201000616 六、發明說明： I：發明戶斤屬之技術領域】 發明領域 本發明係有關於可以作為冷暖空調的熱交換介質、住 宅用的蓄熱材料、防止道路凍結用的蓄熱介質等使用之含 有蓄熱材的蓄熱無縫膠囊及其製造方法。 發明背景 近年來，成為地球暖化原因之二氧化碳排放已成為世 界性的問題。為此，在該領域中之能源消費的削減是重要 課題，不僅居住環境，產業界中所消費之能源也成為其削 減對象。 在該領域中，例如，已有使用隔熱材料之省能源技術 被提出，利用該技術，可以提高建築物的機密性及隔熱性。 但是，此種省能源技術是利用隔熱材料來抑制熱（顯熱）的移 動，不會大幅削減暖氣及冷氣等之空調系統的能源消費。 再者，利用物質的熱移動之省能源技術，可分類成利 用顯熱者和利用潛熱者的2個種類。此處，顯熱意指對物質 給予熱而引起溫度上升時的熱量，潛熱意指物質伴隨一次 相轉移（融解、蒸發、某種結晶間相轉移等）所釋放或吸收的 熱量。例如，在水中，（造成1°C的溫度變化時之）顯熱為 lcal/g，（在0°C之相轉移時的）潛熱為80cal/g，和使用顯熱 的情形相比，使用潛熱時的省能源效率較高。 因此，如上所述，利用隔熱材料之省能源技術，主要 3 201000616 是利用顯熱的技術’並非排尸 除對暖軋及冷氣等之空調系統 的需求之技術’也不是大巾备& 則減居住環境中之能源消費的 技術。 另一方面，利用潛執之少Λμ *、、、义喝旎源技術可以舉例如將呈有 潛熱效果之蓄熱材料微囊仆〃 襄化的技術等。如果將蓄熱材料直 接混練於建材等時’蓄執权+ 、、材枓會因時間經過而有滲出的現 象，長期使用是有困難的， 因此，畜熱材料的膠囊（封入） 化有其必要。此種微膠囊的形士 + 4 ^ 〕^成方法，可舉例如，凝聚法 (coacervationpr〇—、界面聚合法、原位_ 專利文獻1揭4用凝聚法、界面聚合法及原位法作為 微囊化法之，熱父換欢率極高的載熱用微膠囊之製造方 法。詳細地揭示了’「在以内包蓄熱材之微膠囊作為主成分 的載熱用微膠囊刀政液之製造程序中’以所使用之乳化劑 的平均分子量在1000〜100,000的範圍作為特徵之載熱用 微膠囊分散液的製造方法」。專利文獻1中揭示的微膠囊粒 徑為ΐομηι以下，可以提高流動性。 專利文獻2中揭示利用凝聚法、界面聚合法或原位法之 微膠囊的製造方法，詳細地揭示「特徵係在加入了由疏水 性液體和親水性液體組成之被處理液的攪拌容器内，使攪 伴體旋轉以利用離心力讓該被處理液以膜的狀態沿容器内 雙旋轉，使得疏水性液體在親水性液體中乳化分散形成乳 濁液，之後，形成内包有已經乳化分散之疏水性液體的膠 囊壁膜之微膠囊的製造方法」。專利文獻2中揭示的微膠囊製 造方法是一種簡便地製造粒度分布狹窄之粒徑均勻的微膠 201000616 囊之製造方法，玎以製造平均粒徑約為1〜15μηι的微膠囊。 另外，專利文獻3揭示一種利用原位法製造内包有潛熱 蓄熱材之微膠囊的方法。專利文獻3詳細地揭示「由在相對 濕度50%的環境下吸水率為3°/。〜60%的吸水性顏料和，内 包有潛熱蓄熱材之微膠囊的固形物所形成之具有蓄熱性能 的粉體」。專利文獻3中揭示的微膠囊，具有〇·5〜5〇μηι的平 均粒徑，透過照射微波，變成可以加熱及蓄熱。而，其用 途可舉例如懷爐、熱水袋、暖腳爐（foot warmer)等，其特徵 為保溫效果長時間持續。雖然在專利文獻3是使微膠囊乾燥 之後進行粉體化，但是微膠囊的粉體化，通常有粉體彼此 間容易凝集、粉體的流動性變差、粉體化處理時收率降低 等的問題。此外’雖然在專利文獻3是應用三聚氰胺與甲醛的 縮聚反應(polycondensation)來進行微膠囊化，但是從膠囊強 度的面來考慮，會因為皮膜是薄膜而有強度差的問題。 化學、物理性安定的微膠囊之製造方法以原位法為 佳，而從微膠囊的強度的觀點出發，特別是，具有尿素與 甲搭藉縮聚合法而形成之尿素_甲搭聚合璧膜的微膠囊、具 有三聚氰胺與曱醛藉縮聚合法而形成之三聚氰胺-曱醛聚 s壁膜的微膠囊尤其合適。但是，如上所述，從近年來對 %境問題的關心及對人體的影響等來考量，甲醛的使用是 不合需要的。再者，專利文獻4中揭示一穆不含對人體有害 的甲搭1¾且可以既安全且簡單地製造之蓄熱用微膠囊。 專利文獻4更加詳細地揭示「_種含有石蠟之芯材物質被内 包於以聚氨酿樹脂或聚腺樹脂所形成之璧嫉内而形成之蓄 5 201000616 熱用微膠囊，特徵在於前述聚氨酯樹脂或聚脲樹脂是使具 有5倍以上的溶劑豨釋倍率之?灸異氰酸酯與活性氫化物反 應所得到之物質的蓄熱用微膠囊」。 此外，為了使蓄熱用微膠囊具有耐熱性、耐溶劑性、 耐破壞性等物性，以物性優良的材料取代膠囊皮膜的膜質 之作法，使微膠囊的皮膜厚膜化的作法是有效，例如，已 經有利用厚膜化所造成之微膠囊的破壞性改良被提出（專 利文獻5)。詳細地s兒，專利文獻5揭示「内包有溶點為4〇〜 95°C的蓄熱材之微膠囊’平均粒徑為〇.1〜5μηι，且微膠囊 中占有之蓄熱材重量比率為6〇〜75%的蓄熱材微膠囊」。但 是’只是微膠囊皮膜單純的厚膜化，膠囊所含内容物的含 量會降低，微膠囊的機能會下降，故並不理想。尤其是蓄 熱材用微膠囊，如果使微膠囊的皮膜厚膜化就會引起蓄熱 量降低，故不適宜。此外，專利文獻5中的微膠囊中，形成 微膠囊的皮膜也是三聚氰胺-曱醛樹脂。 【專利文獻1】特開平07-2〇4491號公報 【專利文獻2】特開平10-137577號公報 【專利文獻3】特開2001-288458號公報 【專利文獻4】特開20〇4-189843號公報 【專利文獻5】特開平11-152466號公報 【發明内容】 發明揭示 發明欲解決之課題 由於習知的蓄熱膠囊係具有Ο.ίμη〜50μΓη左右的大小 201000616 之微膠囊，對於在建材等中使用時要充分發揮蓄熱效果而 言，難謂是夠大的材料。另外，這些習知之蓄熱膠囊由於 物理強度低、容易瓦解，不適宜用於壁材等建材中。此外， 習知的蓄熱膠囊雖然價格低廉，但多數是以對人體有害的 曱醛為原料利用原位法所製造的，應用於壁材等的建築材 料時，要擔心殘留之甲醛對人體的影響。 因此，本發明之目的在於提供一種在使用用途上並無 特殊限定，卻具備例如，可以適用於壁材等的建材的大小、 強度、安定性、安全性、蓄熱量等之蓄熱膠囊，藉以降低 居住環境中之能源消費。 用以欲解決課題之手段 本發明人等，為解決上述課題進行了積極研究的結 果，發現，將蓄熱膠囊形成為無缝膠囊，此外，利用含有 光硬化性成分之組成物（以下也有稱為「被覆部形成組成 物」的情形）來形成具有多層構造或多核構造之無缝膠囊的 最外殼（以下有時稱為「被覆部」），藉而得以簡便的操作製 造具備亦可適用於建材之大小、強度、安定性、蓄熱量等 之蓄熱膠囊，以及可以正確地規定内容物之蓄熱材的量， 可以簡便地控制蓄熱量的情形，終至完成本發明。因此， 本發明提供以下内容。 [1] 一種蓄熱無缝膠囊，其包含由含有光硬化性成分之 組成物所形成的被覆部以及作為内容物之蓄熱材。 [2] 如上述[1]記載的蓄熱無縫膠囊，其具有2層構造， 且前述光硬化性成分為水性，前述蓄熱材為油性。 [3] 如上述[1]記載的蓄熱無缝膠囊，其具有2層構造， 7 201000616 且前述光硬化性成分為油性，前述蓄熱材為水性。 [4] 如上述[1]記載的蓄熱無缝膠囊，其具有在前述被 覆部和前述蓄熱材之間含有中間層之3層構造，且前述光硬 化性成分為水性，前述中間層為油性，前述蓄熱材為水性。 [5] 如上述[1]記載的蓄熱無縫膠囊，其具有在前述被 覆部和前述蓄熱材之間含有中間層之3層構造，且前述光硬 化性成分為油性，前述中間層為水性，前述蓄熱材為油性。 [6] 如上述[1]記載的蓄熱無縫膠囊，其具有多核構 造，且前述光硬化性成分為水性，前述蓄熱材為油性。 [7] 如上述[1]記載的蓄熱無缝膠囊，其具有多核構 造，且前述光硬化性成分為油性，前述蓄熱材為水性。 [8] 如上述[1]〜[7]的任一項記載的蓄熱無縫膠囊，其 中前述被覆部含有熱傳導性物質。 [9] 如上述[1]〜[8]之任一項記載的蓄熱無缝膠囊，其 中蓄熱材的含量相對於前述膠囊的質量為5〜95質量％。 [10] 如上述[1]〜[9]之任一項記載的蓄熱無縫膠囊，其 平均粒徑為0.1〜20mm。 [11] 一種蓄熱無缝膠囊的製造方法，其係包含由含有 光硬化性成分之組成物所形成的被覆部及作為内容物的蓄 熱材之蓄熱無缝膠囊的製造方法，其中包含 使該含有光硬化性成分之組成物及該蓄熱材通過雙層 喷嘴(double nozzle)、三層喷嘴或多孔材料，調製包含由含 有該光硬化性成分之組成物所形成之未硬化的被覆部，以 及作為内容物的蓄熱材之膠囊前驅物的步驟，及 201000616 將光照射於該光硬化性成分以使膠囊前驅物發生光硬 化的步驟。 [12] —種蓄熱無縫膠囊，係以上述[η]中記載的蓄熱 無縫膠囊之製造方法製得。 用語之定義 本發明書中’「水性」係指’該成分或層或材料整體若 為水性即可，構成成分中即使混合了一部分非水性物質（例 如，油性物質）亦可。此外，本發明書中，「油性」與「水 性」同樣地，係指該成分或層或材料整體若為油性即可， 構成成分中即使混合了一部分非油性物質（例如，水性物質） 亦可。因此，「硬化性成分為水性」是指，當硬化性成分是 由複數種配合劑所構成時，其配合劑的組成整體只要是水 性即可，各別的配合劑並不是只有水性的，也可以含有油 性的。 發明效果 本發明的無缝膠囊，由於具有多層構造或多核構造， 故可提供優良的強度及安定性等之物理特性。 另外，在本發明中可以將膠囊的粒徑做成0.1〜 20mm(亦即’ 1〇〇〜2〇〇〇〇μηι)，可以提供較習知的微膠囊（粒 徑：約Ο.ίμιη〜50μπι)大得多的膠囊。亦即，在本發明中’ 可以將蓄熱材的含量增加到非常大。 再者’在本發明中可利用光硬化性成分的自由基聚合 或陽離子聚合來形成無縫膠囊的被覆部，而且本發明也具 有可以正確地規定内容物，即蓄熱材的量，可以簡便地控 9 201000616 制蓄熱量之優點。 因此，本發明的蓄熱無缝膠囊因為是利用潛熱故熱效 率高，在住宅能源的領域中可以應用於蓄熱空調設備機器 和蓄熱建材、建築體蓄熱等的用途，可以大幅降低居住環 境中之能源消費。 此外，在本發明中因為完全不使用會使曱醛游離的原 料，故有連對環境及人體產生不良影響的可能性都沒有的 優點。 【實施方式3 用以實施發明之最佳形態 本發明之蓄熱無縫膠囊的特徵在於其包含由含有光硬 化性成分之組成物所形成的被覆部及作為内容物的蓄熱 材，並具有多層構造或多核構造。因此，本發明之蓄熱無 缝膠囊的被覆部是由光硬化性樹脂所構成，而且，因為不 使用甲醛等之有害物質作為原料，故可有意義地提供可適 用於住宅能源領域中之蓄熱用途的大小、強度、安定性、 安全性等。 首先，將邊參照所附第1圖〜第3圖，邊說明本發明之 蓄熱無缝膠囊的實施態樣。 第1圖所示為具有由蓄熱材（1)，以及由含有光硬化性成 分之組成物所形成的被覆部（2)構成的2層構造之本發明的 蓄熱無缝膠囊（以下稱第1實施態樣）。 第2圖所示為具有由蓄熱材（3)、中間層（4)，以及由含 有光硬化性成分之組成物所形成之被覆部（5)構成的3層構 10 201000616 造之本發明的蓄熱錢膠囊（以下 本發明的蓄熱無縫谬囊，只要不合#，域樣）。再者， 影響，亦可具有3層以上之多層構^其蓄熱效率帶來不良 第3圖所示為具有由複數個蓄 化性成分之組成物所形成的被覆部(、=以^含有光硬 發明之蓄熱無縫膠囊（以下稱第3實施亥構造的本 中多核構造意指，如第3囷所示，^，再者本發明 複數個分散存在於㈣内的構^ 貝（亦即’ f熱材⑹） 本發明之蓄熱無鏠膠囊中所 性f賴苷细町畜熱材’可以使用水 料親水性）讀材及油性(疏水 之光硬化性成分，也可以㈣…田，、、、材，可以形成被覆部 的任一種光硬化性成分。使用料(親水性)及油性(疏水性） - ，畜熱材和光硬化性成分任 硬公知的蓄熱材及光 成刀。取決於以下將詳細說明 之製造方法，在第i實祐能样士 ㈣,、，、縫膠囊 性成分，其極性 同。亦p’f熱材為油性時，光硬 化生成刀為水性’蓄熱材為水性時， 而，如第2實施態樣所示，因為插入 為插入中間層，故可使用具有 相同極性的蓄熱材和光硬化性成分。亦即，中間層，更具 體地說’水性中間層位在中間時，可以使用油性蓄熱材及 油性的光硬化性成分，而當油性中間層位在中間時，可以 使用水性蓄熱材及水性的光硬化性成分。因此，在本發明 中’可以組合各種極性的f熱材和光硬化性成分。另外， 在第3實施態樣中，盥筮〗趣你能 與弟1貝％恶樣同樣地，蓄熱材及光硬 201000616 化性成分的極性必須不同。亦即，蓄熱材為油性時光硬化 性成分為水性，蓄熱材為水性時光硬化性成分為油性。 以下將詳細說明本發明中使用之蓄熱材及光硬化性成分。 水性(親水性）蓄熱材 本發明可以使用的水性（親水性）蓄熱材，可舉例如，季 戊四醇(pentaerythritol)、赤蘚糖醇(erythrit〇1)、山梨醇、甘 露醇等的糖醇類；聚乙二醇類（例如：乙二醇、二甘醇、四 甘醇、六甘醇、八甘醇、十二甘醇（d〇decaethylene glyc〇l)、 十四甘醇（tetmdeca-ethylene giyc〇i)、二十甘醇 (eicosa-ethylene glycol)等），聚丙二醇等的聚醚類；醋酸鈉、 硫酸鈉、氯化鈣、氣化鎂、硫代硫酸鈉、銨明(ammonium alum)、鉀明礬、硫酸鋁、硝酸鎂、溴化鋰、氫氧化锶、氫 氧化鋇、硝酸鋁、硝酸鐵、硝酸鎳、硫代硫酸鈉、硫酸鋅、 溴化鈣、硝酸鋅、磷酸氫二鈉、碳酸鈉、硝酸鋰、碳酸鈣、 溴化鐵等的無機鹽等，及其等之組合，但是並不限於此。 此外’也可將這些水性（親水性）蓄熱材作為水溶液或水性懸 浮液（slurry)使用。 油性(疏水性）蓄熱材 本發明可以使用的油性(疏水性）蓄熱材，是與水為非混 合性的物質，並且，其要是熔解熱在4〇cal/g以上者即無特 殊限制，可舉例如，十三烷（C13)，十四烷(C14),十五烷 (C15)，十六烷（C16)、十七烷(C17)、十八烷(C18)等的〜石 蠟類，以液體石蠟類為佳；辛酸(caprylicacid)、十二烷酸、 十四烷酸、十六烷酸、十八烷酸等的脂肪酸類；辛醇、癸 12 201000616 醇、十二醇、十四醇、十六醇、十八醇 〜 四院酸甲s旨、十六燒酸甲醋 、〜級醇類；十 »甘姑 况酸甲酯坌 及/、痒之組合，但是並不限於此。 寺的酯類；以 相對於本發明的蓄熱無縫膠囊之質息 在5〜95質量°/〇，以1 〇〜90質量。/。為佳，1 $蓄熱材的含量 蓄熱材的含量若不滿5質 量%，會； 热去發揮蓄潛熱效果等問題之虞，而蓄、3里過小而有 過95質量％，則有無法確彳轉囊強=彳的含量如果超 之虞。 〜去保持安定等問題 光硬化性成分 在本發明中可以使用的光硬化性成分 射而聚合（光硬化性)形成樹脂者即無特：是利用光照 光聚合性寡聚物及其加成聚合物等:：了舉例如’ 也可組合2種以上使用。 刀別單獨使用， 兀取甘性券眾物可舉例如，可藉自 取 光聚合性鋒物、可騎離子聚合 I合而硬化之 物等。可在本發明中使用的光聚合性寡聚=::=聚 子量為，1〇0〜30_，以細〜2〇〇〇〇為佳。里千均为 可藉自由基聚合而硬化的井取人^ — 如，(甲基)丙烯醯基、乙烯基等之：5 : I聚物可以舉例 的光聚合性絲物。再者，本替&不飽和基之下述 醢基」代表丙烯醯基或甲基丙歸/用語「（甲基)丙烯 基之任一者，用語「（甲基） 丙稀酸醋」代表丙稀酸醋和甲基兩歸酸醋的任—者。 (甲基）丙烯酸酯系寡聚物： 13 201000616 聚酯（曱基）丙烯酸酯（ester (meth)acrylate)系低聚物（例 如’院擇鏈(alkylene chain)的礙數為4〜10的聚烧基二醇二 (甲基）丙稀酸酯（polyalkylene glycol di-(meth) acrylate)(例 如，聚乙二醇二（曱基）丙烯酸酯、聚丙二醇二(甲基）丙烯酸 西旨等）’季戊四醇四（甲基）丙烯酸，二季戊四醇六（曱基）丙稀 酸醋），環氧乙烷變成甘油三（甲基）丙烯酸酯，三羥曱基丙 烧二（甲基）丙稀酸酯（Trimethylolpropane trimethacrylate) 等）； 聚氨酯（曱基）丙烯酸酯系募聚物（例如，（曱基）丙烯酸自旨 系不飽和聚乙二醇聚氨酯化物、（曱基）丙烯酸酯系不飽和聚 丙二醇聚氨酯化物等）； 環氧（甲基）丙烯酸酯（epoxy methtacylate)系寡聚物（例 如’雙酚A環氧（甲基）丙烯酸自旨、酚醛環氧（甲基）丙烯酸酸 (novolac expoxy methacrylate)等）； 陰離子性不飽和丙烯酸樹脂類（例如，在使選自（甲基) 丙烯酸及（曱基）丙烯酸酯之至少2種（甲基）丙烯酸系單體共 聚合而得到之含有叛基、鱗酸基及/或石黃酸基之共聚物中， 導入可進行光聚合的乙稀性不飽和基之樹脂等）； 陽離子性不飽和丙烯酸樹脂類（例如，使（甲基）丙稀酸 縮水甘油酯（glycidyl methacrylate)進行加成反應於含有不 飽和氨基化合物之（甲基）丙稀酸酯的共聚物上而得到之不 飽和丙稀酸樹脂等）等。 不飽和聚酯系募聚物（例如，高酸價不飽和聚酯類（例 如’透過含有不飽和多元羧酸之多元羧酸成分和多元醇的 201000616 酯化而得到之酸價為40〜250的不飽和聚酯的鹽類等）等） 不飽和聚環氧系寡聚物（例如，使殘留在環氧樹脂與（曱 基）丙烯酸等之不飽和叛基化合物的加成反應物中之經 基，與酸酐進行加成反應而得到之不飽和環氧樹脂，以高 酸價不飽和聚環氧化物類等） 多烯一硫醇系寡聚物（例如，聚硫醇（例如，季戊四醇、 三羥曱基丙烷等之多元醇與，巯基丙酸、毓基乙酸等之巯 基羧酸所形成的酯類等）等） 肉桂酸系寡聚物（例如，利用聚乙稀醇和肉桂酸的醋化 反應所得之聚肉桂酸醋（polycinnamate)等） 不飽和聚醯胺系寡聚物（例如，不飽和聚醯胺類（例如， 使甲苯二異氰酸酯、二曱苯二異氰酸酯等之二異氰酸酯 與，丙烯酸2-羥乙酯等之乙烯性不飽和羥基化合物的加成 物，和水溶性蛋白質發生加成反應而得到之不飽和聚醯胺 等）等） 另外，也可以適當地組合上述可藉自由基聚合而發生 硬化之光聚合性寡聚物以供使用。 可藉陽離子聚合而發生硬化之光聚合性寡聚物可以舉 例如，含有環氧基、乙烯基醚等官能基之以下的光聚合性 寡聚物等。 環氧系寡聚物（例如，雙酚A型環氧化物、乙二醇二縮 水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、 聚丙二醇二縮水甘油謎、新戍二醇二縮水甘油醚、1，6-己 二醇二縮水甘油ϋ、二漠新戊二醇二縮水甘油醚、丙三醇 15 201000616 二縮水甘油醚、丙三醇三縮水甘油醚、三羥曱基丙烷二縮 水甘油醚、三羥甲基丙烷三縮水甘油醚、二丙三醇聚縮水 甘油醚、雙酚s型環氧化物、雙環戊二烯•酚醛聚合物環氧 樹月旨(dicyclopentadiene·phenolic polymer epoxy resin)、雙酉分 F型環氧化物、溴化雙酚F型環氧化物、氫化雙酚A型環氧 化物、三（2，3-環氧丙烷）異氰酸酯（tri(2,3-epoxypn)pyl) isocyanurate)等） 乙細基鍵糸养聚物（例如，使鹵化乙稀與含有經基之化 合物在驗存在下進行加成反應而得到之乙浠基_樹脂等） 此外，亦可適當地組合可藉陽離子聚合而發生硬化之 光聚合性寡聚物以供使用。 上述之光聚合性募聚物中’尤以（曱基）丙烯酸酯系募聚 物、不飽和聚酯系募聚物及肉桂酸系寡聚物等之含有乙烯 性不飽和基的自由基聚合性寡聚物及其加成聚合物，以及 環氧系寡聚物及乙烯基醚系寡聚物等之陽離子聚合性寡聚 物及其加成聚合物為佳。 本發明可使用之光硬化性成分可由市售商品取得，亦 可依據該領域中公知的方法以不同的方式合成。 本發明中特別合適的光硬化性成分是，含有乙烯性不 飽和基之自由基聚合性寡聚物及其加成聚合物，其中又 以’ 一個分子中至少含有2個乙烯性不飽和基之自由基聚合 性寡聚物及其加成聚合物最為合適，其製造方法將具體說 明於下。 一個分子中至少有2個乙烯性不飽和基之自由基聚合 16 201000616 性募聚物及其加成聚合物可以藉由，例如，將可進行光聚 合之乙烯性不飽和基導入到聚烷撐二醇（P〇1yalkWene glycol)而合成。 (1) 聚乙二醇二（甲基）丙烯酸酯，可透過以（甲基）丙烯酸 (2莫耳當量）使分子量400〜6000的聚乙二醇（1莫耳當莖）兩 末端的經基g旨化之方式而合成。 (2) 聚丙二醇二（曱基）丙烯酸酯，可透過以（曱基）丙烯酸 (2莫耳當量）使分子量2〇〇〜4000的聚丙二醇（1莫耳當量）兩 末端的羥基酯化之方式而合成。 (3)(甲基）丙烯酸酯系不飽和聚乙二醇氨酯，可透過以 二異氰酸酯化合物(2莫耳當量）(例如，甲苯二異氰酸酯、二 曱本一異氰酸醋、異佛爾酮二異氰酸g旨（isophorone isocyanate)等）使分子量4〇〇〜6000的聚乙二醇（〖莫耳當量） 兩末端之羥基氨酯化，並且，加成不飽和單羥基化合物（2 莫耳S里）(例如，2-羥乙基（甲基）丙烯酸酯、2_羥丙基（甲基） 丙烯鷇酉曰3-羥丙基（甲基）丙烯酸酯、4-羥丁基（甲基）丙烯 酸酷、三經甲基丙烧二（甲基)丙稀酸酿、季戍四醇三（甲基) 丙烯酸酯等）的方式而合成。 (4)(甲基）丙稀酸酿系不飽和聚丙二醇聚氨醋，可透過 以二異氰酸自旨化合物(2莫耳當量）使分子量·〜侧的聚 丙二醇(1莫耳當量）兩末端的經以旨化，並且加成不飽 經基化合物(2莫耳當量)的方式來合成。 曱基)丙稀酸SU寡聚物中，奸 性不飽和丙烯酴&β 平又彳土之陰離子 对月日類疋’例如，來自從（甲基）丙稀酸及（甲 17 201000616 基）丙烯酸酯選出之至少2種單體的共聚物，並且，可以遷 過將可光聚合之乙烯性不飽和基導入具有羧基、磷酸基及 /或磺酸基之共聚物的方式來合成。 另外，上述聚酯系募聚物中，合適之高峻價不飽和聚 酯類可藉，例如，可藉含有不飽和鍵之多元羧酸與多元醇 的酯化反應來合成，其形態也可以為鹽類。高酸價不飽和 聚酯類的酸價宜為40〜250，以4〇〜200較佳。 另外，上述聚環氧化物系寡聚物中，合適的高酸價不 飽和聚壞乳化物通可以藉由，例如，調製環氧樹脂和，不 飽和羧基化合物（例如，（曱基）丙烯酸等）的加成反應物，並 將酸酐加成至殘存於該加成反應物之羥基的方式來合成。 高酸價不飽和聚環氧化物類的酸價為4〇〜2〇〇。 此外，上述不飽和聚醯胺系寡聚物中，合適的聚_ 類可以藉由，例如，將一異氰酸酯（例如，曱苯二異氰酸酯、 二甲苯二異氰酸醋等)與’乙稀性不飽和經基化合物(例如， 2_經乙基丙雜S旨等）的加成物’加成至明料的水溶性蛋 白質之方式來合成。 可在本發明中使用之水性(親水性）光硬化性成分可以 舉例如，九（乙二醇）二（甲基）丙稀酸g|(_(ethyiene ^coDd—ryiate)、十四（乙二醇)二（甲基）丙烯酸酿、三 經曱基丙烧三（甲基）丙稀酸自旨、二三經甲基丙烧四丙稀酸 酯、季戊四醇四丙稀酸@旨、雙齡二（甲基）丙稀酸醋等。 而，油性(疏水性）光硬化性成分，可藉由將來自上述水 性（親水性）光硬化性成份所含之聚烷撐二醇的環氧烷鏈 18 201000616 (alkyleneoxy chain)置換成烷基鏈的方式來合成。或者，也 可用對於熟習該項技術者而言為公知的改質劑將上述水性 (親水性）光硬化性成分改質成油性(疏水性）。可以在本發明 中使用之油性(疏水性）光硬化性成分，可舉例如’ 1，&_ 己一 醇二（甲基）丙烯酸酯、1，9-壬二醇二（甲基）丙烯酸酯、二曱 醇—二環癸炫二（甲基）丙稀酸酯（dimethylol tricyclodecane dimethacrylate)、新戊二醇二丙烯酸酯、環氧乙炫變性雙紛 A二（曱基）丙烯酸酯等。 在本發明中雖使用含有上述光硬化性成分之組成物， 亦即，被覆部形成組成物來形成被覆部，不過被覆部形成 組成物亦可僅由上述光硬化性成分構成；另外，被覆部形 成組成物，亦可依需要而進一步含有聚合起始劑、光敏劑、 著色劑、聚合性單體、熱傳導性物質等的添加劑。添加劑 的使用量，相對於被覆部形成組合物的質量，以固形分計 為20質量％以下，以10質量。/。以下為佳。 聚合起始劑，如果是過去所公知的聚合起始劑並無特 別限定，可以對應所使用之光硬化性成分適宜地做選擇， 合適的是使用光聚合起始劑。光聚合起始劑意指，藉光照 射而產生聚合引發劑，可促進聚合反應或交聯反應的化合 物。光聚合反應起始劑可舉例如，安息香（benz〇in)、3-羥基 丁酮(acetoin)、安息香甲醚、安息香乙醚、安息香異丙醚、 安息香異丁醚、二苯曱酮(benzophenone)、笨曱基米希勒酮 (benzyl Michler’s ketone)、氧雜蒽 _、氯硫雜蒽酮 (chlorothioxanthone)、異丙基硫雜蒽酮、笨偶醯二甲基縮酮 19 201000616 (benzil dimethyl ketal)、萘酚、蒽醌、羥基蒽 (hydroxyanthracene)、二乙氧基縮苯乙嗣（aceto- phenone diethyl ketal)、α-經基環己烧苯基酮（α-Hydroxy cyclohexyl phenyl ketone)、2-羥基-2-曱基苯基丙烷、芳香族碘鹽、芳 香族録l鹽、鎭鹽（iodonium salt)、疏鹽（sulfonium salt)、三 ^'基錦_鹽、三敗化碳链鑛鹽（trifluorocarbon sulfonium salt) 等。聚合起始劑可以單獨使用，或者亦可組合2種以上使 用。聚合起始劑相對於被覆部形成組成物的質量，以固形 分計含有為0.001〜20質量％，以含有0.1〜10質量％為佳。 聚合起始劑的使用量如果不滿〇.〇〇 1質量％，會有聚合反應 未完全進行而不能得到皮膜強度等的問題之虞，如果超過 20質量％ ’則有起始反應過度進行而不進行聚合反應，連 帶有皮膜強度減少等的問題之虞。在本發明中，上述光硬 化性成分和聚合起始劑、尤以和光聚合起始劑適當組合再 使用者為佳。 在可見光領域使光硬化性成分硬化時，宜光敏劑混合 到被覆部形成組成物中。光敏劑可舉例如，釕錯合物、外 啉(porphyrin)系化合物等。光敏劑的使用量相對於被覆部形 成之組成物的質量，以固形分計在〇〇〇1〜5質量％，以〇〇1 〜1質量％為佳。 著色劑如果是在過去所公知的著色劑中，不會造成活 性物種的陷阱(trap)作用者並無特殊限定，可舉例如，天然 著色劑、合成著色劑等。著色劑的使用量，相對於被覆部 形成組成物之質量，以固形分計在〇〇〇1〜5質量％，以〇〇1 20 201000616 〜1質量％為佳。 又，為了調卵被覆部形成組成物的量，或者為了調節 被覆部形成物的極性，也可適當地將聚合性單體添加到被 覆部形成物中。聚合性單體可以舉例如，（甲基）丙烯酸、（甲 基）丙烯酸酯（例如，（曱基）丙烯酸曱酯、（曱基）丙歸酸乙酿、 (甲基）丙烯酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸戊酉旨、 (甲基）丙烯酸十二酯、（曱基）丙浠酸十八酯、（曱基）丙烯酸 丁氧乙醋、（曱基）丙稀酸苯氧乙s旨、（曱基）丙稀酸異冰片酉旨 等）等。 另外，使用的光硬化性成分為水性（親水性）時，在進一 步提尚被覆部的強度之目的下’亦可單獨添加或添加組合2 種以上之具有在8 0 °C以下會溶解在水性溶劑中之不飽和鍵 的水溶性單體（例如’依康酸(itaconic acid)、N，N'-亞甲基雙 丙烯酸酯、甲基丙烯酸羥基乙酯、甲基丙烯酸羥基丙酯、 N，N-亞甲基雙丙:fcffj 酿胺（Ν,Ν’-methylenebisacryl- amide)、 N-異丙基丙細酿胺、N-乙婦η比α各烧酮、丙稀醯嗎琳 (acryloylmorpholine)、Ν，Ν'-二曱基丙烯醯胺、Ν-乙烯基曱 醯胺(Ν-vinylformamide)等）。藉此，可以抑制對聚合反應帶 來不良影響之反應。水溶性單體的使用量相對於被覆部形 成組成物的質量，以固形分計在0.01〜3〇質量％，以0.1〜 25質量％為佳。 在本發明中，爲使熱傳導率進一步提高，亦可將熱傳 導性物質適當地添加到被覆部形成組成物中。熱傳導性物 質如果是具有熱傳導性之物質即無特殊限定，可舉例如， 21 201000616 鐵、銀、銅、石墨（black lead)、錄、錫、鶴、黃銅、填青 銅等。熱傳導性物質的使用量相對於被覆部形成組成物的 質量，以固形分計在0.01〜30質量％，以0.1〜25質量％為佳。 本發明之蓄熱無縫膠囊的平均粒徑為0.1〜20mm，以 0.3〜18mm為佳，較佳的是0.5〜16mm;平均粒徑如果不滿 0.1 mm，會有内容量變少，強度不足等問題之虞，平均粒 徑如果超過20mm，則有膠囊比表面積下降，伴隨著傳熱面 積變小等問題之虞。另外，本發明中的蓄熱無缝膠囊，可 以如上所述將膠囊粒徑做成0.1mm〜20mm(亦即，ΙΟΟμιη〜 20000μηι)，和習知的微膠囊（0· 1 μηι〜50μηι)相比，可以提供 非常大的膠囊，可以使蓄熱材含量增加到非常大。 蓄熱無縫膠囊的製造方法 本發明進一步和包含由含有上述光硬化性成分之組成 物所形成的被覆部及作為内容物的蓄熱材之蓄熱無缝膠囊 的製造方法相關，該製造方法之特徵在於，其包含 使含有該光硬化性成分之組成物及該蓄熱材通過雙層 喷嘴、三層喷嘴或多孔材料，調製包含由含有該光硬化性 成分之組成物所形成的未硬化被覆部及作為内容物的蓄熱 材之膠囊前驅物的步驟，及 將光照射於該光硬化性成分以使膠囊前驅物發生光硬 化的步驟。 第1〜3圖分別表示本發明之蓄熱無缝膠囊的較佳實施 態樣（分別為，第1、第2及第3實施態樣），以下將依據各實 施態樣，詳細地說明本發明之蓄熱材無縫膠囊的製造方法。 22 201000616 具有2層構造之蓄熱無缝材料（第i實施能樣声製造方法 模式性地示於第丨圖之具有2層構造的本發明之蓄熱無201000616 VI. Description of the Invention: I: Technical Field of Invention: Field of the Invention The present invention relates to a heat storage medium that can be used as a heating and cooling medium for a heating and cooling air conditioner, a heat storage material for a house, a heat storage medium for preventing road freezing, and the like. Thermal storage seamless capsule and manufacturing method thereof. BACKGROUND OF THE INVENTION In recent years, carbon dioxide emissions, which have been the cause of global warming, have become a worldwide problem. For this reason, the reduction of energy consumption in this field is an important issue, and not only the living environment, but also the energy consumed in the industry has become the target of reduction. In this field, for example, an energy-saving technology using a heat insulating material has been proposed, and the use of the technology can improve the confidentiality and heat insulation of a building. However, such energy-saving technologies use heat-insulating materials to suppress the movement of heat (sensible heat) without significantly reducing the energy consumption of air-conditioning systems such as heating and cooling. Furthermore, energy-saving technologies that utilize the thermal movement of matter can be classified into two types that use sensible heat and those who use latent heat. Here, sensible heat means heat when heat is applied to a substance to cause a rise in temperature, and latent heat means heat released or absorbed by a substance with one phase transfer (melting, evaporation, phase shift of some crystallizing, etc.). For example, in water, the sensible heat (when causing a temperature change of 1 ° C) is lcal / g, and the latent heat (phase transfer at 0 ° C) is 80 cal / g, compared with the case of using sensible heat. The energy efficiency of latent heat is higher. Therefore, as mentioned above, the energy-saving technology using heat-insulating materials, mainly 3 201000616 is a technology that utilizes sensible heat technology, which is not a demand for air-conditioning systems such as warm rolling and cold air, and is not a large towel preparation & Technology that reduces energy consumption in the living environment. On the other hand, for example, a technology that uses a latent heat absorbing material, such as a heat storage material having a latent heat effect, can be used. If the heat storage material is directly mixed into the building materials, etc., the storage right + and the material will leak out due to the passage of time, and it is difficult to use it for a long time. Therefore, it is necessary to enclose the capsule of the animal thermal material. . The method of forming the shape of the microcapsules is, for example, a coacervation method, an interfacial polymerization method, an in situ method, a cohesive method, an interfacial polymerization method, and an in situ method. The microencapsulation method, which is a method for producing a heat-transfer microcapsule with a high heat-return rate, and discloses in detail "the microcapsule containing the microcapsules containing the heat storage material as a main component. In the manufacturing process, the method for producing a microcapsule dispersion liquid for heat transfer characterized by an average molecular weight of the emulsifier used is in the range of 1000 to 100,000. The particle diameter of the microcapsule disclosed in Patent Document 1 is ΐομηι or less, which can be improved. Liquidity. Patent Document 2 discloses a method for producing a microcapsule by a coacervation method, an interfacial polymerization method or an in-situ method, and discloses in detail that "the characteristic is the stirring of a liquid to be treated which is composed of a hydrophobic liquid and a hydrophilic liquid. In the container, the stirring body is rotated to use the centrifugal force to rotate the liquid to be treated in the state of the film in the container, so that the hydrophobic liquid is emulsified and dispersed in the hydrophilic liquid to form an emulsion. A method for producing a microcapsule containing a capsule wall film having a hydrophobic liquid which has been emulsified and dispersed. The method for producing a microcapsule disclosed in Patent Document 2 is to easily produce a microcapsule 201000616 which has a uniform particle size distribution and a uniform particle size distribution. The production method is to produce a microcapsule having an average particle diameter of about 1 to 15 μm. Further, Patent Document 3 discloses a method of producing a microcapsule containing a latent heat storage material by an in-situ method. Patent Document 3 discloses in detail The water absorption rate is 3°/60% of the water-absorbing pigment and the powder having the heat storage property formed by the solid matter of the microcapsules containing the latent heat storage material in an environment of 50% relative humidity. The disclosed microcapsules have an average particle diameter of 〇5 to 5 〇μηι, and can be heated and stored by irradiation with microwaves, and the use thereof can be, for example, a furnace, a hot water bottle, or a foot warmer. It is characterized in that the heat retention effect lasts for a long time. Although in Patent Document 3, the microcapsules are dried and then powdered, but the powder of the microcapsules usually has powders between each other. It is easy to agglomerate, the fluidity of the powder is deteriorated, and the yield is lowered during the powdering treatment. Further, although Patent Document 3 is a microencapsulation using a polycondensation reaction of melamine and formaldehyde, the capsule is obtained. In view of the strength, there is a problem that the film is thin because of the film strength. The method for producing chemically and physically stable microcapsules is preferably in situ, and from the viewpoint of the strength of the microcapsules, in particular, Microcapsules of urea-method-polymerized ruthenium film formed by urea and methacrylate polymerization, and microcapsules of melamine-furfural polys-wall film formed by melamine and furfural by condensation polymerization are particularly suitable. As mentioned above, the use of formaldehyde is undesirable from the consideration of the concern about the % environment in recent years and the impact on the human body. Further, Patent Document 4 discloses a microcapsule for heat storage which can be manufactured safely and simply without containing a nail 13b which is harmful to the human body. Patent Document 4 discloses in more detail that "a type of paraffin-containing core material is contained in a crucible formed of a polyurethane resin or a poly-densified resin." 201000616 Thermal microcapsules characterized by the aforementioned polyurethane resin The polyurea resin is a microcapsule for heat storage which is obtained by reacting a moxibustion isocyanate having a solvent release ratio of 5 times or more with an active hydride. In addition, in order to make the heat storage microcapsules have physical properties such as heat resistance, solvent resistance, and damage resistance, it is effective to replace the film of the capsule film with a material having excellent physical properties, and to thicken the film of the microcapsules, for example, A destructive improvement of microcapsules caused by thick film formation has been proposed (Patent Document 5). In detail, Patent Document 5 discloses that "the average particle diameter of the microcapsules containing the heat storage material having a melting point of 4 〇 to 95 ° C" is 〇. 1 to 5 μηι, and the heat storage material microcapsules having a weight ratio of the heat storage material in the microcapsules are 6 〇 to 75%. However, it is only a simple thick film of the microcapsule film, the content of the contents contained in the capsule is lowered, and the function of the microcapsule is lowered, which is not preferable. In particular, microcapsules for heat storage materials are not suitable because the film thickness of the microcapsules is increased to cause a decrease in the amount of heat storage. Further, in the microcapsules of Patent Document 5, the film forming the microcapsules is also a melamine-furfural resin. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2001-288458 (Patent Document 3) JP-A-2001-288458 (Patent Document 4) Special Opening 20〇4-189843 [Patent Document 5] JP-A-H11-152466A SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the invention. The size of ίμη~50μΓη The microcapsules of 201000616 are difficult to be used for building materials, etc., and it is difficult to say that they are large enough. Further, these conventional heat storage capsules are not suitable for use in building materials such as wall materials because of low physical strength and easy disintegration. In addition, although the conventional heat storage capsules are inexpensive, most of them are manufactured by in situ method using furfural which is harmful to the human body. When applied to building materials such as wall materials, there is a concern about the influence of residual formaldehyde on the human body. . In view of the above, it is an object of the present invention to provide a heat storage capsule which can be applied to a building material such as a wall material, such as size, strength, stability, safety, and heat storage, for example, in order to reduce the number of uses. Energy consumption in the living environment. In order to solve the problem, the inventors of the present invention have found that the heat storage capsule is formed into a seamless capsule, and a composition containing a photocurable component (hereinafter also referred to as In the case where the "covered portion forms a composition", the outermost shell (hereinafter sometimes referred to as a "covered portion") having a multilayer capsule having a multilayer structure or a multi-nuclear structure is formed, and can be easily manufactured and manufactured. The heat storage capsules such as the size, the strength, the stability, and the heat storage amount, and the amount of the heat storage material that can accurately define the contents can easily control the amount of heat storage, and the present invention can be completed. Accordingly, the present invention provides the following. [1] A heat storage seamless capsule comprising a coating portion formed of a composition containing a photocurable component and a heat storage material as a content. [2] The heat storage seamless capsule according to the above [1], which has a two-layer structure, wherein the photocurable component is water-based, and the heat storage material is oily. [3] The heat storage seamless capsule according to the above [1], which has a two-layer structure, 7 201000616, wherein the photocurable component is oily, and the heat storage material is aqueous. [4] The heat storage seamless capsule according to the above [1], which has a three-layer structure including an intermediate layer between the coating portion and the heat storage material, wherein the photocurable component is water-based, and the intermediate layer is oily. The heat storage material is water-based. [5] The heat storage seamless capsule according to the above [1], which has a three-layer structure including an intermediate layer between the coating portion and the heat storage material, wherein the photocurable component is oily, and the intermediate layer is aqueous. The heat storage material is oily. [6] The heat storage seamless capsule according to the above [1], which has a multinuclear structure, wherein the photocurable component is aqueous, and the heat storage material is oily. [7] The heat storage seamless capsule according to the above [1], which has a multinuclear structure, wherein the photocurable component is oily, and the heat storage material is aqueous. [8] The heat storage seamless capsule according to any one of the above [1], wherein the coating portion contains a thermally conductive material. [9] The heat storage seamless capsule according to any one of the above [1], wherein the content of the heat storage material is 5 to 95% by mass based on the mass of the capsule. [10] The heat storage seamless capsule according to any one of the above [1] to [9], wherein the average particle diameter is 0. 1~20mm. [11] A method for producing a heat storage seamless capsule, comprising: a coating portion comprising a composition comprising a photocurable component; and a method of producing a heat storage seamless capsule comprising a heat storage material as a content, wherein the method comprises The composition of the photocurable component and the heat storage material are prepared by a double nozzle, a three-layer nozzle or a porous material, and an unhardened coating portion including a composition containing the photocurable component is prepared, and a step of capsule precursor of the heat storage material of the content, and 201000616 a step of irradiating light to the photocurable component to photoharden the capsule precursor. [12] A heat storage seamless capsule obtained by the method for producing a heat storage seamless capsule according to the above [η]. Definition of Terms In the present invention, "aqueous" means that the component or the layer or the entire material may be aqueous, and a part of the non-aqueous substance (for example, an oily substance) may be mixed in the constituent component. In the present invention, the term "oily" as used in the case of "oily" means that the component, layer or material as a whole is oily, and even a part of non-oily substances (for example, aqueous substances) may be mixed in the constituent components. . Therefore, the term "the curable component is aqueous" means that when the curable component is composed of a plurality of compounding agents, the composition of the compounding agent as a whole may be water-based, and the respective compounding agents are not only water-based. May contain oily. Advantageous Effects of Invention Since the seamless capsule of the present invention has a multilayer structure or a multi-core structure, it can provide physical properties such as excellent strength and stability. In addition, in the present invention, the particle size of the capsule can be made 0. 1~20mm (also known as '1〇〇~2〇〇〇〇μηι), can provide more conventional microcapsules (particle diameter: about Ο. Ίμιη~50μπι) a much larger capsule. That is, in the present invention, the content of the heat storage material can be increased to be very large. Further, in the present invention, the coating portion of the seamless capsule can be formed by radical polymerization or cationic polymerization of the photocurable component, and the present invention can also accurately define the content, that is, the amount of the heat storage material, and can be easily Control 9 201000616 The advantages of heat storage. Therefore, the heat storage seamless capsule of the present invention has high heat efficiency by utilizing latent heat, and can be applied to heat storage air conditioner equipment, heat storage building materials, building heat storage, etc. in the field of residential energy, and can greatly reduce energy consumption in a living environment. . Further, in the present invention, since the raw material which is free of furfural is not used at all, there is an advantage that there is no possibility of adversely affecting the environment and the human body. [Embodiment 3] The heat storage seamless capsule of the present invention is characterized in that it contains a coating portion formed of a composition containing a photocurable component and a heat storage material as a content, and has a multilayer structure. Or multi-core construction. Therefore, the coating portion of the heat-storing seamless capsule of the present invention is composed of a photocurable resin, and since a harmful substance such as formaldehyde is not used as a raw material, it is possible to meaningfully provide a heat storage application suitable for use in the residential energy field. Size, strength, stability, safety, etc. First, an embodiment of the heat storage seamless capsule of the present invention will be described with reference to Figs. 1 to 3 attached. Fig. 1 shows a heat storage seamless capsule of the present invention having a two-layer structure composed of a heat storage material (1) and a coating portion (2) composed of a composition containing a photocurable component (hereinafter referred to as the first Implementation aspect). Fig. 2 is a view showing a three-layer structure 10 201000616 comprising a heat storage material (3), an intermediate layer (4), and a coating portion (5) formed of a composition containing a photocurable component. Heat storage money capsule (hereinafter, the heat storage seamless capsule of the present invention, as long as it does not contain #, domain type). Further, the influence may have a multilayer structure of three or more layers, and the heat storage efficiency may be poor. Fig. 3 is a view showing a coating portion formed of a plurality of components of the accumulating component (== The heat-storing seamless capsule of the hard invention (hereinafter referred to as the third multi-core structure of the third embodiment) means that, as shown in the third section, the second embodiment of the present invention is dispersed in (4). 'f hot material (6)) In the heat-storing and sputum-free capsule of the present invention, it is possible to use a water-hydraulic material (hydrophobic light-curable component), and it is also possible to use (4) And a material, which can form any photocurable component of the coating portion. The material (hydrophilic) and oily (hydrophobic) - the heat storage material and the photo-curing component are hard-known heat storage materials and optical knives. In the following, the manufacturing method will be described in detail, in the case of the i-th solid energy model (four),,, and the capsule-shaped component, the polarity is the same. When the p'f hot material is oily, the photo-curing tool is a water-based heat storage material. When it is water-based, as shown in the second embodiment, because the insertion is for insertion Since the intermediate layer is used, a heat storage material having the same polarity and a photocurable component can be used. That is, when the intermediate layer, more specifically, the aqueous intermediate layer is in the middle, an oily heat storage material and an oily photocurable component can be used. When the oily intermediate layer is in the middle, an aqueous heat storage material and an aqueous photocurable component can be used. Therefore, in the present invention, 'a heat material and a photocurable component of various polarities can be combined. In the third embodiment, In the same way, you can have the same polarity as the heat storage material and the light hardening 201000616. In other words, the heat storage material is oily, the light hardening component is water, and the heat storage material is water. The heat-curing material and the photocurable component used in the present invention are described in detail below. The aqueous (hydrophilic) heat storage material which can be used in the present invention may, for example, be pentaerythritol (for example, pentaerythritol ( Pentaerythritol), erythritol (erythrit〇1), sorbitol, mannitol, etc.; glycols (eg, ethylene glycol, diethylene glycol, tetraglycan) , hexaethylene glycol, octaethylene glycol, dodecaethylene glycoside, tetmdeca-ethylene giyc〇i, eicosa-ethylene glycol, etc., polypropylene glycol Polyethers; sodium acetate, sodium sulfate, calcium chloride, magnesium hydride, sodium thiosulfate, ammonium alum, potassium alum, aluminum sulfate, magnesium nitrate, lithium bromide, barium hydroxide, barium hydroxide , inorganic salts such as aluminum nitrate, iron nitrate, nickel nitrate, sodium thiosulfate, zinc sulfate, calcium bromide, zinc nitrate, disodium hydrogen phosphate, sodium carbonate, lithium nitrate, calcium carbonate, iron bromide, etc., and The combination is not limited thereto. Further, these aqueous (hydrophilic) heat storage materials can also be used as an aqueous solution or an aqueous suspension. Oily (hydrophobic) heat storage material The oily (hydrophobic) heat storage material which can be used in the present invention is a substance which is non-mixable with water, and is not particularly limited if the heat of fusion is 4 〇 cal/g or more. For example, tridecane (C13), tetradecane (C14), pentadecane (C15), hexadecane (C16), heptadecane (C17), octadecane (C18), etc. ~ paraffin, Liquid paraffin is preferred; fatty acids such as caprylic acid, dodecanoic acid, myristic acid, palmitic acid, octadecanoic acid, etc.; octanol, 癸12 201000616 alcohol, dodecanol, fourteen Alcohol, cetyl alcohol, octadecyl alcohol ~ four-in-one acid s, hexadecanoic acid methyl vinegar, ~ alcohols; ten» gans acid methyl ester 坌 and /, itchy combination, but not limited to this . The ester of the temple; the mass of the heat-storing seamless capsule relative to the present invention is 5 to 95 mass ° / 〇, with a mass of 1 〇 ~ 90. /. It is better that if the content of the heat storage material of the heat storage material is less than 5% by mass, the heat will be used to solve the problem of the latent heat effect, and if it is too small and has 95% by mass, it is impossible to confirm. The strength of the sac is as strong as 彳. - To maintain stability, etc. Photocuring component The photocurable component which can be used in the present invention is polymerized (photocurable) to form a resin, that is, it is a special one: it is a photopolymerizable oligomer and its addition polymerization. Things: etc.: For example, 'you can use two or more types in combination. The knife can be used alone, and for example, it can be obtained by taking a photopolymerizable front material, and riding it by ion polymerization. The photopolymerizable oligomer ==::= polymer amount which can be used in the present invention is 1 〇 0 〜 30 _, preferably 〜2 细. All of them are those which can be hardened by radical polymerization. For example, (meth)acryloyl group, vinyl group, etc.: 5: I polymer can be exemplified by photopolymerizable filaments. Furthermore, the following thiol group of the present &unsaturated group represents the propylene fluorenyl group or the methyl propyl group or the term "(meth) propylene group, the term "(meth) acrylate vinegar" Represents any of acrylic acid vinegar and methyl sulphuric acid vinegar. (Meth)acrylate oligomer: 13 201000616 Polyester (meth)acrylate oligomer (for example, 'alkylene chain') is 4 to 10 Polyalkylene glycol di-(meth) acrylate (for example, polyethylene glycol bis(mercapto) acrylate, polypropylene glycol di(meth) acrylate, etc. ''Pentaerythritol tetra(meth)acrylic acid, dipentaerythritol hexa(indenyl) acrylate vinegar), ethylene oxide to tris(meth)acrylate, trishydroxypropylpropane di(meth)propene Trimethylolpropane trimethacrylate, etc.; polyurethane (fluorenyl) acrylate-based polymer (for example, (fluorenyl) acrylic acid-based unsaturated polyethylene glycol urethane, (fluorenyl) acrylate-based unsaturated poly Propylene glycol urethane compound, etc.; epoxy methtacylate oligomer (eg 'bisphenol A epoxy (meth) acrylate, novolac epoxy (meth) acrylate (novolac expoxy) Methacrylate), etc.; A group of unsaturated unsaturated acrylic resins (for example, a copolymerized product obtained by copolymerizing at least two kinds of (meth)acrylic monomers selected from (meth)acrylic acid and (mercapto)acrylic acid ester And/or a copolymer of a rhein-based group, a resin capable of photopolymerizing an ethylenically unsaturated group, etc.); a cationic unsaturated acrylic resin (for example, a glycidyl (meth) acrylate) (glycidyl methacrylate) An unsaturated acrylic resin obtained by addition reaction to a copolymer containing a (meth) acrylate of an unsaturated amino compound. Unsaturated polyester-based polymer (for example, a high acid-value unsaturated polyester (for example, 'the acid value obtained by esterification of 201000616 through a polycarboxylic acid component containing an unsaturated polycarboxylic acid and a polyol is 40 to 250 Unsaturated polyepoxy oligomer (for example, an addition reaction of an epoxy resin with an unsaturated thiol compound such as (meth)acrylic acid) A perylene-thiol-based oligomer (for example, a pentaerythritol (for example, a pentaerythritol), which is obtained by an addition reaction with an acid anhydride and an unsaturated epoxy resin obtained by an addition reaction with an acid anhydride. a cinnamic acid-based oligomer (for example, a polyhydric alcohol and a cinnamic acid), a polyhydric alcohol such as trihydroxyhydrinylpropane, an ester formed from a mercaptocarboxylic acid such as mercaptopropionic acid or thioglycolic acid, or the like. An unsaturated polyamine-based oligomer obtained by a acetation reaction, such as an unsaturated polyamine (for example, an unsaturated polyamine) (for example, a diisocyanate such as toluene diisocyanate or diphenylene diisocyanate) , 2-hydroxyethyl acrylate, etc. An adduct of an ethylenically unsaturated hydroxy compound, an unsaturated polyamine obtained by an addition reaction with a water-soluble protein, or the like), and the above-mentioned photopolymerizable by radical polymerization may be appropriately combined. The oligomer is available for use. The photopolymerizable oligomer which can be cured by cationic polymerization may, for example, be a photopolymerizable oligomer having a functional group such as an epoxy group or a vinyl ether. Epoxy oligomers (for example, bisphenol A type epoxide, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidol puzzle, new two Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl hydrazine, Erqian neopentyl glycol diglycidyl ether, glycerol 15 201000616 diglycidyl ether, glycerol triglycidyl ether, trioxindole Propane diglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol polyglycidyl ether, bisphenol s-type epoxide, dicyclopentadiene • phenolic polymer epoxy tree (dicyclopentadiene· Phenolic polymer epoxy resin, double bismuth F-type epoxide, brominated bisphenol F-type epoxide, hydrogenated bisphenol A-type epoxide, tris(2,3-epoxypropane) isocyanate (tri(2, 3-epoxypn)pyl) isocyanurate), etc.) an ethylenic bond oxime (for example, an ethyl hydrazine-resin obtained by subjecting an ethylene halide to a compound containing a thiol group in the presence of a test compound) , can also be combined with light that can be hardened by cationic polymerization Adhesion oligomer for use. In the above photopolymerizable polymer, a radical polymerization containing an ethylenically unsaturated group such as a (fluorenyl) acrylate-based polymer, an unsaturated polyester-based polymer, and a cinnamic acid-based oligomer The oligomers and their addition polymers, and cationically polymerizable oligomers such as epoxy-based oligomers and vinyl ether-based oligomers, and addition polymers thereof are preferred. The photocurable component which can be used in the present invention can be obtained from commercially available products, or can be synthesized in various ways according to a method known in the art. A particularly suitable photocurable component in the present invention is a radically polymerizable oligomer containing an ethylenically unsaturated group and an addition polymer thereof, wherein 'a molecule contains at least 2 ethylenically unsaturated groups. The radical polymerizable oligomer and the addition polymer thereof are most suitable, and the production method thereof will be specifically described below. Radical polymerization of at least 2 ethylenically unsaturated groups in one molecule 16 201000616 The stimulating polymer and its addition polymer can be obtained, for example, by introducing a photopolymerizable ethylenically unsaturated group into a polyalkylene group. It is synthesized by a diol (P〇1yalkWene glycol). (1) Polyethylene glycol di(meth)acrylate which is permeable to both ends of polyethylene glycol (1 moles stem) having a molecular weight of 400 to 6000 by (meth)acrylic acid (2 molar equivalent) It is synthesized by the way of g. (2) Polypropylene glycol bis(indenyl) acrylate which is esterified with a hydroxyl group at both ends of a polypropylene glycol (1 molar equivalent) having a molecular weight of 2 〇〇 to 4000 by using (mercapto)acrylic acid (2 molar equivalent) Synthesized by way. (3) (Meth) acrylate-based unsaturated polyethylene glycol urethane, permeable to diisocyanate compound (2 molar equivalent) (for example, toluene diisocyanate, diterpene mono-isocyanate, isophor The ketone diisocyanate g (isophorone isocyanate), etc.) urethanes the hydroxyl groups at both ends of polyethylene glycol ([Mole equivalent] having a molecular weight of 4 〇〇 to 6000, and addition of an unsaturated monohydroxy compound (2) Mohr S) (for example, 2-hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) propylene oxime 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl It is synthesized by the method of (meth)acrylic acid, trimethyl methacrylic acid di(meth)acrylic acid brewing, quaternary tetraol tris(meth) acrylate, etc.). (4) (Methyl)acrylic acid-based unsaturated polypropylene glycol polyurethane, which can be passed through a polyisocyanate (1 molar equivalent) of molecular weight from the side of the diisocyanate (2 molar equivalent). Both ends were synthesized in such a manner as to form an unsaturated compound (2 molar equivalent). In the thiol SU oligomer, the anionic unsaturated propylene oxime & beta flat alumina anion to the moon type 疋 'for example, from (meth) acrylic acid and (A 17 201000616 A copolymer of at least two kinds of monomers selected from acrylates, and can be synthesized by introducing a photopolymerizable ethylenically unsaturated group into a copolymer having a carboxyl group, a phosphoric acid group and/or a sulfonic acid group. Further, in the above polyester-based polymer, a suitable high-density unsaturated polyester may be synthesized, for example, by esterification reaction of a polyvalent carboxylic acid having an unsaturated bond with a polyhydric alcohol, and the form may also be Salt. High acid value is not saturated The acid value of the polyester is preferably from 40 to 250, preferably from 4 to 200. Further, in the above polyepoxide-based oligomer, a suitable high acid-valent unsaturated poly-fabric emulsion can be prepared by, for example, preparing an epoxy resin and an unsaturated carboxyl compound (for example, (mercapto)acrylic acid, etc. The addition reaction product is synthesized by adding an acid anhydride to the hydroxyl group remaining in the addition reaction product. The acid value of the high acid value unsaturated polyepoxide is 4 〇 2 〇〇. Further, in the above unsaturated polyamine-based oligomer, a suitable poly-type can be, for example, a monoisocyanate (for example, anthraquinone diisocyanate, xylene diisocyanate, etc.) and 'e. The addition of an unsaturated trans group-based compound (for example, 2 to ethylpropionate, etc.) is added to a water-soluble protein of a clear material. The aqueous (hydrophilic) photocurable component which can be used in the present invention is, for example, ninth (ethylene glycol) di(meth)acrylic acid g|(_(ethyiene ^coDd-ryiate), fourteen (B Glycol) di(meth)acrylic acid, tris-propyl mercapto tris(meth)acrylic acid, di-trimethyl methacrylate tetrapropyl acrylate, pentaerythritol tetrapropyl acid An oleic acid (hydrophobic) photocurable component, which is an epoxy resin derived from the polyalkylene glycol contained in the above aqueous (hydrophilic) photocurable component. The alkyl chain 18 201000616 (alkyleneoxy chain) is synthesized by substituting it into an alkyl chain. Alternatively, the above aqueous (hydrophilic) photocurable component may be modified into a modifier which is well known to those skilled in the art. Oily (hydrophobic). The oily (hydrophobic) photocurable component which can be used in the present invention may, for example, be 1,1&_hexanol di(meth)acrylate or 1,9-nonanediol. Di(meth) acrylate, diterpene-bicyclohexyl di(methyl) acrylate (dimethylol tricyclode) a cane dimethacrylate), a neopentyl glycol diacrylate, an epoxy epoxidation, and a bis(indenyl) acrylate. In the present invention, a composition containing the photocurable component, that is, a coating portion is used. The composition is formed to form a coating portion, but the coating portion forming composition may be composed only of the photocurable component, and the coating portion may be a composition, and may further contain a polymerization initiator, a photosensitizer, and a colorant as needed. An additive such as a polymerizable monomer or a heat conductive material. The amount of the additive used is preferably 20% by mass or less based on the mass of the coating portion forming component, and preferably 10 parts by mass or less. The initiator is not particularly limited as long as it is a polymerization initiator known in the past, and may be appropriately selected depending on the photocurable component to be used, and a photopolymerization initiator is suitably used. Photopolymerization initiator means A compound which generates a polymerization initiator by light irradiation to promote a polymerization reaction or a crosslinking reaction. The photopolymerization initiator may, for example, bebenzin, 3-hydroxyl Acetin (acetoin), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, benzyl Michler's ketone, xanthene, chlorine Chlorothothanthone, isopropyl thioxanthone, stupid dimethyl ketal 19 201000616 (benzil dimethyl ketal), naphthol, anthracene, hydroxyanthracene, diethoxy benzene Acetate (aceto-phenone diethyl ketal), α-Hydroxy cyclohexyl phenyl ketone, 2-hydroxy-2-mercaptophenylpropane, aromatic iodide salt, aromatic record Salt, iodonium salt, sulfonium salt, tri-methyl sulphate, trifluorocarbon sulfonium salt, and the like. The polymerization initiators may be used singly or in combination of two or more. The mass of the composition of the polymerization initiator relative to the coating portion is 0. 001 to 20% by mass to contain 0. 1 to 10% by mass is preferred. If the amount of polymerization initiator is not enough. When the amount of ruthenium is 1% by mass, the polymerization reaction may not proceed completely, and the film strength may not be obtained. If it exceeds 20% by mass, the initial reaction may proceed excessively without polymerization, and the film strength may be reduced. The problem. In the present invention, it is preferred that the above-mentioned photohardenable component and a polymerization initiator, particularly a photopolymerization initiator, are appropriately combined. When the photocurable component is hardened in the visible light region, the photosensitizer is preferably mixed into the coating portion forming composition. The photosensitizer may, for example, be a ruthenium complex, a porphyrin compound or the like. The amount of the photosensitizer to be used is preferably from 1 to 5 mass% in terms of solid content, and more preferably from 1 to 1 mass%, based on the mass of the composition formed in the coating portion. The coloring agent is not particularly limited as long as it does not cause trapping of an active species, and examples thereof include a natural coloring agent and a synthetic coloring agent. The amount of the coloring agent to be used is preferably from 1 to 5 mass% in terms of solid content, and 〇〇1 20 201000616 to 1 mass%, based on the mass of the composition of the coating portion. Moreover, in order to adjust the polarity of the composition of the coating portion or to adjust the polarity of the coating of the covering portion, the polymerizable monomer may be appropriately added to the coating portion. The polymerizable monomer may, for example, be (meth)acrylic acid or (meth)acrylate (for example, (mercapto) decyl acrylate, (mercapto) acrylate, propyl (meth) acrylate, ( Methyl)butyl acrylate, (meth)acrylic acid pentoxide, (meth)acrylic acid dodecyl ester, (decyl) decyl decanoate, (fluorenyl) butyl acrylate, (fluorenyl) Benzyl acrylate acetate, (fluorenyl) acesulfame isobornylate, etc.). In addition, when the photocurable component to be used is aqueous (hydrophilic), it may be added alone or in combination, and may be dissolved in water at 80 ° C or lower for the purpose of further improving the strength of the coated portion. a water-soluble monomer having an unsaturated bond in a solvent (for example, 'itaconic acid, N, N'-methylene diacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, N, N-methylenebispropane: fcffj Amine (Ν, Ν'-methylenebisacryl- amide), N-isopropylpropionamide, N-ethylantene η than α ketone, acryloylmorpholine ), Ν, Ν '-dimercapto acrylamide, Ν-vinylformamide, etc.). Thereby, the reaction which adversely affects a polymerization reaction can be suppressed. The amount of the water-soluble monomer to be used is the mass of the composition with respect to the coating portion, and the solid content is at 0. 01~3〇% by mass, to 0. 1 to 25 mass% is preferred. In the present invention, in order to further increase the thermal conductivity, a heat conductive material may be appropriately added to the coating portion forming composition. The thermally conductive substance is not particularly limited as long as it is thermally conductive, and examples thereof include 21 201000616 iron, silver, copper, black lead, magnet, tin, crane, brass, and bronze. The amount of the thermally conductive substance used is 0. The solid content is 0. 01~30% by mass, with 0. 1 to 25 mass% is preferred. The average particle size of the heat storage seamless capsule of the present invention is 0. 1~20mm, with 0. 3~18mm is preferred, preferably 0. 5~16mm; if the average particle size is less than 0. At 1 mm, there is a problem that the amount of content is small and the strength is insufficient. If the average particle diameter exceeds 20 mm, the specific surface area of the capsule is lowered, and the heat transfer area becomes small. Further, in the heat storage seamless capsule of the present invention, the particle diameter of the capsule can be made 0 as described above. 1mm to 20mm (i.e., ΙΟΟμιη~ 20000μηι), compared with conventional microcapsules (0·1 μηι~50μηι), can provide very large capsules, which can increase the content of heat storage materials to very large. The present invention further relates to a method for producing a heat storage seamless capsule comprising a coating portion formed of a composition containing the photocurable component and a heat storage material as a content, the manufacturing method characterized by Further, the composition containing the photocurable component and the heat storage material are passed through a double nozzle, a three-layer nozzle or a porous material to prepare an uncured coating portion including a composition containing the photocurable component, and And a step of irradiating light to the photocurable component to photoharden the capsule precursor. 1 to 3 are views showing preferred embodiments of the heat storage seamless capsule of the present invention (first, second, and third embodiments, respectively), and the present invention will be described in detail based on the respective embodiments. A method for producing a heat storage material seamless capsule. 22 201000616 Thermal storage seamless material having two-layer structure (I-th implementation sound generation manufacturing method The heat storage of the present invention having a two-layer structure, which is schematically shown in the second drawing
缝膠囊（第1實施態樣），可以接田曰# . L 私用具備例如，τρ：於苐4圖的同 心雙層噴嘴（10)之過去公知 ,,, 旳％囊製造裝置，以液中滴下法 來製造。具體地說係，如第4阎π + & 罘4圖所示，採用具備有第1噴嘴（内 側)及第2喷嘴(外側）的同心嘴嘴⑽的同心雙層喷嘴⑽之 膠囊製造裝置，以包含使蓄熱材⑴)從内側的第〗噴嘴、被 覆部形成組成物（12)從外側的第2噴嘴同時通過，並且在栽 體λΐΙ·體（16)中使畜熱材及被覆部形成組成物同時滴下的步 驟的方法等，製造具有2層構造之蓄熱材無縫膠囊。 ........-_抑們W心叫·表 < 製 造方法中，係通過同心雙層喷嘴（10)將蓄熱材（11)及被覆部 形成組成物（12)同時擠出，當蓄熱材和被覆部形成組成物在 載體液體_賴時，_蓄_的極性與被覆部形成組 成物的極性之差，可以構築2層構造。因此，f熱材及光硬 化性成分的極性必須不同。例如，f熱材的極性為油性時， 被覆部形成組成物（亦即，光硬化性成分）的極性為水性，苦 熱材的極性為水性時被覆部形成組成物（亦即，光硬化性: 分)的極性必須為油性。再者，在本發明的扪實施綠樣中， :畜熱材的極性為油性，被覆部形成組成物為水性者較 乜。其理由可以列舉出，水性（親水性 容易地自市售商品購得、處理簡便等等。 生成分可以 Μ再=龍流體（16)宜具有不同於被覆部形心成物的 破覆部形成組成物為水性(親水性）時，載體流體宜為 23 201000616 液狀的油性(疏水性)物質（液狀油），可以舉例如，撖欖油、 荷荷巴油(jojoba oil)、玉米油、菜軒油、豬油、牛油、錄油、 蓖麻油、大豆油、米油、米胚芽油、椰子油、標摘油、可 可油、鱷梨油、夏威夷堅果油、鯊魚肝油（squalene)、紹油、 海龜油、碳數8〜30的烴類、綿羊油、液態石蠟、凡士林、 矽油、碳數4〜30的脂肪酸、碳數4〜30的脂肪酸與蔗糖形 成的酯、碳數4〜30的脂肪酸與丙三醇形成的酯、碳數4〜 30的脂肪族醇、碳數4〜30的脂肪酸和碳數4〜30的脂肪族 醇形成的醋（例如，稼櫚酸十八烧醇酯（stearyl palmitate)、 錄躐硬脂醇辛酸S旨（cetyl 2-ethylhexanoate)、月桂酸甲_、 肉豆蔻酸異丙醋（isopropyl myristate)、稼禍酸異丙醋、掠摘 酸2-乙基己醋、辛基十二醇豆缝酸g旨（〇ctyid〇decyl myristate)、硬脂酸甲 S旨（methyl stearate)、硬脂酸丁醋、異 十三醇硬脂酸酯（isotridecyl stearate)、肉豆蔻酸肉豆謹醋 (myristyl myristate)、十八烷酸十八烷基酯（stearyl stearate) 等），以及其等之組合等。被覆部形成組成物為油性(疏水性） 時’載體流體（16)為水性(親水性)物質（例如，聚乙烯醇、聚 乙烯吡咯烷酮、（化工）澱粉、羧甲基纖維素、甲基纖維素、 乙基纖維素、褐藻酸鈉（soda alginate)、果膠(pectine)、槐豆 膠（locust bean gum)、羅望子膠(tamarindus gum)、黃原膠 (xanthan gum)、丙三醇、（聚）乙二醇、（聚）丙二醇等）的水溶 液或水為宜。 邊參照第4圖，邊更具體地說明第1實施態樣的蓄熱無 縫膠囊之製造方法。具有2層構造之蓄熱無缝膠囊，可以使 24 201000616 用示於第4圖之具備同心雙層噴嘴（ίο)的膠囊製造裝置’以 液中滴下法來製造。同心雙層喷嘴（1 〇)宜將其吐出口配置成 垂直方向朝下。另外，同心雙層喷嘴（1〇)的吐出口宜配置在 形成管（13)内。載體流體（16)係利用泵等之驅動裝置’宜於 一定速度下在裝置内循環。將通過同心雙層喷嘴（10)的内側 喷嘴之蓄熱材（11)、通過外側噴嘴之被覆部形成組成物（12) 分別同時以一定速度擠壓（射出）到載體流體中。此時，藉作 用於載體流體（16)和被覆部形成組成物之間的界面張力’可 形成2層構造的喷射流。之後，噴射流會因重力的作用而形 成球狀液滴（膠囊前驅物）。此時，藉由對喷射流施加振動的 方式，可以使液滴的粒徑變得均一。 接著，用光源（14)將光照射到膠囊前驅物。往膠囊前驅 物的光照射在任一階段進行皆可，例如，可在載體流體（16) 中、也可在通過篩網等分離手段分離膠囊前驅物和載體流 體（16)之後進行。如此處理即可得到具有示於第1圖之2層構 造的蓄熱無縫膠囊。 光源（14),如果是例如，水銀燈、螢光燈、氙燈、碳弧 燈、金屬鹵化物燈等之可以照射約2〇〇nm〜約8〇〇nm的波長 的光之光源即可，並無特殊限定，可以對應所使用的光硬 化性成分做適當的選擇。另外，如果在上述之光硬化性成 分中混合光敏劑，則可利用可見光來使光硬化性成分硬 化。照射時間依光源的強度和距離而不同，但是一般為〇〇5 秒〜10分鐘，以O.i秒〜2分鐘為佳。 本發明的蓄熱無縫膠囊係利用以下所詳述之製造方 25 201000616 法，具有不需要採用製造微膠囊時必要之所謂的冷凍真空 乾燥或者噴霧乾燥機乾燥的大規模乾燥步驟，而且可以更簡 便地製造膠囊之優點。再者，本發明的蓄熱無缝膠囊，可依 需要，亦可根據其用途以常壓或減壓乾燥法來使之乾燥。 第1實施態樣（第1圖）中，因蓄熱材（1)的極性和，形成 被覆部（2)之光硬化性成分的極性不同（相反），故可獲得能 夠簡便地製造蓄熱無缝膠囊，能夠將粒徑分布設定在狹窄 範圍等的優點。 具有3層構造之蓄熱無缝膠囊（第2實施態樣）的製造方法 模式性地示於第2圖之本發明的蓄熱無縫膠囊，特徵為 其具有在蓄熱材（3)和被覆部（5)之間包含中間層（4)之3層構 造。（第2實施態樣）。 在上述之具有2層構造的第1實施態樣中，由其製造方 法的特徵來看，蓄熱材的極性和被覆部形成組成物的極性 是不同（相反）的，但是在第2實施態樣中，如第2圖所示，由 於蓄熱材（3)和被覆部（5)之間存在中間層（4)，因而可以使用 同一極性的蓄熱材及被覆部形成組成物。另外，第2實施態 樣的蓄熱無縫膠囊同樣可以採用熟習該項技術者過去所知 的具備同心三層喷嘴之膠囊製造裝置，依照第1實施態樣之 蓄熱無缝膠囊的製造方法，同樣地進行製造。因此，當蓄 熱材的極性與被覆部形成組成物的極性都為水性（親水性） 時，形成中間層（4)之組成物宜為油性（疏水性），而，當蓄 熱材的極性與被覆部形成組成物的極性都為油性（疏水性) 時，形成中間層（4)之組成物宜為水性（親水性）。 26 201000616 可以形成中間層（4)之水性（親水性）組成物可以舉例 如，載體流體項中所示之水性（親水性)物質的水溶液等，但 是並無特殊限定。而，可以形成中間層（4)之油性（疏水性) 組成物，可以舉例如，載體流體項中所示之疏水性物質等， 但是並無特殊限定。 此外，在第2施態樣中是以蓄熱材的極性為水性，被覆 部形成組成物（亦即，光硬化性成分）的極性也是水性者為 佳。其理由可列舉如，水性（親水性）的光硬化性成分，可以 容易地自市售商品購得，且處理簡便等。 進一步具體說明第2實施態樣之蓄熱無縫膠囊的製造 方法。具有3層構造之蓄熱無缝膠囊可以使用習知的具備同 心三層喷嘴之膠囊製造裝置，同樣依據第4圖所示之液中滴 下法加以製造。將通過同心三層噴嘴最内側喷嘴之蓄熱 材，通過中間的喷嘴之中間層形成組成物，通過最外側噴 嘴的被覆部形成組成物分別同時以一定速度擠壓（射出）到 載體流體中。此時，因載體流體與被覆部形成組成物的作 用，會形成3層構造的喷射流，之後，喷射流會因界面張力 的作用而形成球狀的液滴（膠囊前驅物）。此時，透過對喷射 流加上振動，可以使液滴粒徑變得均勻。接著，使用光源 將光照射到膠囊前驅物。對膠囊前體所施之光照射可在任 一階段進行。如此處理即可獲得具有示於第2圖之3層構造 的蓄熱無縫膠囊。 在第2實施態樣中，因插入中間層而可以使用具有同一 極性的蓄熱材及光硬化性成分。亦即，當插入中間層，較 27 201000616 佳的是由水性組成物所形成之中間層（亦即，水性中間層） 時，可以使用油性的蓄熱材及油性的光硬化性成分，當插 入的是由油性組成物所形成之中間層（亦即，油性中間層） 時，則可以使用水性的蓄熱材及水性的光硬化性成分。因 此，在本發明中，可以組合各種極性的蓄熱材和光硬化性 成分。另外，依據第1實施態樣及第2實施態樣，也可以製 造含有3層以上的層之多層構造的蓄熱無縫膠囊。 具有多核層構造之蓄熱無縫膠囊（第3實施態樣）的製造方法 具有多核構造之蓄熱無縫膠囊（第3實施態樣）係如第3 圖所示，含有複數個蓄熱材作為芯物質，被覆部（7)則存在 其周圍。具有此種多核構造之蓄熱無缝膠囊係如第5圖所 示，可以使蓄熱材（6)及被覆部形成組成物（8)通過多孔材料 進行製造。 可以在本發明中使用的多孔材料，如果是貫通型多孔 材料即無特殊限定，習知的多孔材料可以舉例如，合成高 分子、白砂、沸石、矽石、陶瓷、碳、金屬，及其等之複 合材等。多孔材料的細孔徑及密度可以對應目的的膠囊粒 徑及内容量等做適當選擇。此外，也可以利用市售的多孔 材料。 蓄熱材（6)及被覆部形成組成物（8)並無特殊限定，可以 適宜地選擇上述物質來使用，但是與第1實施態樣相同地， 蓄熱材及被覆部形成組成物的極性必須彼此不同。亦即， 蓄熱材的極性為油性時，被覆部形成組成物的極性為水 性；蓄熱材的極性為水性時，被覆部形成組成物的極性為 28 201000616 油性。再者，在第3實施態樣中係以蓄熱材的極性為油性， 被覆部形成組成物的極性是水性者為佳。其理由可列舉 出，水性（親水性）的光硬化性成分，可從市售商品容易地取 得、處理簡便等。 在此，將邊芩照第5圖，邊詳細說明具有多核構造之蓄 熱無縫膠囊（第3實施態樣）的製造方法。首先，預先混合蓄 熱材（6)及被覆部形成組成物（8)以形成乳液。所形成之乳液 可以是油性（疏水性）蓄熱材分散在水性（親水性）被覆部形 成組成物（8)中之水中油型（〇/w (〇il-in_ water))乳液，也可 以是水性（親水性）蓄熱材分散在油性（疏水性）被覆部形成 組成物（8)中之油中水型（W/O (water-in-oil))乳液。依需要， 於乳液形成時’亦可適當地添加界面活性劑（例如，陰離子 性界面活性劑、陽離子性界面活性劑、非離子性界面活性 劑、兩性界面活性劑等）等的添加劑。 陰離子性界面活性劑雖無特殊限定，惟可舉例如，十 一烧基硫酸納（sodium lauryl sulfate)、十二烧基硫酸三乙醇 胺、十二烷基硫酸銨、十二烷基苯磺酸納（s〇dium dodecylbenzenesulfonate)、硬脂酸鈉、半硬化牛脂肪酸鈉、 半硬化牛脂肪酸鉀、油酸鉀(potassium oleate)、萬麻油奸 鹽、烧基秦確酸鈉、琥轴酸二烧基酿確酸納（sodium dialkyl sulfosuccinate)、烷基二苯醚二磺酸鈉（SO(jium alkyl diphenyl ether disulfonate)、烷基磷酸二乙醇胺、烷基磷酸鉀、聚氧 乙細烧基硫酸鈉（Sodium polyoxyethylene alkyl sulfate)、聚 氧乙烯烷基醚硫酸三乙醇胺、聚氧乙烯烷基笨基醚硫酸鈉 29 201000616 等。 陽離子性界面活性劑並無特殊限定，可舉例如，十二 烧基三曱基氯化敍（lauryl trimethyl ammonium chloride)、十 八烷基三甲基氯化銨、十六烷基三曱基氯化銨、雙十八燒 基二甲基氯化銨、烷基苯基二甲基氣化銨、十八烷胺油酸 酯、十八烷胺乙酸酯、十八烷胺酸等。 非離子性界面活性劑無特殊限定，可舉例如，甘油月旨 肪酸酯、丙二醇脂肪酸酯、山梨糖醇酐脂肪酸酯、聚氧乙 烯山梨糖醇酐脂肪酸酯、脂肪酸丙二酯、甘油脂肪酸酯、 蔗糖脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯（poly〇Xy_ ethylene sorbitol fatty acid ester)、四油酸聚氧乙稀山梨糖 醇、聚氧乙烯烷基醚、聚氧丙烯烷基醚、聚氧乙烯聚氧两 烯二醇（polyoxyethylene-polyoxypropylene glycol)、聚氧乙 稀聚氧丙稀炫基醚、聚乙二醇脂肪酸S旨（poluethylene glycQi fatty acid ester)、聚氧乙稀萬麻油、聚氧乙稀硬化萬麻油等。 兩性界面活性劑雖無特殊限定，但可舉例如，烷基二 曱氨基醋酸甜菜鹼、烷基二曱基氧化胺（alkyl dimethyl amine oxide)、烧基叛甲基經乙基咪唾鑷甜菜域（alkyl carboxymethyl hydroxyethyl imidazolium betaine)、印碟月旨、 十二烧基氨基丙酸酯（laurylamino propionate)、烧基二氨基 乙基甘氨酸(alkyldiamino-ethylglycine)等。 如第5圖所示，將乳液（亦即，蓄熱材（6)及被覆部形成 組成物（8))配置在多孔材料的一邊，載體流體（16)配置在另 一邊。載體流體（16)可以使用上述之第1實施態樣及第2實施 30 201000616 怨樣中使㈣紐流體。但是，紐越（1δ)的極性必須不 同於被覆部的極性。料，當««成喊物的極性為 水性(親水性）時’載體流體（16)宜為液狀的油性(疏水性)物 質，當被覆部形成組成物的極性為油性(疏水性）時，載體流 體（16)宜為水性(親水性）物質的水溶液或者水。 利用被覆部形成組成物與載體流體極性的差，通過多 孔材料，將上述調製好之乳液擠壓到載體流體側（16)，可藉 而形成包含複數個蓄熱材⑹作為芯物質之多核構造的膠囊 前驅物。從光源（14)將光照射到膠囊前驅物，藉以使被覆部 升> 成組成物中所含有之光硬化性成分發生硬化而形成被覆 部（7)，可以獲得本發明第3實施態樣之具有多核構造的蓄熱 無缝膠囊。再者，如第5圖所示，光照射可以在載體流艘（1 中進行，也可以在使用熟習該項技術者所公知的万法從 體流體回收膠囊前驅物之後進行。Sewing capsule (first embodiment), can be connected to the field 曰#. L privately available, for example, τρ: the concentric double-layer nozzle (10) of the 苐4 diagram is known in the past, 旳% capsule manufacturing device, liquid Made by dropping in the middle. Specifically, as shown in the fourth 阎π + & 罘4, a capsule manufacturing apparatus using a concentric double nozzle (10) having a concentric nozzle (10) of a first nozzle (inner side) and a second nozzle (outer side) is used. The second nozzle that includes the first nozzle and the covering portion forming component (12) from the inside is simultaneously passed through, and the hot material and the covering portion are placed in the carrier λ ΐΙ body (16). A method of forming a composition in which a composition is simultaneously dropped, and the like, a seamless capsule of a heat storage material having a two-layer structure is produced. ........- _ ̄ ̄ ̄ W W W W H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H When the heat storage material and the coating portion forming composition are in the carrier liquid, the polarity of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Therefore, the polarities of the f hot material and the photohardenable component must be different. For example, when the polarity of the f hot material is oily, the polarity of the composition of the coating portion (that is, the photocurable component) is water, and when the polarity of the bitter hot material is water, the coating portion forms a composition (that is, photocurability). : The polarity of the minute must be oily. Further, in the green sample of the present invention, the polarity of the heat material of the animal is oily, and the composition of the coated portion is water-based. The reason for this can be exemplified by water-based (hydrophilic property is easily obtained from a commercially available product, and the treatment is simple, etc. The formation component can be Μ = = dragon fluid (16) should have a different portion than the coated portion When the composition is aqueous (hydrophilic), the carrier fluid is preferably 23 201000616 liquid oily (hydrophobic) substance (liquid oil), and for example, eucalyptus oil, jojoba oil, corn oil , vegetable oil, lard, butter, oil, castor oil, soybean oil, rice oil, rice germ oil, coconut oil, oil, cocoa butter, avocado oil, macadamia nut oil, shark liver oil (squalene) , Shao oil, sea turtle oil, hydrocarbons with carbon number 8~30, lanolin, liquid paraffin, petrolatum, eucalyptus oil, fatty acids with carbon number 4~30, esters of fatty acids with carbon number 4~30 and sucrose, carbon number 4 An ester of 〜30 fatty acid with glycerol, an aliphatic alcohol having 4 to 30 carbon atoms, a fatty acid having 4 to 30 carbon atoms, and an aliphatic alcohol having 4 to 30 carbon atoms (for example, 18 Stearyl palmitate, stearyl octanoic acid S (cetyl 2-ethylhexanoat) e), lauric acid A, isopropyl myristate, vinegar acid isopropyl vinegar, grazing acid 2-ethylhexyl vinegar, octyldodecanol succinic acid g (〇ctyid〇 Decyl myristate), methyl stearate, butyl sulphate, isotridecyl stearate, myristyl myristate, octadecanoic acid A stearyl stearate or the like, a combination thereof, etc. When the coated portion is formed into an oily (hydrophobic) composition, the carrier fluid (16) is an aqueous (hydrophilic) substance (for example, polyvinyl alcohol). , polyvinylpyrrolidone, (chemical) starch, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, sodium soda alginate, pectine, locust bean gum, Luo An aqueous solution or water of tamarindus gum, xanthan gum, glycerol, (poly)ethylene glycol, (poly)propylene glycol, etc.) is preferred. A method for producing a heat storage seamless capsule according to a first embodiment, which has a two-layer structure of heat storage seamlessly The capsule can be manufactured by the liquid droplet dropping method using the capsule manufacturing apparatus of the concentric double-layer nozzle (Fig. 4) shown in Fig. 4. The concentric double-layer nozzle (1 〇) should be configured to be vertically arranged. The direction of the discharge is downward. In addition, the discharge port of the concentric double nozzle (1〇) is preferably disposed in the forming tube (13). The carrier fluid (16) is circulated within the apparatus at a constant speed by means of a drive unit such as a pump. The heat accumulating material (11) passing through the inner nozzle of the concentric double nozzle (10) and the covering portion forming composition (12) passing through the outer nozzle are simultaneously pressed (ejected) into the carrier fluid at a constant speed. At this time, a jet flow of a two-layer structure can be formed by using the interfacial tension between the carrier fluid (16) and the coating portion forming composition. Thereafter, the jets form spherical droplets (capsule precursors) due to the action of gravity. At this time, the particle diameter of the droplets can be made uniform by applying vibration to the jet. Next, light is irradiated to the capsule precursor with a light source (14). The light irradiation to the capsule precursor can be carried out at any stage, for example, after the capsule precursor and the carrier fluid (16) can be separated in the carrier fluid (16) or by a separation means such as a screen. By this treatment, a heat storage seamless capsule having the two-layer structure shown in Fig. 1 can be obtained. The light source (14), for example, a mercury lamp, a fluorescent lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, or the like, which can illuminate a light having a wavelength of about 2 〇〇 nm to about 8 〇〇 nm, and It is not particularly limited and can be appropriately selected depending on the photocurable component to be used. Further, when a photosensitizer is mixed in the above photocurable component, visible light can be used to harden the photocurable component. The irradiation time varies depending on the intensity and distance of the light source, but is generally 〇〇5 seconds to 10 minutes, preferably in O.i seconds to 2 minutes. The heat storage seamless capsule of the present invention has a large-scale drying step which does not require the so-called freeze vacuum drying or spray dryer drying necessary for manufacturing the microcapsules, and can be more easily used, by the method of the manufacturer 25 201000616, which is described in detail below. The advantages of making capsules. Further, the heat storage seamless capsule of the present invention may be dried by a normal pressure or a reduced pressure drying method according to the use thereof as needed. In the first embodiment (Fig. 1), since the polarities of the heat storage material (1) and the polarities of the photocurable components forming the covering portion (2) are different (opposite), it is possible to easily manufacture the heat storage seamlessly. The capsule has the advantage of being able to set the particle size distribution in a narrow range or the like. A method for producing a heat storage seamless capsule having a three-layer structure (second embodiment) is schematically shown in the heat storage seamless capsule of the present invention according to Fig. 2, and is characterized in that it has a heat storage material (3) and a coating portion ( 5) A 3-layer structure comprising an intermediate layer (4). (Second embodiment). In the first embodiment having the two-layer structure described above, the polarity of the heat storage material and the polarity of the coating portion forming composition are different (opposite), but the second embodiment is different from the second embodiment. As shown in Fig. 2, since the intermediate layer (4) is present between the heat storage material (3) and the covering portion (5), the heat storage material and the covering portion of the same polarity can be used to form the composition. Further, in the heat storage seamless capsule according to the second embodiment, a capsule manufacturing apparatus having a concentric three-layer nozzle known to those skilled in the art can be used, and the method for manufacturing a heat storage seamless capsule according to the first embodiment is similar. Manufacturing. Therefore, when both the polarity of the heat storage material and the polarity of the composition forming the coating portion are aqueous (hydrophilic), the composition forming the intermediate layer (4) is preferably oily (hydrophobic), and when the polarity and coating of the heat storage material are When the polarity of the component forming composition is oily (hydrophobic), the composition forming the intermediate layer (4) is preferably aqueous (hydrophilic). 26 201000616 The aqueous (hydrophilic) composition which can form the intermediate layer (4) can be, for example, an aqueous solution of an aqueous (hydrophilic) substance shown in the carrier fluid, but is not particularly limited. Further, an oily (hydrophobic) composition of the intermediate layer (4) may be formed, and examples thereof include a hydrophobic substance shown in the carrier fluid term, but are not particularly limited. Further, in the second aspect, the polarity of the heat storage material is water-based, and the polarity of the composition (i.e., photocurable component) of the coating portion is also aqueous. The reason for this is, for example, an aqueous (hydrophilic) photocurable component which can be easily obtained from a commercially available product, and which is easy to handle. The method for producing the heat storage seamless capsule of the second embodiment will be further specifically described. The heat storage seamless capsule having a three-layer structure can be produced by using a conventional capsule manufacturing apparatus having a concentric three-layer nozzle, and also by the liquid dropping method shown in Fig. 4. The heat accumulating material passing through the innermost nozzle of the concentric three-layer nozzle is formed into a composition through the intermediate layer of the intermediate nozzle, and the composition forming portion of the outermost nozzle is simultaneously pressed (ejected) into the carrier fluid at a constant speed. At this time, since the carrier fluid forms a composition with the coating portion, a jet having a three-layer structure is formed, and thereafter, the jet flows into a spherical droplet (capsule precursor) due to the interfacial tension. At this time, by adding vibration to the jet flow, the droplet size can be made uniform. Next, a light source is used to illuminate the capsule precursor. Irradiation of the light applied to the capsule precursor can be carried out at any stage. By this treatment, a heat storage seamless capsule having the three-layer structure shown in Fig. 2 can be obtained. In the second embodiment, a heat storage material having the same polarity and a photocurable component can be used by inserting the intermediate layer. That is, when the intermediate layer is inserted, it is preferable that 27 201000616 is an intermediate layer formed of an aqueous composition (that is, an aqueous intermediate layer), and an oily heat storage material and an oily photocurable component can be used when inserted. When the intermediate layer (that is, the oily intermediate layer) is formed of the oily composition, an aqueous heat storage material and an aqueous photocurable component can be used. Therefore, in the present invention, heat storage materials and photocurable components of various polarities can be combined. Further, according to the first embodiment and the second embodiment, it is also possible to manufacture a heat storage seamless capsule having a multilayer structure of three or more layers. Method for producing a heat-storing seamless capsule having a multi-core layer structure (third embodiment) A heat-storing seamless capsule having a multi-core structure (third embodiment) is as shown in Fig. 3, and includes a plurality of heat storage materials as a core material. The covered part (7) exists around it. As shown in Fig. 5, the heat storage seamless capsule having such a multinuclear structure can be manufactured by using a porous material as the heat storage material (6) and the coating portion forming composition (8). The porous material which can be used in the present invention is not particularly limited as long as it is a through-type porous material, and examples of the conventional porous material include synthetic polymers, white sand, zeolites, vermiculite, ceramics, carbon, metals, and the like. Composite materials, etc. The pore diameter and density of the porous material can be appropriately selected in accordance with the capsule diameter and content of the object. Further, commercially available porous materials can also be utilized. The heat storage material (6) and the coating portion forming composition (8) are not particularly limited, and may be appropriately selected and used. However, in the same manner as in the first embodiment, the polarities of the heat storage material and the coating portion forming composition must be mutually different. In other words, when the polarity of the heat storage material is oily, the polarity of the composition of the coating portion is watery; and when the polarity of the heat storage material is water, the polarity of the composition of the coating portion is 28 201000616. Further, in the third embodiment, the polarity of the heat storage material is oily, and the polarity of the composition forming the coating portion is preferably water. The reason for this is that an aqueous (hydrophilic) photocurable component can be easily obtained from a commercially available product, and is easily handled. Here, a method of manufacturing a heat storage seamless capsule having a multi-core structure (third embodiment) will be described in detail with reference to Fig. 5. First, the heat storage material (6) and the coating portion are mixed in advance to form a composition (8) to form an emulsion. The emulsion formed may be an oily (〇 - --in_water) emulsion in which an oily (hydrophobic) heat storage material is dispersed in an aqueous (hydrophilic) coating portion forming composition (8), or may be The aqueous (hydrophilic) heat storage material is dispersed in an oil-type (W/O (water-in-oil)) emulsion in the oily (hydrophobic) coating portion forming composition (8). If necessary, an additive such as a surfactant (for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or the like) may be added as appropriate during the formation of the emulsion. The anionic surfactant is not particularly limited, and examples thereof include sodium lauryl sulfate, triethanolamine dodecyl sulfate, ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate. (s〇dium dodecylbenzenesulfonate), sodium stearate, semi-hardened bovine fatty acid sodium, semi-hardened bovine fatty acid potassium, potassium oleate, naring oil, sodium sulphate, sodium succinate Sodium dialkyl sulfosuccinate, sodium (zium alkyl diphenyl ether disulfonate), alkyl diethanolamine, potassium alkyl phosphate, sodium polyoxysulfonate (Sodium) Polyoxyethylene alkyl sulfate), polyoxyethylene alkyl ether triethanolamine sulfate, sodium polyoxyethylene alkyl stearate sulfate 29 201000616, etc. The cationic surfactant is not particularly limited, and examples thereof include a decyl tridecyl group. Lauryl trimethyl ammonium chloride, octadecyltrimethylammonium chloride, cetyltrimethylammonium chloride, octadecyl dimethylammonium chloride, alkylphenyl dimethyl Base gasification The octadecylamine oleate, stearylamine acetate, octadecylamine, etc. The nonionic surfactant is not particularly limited, and examples thereof include glycerol fatty acid ester and propylene glycol fatty acid ester. Sorbitol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid propylene glycol ester, glycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitol fatty acid ester (poly〇Xy_ethylene sorbitol fatty acid) Acid ester), polyoxyethylene sorbitan tetrahydrate, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene polycondensation An oxypropylene ether, a polyethylene glycol fatty acid ester, a polyoxyethylene eucalyptus oil, a polyoxyethylene hardened kenaf oil, etc. The amphoteric surfactant is not particularly limited, but may be exemplified For example, alkyl diterpene aminoacetate betaine, alkyl dimethyl amine oxide, alkyl carboxymethyl hydroxyethyl imidazolium betaine, printed moon , Dodecyl aminopropionate burning (laurylamino propionate), burning glycine diamino group (alkyldiamino-ethylglycine) and the like. As shown in Fig. 5, the emulsion (i.e., the heat storage material (6) and the coating portion forming composition (8)) are disposed on one side of the porous material, and the carrier fluid (16) is disposed on the other side. The carrier fluid (16) can be used in the first embodiment described above and in the second embodiment 30 201000616. However, the polarity of New Zealand (1δ) must be different from the polarity of the covered portion. When the polarity of the «« shout is water-based (hydrophilic), the carrier fluid (16) is preferably a liquid oily (hydrophobic) substance, when the polarity of the composition forming the coating is oily (hydrophobic). The carrier fluid (16) is preferably an aqueous solution of aqueous (hydrophilic) material or water. The difference between the polarity of the composition and the carrier fluid is formed by the coating portion, and the prepared emulsion is extruded to the carrier fluid side (16) through the porous material, thereby forming a multinuclear structure including a plurality of heat storage materials (6) as a core material. Capsule precursor. The third embodiment of the present invention can be obtained by irradiating light to the capsule precursor from the light source (14), thereby causing the coating portion to rise and harden the photocurable component contained in the composition to form the covering portion (7). A heat storage seamless capsule having a multi-core structure. Further, as shown in Fig. 5, the light irradiation may be carried out in the carrier flow vessel (1), or may be carried out after recovering the capsule precursor using a universal fluid known to those skilled in the art.
V 此外，在本發明的其他實施態樣中，被覆部衫成辑 1膠 物亦可進一步含有角叉菜膠(carrageenan)、寒天、十德障 (curdlan)等的膠凝。 而，在本發明之又另一種實施態樣中，被覆鄯形成’組 成物並不含光硬化性成分，而也可以含有角叉菜膠，赛天 .,if 卡德蘭膠等的膠凝劑作為其代替物。在該實施態槔f 以利用冷卻或加熱來形成被覆部。 在以下的實施例中將更詳細地說明本發明，俱疼$ 明並不限定於這些實施例。 實施例 31 201000616 實施例1 ··具有2層構造之蓄熱無縫膠囊(被覆部：由水性光 硬化性成分所形成之光硬化樹脂皮膜）的製造 混合九（乙一醇）一丙烯酸醋（nona(ethyleneglycol) diacrylate)60質量份、十四（乙二醇）二丙稀酸酯（tetra (ethyleneglycol)diacrylate)20 質量份及安息香異丁醚 (benzoinisobutylether)0.6質量份，調製成被覆部形成組成 物。將上述的水性被覆部形成組成物填充於具有同心雙層 喷嘴之膠囊製造裝置（森下仁丹公司製，製造機KC-1)的外 側喷嘴’内側噴嘴填充油性蓄熱材之液態石蠟（松村石油研 究所製’ MORESCO WHITE P-350)。將上述之水性被覆部 形成組成物及油性蓄熱材同時射出至冷卻到13。(3的菜籽油 中，形成2層構造的液滴（膠囊前驅物）。 用南壓水銀燈（GS YUASA Lighting公司製、HAL200L) 對液滴照射紫外線（波長：320〜400nm)。所得到之具有2層 構造的蓄熱無縫膠囊，其粒徑是1mm。 實施例2:具有2層構造之蓄熱無縫膠囊(被覆部：由油性光 硬化性成分所形成之光硬化樹脂皮膜）的製造 混合二甲基丙稀酸-1，6-己二S旨（1,6-hexanediol dimethacrylate)60質量份、環氧乙烷變性雙酚A二甲基丙烯 酸酉旨（日本油脂製，blemmerPDPER-l5〇)2〇質量份及聚合起 始劑（Ciba-Geigy公司製，lrgacure 184)0·6質量份，調製成 油性被覆部形成組合物。將上述的油性被覆部形成組成物 填充於具有同心雙層喷嘴之膠囊製造裝置（森下仁丹公司 製，製造機KC-1)的外側喷嘴，内側喷嘴填充水性蓄熱材之 32 201000616 四乙二醇(tetraethyleneglycol)。將上述之油性被覆部形成組 成物及水性蓄熱材同時射出至冷卻到13。(：之2%聚乙烯醇 中’形成2層構造的液滴（膠囊前驅物 用高壓水銀燈(GSYUASA Lighting公司製、HAL200L) 對液滴照射紫外線（波長：320〜400nm)。所得之具有2層構 造的蓄熱無縫膠囊，其粒徑是1.5mm。 實施例3 :具有3層構造之蓄熱無縫膠囊的製造 混合十四（乙二醇）二丙烯酸酯6〇質量份、環氧系水性光 硬化性成分（昭和高分子公司製、Rip〇xySp 6〇〇〇)1〇質量份 及3-經基丁酮(acetoin)〇6質量份，調製成水性被覆部形成 組成物。將上述水性被覆部形成組成物填充於具有同心三 層喷嘴之勝囊製造裝置（森下仁丹公司製，製造機Κ(>1)的 最外側噴嘴’最内側噴嘴填充保溫於40。(：之氯化鈣6水合物 液體（融點：30。〇作為水性蓄熱材，中間的噴嘴填充加熱至 7 0 C之十八燒酸酸十八烷基酯作為油性中間層形成組成 物。將上述之水性被覆部形成組成物、油性中間層形成組 成物及水性蓄熱材同時射出至冷卻到13。(：的玉米油中，形 成3層構造的液滴（膠囊前驅物）。 用金屬鹵化物燈(GS YUASA Lighting公司製、]V1AN 250L)對液滴照射紫外線（波長：32〇〜4〇〇nm卜所獲得之具 有3層構造的蓄熱無縫膠囊，其粒徑為1.5mm。 實施例4 :被覆部中含有熱傳導性物質之具有2層構造的蓄 熱然縫膠囊(被覆部：由水性光硬化性成分所形成之光硬化 性樹脂皮膜）的製造 33 201000616 調製十四（乙二醇）二丙烯酸酯50質量份、雙三羥曱基丙 烷四丙烯酸酯20質量份、錫粉末(38μηι)2.5質量份及3-羥基 丁酮0.8質量份的混合物，添加至以實施例丨所調製成的水 性被覆部形成組成物，實施例1同樣地施行操作，得到具有 2層構造之蓄熱無縫膠囊。所獲得之蓄熱無縫膠囊的粒徑是 7.5mm。 實施例5 :具有多核構造之蓄熱無縫膠囊（被覆部：由水性 光硬化性成分所形成之光硬化樹脂皮膜）的製造 以60質量份的十四（乙二醇）二丙稀酸酯、1 〇質量份的 RipoxySP-6000及0.6質量份的安息香異丁基醚作為水性被 覆部形成組成物，50質量份的液態石壤（松忖石油研究所 製，MORESCO WHITEP-350)作為油性蓄熱材，以及1質量 份的月桂醇聚氧乙烯醚(polyoxyethylene lauryl ether)作為 乳化劑，在均質機(homomixer)中加以混合，調製成乳液。 使上述乳液通過細孔徑75μιη的尼龍膜，射出至冷卻到9°C 的菜籽油中，形成多核構造的液滴（膠囊前驅物）。 使用高壓水銀燈對液滴照射紫外線（波長：320〜 4〇〇nm)。所獲得之具有多核構造的蓄熱無縫膠囊，其粒徑 是〇.5mm。 用以下方法評估本發明的蓄熱無縫膠囊。 (a)蓄熱無縫膠囊的蓄熱量測定 用差示掃描量熱計（(Differential Scanning Calorimetry), 島津製作所製，DSC-60A)測定本發明之蓄熱無缝膠囊的潛 熱量（升溫速度：5°C/分，溫度：-10°C〜65°C)。結果示於 34 201000616 以下的表1。 (b)蓄熱無缝膠囊的安定性試驗 在5°C〜40°C之間反復加熱及冷卻本發明之蓄熱無縫 膠囊100次，目視觀察蓄熱無縫膠囊的外觀，藉以評估安定 性。結果示於以下之表1。 【表1】 實施例 大小 (mm) 潛熱量 (cal / g) 安定性 實施例1 1 42 良好 實施例2 1.5 48 良好 實施例3 1.5 45 良好 實施例4 7.5 38 良好 實施例5 0.5 41 良好 從以上的結果可知，本發明的蓄熱無缝膠囊具有良好 的尺寸、蓄熱量及安定性。 產業之可利用性 由於本發明的蓄熱無缝膠囊具有多層構造或多核構 造，故可以提供優良的強度及安定性等之物理特性。 另外，在本發明中可以將膠囊的粒徑做成0.1〜 20mm(亦即，100〜20000μηι)，和習知的微膠囊（粒徑：約 0· Ιμηι〜50μηι)相比，可以提供非常大的膠囊。亦即，在本 發明中，可以將蓄熱材的含量做得非常大。 再者，在本發明中可以利用光硬化性成分的自由基聚 合或者陽離子聚合來形成無縫膠囊的被覆部，在本發明中 可以正確地規定内容物，即蓄熱材的量，也有可以簡便地 控制蓄熱量之優點。 35 201000616 此外，由於本發明的蓄熱無缝膠囊不使用曱醛等之對 人體有害的物質作為原料，故安全性高。 因此，本發明的蓄熱無縫膠囊因為是利用潛熱故熱效 率高，可應用於各種建材，尤其是壁材等之建材，可以大 幅地降低居住環境中之能源消費。 【圖式簡單說明】 第1圖為本發明之蓄熱無缝膠囊的較佳實施態樣示意 模式圖，顯示具有由蓄熱材（1)及含有光硬化性成分之組成 物所形成的被覆部（2)構成之2層構造的蓄熱材無缝膠囊（第 1實施態樣）。 第2圖為本發明之蓄熱無缝膠囊的較佳實施態樣示意 模式圖，顯示具有由蓄熱材（3)、中間層（4)及由含有光硬化 性成分之組成物所形成的被覆部（5)構成之具有3層構造的 蓄熱無缝膠囊（第2實施態樣）。 第3圖為本發明之蓄熱無缝膠囊的較佳實施態樣示意 模式圖，顯示具有複數個蓄熱材（6)及由含有光硬化性成分 的組成物所形成之被覆部（7)所構成的多核構造之蓄熱無缝 膠囊（第3實施態樣）。 第4圖為第1圖所示之具有2層構造的本發明的蓄熱無 缝膠囊之製造方法的概略圖。 第5圖為第3圖所示之具有多核構造的本發明的蓄熱無 缝膠囊之製造方法的概略圖。 36 201000616 【主要元件符號說明】 1···蓄熱材 2 · · ·被覆部 3…蓄熱材 4…中間層 5…被覆部 6···蓄熱材 7…被覆部 8···被覆部形成組成物 9··.多孔材料 10…雙層喷嘴 11…蓄熱材 12…被覆部形成組成物 13…形成管 14…光源 15···分離裝置 16…載體流體 17…驅動裝置 37V Further, in other embodiments of the present invention, the coated vestibule may further contain gelatinized carrageenan, cold weather, curdlan, or the like. However, in still another embodiment of the present invention, the coated ruthenium forms a composition which does not contain a photocurable component, and may also contain gelatin of carrageenan, Saito., ifkadlan, etc. The agent acts as a substitute. In this embodiment, the coating portion is formed by cooling or heating. The invention will be described in more detail in the following examples, which are not limited to these examples. Example 31 201000616 Example 1 Production of a heat-storing seamless capsule having a two-layer structure (covered portion: a photo-curable resin film formed of an aqueous photocurable component) mixed with nin (ethyl alcohol)-acrylic acid vinegar (nona ( Ethyleneglycol) Diacrylate) 20 parts by mass of tetrakis(ethyleneglycol) diacrylate and 0.6 parts by mass of benzoin isobutylether were prepared into a coating portion to form a composition. The liquid-coated paraffin (the Matsumura Petroleum Research Institute) is filled with the oil-based heat storage material inside the nozzle of the outer nozzle of the capsule manufacturing apparatus (manufactured by Morishita Renden Co., Ltd., KC-1). 'MORESCO WHITE P-350). The above-mentioned aqueous coating portion forming composition and the oily heat storage material were simultaneously injected and cooled to 13. In the rapeseed oil of 3, a droplet of a two-layer structure (capsule precursor) was formed. The droplet was irradiated with ultraviolet light (wavelength: 320 to 400 nm) with a South Pressure mercury lamp (manufactured by GS YUASA Lighting Co., Ltd., HAL200L). A heat storage seamless capsule having a two-layer structure having a particle diameter of 1 mm. Example 2: Manufacturing and mixing of a heat storage seamless capsule having a two-layer structure (covered portion: a photo-curable resin film formed of an oil-based photocurable component) 60 parts by mass of 1,6-hexanediol dimethacrylate, ethylene oxide-denatured bisphenol A dimethacrylate (made by Nippon Oil Co., blemmerPDPER-l5〇) 2 parts by mass and a polymerization initiator (lrgacure 184, manufactured by Ciba-Geigy Co., Ltd.), 0.6 parts by mass, to prepare an oil-coated portion forming composition. The oil-coated portion forming composition described above is filled in a concentric double layer. The outer nozzle of the nozzle manufacturing apparatus (manufactured by Morishita Rendan Co., Ltd., manufacturing machine KC-1), and the inner nozzle filled with the aqueous heat storage material 32 201000616 tetraethylene glycol (colethylene glycol). The above oily coating portion is formed into a composition and aqueous heat storage. material When it is cooled to 13. (: 2% of polyvinyl alcohol is formed in a two-layer structure (high-pressure mercury lamp for capsule precursor (manufactured by GSYUASA Lighting Co., Ltd., HAL200L). The droplet is irradiated with ultraviolet light (wavelength: 320 to 400 nm) The obtained heat-storing seamless capsule having a two-layer structure has a particle diameter of 1.5 mm. Example 3: Production of a heat-storing seamless capsule having a three-layer structure Mixed with fourteen (ethylene glycol) diacrylate 6 〇 mass The epoxy-based water-based photocurable component (Rip〇xySp 6〇〇〇, manufactured by Showa Polymer Co., Ltd.) was prepared in an amount of 1 part by mass and 6 parts by mass of acetoin(R) to form an aqueous coating portion. In the composition of the above-mentioned aqueous coating part, the innermost nozzle of the sac capsule manufacturing apparatus (the outermost nozzle of the manufacturing machine &(> 1) manufactured by Morishita Rendan Co., Ltd.) is filled and kept at 40. (: Calcium chloride 6 hydrate liquid (melting point: 30. 〇 as an aqueous heat storage material, the middle nozzle is filled with octadecyl octadecanoate heated to 70 C as an oily intermediate layer forming composition. Forming the above-mentioned aqueous coating portion into a group The composition of the oily intermediate layer and the aqueous heat storage material are simultaneously injected and cooled to 13. (In the corn oil, a droplet of a three-layer structure (capsule precursor) is formed. A metal halide lamp (manufactured by GS YUASA Lighting Co., Ltd.) ] V1AN 250L) A heat storage seamless capsule having a three-layer structure obtained by irradiating ultraviolet rays (wavelength: 32 〇 to 4 〇〇 nm) to a droplet, and having a particle diameter of 1.5 mm. Example 4: Production of a heat-storing capsule having a two-layer structure containing a thermally conductive substance in a coating portion (covered portion: a photocurable resin film formed of an aqueous photocurable component) 33 201000616 Modulation 14 (Ethylene) 50 parts by mass of an alcohol) diacrylate, 20 parts by mass of bistrihydroxydecylpropane tetraacrylate, 2.5 parts by mass of tin powder (38 μm), and 0.8 parts by mass of 3-hydroxybutanone were added to the mixture prepared in Example 丨The formed aqueous coating portion was formed into a composition, and in the same manner as in Example 1, a heat storage seamless capsule having a two-layer structure was obtained. The obtained heat-storing seamless capsule had a particle diameter of 7.5 mm. Example 5: Production of a heat-storing seamless capsule having a multi-nuclear structure (coated portion: a photo-curable resin film formed of an aqueous photocurable component), 60 parts by mass of tetrakis(ethylene glycol) diacrylate, 1 part by mass of Ripoxy SP-6000 and 0.6 part by mass of benzoin isobutyl ether as a water-based coating part forming composition, and 50 parts by mass of liquid stone soil (MORESCO WHITEP-350, manufactured by Matsuzaka Petroleum Research Institute) as an oily heat storage material And 1 part by mass of polyoxyethylene lauryl ether as an emulsifier, and mixed in a homomixer to prepare an emulsion. The emulsion was passed through a nylon membrane having a pore diameter of 75 μm and ejected to rapeseed oil cooled to 9 ° C to form a droplet of a multinuclear structure (capsule precursor). The droplets were irradiated with ultraviolet rays (wavelength: 320 to 4 〇〇 nm) using a high pressure mercury lamp. The obtained heat-storing seamless capsule having a multi-nuclear structure has a particle diameter of 〇5 mm. The heat storage seamless capsule of the present invention was evaluated by the following method. (a) Measurement of the calorific value of the heat storage seamless capsule The differential heat of the heat storage seamless capsule of the present invention was measured by Differential Scanning Calorimetry (DSC-60A, manufactured by Shimadzu Corporation) (temperature up rate: 5°) C / min, temperature: -10 ° C ~ 65 ° C). The results are shown in Table 1 below 34 201000616. (b) Stability test of heat storage seamless capsule The heat storage seamless capsule of the present invention was repeatedly heated and cooled 100 times between 5 ° C and 40 ° C, and the appearance of the heat storage seamless capsule was visually observed to evaluate the stability. The results are shown in Table 1 below. [Table 1] Example size (mm) Latent heat (cal / g) Stability Example 1 1 42 Good example 2 1.5 48 Good example 3 1.5 45 Good example 4 7.5 38 Good example 5 0.5 41 Good from As a result of the above, it is understood that the heat storage seamless capsule of the present invention has good size, heat storage capacity, and stability. INDUSTRIAL APPLICABILITY Since the heat storage seamless capsule of the present invention has a multilayer structure or a multi-nuclear structure, it is possible to provide physical properties such as excellent strength and stability. Further, in the present invention, the particle diameter of the capsule can be made 0.1 to 20 mm (i.e., 100 to 20000 μm), which is very large compared with the conventional microcapsules (particle size: about 0·Ιμηι 5050 μm). Capsules. That is, in the present invention, the content of the heat storage material can be made very large. Further, in the present invention, the coating portion of the seamless capsule can be formed by radical polymerization or cationic polymerization of the photocurable component, and in the present invention, the content, that is, the amount of the heat storage material can be accurately specified, and the content of the heat storage material can be easily determined. Control the advantages of heat storage. Further, since the heat storage seamless capsule of the present invention does not use a substance harmful to human body such as furfural as a raw material, it is highly safe. Therefore, the heat storage seamless capsule of the present invention has high heat efficiency due to the use of latent heat, and can be applied to various building materials, particularly building materials such as wall materials, and can greatly reduce energy consumption in a living environment. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a preferred embodiment of a heat storage seamless capsule of the present invention, showing a coating portion formed of a heat storage material (1) and a composition containing a photocurable component ( 2) A heat storage material seamless capsule having a two-layer structure (first embodiment). Fig. 2 is a schematic view showing a preferred embodiment of the heat storage seamless capsule of the present invention, showing a coating portion formed of a heat storage material (3), an intermediate layer (4), and a composition containing a photocurable component. (5) A heat storage seamless capsule having a three-layer structure (second embodiment). Fig. 3 is a schematic view showing a preferred embodiment of the heat storage seamless capsule of the present invention, showing a plurality of heat storage materials (6) and a coating portion (7) formed of a composition containing a photocurable component. The heat storage seamless capsule of the multi-core structure (the third embodiment). Fig. 4 is a schematic view showing a method of producing a heat-storing seamless capsule of the present invention having a two-layer structure shown in Fig. 1. Fig. 5 is a schematic view showing a method of manufacturing the heat-storing seamless capsule of the present invention having a multi-core structure shown in Fig. 3. 36 201000616 [Description of main component symbols] 1········································································································· Material 9·. Porous material 10... Double nozzle 11... Heat storage material 12... Covered part forming composition 13... Forming tube 14... Light source 15··· Separation device 16... Carrier fluid 17... Drive device 37