201114857 六、發明說明： 【發明所屬之技術領域】 本發明係關於塗佈液。 【先前技術】 塗佈液’係使用在多孔質薄膜製造用或層合薄膜製造 用，此等薄膜’係將塗佈液塗佈於基材上所得。多孔質薄 膜或層合薄膜，例如用作爲電池的分隔器，可發揮防止正 極-負極間的短路等之功用。塗佈液爲人所知者有將聚合 物溶解於溶劑者，例如在日本特開平6-41298號公報（專 利文獻1)中，記載一種具有光學異向性之醯胺摻雜。 【發明內容】 然而，在塗佈上述具有光學異向性之醯胺摻雜所得之 多孔質薄膜中，薄膜的強度具有異向性，且塗佈性仍有改 善的空間。因此，本發明之目的在於提供一種適用於多孔 質薄膜或層合薄膜的製造用之實用性佳的塗佈液及其用途 〇 本發明係提供下列< 1 >〜< 1 2> » <1>一種塗佈液，其係於溶劑中溶解有100重量份的 含氮芳香族聚合物以及16〇重量份以上300重量份以下的 助溶劑者。 <2>如前述<1>之塗佈液，其中令含氮芳香族聚合物 、助溶劑及溶劑的合計重量爲100時之含氮芳香族聚合物 -5- 201114857 的重量爲〇·5以上3.5以下。 <3>如前述<1>或<2>之塗佈液，其中含氮芳香族聚合 物爲醯胺。 <4>如前述中任—項之塗佈液’其中助溶劑 爲鹼金屬的氯化物或鹼土類金屬的氯化物。 <5>如前述<4>之塗佈液’其中助溶劑爲氯化鋰或氯 化鈣。 <6>如前述<1>至<5>中任一項之塗佈液，其中溶劑爲 極性有機溶劑。 <7>如前述<1>至<6>中任一項之塗佈液’其中更含有 塡充材。 <8>如前述<7>之塗佈液，其中令含氮芳香族聚合物 的重量爲100時之塡充材的重量爲10以上500以下。 <9>如前述<1>至<8>中任一項之塗佈液，其中黏度爲 0.5 〜20Pa· s。 <10> —種多孔質薄膜的製造方法，其係依序包含下 列（la)、（2a)及（3a)之步驟。 (la)塗佈前述<1>至<9>中任一項之塗佈液而得塗佈膜 之步驟。 (2 a)使該塗佈膜中所含有之含氮芳香族聚合物析出而 得析出膜之步驟。 (3 a)去除該析出膜中所含有之助溶劑及溶劑而得多孔 質薄膜之步驟。 <U>—種層合薄膜的製造方法’其係依序包含下列 -6 - 201114857 (lb)、（2b)及（3b)之步驟。 (lb)將前述<1>至<9>中任一項之塗佈液塗佈於多孔質 基材而得塗佈膜之步驟。 (2b)使該塗佈膜中所含有之含氮芳香族聚合物析出而 得析出膜之步驟。 (3b)去除該析出膜中所含有之助溶劑及溶劑而得層合 薄膜之步驟。 <12>—種電池，其係具有藉由前述<10>之製造方法 所得的多孔質薄膜或是藉由前述<11>之製造方法所得的 層合薄膜作爲分隔器。 根據本發明，可賦予一種薄膜的強度及熱收縮率經改 良之多孔質薄膜，且可得不易偏往單向裂開之薄膜。此外 ’本發明之塗佈液，其塗佈性佳，尤其當添加塡充材時， 亦可緩和黏度的急遽上升，例如在加快塗佈液的塗佈速度 時，更能夠抑制所得之多孔質薄膜或層合薄膜的缺陷產生 等，其實用性佳。 【實施方式】 本發明之塗佈液，係於溶劑中溶解有100重量份的含 氮芳香族聚合物以及160重量份以上300重量份以下的助 溶劑之塗佈液。當塗佈液的助溶劑較少時，就塗佈液之流 動性的觀點來看較不佳，當較多時，就塗佈液之保存安定 性的觀點來看較不佳。本發明中，較佳之助溶劑的量，相 對於含氮芳香族聚合物1〇〇重量份爲17〇重量份以上250 201114857 重量份以下，尤佳爲180重量份以上220重量份以下。 本發明中’含氮芳香族聚合物可列舉出醯胺（對醯胺 、間醯胺）、芳香族聚醯亞胺、芳香族聚醯胺醯亞胺等， 當含氮芳香族聚合物爲醯胺，尤其是對醯胺時，可較佳地 運用本發明。 前述對醯胺，係藉由對位配向芳香族二胺與對位配向 芳香族二羧酸鹵化物的縮聚合所得者，且實質上由醯胺鍵 以芳香族環的對位或是以此爲準之配向位（例如4，4 ·-聯苯 、1，5-萘、2,6-萘等之往相反方向爲同軸或平行地延伸之 配向位）所鍵結之重複單位而構成者。具體而言，可例示 出聚（對苯二甲醯對苯二胺）、聚（對苯甲醯胺）、聚（4,41-苯 甲醯胺苯對苯二甲醯胺）、聚（對苯-4，4’·聯苯二羧酸醯胺） 、聚（對苯-2，6-萘二羧酸醯胺）、聚（2-氯-對苯二甲醯對苯 二胺）、對苯二甲醯對苯二胺/2,6-二氯對苯二甲醯對苯二 胺共聚物等之對位配向型或具有以對位配向爲準之構造之 對醯胺。 前述芳香族聚醯亞胺，較佳爲以芳香族二酸酐與芳香 族二胺之縮聚合所製造出之全芳香族聚醯亞胺。該二酸酐 的具體例，可列舉出焦蜜石酸二酐、3,3’，4,4’-二苯基颯四 羧酸二酐、3,3'，4,4'-二苯基酮四羧酸二酐、2,2’-雙（3,4-二羧苯基）六氟丙烷、3,3’，4,4’-聯苯四羧酸二酐等。該芳 香族二胺的具體例，可列舉出氧化二苯胺、對苯二胺、二 苯基酮二胺、3,3，-亞甲二胺、3,3、二胺基二苯基酮' 3,3'-二胺基二苯基楓、1，5’-萘二胺等。此外，較佳爲使 -8- 201114857 用可溶於溶劑之芳香族聚醯亞胺。此般聚醯 列舉出二苯基颯四羧酸二酐與芳 縮合物的聚醯亞胺。 前述芳香族聚醯胺醯亞胺，可列舉出使 酸及芳香族二異氰酸酯並將此等進行縮聚合 使用芳香族二酸酐及芳香族二異氰酸酯並將 合所得者。芳香族二羧酸的具體例，可列舉 、對苯二甲酸等。芳香族二酸酐的具體例， 三甲酸酐等。芳香族二異氰酸酯的具體它 4,4'-二苯基甲烷二異氰酸酯、2，4-甲苯二異 甲苯二異氰酸酯、鄰三苯基甲烷二異氰酸 diisocyanate)、間二甲苯二異氰酸酯等。 本發明中，助溶劑可列舉出鹼金屬的溴 金屬的溴化物、鹼金屬的氯化物及鹼土類金 較佳爲鹼金屬的氯化物或鹼土類金屬的氯化 之溶解性的觀點來看，尤佳爲氯化鋰或氯化 因應所用之含氮芳香族聚合物的種類來選擇 本發明中，溶劑可列舉出有機溶劑，就 香族聚合物之溶解性的觀點來看，較佳爲極 極性有機溶劑可列舉出極性醯胺系溶劑、極 具體而言，可列舉出Ν,Ν-二甲基甲醯胺、] 醯胺、Ν -甲基-2-咯烷酮 '四甲基脲。 本發明之塗佈液中，令含氮芳香族聚合 溶劑的合計重量爲100時之含氮芳香族聚合 亞胺，例如可 香族二胺之聚 用芳香族二羧 所得者，以及 此等進行縮聚 出間苯二甲酸 可列舉出偏苯 可，可列舉出 氰酸酯、2,6-醋（orthotrilan 化物、鹼土類 屬的氯化物， 物，就對溶劑 鈣。助溶劑可 使用。 相對於含氮芳 性有機溶劑。 性脲系溶劑， N，N-二甲基乙 物、助溶劑及 物的重量，考 -9 - 201114857 量到塗佈液的流動性提升、多孔質薄膜的生產性等，較佳 爲〇 · 5以上3 . 5以下，尤佳爲0.8以上2.0以下。 此外，本發明之塗佈液更可含有塡充材。藉由使塗佈 液更含有塡充材，亦有能夠對所得之多孔質薄膜的空隙（ 空隙率、空隙尺寸等）進行精密控制時。此外，塡充材的 材質爲有機粉末、無機粉末或此等之混合物，可選擇使用 對前述溶劑爲難溶性者。 作爲塡充材之有機粉末，例如可列舉出由苯乙烯、乙 烯酮、丙烯腈、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基 丙烯酸縮水甘油酯、丙烯酸縮水甘油酯、丙烯酸甲酯等之 單獨或2種以上的共聚物、聚四氟乙烯、四氟乙烯-六氟 丙烯共聚物、四氟乙烯-乙烯共聚物、聚偏二氟乙烯等之 氟系樹脂；三聚氰胺樹脂；脲樹脂；聚烯烴；聚甲基丙烯 酸酯等之有機物所構成之粉末。該有機粉末，可單獨使用 或混合2種以上使用。此等有機粉末中，就化學安定性的 觀點來看，較佳爲聚四氟乙烯粉末。 作爲塡充材之無機粉末，例如可列舉出由金屬氧化物 、金屬氮化物、金屬碳化物、金屬氫氧化物、碳酸鹽、硫 酸鹽等之無機物所構成之粉末，此等之中，更以使用由導 電性低的無機物所成之粉末爲佳。具體地例示時，可列舉 出由氧化鋁、二氧化矽、二氧化鈦、硫酸鋇或碳酸鈣所構 成之粉末。該無機粉末，可單獨使用或混合2種以上使用 。此等無機粉末中，就化學安定性的觀點來看，較佳爲氧 化鋁粉末。在此，尤佳爲構成塡充材之所有粒子爲氧化鋁 -10- 201114857 粒子，更佳爲構成塡充材之所有粒子爲氧化鋁粒子，且其 一部分或全部爲大致呈球狀之氧化鋁粒子。 構成塡充材之粒子的形狀，可列舉出大致呈球狀、板 狀、柱狀、針狀、細絲狀、纖維狀等，可使用任一種粒子 ，但就容易形成均一的孔來看，較佳爲大致呈球狀之粒子 。大致呈球狀之粒子，可列舉出粒子的長寬比（粒子的長 徑/粒子的短徑）爲1以上1 · 5以下之粒子。粒子的長寬比 可藉由電子顯微鏡照片來測定。 構成塡充材之粒子的大小，雖因所得之多孔質薄膜的 用途而有所不同，但當將多孔質薄膜用作爲電池分隔器時 ’就維持平滑性的觀點來看，構成塡充材之粒子的平均粒 徑較佳爲Ο.ΟΙμηι以上Ιμηι以下。 本發明之塗佈液，含有塡充材時之塡充材的重量，可 藉由塡充材之材質的比重來適當地設定，令含氮芳香族聚 合物的重量爲100時之塡充材的重量，一般爲1以上 1500以下’較佳爲10以上5〇〇以下，尤佳爲1〇〇以上 300以下。塡充材，較佳爲分散於在溶劑中溶解有含氮芳 香族聚合物及助溶劑之塗佈液中使用，分散可使用壓力式 分散機（戈林均質機、奈米加工機）等來進行。 此外’本發明之塗佈液的黏度爲0.5〜20Pa· s者， 就使塗佈性變得良好之觀點來看係較佳。尤佳之塗佈液的 黏度爲〇 · 5〜1 5 P a · s。藉由使塗佈性變得更良好，可加 快塗佈液的塗佈速度，且更能夠抑制所得之多孔質薄膜的 缺陷產生。 -11 - 201114857 接著說明使用上述塗佈液來製造多孔質薄膜之方法^ 本發明中，多孔質薄膜，可藉由依序包含下列（la)、（2 a) 及（3 a)之步驟的製造方法來製造出》 (1 a)塗佈上述塗佈液而得塗佈膜之步驟。 (2a)使該塗佈膜中所含有之含氮芳香族聚合物析出而 得析出膜之步驟。 (3 a)去除該析出膜中所含有之助溶劑及溶劑而得多孔 質薄膜之步驟。 步驟（la)中，係將本發明之塗佈液塗佈於底膜、鋼帶 、輥、轉筒上等之基材而得塗佈膜。底膜例如可列舉出聚 對苯二甲酸乙二酯、經脫模處理之紙等。此外，亦可塗佈 於經鏡面加工之具耐蝕性的鋼帶上，或是塗佈於經鏡面加 工之具耐蝕性的輥或轉筒上。塗佈的方法，例如可列舉出 刀、刮刀、棒、凹版、壓模等之塗佈方法棒、刀等之塗佈 較爲簡便，故較佳。此外，塗佈可進行2次以上。 步驟（2 a)中，係使步驟（la)中所得之塗佈膜中所含有 之含氮芳香族聚合物析出而得析出膜。在此，析出例如係 將塗佈膜放置在2〇t以上的溫度下經控制濕度的環境氣 中，使含氮芳香族聚合物析出並浸漬於凝固液中而得析出 膜。或者是，亦可將塗佈膜浸漬於凝固液中，同時進行含 氮芳香族聚合物的析出與凝固而得析出膜。此外，爲了均 一且快速地進行析出，可預先將水等之不良溶劑添加於塗 佈液。前述凝固液可使用水系溶液或醇系溶液等。 步驟（2 a)中，可藉由使塗佈膜中所含有之溶劑的一部 -12- 201114857 分或全部蒸發’使含氮芳香族聚合物析出而得析出膜，此 時可得半乾燥或經乾燥之析出膜。 步驟（3 a)中，係從析出膜中去除助溶劑及溶劑而得多 孔質薄膜。溶劑的去除方法，可藉由使溶劑的一部分或全 部蒸發來進行’或是以可溶解水、水系溶液或醇系溶液等 之塗佈 '液的調製中所用之溶劑的溶劑，洗淨析出膜以去除 溶劑。當使用水來去除時，爲了抑制金屬離子的混入，較 佳爲使用離子交換水。此外，在含有一定濃度之塗佈液的 調製中所用之溶劑的水溶液中洗淨析出膜厚，較加更進行 水洗。此外，助溶劑的去除方法，可列舉出以水、水系溶 液或醇系溶液等來進行洗淨去除之方法。當使用水來去除 時，爲了抑制金屬離子的混入.，較佳爲使用離子交換水。 此外，助溶劑的去除可與上述溶劑的去除同時進行，或是 藉由乾燥等先去除溶劑後，再進行助溶劑的去除。 步驟（3 a)中，所得之多孔質薄膜，可因應必要，藉由 加熱乾燥、風乾等來進行乾燥，或是從基材中剝離。 此外，本發明中，層合薄膜可藉由依序包含下列（lb) 、（2b)及（3b)之步驟的製造方法來製造出。 (1 b)將上述塗佈液塗佈於多孔質基材而得塗佈膜之步 驟。 (2b)使該塗佈膜中所含有之含氮芳香族聚合物析出而 得析出膜之步驟。201114857 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a coating liquid. [Prior Art] The coating liquid is used for the production of a porous film or a laminated film, and the film is obtained by applying a coating liquid onto a substrate. The porous film or the laminated film can be used as a separator for a battery to prevent the short circuit between the positive electrode and the negative electrode. In the case of the coating liquid, it is known that the polymer is dissolved in a solvent. For example, JP-A-6-41298 (Patent Document 1) discloses a phthalamide doping having optical anisotropy. SUMMARY OF THE INVENTION However, in the porous film obtained by coating the above-mentioned optically anisotropic guanamine doping, the strength of the film is anisotropic, and there is still room for improvement in coatability. Accordingly, it is an object of the present invention to provide a coating liquid which is suitable for use in the production of a porous film or a laminated film and its use. The present invention provides the following <1>~<1 2><1> A coating liquid obtained by dissolving 100 parts by weight of a nitrogen-containing aromatic polymer and 16 parts by weight or more and 300 parts by weight or less of a co-solvent in a solvent. <2> The coating liquid of the above <1>, wherein the weight of the nitrogen-containing aromatic polymer-5-201114857 when the total weight of the nitrogen-containing aromatic polymer, the co-solvent and the solvent is 100 is 〇· 5 or more and 3.5 or less. <3> The coating liquid of <1> or <2>, wherein the nitrogen-containing aromatic polymer is decylamine. <4> The coating liquid of the above-mentioned item wherein the co-solvent is an alkali metal chloride or an alkaline earth metal chloride. <5> The coating liquid of the above <4> wherein the co-solvent is lithium chloride or calcium chloride. The coating liquid according to any one of the above-mentioned <1> to <5>, wherein the solvent is a polar organic solvent. The coating liquid of any one of the above-mentioned <1> to <6> further contains an enamel material. <8> The coating liquid according to the above <7>, wherein the weight of the cerium filling material when the weight of the nitrogen-containing aromatic polymer is 100 is 10 or more and 500 or less. The coating liquid according to any one of the above-mentioned <1> to <8>, wherein the viscosity is 0.5 to 20 Pa·s. <10> A method for producing a porous film comprising the steps (la), (2a) and (3a) below. (la) A step of coating a coating liquid according to any one of the above <1> to <9> to obtain a coating film. (2a) A step of precipitating a film containing a nitrogen-containing aromatic polymer contained in the coating film to form a film. (3 a) A step of removing a co-solvent and a solvent contained in the precipitated film to obtain a porous film. <U> - Method for producing a laminated film' The steps of the following -6 - 201114857 (lb), (2b) and (3b) are sequentially included. (lb) The step of applying a coating liquid of any one of the above <1> to <9> to a porous substrate to obtain a coating film. (2b) A step of precipitating a nitrogen-containing aromatic polymer contained in the coating film to form a film. (3b) A step of removing the co-solvent and the solvent contained in the precipitated film to obtain a laminated film. <12> A battery comprising a porous film obtained by the above-described method of <10> or a laminated film obtained by the above-mentioned <11> manufacturing method as a separator. According to the present invention, it is possible to impart a porous film whose strength and heat shrinkage ratio are improved, and a film which is not easily biased toward unidirectional cracking. Further, the coating liquid of the present invention has excellent coatability, and particularly when the ruthenium filler is added, the viscosity can be gradually increased. For example, when the coating speed of the coating liquid is increased, the obtained porous material can be more suppressed. Defects such as film or laminate film are produced, and their practicability is good. [Embodiment] The coating liquid of the present invention is a coating liquid in which 100 parts by weight of a nitrogen-containing aromatic polymer and 160 parts by weight or more and 300 parts by weight or less of a co-solvent are dissolved in a solvent. When the amount of the co-solvent of the coating liquid is small, it is less preferable from the viewpoint of the fluidity of the coating liquid, and when it is large, it is not preferable from the viewpoint of the storage stability of the coating liquid. In the present invention, the amount of the co-solvent is preferably 17 parts by weight or more and 250 201114857 parts by weight or less, more preferably 180 parts by weight or more and 220 parts by weight or less based on 1 part by weight of the nitrogen-containing aromatic polymer. In the present invention, the nitrogen-containing aromatic polymer may, for example, be amidoxime (p-guanamine or m-decylamine), an aromatic polyimide, an aromatic polyamidimide or the like, and when the nitrogen-containing aromatic polymer is The present invention is preferably used in the case of guanamine, especially guanamine. The above-mentioned p-nonylamine is obtained by polycondensation of a para-oriented aromatic diamine and a para-oriented aromatic dicarboxylic acid halide, and substantially consists of a transposition of an aromatic ring by a guanamine bond or The alignment unit (for example, 4,4 ·-biphenyl, 1,5-naphthalene, 2,6-naphthalene, etc., which is an alignment direction extending coaxially or in parallel in the opposite direction) constitutes a repeating unit of the bond . Specifically, poly(p-xylylene terephthalamide), poly(p-benzamide), poly(4,41-benzamide-p-xylyleneamine), poly(() P-Benzene-4,4'-biphenyldicarboxylate, poly(p-phenylene-2,6-naphthalene dicarboxylate), poly(2-chloro-p-phenylene terephthalamide) And p-phthalamide having a para-alignment type of p-xylylene p-phenylenediamine/2,6-dichloro-p-xylylene terephthalate copolymer or the like having a structure in which the alignment is correct. The aromatic polyimine is preferably a wholly aromatic polyimine produced by polycondensation of an aromatic dianhydride and an aromatic diamine. Specific examples of the dianhydride include pyromellitic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl group. Ketone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the like. Specific examples of the aromatic diamine include diphenylamine oxide, p-phenylenediamine, diphenyl ketone diamine, 3,3,-methylenediamine, 3,3, and diaminodiphenyl ketone. 3,3'-diaminodiphenyl maple, 1,5'-naphthalenediamine, and the like. Further, it is preferred to use a solvent-soluble aromatic polyimine in -8-201114857. Polycondensation of diphenylphosphonium tetracarboxylic dianhydride and an aromatic condensate is exemplified. Examples of the aromatic polyamidoximine include an acid and an aromatic diisocyanate, and these are subjected to polycondensation polymerization using an aromatic dianhydride and an aromatic diisocyanate. Specific examples of the aromatic dicarboxylic acid include terephthalic acid and the like. Specific examples of the aromatic dianhydride include tricarboxylic anhydride and the like. The aromatic diisocyanate is specifically 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate diisocyanate, o-triphenylmethane diisocyanate, or m-xylene diisocyanate. In the present invention, the bromide of the bromine metal of the alkali metal, the chloride of the alkali metal, and the alkaline earth gold are preferably those of the alkali metal chloride or the alkaline earth metal. In particular, in the present invention, lithium chloride or a type of nitrogen-containing aromatic polymer used for chlorination is selected, and the solvent is exemplified by an organic solvent. From the viewpoint of solubility of the aromatic polymer, it is preferably extremely polar. The polar organic solvent may, for example, be a polar amide-based solvent, and more specifically, hydrazine, hydrazine-dimethylformamide, decylamine, hydrazine-methyl-2-pyrrolidone-tetramethylurea . In the coating liquid of the present invention, the nitrogen-containing aromatic polymeric imine having a total weight of the nitrogen-containing aromatic polymerization solvent of 100, for example, an aromatic dicarboxylic acid obtained by agglomerating a diamine, and the like Examples of the polycondensation of isophthalic acid include a benzoic acid ester, a cyanate ester, a 2,6-vinegar (orthotrilan compound, an alkaline earth chloride), and a solvent calcium. A co-solvent can be used. Nitrogen-containing aromatic organic solvent. Urea-based solvent, N, N-dimethylethane, co-solvent and weight of the test, -9 - 201114857 The amount of the coating liquid is improved, and the productivity of the porous film is improved. The coating liquid of the present invention may further contain a ceramium filling material. Further, the coating liquid further contains a cerium filling material, and is preferably 5% or more and 5% or less. When the void (void ratio, void size, etc.) of the obtained porous film can be precisely controlled, the material of the ruthenium material is an organic powder, an inorganic powder or a mixture thereof, and it is optional to use a solvent which is poorly soluble. As a filling material Examples of the powder include styrene, ketene, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, methyl acrylate, and the like, alone or in combination of two or more. Copolymer, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, fluorine-based resin such as polyvinylidene fluoride; melamine resin; urea resin; polyolefin; polymethyl A powder composed of an organic substance such as acrylate, and the organic powder may be used singly or in combination of two or more. Among these organic powders, polytetrafluoroethylene powder is preferred from the viewpoint of chemical stability. The inorganic powder of the filler may, for example, be a powder composed of an inorganic substance such as a metal oxide, a metal nitride, a metal carbide, a metal hydroxide, a carbonate or a sulfate, and among these, A powder made of an inorganic material having low conductivity is preferred. Specifically, it may be exemplified by alumina, ceria, titania, barium sulfate or calcium carbonate. The inorganic powder may be used singly or in combination of two or more. Among these inorganic powders, alumina powder is preferred from the viewpoint of chemical stability. The particles are alumina-10-201114857 particles, and more preferably all particles constituting the cerium material are alumina particles, and some or all of them are substantially spherical alumina particles. The shape of the particles constituting the cerium material can be Although it is a substantially spherical shape, a plate shape, a column shape, a needle shape, a filament shape, a fiber shape, etc., any particle can be used, but it is easy to form a uniform hole, and it is preferable that it is a substantially spherical particle. The particles having a substantially spherical shape include particles having an aspect ratio (longitudinal diameter of the particles/short diameter of the particles) of 1 or more and 1.5 or less. The aspect ratio of the particles can be measured by an electron micrograph. The size of the particles constituting the ruthenium material differs depending on the use of the porous film obtained. However, when the porous film is used as a battery separator, the sap of the sputum is formed from the viewpoint of maintaining smoothness. The average particle diameter of the particles is preferably Ο.ΟΙμηι or more Ιμηι or less. In the coating liquid of the present invention, the weight of the ruthenium filler in the case of containing the ruthenium filler material can be appropriately set by the specific gravity of the material of the ruthenium filler material, and the weight of the nitrogen-containing aromatic polymer is 100 塡. The weight is generally 1 or more and 1,500 or less', preferably 10 or more and 5 or less, and more preferably 1 to 300. The ruthenium filler is preferably used in a coating liquid in which a nitrogen-containing aromatic polymer and a co-solvent are dissolved in a solvent, and a dispersion type disperser (Goring homogenizer, nano processing machine) or the like can be used for dispersion. get on. Further, the viscosity of the coating liquid of the present invention is preferably 0.5 to 20 Pa·s, which is preferable from the viewpoint of improving coatability. The viscosity of the coating solution of Optima is 〇 · 5~1 5 P a · s. By improving the coatability, the coating speed of the coating liquid can be increased, and the occurrence of defects of the obtained porous film can be further suppressed. -11 - 201114857 Next, a method of producing a porous film using the above coating liquid will be described. In the present invention, the porous film can be produced by sequentially including the following steps (la), (2 a) and (3 a). The method is to produce a step of coating a coating film by coating the above coating liquid. (2a) A step of precipitating a nitrogen-containing aromatic polymer contained in the coating film to form a film. (3 a) A step of removing a co-solvent and a solvent contained in the precipitated film to obtain a porous film. In the step (la), the coating liquid of the present invention is applied onto a substrate such as a base film, a steel strip, a roll or a drum to obtain a coating film. Examples of the base film include polyethylene terephthalate, release-treated paper, and the like. It can also be applied to mirror-treated corrosion-resistant steel strips or to mirror-resistant, corrosion-resistant rolls or drums. The coating method is preferably a coating method such as a knife, a doctor blade, a bar, a gravure, a stamper, or the like, and the coating of a knife or the like is relatively simple. Further, the coating can be carried out twice or more. In the step (2a), the nitrogen-containing aromatic polymer contained in the coating film obtained in the step (la) is precipitated to obtain a precipitated film. Here, for example, the coating film is placed in an atmosphere having a controlled humidity at a temperature of 2 Torr or more, and a nitrogen-containing aromatic polymer is precipitated and immersed in a coagulating liquid to obtain a precipitated film. Alternatively, the coating film may be immersed in the coagulating liquid, and the precipitation and solidification of the nitrogen-containing aromatic polymer may be carried out to obtain a precipitated film. Further, in order to carry out the precipitation uniformly and rapidly, a poor solvent such as water may be added to the coating liquid in advance. As the coagulation liquid, an aqueous solution, an alcohol solution or the like can be used. In the step (2a), the film can be precipitated by precipitating a part of -12-201114857 of the solvent contained in the coating film to precipitate a nitrogen-containing aromatic polymer, thereby obtaining a semi-drying state. Or a dried precipitated film. In the step (3a), a co-solvent and a solvent are removed from the precipitated film to form a porous film. The method of removing the solvent can be carried out by evaporating a part or all of the solvent, or by washing the solvent with a solvent which can dissolve the solvent used in the preparation of the coating liquid such as water, an aqueous solution or an alcohol solution. To remove the solvent. When water is used for removal, it is preferred to use ion-exchanged water in order to suppress the incorporation of metal ions. Further, the film thickness is washed out in an aqueous solution of a solvent used for preparation of a coating liquid having a certain concentration, and is further washed with water. Further, as a method of removing the co-solvent, a method of washing and removing with water, an aqueous solution or an alcohol-based solution may be mentioned. When water is used for removal, ion exchange water is preferably used in order to suppress the incorporation of metal ions. Further, the removal of the co-solvent may be carried out simultaneously with the removal of the above solvent, or the removal of the solvent may be carried out by drying or the like, followed by removal of the co-solvent. In the step (3a), the obtained porous film may be dried by heating, air drying, or the like as necessary, or may be peeled off from the substrate. Further, in the present invention, the laminated film can be produced by a production method comprising the following steps (lb), (2b) and (3b). (1b) A step of applying the coating liquid to a porous substrate to obtain a coating film. (2b) A step of precipitating a nitrogen-containing aromatic polymer contained in the coating film to form a film.
(3b)去除該析出膜中所含有之助溶劑及溶劑而得層合 薄膜之步驟。 S -13- 201114857 亦即’本發明中，層合薄膜係在多孔質基材上層合有 上述多孔質薄膜之層合多孔質薄膜。 步驟Ub)，除了使用多孔質基材來取代步驟（la)的基 材之外’其他與步驟（la)相同。多孔質基材可使用織物' 不織布 '紙或薄膜狀者，均爲薄片狀。此外，亦可使用上 述多孔質薄膜。步驟（lb)中，塗佈，可藉由將塗佈液塗佈 於輥或轉筒上，然後再接觸於多孔質基材來進行。 此外，上述步驟（2b)可與上述步驟（2a)同樣地進行， 上述步驟（3b)可與上述步驟（3a)同樣地進行。此外，步驟 (3b)中，·所得之層合薄膜，亦可因應必要，藉由加熱乾燥 、風乾等來進行乾燥。此外，亦可將塗佈液塗佈於多孔質 基材的雙面而得層合薄膜。 本發明中，所得之多孔質薄膜或層合薄膜，由於含有 含氮芳香族聚合物，所以至200°C爲止幾乎無強度劣化， 且在3 00°C爲止可保持形態，爲耐熱性極佳之薄膜，尤其 有用於作爲鋰離子二次電池、鋰聚合物二次電池等之非水 電解質二次電池的分隔器，並且亦可充分使用於水系電解 質二次電池用、非水電解質一次電池用、電容器用的分隔 器。 此外，本發明中，當將層合薄膜用作爲鋰二次電池等 之非水電解質二次電池用的分隔器時，前述多孔質基材較 佳爲含有熱可塑性樹脂。非水電解質二次電池中，由於正 極-負極間的短路等原因使異常電流於電池內流通時，較 佳爲具有可阻斷電流以阻止（關閉）過大電流的流通之功能 -14- 201114857 ，藉由使層合薄膜的多孔質基材含有熱可 池溫度超過一般的使用溫度時，可藉由該 軟化來阻塞層合薄膜的空隙，而能夠將電 熱可塑性樹脂，可列舉出聚乙烯、聚 樹脂、熱可塑性聚胺基甲酸酯樹脂，亦可 以上的混合物。就在更低溫下軟化使其關 較佳爲含有聚乙烯。聚乙烯，具體而言可 乙烯、高密度聚乙烯、線狀低密度聚乙烯 可列舉出分子量爲100萬以上之超高分子 爲提高多孔質基材的穿刺強度之觀點來看 較佳爲含有超高分子量聚乙烯。此外，亦 較佳是含有由低分子量（重量平均分子量 烯所形成之蠟之情形。 此外，當將本發明之多孔質薄膜或層 池等的分隔器時，就離子穿透性之觀點來 據加雷法所測得的透氣度，一般約爲2(L· ，較佳爲50〜300秒/100cc，更佳爲50~ 此外，分隔器的空隙率，一般爲20〜90 3〇〜80體積％，尤佳爲40〜70體積％。 厚度，就使電池等之體積能量密度上升以 觀點來看，較佳係在保持機械強度下盡可 爲5〜200μηι，較佳爲5〜40μιη，尤佳爲 ，分隔器之細孔的大小，一般爲3μιη以· 以下。 塑性樹脂，當電 熱可塑性樹脂的 池關閉。 丙烯等之聚烯烴 使用此等之2種 閉之觀點來看， 列舉出低密度聚 等之聚乙烯，亦 量聚乙烯。就更 ，熱可塑性樹脂 有熱可塑性樹脂 I萬以下）的聚乙 合薄膜用作爲電 看，分隔器之依 -2000 秒 /100cc 200 秒/100cco 體積％，較佳爲 此外，分隔器的 降低內部電阻之 能的薄化，一般 5〜3 0 μ m °此外 F，較佳爲1 μ m -15- 201114857 接著以非水電解質二次電池之鋰二次電池爲例，說明 具有本發明之多孔質薄膜或層合薄膜作爲分隔器之電池。 鋰二次電池的製造，可使用一般所知的技術。亦即， 例如將正極、負極、分隔器予以層合並捲繞所得之電極群 ，收納於電池罐等之容器內，並將電池液含浸於電極群而 製造出。 前述電極群的形狀，例如可列舉出將該電極群往垂直 於捲繞軸之方向切斷時之剖面，成爲圓、橢圓、長方形、 去角的長方形等之形狀。此外，電池的形狀，例如可列舉 出紙電池型、硬幣電池型、圓筒型、方型等形狀。 前述正極，一般係使用將含有正極活性物質、導電劑 及黏結劑之正極用電極合劑塗佈於正極集電體者。正極用 電極合劑，較佳係含有可將鋰離子進行摻雜•脫摻雜之材 料作爲正極活性物質，並含有碳材料作爲導電劑，含有熱 可塑性樹脂作爲黏結劑。 前述正極活性物質，具體而言可列舉出含有選自V、 Mn、Fe、Co、Ni、Cr及Ti之至少1種過渡金屬元素， 以及Li、Na等之鹼金屬元素之金屬複合氧化物，較佳爲 以a-NaFe02型構造爲母體之複合氧化物，就平均放電電 位較高之觀點來看，尤佳爲鈷酸鋰、鎳酸鋰 '鎳酸鋰之鎳 的一部分經Mn、Co等其他元素所取代之複合氧化物。此 外，亦可列舉出以鋰錳螺旋等之螺旋構造爲母體之複合氧 化物。 前述黏結劑可列舉出熱可塑性樹脂，具體而言可列舉 -16- 201114857 出聚偏二氟乙烯、偏二氟乙烯的共聚物、聚四氟乙烯、四 氟乙稀-六氟丙烯的共聚物、四氟乙烯-全氟烷基乙烯醚的 共聚物、'乙烯-四氟乙烯的共聚物、偏二氟乙烯—六氟丙 稀-四氟乙烯共聚物 '熱可塑性聚醯亞胺、羧甲基纖維素 、聚乙烯、聚丙烯等。 前述導電劑可列舉出碳材料，具體而言可列舉出天然 石墨、人造石墨、煤焦類、碳黑等，此等可混合2種以上 而使用。 前述正極集電體，可列舉出A1、不鏽鋼等，就輕量 、便宜 '加工容易性之觀點來看，較佳爲A1。將前述正極 用電極合劑塗佈於正極集電體之方法，可列舉出依據加壓成 型之方法’以及使用溶劑等將正極用電極合劑進行膏化，塗 佈於正極集電體上並進行乾燥後，進行模壓而壓著之方法等 〇 前述負極，只要在較正極還低的電位下可將鋰離子進 行摻雜•脫摻雜者即可，可列舉出將含有負極材料之負極 合劑撐持於負極集電體之電極，或是單獨由負極材料所構 成之電極。負極材料可列舉出碳材料、硫族元素化合物（ 氧化物、硫化物等）、氮化物、金屬或合金，且在較正極 還低的電位下可將鋰離子進行摻雜•脫摻雜之材料。此外 ’可混合此等負極材料而使用。 關於前述負極材料，係例示如下。前述負極材料，具 體而言可列舉出天然石墨、人造石墨等之石墨、煤焦類、 碳黑 '熱分解碳類、碳纖維、有機高分子燒結體等。前述 -17- 201114857 氧化物，具體而言可列舉出Si02、SiO等之以式SiOx(在 此，X爲正的實數）所表示之矽的氧化物；Ti〇2 ' TiO等之 以式TiOx(在此，X爲正的實數）所表示之鈦的氧化物； V205、V〇2等之以式V〇x(在此，X爲正的實數）所表示之 釩的氧化物；Fe3〇4、Fe2〇3、FeO等之以式FeOx(在此，X 爲正的實數）所表示之鐵的氧化物；Sn02、SnO等之以式 SnOx(在此，X爲正的實數）所表示之錫的氧化物；W03、 W02等之以一般式WOx(在此，X爲正的實數）所表示之鎢 的氧化物；Li4Ti5012、LiV02(例如 LiuVuOd等之含有 鋰與鈦及/或鋰與釩之複合金屬氧化物等》前述硫化物， 具體而言可列舉出Ti2S3、TiS2、TiS等之以式TiSx(在此 ，X爲正的實數）所表示之鈦的硫化物；V3S4、VS2、VS 等之以式VSX(在此，x爲正的實數）所表示之釩的硫化物 ;Fe3S4、FeS2、FeS等之以式FeSx(在此，X爲正的實數） 所表示之鐵的硫化物；Mo2S3、M〇S2等之以式MoSx(在此 ，：X爲正的實數）所表示之鉬的硫化物；SnS2、SnS等之以 式SnSx(在此，X爲正的實數）所表示之錫的硫化物；WS2 等之以式WSX(在此’ X爲正的實數）所表示之鎢的硫化物 ;Sb2S3等之以式 SbSx(在此’ X爲正的實數）所表示之銻 的硫化物；Se5S3、SeS2、SeS等之以式SeSx(在此，X爲 正的實數）所表示之硒的硫化物等。前述氮化物，具體而 言可列舉出Li3N、Li3-XAXN(在此，A爲Ni及/或c〇，〇< x<3)等之含有鋰的氮化物。此等碳材料、氧化物、硫化 物、氮化物可合倂使用，亦可爲結晶質或非晶質。此外， -18- 201114857 此等碳材料、氧化物'硫化物、氮化物主要係撐持於負極 集電體而用作爲電極。 此外’則述金屬，具體而言可列舉出鋰金屬、矽金屬 、錫金屬。此外’ HU述合金可列舉出Li-Al' Li-Ni、Li-Si 寺之鋰合金；Si-Zn等之砂合金；sn-Mn、Sn-Co、Sn-Ni 、Sn-Cu、Sn-La等之錫合金，亦可列舉出Cu2Sb、 LasNhSn·/等之合金。此等金屬、合金，主要係單獨用作 爲電極（例如以薄片狀來使用）。 上述負極材料中，就電位平坦性高、平均放電電位低 、循環性佳等之觀點來看’較佳係使用以天然石墨 '人造 石墨等之石墨爲主成分之碳材料。碳材料的形狀，例如可 爲天然石墨般之薄片狀，中碳微粒般之球狀，以及石墨化 碳纖維般之纖維狀，或視爲粉末的凝聚體等。 前述負極合劑’可因應必要含有黏合劑。黏合劑可列 舉出熱可塑性樹脂，具體而言可列舉出p V d F、熱可塑性 聚醯亞胺、羧甲基纖維素、聚乙烯、聚丙烯等。 前述負極集電體，可列舉出Cu、Ni、不鏽鋼等，就 不易與鋰製作合金之觀點，以及溶液加工爲薄膜之觀點來 看’較佳爲Cu。將負極合劑撐持於該負極集電體之方法 ’與正極時相同，可列舉出依據加壓成型之方法，以及使 用溶劑等進行膏化’塗佈於負極集電體上並進行乾燥後， 進行模壓而壓著之方法等。(3b) A step of removing the co-solvent and the solvent contained in the precipitated film to obtain a laminated film. In the present invention, the laminated film is a laminated porous film in which the porous film is laminated on a porous substrate. Step Ub) is the same as step (la) except that a porous substrate is used instead of the substrate of the step (la). The porous substrate can be made of a fabric 'non-woven fabric' or a film, and is in the form of a sheet. Further, the above porous film can also be used. In the step (lb), the coating can be carried out by applying the coating liquid onto a roll or a drum and then contacting the porous substrate. Further, the above step (2b) can be carried out in the same manner as in the above step (2a), and the above step (3b) can be carried out in the same manner as in the above step (3a). Further, in the step (3b), the obtained laminated film may be dried by heating, drying, air drying or the like as necessary. Further, the coating liquid may be applied to both surfaces of the porous substrate to obtain a laminated film. In the present invention, since the obtained porous film or laminate film contains a nitrogen-containing aromatic polymer, it has almost no strength deterioration up to 200 ° C, and can maintain its shape at 300 ° C, and is excellent in heat resistance. The film is used as a separator for a nonaqueous electrolyte secondary battery such as a lithium ion secondary battery or a lithium polymer secondary battery, and can be sufficiently used for a water-based electrolyte secondary battery or a non-aqueous electrolyte primary battery. , separator for capacitors. In the present invention, when the laminated film is used as a separator for a nonaqueous electrolyte secondary battery such as a lithium secondary battery, the porous substrate preferably contains a thermoplastic resin. In the nonaqueous electrolyte secondary battery, when an abnormal current flows in the battery due to a short circuit between the positive electrode and the negative electrode, it is preferable to have a function of blocking current to prevent (turn off) excessive current flow-14-201114857, When the porous substrate of the laminated film contains a hot pool temperature exceeding a normal use temperature, the void of the laminated film can be blocked by the softening, and the electroplastic resin can be exemplified by polyethylene or poly. A resin, a thermoplastic polyurethane resin, or a mixture of the above. It is preferred to soften it at a lower temperature to contain polyethylene. In particular, the polyethylene, the high-density polyethylene, and the linear low-density polyethylene may have an ultrahigh molecular weight of 1,000,000 or more, and it is preferable to increase the puncture strength of the porous substrate. High molecular weight polyethylene. Further, it is also preferred to contain a wax having a low molecular weight (weight average molecular weight olefin). Further, when a separator such as a porous film or a layer cell of the present invention is used, it is based on ion permeability. The air permeability measured by the Gareth method is generally about 2 (L·, preferably 50 to 300 sec/100 cc, more preferably 50 Å. In addition, the porosity of the separator is generally 20 to 90 3 〇 80 The volume %, particularly preferably 40 to 70% by volume. The thickness, so that the volumetric energy density of the battery or the like is increased, from the viewpoint of maintaining the mechanical strength, preferably 5 to 200 μm, preferably 5 to 40 μm. In particular, the size of the pores of the separator is generally 3 μm or less. Plastic resin, when the pool of the electro-plastic resin is closed. Polyolefins such as propylene are listed as low-cut using these two types of closures. Polyethylene film with a density of polyethylene and polyethylene, or a thermoplastic resin with a thermoplastic resin of less than 10,000) is used as a battery. The separator is based on -2000 sec / 100 cc, 200 sec / 100 cco. %, preferably, in addition, the divider The thinning of the energy of the internal resistance is generally 5 to 30 μm °, and F, preferably 1 μm -15 - 201114857. Next, a lithium secondary battery of a nonaqueous electrolyte secondary battery is taken as an example, The porous film or the laminated film of the invention is used as a battery for a separator. For the production of a lithium secondary battery, a generally known technique can be used, that is, for example, an electrode group obtained by laminating and winding a positive electrode, a negative electrode, and a separator. The battery pack is housed in a container such as a battery can, and the battery liquid is impregnated into the electrode group. The shape of the electrode group is, for example, a cross section when the electrode group is cut perpendicular to the winding axis. The shape of the battery is, for example, a shape of a paper battery, a coin battery, a cylinder, or a square. The positive electrode is generally used. The electrode mixture for the positive electrode active material, the conductive agent, and the binder is applied to the positive electrode current collector. The electrode mixture for the positive electrode preferably contains a material capable of doping and dedoping lithium ions. The positive electrode active material contains a carbon material as a conductive agent and contains a thermoplastic resin as a binder. The positive electrode active material specifically includes at least one selected from the group consisting of V, Mn, Fe, Co, Ni, Cr, and Ti. One type of transition metal element and a metal composite oxide of an alkali metal element such as Li or Na are preferably a composite oxide having a structure of a-NaFeO type as a matrix, and it is particularly preferable from the viewpoint of a high average discharge potential. A composite oxide in which a part of nickel of lithium cobaltate or lithium nickelate lithium nickelate is substituted with another element such as Mn or Co. Further, a composite oxide having a spiral structure such as a lithium manganese spiral as a parent may be used. The above-mentioned binder may, for example, be a thermoplastic resin, and specific examples thereof include copolymerization of polyvinylidene fluoride and vinylidene fluoride, copolymerization of polytetrafluoroethylene and tetrafluoroethylene-hexafluoropropylene. , tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, 'ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer' thermoplastic polyimine, carboxy Methyl cellulose, poly Alkenyl, polypropylene and the like. The conductive material is exemplified by a carbon material, and specific examples thereof include natural graphite, artificial graphite, coal char, carbon black, and the like. These may be used in combination of two or more kinds. The positive electrode current collector may, for example, be A1 or stainless steel, and is preferably A1 from the viewpoint of light weight and low cost. The method of applying the positive electrode electrode mixture to the positive electrode current collector is a method of press molding, and a positive electrode electrode mixture is paste-formed using a solvent or the like, and applied to a positive electrode current collector and dried. Thereafter, the negative electrode is subjected to a method of molding and pressing, and the lithium ion may be doped or dedoped at a potential lower than that of the positive electrode, and a negative electrode mixture containing the negative electrode material may be supported. The electrode of the negative electrode current collector or the electrode composed of the negative electrode material alone. Examples of the negative electrode material include a carbon material, a chalcogen compound (oxide, sulfide, etc.), a nitride, a metal, or an alloy, and a material capable of doping/de-doping lithium ions at a potential lower than that of the positive electrode. . Further, 'the negative electrode materials can be mixed and used. The foregoing negative electrode material is exemplified as follows. The negative electrode material may, for example, be graphite such as natural graphite or artificial graphite, coal char, carbon black 'thermal decomposition carbon, carbon fiber, or organic polymer sintered body. Specific examples of the oxide of -17 to 201114857 include an oxide of yttrium represented by SiOx (here, X is a positive real number) such as SiO 2 or SiO; and TiO x of Ti 〇 2 ' TiO or the like. (here, X is a positive real number), an oxide of titanium; V205, V〇2, etc., an oxide of vanadium represented by the formula V〇x (here, X is a positive real number); Fe3〇 4. Fe2〇3, FeO, etc., an oxide of iron represented by the formula FeOx (here, X is a positive real number); Sn02, SnO, etc. are represented by the formula SnOx (here, X is a positive real number) An oxide of tin; an oxide of tungsten represented by a general formula WOx (here, X is a positive real number) such as W03, W02, etc.; Li4Ti5012, LiV02 (for example, LiuVuOd or the like containing lithium and titanium and/or lithium and Specific examples of the sulfide of vanadium, etc., the sulfides of titanium such as Ti2S3, TiS2, and TiS, which are represented by the formula TiSx (here, X is a positive real number); V3S4, VS2 a sulfide of vanadium represented by VS or the like VSX (here, x is a positive real number); Fe3S4, FeS2, FeS, etc. expressed by the formula FeSx (here, X is a positive real number) a sulfide of iron; a sulfide of molybdenum represented by MoSx (here, X is a positive real number) of Mo2S3, M〇S2, etc.; SnSx of SnS2, SnS, etc. (here, X is positive) The sulfide of tin expressed by the real number; the sulfide of tungsten represented by the formula WSX (where X is a positive real number); the SbSx of the Sb2S3, etc. (where X is a positive real number) Sulfide represented by ruthenium; sulfide of selenium represented by the formula SeSx (here, X is a positive real number) such as Se5S3, SeS2, and SeS, etc. Specific examples of the nitride include Li3N and Li3. -XAXN (here, A is a Ni-containing nitride such as Ni and/or c〇, 〇<x<3), etc. These carbon materials, oxides, sulfides, and nitrides may be used in combination, or may be used. It is crystalline or amorphous. In addition, -18- 201114857 These carbon materials, oxides, sulfides, and nitrides are mainly supported by the negative electrode current collector and used as an electrode. Lithium metal, base metal, and tin metal are listed. In addition, 'Li described alloys include Li-Al' Li-Ni, Li-Si temple lithium alloy; Si-Zn sand alloy Examples of tin alloys such as sn-Mn, Sn-Co, Sn-Ni, Sn-Cu, and Sn-La include alloys such as Cu2Sb and LasNhSn·/. These metals and alloys are mainly used alone as electrodes ( For example, in the above-mentioned negative electrode material, it is preferable to use graphite such as natural graphite 'artificial graphite as a main component from the viewpoints of high potential flatness, low average discharge potential, and good cycle property. Carbon material. The shape of the carbon material may be, for example, a natural graphite-like flaky shape, a spherical shape like a carbon particle, a fibrous shape like a graphitized carbon fiber, or an aggregate of powder. The above negative electrode mixture ' may contain a binder as necessary. The binder may, for example, be a thermoplastic resin, and specific examples thereof include p V d F, thermoplastic polyimine, carboxymethylcellulose, polyethylene, and polypropylene. Examples of the negative electrode current collector include Cu, Ni, and stainless steel. From the viewpoint of making it difficult to form an alloy with lithium, and from the viewpoint of processing a solution into a film, it is preferable that Cu is preferable. The method of supporting the negative electrode mixture on the negative electrode current collector is the same as in the case of the positive electrode, and is carried out by applying a method such as press molding and applying a solvent to the negative electrode current collector and drying it. The method of molding and pressing, and the like.
電解液，一般係含有電解質及有機溶劑。電解質，可 列舉出 LiC104、LiPF6、LiAsF6、LiSbF6、LiBF4、LiCF3S03 S -19- 201114857 、LiN(S02CF3)2、LiN(S02C2F5)2、LiN(S02CF3)(C0CF3)、 Li(C4F9S03)、LiC(S02CF3)3、LLBhCI,。、LiBOB(在此， BOB爲bis(oxalato)borate;雙（草酸基）硼酸）' 低級脂肪族 羧酸鋰鹽、Li A1C14等之鋰鹽，可使用此等之2種以上的混 合物。鋰鹽，一般係使用含有選自此等中含有氟之LiPF6、 LiAsF6、LiSbF6、LiBF4、LiCF3S03、LiN(S02CF3)2 及 LiC(S02CF3)3所成群之至少1種者。 此外，前述電解液中，有機溶劑例如可列舉出碳酸丙 烯酯、碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸乙基 甲酯、4-三氟甲基-1,3-二氧戊環-2-酮、1,2-二（甲氧基羰 氧基）乙烷等之碳酸酯類；1，2-二甲氧基乙烷、1,3-二甲氧 基丙烷、五氟丙基甲基醚、2,2,3,3-四氟丙基二氟甲基醚 、四氫呋喃、2 -甲基四氫呋喃等之醚類；甲酸甲酯、乙酸 甲酯、丁內酯等之酯類：乙腈、丁腈等之腈類；N，N-二甲基甲醯胺、N，N-二甲基乙醯胺等之醯胺類；3-甲基-2-噁唑烷酮等之氨基甲酸鹽類；環丁楓、二甲基亞颯1,3-丙烷磺內酯等之含硫化合物；此外，可使用更將氟取代基 導入至上述有機溶劑者，一般係混合此等的2種以上而使 用。當中較佳爲含有碳酸酯類之混合溶劑，更加爲環狀碳 酸酯與非環狀碳酸酯，或是環狀碳酸酯與醚類之混合溶劑 。環狀碳酸酯與非環狀碳酸酯之混合溶劑，就動作溫度範 圍廣，負載特性佳，且即使在將天然石墨、人造石墨等之 石墨材料用作爲負極活性物質時亦具有難分解性之觀點來 看，較佳爲含有碳酸乙烯酯、碳酸二甲酯及碳酸乙基甲酯 -20- 201114857 之混合溶劑。此外，就可獲得特佳的安全性提升效果之觀 點來看，較佳爲使用含有LiPF6等之含氟鋰鹽以及具有氟取 代基之有機溶劑之電解液。含有五氟丙基甲基醚、2,2,3,3-四氟丙基二氟甲基醚等之具有氟取代基之醚類、與碳酸二 甲酯之混合溶劑，其大電流放電特性亦佳，故更佳。 實施例 接下來藉由實施例更具體地說明本發明，但本發明並 不限定於此等實施例。此外，以下係顯示各種試驗•評估 方法。 (1) 聚合溶液的溶液黏度 使用B型黏度計，在2 5 °C、1 2 r p m下進行測定。 (2) 塗佈性 以目視來確認。 -21 - 201114857 空隙率（體積WhlOOxn-iWl/真比重1+W2/真比重2 + • ♦ · +Wn/真比重 n)/(10xl0xD)} (4)依據加雷法（Gurley Method)所進行之透氣度的測定 多孔質薄膜、層合薄膜、多孔質基材的透氣度，係根 據JIS P8 1 17，藉由安田精機製作所股份公司製的數位計 時式加雷式密度計來測定。 (5)厚度測定 多孔質薄膜、層合薄膜 '多孔質基材的厚度，係依循 JIS規格（K7 1 3 0- 1 992)進行測定。此外，可藉由從層合薄 膜的厚度減去多孔質基材的厚度，而得層合於多孔質基材 之多孔質薄膜的厚度之値。 製造例1(含氮芳香族聚合物的製造） 作爲含氮芳香族聚合物之醯胺之聚（對苯二甲醯對苯 二胺）（以下有略稱爲PPTA時）的製造，係以下列方式進行 。將具有攪拌槳、溫度計、氮流入管及粉體添加口之3公 升的可分離式燒瓶進行充分的乾燥，將作爲溶劑的N-甲 基-2-咯烷酮（以下有略稱爲NMP時）2200g裝入於燒瓶內 ，添加作爲助溶劑的氯化鈣（200°C下進行2小時的真空乾 燥來使用）158.37g，升溫至l〇〇°C以完全地溶解。返回室 溫，添加對苯二胺70. 1 3 6g並完全地溶解。一邊將此溶液 保持在20t： ±2°C —邊攪拌，將對苯二甲酸二氯l28.〇5g -22- 201114857 分爲3次，大約每隔1 0分鐘予以添加。然後亦一邊攪拌 —邊將此溶液保持在2(TC ±2°C，以進行1小時的熟化。 所得之PPTA溶液係顯現出光學異向性，令含氮芳香族聚 合物、助溶劑及溶劑的重量爲100時之含氮芳香族聚合物 的重量爲6.0，助溶劑的重量爲6.5。所得之PPTA溶液中 ，相對於含氮芳香族聚合物100重量份，助溶劑爲110重 量份。 實施例1 -1 1.塗佈液的製造 將製造例1中所得之PPTA溶液1 OOg ’量秤於具有 攪拌槳、溫度計、氮流入管及液體添加口之1 2 3 4〇〇ml的可 分離式燒瓶，添加150g的NMP以及50g的氯化鈣/NMP 溶液，攪拌60分鐘而得塗佈液1。塗佈液1的黏度爲IPa · s 。塗佈液1中，令含氮芳香族聚合物、助溶劑及溶劑的重 量爲100時之含氮芳香族聚合物的重量爲2.0，助溶劑的 重量爲4.0。塗佈液1中，相對於含氮芳香族聚合物1〇〇 重量份，助溶劑爲200重量份。 -23- 1 ·多孔質薄膜的製造 2 將厚度ΙΟΟμηι的PET薄膜用作爲基材’藉由 3 TESTER產業股份公司製的棒塗佈機，將塗佈液1塗佈於 4 該PET薄膜上，於PET薄膜上獲得塗佈膜，並浸漬於不 良溶劑的離子交換水中，使含氮芳香族聚合物析出’去除 s 201114857 助溶劑並藉由乾燥來去除溶劑後，從PET薄膜中將多孔 質薄膜剝離，而得多孔質薄膜1。塗佈時的塗佈不均並未 觀察到，且所得之多孔質薄膜1中，亦未觀察到起因於塗 佈不均之長條狀缺陷。 實施例1-2 1. 塗佈液（含塡充材）的製造 於具有攪拌槳、溫度計、氮流入管及液體添加口之 500ml的可分離式燒瓶內，將氧化鋁塡充材（Nippon Aerosil公司製品；Alumina C、平均粒徑0.013pm)6g以 及氧化鋁塡充材（住友化學公司製品；A A0 3、平均粒徑 0.3 pm)6g添加於與上述實施例1-1相同地製造出之塗佈 液1，以3000rpm高速攪拌10分鐘。將內容物移往壓力 式分散機（戈林均質機；60MPa、通過2次）’將其中的氧 化鋁塡充材充分地分散’以1 000網目的金網進行過濾’ 而得塗佈液2。塗佈液2的黏度爲6Pa· s。塗佈液2中， 與塗佈液1相同，相對於含氮芳香族聚合物1〇〇重量份’ 助溶劑爲200重量份。此外’令含氮芳香族聚合物的重量 爲100時之塡充材的重量爲200。 -24 - 201114857 均之長條狀缺陷。 3.層合薄膜的製造 使用聚乙烯製的多孔質基材作爲多孔質基材（厚度 12μιη、透氣度140秒/lOOcc、空隙率50%)。將上述多孔 質基材固定於厚度ΙΟΟμιη的PET薄膜上，藉由TESTER 產業公司製的棒塗佈機，將塗佈液2塗佈於多孔質基材上 ’於多孔質基材上獲得塗佈膜，並直接放置在23 °C、濕 度50%的環境氣體中10分鐘，使含氮芳香族聚合物析出 ，並藉由離子交換水進行洗淨，去除助溶劑、溶劑並進行 乾燥後，從PET薄膜中將多孔質基材剝離，而得層合薄 膜1(厚度16μιη、透氣度300秒/100cc、空隙率56%)。塗 佈時的塗佈不均並未觀察到，且所得之層合薄膜1中，亦 未觀察到起因於塗佈不均之長條狀缺陷。 實施例2 -1 1 .塗佈液的製造 將製造例1中所得之PPTA溶液60g，量秤於具有攪 拌槳、溫度計、氮流入管及液體添加口之500ml的可分離 式燒瓶，添加210g的NMP以及30g的氯化鈣/NMP溶液’The electrolyte generally contains an electrolyte and an organic solvent. Examples of the electrolyte include LiC104, LiPF6, LiAsF6, LiSbF6, LiBF4, LiCF3S03 S -19- 201114857, LiN (S02CF3) 2, LiN (S02C2F5) 2, LiN (S02CF3) (C0CF3), Li (C4F9S03), and LiC (S02CF3). ) 3, LLBhCI,. LiBOB (here, BOB is bis(oxalato)borate; bis(oxalate)boronic acid)' lithium salt of a lower aliphatic carboxylic acid salt or lithium salt such as Li A1C14, and a mixture of two or more of these may be used. As the lithium salt, at least one selected from the group consisting of LiPF6, LiAsF6, LiSbF6, LiBF4, LiCF3S03, LiN(S02CF3)2, and LiC(S02CF3)3 containing fluorine selected from these is used. Further, examples of the organic solvent in the electrolytic solution include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-trifluoromethyl-1,3-dioxo. a carbonate such as pentocyclo-2-one or 1,2-bis(methoxycarbonyloxy)ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, and five An ether such as fluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran or 2-methyltetrahydrofuran; methyl formate, methyl acetate, butyrolactone, etc. Esters: nitriles such as acetonitrile and butyronitrile; decyl amines such as N,N-dimethylformamide, N,N-dimethylacetamide; 3-methyl-2-oxazolidinone Or a carbamate; a sulfur-containing compound such as cyclopentane, dimethyl sulfonium 1,3-propane sultone or the like; in addition, a fluorine substituent may be used to introduce the above organic solvent, generally mixing It is used in two or more types. Among them, a mixed solvent containing a carbonate is preferable, and a cyclic carbonate and an acyclic carbonate are further used, or a mixed solvent of a cyclic carbonate and an ether. A mixed solvent of a cyclic carbonate and an acyclic carbonate has a wide operating temperature range and a good load characteristic, and has a viewpoint of being difficult to decompose even when a graphite material such as natural graphite or artificial graphite is used as a negative electrode active material. In view of the above, a mixed solvent containing ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate-20-201114857 is preferred. Further, from the viewpoint of obtaining a particularly excellent safety-improving effect, it is preferred to use an electrolytic solution containing a fluorine-containing lithium salt of LiPF6 or the like and an organic solvent having a fluorine-substituted group. High-current discharge characteristics of a mixed solvent of a fluorine-containing substituent such as pentafluoropropyl methyl ether and 2,2,3,3-tetrafluoropropyl difluoromethyl ether and dimethyl carbonate It is also better, so it is better. EXAMPLES Next, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. In addition, the following shows various test and evaluation methods. (1) Solution viscosity of the polymerization solution The measurement was carried out at 25 ° C and 1 2 r p m using a B-type viscometer. (2) Coating property Confirmed by visual inspection. -21 - 201114857 Void ratio (volume WhlOOxn-iWl/true specific gravity 1+W2/true specific gravity 2 + • ♦ · +Wn/true specific gravity n)/(10xl0xD)} (4) according to the Gurley Method Measurement of the air permeability The air permeability of the porous film, the laminated film, and the porous substrate was measured by a digital chronograph-type lightning-density densitometer manufactured by Yasuda Seiki Co., Ltd. in accordance with JIS P8 1-17. (5) Measurement of thickness Porous film, laminated film The thickness of the porous substrate was measured in accordance with JIS standard (K7 1 30 - 1 992). Further, the thickness of the porous film which is laminated on the porous substrate can be obtained by subtracting the thickness of the porous substrate from the thickness of the laminated film. Production Example 1 (Production of Nitrogen-Containing Aromatic Polymer) The production of poly(p-xylylene terephthalamide) (hereinafter, abbreviated as PPTA) of guanamine as a nitrogen-containing aromatic polymer is as follows Column mode. A 3 liter separable flask having a stirring paddle, a thermometer, a nitrogen inflow pipe, and a powder addition port was sufficiently dried to use N-methyl-2-pyrrolidone as a solvent (hereinafter abbreviated as NMP) 2200 g was placed in a flask, and 158.37 g of calcium chloride (used by vacuum drying at 200 ° C for 2 hours) as a co-solvent was added, and the temperature was raised to 10 ° C to completely dissolve. Return to room temperature, add p-phenylenediamine 70. 1 3 6g and completely dissolve. While maintaining the solution at 20 t: ± 2 ° C - while stirring, dichloro terephthalate l28. 〇 5g -22 - 201114857 was divided into 3 times, and was added approximately every 10 minutes. Then, while stirring, the solution was maintained at 2 (TC ± 2 ° C for 1 hour of aging. The resulting PPTA solution exhibited optical anisotropy, nitrogen-containing aromatic polymer, co-solvent and solvent. The weight of the nitrogen-containing aromatic polymer at a weight of 100 was 6.0, and the weight of the co-solvent was 6.5. The obtained PPTA solution had a cosolvent of 110 parts by weight based on 100 parts by weight of the nitrogen-containing aromatic polymer. Example 1-1 1. Production of coating liquid The amount of PPTA solution obtained in Production Example 1 was weighed to 1 2 3 4 ml of a stirring paddle, a thermometer, a nitrogen inflow pipe, and a liquid addition port. In a flask, 150 g of NMP and 50 g of calcium chloride/NMP solution were added, and the mixture was stirred for 60 minutes to obtain a coating liquid 1. The viscosity of the coating liquid 1 was IPa · s. In the coating liquid 1, the nitrogen-containing aromatic polymerization was carried out. The weight of the nitrogen-containing aromatic polymer when the weight of the solvent, the solvent and the solvent is 100 is 2.0, and the weight of the cosolvent is 4.0. In the coating liquid 1, the weight of the nitrogen-containing aromatic polymer is 1 part by weight. The co-solvent is 200 parts by weight. -23- 1 ·Manufacture of porous film 2 Thickness ΙΟΟμ The PET film of ηι was used as a substrate. The coating liquid 1 was applied onto 4 PET films by a bar coater manufactured by 3 TESTER Industries, Ltd., and a coating film was obtained on the PET film, and immersed in the film. In the ion exchange water of the solvent, the nitrogen-containing aromatic polymer is precipitated to remove the sol 201114857 cosolvent and the solvent is removed by drying, and then the porous film is peeled off from the PET film to obtain a porous film 1. The coating unevenness was not observed, and in the obtained porous film 1, no long defects caused by coating unevenness were observed. Example 1-2 1. Coating liquid (containing cerium filling material) Manufactured in a 500 ml separable flask equipped with a stirring paddle, a thermometer, a nitrogen inflow tube, and a liquid addition port, the alumina crucible (Nippon Aerosil product; Alumina C, average particle diameter 0.013 pm) 6 g and alumina 6 g of the ruthenium (product of Sumitomo Chemical Co., Ltd.; A A0 3, average particle diameter 0.3 pm) was added to the coating liquid 1 manufactured in the same manner as in the above Example 1-1, and the mixture was stirred at 3000 rpm for 10 minutes at high speed. To pressure disperser (Golin homogenizer; 60 MPa, passed twice) 'The alumina cerium filling material therein was sufficiently dispersed 'filtered with a gold mesh of 1 000 mesh' to obtain a coating liquid 2. The viscosity of the coating liquid 2 was 6 Pa·s. In the same manner as the coating liquid 1, the amount of the co-solvent is 200 parts by weight based on 1 part by weight of the nitrogen-containing aromatic polymer. In addition, the weight of the cerium filling material when the weight of the nitrogen-containing aromatic polymer is 100 is 200. -24 - 201114857 Both long strip defects. 3. Production of laminated film A porous substrate made of polyethylene was used as a porous substrate (thickness: 12 μm, air permeability: 140 sec/100 cc, void ratio: 50%). The porous substrate was fixed on a PET film having a thickness of ΙΟΟμηη, and the coating liquid 2 was applied onto a porous substrate by a bar coater manufactured by TESTER Industries, Inc. The membrane was placed directly in an ambient gas at 23 ° C and a humidity of 50% for 10 minutes to precipitate a nitrogen-containing aromatic polymer, which was washed with ion-exchanged water to remove the co-solvent, solvent and dried. In the PET film, the porous substrate was peeled off to obtain a laminated film 1 (thickness: 16 μm, air permeability: 300 sec/100 cc, void ratio: 56%). The coating unevenness at the time of coating was not observed, and in the obtained laminated film 1, no long defects due to uneven coating were observed. Example 2 -1 1. Preparation of Coating Liquid 60 g of the PPTA solution obtained in Production Example 1 was weighed in a 500 ml separable flask having a stirring blade, a thermometer, a nitrogen inflow tube, and a liquid addition port, and 210 g of the solution was added. NMP and 30g calcium chloride/NMP solution'
攪拌6 0分鐘而得塗佈液3。塗佈液3的黏度爲0 · 5 P a · s。 塗佈液3中’令含氮芳香族聚合物、助溶劑及溶劑的重量 爲100時之含氮芳香族聚合物的重量爲1.2，助溶劑的重 量爲2.3。塗佈液3中，相對於含氮芳香族聚合物100重 S -25- 201114857 量份，助溶劑爲190重量份^ 2.多孔質薄膜的製造 除了使用塗佈液3取代塗佈液1之外，其他與實施例 1-1相同而得多孔質薄膜3。塗佈時的塗佈不均並未觀察 到’且所得之多孔質薄膜3中，亦未觀察到起因於塗佈不 均之長條狀缺陷。 實施例2-2 1.塗佈液（含塡充材）的製造 於具有攪拌槳、溫度計、氮流入管及液體添加口之 500ml的可分離式燒瓶內，將氧化鋁塡充材（Nippon Aerosil 公司製品；Alumina C、平均粒徑 0.013pm)7.2g 以及氧化鋁塡充材（住友化學公司製品；A A 0 3、平均粒徑 0.3pm)3.6g添加於與上述實施例2-1相同地製造出之塗佈 液3’以3000rpm高速攪拌10分鐘。將內容物移往壓力 式分散機（戈林均質機；60MPa、通過2次），將其中的氧 化鋁塡充材充分地分散，以1 〇〇〇網目的金網進行過濾， 而得塗佈液4。塗佈液4的黏度爲4Pa· s。塗佈液4中， 與塗佈液3相同，相對於含氮芳香族聚合物100重量份， 助溶劑爲190重量份。此外，令含氮芳香族聚合物的重量 爲100時之塡充材的重量爲300。 2·多孔質薄膜的製造 -26- 201114857 除了使用塗佈液4取代塗佈液1之外，其他與實施例 1-1相同而得多孔質薄膜4。塗佈時的塗佈不均並未觀察 到’且所得之多孔質薄膜4中，亦未觀察到起因於塗佈不 均之長條狀缺陷。 3.層合薄膜的製造 除了使用塗佈液4取代塗佈液2之外，其他與實施例 卜2相同而得層合薄膜2(厚度17μηι、透氣度280秒/ l〇〇cc、 空隙率6 0 % )。塗佈時的塗佈不均並未觀察到，且所得之 層合薄膜2中，亦未觀察到起因於塗佈不均之長條狀缺陷 比較例1 於具有攪拌槳、溫度計、氮流入管及液體添加口之 500ml的可分離式燒瓶內，將製造例1中所得之ρρτA溶 液1 00g，量秤於具有攪拌槳、溫度計、氮流入管及液體 添加口之500ml的可分離式燒瓶，添加200g的NMP，攪 拌60分鐘，並添加氧化鋁塡充材（Nippon Aerosil公司製 品；Alumina C、平均粒徑0.01 3 Rm)6g以及氧化鋁塡充材 (住友化學公司製品；AA〇3、平均粒徑 0.3pm)6g，以 3000rpm高速攪拌10分鐘。將內容物移往壓力式分散機（ 戈林均質機：60MPa、通過2次），將其中的氧化鋁塡充 材充分地分散，以1 000網目的金網進行過瀘，而得塗佈 液A。塗佈液A的流動性差’該黏度爲21.0Pa· s。塗佈 s -27 - 201114857 液A中’令含氮芳香族聚合物、助溶劑及溶劑的重量爲 100時之含氮芳香族聚合物的重量爲2.0，助溶劑的重量 爲2.9。塗佈液A中，相對於含氮芳香族聚合物100重量 份，助溶劑爲1 5 0重量份。除了使用塗佈液A取代塗佈 液2之外’其他與實施例1 -2相同而進行用以獲得層合薄 膜之實驗，但於塗佈時產生塗佈不均，無法獲得良好的層 合薄膜。 比較例2 於具有攪捽槳、溫度計、氮流入管及液體添加口之 500ml的可分離式燒瓶內，將製造例1中所得之ρρτΑ溶 液60g，量秤於具有攪拌槳、溫度計、氮流入管及液體添 加口之500ml的可分離式燒瓶，添加240g的NMP，攪拌 60分鐘，並添加氧化塡充材（Nippon Aerosil公司製品 ;Alumina C、平均粒徑0.013 pm)7.2g以及氧化鋁塡充材 (住友化學公司製品；AA03、平均粒徑 0.3pm)3.6g，以 300〇rpm高速攪拌1〇分鐘。將內容物移往壓力式分散機（ 戈林均質機；60MPa、通過2次），將其中的氧化鋁塡充 材充分地分散，以1 00 0網目的金網進行過濾，而得塗佈 液B。塗佈液B爲膠體狀，其流動性差，該黏度爲21 Pa ♦ s。 塗佈液B中，令含氮芳香族聚合物、助溶劑及溶劑的重 量爲100時之含氮芳香族聚合物的重量爲1_2，助溶劑的 重量爲1.7。塗佈液B中，相對於含氮芳香族聚合物1〇〇 重量份，助溶劑爲140重量份。除了使用塗佈液B取代 28 - 201114857 塗佈液2之外’其他與實施例1 - 2相同而進行用以獲得層 合薄膜之實驗，但於塗佈時產生塗佈不均，無法獲得層合 薄膜。 比較例3 於具有攪拌槳、溫度§十、氣流入管及液體添加口之 500ml的可分離式燒瓶內，將製造例1中所得之ρρτΑ溶 液60g，量秤於具有攪拌槳、溫度計、氮流入管及液體添 加口之500ml的可分離式燒瓶，添加135g的NMP以及 l〇5g的氯化鈣/NMP溶液，攪拌60分鐘，並添加氧化鋁 塡充材（Nippon Aerosil公司製品；Alumina C、平均粒徑 0.013pm)7.2g以及氧化鋁塡充材（住友化學公司製品： AA03、平均粒徑0.3pm)3.6g，以3000rpm高速攪拌10分 鐘。將內容物移往壓力式分散機（戈林均質機；6 OMP a、 通過2次），將其中的氧化鋁塡充材充分地分散，以100 0 網目的金網進行過濾，而得塗佈液C。對於塗佈液C ’係 於室溫下靜置3天，觀察塗佈液中之含氮芳香族聚合物的 析出所產生之固化，可得知其保存安定性並不佳。塗佈液 C中，令含氮芳香族聚合物、助溶劑及溶劑的重量爲100 時之含氮芳香族聚合物的重量爲3.6g’助溶劑的重量爲 11.4g。塗佈液C中，相對於含氮芳香族聚合物100重量 份，助溶劑爲3 1 5重量份。The coating liquid 3 was obtained by stirring for 60 minutes. The viscosity of the coating liquid 3 was 0 · 5 P a · s. In the coating liquid 3, the weight of the nitrogen-containing aromatic polymer when the weight of the nitrogen-containing aromatic polymer, the co-solvent, and the solvent was 100 was 1.2, and the weight of the co-solvent was 2.3. In the coating liquid 3, the amount of the co-solvent is 190 parts by weight based on the weight of the nitrogen-containing aromatic polymer 100, and the amount of the co-solvent is 190 parts by weight. 2. The production of the porous film is carried out except that the coating liquid 3 is used instead of the coating liquid 1. The porous film 3 was obtained in the same manner as in Example 1-1. The coating unevenness at the time of coating was not observed, and in the obtained porous film 3, no long defects due to coating unevenness were observed. Example 2-2 1. Production of a coating liquid (containing a ruthenium-filled material) in a 500 ml separable flask having a stirring blade, a thermometer, a nitrogen inflow tube, and a liquid addition port, and filling the alumina with Nippon Aerosil Company product; Alumina C, average particle diameter 0.013 pm) 7.2 g, and alumina lanthanum (product of Sumitomo Chemical Co., Ltd.; AA 0 3, average particle diameter 0.3 pm) 3.6 g was added in the same manner as in the above Example 2-1. The coating liquid 3' was stirred at a high speed of 3000 rpm for 10 minutes. The contents were transferred to a pressure disperser (Goring homogenizer; 60 MPa, passed 2 times), and the alumina crucible was sufficiently dispersed, and filtered with a gold mesh of 1 〇〇〇 mesh to obtain a coating liquid. 4. The viscosity of the coating liquid 4 was 4 Pa·s. In the coating liquid 4, similarly to the coating liquid 3, the working solvent was 190 parts by weight based on 100 parts by weight of the nitrogen-containing aromatic polymer. Further, the weight of the cerium filling material when the weight of the nitrogen-containing aromatic polymer was 100 was 300. 2. Production of Porous Film -26-201114857 A porous film 4 was obtained in the same manner as in Example 1-1, except that the coating liquid 4 was used instead of the coating liquid 1. The coating unevenness at the time of coating was not observed, and in the obtained porous film 4, no long defects due to coating unevenness were observed. 3. Production of Laminated Film A laminated film 2 (thickness: 17 μm, air permeability: 280 sec/l cc, void ratio) was obtained in the same manner as in Example 2 except that the coating liquid 4 was used instead of the coating liquid 2. 60%). Coating unevenness at the time of coating was not observed, and in the obtained laminated film 2, no long defects due to uneven coating were observed. Comparative Example 1 was provided with a stirring blade, a thermometer, and a nitrogen inflow tube. In a 500 ml separable flask having a liquid addition port, 100 g of the ρρτA solution obtained in Production Example 1 was weighed and weighed into a 500 ml separable flask having a stirring paddle, a thermometer, a nitrogen inflow tube, and a liquid addition port, and added. 200g of NMP, stirred for 60 minutes, and added alumina crucible (Nippon Aerosil products; Alumina C, average particle size 0.01 3 Rm) 6g and alumina crucible (Sumitomo Chemical Company products; AA〇3, average grain The diameter was 0.3 pm) 6 g, and the mixture was stirred at 3000 rpm for 10 minutes. The contents were transferred to a pressure disperser (Goring homogenizer: 60 MPa, passed 2 times), and the alumina crucible was sufficiently dispersed, and the gold mesh of 1 000 mesh was used for the coating, and the coating liquid A was obtained. . The fluidity of the coating liquid A was poor, and the viscosity was 21.0 Pa·s. Coating s -27 - 201114857 In the liquid A, the weight of the nitrogen-containing aromatic polymer when the weight of the nitrogen-containing aromatic polymer, the co-solvent and the solvent was 100 was 2.0, and the weight of the co-solvent was 2.9. In the coating liquid A, the co-solvent was 150 parts by weight based on 100 parts by weight of the nitrogen-containing aromatic polymer. Except that the coating liquid A was used instead of the coating liquid 2, the other experiment was carried out in the same manner as in Example 1-2 to obtain a laminated film, but coating unevenness occurred at the time of coating, and good lamination could not be obtained. film. Comparative Example 2 In a 500 ml separable flask having a stirring paddle, a thermometer, a nitrogen inflow tube, and a liquid addition port, 60 g of the ρρτΑ solution obtained in Production Example 1 was weighed to have a stirring paddle, a thermometer, and a nitrogen inflow tube. And a 500 ml separable flask with a liquid addition port, 240 g of NMP was added, stirred for 60 minutes, and cerium oxide filled material (Nippon Aerosil product; Alumina C, average particle diameter 0.013 pm) 7.2 g and alumina crucible were added. (Sumitomo Chemical Co., Ltd.; AA03, average particle size 0.3 pm) 3.6 g, stirred at 300 rpm for 1 minute at high speed. The contents were transferred to a pressure disperser (Goring homogenizer; 60 MPa, passed 2 times), and the alumina crucible was sufficiently dispersed, and filtered with a gold mesh of 100 mesh to obtain a coating liquid B. . The coating liquid B was in the form of a gel and had poor fluidity, and the viscosity was 21 Pa ♦ s. In the coating liquid B, the weight of the nitrogen-containing aromatic polymer when the weight of the nitrogen-containing aromatic polymer, the co-solvent, and the solvent was 100 was 1 - 2, and the weight of the co-solvent was 1.7. In the coating liquid B, the cosolvent was 140 parts by weight based on 1 part by weight of the nitrogen-containing aromatic polymer. Except that the coating liquid B was used instead of the coating liquid 2 of 28 - 201114857, the experiment was carried out to obtain a laminated film in the same manner as in Example 1-2, but uneven coating was caused at the time of coating, and a layer could not be obtained. Film. Comparative Example 3 60 g of the ρρτΑ solution obtained in Production Example 1 was weighed in a 500 ml separable flask having a stirring paddle, a temperature of § ten, a gas flow inlet, and a liquid addition port, and was weighed to have a stirring paddle, a thermometer, and a nitrogen inflow tube. And 500 ml separable flask with liquid addition port, adding 135 g of NMP and 10 g of calcium chloride/NMP solution, stirring for 60 minutes, and adding alumina crucible (product of Nippon Aerosil; Alumina C, average grain) The diameter of 0.013 pm) was 7.2 g, and the alumina crucible (product of Sumitomo Chemical Co., Ltd.: AA03, average particle diameter 0.3 pm) was 3.6 g, and the mixture was stirred at 3000 rpm for 10 minutes. The contents were transferred to a pressure disperser (Golin homogenizer; 6 OMP a, passed 2 times), and the alumina crucible was sufficiently dispersed, and filtered with a gold mesh of 100 0 mesh to obtain a coating liquid. C. The coating liquid C' was allowed to stand at room temperature for 3 days, and the solidification caused by the precipitation of the nitrogen-containing aromatic polymer in the coating liquid was observed, and it was found that the storage stability was not good. In the coating liquid C, the weight of the nitrogen-containing aromatic polymer when the weight of the nitrogen-containing aromatic polymer, the co-solvent and the solvent was 100 was 3.6 g', and the weight of the co-solvent was 11.4 g. In the coating liquid C, the co-solvent was 3 to 15 parts by weight based on 100 parts by weight of the nitrogen-containing aromatic polymer.
S 比較例4 -29- 201114857 除了使用製造例1中所得之ΡΡΤΛ溶液（含氮芳香族 尔π物ί谷液）來取代塗佈液丨之外，其他與實施例丨-1相 同而得多孔質薄膜。此多孔質薄膜係顯現出異向性，且偏 往單向裂開之薄膜。此外，對於ΡΡΤΑ溶液，係於案溫下 靜置3天，觀察ΡΡΤΑ溶液中之含氮芳香族聚合物的析出 所產生之固化，可得知其保存安定性並不佳。 產業上之可利用性： 根據本發明’可賦予一種薄膜的強度及熱收縮率經改 良之多孔質薄膜，且可得不易偏往單向裂開之薄膜。此外 ’本發明之塗佈液，其塗佈性佳，尤其當添加塡充材時， 亦可緩和黏度的急遽上升，例如在加快塗佈液的塗佈速度 時’更能夠抑制所得之多孔質薄膜或層合薄膜的缺陷產生 等’其實用性佳。 -30-S Comparative Example 4 -29-201114857 Other than the ruthenium solution (nitrogen-containing aromatic π-solution gluten solution) obtained in Production Example 1, except for the coating liquid 丨, the other was obtained in the same manner as in Example 丨-1. Quality film. This porous film exhibits an anisotropy and is biased toward a unidirectionally split film. Further, the cerium solution was allowed to stand at the temperature for 3 days, and the solidification of the nitrogen-containing aromatic polymer in the cerium solution was observed, and it was found that the storage stability was not good. Industrial Applicability: According to the present invention, a porous film which is improved in strength and heat shrinkage ratio of a film can be provided, and a film which is less likely to be unidirectionally cracked can be obtained. Further, the coating liquid of the present invention has excellent coatability, and particularly when the ruthenium filler is added, the viscosity can be gradually increased, for example, when the coating speed of the coating liquid is increased, the obtained porous material can be more suppressed. The defect of the film or the laminated film is produced, etc., and its practicality is good. -30-