201215634 六、發明說明： 【考务明戶斤屬之_技_系奸々貝】 發明領域 本發明係有關於氟樹脂有機溶膠的製造方法、及藉其 所獲得之氟樹脂有機溶膠、以及以之為主成分之塗覆用組 成物。 【先前技術：！ 發明背景 氣樹脂因财溶劑性、低介電性、低表面能性、非黏著 性、耐候性等優異’故可使用在—般泛用轉無法使用的 各種用途。其中乙烯/四氟乙烯共聚物（以下稱etfe)因财熱 性、阻燃性、耐藥品性、耐候性、低磨擦性、低介電特性、 透明性等優異，故可被採用於耐熱電線用被覆材料、化工 廠用耐蝕配管材料、農業用塑膠溫室用材料、模具用脫模 膜等廣泛領域上。 然而，ETFE由於一般不溶於溶劑而無法藉由溶液塗佈 進行塗膜形成，因此，ETFE之成形方法，除了如下述專利 文獻之特殊情況外，皆如押出成形、射出成形、粉體塗裝 等般，侷限於將ETFE熱熔融而成形之方法。 於基材上形成ETFE塗膜之方法方面，已知者有ETFE 粉末之旋轉熔融成形法或靜電粉體塗裴法等。然而，該等 方法需要特殊的裝置。 進而，欲形成密著於基材且無針孔之具備充分物性之 塗膜，必須如前述將ETFE熔融並成形，亦即必須加熱至 201215634 ETFE的熔點以上。因此，在ETFE熔點以下會產生變形的基 材上，難以形成ETFE塗膜。 另一方面，有報告提出試圖獲得ETFE溶液。例如，依 據專利文獻1、專利文獻2、專利文獻3，其中主旨記載了將 己二酸二異丁酯此種高沸點化合物與ETFE在230°C以上之 高溫下攪拌將ETFE溶解之後，進一步一面激烈攪拌並同時 一面進行冷卻，藉以獲得ETFE懸浮液。接下來，將ETFE 過遽而分離，進而分散於煤油與己二酸二異丁酯之混合溶 劑中以獲得ETFE分散液。將該分散液塗佈於銅線，以450 °c此種高溫形成塗膜。然而，該方法中，ETFE懸浮液之調 製上需要繁雜的操作。又，欲獲得具備充分物性之ETFE被 覆電線，必須經高溫處理之步驟。 此外，有報告提出嘗試以低分子量之三氟氣乙烯寡聚 物油作為媒質來獲得ETFE溶液(參考專利文獻4)〇然而，該 油係沸點高且不易乾燥，因此用於ETFE塗膜之形成實非易 事。再者，利用該油所獲得之ETFE分散液，在室溫附近沒 有流動性，並不適用於塗膜之形成。 不過，最近，一如專利文獻5、6所揭示，有報告指出， ETFE對特定媒質可在比咖熔點低％ t以上此種低溫下 溶解的例子。若採用該方法，可在相對較低的溫度下獲得 ETFE溶液’藉由將之冷卻即可獲得£則分散液，然而，一 旦使ETFE濃度提高，就會出現凝膠化、無法獲得均句分散 液等問題。 先行技術文獻 201215634 【專利文獻】 專利文獻1 :美國專利第2,412,960號說明書 專利文獻2:美國專利第2,448,952號說明書 專利文獻3 :美國專利第2,484,483號說明書 專利文獻4:美國專利第4,933,388號說明書 專利文獻5 :國際公開第2010/044421號說明書 專利文獻6:國際公開第2010/044425號說明書 【發明内容3 發明概要 發明欲解決之課題 本發明係有鑑於前述情況而完成者，目的係提供一種 可在較低溫下製造業已使含氟共聚物以高濃度均勻分散於 有機媒質之氟樹脂有機溶膠的方法，該含氟共聚物含有以 乙烯為主體之重複單元與以四氟乙烯為主體之重複單元。 本發明並提供藉由該方法所獲得之氟樹脂有機溶膠、以及 以其為主成分之塗覆用組成物。 用以欲解決課題之手段 本發明提供具有以下構成之氟樹脂有機溶膠的製造方 法及藉由該方法所獲得之氟樹脂有機溶膠、以及使用該氟 樹脂有機溶膠之塗覆用組成物。 [1]一種氟樹脂有機溶膠的製造方法，係以含氟共聚物 作為分散質，且以可在前述含氟共聚物熔點以下之溫度下 溶解該含氟共聚物之溶劑作為分散媒者，該含氟共聚物具 有以乙烯為主體之重複單元與以四氟乙烯為主體之重複單 5 201215634 元，該方法之特徵在於包含有下列步驟： 溶解步驟，係將前述含氟共聚物溶解於前述溶劑而構 成溶液； 析出步驟，係使前述溶劑中前述含氟共聚物以微粒子 析出於前述溶液；及 解碎•分散步驟，係施加高剪切力於以微粒子含有前 述含氟共聚物之前述溶劑與含氟共聚物之混合物，使該含 氟共聚物之微粒子均勻分散於前述溶劑中。 [2] 如[1]記載之氟樹脂有機溶膠的製造方法，其係同時 進行前述析出步驟與解碎•分散步驟。 [3] 如[1]或[2]記載之氟樹脂有機溶膠的製造方法，其係 採用選自於由高速旋轉、高壓喷射、高速振動、超音波處 理及高壓過濾所構成群組之至少1種方法來施加前述高剪 切力。 [4] 如[1]〜[3]中任一項記載之氟樹脂有機溶膠的製造方 法，其係在40°C以上且前述含氟共聚物熔點以下之溫度下 進行前述溶解，並藉由冷卻進行前述析出。 [5] 如[1]〜[4]中任一項記載之氟樹脂有機溶膠的製造方 法，其中前述溶解步驟中的含氟共聚物與溶劑之摻混比 率，以含氟共聚物：溶劑所示之質量比計為1.0: 99.0〜70.0 : 30.0。 [6] 如[1]〜[5]中任一項記載之氟樹脂有機溶膠的製造方 法，其中前述溶劑對前述含氟共聚物的溶解指標(R)為小於 25，且該溶解指標(R)係依據以下述式（1)所示之漢森溶解度 201215634 (Hansen Solubility)參數者： ΙΙ=4χ(δ(1-15.7)2+(δρ-5.7)2+(δ1ι-4·3)2 …⑴ (式（1)中’ δίΐ、δρ及δΐι係分別表示漢森溶解度參數中的 分散項、極性項及氫鍵結項）。 [7] 如[1]~[6]中任一項記載之氟樹脂有機溶膠的製造方 法’其中前述含氟共聚物之微粒子的平均粒徑，在25°C下 以動態光散射法測定之個數平均粒徑在〇_〇〇5〜5μιη之範圍 内。 [8] 如[1]〜[7]中任一項記載之氟樹脂有機溶膠的製造方 法，其係在黏度調整劑之存在下施加前述高剪切力。 [9] 如[1]〜[8]中任一項記載之氟樹脂有機溶膠的製造方 法’其中前述黏度調整劑係具有選自於由可由_化基所取 代且鍵結末端以外的任意一CH2—可由氧原子所取代之碳 原子數1〜20之烧基、胺基、醯胺基、續酿胺基、經基及氫 硫基所構成群組之至少1種官能基的化合物。 [10] 如[1]〜[9]中任一項記載之氟樹脂有機溶膠的製造 方法，其中構成前述含氟共聚物之以四氟乙烯及乙烯以外 之共單體為主體之重複單元所佔比率為〇1〜5〇莫耳0/〇。 [11] 如[1]〜[10]項中任一項記載之氟樹脂有機溶膠的製 造方法，其中前述含氟共聚物是具有選自於由羧酸基、酸 酐基及羧醯鹵化基所構成群組之至少丨種的含氟共聚物。 [12] 種氟樹爿曰有機溶膠，係依據如[1]〜[11]中任一項 記載之製造方法所獲得者。 [13] —種塗覆用組成物，係以氟樹脂有機溶膠為主成 201215634 分’且該氟樹脂有機溶膠係依據如[1]〜[11]中任一項記載之 製造方法所獲得者。 發明效果 依據本發明，可於較低溫製造業已使含氟共聚物以高 濃度且均勻分散於有機媒質之氟樹脂有機溶膠，而該含氟 共聚物係含有以乙稀為主體之重複單元與以四氟乙稀為主 體之重複單元。又’若使用本發明之Mm有機溶膠及以 其為主成分之塗覆賴成物，則可依於較低溫 、 乾燥之簡便方法，形成均質之塗膜。 土 圖式簡單說明 第1圖係實施例1中製備之敦樹脂有機溶膠所含有的 ETFE微粒子之穿透式電子顯微鏡(丁网相片⑽萬倍）。 第2圖係彻實施例1巾製備之氟樹脂有機轉所獲得 的ETFE塗膜表面之光學顯微鏡相片（刪倍）。 【實施冷式】 用以實施發明之形離 、下羊、、’田說明本發明之實施形態。 本說明書中，所神 有機溶劑者 所明有機溶膠係指固體微粒子已分散於 5 j. ，所謂氟樹脂有機溶膠係指含有氟榭 粒子作為前述固體微粒子者。 月曰被 [氟樹脂有機溶膠的製造方法] 本發月係〜種氟樹月旨有機溶膠的製造方法 以具有以乙烯為主舻夕各 /万沄係 體重複單元與以四氟乙稀為主體之重 Η 3 、聚物作為分散質，並且以可在前述含氟共 201215634 聚物之熔點以下溫度將該含氟共聚物溶解的溶劑作為分散 媒者，該方法之特徵在於包含了以下（1)溶解步驟、（2)析出 步驟、及(3)解碎•分散步驟。 (1) 溶解步驟，係將前述含氟共聚物溶解於前述溶劑而 構成溶液； (2) 析出步驟，係使前述溶劑中前述含氟共聚物以微粒 子析出於前述溶液； (3) 解碎•分散步驟，係施加高剪切力於以微粒子含有 前述含氟共聚物之前述溶劑與含氟共聚物之混合物，使該 含氟共聚物之微粒子均勻分散於前述溶劑中。 再者，藉由本發明的製造方法所獲得之所謂氟樹脂有 機溶膠，只要是在常溫(5°C〜40°〇、常壓（O.lMPa)條件下顯 示出有機溶膠之性狀者，而在其他溫度、壓力條件下之性 狀則沒有特別限制。例如，在常溫以上含氟共聚物熔點以 下之某溫度下呈溶液狀態者亦可。又，藉由本發明的製造 方法所獲得之氟樹脂有機溶膠，只要是在屬必須成分之含 氟共聚物微粒子與溶劑係形成有機溶膠的前提下，則亦可 含有該等以外之任意成分。 (1)溶解步驟 本發明的製造方法中之溶解步驟，係將在氟樹脂有機 溶膠中以微粒子形態成為分散質的含氟共聚物，溶解於在 氟樹脂有機溶膠中作為分散媒功能的溶劑中之步驟，其中 前述成為分散質的含氟共聚物係含有以乙烯為主體之重複 單元與以四氟乙烯為主體之重複單元者，且前述作為分散 9 201215634 媒功能的溶劑係可在前述含氟共聚物熔點以下溫度溶解該 含氟共聚物者。 (含氟共聚物） 本發明之氟樹脂有機溶膠的製造方法中所採用的含氟 共聚物，只要是含有以乙烯為主體之重複單元與以四氟乙 烯為主體之重複單元之含氟共《，舰無特別限定。此 種含氟共聚物之例子，具體而言可舉將以乙烯為主體之重 複單元與以四氟乙烯(CF2=CF2: TFE)為主體之重複單元作 為共聚物中主要重複單元的ETFE等。在此，本說明書中， 「ETFE」之用語’係、絲作為以TFE及乙烯作為共聚物中 主要重複單元之含氟共聚物的總稱，其亦可包含將以TFE 及乙烯以外之共聚單體為主體之重複單元來作為共聚物之 構成单元者。 作為本發明中之ETFE者，可適當舉例以TFE為主體之 重複卓元/以乙稀為主體之重複單元的莫耳比為 70/30〜30/70者’較佳為65/35〜40/60者’尤佳為65/35〜45/55 者0 又’本發明之ETFE中，爲了賦予所獲得之共聚物各種 機能，除了 TFE及乙烯，宜含有該等以外之共聚單體 (comonomer)為主體之重複單元。此種共聚單體方面，可舉 CF2 = CFa、CF2 = CH2等氣乙烯類（惟，TFE除外）；CF2 = cfcf3、cf2=chcf3、ch2=chcf3等氟丙烯類；cf3cf2ch =ch2、cf3cf2cf2cf2ch=ch2、cf3cf2cf2cf2cf=ch2、 CF2HCF2CF2CF = CH2等碳數2〜12之具有氟烷基（聚氟烷基) 201215634 乙烯類；Rf(OCF X CFJmOCF = CF2(式中R/表示碳數1〜6的全 氟烷基，X表示氟原子或三氟甲基，m表示0〜5的整數。）等 的全氟乙烯基醚類；CH30C( = 0)CF2CF2CF20CF = CF2或 fso2cf2cf2ocf(cf3)cf2ocf = CF2 等具有可容易變換為 羧酸基或磺酸基之基的全氟乙烯基醚類；丙烯等碳數3個的 C3烯烴、丁烯、異丁烯等碳數4個的C4烯烴、4-曱基-1-戊 烯、環己烯、苯乙烯、α-曱基苯乙烯等的烯烴(惟，乙烯除 外）類；乙酸乙烯酯、乳酸乙烯酯、丁酸乙烯酯、三曱基乙 酸乙烯酯、苯曱酸乙烯酯等的乙烯酯類；乙酸烯丙酯等的 烯丙酯類；曱基乙烯基醚、乙基乙烯基醚、丁基乙烯基醚、 異丁基乙烯基醚、三級丁基乙烯基醚、環己基乙烯基醚、 2- 羥乙基乙烯基醚、4-羥丁基乙烯基醚、聚氧伸乙基乙烯基 醚、2-胺基乙基乙烯基醚、環氧丙基乙烯基醚、2-(乙烯基 氧）四氫-2Η-。比喃等乙烯基醚類；（曱基）丙烯酸甲酯、（甲基) 丙烯酸乙酯、（曱基）丙烯酸酸正丁酯、（曱基）丙烯酸異丁 酯、（曱基）丙烯酸環己酯、（曱基）丙烯酸2-羥乙酯、（曱基) 丙烯酸4-羥丁酯、（曱基）丙烯酸2-胺基乙酯、（曱基）丙烯酸 環氧丙酯、（曱基）丙烯酸2-異氰酸基乙酯、（甲基）丙烯酸 3- (三曱氧基矽基）丙酯、（甲基）丙烯酸3-(三乙氧基矽基）丙 酯等（曱基）丙烯酸酯類；（甲基）丙烯醯胺、Ν-甲基（曱基）丙 烯醯胺、Ν-異丙基丙烯醯胺、Ν,Ν-二曱基（曱基）丙烯醯胺 等（曱基）丙烯醯胺類；丙烯腈等含氰基單體類；異戊二烯、 1,3-丁二烯等二烯類；氣化乙烯、氯化亞乙烯等氯烯烴類； 馬來酐、依康酐、檸康酐、5-降莰烯-2,3-二羧酸酐等含羧 201215634 酸酐之乙烯基化合物等。 該等共聚單體可單獨使用或組合2種以上來使用。 前述ETFE含有以該等TFE及乙稀 :之重複單元時，其含有比率係在難之全單 中，以0.1〜50莫耳％為佳，Q1〜轉耳％較佳，q i〜2〇莫耳 %甚佳⑴〜_耳％愈佳。本發明的製造方法所使用的 ETFE中’以TFE及乙稀以外之共聚單體為主體之重複單元 的含量在該範圍時，則可㈣及僅以咖及㈣構成之 咖E所具備的特性，又可賦予高溶解性、拒水性、拒油性' 交聯性、對基材之接著性等之機能。 再者，基於對基材之接著性的觀點，本發明的製造方 法所採用的ETFE ’可在分子結構内具備對基材有接著性之 官能基。該官能基可存在於ETFE之分子末端或側鏈或主鏈 之任一者。進一步，該官能基係可在ETFE中採用單獨丨種， 或亦可倂用2種以上。對基材有接著性之官能基的種類、含 量，係依據該製造方法所獲得之氟樹脂有機溶膠被應用的 用途，而因應其所尋求的性能適當選擇。例如，作為塗覆 用組成物來使用時，可依據加以塗佈之基材的種類、形狀、 用途、所要求的接著性、接著方法、官能基導入方法等來 適當選擇。 前述對基材有接著性之官能基方面，具體而言，可例 舉選自於由羧酸基、1分子中的2個羧基已脫水縮合之殘義 (以下稱酸酐基）、羥基、磺酸基、環氧基、氰基、碳酸能基、 異氰酸酯基、酯基、醯胺基、酸基、胺基、水解性妙武 12 201215634 碳-碳雙鍵、醚基及叛醯顧化基所構成群組之至少1種。前 述羧酸基係意指羧基與其鹽（一 COOM1 : M1係可與叛酸形 成鹽之金屬原子或原子團），而磺酸基係意指磺基與其鹽（一 SC^M2 : M2係可與磺酸形成鹽之金屬原子或原子團）。 前述官能基中，尤其以選自於由羧酸基、酸酐基、羥 基、環氧基、碳酸酯基、水解性矽基、碳一碳雙鍵、及羧 醯鹵化基所構成群組之至少1種為佳。而甚佳者為選自於由 羧酸基、酸酐基及羧醯_化基所構成群組之至少丨種。此種 官能基，在含氟共聚物1分子中可有不同種類的2種以上存 在，或是在1分子中存在2個以上皆可。 ETFE中，導入有接著性之官能基（以下亦稱「接著性官 能基」）的方法方面’可例舉：（i)ETFE聚合時，使有接著性 官能基之可共聚合單體與其他原料單體一起共聚合的方 法’（ii)利用有接著性官能基之聚合起始劑、鏈轉移劑等， 於聚合時在ETFE分子末端將接著性官能基予以導入的方 法；（Hi)使具有可與接著性官能基接枝之官能基之化合物 (接枝化合物）接枝於ETFE的方法等。該等導入方法可以M 獨進行，或者亦可以適當組合使用。若考量到耐久性時 則以前述⑴及/或(ii)的方法所製造之ETFE為佳。 再者’除前述接著性官能基以外，就因應需要所導入 之具有各種機能的官能基而言，也可以利用與導入前迷接 著性官能基相同的方法導入ETFE。 本發明的製造方法中，作為前述具有以乙烯為主體 重複單元與以TFE為主體之重複單元的含氟共聚物，亦可採 13 201215634 用市售品。此種含氟共聚物：ETFE的市售品方面，具體而 言，可舉旭硝子公司製：Fluon(註冊商標）ETFE Series、 Fluon(註冊商標）LM-ETFE Series、Fluon(註冊商 標）LM-ETFE AH Series、大金工業公司製：(註冊 商標）、Dyneon公司製：Dyneon(註冊商標）ETFE、DuPont 公司製：Tefzel(註冊商標）等。 本發明中的含氟共聚物之熔點方面，以13〇〜275。(：為 佳，140〜265 C較佳，150〜260°C尤佳。若在該範圍内，則 溶解步驟時對溶劑之溶解性優異，強度方面也很卓越。 本發明所採用的含氟共聚物之容量流速（以下稱Q値) 係以0· 1〜2000mm3/秒為佳。Q値係顯示含氟共聚物之溶融流 動性的指標，成為分子量的標準。q値大則表示分子量低， 卜則表示分子量高《本說明書中的所謂Q値，係採用島津製 作所製流況試驗機(Flow tester)，在高於樹脂熔點5〇°c的溫 度下，以荷重7kg下於直徑2.1mm、長度8mm之孔口中擠押 而出時含氟共聚物的擠壓速度。Q値一旦過小則溶解性差， 而一旦過大則含氟共聚物的機械性強度低劣，且在作成塗 犋時谷易發生龜裂等。本發明所採用的含氟共聚物之Q値， 係以5〜500mm3/秒較佳’ 10〜200mm3/秒尤佳。若在該範圍 内，則含氟共聚物的機械性強度優異，並且在作為塗覆用 級成物使用的情況下，塗膜不致發生龜裂等，塗膜特性優 異。 本發明的製造方法中，可單獨使用該等含氟共聚物的丄 種’或者亦可併用2種以上。 14 201215634 (溶劑） 本發明之氟樹脂有機溶膠的製造方法所採用的溶劑， 是可在前述含氟共聚物之魅町的溫度溶解該含氟共聚 物之溶劑’且是可進_步在以下步驟中自該溶液使含敗共 聚物微粒子析出且均勻分散之後，至少在"常壓下，使 該微粒子⑽餘態存在之作為分散賴能的溶劑。 本勒明之冷劑，可在符合上述條件之範圍内舉出各種 溶劑。在此’為了使所使㈣溶料合前述條件，其溶劑 所具有的極性細在某特定範圍為宜。本發明中，係使用 以下的方法，依據漢森溶解度參數（Hansen s〇iubimy parameters),選擇合於上述條件之溶劑來作為具有某特定 範圍極性之溶劑。 漢森(Hansen)溶解度參數係將藉希德布朗（招丨如汾⑽幻 導入之溶解度參數，分割成分散項砧、極性項邱、氫鍵結 項δΐι此3成分，表現於3次元空間者。分散項如係表示由分 散力所獲致之效果，極性項δρ係表示由偶極矩間作用力所 獲致之效果，氫鍵結項δΐι係表示由氫鍵結力所獲致之效果。 此外’漢森溶解度參數的定義與計算，記載於Charles M.Hansen 者、Hansen Solubility Parameters : A Users Handbook(CRC Press，2007年）。又’藉由使用電腦軟體 Hansen Solubility Parameters in Practice(HSPiP)，則即使是 關於文獻值等未知的媒質，也可從其化學結構簡便地推算 出漢森溶解度參數。 本發明中的溶劑，係採用HSPiP版本3，關於有註冊於 15 201215634 資料庫之溶劑，則採用該值，而關於未註冊的溶劑，則採 用推算值，藉此選定所使用的溶劑。 一般而言，特定聚合物的漢森溶解度參數，可藉由使 該聚合物之樣本溶解於漢森溶解度參數已確定之大量不同 溶劑中，進行測定溶解度之溶解度試驗來決定。具體而言， 係在用於前述溶解度試驗之溶劑當中，找出已溶解該聚合 物之溶劑其3次元上之點全部内包在球的内側、而不溶解之 溶劑之點在球的外側此種球(溶解度球），並以該球的中心座 標作為聚合物的漢森溶解度參數。 在此，例如，若是屬於未使用於測定前述聚合物之漢 森溶解度參數的某其他溶劑，而其漢森溶解度參數為 (δ(1，δρ，δ!ι)時，若其座標上顯示的點内包於前述聚合物之溶 解度球内側，則推測此溶劑應可溶解前述聚合物。另一方 面，其座標點若是位在前述聚合物之溶解度球外側，則推 測該溶劑並無法溶解前述聚合物。 本發明中，利用該漢森溶解度參數，對於氟樹脂有機 溶膠所含有的含氟共聚物而言，可在其熔點以下的溫度將 之溶解之溶劑並且在室溫下可將該含氟共聚物分散成微粒 子而屬於最適當之溶劑為二異丙基酮，以該二異丙基酮作 為基準，距離其漢森溶解度參數之座標（15.7,5.7,4.3)起在一 定距離之溶劑群，可作為適當之溶劑加以使用。 亦即，將依據以下述式（1)所示之漢森溶解度參數之値 R，作為對前述含氟共聚物：ETFE之溶解指標。 R=4x(5d-15.7)2+ (δρ-5.7)2+ (5h-4.3)2...(1) 16 201215634 〜（式⑴中，Μ、δρ及δΐι係分別表示漢森溶解度參數中的 分散項、極性項及氫鍵結項’且單位皆為（Mpa)1/2)。 * *本發明中所使用的溶劑，該溶劑利用漢森溶解度參數 座標（Μ，δΡ，^)以上述式（1)求出之溶解指標（R)以小於25為 佳，小於16更佳，小於9尤佳。若一溶劍所具有⑷莫森溶解 又參數’以上述式（1)所示之R落在該範圍内，則此溶劑與 含氣共聚物之親和性高’且溶解性及微粒子分散性亦高。 又’本發明中的溶劑，無論是由1種化合物構成的溶 劑、或是由2種以上的化合物構成之混合溶劑，皆可將依據 ^莫森’谷解度參數藉上述式（1)所求出的R値，作為含敗共聚 物的溶解指標。例如，採用混合溶劑的情況下，可求出由 所採用的溶劑之混合比（體積比）所獲致之平均漢森溶解度 參數’並以之作為漢森溶解度參數求算出上述溶解指標 ⑻。 另’本發明中的溶劑之沸點，以處理性及塗佈後溶劑 除去性之觀點來看，宜在21〇。(：以下，在200。(：以下較佳’ 180 C以下甚佳。還有，若溶劑之沸點過低，則有例如在將 組成物塗覆後進行溶劑蒸發除去（以下亦稱乾燥）時容易產 生氣泡等問題’故宜在啊以上，在饥以上更佳，在8〇 C以上尤佳。 滿足上述此種條件的溶劑，可適當例舉碳數3〜10的銅 類、醋類、碳酸_、_#，碳數5〜9的酮類、賴更佳。 具體例方面，可舉甲基乙基酮、2_戊酮、甲基異丙基綱、 2己酮、曱基異丁基酮、苯品納可林、2_庚酮、4_庚酮、二 17 201215634 異丙基酮、異戊基曱基酮、2-辛酮、2-壬酮、二異丁基酮、 2-曱基環己酮、3-曱基環己酮、4-乙基環己酮、2,6-二曱基 環己酮、3,3,5-三曱基環己酮、異佛酮、（-)-葑酮、甲酸乙 酯、甲酸丙酯、甲酸異丙酯、曱酸丁酯 '甲酸異丁酯、曱 酸二級丁酯、甲酸三級丁酯 '甲酸戊酯、甲酸異戊酯、曱 酸己酯、甲酸環己酯、曱酸庚酯、曱酸辛酯、曱酸2-乙基 己酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸異丙酯、乙 酸丁酯、乙酸異丁酯、乙酸二級丁酯、乙酸三級丁酯、乙 酸戊酯、乙酸異戊酯、乙酸己酯、乙酸環己酯、乙酸庚酯、 乙酸辛酯、乙酸2-乙基己酯、乙酸2,2,2-三氟乙酯、乙酸 2,2,3,3-四氟丙酯、乙酸1,1，1,3,3,3-六氟-2-丙酯、乙酸2,2-雙（三氟甲基）丙酯、乙酸2,2,3,4,4,4-六氟丁酯、乙酸 2,2,3,3,4,4,5,5-八氟戊酯、乙酸3,3,4,4,5,5,6,6,6-九氟己酯、 乙酸4,4,5,5,6,6,7,7,7-九氟庚酯、乙酸7,7,8,8,8-五氟辛酯、 丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸異丙酯、丙酸丁酯、 丙酸異丁酯、丙酸二級丁酯、丙酸三級丁酯、丙酸戊酯、 丙酸異戊酯、丙酸己酯、丙酸環己酯、丙酸庚酯、丁酸甲 酯、丁酸乙酯、丁酸丙酯、丁酸異丙酯、丁酸丁酯、丁酸 異丁酯、丁酸二級丁酯、丁酸三級丁酯、丁酸戊酯、丁酸 異戊酯、丁酸己酯、丁酸環己酯、異丁酸甲酯、異丁酸乙 酯 '異丁酸丙酯、異丁酸異丙酯、異丁酸丁酯、異丁酸異 丁酯、異丁酸二級丁酯、異丁酸三級丁酯、異丁酸戊酯、 異丁酸異戊酯、異丁酸己酯、異丁酸環己酯、戊酸曱酯、 戊酸乙酯、戊酸丙酯、戊酸異丙酯、戊酸丁酯、戊酸異丁 18 201215634 酯、戊酸二級丁酯、戊酸三級丁酯、戊酸戊酯、戊酸異戊 酯、異戊酸甲酯、異戊酸乙酯、異戊酸丙酯、異戊酸異丙 酉曰、異戊酸丁酯、異戊酸異丁酯、異戊酸二級丁酯、異戊 酸二級丁酯、異戊酸戊酯、異戊酸異戊酯、己烷酸甲酯、 己烷酸乙酯、己烷酸丙酯、己烷酸異丙酯、己烷酸丁酯、 己烧酸異丁酯、己烧酸二級丁酯、己烧酸三級丁酯、庚烧 酸曱酯、庚烷酸乙酯、庚烷酸丙酯、庚烷酸異丙酯、辛烷 酸甲酯、辛烷酸乙酯、壬烷酸甲酯、環己烷羧酸曱酯、環 己烷羧酸乙酯、環己烷羧酸丙酯、環己烷羧酸異丙酯、環 已烷羧酸2,2,2-三氟乙酯 '琥珀酸雙(2,2,2-三氟乙酯）、戊二 酸雙（2,2,2-二氟乙酯）、三氟乙酸乙酯、三氟乙酸丙酯、三 氟乙酸異丙酯、三氟乙酸丁酯、三氟乙酸異丁酯、三氟乙 酸二級丁酯、三氟乙酸三級丁酯、三氟乙酸戊酯、三氟乙 酸異戊酯、二氟乙酸已酯、三氟乙酸庚酯、三氟乙酸辛酯、 二氟乙酸2-乙基己酯、二敗乙酸甲酯、二氟^乙酸乙酯、乙 酸2-丙氧基乙酯、乙酸2_丁氧基乙酯、乙酸2_戊氧基乙酯、 乙酸2-己氧基乙酯、ι_乙氧基_2_乙醯氧基丙烧、丨_丙氧基 乙醯氧基丙烷、1-丁氧基-2-乙醯氧基丙烷、卜戊氧基_2_乙 醯氧基丙烷、乙酸3-甲氧基丁酯、乙酸3_乙氧基丁酯、乙酸 3-丙氧基丁酯 '乙酸3-丁氧基丁酯、乙酸3_甲氧基_3_甲基丁 酯、乙酸3-乙氧基_3_曱基丁酯、乙酸3_丙氧基_3_甲基丁酯、 乙酸4-甲氧基丁酯、乙酸4_乙氧基丁酯、乙酸4_丙氧基丁 酯、乙酸4-丁氧基丁酯、五氟苯甲酸曱酯、五氟苯曱酸乙 酯、3-(三氟曱基）苯曱酸曱酯、3,5_雙（三氟甲基）苯甲酸曱 19 201215634 酯、苯曱酸2,2,2-三氟乙酯、苯甲酸2,2,3,3-四氟丙酯、苯甲 酸2,2,3,3,3-五氟丙酯、苯曱酸1，1，1，3,3,3-六氟-2-丙酯、苯 甲酸2,2-雙（三氟曱基）丙酯、苯甲酸2,2,3,3,4,4,4-七氟丁 酯、苯曱酸2,2,3,4,4,4-六氟丁酯、苯曱酸2,2,3,3,4,4,5,5,5-九氟戊酯、碳酸乙基曱酯、碳酸二乙酯、碳酸二丙酯、碳 酸二丁酯 '雙（2,2,2-三氟乙基)碳酸酯、雙(2,2,3,3-四氟丙基） 碳酸酯、四氫呋喃、五氟苯甲醚、3,5-雙（三氟甲基）苯甲醚 等。又，該等溶劑皆屬於由上述式（1)求出之R小於25的溶 劑。 該等當中，較適宜作為本發明所使用之溶劑的化合 物，具體而言可例示以下化合物。 曱基乙基酮、2-戊酮、甲基異丙基酮、2-己酮、曱基異 丁基酮、苯品納可林、2-庚酮、4-庚酮、二異丙基酮、異戊 基甲基酮、2-辛酮、2-壬酮、二異丁基酮、4-乙基環己酮、 3,3,5-三甲基環己酮、異佛酮、曱酸異丙酯、曱酸異丁酯、 曱酸二級丁酯、甲酸三級丁酯、曱酸戊酯、曱酸異戊酯、 曱酸己酯、曱酸庚酯、曱酸辛酯、曱酸2-乙基己酯、乙酸 曱酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙 酸戊酯、乙酸異戊酯、乙酸己酯、乙酸環己酯、乙酸庚酯、 乙酸辛酯、乙酸2-乙基己酯、乙酸2,2,2-三氟乙酯、乙酸 2,2,3,3-四氟丙酯、乙酸1，1，1，3,3,3-六氟-2-丙酯、乙酸2,2_ 雙（三氟曱基）丙酯、乙酸2,2,3,4,4,4-六氟丁酯、丙酸甲酯、 丙酸乙酯、丙酸丙酯、丙酸異丙酯、丙酸丁酯、丙酸異丁 酯、丙酸二級丁酯、丙酸三級丁酯、丙酸戊酯、丙酸異戊 20 201215634 酯、丙酸己酯、丙酸環己酯、丙酸庚酯、丁酸曱酯、丁酸 乙酯、丁酸丙酯、丁酸異丙酯、丁酸丁酯、丁酸異丁酯、 丁酸二級丁酯、丁酸三級丁酯、丁酸戊酯、丁酸異戊酯、 丁酸己醋、丁酸環己酯、異丁酸甲酯、異丁酸乙酯、異丁 酸丙醋、異丁酸異丙酯、異丁酸丁酯、異丁酸異丁酯、異 丁酸二級丁酯、異丁酸三級丁酯、異丁酸戊酯、異丁酸異 戊醋、異丁酸己酯、異丁酸環己酯、戊酸甲酯、戊酸乙酯、 戊酸丙醋、戊酸異丙酯、戊酸丁酯、戊酸異丁酯、戊酸二 級丁酯、戊酸三級丁酯、戊酸戊酯、戊酸異戊酯、異戊酸 曱醋、異戊酸乙酯、異戊酸丙酯、異戊酸異丙酯、異戊酸 丁商曰、異戊酸異丁酯、異戊酸二級丁酯、異戊酸三級丁醋' 異戊酸戊酯、異戊酸異戊酯、己烷酸甲酯、己烷酸乙酯、 己烧酸丙酯、己烧酸異丙酯、己烧酸丁酯、己烧酸異丁酯、 己烷酸二級丁酯、己烷酸三級丁酯、庚烷酸甲酯、庚烷酸 乙酯、庚烷酸丙酯、庚烷酸異丙酯、辛烷酸甲酯、辛烷酸 乙酯、壬烷酸甲酯、環己烷羧酸曱酯、環己烷羧酸乙酯、 環己烷羧酸丙酯、環己烷羧酸異丙酯、環已烷羧酸2,2,2_三 氟乙i曰、琥珀酸雙(2,2,2-三氟乙酯）、戊二酸雙(2,2,2_三氟 乙酯）、三氟乙酸乙酯、三氟乙酸丙酯、三氟乙酸異丙酯、 三氟乙酸丁酯、三氟乙酸異丁酯、三氟乙酸二級丁酯、三 氟乙酸二級丁酯、三氟乙酸戊酯、三氟乙酸異戊酯、三氟 乙酸已醋、三氟乙酸庚醋、三氣乙酸辛§旨、三說乙酸2_乙 基己酯、二敗乙酸甲酯、二氟乙酸乙酯、乙酸2_丙氧基乙 醋、乙酸2-丁氧基乙醋、乙酸2_戊氧基乙醋、卜乙氧基_2_ 21 201215634 乙酿乳基丙烧、1-丙氧基-2-乙酿氧基丙院、1-丁氧基-2-乙 醯氧基丙烷、乙酸3-乙氧基丁酯、乙酸3-丙氧基丁酯、乙酸 3-曱氧基-3-甲基丁酯、乙酸3-乙氧基-3-曱基丁酯、乙酸4-甲氧基丁醋、乙酸4-乙氧基丁醋、乙酸4-丙氧基丁醋、苯甲 酸2,2,3,3-四氟丙酯、苯甲酸2,2,3,3,3-五氟丙酯、苯甲酸 1，1，1，3,3,3-六氟4-2-丙酯、苯曱酸2,2-雙（三氟曱基）丙酯、苯 甲酸2,2,3,3,4,4,4-七氟丁酯、苯曱酸2,2,3,4,4,4-六氟丁酯、 笨曱酸2,2,3,3,4,4,5,5,5-九氟戊酯'碳酸乙基甲酯、碳酸二 乙酯、碳酸二丙酯、碳酸二丁酯、雙(2,2,2_三氟乙基)碳酸 酯、五氟苯曱醚、3,5-雙（三氟曱基）苯甲醚。又，該等溶劑 皆屬於由上述式（1)求出之R小於16的溶劑。 月1J述溶劑只要是在滿足前述本發明條件之範圍，可單 獨使用或混合2種以上來使用。又，只要滿足前述條件，亦 可在前述溶劑中混合前述以外之溶劑來使用。 本發明的製造方法令’藉由與前述可單獨使用的溶劑 組合使用而可採用的溶劑，只要是以混合溶劑之狀態滿足 前述條件之溶劑，則並無特舰定。若㈣此種組合的具 體例，有前述苯品納可林(漢森溶解度參數U5 2、5 7、5 3、 R : 2.0)與苯甲腈(漢森溶解度參數：18 8、12 〇、3 3、r : 79取體飢90 : _混合溶#丨（漢森轉度參數：15 6、 6·3 5’卜R· U)、甲酸二級丁 g旨（漢森溶解度參數： 5.4、7.4、R : 12·9)與苯乙酮(漢森溶解度參數：i8 8、9 〇、 4.0、R. 49.4)之體積比71 .29的混合溶劑（漢森溶解度參數： '6m3)、乙酸異了㈣漢森溶解度參數： 22 201215634 15.1、3_7、6.3、11:9.4)與苯曱酸甲酯（漢森溶解度參數： 18.9、8.2、4.7、R : 47.4)之體積比74 : 26的混合溶劑（漢森 溶解度參數：16.1、4.9、5.9、R : 3.8)、甲酸三級丁酯（漢 森溶解度參數：14.8、5.4、7.4、R : 12.9)與1，3-雙（三氟曱 基）苯（漢森溶解度參數：17.0、6.8、0.0、R : 26.5)之體積 比59 : 41的混合溶劑（漢森溶解度參數：15.7、6.0、4.4、R : 0.1)等組合。 此種混合溶劑中，依據構成混合溶劑之各溶劑的漢森 溶解度參數及其體積比所算出的溶解指標(R)，以小於25為 佳，小於16較佳，小於9甚佳。還有，前述組合為例示，本 發明之氟樹脂有機溶膠的製造方法可使用的混合溶劑並不 限定於該等組合。 又，於本發明之氟樹脂有機溶膠的製造方法中，於溶 解步驟使前述含氟共聚物溶解於前述溶劑而獲得含氟共聚 物溶液。用於含氟共聚物溶液之調製的含氟共聚物與溶劑 之摻混比率，係以含氟共聚物：溶劑所表示之質量比計， 以 1.0 : 99_0〜70.0 : 30.0為佳，2.0 : 98_0〜60.0 : 40.0較佳。 又，於溶解步驟中含氟共聚物與溶劑之摻混比率，係 與所獲得之氟樹脂有機溶膠中含氟共聚物微粒子與分散媒 之含有比一致。將氟樹脂有機溶膠作為例如塗覆用組成物 使用的情況下，可因應作為目的之成形物的膜厚而適當變 更前述摻混比率。氟樹脂有機溶膠中含氟共聚物與溶劑之 摻混比率在該範圍内時，在例如作為塗覆用組成物使用的 情況下，黏度、乾燥速度、膜均一性等處理性優異，可形 23 201215634 成由=氟共聚物構成之均質塗膜。 要“f的溫度、屋力、授拌等條件方面，只 二：含氟共聚物可溶解於前述溶劑之條件則並無特別 溶解步驟巾的溫祕件方面，宜為在所使用的含 w下的溫度。本發”的含氟共聚物、亦 P月二已明之ETFE之雜，最高者大致為275°c ，由此， ^ ^解於前述溶劑之步驟的溫度，以大致為2 751以下的 佳將則述含氟共聚物溶解於前述溶劑之溫度方 、 C以下較佳’ 2〇〇 ◦以下尤佳。又，該溶解步驟 的二度下限方面，⑽。c為佳，赃較佳若考量到操作 則以80 c更佳。若前述溶解步驟溫度低於4〇t，可 此不易獲得充分的溶解狀態’若超過275t的溫度，在進行 實際作業上會不易執行。 本發明之氟樹脂有機溶膠的製造方法所具備的前述溶 解步驟中，溫度以外的條件並無特別限定，通常宜在常壓 •5MPa左右的微加壓條件下進行溶解。溶解時的壓力，若 依含氣共聚物或溶劑的種類而使得溶劑沸點比溶解步驟溫 度低等情況時，於耐壓容器中，至少在自然產生壓力以下， 且為3MPa以下、較宜為2MPa以下、更宜為iMPa以下、尤 且為吊壓以下。—般而言，可在〇.〇1〜IMPa左右之壓力下溶 解。 溶解時間視本發明製造方法所獲得之氟樹脂有機溶膠 中月』述3氟共聚物之含量或該含氟共聚物之形狀等而異。 所使用的含氟共聚物之形狀，若以縮短溶解時間之作業效 24 201215634 率此點，以粉末狀為佳，又，以取得容易等而言則為珠粒 狀等，亦可採用其他形狀之物。 前述溶解步驟中的溶解方式並無特別限制，可採用一 般方法。秤量氟樹脂有機溶膠必要構成成分之含氟共聚物 與溶劑之預定量、與摻混之任意成分的添加量，加以均勻 混合使之溶解即可，該任意成分係依據藉以獲得之氟樹脂 有機溶膠欲利用之用途，而因應所尋求的性能加以適當選 擇並摻混者。作為塗覆用組成物來使用的情況下，可添加 以下記載之各種成分作為任意成分 又，在製造本發明之氟樹脂有機溶膠的過程中，所添 加的任意成分，可舉例如具有黏度調節機能之增黏劑、減 黏劑等、具有防劣化機能之紫外線吸收劑、光穩定劑等。 再者，本發明的製造方法中獲得之氟樹脂有機溶膠所含有 的該等任意成分之合計掺混量，係相對於氟樹脂有機溶膠 全量計在30質量％以下為佳，10質量％以下更佳。換言之， 氟樹脂有機溶膠所含有的前述含氟共聚物與溶劑之合計 量，係相對於氟樹脂有機溶膠全量計在70質量％以上為 佳，90質量％以上更佳。 進一步，關於使用氟樹脂有機溶膠上發揮機能之任意 成分，可在以下的（3)解碎•分散步驟之後，添加於所獲得 之氟樹脂有機溶膠。 含氟共聚物、溶劑及任意成分之混合溫度宜在40°C以 上且在所使用的含氟共聚物之熔點以下的溫度。具體而 言，60〜230°C更佳，80〜200°C甚佳。溶解步驟中各種原料 25 201215634 成分之混合與加熱可同時進行，亦可在混合各種原料成分 之後，因應需要一邊攪拌並一邊加熱。 在加壓下進m解之情况’可使用賴拌機之熱壓爸 等裝置。_翼的形狀方面，可使用船㈣、明輪葉、固 定柴、渦輪壤等。若是以小規模進行時，也可使用磁性撥 拌器等。 (2)析出步驟 使前述⑴溶解步驟所獲得之溶液亦即前述含說共聚物 已溶解於前祕劑後之錢，在該含氟共聚物以微粒子態 析出至前述溶财之條件下，含氣共聚物之微粒子可析出 前述溶劑中，而獲得含氣共聚物微粒子業已分散於溶劑中 之組成物。該析出條件係以常溫常壓為佳。 析出步驟中之具體性操作例，可舉將前述⑴溶解步驟 所獲得之溶液冷卻至f溫，藉此使前述含㈣聚物微粒子 析出至前祕射。㈣，冷卻方法並無_蚊，可採 用徐冷卻，亦可採用驟冷。 成物係意指以微粒子態含有含I共聚物 之溶劑與含氟絲混合物。 於析出步驟所捭p a 足于之組成物中的含氟共聚物微粒子的 分散狀態’不僅限於^ 於该微粒子於溶劑中均勻分散之情況， 此外還會有含有微* 子之溶劑的一部分或全體凝膠化之形 況、或該微粒子於、^ 者此種分m ”劑中偏在而呈不均句分散之情況1 有此禋刀月欠狀態，你 ^ 、3氟共聚物對溶劑之摻混比率愈高京 愈顯著地呈現。遇从 匕種不均勻組成物之情況，爲了使之¥ 26 201215634 為含氟共聚物微粒子已均勻分散於溶劑中之處理性優異之 氟樹脂有機溶膠，乃進行以下的解碎•分散步驟。 (3)解碎•分散步驟 解碎•分散步雜對前述⑺析丨步賴獲得之組成物 亦即與微粒子態之前述含氟共聚物之組成物，施加高剪切 力以使該純絲物微好更均自齡散赠劑之步驟。 於前述混合物施加高剪切力之方法，具體上可舉高速 旋轉 '高壓喷射、高速振動、超音波處理、高壓過渡等方 法。其中，以簡便之方法而言，係 保从藉由咼速旋轉、高壓 喷射、或高速振動（以下將該等總稱 饵馮攪拌」）所行之方法 為佳。又，該等施加高剪切力之方 + 耷了早獨進行，亦可倂 用2種以上之方法，例如倂用授拌與超音波處理。 藉由檀拌對前述混合物施加高前 通常用以一面施加高剪切力同時之裝置’可採用 置，並無制限制。此雜拌^ ^液狀物之授拌裝 .,. 石面，於前述解碎•分 散步驟中，可使用具有渦輪槳或有 刀 »3 . . κ /尚輪槳等在通常的搜 摔翼中亦屬於剪切力大之攪拌翼的 兔伴裳置。又，以伟闲 I得更高剪切力之下述獅裝置或分散裝置為佳：用 :剪切力之養裝4，對前述_與含氟共㈣之混合物 施加高剪切力時的旋轉數、壓力 ^ ^ ^ 處理時間、處理溫度等 條件，可依據混合物之狀態或所俅 ^ 尤用的裝置來適當選擇。 以下⑷〜(c)及(e)係藉高速旋轉所扞 丁之攪拌裝置，（d)#蕤古 壓噴射所行之分散裝置。 错呵 ⑷以TK均質混合機201215634 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a fluororesin organosol, and a fluororesin organosol obtained therefrom, and The coating composition of the main component. [Prior technology:! Background of the Invention Gas resins are excellent in terms of solvent solubility, low dielectric property, low surface energy, non-adhesiveness, weather resistance, etc., and can be used in various applications that cannot be used in general use. Among them, ethylene/tetrafluoroethylene copolymer (hereinafter referred to as etfe) can be used for heat-resistant wires because of its excellent heat, flame retardancy, chemical resistance, weather resistance, low friction, low dielectric properties, and transparency. Coating materials, corrosion-resistant piping materials for chemical plants, materials for agricultural plastic greenhouses, mold release films for molds, etc. However, since ETFE is generally insoluble in a solvent and cannot be formed by coating with a coating film, the forming method of ETFE is, for example, extrusion molding, injection molding, powder coating, etc., except for the special case of the following patent documents. Generally, it is limited to a method of forming ETFE by heat fusion. As a method of forming an ETFE coating film on a substrate, there are known a rotary melt molding method or an electrostatic powder coating method of ETFE powder. However, such methods require special equipment. Further, in order to form a coating film having sufficient physical properties adhered to the substrate and having no pinholes, it is necessary to melt and shape the ETFE as described above, i.e., it is necessary to heat up to the melting point of 201215634 ETFE. Therefore, it is difficult to form an ETFE coating film on a substrate which is deformed below the melting point of ETFE. On the other hand, there have been reports of attempts to obtain ETFE solutions. For example, according to Patent Document 1, Patent Document 2, and Patent Document 3, the main point is that after the high boiling point compound such as diisobutyl adipate and ETFE are stirred at a high temperature of 230 ° C or higher, ETFE is dissolved, and further, Stir vigorously and simultaneously while cooling to obtain an ETFE suspension. Next, ETFE was separated by excessive enthalpy, and further dispersed in a mixed solvent of kerosene and diisobutyl adipate to obtain an ETFE dispersion. The dispersion was applied to a copper wire to form a coating film at a high temperature of 450 °C. However, in this method, the handling of the ETFE suspension requires complicated operations. In addition, in order to obtain an ETFE coated electric wire having sufficient physical properties, it is necessary to perform a high temperature treatment step. Further, it has been reported that an attempt is made to obtain an ETFE solution using a low molecular weight trifluoroethylene ethylene oligomer oil as a medium (refer to Patent Document 4). However, the oil has a high boiling point and is not easily dried, and thus is used for formation of an ETFE coating film. It is not easy. Further, the ETFE dispersion obtained by using the oil has no fluidity at room temperature and is not suitable for the formation of a coating film. However, recently, as disclosed in Patent Documents 5 and 6, there have been reports of an example in which ETFE can be dissolved at a low temperature lower than the melting point of coffee by a specific medium. If this method is used, the ETFE solution can be obtained at a relatively low temperature, and the dispersion can be obtained by cooling it. However, once the concentration of ETFE is increased, gelation occurs and the uniform dispersion cannot be obtained. Liquid and other issues. [Patent Document 1] Patent Document 1: U.S. Patent No. 2,412,960, Patent Document 2: U.S. Patent No. 2,448,952, Patent Document 3: U.S. Patent No. 2,484,483, Patent Document 4: U.S. Patent No. 4,933,388 5: International Publication No. 2010/044421, Patent Document 6: International Publication No. 2010/044425 [Invention Summary] SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the foregoing circumstances, and an object is to provide an A method of uniformly dispersing a fluorinated copolymer in a high concentration in a fluororesin organosol of an organic medium having a repeating unit mainly composed of ethylene and a repeating unit mainly composed of tetrafluoroethylene. The present invention also provides a fluororesin organosol obtained by the method, and a coating composition containing the same as a main component. Means for Solving the Problem The present invention provides a method for producing a fluororesin organosol having the following constitution, a fluororesin organosol obtained by the method, and a coating composition using the fluororesin organosol. [1] A method for producing a fluororesin organosol, wherein a fluorinated copolymer is used as a dispersoid, and a solvent capable of dissolving the fluorinated copolymer at a temperature lower than a melting point of the fluorinated copolymer is used as a dispersion medium. The fluorinated copolymer has a repeating unit mainly composed of ethylene and a repeating unit 5 201215634 which is mainly composed of tetrafluoroethylene, and the method is characterized by comprising the following steps: a dissolving step of dissolving the fluorocopolymer in the solvent And constituting the solution; the precipitating step of dissolving the fluorocopolymer in the solvent as a fine particle in the solution; and dissolving and dispersing the step of applying a high shear force to the solvent containing the fluorocopolymer The mixture of the fluorinated copolymers allows the fine particles of the fluorinated copolymer to be uniformly dispersed in the solvent. [2] The method for producing a fluororesin organosol according to [1], wherein the precipitation step and the disintegration/dispersion step are simultaneously performed. [3] The method for producing a fluororesin organosol according to [1] or [2], which is at least 1 selected from the group consisting of high-speed rotation, high-pressure injection, high-speed vibration, ultrasonic treatment, and high-pressure filtration. A method to apply the aforementioned high shear force. [4] The method for producing a fluororesin organosol according to any one of [1] to [3] wherein the dissolution is carried out at a temperature of 40 ° C or higher and a melting point of the fluorinated copolymer or less, and The above precipitation was carried out by cooling. [5] The method for producing a fluororesin organosol according to any one of [1] to [4] wherein the blend ratio of the fluorinated copolymer and the solvent in the dissolving step is a fluorinated copolymer: solvent The mass ratio shown is 1. 0: 99. 0~70. 0 : 30. 0. [6] The method for producing a fluororesin organosol according to any one of the above aspects, wherein the solvent has a solubility index (R) of the fluorinated copolymer of less than 25, and the dissolution index (R) Based on the Hansen Solubility 201215634 (Hansen Solubility) parameter shown by the following formula (1): ΙΙ=4χ(δ(1-15. 7) 2+(δρ-5. 7) 2+(δ1ι-4·3)2 (1) (In the formula (1), δίΐ, δρ, and δΐι are the dispersion term, the polar term, and the hydrogen bonding term in the Hansen solubility parameter, respectively. [7] The method for producing a fluororesin organosol according to any one of [1] to [6] wherein the average particle diameter of the fine particles of the fluorinated copolymer is measured by dynamic light scattering at 25 ° C. The number average particle diameter is in the range of 〇_〇〇5 to 5 μmη. [8] The method for producing a fluororesin organosol according to any one of [1] to [7], wherein the high shear force is applied in the presence of a viscosity modifier. [9] The method for producing a fluororesin organosol according to any one of [1] to [8] wherein the viscosity adjusting agent has any one selected from the group consisting of a substituent which may be substituted by a sulfonating group and a bonding terminal. CH2—a compound having at least one functional group consisting of a group of a carbon atom having 1 to 20 carbon atoms, an amine group, a decylamino group, a continuating amine group, a trans group and a hydrogenthio group, which may be substituted by an oxygen atom. The method for producing a fluororesin organosol according to any one of the above aspects, wherein the fluoropolymer is a repeating unit mainly composed of a eucommonomer other than tetrafluoroethylene and ethylene. The ratio is 〇1~5〇莫耳0/〇. The method for producing a fluororesin organosol according to any one of the above aspects, wherein the fluorocopolymer has a halogenated group selected from the group consisting of a carboxylic acid group, an acid anhydride group, and a carboxylic acid halide group. At least one of the fluorochemical copolymers constituting the group. [12] The fluorophyllin organosol is obtained by the production method according to any one of [1] to [11]. [13] A coating composition comprising a fluororesin organosol as a main ingredient 201215634 minutes and the fluororesin organosol is obtained according to the production method according to any one of [1] to [11] . Advantageous Effects of Invention According to the present invention, a fluororesin copolymer having a high concentration and uniform dispersion of a fluorocopolymer in an organic medium can be used in a lower temperature manufacturing process, and the fluorocopolymer contains a repeating unit mainly composed of ethylene. Tetrafluoroethylene is the main repeating unit. Further, when the Mm organosol of the present invention and the coating composition containing the main component thereof are used, a homogeneous coating film can be formed in accordance with a simple method of lower temperature and drying. Brief Description of the Drawings Fig. 1 is a transmission electron microscope (400 mesh 10,000 times) of ETFE microparticles contained in the dendritic organosol prepared in Example 1. Fig. 2 is an optical micrograph (deletion) of the surface of an ETFE coating film obtained by organic transfer of a fluororesin prepared in the towel of Example 1. [Implementation of the cold type] The embodiment of the present invention will be described for the purpose of implementing the invention, the lower part, and the lower field. In this specification, the organic solvent of the organic solvent means that the solid particles have been dispersed in 5 j. The fluororesin organosol refers to a fluoroquinone particle as the solid fine particle.曰 曰 [ 制造 制造 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟The weight of the main body 3, the polymer as a dispersoid, and a solvent capable of dissolving the fluorinated copolymer at a temperature lower than the melting point of the fluorine-containing 201215634 polymer as a dispersion medium, the method is characterized by comprising the following ( 1) a dissolution step, (2) a precipitation step, and (3) a disintegration/dispersion step. (1) a dissolving step of dissolving the fluorinated copolymer in the solvent to form a solution; (2) a precipitating step of precipitating the fluorinated copolymer in the solvent as a fine particle; (3) pulverizing In the dispersing step, a high shear force is applied to the mixture of the solvent and the fluorinated copolymer containing the fluorinated copolymer in the fine particles, and the fine particles of the fluorinated copolymer are uniformly dispersed in the solvent. Further, the so-called fluororesin obtained by the production method of the present invention has an organic sol as long as it is at a normal temperature (5 ° C to 40 ° 〇, atmospheric pressure (O. The properties of the organosol are shown under the conditions of lMPa), and the properties under other conditions of temperature and pressure are not particularly limited. For example, it may be in a solution state at a temperature below the melting point of the fluorinated copolymer at a normal temperature or higher. In addition, the fluororesin organosol obtained by the production method of the present invention may contain any component other than the fluorochemical copolymer fine particles and the solvent-based organosol. (1) Dissolution step The dissolution step in the production method of the present invention is a fluorine-containing copolymer which is dispersed in the form of fine particles in a fluororesin organosol, and is dissolved in a solvent which functions as a dispersion medium in a fluororesin organosol. In the step of the above-mentioned fluorine-containing copolymer which is a dispersoid, the repeating unit mainly composed of ethylene and the repeating unit mainly composed of tetrafluoroethylene are used, and the solvent which is a function of dispersing 9 201215634 can be used in the above-mentioned fluorine-containing copolymer. The copolymer is dissolved at a temperature below the melting point of the copolymer. (Fluorinated Copolymer) The fluorine-containing copolymer used in the method for producing a fluororesin organosol of the present invention is a fluorine-containing copolymer containing a repeating unit mainly composed of ethylene and a repeating unit mainly composed of tetrafluoroethylene. The ship is not limited. Specific examples of such a fluorinated copolymer include ETFE having a repeating unit mainly composed of ethylene and a repeating unit mainly composed of tetrafluoroethylene (CF2 = CF2: TFE) as a main repeating unit in the copolymer. Here, in the present specification, the term "ETFE" is a generic term for a fluorinated copolymer containing TFE and ethylene as the main repeating unit in the copolymer, and may also include a comonomer other than TFE and ethylene. The repeating unit of the main body serves as a constituent unit of the copolymer. As the ETFE in the present invention, the repeating unit of TFE as the main body/the molar ratio of the repeating unit mainly composed of ethylene is 70/30 to 30/70, preferably 65/35 to 40. /60's particularly preferred is 65/35 to 45/55. In the ETFE of the present invention, in order to impart various functions of the obtained copolymer, in addition to TFE and ethylene, it is preferred to contain a comonomer other than the above (comonomer). ) is the repeating unit of the subject. For such comonomers, there are gas ethylene such as CF2 = CFa, CF2 = CH2 (except TFE); CF2 = cfcf3, cf2 = chcf3, ch2 = chcf3, etc.; cf3cf2ch = ch2, cf3cf2cf2cf2ch = ch2 , cf3cf2cf2cf2cf=ch2, CF2HCF2CF2CF = CH2 and other carbon number 2~12 with fluoroalkyl (polyfluoroalkyl) 201215634 ethylene; Rf (OCF X CFJmOCF = CF2 (where R / represents carbon number 1~6 perfluoro) Alkyl, X represents a fluorine atom or a trifluoromethyl group, m represents an integer of 0 to 5.), etc., perfluorovinyl ethers; CH30C(=0)CF2CF2CF20CF = CF2 or fso2cf2cf2ocf(cf3)cf2ocf = CF2, etc. Perfluorovinyl ethers which are easily converted into a carboxylic acid group or a sulfonic acid group; C3 olefins such as propylene, C4 olefins having 4 carbon atoms such as butene and isobutylene, and 4-mercapto-1- Olefins (except ethylene) such as pentene, cyclohexene, styrene, α-mercaptostyrene; vinyl acetate, vinyl lactate, vinyl butyrate, tridecyl vinyl acetate, benzoic acid Vinyl esters such as vinyl ester; allyl esters such as allyl acetate; mercapto vinyl ether, ethyl vinyl ether, butyl vinyl , isobutyl vinyl ether, tertiary butyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, polyoxyethylene ethyl vinyl ether, 2 -Aminoethyl vinyl ether, propylene propyl vinyl ether, 2-(vinyloxy)tetrahydro-2-indole-. Vinyl ethers such as pyran; methyl (meth) acrylate, (methyl) Ethyl acrylate, n-butyl (mercapto) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (fluorenyl) acrylate 4- Hydroxybutyl ester, 2-aminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 3-(trimethylene) (oxyalkyl) propyl ester, (meth) acrylate (meth) acrylate (meth) acrylate; (meth) acrylamide, Ν-methyl (fluorenyl) Propylene amide, hydrazine-isopropyl acrylamide, hydrazine, hydrazine-dimercapto (fluorenyl) acrylamide, etc. (fluorenyl) acrylamide; cyano-containing monomer such as acrylonitrile; Alkene, 1,3-butadiene Diene; gasified ethylene, vinyl chloride and other chlorine olefins; maleic anhydride, isaconic anhydride, citraconic anhydride, 5-northene-2,3-dicarboxylic anhydride and other vinyl containing 201215634 anhydride These comonomers may be used singly or in combination of two or more. When the ETFE contains a repeating unit of the above TFE and ethylene: the content ratio is in a difficult single sheet, and is 0. 1 to 50 mol% is better, Q1~ear ear% is better, q i~2〇mole % is very good (1) ~_ ear% is better. In the ETFE used in the production method of the present invention, when the content of the repeating unit mainly composed of a comonomer other than TFE and ethylene is in this range, the characteristics of the coffee E which can be composed of (4) and only coffee and (4) can be used. Further, it can impart high solubility, water repellency, oil repellency, crosslinkability, and adhesion to a substrate. Further, from the viewpoint of the adhesion to the substrate, ETFE' employed in the production method of the present invention may have a functional group having an adhesive property to the substrate in the molecular structure. The functional group may be present at the molecular end or either the side chain or the main chain of the ETFE. Further, the functional group may be used alone or in combination of two or more kinds in ETFE. The type and content of the functional group having an adhesive property to the substrate are used in accordance with the application of the fluororesin organosol obtained by the production method, and are appropriately selected in accordance with the properties sought. For example, when it is used as a coating composition, it can be appropriately selected depending on the type, shape, use, desired adhesion, subsequent method, functional group introduction method, and the like of the substrate to be coated. In the above-mentioned functional group having an adhesive property to the substrate, specifically, a residue (hereinafter referred to as an acid anhydride group) selected from a carboxylic acid group and two carboxyl groups in one molecule (hereinafter referred to as an acid anhydride group), a hydroxyl group, and a sulfonate may be mentioned. Acid group, epoxy group, cyano group, carbonic acid group, isocyanate group, ester group, decylamino group, acid group, amine group, hydrolyzable Mt. 12 201215634 Carbon-carbon double bond, ether group and rebel base At least one of the groups formed. The aforementioned carboxylic acid group means a carboxyl group and a salt thereof (a COOM1: M1 system may form a salt or a metal atom or a group of atoms), and a sulfonic acid group means a sulfo group and a salt thereof (a SC^M2: M2 system may be used) The sulfonic acid forms a metal atom or atomic group of the salt). Among the above functional groups, in particular, at least selected from the group consisting of a carboxylic acid group, an acid anhydride group, a hydroxyl group, an epoxy group, a carbonate group, a hydrolyzable thiol group, a carbon-carbon double bond, and a carboxy hydrazine group. One is better. More preferably, it is at least one selected from the group consisting of a carboxylic acid group, an acid anhydride group, and a carboxylic acid group. The functional group may have two or more different types of the fluorocopolymer, or two or more of them may be present in one molecule. In the ETFE, a method of introducing an adhesive functional group (hereinafter also referred to as "adjacent functional group") can be exemplified by (i) copolymerizable monomer having an adhesive functional group and other components during ETFE polymerization. a method of copolymerizing a raw material monomer together (ii) a method of introducing an adhesive functional group at the end of an ETFE molecule by a polymerization initiator having a bonding functional group, a chain transfer agent, or the like; (Hi) A method of grafting a compound (graft compound) having a functional group graftable with a functional group to ETFE. These import methods may be performed separately or in combination as appropriate. When durability is considered, the ETFE produced by the method (1) and/or (ii) above is preferred. Further, in addition to the above-mentioned adhesive functional group, the functional group having various functions to be introduced may be introduced into the ETFE by the same method as the introduction of the functional group before the introduction. In the production method of the present invention, a fluorinated copolymer having a repeating unit mainly composed of ethylene and a repeating unit mainly composed of TFE may be used as a commercially available product in 201215634. In the case of the fluorinated copolymer: ETFE, the product is specifically manufactured by Asahi Glass Co., Ltd.: Fluon (registered trademark) ETFE Series, Fluon (registered trademark) LM-ETFE Series, Fluon (registered trademark) LM-ETFE AH Series, Daikin Industries Co., Ltd.: (registered trademark), manufactured by Dyneon Co., Ltd.: Dyneon (registered trademark) ETFE, manufactured by DuPont Co., Ltd.: Tefzel (registered trademark). The melting point of the fluorinated copolymer in the present invention is from 13 Torr to 275. (: preferably, 140 to 265 C is preferable, and 150 to 260 ° C is particularly preferable. If it is within this range, the solubility in the solvent is excellent in the dissolution step, and the strength is also excellent. The volume flow rate of the copolymer (hereinafter referred to as Q値) is preferably from 0.1 to 2000 mm 3 /sec. The Q値 system indicates an index of the melt fluidity of the fluorinated copolymer, and is a standard of molecular weight. , 卜 indicates high molecular weight. The so-called Q 本 in this specification is a flow tester manufactured by Shimadzu Corporation. At a temperature higher than the melting point of the resin of 5 ° C, the load is 7 kg at a diameter of 2. The extrusion speed of the fluorinated copolymer when extruded in a 1 mm, 8 mm length orifice. When Q is too small, the solubility is poor, and when it is too large, the mechanical strength of the fluorinated copolymer is inferior, and cracks are likely to occur in the valley when the coating is applied. The Q 値 of the fluorinated copolymer used in the present invention is preferably from 5 to 500 mm 3 /sec, preferably from 10 to 200 mm 3 /sec. When it is in this range, the mechanical strength of the fluorinated copolymer is excellent, and when it is used as a coating grade, the coating film does not cause cracking or the like, and the coating film characteristics are excellent. In the production method of the present invention, the fluorinated copolymers may be used singly or in combination of two or more kinds. 14 201215634 (solvent) The solvent used in the method for producing a fluororesin organosol of the present invention is a solvent capable of dissolving the fluorinated copolymer at the temperature of the fluorinated copolymer of Mizu-machi, and is capable of In the step, after the solution is allowed to precipitate and uniformly disperse the fine particles of the copolymer, the residual state of the fine particles (10) is present as a solvent for dispersing the lanthanum at least under normal pressure. The solvent of Benleming can be exemplified by various solvents within the above conditions. Here, in order to combine the above conditions with the (4) solvent, it is preferred that the solvent has a polarity which is fine in a specific range. In the present invention, a solvent having the above-described conditions is selected as a solvent having a specific range of polarities according to Hansen's solubility parameter (Hansen s〇iubimy parameters). The Hansen solubility parameter system will be divided into the dispersing anvil, the polar term Qiu, and the hydrogen bonding term δΐι by the solubility parameter of Hidden Brown (10), which is expressed in the 3 dimensional space. The dispersion term indicates the effect obtained by the dispersing force, the polarity term δρ indicates the effect obtained by the force between the dipole moments, and the hydrogen bonding term δΐι indicates the effect obtained by the hydrogen bonding force. The definition and calculation of Hansen solubility parameters are described in Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007). Furthermore, by using the computer software Hansen Solubility Parameters in Practice (HSPiP), even Hansen Solubility parameters can be easily derived from the chemical structure even for unknown media such as literature values. The solvent in the present invention is HSPiP version 3, and the solvent is used in the case of the solvent registered in the 15 201215634 database, and the unregistered solvent is used to select the solvent to be used. In general, the Hansen solubility parameter for a particular polymer can be determined by dissolving a sample of the polymer in a number of different solvents as determined by the Hansen solubility parameter and performing a solubility test to determine solubility. Specifically, among the solvents used in the solubility test described above, it is found that the solvent in which the polymer has been dissolved has a point on the 3rd element which is entirely contained inside the ball, and the solvent is not dissolved at the outer side of the ball. The ball (solubility ball) and the central coordinate of the ball as the Hansen solubility parameter of the polymer. Here, for example, if it belongs to some other solvent that is not used to measure the Hansen solubility parameter of the polymer, and the Hansen solubility parameter is (δ(1, δρ, δ!)), if it is displayed on its coordinates If the dot is contained inside the solubility sphere of the polymer, it is presumed that the solvent should dissolve the polymer. On the other hand, if the coordinate point is outside the solubility sphere of the polymer, it is presumed that the solvent does not dissolve the polymer. In the present invention, by using the Hansen solubility parameter, the fluorine-containing copolymer contained in the fluororesin organosol can be dissolved in a solvent at a temperature below its melting point and the fluorine-containing copolymer can be copolymerized at room temperature. The most suitable solvent for dispersing into fine particles is diisopropyl ketone, and the diisopropyl ketone is used as a reference from the coordinates of its Hansen solubility parameter (15. 7,5. 7,4. 3) A solvent group at a certain distance can be used as a suitable solvent. In other words, 値 R based on the Hansen solubility parameter shown by the following formula (1) is used as a solubility index for the fluorinated copolymer: ETFE. R=4x (5d-15. 7) 2+ (δρ-5. 7) 2+ (5h-4. 3) 2. . . (1) 16 201215634 ~ (In the formula (1), Μ, δρ, and δΐι represent the dispersion term, the polar term, and the hydrogen bonding term in the Hansen solubility parameter, respectively, and the units are (Mpa) 1/2). * The solvent used in the present invention, wherein the solvent has a dissolution index (R) determined by the above formula (1) using a Hansen solubility parameter coordinate (Μ, δΡ, ^), preferably less than 25, more preferably less than 16. Less than 9 is especially good. If a solution has (4) Mosen dissolved and the parameter R is within the range represented by the above formula (1), the solvent has a high affinity with the gas-containing copolymer, and the solubility and the dispersibility of the particles are also high. Further, the solvent in the present invention may be a solvent composed of one compound or a mixed solvent composed of two or more kinds of compounds, and may be subjected to the above formula (1) according to the Mossen's solution degree parameter. The obtained R 値 is used as a dissolution index of the copolymer. For example, in the case of using a mixed solvent, the average Hansen solubility parameter 'obtained from the mixing ratio (volume ratio) of the solvent to be used can be determined and used as the Hansen solubility parameter to calculate the above dissolution index (8). Further, the boiling point of the solvent in the present invention is preferably 21 Å from the viewpoint of handleability and solvent removal after coating. (The following is 200. (The following is preferably '180 C or less. It is preferable that if the boiling point of the solvent is too low, for example, when the solvent is removed by coating after the composition is applied (hereinafter also referred to as drying) It is easy to cause bubbles and the like. Therefore, it is preferable to be above ah, and it is more preferable to be hungry or higher, and it is preferably 8 〇C or more. The solvent satisfying the above conditions may suitably be a copper or vinegar having a carbon number of 3 to 10. Carbonic acid _, _#, ketones having a carbon number of 5 to 9 are preferred. Specific examples thereof include methyl ethyl ketone, 2-pentanone, methyl isopropyl, 2 hexanone, and decyl Butyl ketone, benzene pinnacol, 2_heptanone, 4_heptanone, bis 17 201215634 isopropyl ketone, isoamyl decyl ketone, 2-octanone, 2-nonanone, diisobutyl ketone , 2-nonylcyclohexanone, 3-mercaptocyclohexanone, 4-ethylcyclohexanone, 2,6-dimercaptocyclohexanone, 3,3,5-trimethylcyclohexanone, different Carbaryl, (-)-fluorenone, ethyl formate, propyl formate, isopropyl formate, butyl phthalate 'isobutyl formate, butyl phthalate, butyl butyl formate' Isoamyl formate, hexyl decanoate, cyclohexyl formate, decanoate , octyl phthalate, 2-ethylhexyl phthalate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, butyl acetate, tertiary butyl acetate Ester, amyl acetate, isoamyl acetate, hexyl acetate, cyclohexyl acetate, heptyl acetate, octyl acetate, 2-ethylhexyl acetate, 2,2,2-trifluoroethyl acetate, acetic acid 2 , 2,3,3-tetrafluoropropyl ester, 1,1,1,3,3,3-hexafluoro-2-propyl acetate, 2,2-bis(trifluoromethyl)propyl acetate, acetic acid 2 , 2,3,4,4,4-hexafluorobutyl ester, acetic acid 2,2,3,3,4,4,5,5-octafluoropentyl acetate, acetic acid 3,3,4,4,5,5 ,6,6,6-nonafluorohexyl ester, acetic acid 4,4,5,5,6,6,7,7,7-nonafluoroheptyl ester, acetic acid 7,7,8,8,8-pentafluorooctane Ester, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, butyl propionate, butyl butyrate, propionic acid Amyl ester, isoamyl propionate, hexyl propionate, cyclohexyl propionate, heptyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate , isobutyl butyrate, butyl butyrate, butyl butyrate, amyl butyrate, butyl Acid isoamyl ester, hexyl butyrate, cyclohexyl butyrate, methyl isobutyrate, ethyl isobutyrate propyl isobutyrate, isopropyl isobutyrate, butyl isobutyrate, isobutyric acid Isobutyl ester, isobutyl butyl butyrate, butyl butyl isobutyrate, amyl isobutyrate, isoamyl isobutyrate, hexyl isobutyrate, cyclohexyl isobutyrate, decyl valerate , Ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate 18 201215634 Ester, butyl valerate, butyl valerate, amyl valerate, pentane Isoamyl acid ester, methyl isovalerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, secondary isovalerate Ester, secondary butyl pivalate, amyl isovalerate, isoamyl isovalerate, methyl carboxylate, ethyl carboxylate, propyl hexane, isopropyl hexane, hexane Butyl acrylate, isobutyl hexanoate, butyl hexanoate, butyl hexanoate, decyl succinate, ethyl heptanoate, propyl heptanoate, isopropyl heptanoate Ester, methyl octanoate, ethyl octanoate, methyl decanoate, decyl carboxylate Ethyl cyclohexanecarboxylate, propyl cyclohexanecarboxylate, isopropyl cyclohexanecarboxylate, 2,2,2-trifluoroethyl succinic acid bis(2,2, 2-trifluoroethyl ester), bis(2,2,2-difluoroethyl glutarate), ethyl trifluoroacetate, propyl trifluoroacetate, isopropyl trifluoroacetate, butyl trifluoroacetate, Isobutyl trifluoroacetate, butyl trifluoroacetate, butyl trifluoroacetate, amyl trifluoroacetate, isoamyl trifluoroacetate, difluoroacetic acid ester, heptyl trifluoroacetate, trifluoro Octyl acetate, 2-ethylhexyl difluoroacetate, methyl 2-acetate, ethyl difluoroacetate, 2-propoxyethyl acetate, 2-butoxyethyl acetate, 2-pentyloxyacetate Ethyl ethyl ester, 2-hexyloxyethyl acetate, ι_ethoxy-2-pethoxypropane, 丨-propoxy ethoxypropane, 1-butoxy-2-ethoxime Propane, pentyloxy-2-methoxypropane, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, 3-propoxybutyl acetate, 3-butoxybutyrate Ester, 3-methoxy-3-methylbutyrate acetate, 3-ethoxy-3-ylmercaptobutyl acetate, 3-propoxy-3-methylbutyrate acetate, 4-methoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 4-butoxybutyl acetate, decyl pentafluorobenzoate, ethyl pentafluorobenzoate , 3-(trifluoromethyl)benzoic acid decyl ester, 3,5-bis(trifluoromethyl)benzoate hydrazine 19 201215634 ester, benzoic acid 2,2,2-trifluoroethyl ester, benzoic acid 2 , 2,3,3-tetrafluoropropyl ester, 2,2,3,3,3-pentafluoropropyl benzoate, 1,1,1,3,3,3-hexafluoro-2-propenic acid Ester, 2,2-bis(trifluoromethyl)propyl benzoate, 2,2,3,3,4,4,4-heptafluorobutyl benzoate, 2,2,3,4 benzoic acid 4,4-hexafluorobutyl ester, benzoic acid 2,2,3,3,4,4,5,5,5-nonafluoropentyl ester, ethyl decyl carbonate, diethyl carbonate, dipropyl carbonate , dibutyl carbonate 'bis(2,2,2-trifluoroethyl) carbonate, bis(2,2,3,3-tetrafluoropropyl) carbonate, tetrahydrofuran, pentafluoroanisole, 3, 5-bis(trifluoromethyl)anisole and the like. Further, all of the solvents belong to the solvent having R of less than 25 as determined by the above formula (1). Among these, a compound which is more preferably a solvent used in the present invention, specifically, the following compounds can be exemplified. Mercaptoethyl ketone, 2-pentanone, methyl isopropyl ketone, 2-hexanone, decyl isobutyl ketone, benzene pinnacol, 2-heptanone, 4-heptanone, diisopropyl Ketone, isoamyl methyl ketone, 2-octanone, 2-nonanone, diisobutyl ketone, 4-ethylcyclohexanone, 3,3,5-trimethylcyclohexanone, isophorone, Isopropyl phthalate, isobutyl phthalate, butyl citrate, butyl citrate, amyl citrate, isoamyl citrate, hexyl decanoate, heptyl decanoate, octyl citrate, 2-ethylhexyl citrate, decyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, cyclohexyl acetate, acetic acid Ester, octyl acetate, 2-ethylhexyl acetate, 2,2,2-trifluoroethyl acetate, 2,2,3,3-tetrafluoropropyl acetate, 1,1,1,3,3 acetic acid ,3-hexafluoro-2-propyl ester, 2,2-bis(trifluoromethyl)propyl acetate, 2,2,3,4,4,4-hexafluorobutyl acetate, methyl propionate, propionic acid Ethyl ester, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, butyl propionate, butyl tertiary propionate, amyl propionate, isoamyl propionate 20 201215634, hexyl propionate, cyclohexyl propionate, heptyl propionate, decyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl Acid butyl butylate, butyl butyrate, amyl butyrate, isoamyl butyrate, hexanoic acid butyrate, cyclohexyl butyrate, methyl isobutyrate, ethyl isobutyrate, isobutyric acid Propylene vinegar, isopropyl isobutyrate, butyl isobutyrate, isobutyl isobutyrate, secondary butyl isobutyrate, tertiary butyl isobutyrate, amyl isobutyrate, isoammonium isobutyrate Vinegar, hexyl isobutyrate, cyclohexyl isobutyrate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, valeric acid Butyl butyl ester, tertiary butyl valerate, amyl valerate, isoamyl valerate, guanidine valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, isovaleric acid Dingshang, isobutyl isovalerate, dibutyl butyl valerate, tertiary valeric acid isovalerate, amyl isovalerate, isoamyl isovalerate, methyl hexane, hexane Ester, propyl hexanoate, isopropyl hexanoate, butyl hexanoate, isobutyl hexanoate, Acid butyl butylate, butyl butyl hexate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, isopropyl heptanoate, methyl octanoate, ethyl octanoate , methyl decanoate, decyl carboxycarboxylate, ethyl cyclohexanecarboxylate, propyl cyclohexanecarboxylate, isopropyl cyclohexanecarboxylate, cyclohexanecarboxylic acid 2, 2, 2 _Trifluoroethyl hydrazine, bis(2,2,2-trifluoroethyl succinate), bis(2,2,2-trifluoroethyl glutarate), ethyl trifluoroacetate, trifluoroacetic acid Ester, isopropyl trifluoroacetate, butyl trifluoroacetate, isobutyl trifluoroacetate, secondary butyl trifluoroacetate, secondary butyl trifluoroacetate, amyl trifluoroacetate, isoamyl trifluoroacetate , trifluoroacetic acid vinegar, trifluoroacetic acid heptane vinegar, tri-gas acetic acid 辛§, three said acetic acid 2-ethylhexyl ester, di-acetic acid methyl ester, difluoroacetic acid ethyl acetate, acetic acid 2-propoxy acetoacetate , 2-butoxyacetic acid acetate, 2-pentyloxyacetic acid acetate, ethoxylated _2_ 21 201215634 E-flavored acrylic, 1-propoxy-2-ethyloxypropyl, 1 -butoxy-2-ethoxypropane, 3-ethoxybutyl acetate, 3-propoxybutyl acetate, acetic acid 3- Oxy-3-methylbutyl ester, 3-ethoxy-3-mercaptobutyl acetate, 4-methoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate , 2,2,3,3-tetrafluoropropyl benzoate, 2,2,3,3,3-pentafluoropropyl benzoate, 1,1,1,3,3,3-hexafluoro 4 2-propyl ester, 2,2-bis(trifluoromethyl)propyl benzoate, 2,2,3,3,4,4,4-heptafluorobutyl benzoate, benzoic acid 2,2 ,3,4,4,4-hexafluorobutyl ester, 2,2,3,3,4,4,5,5,5-nonafluoropentyl bromide, ethyl methyl carbonate, diethyl carbonate , dipropyl carbonate, dibutyl carbonate, bis(2,2,2-trifluoroethyl) carbonate, pentafluorophenyl ether, 3,5-bis(trifluoromethyl)anisole. Further, all of the solvents belong to the solvent wherein R is less than 16 as determined by the above formula (1). The solvent may be used singly or in combination of two or more kinds as long as it satisfies the conditions of the above-described conditions of the present invention. Further, as long as the above conditions are satisfied, a solvent other than the above may be used in the above solvent. The production method of the present invention is such that a solvent which can be used in combination with the solvent which can be used alone can be used as long as it satisfies the above conditions in the state of a mixed solvent. If (4) a specific example of such a combination, there is the aforementioned benzene pinnacolin (Hansen solubility parameter U5 2, 5 7, 5 3, R: 2. 0) with benzonitrile (Hansen solubility parameters: 18 8, 12 〇, 3 3, r: 79 take body hunger 90: _ mixed solution # 丨 (Hansen rotation parameters: 15 6 , 6 · 3 5 ' R· U), formic acid secondary butyl g (Hansen solubility parameter: 5. 4, 7. 4, R: 12·9) and acetophenone (Hansen solubility parameters: i8 8, 9 〇, 4. 0, R. 49. 4) Volume ratio 71. Mixed solvent of 29 (Hansen solubility parameter: '6m3), acetic acid is different (4) Hansen solubility parameter: 22 201215634 15. 1, 3_7, 6. 3, 11:9. 4) with methyl benzoate (Hansen solubility parameters: 18. 9, 8. 2, 4. 7, R: 47. 4) A mixed solvent of 74:26 by volume ratio (Hansen solubility parameter: 16. 1, 4. 9, 5. 9, R: 3. 8), tertiary butyl formate (Hansen solubility parameter: 14. 8, 5. 4, 7. 4, R: 12. 9) with 1,3-bis(trifluoromethyl)benzene (Hansen solubility parameter: 17. 0, 6. 8, 0. 0, R: 26. 5) Volume ratio 59: 41 mixed solvent (Hansen solubility parameter: 15. 7,6. 0, 4. 4, R: 0. 1) Other combinations. In the mixed solvent, the solubility index (R) calculated based on the Hansen solubility parameter and the volume ratio of each solvent constituting the mixed solvent is preferably less than 25, more preferably less than 16, and more preferably less than 9. In addition, the above-mentioned combination is exemplified, and the mixed solvent which can be used in the method for producing a fluororesin organosol of the present invention is not limited to these combinations. Further, in the method for producing a fluororesin organosol of the present invention, the fluorinated copolymer is dissolved in the solvent in a dissolution step to obtain a fluorinated copolymer solution. The blend ratio of the fluorine-containing copolymer to the solvent used for the preparation of the fluorine-containing copolymer solution is expressed by the mass ratio of the fluorine-containing copolymer: solvent. 0 : 99_0~70. 0 : 30. 0 is better, 2. 0 : 98_0~60. 0 : 40. 0 is preferred. Further, the blend ratio of the fluorinated copolymer to the solvent in the dissolution step is the same as the content ratio of the fluorinated copolymer fine particles to the dispersion medium in the obtained fluororesin organosol. When the fluororesin organosol is used as, for example, a coating composition, the blending ratio can be appropriately changed depending on the film thickness of the intended molded article. When the blend ratio of the fluorinated copolymer and the solvent in the fluororesin organosol is within this range, when used as a coating composition, for example, the handleability is excellent, such as viscosity, drying speed, and film uniformity, and can be shaped 23 201215634 A homogeneous coating composed of fluoropolymer. To "f temperature, house strength, mixing conditions, etc., only two: the fluorocopolymer can be dissolved in the above solvent conditions, there is no special solution for the temperature of the step towel, it should be used in the w The lower temperature. The fluorinated copolymer of the present invention, which is also known as ETFE of P2, the highest is approximately 275 ° C, whereby the temperature at which the solvent is applied to the step of the solvent is approximately 2 751. In the following, it is preferred that the fluorinated copolymer is dissolved in the temperature of the solvent, preferably C or less, preferably less than 2 Torr. Further, in terms of the second lower limit of the dissolution step, (10). c is better, and it is better to use 80 c if it is considered to be an operation. If the temperature of the dissolution step is lower than 4 Torr, it is difficult to obtain a sufficient dissolution state. If the temperature exceeds 275 Torr, it is difficult to perform the actual operation. In the above-described dissolution step of the method for producing a fluororesin organosol of the present invention, the conditions other than the temperature are not particularly limited, and it is usually preferred to dissolve under a micro-pressurization condition of about 5 MPa under normal pressure. When the pressure at the time of dissolution is such that the boiling point of the solvent is lower than the temperature of the dissolution step depending on the type of the gas-containing copolymer or the solvent, the pressure vessel is at least naturally generated at a pressure lower than 3 MPa, preferably 2 MPa. Hereinafter, it is more preferably iMPa or less, and particularly preferably below the lifting pressure. In general, it can be. Dissolve at a pressure of about 1 to about 1 MPa. The dissolution time varies depending on the content of the fluororesin or the shape of the fluorinated copolymer in the fluororesin organosol obtained by the production method of the present invention. The shape of the fluorinated copolymer to be used is preferably in the form of a powder in order to shorten the dissolution time, and it is preferably in the form of a bead or the like. Things. The manner of dissolution in the aforementioned dissolution step is not particularly limited, and a general method can be employed. Weighing a predetermined amount of the fluorine-containing copolymer and the solvent of the essential component of the fluororesin organosol, and adding the amount of any component blended, and uniformly mixing and dissolving it, the arbitrary component is obtained by the obtained fluororesin organosol The intended use, and the appropriate selection and blending according to the performance sought. When it is used as a coating composition, various components described below may be added as an optional component, and in the process of producing the fluororesin organosol of the present invention, any component to be added may have, for example, a viscosity adjusting function. A tackifier, a viscosity reducing agent, etc., an ultraviolet absorber having a function of preventing deterioration, a light stabilizer, and the like. In addition, the total blending amount of the optional components contained in the fluororesin organosol obtained in the production method of the present invention is preferably 30% by mass or less based on the total amount of the fluororesin organosol, and more preferably 10% by mass or less. good. In other words, the total amount of the fluorinated copolymer and the solvent contained in the fluororesin organosol is preferably 70% by mass or more based on the total amount of the fluororesin organosol, and more preferably 90% by mass or more. Further, any component which exhibits function on the fluororesin organosol can be added to the obtained fluororesin organosol after the following (3) disintegration/dispersion step. The mixing temperature of the fluorinated copolymer, the solvent and the optional components is preferably 40 ° C or higher and at a temperature below the melting point of the fluorinated copolymer to be used. Specifically, 60 to 230 ° C is better, and 80 to 200 ° C is very good. Various raw materials in the dissolving step 25 201215634 The mixing and heating of the components can be carried out simultaneously, and after mixing various raw material components, they can be stirred and heated as needed. In the case of a m solution under pressure, a device such as a hot-pressed dad of a laminating machine can be used. For the shape of the wing, the ship (4), the paddle wheel, the fixed wood, the turbine soil, etc. can be used. If it is carried out on a small scale, a magnetic stirrer or the like can also be used. (2) a step of precipitating the solution obtained by the above (1) dissolving step, that is, the above-mentioned copolymer containing the copolymer has been dissolved in the prodrug, and the fluorinated copolymer is precipitated in the form of fine particles to the aforementioned conditions, including The fine particles of the gas copolymer can be precipitated in the above solvent to obtain a composition in which the gas-containing copolymer fine particles have been dispersed in a solvent. The precipitation conditions are preferably normal temperature and normal pressure. In the specific operation example in the precipitation step, the solution obtained by the above (1) dissolution step is cooled to a f temperature, whereby the (tetra) polymer-containing fine particles are precipitated to the front emulsion. (4) There is no cooling method for the cooling method, and it can be cooled by Xu or quenched. The adult system means a mixture of a solvent containing a copolymer of I and a fluorine-containing filament in a fine particle state. The dispersion state of the fluorinated copolymer fine particles in the composition in which the 捭pa is sufficient in the precipitation step is not limited to the case where the fine particles are uniformly dispersed in the solvent, and a part or the whole of the solvent containing the micro-particles The condition of gelation, or the fact that the microparticles are biased in the disperse sentence in the sub-m" agent, there is a case of the stagnation of the scorpion, and the addition of the fluoropolymer to the solvent The higher the mixing ratio, the more prominent the Kyogo. In the case of the heterogeneous composition, in order to make it 260 201215634, the fluorine-containing copolymer organoparticles in which the fine particles of the fluorine-containing copolymer have been uniformly dispersed in the solvent are the following. (3) Disintegration • Dispersion step disintegration • Dispersion step The high-shear is applied to the composition obtained by the above (7) precipitation step, that is, the composition of the fluorocopolymer with the microparticle state. The cutting force is such that the pure silk material is finer and more self-dispersing. The method of applying high shear force to the foregoing mixture, specifically high speed rotation 'high pressure jet, high speed vibration, ultrasonic processing, high pressure Crossing method, etc. Among them, in terms of a simple method, system security from rotating by 咼 speed, high-pressure jet, or high-speed vibration (hereinafter, a generic term like the Von stirred bait ") line of the preferred method. Moreover, these methods of applying high shear force can be carried out as early as possible, and two or more methods can be used, for example, mixing and ultrasonic processing. The application of the high-shearing force to the foregoing mixture by sandalwood is usually used to apply a high shear force while the device is employed. Mixing of this mixed liquid ^ ^ liquid. , For stone surface, in the aforementioned disintegration and dispersion steps, use a turbine or a knife »3. . κ / 尚轮桨, etc., are also included in the usual search wings for rabbits with large shearing wings. Moreover, it is preferable to use the following lion device or dispersing device which has a higher shearing force: the use of the shearing force 4, when the high shear force is applied to the mixture of the aforementioned _ and the fluorine-containing co-(four) The number of rotations, pressure ^ ^ ^ processing time, processing temperature, etc., can be appropriately selected depending on the state of the mixture or the device to be used. The following (4) to (c) and (e) are dispersion devices by means of high-speed rotation of the stirring device, and (d) #蕤古压喷. Wrong (4) with TK homogenizer
27 201215634 ULTRA-TURRAX(IKA公司製）、p〇lyt_(KINEMATICA公 司製）等為代表之攪拌裝置，亦即，該攪拌裝置係於攪拌翼 之外周附近組合有固定環，使該轉子以高速旋轉，並利用 於攪拌翼與固定環之微細間隙產生的強力剪切效果、衝擊 力，來提咼微粒化效果者；施加高剪切力之際的旋轉數， 具體而言可舉1000〜30000旋轉/分等。 (b) 以CLEARMIX(M. TECHNIQUE公司製）等為代表之 攪拌裴置，亦即，該裝置係以高速旋轉之轉子、與將之包 圍之網所產生的剪切力、衝突力、壓力變動、空腔現象及 勢流心作用進行攪拌者；施加高剪切力之際的旋轉數，具 體而言可舉1000〜22000旋轉/分等。 (c) 以 CAVITR〇N(EUROTEC公司製）、DRS20〇〇(IKA公 司製）等為代表之攪拌裝置，亦即，該攪拌裝置係具備配置 於同心上之梳齒狀旋轉子及固定子，使該旋轉子以高速旋 轉，並使攪拌之混合液自該旋轉子内側流通於固定子外 側，使混合液於旋轉子與固定子之間隙攪拌者；施加高剪 切力之際的攪拌翼前端速度方面，具體而言可舉2〜5〇m/秒 等。 / (d) 以Manton-Gaulin均質機(Gaulin公司製）等為代表之 分散裝置，亦即，該裝置係以高壓柱塞泵等將處理液壓入， 並利用排出部特殊閥之調整使之以高壓喷射，以超高速於 出口固定板猛摔使之分散者；施加高剪切力之際的壓力方 面，具體而言可舉1〜l〇〇MPa等。 (e) 以TK . FILMICS(PRIMIX公司製）為代表之攪拌裝 28 201215634 置’亦即’該裝置係利用離心力將所處理之混合液按壓至 刀政槽側壁而形成液膜，並利用超高速旋轉之攪拌具前端 碰觸°亥液膜來進行攪拌者；施加高剪切力之際的攪拌翼前 立而速度，具體而言可舉2〜5〇m/秒。 右人藉由高壓過濾對前述混合物施加高剪切力，可適用 使/夜狀物以高壓通過過濾器等細孔之市售高壓過濾裝置， 並無特別限制。再者’使用高壓過慮裝置，對前述溶劑與 έ亂1物之混合物施加高剪切力時的具體條件例如壓 力過;處器孔徑、處理時間、處理溫度等，可依據混合物 狀t或所採用的裝置而適當選擇。更具體而言，可例舉壓 力0·1〜2.0MPa、過濾器孔徑0.1〜5μηι等條件。 名人藉由超音波處理對前述混合物施加高剪切力，可使 用市售之超音波洗淨機或超音波產生器等。此時亦同對前 述溶劑與§氟共聚物之混合物施力σ高剪切力時，其具體條 件例士頻率 '處理時間、處理溫度等’可依據混合物狀態 或所採用的裝置而適當選擇。更具體而言，可舉振盡頻率 10〜200kHz等條件。 再者’本發明的製造方法中，亦可因應需要而同時進 行前述(2)析出步驟與(3)解碎•分散步驟。 又’爲了使含氟共聚物微粒子在溶劑中更均句地分散， 本發明的製造方法之(3)解碎·分散步 舣少驟以添加黏度調整劑 (亦稱「減黏劑」）來實施為佳。 述溶劑與含氟 具體而言，可 所使用的黏度調整劑，只要是可降低此 共聚物之混合物的黏度，則並無特別限制。 29 201215634 例舉具有選自於由可由函化基所取代且鍵結末端以外的任 意一CH2—可由氧原子所取代之碳原子數1~2〇之烧基、甚至 胺基、醯胺基、磺醯胺基、咪唑基、羥基及氫硫基所構成 群組之至少1種官能基的化合物。 此種黏度調整劑，更具體而言可舉丁基胺、戊基胺、 己基胺、庚基胺、辛基胺、壬基胺、癸基胺、十一烧胺、 十二烷基胺、十三烷基胺、十四烷基胺、十五烷基胺、十 六烧基胺、十七烧基胺、十八烧基胺、十九燒基胺、二十 院基胺、2-乙氧基乙基胺、3-丁氧基丙基胺、2-(乙基胺基) 乙酵、4-乙基胺基-1-丁醉、2-( 丁基胺基）乙醇、4-( 丁基胺 基)-1-丁醇、辛烷醯胺、壬烷醯胺、癸烷醯胺、十二烧酿胺、 十三醯胺、十四炫•醯胺、十五烷醯胺、十六境醯胺、十七 烷醯胺、十八烷醯胺、卜辛烷磺醯胺、1-壬烷續醯胺、b 癸烷磺醯胺、1-十一烷磺醯胺、i-十二烷磺醯胺、丨_十三烧 磺醯胺、1-十四烷磺醯胺、卜十五烷磺醯胺、1-十六烧績酿 胺、1-十七烷磺醯胺、1-十八烷磺醯胺、2-丁基味哇、2_戊 基咪唑、2-己基咪唑、2-庚基咪唑、2-辛基咪唑、2_壬基味 唑、2-癸基咪唑、2-十一烷咪唑、2-十二烷基咪唾、2_十三 燒基咪唑、2-十四烷基咪唑、2-十五烧基咪唑、2_十六烧基 咪嗤、2-十七烧基°米。坐、2-十八烧基°米唾、1-辛醇、ι_壬醇、 1-癸醇、1-十一烷醇、1-十二烷醇' 1-十三烷醇、丨·十四烧 醇、1-十五烷醇、1-十六烷醇、1-十七烷醇、1_十八烧醇、 1 -辛硫醇、卜壬硫醇、1 -癸硫醇、I-十一硫醇、十二硫醇、 1-十三硫醇、1-十四硫醇、1-十五硫醇、1-十六硫醇、丨_十 30 201215634 七硫醇、1-十八硫醇等。該等當中，以3-丁氧基丙基胺、辛 基胺、壬基胺、癸基胺、Η—烧胺、十二烧基胺、十三烧 基胺、十四烧基胺、十五烧基胺、十六烧基胺、十七院基 胺、十八烷基胺等為佳。該等可單獨使用1種，亦可併用2 種以上。 又，所使用的黏度調整劑之量方面，係相對於前述混 合物中之含氟共聚物，以0.1〜20質量％之量為佳，0.5〜10質 量％之量更佳。又，黏度調整劑之量與其他任意成分之合 計量，以相對於氟樹脂有機溶膠之全量計，在30質量％以 下為佳，15質量％以下更佳。又，黏度調整劑之添加時期， 只要是在(3)解碎•分散步驟之前則並無特別限制。例如， 可於前述（1)溶解步驟時添加，也可於前述(2)析出步驟後添 加。惟，若是在析出步驟後添加之情況，爲了使黏度調整 劑可均勻存在於前述溶劑與含氟共聚物之混合物中，宜利 用球磨機等進行充分攪拌。 如此獲得之含氟共聚物的分散液中，有時會殘存粗大 之凝聚粒子。基於除去此種凝聚粒子為目的，可實施將前 述分散液過濾之步驟。過濾方法可採用加壓過濾、減壓吸 濾、常壓自然過濾等任何方法。就過濾方法而言，以加壓 過濾為佳，濾材方面可使用不鏽鋼製濾器、樹脂製濾器。 如此進行而利用本發明的製造方法，即可獲得一種氟 樹脂有機溶膠，其係以前述含氟共聚物之微粒子為分散 質、以前述溶劑為分散媒，且前述含氟共聚物之微粒子已 均勻分散於前述溶劑者。 31 201215634 [氟樹脂有機溶膠] 依據前述本發明的製造方法所獲得的氟樹脂有機溶膠 (以下稱本發明之氟樹脂有機溶膠）中，前述含氟共聚物之微 粒子，係以前述溶劑作為分散媒而均勻分散於該分散媒中 之狀態存在。本發明之氟樹脂有機溶膠中，含氟共聚物之 微粒子的平均粒徑，在25°C下以動態光散射法所測定之個 數平均粒徑，係以0.005〜5μιη為佳，0.005〜2μηι較佳， 0.01〜Ιμιη甚佳。此處，個數平均粒徑係由所獲得的平均粒 徑來看，粒徑比較小的粒子數、與粒徑比較大的粒子數之 比率相同的粒徑。 本發明之氟樹脂有機溶膠中，含氟共聚物之微粒子的 平均粒徑，只要是在前述範圍，在例如將之作為塗覆用組 成物之情況下，可形成均質且透明性、平坦性、密著性優 異之塗膜。再者，只要是未特別預先申明，本說明書中所 謂的平均粒徑是指平均一次粒徑。 [塗覆用組成物] 本發明之塗覆用組成物係含有前述本發明之氟樹脂有 機溶膠作為主成分者。本發明之塗覆用組成物是僅由前述 含氟共聚物之微粒子與前述溶劑所構成的氟樹脂有機溶 膠、或者是前述含氟共聚物之微粒子與前述溶劑且進一步 含有任意成分的氟樹脂有機溶膠。又，也可以是此種氟樹 脂有機溶膠中添加了任意成分之物。 本發明之塗覆用組成物含有由前述含氟共聚物之微粒 子與滿足前述條件之溶劑形成有機溶膠之物作為必須成 32 201215634 分。進一步’可因應需要，在不損及本發明效果之範圍含 有其他任意成分。此種任意成分的例子，可舉抗氧化劑、 光穩定劑、紫外線吸收劑、交聯劑、潤滑劑、塑化劑、增 黏μ、分散穩定劑、充填劑（填料）、強化劑、顏料 '染料、 阻燃劑、抗靜電劑等各種添加劑。又，任意成分之含量方 面係相對於塗覆用組成物全量計，宜在3〇質量％以下， 又以10質量％以下為佳。 又，欲將本發明之塗覆用組成物作為塗料使用時亦 可如-般性氟塗料所進行般，混合非氟樹脂。 任思成分係可於前述氟樹脂有機溶膠之製造步驟的 今解步驟巾添加於原料成分，亦可添加於僅由前述含氣共 =之雜子與前述溶軸構成的氣職有機轉。又， 右疋添加多餘意成分的情況下，可將任意成分當中的數 種二前述⑴溶解步驟中添加於原料成分而製造氟樹脂有 機浴膝之後，於_脂有機溶射添加相同或其他 類的任意成分。 饱 利用本發明之塗覆用組成物所行之於基材上形成 共聚物塗膜’可藉由巧之塗膜形成方法來進行。 丄由將本發明之塗覆用組成物塗佈於基材而形成含六 劑塗膜的塗佈步驟、及自前述含溶劑塗膜除去溶劑而作 不含冷劑之塗膜的溶劑除去步驟，可由本發明之塗覆 成物簡便地獲得含氣共聚物塗膜。 、、’ (塗佈步驟） 利用本發明之塗覆用組成物之塗膜形成方法之塗佈步 33 201215634 驟中’朝基材塗佈塗覆敎錄所使㈣方^並無特別限 定’可使用-般採用的方法。塗佈方法方面，可舉例如凹 版印刷’塗覆、浸潰塗覆、模頭塗覆、喷霧塗覆、靜電塗裝、 刷毛塗抹、網板印刷、輥塗覆、旋轉塗覆等。 則述塗佈步驟中’本發明之塗覆用組成物未必—定要 在含氟共聚物已溶解於前述溶劑之狀態下進行塗佈。本發 明之塗覆賴成物’其雜為即使在已分散於前述溶劑之 含氟共聚物可溶解之溫度以下，仍呈含敗共聚物已均句分 散於削述溶劑之狀態。因此，於前述塗佈步驟中，可在溫 度低於削述含氟共聚物溶解於前述溶劑的溫度下，將本發 明之塗覆用組成物塗佈於基材，並在以下說明之較低溫度 下除去溶劑（乾燥）。如此實施塗佈，就以下此點或作業性之 觀點而言頗佳。使用本發明之塗覆用組成物的塗膜形成方 法中’藉由依此將塗佈溫度或乾燥溫度調整於低溫，可獲 得緻也、且平坦之塗膜。 前述塗佈步驟中的塗佈溫度，雖依據所使用的塗覆用 組成物而有所變化，惟以〇〜210。(：為佳，0〜130°C更佳，〇〜50 c甚佳。前述塗佈溫度低於〇 t時含氟共聚物之分散狀態稱 不上充分，而若超過21〇。〇則所含之溶劑變得容易揮發，恐 有產生氣泡等的可能性，故不甚佳。 (溶劑除去步驟） 月’J述溶劑除去步驟係自已於前述塗佈步驟獲得之含溶 劑塗臈將溶劑除去而作成不含溶劑之塗膜的步驟。 月’J述溶劑除去步驟中的溶劑除去溫度，亦即乾燥溫 34 201215634 度’且為0~350°C ’以ι〇〜270°C較佳，20~240。(：尤佳。 該溶劑除去時之溫度(乾燥溫度）若低於(TC，則溶劑除 去花費時間太長，若超過350t：則恐有產生著色或分解等的 可能性，故不甚佳。 又，使用塗覆用組成物形成塗膜之後，亦宜以 C進行熱處理。熱處理溫度較佳為70〜270。(：，更佳為 100〜250°C。藉由進行熱處理，塗膜可變得更緻密，提高與 基材之密著性。藉此，耐久性可提升，可更有效地保護基 材。 如此，採用本發明之塗覆用組成物之含氟共聚物塗犋 的形成方法中，不須在高溫下進行塗覆用組成物之塗佈或 乾燥。因此，即使是對塑膠或紙、布此種耐熱性低的材料， 也可形成塗膜又不致引起基材分解或變形。 再者，藉由含氟共聚物加以塗覆之基材的材質或形狀 並無特別限定，可塗佈於鐵、不鏽鋼、銘、鈦、銅、銀等 金屬類、窗玻璃、鏡子、合成石英等玻璃、矽、聚碳酸酯 (pc)、聚對苯二曱酸乙二酯（PET)、聚曱基丙烯酸甲酯 (PMMA)、玻璃纖維強化塑膠(FRP)、聚氯乙烯(pvc)、氟樹 月a等有機材料、石材、木材、陶竞、布、紙等。 此處，採用本發明之塗覆用組成物的含氟共聚物塗祺 之形成方法中，基於提高基材與塗膜之密著性等目的可 對基材進行前處理。例如，可對基材進行塗佈矽烷偶合劑 或聚乙亞胺等；利用喷砂等將表面進行物理性處理；藉電 暈放電等所行之處理等。 35 201215634 藉由前述本發明製造方法所獲得之氟樹脂有機溶膠作 為主成分之塗覆用組成物，將之依此進行而塗工於基材， 即可提供前述含氟共聚物塗膜及業已藉該塗膜塗佈之物 品。 又，藉由前述塗膜形成方法所獲得之前述含氟共聚物 塗膜，亦可藉由與基材分離，作為薄膜狀成型體來使用。 如此獲得之前述含氟共聚物亦即ETFE膜，與利用一般熔融 成形所獲得之ETFE膜相較，更薄且均勻。 所獲得之塗膜、或薄膜狀成型體之厚度，可因應目的 自由選擇。若是使用濃度高的溶液或分散液，則可獲得具 有厚度的膜，若是使用濃度低的溶液或分散液，則可獲得 薄塗膜。又，藉由多次重複進行塗佈步驟，可獲得更具厚 度的膜。 由於具有前述此種特徵，以本發明氟樹脂有機溶膠作 為主成分之塗覆用組成物的用途，可例舉光纖包層材、透 鏡、太陽電池用物品、顯示面板·顯示器用物品、光碟片、 半導體元件、拼合積體電路1C、液晶晶胞、印刷基板、1C 卡、光導鼓、薄膜電容器、玻璃窗、樹脂窗、各種薄膜、 各種感測器、天線、被覆電線、馬達、發電裝置等光學領 域、電氣、電子領域中的保護塗覆劑、拒水塗覆劑、低反 射塗覆劑、電絕緣性被覆材、電荷滯留層、電車、巴士、 卡車、汽車、船舶、飛航機等運輸機器用物品、外牆、屋 頂材、封合部分、橋樑或隧道等土木建築用物品、注射器、 吸管、體溫計、燒杯類、培養孤、量筒等醫療領域、化學 36 201215634 領域中的物品、其他可作為焊料遮罩、阻焊劑、橡膠、塑 膠之保濩、耐候、防污塗覆劑、纖維、布第之保護塗覆劑、 进&㈣之防/¾塗覆劑、IC密封劑、防鏽塗料、抗樹脂附著 H由墨附著劑、分離膜用物品、積層鋼板用底漆、各 種接著劑、黏結劑等。 月|J述太陽電池用物品方面，可例舉以玻璃或樹脂所構 成之保4覆蓋材、透明導電構件、背板等保護塗覆劑、氣 體屏障層、薄板玻璃之支擇樹脂層、接著層等。 刖述顯不面板•顯示器用物品方面，可例舉液晶顯示 面板、電_示器面板 '電致變色顯示器面板、電激發光 顯不β面板、觸控面板所使用的透明構件(玻璃基板及樹脂 基板)之保護塗覆劑、防污塗覆劑、低反射塗覆劑、薄板玻 璃之支撐樹脂等。 前述運輸機器用物品方面，可例舉安裝於運輸機器之 顯示機器表面材等的外裝構件、儀表板表面材等的内裝構 件機體、鏡子等的保護塗覆劑、防污塗覆劑、低反射塗 覆劑、安全玻璃用積層材等。 前述分離膜用物品方面，可舉逆滲透膜、奈米過濾膜 等的機能層、分離二氧化碳、氫等之氣體分離膜的機能層、 膜模組製造上的接著劑、防污塗覆劑等。 又，本發明之塗覆用組成物，可有益地使用作為材料 組成物’用於製作半導體元件或積體電路裝置中的層間絶 緣膜或保護膜。此種用途上，若使用以本發明氟樹脂有機 溶膠作為主成分之塗覆用組成物，則可活用含氟共聚物所 37 201215634 具備的低吸水性、低介電率、高耐熱性此等特性，獲得應 答速度迅速且錯誤動作少的半導體元件積體電路裝置。 進而，本發明之塗覆用組成物，可有益地使用於聚光 型太陽能發電上所採用的聚光用鏡之保護塗覆劑、防污塗 覆劑、聚光鏡之裱褙樹脂等密封部分之保護塗覆劑等。在 此種用途上，若使用以本發明氟樹脂有機溶膠作為主成分 之塗覆用組成物’則可活用氟樹脂所具備的高财熱性、低 吸水性此等特性’獲得高埘久性且不須維修的發電系統。 又’本發明之氟樹脂有機溶膠，除了塗覆用途以外， 亦可利用在接著劑、黏結劑、色劑用添加劑等之用途。 實施例 以下，說明本發明之實施例，惟本發明並不限定於該等 實施例。 (溶解程序） 以下所示之實施例及比較例，只要是未特別記載，皆以 後述方法來進行。 於厚度4mm、外徑30mmi硼矽酸玻璃製耐壓反應容器 中:置入含氣共聚物、溶劑及搜拌子。含貌共聚物與溶劑之 相對篁’以含氟共聚物相對於溶劑量之量計係使其為5〜⑺ 質量％ 〇 反應谷$ _用業已充分獅且進行溫度控制之油浴來 進行加熱。 ▲以目顺察來決定錢共㈣是E溶解。若試管内容 物隻成透明且均勻之溶液則判定為溶解狀態。 38 201215634 微粒子分散液、塗膜評價方法） 就以下項目，依以下方法，進行對實施例所獲得之微粒 子分散液、及塗膜之評價， (1) 個數平均粒徑 分散液中的ETFE微粒子之個數平均粒徑，係利用粒徑分 布測疋瓜置(Microtrac公司製Nanotrac)，在25。(：溫度條件下， 以動態光散射法進行測定。又，利用穿透式電子顯微鏡 (TEM)(日本電子公司製舰_123〇)，觀察ETF^粒子的一次 粒徑，來確認以前述動態光散射法所獲得之結果確實。 (2) 膜厚 針對依嵌裝及棒塗佈器所獲得之塗膜，利用觸針式表面 形狀測定器（Sloan公司製、DEKTAK 3ST)測定膜厚，而針對 依則述以外方法所獲得之塗膜，利用非接觸光學式薄膜測定 裝置(Filmetrics公司製、nimetricsF-20)測定膜厚。 (3) 密著性 畨著性之s式驗係準據JIS-K-5600(1999年)進行。亦即，利 用截切刀於基材上之含就共聚物薄膜施予2_間隔之n條直 行切痕，做出100個棋盤式格子，於該棋盤式格子上強力壓黏 赛珞玢黏著膠帶，持該膠帶端部瞬間撕除，觀察表皮表面上 未剝離而仍殘留之薄膜狀態。根據5次剝離試驗之後的剝離狀 態進行評價。91格以上仍接著者計為◦(優）、9〇〜51格仍接著 者5十為△(普通）、50〜0格仍接著者計為χ(不良）。 [實施例1] 於30mL硼矽酸玻璃製耐壓反應容器中，置入作為含氟共 39 201215634 聚物之ETFE(以構成單體為主體之重複單元的莫耳比：以四氟 乙烯為主體之重複單元/以乙烯為主體之重複單元/以 3,3,4,4,4-五氟-1-丁烯為主體之重複單元/以依康酐為主體之 重複單元=57·5/39_9/2·3/0·3、熔點：240 °C、以下稱 「ETFE1」）0.80g、二異丙基酮(依前述式（1)算出之R(以下僅 以「R」表示)=0)15.20g ’ 一面授拌並同時一面加熱至185°C， 結果變成均勻且透明之溶液。 將該試管徐緩冷卻至室溫為止，結果獲得均勻的含氟共 聚物之凝膠狀物(ETFE1濃度5質量％)。將該凝膠狀物利用 PRIMIX公司製、TK FILMICS 40-40型，以30m/秒進行攪拌2 分鐘，獲得均勻之分散液(本發明之氟樹脂有機溶膠含氟共 聚物之微粒子的平均粒徑，在25°C下，以動態光散射法測定 之個數平均粒徑為58nm。 又，將该分散液稀釋成〇.〇5質量。/〇，以穿透式電子顯微鏡 觀察，結果確認一次粒徑為40〜5〇nm。第丨圖中顯示穿透式電 子顯微鏡(TEM)相片（1〇萬倍）。 TEM相#攝&巾’樣本製備時分散液巾的溶劑被除去， 故推測所獲得之相片中’例如第1圖之相片中所示，含氣共聚 物之粒子形成聚集粒子。觀察第1圖之相片時，相片内存在有 1個大塊狀好，並可知賴_子是由各她小之粒子多數 聚集而形成。該塊狀粒子表示ETFE1之聚集粒子，而構成該 塊狀粒子之各姉子縣ETF㈣-餘子。前述所觀察的 個數平均粒徑’係意指推測㈣之粒子，以如此般可識別之 謂幻-次好在分舰t單神在、或讀個—次粒子聚 40 201215634 集形成的二次粒子存在的情況下，整體粒子個數之相當於 50%之粒子的粒徑。 將該分散液在室溫下於玻璃基板(冕玻璃、厚度lmm)上藉 由棒塗佈器進行塗佈，且在室溫下乾燥。於丨⑽它之熱板上加 熱3分鐘，獲得表面上形成了ETFE1之薄膜之玻璃基板。以光 學顯微鏡(100倍)觀察所獲得之薄膜表面，結果確認是均勻且 平滑之膜。第2圖中顯示由該ETFE1構成之薄膜表面的光學顯 微鏡相片（100倍）。又，以觸針式表面形狀測定器測定膜厚， 結果為3μηι。評價所獲得之ETFE1膜的密著性時，完全未見任 何剝離。亦即密著性評價為〇(優卜 [實施例2] 將貫施例1所獲得之氣樹脂有機溶膠，在室溫下於ΡΕτ(聚 對苯二甲酸乙二酯）膜（東洋紡公司製c〇sm〇shine(註冊商 標)A4300 ;厚度ι00μιη)上藉由棒塗佈器進行塗佈，且在室溫 下乾燥。於10〇£>C之熱板上加熱3分鐘，於PET膜上形成£71^1 之薄膜。又，以觸針式表面形狀測定器測定膜厚，結果為 3μιη。評價所獲得之ETFm膜與pET膜之密著性時，完全未見 任何剝離。亦即密著性評價為〇(優）。 [貫施例3] 將實施例1所獲得之氟樹脂有機溶膠，在室溫下於鋁板 (厚度2’m)上藉由棒塗佈器進行塗佈、乾燥後於2紙之 熱板上加熱3分鐘，於鋁板上形成£17£1之薄膜。評價所獲得 之ETFE1膜與銘板之密著性時，完全未見任何制離。亦即密 著性評價為〇(優）。 201215634 [實施例4] 作為含氟共聚物係採用ETFE1計1.60g、二異丙基酮 14.4g ’此外與貫施例1同樣地施行’獲得均勻的含氟共聚物之 凝膠狀物(ETFE1濃度10質量％)。於該凝膠狀物添加十二烧基 胺(0.03g)作為黏度調整劑，使用行星式球磨機(Thinky公司 製、AWATORI練太郎ARE-310)，以2000旋轉/分攪拌1〇分鐘。 利用PRIMIX公司製、TK FILMICS 40-40型，將所獲得之衆體 以30m/秒攪拌2分鐘，得到均勻之分散液(本發明之氟樹脂有 機溶膠）。使用該分散液與實施例1同樣地施行，獲得表面形 成有ETFE1之薄膜之玻璃基板。以光學顯微鏡觀察獲得之 ETFE1膜，結果確認是均勻且平滑之膜。又，以觸針式表面 形狀測定器測定膜厚，結果為6μηι。評價所獲得之ETFE1膜的 密著性時’完全未見任何剝離。亦即密著性評價為〇(優）。 [實施例5] 與實施例1同樣地施行，獲得ETFE1之均勻之凝膠狀物 (ETFE1濃度5質量％”將該凝膠狀物利用KINEMATICΑ公司 製PolytronPT10-35型，以22000旋轉/分攪拌5分鐘，獲得均勻 之分散液(本發明之氟樹脂有機溶膠）。 將該分散液與實施例1同樣地施行獲得表面上形成有 ETFE1之薄膜之玻璃基板。以光學顯微鏡觀察所獲得之ETFE1 膜表面，結果確認是均勻且平滑之膜。 (耐藥品性保護塗覆） [實施例6] 將實施例3所獲得之已塗佈ETFE1i鋁基板(附保護塗覆 42 201215634 鋁基板)浸於IN鹽酸，觀察變化。結果係與針對無保護塗覆之 鋁基板進行相同處理之結果，一併顯示於表1。 43 20121563427 201215634 ULTRA-TURRAX (made by IKA), p〇lyt_ (made by KINEMATICA Co., Ltd.), etc., that is, the stirring device is combined with a fixing ring near the outer circumference of the stirring blade to rotate the rotor at a high speed. And use the strong shearing effect and impact force generated by the fine gap between the stirring wing and the fixing ring to improve the atomizing effect; the number of rotations when high shear force is applied, specifically, 1000 to 30000 rotation / points and so on. (b) A stirring device represented by CLEARMIX (manufactured by M. TECHNIQUE Co., Ltd.), that is, the device is a shearing force, a conflicting force, and a pressure change generated by a rotor that rotates at a high speed and a net that is surrounded by the same. The cavity phenomenon and the potential flow center are agitated; the number of rotations when high shear force is applied, specifically, 1000 to 22000 rotations/min. (c) a stirring device represented by CAVITR® N (manufactured by EUROTEC Co., Ltd.), DRS20® (manufactured by IKA Co., Ltd.), or the like, that is, the agitation device includes a comb-shaped rotor and a stator disposed on the same concentric line. Rotating the rotator at a high speed, and allowing the agitated mixture to flow from the inside of the rotator to the outside of the stator to stir the mixture between the rotor and the stator; the agitating blade tip at the time of applying high shear force In terms of speed, specifically, it is 2 to 5 〇 m / sec. / (d) A dispersing device represented by a Manton-Gaulin homogenizer (manufactured by Gaulin Co., Ltd.), that is, the device is hydraulically introduced by a high-pressure plunger pump or the like, and is adjusted by a special valve of the discharge portion. The high-pressure jet is smashed at a super-high speed on the outlet fixing plate to disperse it; and the pressure at the time of applying high shear force is specifically 1 to 10 MPa. (e) Stirring device represented by TK. FILMICS (manufactured by PRIMIX Co., Ltd.) 201220123 The device is used to press the treated mixture to the side wall of the knife-operated tank to form a liquid film, and to use ultra-high speed. The front end of the rotating stirrer touches the liquid film to stir the person; when the high shear force is applied, the stirring wing stands forward and the speed is specifically 2 to 5 〇 m / sec. The right person applies a high shear force to the above mixture by high-pressure filtration, and is applicable to a commercially available high-pressure filtration device which allows a high-pressure/night substance to pass through a fine hole such as a filter at a high pressure, and is not particularly limited. Further, 'using a high-pressure filter device, specific conditions for applying a high shear force to the mixture of the solvent and the disorder, such as pressure; the pore size of the vessel, the treatment time, the treatment temperature, etc., may be based on the mixture t or The device is appropriately selected. More specifically, conditions such as a pressure of 0.1 to 2.0 MPa and a filter pore diameter of 0.1 to 5 μm can be exemplified. The celebrity applies high shear force to the aforementioned mixture by ultrasonic treatment, and a commercially available ultrasonic cleaner or ultrasonic generator or the like can be used. In this case, when the mixture of the solvent and the § fluorocopolymer is applied with a high shear force, the specific condition frequency "treatment time, treatment temperature, etc." may be appropriately selected depending on the state of the mixture or the apparatus to be used. More specifically, conditions such as a vibration frequency of 10 to 200 kHz may be employed. Further, in the production method of the present invention, the above (2) precipitation step and (3) pulverization/dispersion step may be simultaneously performed as needed. Further, in order to disperse the fine particles of the fluorinated copolymer more uniformly in the solvent, (3) the method of the present invention, the disintegration and dispersion step, is added with a viscosity adjusting agent (also referred to as "viscosity reducing agent"). Implementation is better. The solvent and the fluorine-containing compound are specifically, and the viscosity adjusting agent to be used is not particularly limited as long as it can lower the viscosity of the mixture of the copolymer. 29 201215634 exemplified by an alkyl group having a carbon number of 1 to 2 Å selected from any one of CH 2 - which may be substituted by a functional group and which may be substituted by an oxygen atom, or even an amine group or a guanamine group. A compound having at least one functional group of a group consisting of a sulfonamide group, an imidazolyl group, a hydroxyl group, and a hydrogenthio group. More specifically, such a viscosity adjusting agent may be butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, decylamine, undecylamine, dodecylamine, Tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, decylamine, decylamine, 2- Ethoxyethylamine, 3-butoxypropylamine, 2-(ethylamino)ethylation, 4-ethylamino-1-butanol, 2-(butylamino)ethanol, 4 -(butylamino)-1-butanol, octyl decylamine, decane decylamine, decane decylamine, dodecylamine, tridecylamine, tetradecylamine, decylamine Amine, hexadecanolamine, heptadecylamine, octadecylamine, octane sulfonamide, 1-decane decylamine, b-decanesulfonamide, 1-undecanesulfonamide , i-dodecanesulfonamide, 丨_13 sulfonamide, 1-tetradecanesulfonamide, pentadecane sulfonamide, 1-hexadecane, 1-heptadecane Sulfonamide, 1-octadecanesulfonamide, 2-butyl miso, 2-pentyl imidazole, 2-hexylimidazole, 2-heptyl imidazole, 2-octyl imidazole, 2-nonyl oxazole, 2-癸Imidazole, 2-undecylimidazole, 2-dodecylmeridene, 2-tridecyl imidazole, 2-tetradecylimidazole, 2-pentadecyl imidazole, 2-hexadecane , 2-seven burning base ° meters. Sit, 2-octadecane, rice, salicile, 1-octanol, ι_sterol, 1-nonanol, 1-undecyl alcohol, 1-dodecanol 1-tridecyl alcohol, hydrazine Tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-octylthiol, diterpene thiol, 1-nonyl mercaptan, I-undecyl mercaptan, dodecyl mercaptan, 1-tridecanl mercaptan, 1-tetradecyl mercaptan, 1-dodecanethiol, 1-hexadecanethiol, antimony _ 10 30 201215634 heptathiol, 1 - octadecyl mercaptan, etc. Among these, 3-butoxypropylamine, octylamine, decylamine, decylamine, hydrazine-amine, dodecylamine, tridecylamine, tetradecylamine, ten Preferably, pentylamine, hexadecylamine, heptylamine, octadecylamine, and the like are preferred. These may be used alone or in combination of two or more. Further, the amount of the viscosity modifier to be used is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, based on the total amount of the fluorinated copolymer in the mixture. Further, the amount of the viscosity modifier and the amount of the other optional components are preferably 30% by mass or less, and more preferably 15% by mass or less based on the total amount of the fluororesin organosol. Further, the addition timing of the viscosity modifier is not particularly limited as long as it is before the (3) disintegration/dispersion step. For example, it may be added during the above (1) dissolution step, or may be added after the above (2) precipitation step. However, in the case where the viscosity adjusting agent is uniformly present in the mixture of the solvent and the fluorinated copolymer, it is preferably stirred by a ball mill or the like in the case where it is added after the precipitation step. In the dispersion of the fluorinated copolymer thus obtained, coarse aggregated particles may remain. The step of filtering the above dispersion liquid can be carried out for the purpose of removing such aggregated particles. The filtration method may be any method such as pressure filtration, vacuum filtration, atmospheric filtration or the like. The filtration method is preferably a pressure filtration, and a stainless steel filter or a resin filter can be used as the filter material. By performing the production method of the present invention in this manner, a fluororesin organosol can be obtained, wherein the fine particles of the fluorinated copolymer are dispersed, the solvent is used as a dispersion medium, and the fine particles of the fluorinated copolymer are uniform. Dispersed in the aforementioned solvent. 31 201215634 [Fluororesin organosol] In the fluororesin organosol (hereinafter referred to as the fluororesin organosol of the present invention) obtained by the above-described production method of the present invention, the fine particles of the fluorinated copolymer are the solvent as the dispersion medium. There is a state in which it is uniformly dispersed in the dispersion medium. In the fluororesin organosol of the present invention, the average particle diameter of the fine particles of the fluorinated copolymer is preferably 0.005 to 5 μm, and 0.005 to 2 μm, which is determined by dynamic light scattering at 25 ° C. Preferably, 0.01~Ιμιη is very good. Here, the number average particle diameter is a particle diameter which is the same as the ratio of the number of particles having a relatively small particle diameter to the number of particles having a relatively large particle diameter, as viewed from the average particle diameter obtained. In the fluororesin organosol of the present invention, the average particle diameter of the fine particles of the fluorinated copolymer can be uniform, transparent, and flat, as long as it is in the above range, for example, as a coating composition. A coating film excellent in adhesion. Further, the average particle diameter referred to in the present specification means an average primary particle diameter as long as it is not specifically stated in advance. [Coating composition] The coating composition of the present invention contains the fluororesin organic sol of the present invention as a main component. The coating composition of the present invention is a fluororesin organosol composed only of the fine particles of the fluorinated copolymer and the solvent, or a fluororesin having a fine particle of the fluorinated copolymer and the solvent and further containing an optional component. Sol. Further, it is also possible to add an optional component to the fluororesin organosol. The coating composition of the present invention contains an essential amount of the particles of the fluorocopolymer and the solvent which satisfies the above conditions to form an organosol as 32 201215634. Further, other optional components may be included as needed within the scope of not impairing the effects of the present invention. Examples of such an optional component include an antioxidant, a light stabilizer, an ultraviolet absorber, a crosslinking agent, a lubricant, a plasticizer, a viscosity-increasing agent, a dispersion stabilizer, a filler (filler), a reinforcing agent, and a pigment. Various additives such as dyes, flame retardants, and antistatic agents. Further, the content of the optional component is preferably 3% by mass or less and preferably 10% by mass or less based on the total amount of the coating composition. Further, when the coating composition of the present invention is used as a coating material, a non-fluororesin may be mixed as in the case of a general fluorine coating material. The Rinse component may be added to the raw material component in the step of preparing the fluororesin organosol, or may be added to the gas-organic organic conversion consisting only of the gas-containing hetero-hybrid and the melting axis. In addition, when the right side is added with a superfluous component, the fluororesin organic bath knee can be produced by adding a plurality of the above-mentioned (1) dissolution steps to the raw material component, and the same or other types can be added to the _lipid organic solvent. Any ingredient. The use of the coating composition of the present invention to form a copolymer coating film on a substrate can be carried out by a method of forming a coating film.溶剂 a step of applying a coating composition of the present invention to a substrate to form a coating process containing a six-coat film, and a solvent removing step of removing a solvent from the solvent-containing coating film to form a coating film containing no refrigerant The gas-containing copolymer coating film can be easily obtained from the coating material of the present invention. , ('Coating step) Coating step 33 using the coating film forming method of the coating composition of the present invention 201215634 In the step of 'coating the substrate to the substrate (4), there is no particular limitation' A general method can be used. As the coating method, for example, gravure printing, coating, dip coating, die coating, spray coating, electrostatic coating, brush application, screen printing, roll coating, spin coating, and the like can be given. In the coating step, the coating composition of the present invention is not necessarily coated in a state where the fluorine-containing copolymer has been dissolved in the solvent. The coated lysate of the present invention is a state in which the ruthenium copolymer is uniformly dispersed in a solvent, even if it is below the temperature at which the fluorinated copolymer which has been dispersed in the solvent is soluble. Therefore, in the coating step, the coating composition of the present invention can be applied to the substrate at a temperature lower than the temperature at which the fluorinated copolymer is dissolved in the solvent, and is described below. The solvent was removed at temperature (dry). The coating is carried out in such a manner that it is preferable from the viewpoint of the following point or workability. In the coating film forming method using the coating composition of the present invention, by adjusting the coating temperature or the drying temperature to a low temperature, a coating film which is uniform and flat can be obtained. The coating temperature in the above coating step varies depending on the coating composition to be used, but it is ～210. (: preferably, 0 to 130 ° C is better, 〇 ~ 50 c is very good. The above-mentioned coating temperature is lower than 〇t, the dispersion state of the fluorinated copolymer is not sufficient, and if it exceeds 21 〇. The solvent contained therein is easily volatilized, and there is a possibility that bubbles or the like may occur, which is not preferable. (Solvent removal step) The solvent removal step of the solvent is removed from the solvent-containing coating obtained in the above coating step. The step of preparing a solvent-free coating film. The solvent removal temperature in the solvent removal step, that is, the drying temperature of 34 201215634 degrees ' and 0 to 350 ° C ' is preferably ι 〇 270 ° C, 20 to 240. (: It is particularly preferable. If the temperature (drying temperature) at the time of solvent removal is lower than (TC, the solvent removal takes too long, and if it exceeds 350t: there is a possibility of coloring or decomposition, etc.) Further, after the coating composition is formed using the coating composition, heat treatment is preferably carried out at C. The heat treatment temperature is preferably 70 to 270. (:, more preferably 100 to 250 ° C. By heat treatment, The coating film can be made denser and the adhesion to the substrate can be improved. Thereby, the durability can be improved. The substrate can be more effectively protected. Thus, in the method for forming a fluorinated copolymer coated with the coating composition of the present invention, coating or drying of the coating composition is not required at a high temperature. Even if it is a material with low heat resistance such as plastic or paper or cloth, the coating film can be formed without causing decomposition or deformation of the substrate. Further, the material or shape of the substrate coated by the fluorocopolymer is used. It is not particularly limited and can be applied to metals such as iron, stainless steel, ingots, titanium, copper, silver, etc., glass, mirrors, synthetic quartz, etc., glass, bismuth, polycarbonate (pc), poly(terephthalic acid) Diester (PET), polymethyl methacrylate (PMMA), glass fiber reinforced plastic (FRP), polyvinyl chloride (pvc), fluorine tree moon a and other organic materials, stone, wood, Tao Jing, cloth, paper, etc. Here, in the method for forming a fluorinated copolymer coating using the coating composition of the present invention, the substrate may be pretreated for the purpose of improving the adhesion between the substrate and the coating film, etc. For example, Coating the substrate with a decane coupling agent or polyethyleneimine; using sandblasting, etc. The surface is subjected to a physical treatment, a treatment by a corona discharge, etc. 35 201215634 The fluororesin organosol obtained by the above-described production method of the present invention is used as a coating composition for a main component, and is coated thereon. The fluorocopolymer coating film and the article coated by the coating film can be provided on the substrate, and the fluorocopolymer coating film obtained by the coating film forming method can also be used. It is separated from the substrate and used as a film-like molded body. The PTFE film thus obtained, that is, the ETFE film, is thinner and more uniform than the ETFE film obtained by general melt molding. The thickness of the film-like molded body can be freely selected depending on the purpose. If a solution or a dispersion having a high concentration is used, a film having a thickness can be obtained, and if a solution or a dispersion having a low concentration is used, a thin coating film can be obtained. Further, by repeating the coating step a plurality of times, a film having a thicker thickness can be obtained. The use of the coating composition containing the fluororesin organosol as a main component of the present invention may be, for example, an optical fiber cladding material, a lens, a solar cell article, a display panel, a display article, or an optical disk. , semiconductor element, integrated circuit 1C, liquid crystal cell, printed circuit board, 1C card, photoconductor drum, film capacitor, glass window, resin window, various films, various sensors, antennas, covered wires, motors, power generation devices, etc. Protective coating agents, water repellent coating agents, low reflection coating agents, electrically insulating coating materials, charge retention layers, electric cars, buses, trucks, automobiles, ships, aircrafts, etc. in the field of optics, electrical and electronics Transportation machinery items, exterior walls, roofing materials, sealing parts, bridges or tunnels, civil engineering objects, syringes, straws, thermometers, beakers, cultures, ores, measuring cylinders, etc., in the field of chemistry 36 201215634 It can be used as a solder mask, solder resist, rubber, plastic, weathering, antifouling coating agent, fiber, cloth protective coating agent, (4) Anti-/3⁄4 coating agent, IC sealant, rust preventive paint, anti-resin adhesion H ink-adhering agent, separation film article, laminated steel plate primer, various adhesives, binders, and the like. In the case of the solar cell article, a protective coating agent such as a protective cover material such as a cover sheet made of glass or a resin, a transparent conductive member or a back sheet, a gas barrier layer, or a thin resin layer may be exemplified, and then Layers, etc. For the display items, the liquid crystal display panel, the electro-optical display panel, the electro-optic display panel, the transparent panel used for the touch panel, and the transparent member (glass substrate and Protective coating agent for resin substrate), antifouling coating agent, low reflection coating agent, supporting resin for sheet glass, and the like. In the case of the article for transporting equipment, an exterior member such as an exterior surface of a display machine surface material of a transport machine, an interior member body such as an instrument panel surface material, a protective coating agent such as a mirror, an antifouling coating agent, and the like may be mentioned. Low-reflection coating agent, laminated material for safety glass, and the like. The article for the separation membrane may be a functional layer such as a reverse osmosis membrane or a nanofiltration membrane, a functional layer for separating a gas separation membrane such as carbon dioxide or hydrogen, an adhesive for producing a membrane module, an antifouling coating agent, or the like. . Further, the coating composition of the present invention can be advantageously used as a material composition for producing an interlayer insulating film or a protective film in a semiconductor element or an integrated circuit device. When such a coating composition containing the fluororesin organosol of the present invention as a main component is used, the low water absorbability, low dielectric constant, and high heat resistance of the fluorinated copolymer 37 201215634 can be utilized. In the characteristics, a semiconductor element integrated circuit device having a fast response speed and a small number of erroneous actions is obtained. Further, the coating composition of the present invention can be advantageously used for protection of a sealing portion such as a protective coating agent for a collecting mirror, an antifouling coating agent, and a enamel resin for a concentrating mirror used for concentrating solar power generation. Coating agent, etc. In such a use, when the coating composition of the fluororesin organosol of the present invention as a main component is used, the properties of high fluororesin and low water absorption of the fluororesin can be utilized to obtain high durability without Maintenance of the power generation system. Further, the fluororesin organosol of the present invention can be used for applications such as an adhesive, a binder, and an additive for a toner, in addition to the application. EXAMPLES Hereinafter, examples of the invention will be described, but the invention is not limited to the examples. (Dissolution Procedure) The examples and comparative examples shown below were carried out by the methods described below unless otherwise specified. In a pressure-resistant reaction vessel made of boric acid glass having a thickness of 4 mm and an outer diameter of 30 mmi, a gas-containing copolymer, a solvent, and a stir-feed were placed. The relative 篁 of the surface-containing copolymer and the solvent is 5 to (7) mass % based on the amount of the fluorinated copolymer relative to the amount of the solvent. 〇Reaction Valley $ _ is heated by a lion bath and a temperature-controlled oil bath . ▲ It is determined by the fact that the money (four) is E dissolved. If the contents of the test tube are only transparent and uniform, the solution is judged to be in a dissolved state. 38 201215634 Microparticle Dispersion and Coating Film Evaluation Method The following examples were carried out to evaluate the fine particle dispersion and the coating film obtained in the examples. (1) ETFE microparticles in the number average particle size dispersion The number average particle diameter is measured by a particle size distribution (manufactured by Microtrac Corp., Nanotrac) at 25. (The measurement was carried out by the dynamic light scattering method under temperature conditions. The first particle diameter of the ETF^ particles was observed by a transmission electron microscope (TEM) (manufactured by JEOL Ltd.) to confirm the above-mentioned dynamics. The results obtained by the light scattering method were confirmed. (2) Film thickness The film thickness was measured by a stylus type surface shape measuring device (DEKTAK 3ST, manufactured by Sloan Co., Ltd.) for the coating film obtained by the insert and the bar coater. For the coating film obtained by the method other than the above, the film thickness was measured by a non-contact optical film measuring device (manufactured by Filmetrics, nimetrics F-20). (3) The sensibility of the adhesiveness is based on JIS. -K-5600 (1999). That is, using a cutting knife on the substrate to apply a straight line of 2 slits to the copolymer film, and making 100 checkerboard lattices on the board. On the grid, the adhesive tape was strongly adhered to the adhesive tape, and the end of the tape was peeled off instantaneously to observe the state of the film remaining on the surface of the skin without being peeled off. The evaluation was carried out according to the peeling state after 5 peeling tests. The next one is counted as ◦(Excellent), 9〇~51 The authors are △ (general), 50 to 0, and still count as χ (bad). [Example 1] In a pressure-resistant reaction vessel made of 30 mL of borosilicate glass, it was placed as a fluorine-containing total of 39 201215634 ETFE (molar ratio of repeating units mainly composed of monomers: repeating unit mainly composed of tetrafluoroethylene / repeating unit mainly composed of ethylene / 3,3,4,4,4-pentafluoro- 1-butene-based repeating unit / repeating unit mainly composed of isaconic anhydride = 57·5/39_9/2·3/0·3, melting point: 240 °C, hereinafter referred to as "ETFE1") 0.80 g, two Isopropyl ketone (R calculated according to the above formula (1) (hereinafter referred to as "R" only) = 0) 15.20 g ' While mixing and heating to 185 ° C while heating, a uniform and transparent solution was obtained. The test tube was gradually cooled to room temperature, and as a result, a gel of a uniform fluorinated copolymer (concentration of ETFE1 of 5% by mass) was obtained. The gel was obtained by TRIM FILMICS 40-40, manufactured by PRIMIX Co., Ltd., at 30 m. /second stirring for 2 minutes to obtain a uniform dispersion (the average particle diameter of the fluororesin organosol fluorocopolymer granules of the present invention, at 25 ° C, with dynamic light The number average particle diameter of the measurement was 58 nm. The dispersion was diluted to a mass of 〇.〇5. /〇, and observed by a transmission electron microscope, the primary particle diameter was 40 to 5 〇 nm. A transmission electron microscope (TEM) photograph (100,000 times) is shown in the figure. TEM phase #photo & towel's solvent is removed from the sample preparation, so it is estimated that the obtained photo is 'for example, the first As shown in the photograph of the figure, the particles of the gas-containing copolymer form aggregated particles. When observing the photo in Fig. 1, there is a large block in the photo, and it can be known that the _ sub is formed by the aggregation of each of her small particles. The lumpy particles represent aggregated particles of ETFE1, and each of the scorpion prefecture ETFs (four)-the remainder of the lumps. The above-mentioned observed average particle size 'means means that the particles of (4) are presumed to be so identifiable that the illusion-time is good in the division of the ship, or the reading of the second-particle aggregate 40 201215634 In the case where the secondary particles are present, the particle size of the particles corresponding to 50% of the total number of particles. The dispersion was applied to a glass substrate (glass glass, thickness 1 mm) by a bar coater at room temperature, and dried at room temperature. On a hot plate of Yu (10), it was heated for 3 minutes to obtain a glass substrate on which a film of ETFE1 was formed. The surface of the obtained film was observed with an optical microscope (100 times), and as a result, it was confirmed that it was a uniform and smooth film. Fig. 2 shows an optical microscope photograph (100 times) of the surface of the film composed of the ETFE1. Further, the film thickness was measured by a stylus type surface shape measuring device and found to be 3 μm. When the adhesion of the obtained ETFE1 film was evaluated, no peeling was observed at all. That is, the adhesion evaluation is 〇 (Ub [Example 2] The gas-solubilized organosol obtained in Example 1 was prepared at a room temperature in a ΡΕτ (polyethylene terephthalate) film (manufactured by Toyobo Co., Ltd.). C〇sm〇shine (registered trademark) A4300; thickness ι00μιη) was coated by a bar coater and dried at room temperature. It was heated on a hot plate of 10 Å > C for 3 minutes on a PET film. A film of £71^1 was formed thereon. The film thickness was measured by a stylus type surface shape measuring device and found to be 3 μm. When the adhesion between the obtained ETFm film and the pET film was evaluated, no peeling was observed at all. The adhesion was evaluated as 〇 (excellent). [Example 3] The fluororesin organosol obtained in Example 1 was coated on a aluminum plate (thickness 2'm) by a bar coater at room temperature. After drying, it was heated on a hot plate of 2 papers for 3 minutes to form a film of £17£1 on the aluminum plate. When the adhesion of the obtained ETFE1 film to the nameplate was evaluated, no separation was observed at all. The evaluation was 〇 (excellent). 201215634 [Example 4] As the fluorinated copolymer, 1.60 g of ETFE1 and 14.4 g of diisopropyl ketone were used. In the same manner as in Example 1, a gel obtained by obtaining a uniform fluorinated copolymer (concentration of ETFE1 of 10% by mass) was added. To the gel, dodecylamine (0.03 g) was added as a viscosity adjuster, and a planet was used. A ball mill (manufactured by Thinky, AWATORI ARE-310) was stirred at 2000 rpm for 1 minute. The obtained body was stirred at 30 m/sec for 2 minutes using a TK FILMICS 40-40 model manufactured by PRIMIX. A uniform dispersion (the fluororesin organosol of the present invention) was obtained, and a glass substrate having a film on which ETFE1 was formed on the surface was obtained in the same manner as in Example 1. The ETFE1 film obtained by optical microscopy was confirmed. The film was uniform and smooth, and the film thickness was measured by a stylus type surface shape measuring device, and it was 6 μm. When the adhesion of the obtained ETFE1 film was evaluated, "no peeling was observed at all. That is, the adhesion was evaluated as [Example 5] In the same manner as in Example 1, a uniform gel of ETFE1 (concentration of ETFE1 of 5% by mass) was obtained, and the gel was obtained by using Polytron PT10-35 manufactured by KINEMATIC Co., Ltd. 22000 rotation / minute mixing The mixture was mixed for 5 minutes to obtain a uniform dispersion (the fluororesin organosol of the present invention). A glass substrate having a film on which ETFE1 was formed on the surface was obtained in the same manner as in Example 1. The ETFE1 obtained by optical microscopy was observed. The film surface was confirmed to be a uniform and smooth film. (Chemical resistance protective coating) [Example 6] The coated ETFE1i aluminum substrate obtained in Example 3 (with protective coating 42 201215634 aluminum substrate) was immersed in IN hydrochloric acid, observe the change. The results are shown in Table 1 together with the results of the same treatment for the unprotected coated aluminum substrate. 43 201215634
试驗片 铭基板 1小時後腐蝕 蔓塗覆） 塗覆鋁基板 3小時後無變化 如表1料，藉由塗覆本㈣之氟樹脂有機溶膠，可使銘 极之耐藥品性顯著提升。 產業上可利用性 本發明之氟樹脂有機溶膠，在作A n± 卜馬塗覆用組成物使用 寺’可容易藉由塗佈形成腹E塗膜，適用於需要雜性、阻 燃性、耐藥品性、嚷性、低磨擦性、低介電特性、透明性 等之表面處理等的用途上。 之曰本專利申請 、及摘要之全部内 又’在此爰用2〇10年9月3曰申請 2010-198288號之說明書、申請專利範圍 容’並納入作為本發明說明書之揭示。 【圖式簡單説明】 第1圖係實施例i中製備之氟樹脂有機溶膠所含有的 ETFE微粒子之穿透式電子顯微鏡(TEM)相片萬倍）、 第2圖係利用實施例丨中製備之氟樹脂有機溶膠^獲得 的ETFE塗膜表面之光學顯微鏡相片（1〇〇倍）。 【主要元件符號說明】 (無） 44Test piece Ming substrate Corrosion after 1 hour vine coating) No change after coating for 3 hours As shown in Table 1, by applying the fluororesin organosol of (4), the chemical resistance of Mingji can be significantly improved. INDUSTRIAL APPLICABILITY The fluororesin organosol of the present invention can be easily formed into a film by forming an abdomen E coating film by using a composition of the A n± 卜马 coating composition, and is suitable for use in requiring impurities, flame retardancy, and Uses such as surface treatment such as chemical resistance, inertness, low friction, low dielectric properties, and transparency. The entire disclosure of the present application and the Abstract is hereby incorporated herein by reference in its entirety in its entirety in its entirety in its entirety in BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a transmission electron microscope (TEM) image of ETFE microparticles contained in the fluororesin organosol prepared in Example i, and Fig. 2 is prepared by using the examples. Optical micrograph of the surface of the ETFE coating obtained from the fluororesin organosol (1 〇〇). [Main component symbol description] (none) 44