊的製造。完成後的微膠囊分散存在於水 中，而有機溶劑由於和水不互溶，可以以簡單的減壓蒸餾 方式去除。Polyurethane, 2,2-bis(fluorenyl)propionic acid or its triethylsulfonate-containing diamine (here identified with Dr.) and its constituents. The aqueous polyurethane has a weight percent concentration of between about 40% and a preferred weight percent concentration of between about 15% and about 3. The organic phase includes at least a phase change material, an oil phase monomer and (S ο I i d W a X ). Wherein, the phase change material is a carboxylate to replace a conventional alkyl or aromatic hydrocarbon to provide a polarity to dissolve the oil phase monomer, wherein the carboxylate of the carboxylate is an acid group, acetic acid The group consisting of a base and a propionic acid group, and the carboxylate is a saturated alkanol having a carbon number of from 1 Torr to 18. This carboxylic acid ester phase transition is suitable for temperatures ranging from minus 20 degrees Celsius to 40 degrees Celsius. The use of longer alcohol-based carbon chains can be applied to higher temperature ranges, such as 20 to 28 carbons. The linear alcohol group carboxylic acid ester can be in the range of 45 to 80 degrees. The oil phase single system reacts with the aqueous polyurethane in an interfacial polymerization process to form an outer shell of the microcapsules. The oil phase monomer may be melamine isocyanate, and the weight percentage of the oil phase monomer relative to the phase change material is between 3% and 12%, and the preferred weight percentage concentration is about % to 10%. %between. Further, the oil phase monomer to water-to-weight ratio used is between about 25 % and 50%, preferably between about % and about 45% by weight. After forming the microcapsules, the solid wax and the phase change are coated by the polymerized aqueous polyurethane outer shell, and the melting point of the solid wax changes the melting point of the material, and the use thereof is in the phase change material in the phase change amine salt, the group and the 5% to L 35% solid waxy carboxylate is higher from the sterol-based material, when it is used, the polymerization of the decylamine or the concentration of the 5 amine ester is between 30 9 1248377 is used for seed crystals. The aqueous phase and the organic phase are placed in a reaction vessel, and heated at a high speed by a homogenizer, wherein the homogenizer is fed at a rate of about 9000 rpm and emulsified for 2 minutes to 5 minutes; The addition temperature is between about 20 degrees Celsius and 90 degrees Celsius. A gradient heating gradient heating process system divides the temperature rising process into at least two stages, maintaining a fixed temperature for 1 hour to 5 hours in the stage, and then heating up the next one. In the stage, for example, the temperature is raised to a first temperature, the first temperature is between 20 and 40 degrees Celsius, the first temperature is maintained for 2 hours to 5 hours, and the temperature is raised to a second temperature, and the second temperature is approximately 1 hour to 3 hours between 40 degrees Celsius, and finally to a third temperature, the first degree is between 60 degrees Celsius and 90 degrees Celsius, maintaining 30 minutes to 2 total heating time is about 3.5 Between hours and 10 hours, microcapsules of phase change material can be formed. In the interfacial polymerization process, the aqueous polyurethane is not only used as a polymerization anti-monomer but also as a surfactant. The aqueous polyurethane melts into the aqueous phase after being formed into a microcell, and at the interface of the microcell, the monomer in the organic phase and the monomer in the aqueous phase are polymerized to form a microcapsule (Shell), which will exist in the micro The phase change material in the cell is coated. Therefore, the use of the present invention for the composition of the interfacial polymerization capsule does not require the addition of a surfactant. There is no need to add an additional active agent, which not only saves manufacturing costs, but also avoids the environmental impact of the interface agent in the waste liquid. Emulsified 4000 heat. Each enters the camera and is connected to 60 three warm hours. The phase-like monomer shell of the package is formed into a micro-interface activity 10 1248377 λλ, (7) is called the 沄 沄 沄 沄 沄 沄 沄 沄 沄 沄 、 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 , , , , , , , There are 卽 - the composition of this ^ to provide microcapsules. In the case of having an organic solvent, the composition of the σ material is also determined by the composition of the π material in the case where the composition of the σ material is also π in the case where the surfactant is added. [Embodiment] In order to make the composition and manufacturing method of the interfacial polymerization method provided by the present invention, the total #+, the main aggravation & the S' cargo I capsule formation and the h method are more clear, the following The advantages and disadvantages of the present invention are set forth in the Detailed Description of the Invention. k Example 1 Aqueous polyamine phthalate 6 9 g, water 30 g, hydrazine, 6 hexamethylene diisocyanate iso-cyanate (丨s〇cyanurate 〇f 1' 6-Hexamethylene Diisocyanate) 克, Hexadecanyl Formate 207 g and solid wax u g are placed in the reaction tank, where the 'aqueous phase' includes aqueous polyamino phthalate and water, and the organic phase includes The above isomeric cyanurate, hexadecyl phthalate and solid fiber. After emulsification and stirring for 3 minutes at 7,000 rpm, it was heated at 40 ° C for 彳 hours, and then heated at 1 Torr to 90 ° C for one hour every hour. Finally, 7.7 g of sodium dodecylsulfate 11 1248377 (Natriumdodecylsulfate) was added as a stabilizer. Finally, an aqueous solution having a 3 % solids was obtained. Wherein the microcapsules have a particle size of between about 1 micrometer and 2 micrometers. The phase change temperature is about 28 degrees Celsius. Example 2: Hydrophobic polyurethane 9 1 g, water 300 g, 1,6-hexamethylene-Isocyanurate of 1,6-Hexamethylene Diisocyanate 15 g, Octadecanyl Acetate 1 95 g and solid wax 1 g are placed in the reaction tank, wherein the aqueous phase includes aqueous polyamino phthalate and water, and the organic phase includes The above isomeric cyanurate, octadecyl acetate and solid soil. After emulsification and stirring for 3 minutes at a rotation speed of 6 500 rpm, the mixture was heated at 60 ° C for 3 hours, and then heated to 80 ° C for 3 hours. Finally, 4 grams of sodium dodecyl sulphate was added as a stabilizer. Finally, an aqueous solution having 40% solids was obtained. The microcapsules have a particle size of between about 1 _ 5 microns and 2 _ 5 microns. The phase change temperature is approximately 30 degrees Celsius. Example 3 is an aqueous solution of 1,5 g of water-based polyurethane, 300 g of water, and 1,6-hexamethylene diisocyanate (Isocyanurate of 1,6-Hexamethylene Diisocyanate) 18 g, Hexadecanyl Acetate 182 g and solid wax are placed in the reaction 12 1248377 tank, wherein the aqueous phase includes aqueous polyurethane and water, and the organic phase includes the above Isocyanurate, hexadecyl acetate and solid wax. After emulsification and stirring for 4,000 rpm for 4 minutes, the mixture was heated at 40 ° C for 3 hours, and then heated to 60 ° C for 2 hours, and then heated to 80 ° C for one hour. Finally, 64 g of sodium dodecylsulfonate was added as a stabilizer. Finally, an aqueous solution having 45% solids was obtained. The microcapsules have a particle size of between about 2 microns and about 3. 5 microns. The phase change temperature is approximately 24 degrees Celsius. Example 4: 8 3 g of aqueous polyurethane, 300 g of water, 1,6-Hexamethylene Diisocyanate, 1,6-Hexamethylene Diisocyanate 13 grams, Octadecanyl Acetate and Hexadecanyl Formate are mixed with a total of 200 grams of 1:1 and 11 grams of solid wax in a reaction tank, in which the aqueous phase is included. Aqueous polyamino phthalate and water, and the organic phase includes the above-mentioned iso-cyanate, octadecyl acetate, hexadecyl citrate and solid wax. After emulsification and stirring for 3 minutes at 6,000 rpm, the mixture was heated at 45 ° C for 3 hours, and then heated to 65 ° C for 2 hours, and then heated to 85 ° C for one hour. Finally, 6 grams of sodium dodecylsulfonate was added as a stabilizer. Finally, an aqueous solution having 35% solids was obtained. Among them, the particle size of the microcapsules is between about 1.5 microns and 2.5 micro 13 1248377 meters. The phase change temperature is about 28 degrees Celsius. Example 5: 124 g of aqueous polyurethane, 300 g of water, 1,oc-hexamethyl diisocyanate (Isocyanurate 〇f 1,6-Hexamethylene Diisocyanate) 20 g Acetic acid 18 octacarbon I, octadecyl propionate (H e X adecany 丨 P r 〇pi ο nate ) 1:1 mixture of 1:1 and 9 grams of solid wax in the reaction tank, wherein the water phase The aqueous polyamino phthalate and water are included, and the organic phase includes the above-mentioned isomeric cyanurate, octadecyl acetate, octadecyl propionate and solid wax. After emulsification stirring at 750 rpm for 2 _ 5 minutes, heating at 45 ° C for 3 hours, heating to 60 ° C for 1 hour, and heating to 75 ° C for 1 hour, after that, Heat up to 90 degrees Celsius for one hour. Finally, 6.4 g of sodium dodecylsulfonate was added as a stabilizer. Finally, an aqueous solution having 45% solids was obtained. The microcapsules have a particle size of between about _ 5 μm and 15 μm. The phase change temperature is approximately 29 degrees Celsius. Example 6 Aqueous polyamino phthalate 1 1 gram, 300 g of water, 1,6-hexamethylene diisocyanate (Isocyanurate of 1 , 6-Hexamethylene Diisocyanate) 16 185 grams of hexadecyl vinegar 14 1248377 (Hexadecanyl Propionate) and 10 grams of solids are placed in the reaction tank, wherein the aqueous phase includes aqueous polyamine phthalic acid and water, and the organic phase includes the above Iso-cyanolate, octadecyl propionate and solid wax. After emulsification and stirring for 2 minutes at a rotation speed of 8,000 rpm, it was heated at 40 ° C for 1 hour, and then heated at 10 ° C to 90 ° C for one hour every hour. Finally, 3 g of sorbitol monoglyceride (S 〇 r b i t a η ο ο η ο ο丨 e a t e ) was added as a stabilizer. Finally, an aqueous solution having 45% solids was obtained. Among them, the microcapsules have a particle diameter of between about 0.5 micrometers and 1.5 micrometers. The phase change temperature is about 27 degrees Celsius. Example 7 85 g of aqueous polyurethane, water 300 g, 1,6-hexamethylene diisocyanate isocyanurate of 1 (6-Hexamethylene Diisocyanate) 13 grams, 200 grams of Octyl Acetate and 11 grams of solid wax are placed in the reaction tank, wherein the aqueous phase includes aqueous polyamino phthalate and water, and the organic phase includes the above-mentioned differences Cyanuric acid, decacarbonate acetate and solid wax. After emulsification and stirring for 3 minutes at a rotation speed of 6,000 rpm, the mixture was heated at 45 ° C for 3 hours, and then heated to 65 ° C for 2 hours, and then heated to 85 ° C for one hour. Finally, 6 grams of sodium dodecylsulfonate was added as a stabilizer. Finally, an aqueous solution having 38% solids was obtained. The microcapsules have a particle size of between about 1.5 microns and 2.5 microns. The phase change temperature is about minus 13 degrees Celsius. 15 1248377 It can be seen from the above examples that the composition of the microcapsules and the method for producing the microcapsules which are suitable for the interfacial polymerization method disclosed in the present invention can surely be a carboxylate having a decanoic acid group, an acetic acid group or a propionic acid group. The phase change material is coated in an outer shell formed by the aqueous polyurethane to form microcapsules, wherein the alcoholic group of the phase change material carboxylate is a saturated alkanol having a carbon number of from 1 to 18. Since the phase change material can dissolve the oil phase monomer, it is not necessary to add an organic solvent, and the aqueous polyurethane monomer or prepolymer has the effect of a surfactant, so that no additional surfactant is required. The resulting microcapsules with a hydrophilic outer shell are dispersed directly in the water, avoiding damage to the microcapsules caused by the heating step to remove the organic solvent. Next, in the next two examples, an organic solvent is added to the organic phase. The purpose of these two examples is to show that the composition of the present invention for the formation of microcapsules by interfacial polymerization can be used for the manufacture of microcapsules even in the presence of an organic solvent, and further highlights the composition by replacing with aqueous polyurethane. The efficacy of water soluble monomers in the conventional process. Aqueous polyurethanes are used not only as water-soluble monomers or prepolymers (P r e - ρ ο I y m e r), but also as surfactants, so that no additional surfactant is required. Example 8: 48 g of aqueous polyamine phthalate, 300 g of water, and Isocyanurate of 1,6-Hexamethylene Diisocyanate, 7 g, Ethyl Acetate 120 g, Octadecanyl Formate 16 1248377 217 g and 17 g of solid wax were placed in the reaction tank, wherein the aqueous phase included aqueous polyurethane and Water, and the organic phase includes ethyl acetate, the above-mentioned isomeric cyanurate, octadecyl citrate and solid butterfly. After emulsification and stirring for 3 minutes at a rotation speed of 70 rpm, the mixture was heated at 40 ° C for 3 hours, and then heated to 60 ° C for 2 hours, and then heated to 80 ° C for one hour. Finally, 2.6 grams of Natriumdodecylsulfate was added as a stabilizer. Finally, an aqueous solution having 20% solids was obtained. Among them, the microcapsules have a particle diameter of between about 1 micrometer and 2 micrometers. The phase change temperature is about 37 degrees Celsius. Example 9 is a water-based polyurethane 14 3 g, water 300 g, 1,6-hexamethylene diisocyanate isocyanate (Isocyanurate of 1,6-Hexamethylene Diisocyanate 21 grams, 120 grams of Ethyl Acetate, 169 grams of Octadecanyl Acetate, and 13 grams of solid wax are placed in the reaction tank, wherein the aqueous phase includes aqueous polyaminophthalate and Water, and the organic phase includes ethyl acetate, the above isomeric cyanurate, octadecyl acetate and solid wax. After emulsification and stirring for 3 minutes at a rotation speed of 6 500 rpm, the mixture was heated at 60 ° C for 3 hours, and then heated to 80 ° C for 3 hours. Finally, add 5 grams of sodium natriumdodecylsulfate as a stabilizer. Finally, an aqueous solution having 25% solids was obtained. Wherein, the microcapsules have a particle size of between about 1.5 microns and 17 1248377 2.5 microns. The phase change temperature is approximately 30 degrees Celsius. As is apparent from the above two examples, the composition of the present invention which is suitable for the interfacial polymerization forming microcapsules can be used for the production of microcapsules even in the presence of an organic solvent. The completed microcapsules are dispersed in water, and the organic solvent is removed by a simple vacuum distillation because it is immiscible with water.
雖然本發明已以數個較佳實施例揭露如上，然其並非 用以限定本發明，本發明所揭露之適用於界面聚合法形成 微膠囊的組成及微膠囊的製造方法當可應用於各種親水性 微膠囊的製程之上，任何熟習此技藝者，在不脫離本發明 之精神和範圍内，當可作各種之更動與潤飾，因此本發明 之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in several preferred embodiments as above, it is not intended to limit the present invention, and the composition of the microcapsules and the method for producing the microcapsules which are suitable for the interfacial polymerization method disclosed in the present invention can be applied to various hydrophilic substances. Above the process of the microcapsules, any person skilled in the art can make various changes and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention is defined by the scope of the appended patent application. Subject to it.
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