201237891 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種經壓光加工之芳族聚醯胺紙之再利用 方法，以及耐熱性電氣絕緣片材《進而詳細而言，係關於 一種可不使用藥液等而對焚燒或廢棄處理之經壓光加工之 芳族聚醯胺紙進行再利用的經壓光加工之芳族聚醯胺紙之 再利用方法，以及耐熱性電氣絕緣片材。 【先前技術】 為賦予紙經改善之強度及/或熱穩定性而開發出由高性 能材料製造之紙。例如，芳族聚醯胺紙係包含芳香族聚醯 胺之合成紙。由於其耐熱性及耐燃性、電氣絕緣性、強韌 性及可撓性，該紙被用作電氣絕緣材料及飛機蜂窩用基 材°該等材料之中，包含杜邦（DuPont)(美國）之諾梅克斯 (Nomex)(註冊商標）纖維而成之紙係藉由使聚（間笨二曱醯 間笨二胺）纖維屬與纖條體於水中混合，繼而對經混合之 漿料進行造紙之後再進行壓光加工而製造。已知，該紙甚 至於高溫下依然具有較高之強度及強韌性並且具有優異之 電氣絕緣性。 方族聚醯胺紙之邊角材料或破損材料等由於經實施壓光 加工之向溫、高壓之處理，纟而僅以水則完全*會解纖。 因此，進订焚燒或廢棄處理。又，於溶解於有機溶劑中之 後’再次與原始之原料相同地實施成形為造紙原料即纖維 屬或纖條體、紙激等之化學再利用，但該方法必需考慮環 境，且存在成本變高之傾向。 161777.doc 201237891 又’關於未實施壓光加工之高溫、高壓之處理且經乾燥 之芳族聚醯胺紙或芳族聚醯胺板的再利用，日本專利特開 平4-228696號公報、日本專利特開2003-290676號公報中記 載有其處理方法。然而，實際上芳族聚醯胺紙經壓光加工 而使用之情形為大多數’因此該等方法並不實用。 進而’於日本專利特開平7_243 189號公報中，有使用芳 族聚醯胺紙粉碎而成之芳族聚醯胺紙紙漿的多孔性芳族聚 醯胺成形物之記載。然而，一般認為上述成形物由於多孔 性故而電氣絕緣性不充分。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開平4·228696號公報 [專利文獻2]日本專利特開2003-290676號公報 [專利文獻3]曰本專利特開平43 1 89號公報 【發明内容】 [發明所欲解決之問題] 本發明之目的在於提供-種*使用藥液等而對經壓光加 工之芳族聚醯胺紙進行再利用之耐熱性電氣絕緣片材。 [解決問題之技術手段] 一 ·- W |工％牙七粑緣片 其特徵在於含有··#由將包含芳香族聚醯胺之合成紙! 壓光加工之芳族聚醯胺紙粉碎而獲得之長度加權平均名 長為1 mm以下的微粒子，及芳族聚醯胺纖條體。 於第2態樣中，本發明提供一鍤而+跑ω +户 檀耐熱性電氣絕緣片才 I61777.doc 201237891 製造方法’其特徵在於：將句冬笔条 _ 將匕a方香族聚醯胺之合成紙即 經壓光加工之芳族聚醯胺紙 、 妝、、、氏乾式叔碎而製備微粒子，將製 備而成之微粒子、芳族聚醯脸鑰你脚 鼴胺纖條體、及水組合而形成混 合漿料，使用形成之漿料進行造紙。 【實施方式】 (芳族聚醯胺） ㈣M t ’㈣胺，係指醯胺鍵之6〇%以上 與芳香環直接鍵結之線性高分子化合物(芳香族聚醯胺)。 作為此種芳族聚醯胺，例如可列舉：$間苯二曱醯間笨二 胺及其共聚物、㈣笨二甲酿對笨二胺及其共聚物、聚 (對苯）-共聚合（3,4·二笨鍵）對苯二曱酿胺等。該等芳族聚 醯胺藉由例如使賴苯二甲醯氣及間笨二胺之先前已知之 界面聚合法、溶液聚合法等而於工業上製造，可作為市售 品而獲取，但並不限定於此。該等芳族聚醯胺之中，就具 備良好之成型加工性、熱接著性、難燃性、耐熱性等特性 之方面而言，可較佳地使用聚間苯二甲醯間苯二胺。 (芳族聚醯胺纖條體） 於本發明中，所謂芳族聚醯胺纖條體，係指具有造紙性 之薄膜狀之芳族聚醯胺粒子，亦稱為芳族聚醯胺紙漿（參 照曰本專利特公昭35-1 1851號公報、日本專利特公昭 5732號公報等）。 眾所周知，芳族聚醯胺纖條體與通常之木漿相同，係實 施離解、叩解處理而用作造紙原料，可為保持適於造紙之 品質而實施所謂叩解處理。該叩解處理可利用盤磨機 161777.doc 201237891 refiner)、打漿機（beater)、其他帶來機械性切割作用之造 紙原料處理機器而實施。於該操作中，纖條體之形態變化 可以日本工業規格P8121中規定之濾水度試驗方法（游離 度）進行監控。於本發明中，實施叩解處理後之芳族聚醯 胺纖條體之濾水度較佳為處於1〇 cm3〜3〇〇 cm3(加拿大標準 游離度）之範圍内。大於該範圍之濾水度之纖條體存在由 其成形之耐熱性電氣絕緣片材之強度降低之可能性。另一 方面，若欲獲得小於！〇 cm3之濾水度，則多數情況下投入 T機械動力之利用效率變小，又平均單位時間之處理量變 ^進而，容易因過度進行纖條體之細微化而招致所謂黏 合劑功能之下降。因此，如上所述即便欲獲得小於1〇咖3 之壚水度’亦未見明顯之優點。 (芳族聚醯胺短纖維） 芳族聚醢胺短纖維係將以芳族聚酿胺作為材料之纖維切 割而成者，作為此種纖維，例如可列舉可以帝人股份有限 ^司之「侧1N C〇NEX(註冊商標）」、杜邦公司之 j〇MEX(d冊商標）」等商品名而獲取者，但並不限定於 該等。 方務聚醯胺短纖 又—力又可自1 mm从工且禾立 嶋、較佳為2〜H) mm之範圍内選擇。若短纖維之長度， lmm ’則片材之力學特性降低；另一方面，50麵以_ 於以濕式法製造芳族聚酿脫& 万務眾胺紙時容易產生「接結」、 結」等而容易成為缺陷之原因。 (芳族聚醯胺紙） '61777.doc 201237891 主要由上述芳族聚 之薄片狀物，一般 於本發明中’所謂芳族聚醯胺紙，為 醯胺纖條體及芳族聚醯胺短纖維所構成 具有20 μπι〜1〇〇〇 μηι之範圍内之厚 ^ 進而，方族聚醯胺 紙一般具有10 g/m2〜1〇〇〇 g/m2之範圍内之基重。 一般而言’芳族聚醯胺紙係藉由使 风上述方族聚醯胺纖條 體與芳族聚《短纖維混合之後進行薄片化之方法而製 造。具體而言’例如可使用：使上述芳族聚酿胺纖條體與 芳族聚酿胺短纖維乾式摻合之後，利用氣流形成薄片的方 法；使芳族聚醯胺纖條體與芳族聚醯胺短纖維於液體介質 中分散混合之後，噴出於透液性之支撐體、例如網或帶上 進行薄片化，去除液體進行乾燥的方法等；但該等之中較 佳地選擇使用水作為介質的所謂濕式抄造法。 濕式抄造法中，將含有至少芳族聚醯胺纖條體、芳族聚 醯胺短纖維之單一或混合物之水性漿料向造紙機送液並分 散之後，進行脫水、搾水及乾燥操作，藉此作為薄片而捲 取之方法較為常見。作為造紙機，可利用長網造紙機 '圓 網造紙機、傾斜型造紙機及將該等組合而成之組合造紙機 等。於以組合造紙機進行製造之情形時，可藉由使調配比 率不同之幾:料進行薄片成形並合而為一而獲得包含複數層 紙層之複合體薄片。於抄造時視需要使用分散性提高劑、 消泡劑、紙力增強劑等添加劑。 (壓光加工） 以上述方式獲得之芳族聚醯胺紙可藉由於一對輥間以高 溫高壓進行熱壓而提高密度、機械強度。關於熱壓之條 161777.doc 201237891 件’例如於使用金屬製輥之情形時，可例示溫度 100〜350°C、線壓50〜400 kg/cmi範圍内，但並不限定於 該等《亦可於熱壓時積層複數張芳族聚醯胺紙。亦可以任 意之順序將上述熱壓加工進行複數次。 (經壓光加工之芳族聚醯胺紙粉碎而成之微粒子） 所謂本發明中使用之微粒子，較佳為將上述經壓光加工 之芳族聚醯胺紙粉碎之後，以光學纖維長度測定裝置測定 時之長度加權平均纖維長為丨mm以下。此處，作為光學纖 維長度測定裝置，可使 fflFiber QuaHty Analyzer(〇p Test201237891 VI. Description of the Invention: [Technical Field] The present invention relates to a method for recycling a calendered aromatic polyamide paper, and a heat-resistant electrical insulating sheet. Recycling method of calendered aromatic polyamide paper which can be used for reprocessing of calcined aromatic polyimide paper by incineration or disposal without using a chemical solution, etc., and heat-resistant electrical insulating sheet . [Prior Art] Paper made of high performance materials has been developed to impart improved strength and/or thermal stability to paper. For example, the aromatic polyamide paper is a synthetic paper containing an aromatic polyamine. Due to its heat resistance and flame resistance, electrical insulation, toughness and flexibility, the paper is used as an electrical insulating material and a substrate for aircraft honeycombs. Among these materials, DuPont (USA) The paper of Nomex (registered trademark) fiber is made by mixing the poly (meta-diphenyl) diamine fiber with the fibrid in water, and then the paper is mixed with the mixed slurry. Then, it is produced by calendering. It is known that the paper still has high strength and toughness even at high temperatures and has excellent electrical insulation. The corner material or damaged material of the square polyamide paper is treated by the calendering process to the temperature and high pressure, and the water is completely defibrated only by the water. Therefore, incineration or disposal is ordered. Further, after being dissolved in an organic solvent, the chemical re-use of a fiber raw material, that is, a fiber, a fibrid, or a paper, which is formed into a papermaking material, is carried out again in the same manner as the original raw material, but the method must take into consideration the environment and the cost becomes high. The tendency. 161777.doc 201237891 Further, "Recycling of a wide-area, high-pressure treated and dried aromatic polyamide paper or an aromatic polyamide sheet, which has not been subjected to calendering processing, Japanese Patent Laid-Open No. Hei 4-228696, Japan The processing method is described in Japanese Laid-Open Patent Publication No. 2003-290676. However, in practice, the use of aramid paper by calendering is the majority' so these methods are not practical. Further, in Japanese Laid-Open Patent Publication No. Hei 7-243 189, there is a description of a porous aromatic polyamide molding of an aromatic polyamide paper pulp obtained by pulverizing an aromatic polyamide paper. However, it is considered that the above-mentioned molded article is insufficient in electrical insulation due to porosity. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. 2003-290676 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2003-290676 [Patent Document 3] SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a heat-resistant electrical insulating sheet which is re-used by calendering of aramid paper using a chemical solution or the like. . [Technical means to solve the problem] I·- W|工%牙七粑缘片 is characterized by containing ··# from a synthetic paper containing aromatic polyamines; calendering of aromatic polyamide paper Microparticles having a length-weighted average length of 1 mm or less and an aromatic polyamine fibrid are obtained. In the second aspect, the present invention provides a 锸 + + ω ω + hutan heat-resistant electrical insulation sheet only I61777.doc 201237891 manufacturing method 'characteristics is: will sentence sentence pen _ will 匕a Fangxiang group The synthetic paper of amine is prepared by calendering aramid paper, makeup, and dry powder, and the prepared microparticles, aromatic polyaluminium, and your ankle The water is combined to form a mixed slurry, and the formed slurry is used for papermaking. [Embodiment] (Aromatic Polyamide) (4) M t '(tetra)amine means a linear polymer compound (aromatic polyamine) in which 6 % by weight of a guanamine bond is directly bonded to an aromatic ring. Examples of such an aromatic polyamines include: m-phenylene diphenyl stilbene diamine and copolymers thereof; (iv) stupid dimethyl di-p-diamine and copolymers thereof, and poly(p-phenylene)-copolymerization. (3,4·two stupid bond) p-benzoquinone-branching amine. The aromatic polyamines are industrially produced by, for example, a previously known interfacial polymerization method, solution polymerization method, or the like, which is known as a phthalic acid and a meta-diamine, and are commercially available, but It is not limited to this. Among these aromatic polyamines, polym-xylylene m-phenylenediamine can be preferably used in terms of characteristics such as good moldability, thermal adhesion, flame retardancy, and heat resistance. . (Aromatic Polyamide Fibrid) In the present invention, the term "aromatic polyamine fibrid" refers to a paper-like film of aromatic polyamine particles, also known as aromatic polyamine pulp. (Japanese Patent Publication No. Sho 35-1 1851, Japanese Patent Publication No. Sho. No. 5732, etc.). It is known that the aromatic polyamine fibrids are the same as the conventional wood pulp, and are used as a papermaking raw material by dissociation and decomposing treatment, and a so-called hydrolytic treatment can be carried out to maintain the quality suitable for papermaking. This hydrolytic treatment can be carried out by using a disc mill 161777.doc 201237891 refiner), a beater, and other papermaking material processing machines that provide mechanical cutting action. In this operation, the morphology change of the fibrid can be monitored by the filtration test method (freeness) specified in Japanese Industrial Standard P8121. In the present invention, the degree of filtration of the aromatic polyamidamine fibrid after the hydrolytic treatment is preferably in the range of 1 〇 cm 3 to 3 〇〇 cm 3 (Canadian standard freeness). The fibrids having a degree of filtration greater than this range have a possibility that the strength of the heat-resistant electrically insulating sheet formed therefrom is lowered. On the other hand, if you want to get less than! In the case of the filtration degree of 〇 cm3, the utilization efficiency of the T mechanical power is reduced in many cases, and the treatment amount per unit time is changed. Further, it is easy to cause a decrease in the function of the so-called adhesive due to excessive finening of the fibrid. Therefore, as described above, no significant advantage is obtained even if it is desired to obtain a water level of less than 1 coffee. (Aromatic Polyamide Short Fiber) The aromatic polyamine short fiber is a fiber obtained by cutting a fiber of an aromatic polyamine as a material, and as such a fiber, for example, "the side of the company" 1N C〇NEX (registered trademark), and DuPont's j〇MEX (d-brand trademark) are acquired, but are not limited to these. The genomic polystyrene staple fiber can also be selected from the range of 1 mm from the work and the erbium, preferably 2 to H) mm. If the length of the short fiber, lmm 'the mechanical properties of the sheet is reduced; on the other hand, the 50 side is easy to produce "bonding" when the aramid method is used to produce the aromatic polystyrene & It is easy to become a cause of defects. (Aromatic Polyamide Paper) '61777.doc 201237891 Mainly composed of the above-mentioned aromatic polycrystalline flakes, generally in the present invention, the so-called aromatic polyamidamine paper, which is a guanamine fibrid and an aromatic polyamine. The short fibers are formed to have a thickness in the range of 20 μπι to 1 〇〇〇μηι. Further, the rectangular polyimide paper generally has a basis weight in the range of 10 g/m 2 to 1 〇〇〇 g/m 2 . In general, the "aromatic polyamide paper" is produced by a method in which the above-mentioned aromatic polyamine fiber strips are mixed with an aromatic poly short fiber and then subjected to flaking. Specifically, for example, a method of forming a sheet by using a gas stream after dry blending the above-mentioned aromatic polystyrene fibrids and aromatic polyamine fibers, and an aromatic polyamine fibrid and an aromatic group can be used. After the polybenzamine short fibers are dispersed and mixed in a liquid medium, a liquid-permeable support such as a mesh or a belt is flaky, a liquid is removed, and the like is dried; however, water is preferably selected among the above. A so-called wet papermaking method as a medium. In the wet papermaking method, the aqueous slurry containing at least a single or a mixture of an aromatic polyamine fibril and an aromatic polyamine short fiber is sent to a paper machine and dispersed, and then subjected to dehydration, water pressing and drying operations. Therefore, the method of taking up as a sheet is more common. As the paper machine, a Fourdrinier paper machine, a rotary paper machine, a combination paper machine, and the like can be used. In the case of manufacturing in a combined paper machine, a composite sheet comprising a plurality of paper layers can be obtained by forming and combining the sheets by a different ratio of the blending ratios. Additives such as a dispersibility improver, an antifoaming agent, and a paper strength enhancer are used as needed during the production. (Calendering) The aromatic polyamide paper obtained in the above manner can be increased in density and mechanical strength by hot pressing at a high temperature and a high pressure between a pair of rolls. Regarding the hot-pressing strip 161777.doc 201237891 piece 'For example, when using a metal roll, the temperature can be exemplified in the range of 100 to 350 ° C and the line pressure is 50 to 400 kg / cmi, but it is not limited to these A plurality of aromatic polyurethane papers can be laminated during hot pressing. The above hot press processing may be carried out in plurals in any order. (Microparticles pulverized by calendering of aramid paper) The microparticles used in the present invention are preferably obtained by pulverizing the calendered aromatic polyamide paper and measuring the length of the optical fiber. The length-weighted average fiber length at the time of device measurement was 丨mm or less. Here, as the optical fiber length measuring device, fflFiber QuaHty Analyzer (〇p Test) can be used.
Equipment公司製）、Kajaani型測定裝置（Kajaani&司製）等 測定機器。於此種機器中，通過某光路之微粒子之纖維長 與形態被個別觀測，所測定之纖維長會進行統計學處理。 於使用經長度加權平均之纖維長超過丨mm之微粒子之情形 時，耐熱性電氣絕緣片材之表面之凹凸變大，絕緣破壞電 壓局部降低。進而，因薄片製造中之微粒子之脫離導致薄 片中產生孔而容易引起絕緣破壞電壓之降低等。 作為將上述經壓光加工之芳族聚醯胺紙粉碎之方法較 佳為以乾式法 '濕式法或兩種方法進行粉碎而微粒子化之 方法。所謂乾式法，為使用撕碎機、破碎機、捏合機等， 實質上使水分不介在地對芳族聚醯胺紙給予衝擊而分解為 微粒子的方法。又，所謂濕式法，為於水介質中對芳族聚 醯胺紙給予衝擊而縮小粒度之方& ^作為有效地實施此種 式叙碎之。又備，可例示高速離解機、精磨機、打漿機 4 ’但並不限定於該等。 161777.doc 201237891 本發明中較佳為如下方法：於製造微粒子時利用乾式 法實施粉碎之後制濕式法實施粉碎，進而於制濕式法 貫施粉碎時’於與芳族聚酿胺纖條體混合之狀態下利用濕 式法進行粉碎。藉由與芳族聚醯胺纖條體混合，容易使混 合液均質化而容易製造均質且細小之微粒子，冑而藉由同 時進行濕式處理，亦可省略為製造薄片所必需實施之對芳 族聚醯胺纖條體單體之叩解處理。 (耐熱性電氣絕緣片材） 所謂本發明之耐熱性電氣絕緣片材，為主要由上述微粒 子與芳族聚醯胺纖條體所構成之薄片狀物，一般具有20 μπι〜5 mm之範圍内之厚唐。推 ^ ^ 手又進而，耐熱性電氣絕緣片材一 般具有1 0 g/m2〜5000 g/m2之範圍内之基重。 对熱性電氣絕緣片材中之芳族聚醯胺纖條體之含量只要 達成所需之電氣絕緣性便無特別限制，但為保持耐熱性電 氣絕緣片材於製造中之工程強度而較佳為5〜80重量％，進 而為獲得充分之電氣絕緣性而較佳為15，重量％，進而 為表現充分之強度而尤佳為3G，重量％。耐熱性電氣絕 緣片材中之微粒子之含量較佳為 。里平乂住马20〜95重量。/。之範圍，但 並不限定於該範圍，就再利用之觀點而言㈣為3〇重㈣ 以上’為保持工程強度而更佳為3〇〜85重量％之範圍，尤 佳為50〜85重量％之範圍。 -般而言，4熱性電氣絕緣片材係藉由使上述微粒子與 芳族聚醯胺纖條體混合之後進行薄片化之方法而製造。呈 體而言’例如可使用：使上述微粒子與芳族聚醯胺纖條體 161777.doc 201237891 乾式摻合之後’利用氣流形成薄片之方法；使上述微粒子 及芳族聚酿胺纖條體於液趙介質中分散混合之後，喷出於 透液性之支樓體、例如網或帶上進行薄片&，去除液體進 订乾燥之方法等’㈣等之中較佳地選擇使用水作為介質 之所謂濕式抄造法。 式〇 &法+冑含有至少微粒子、芳族聚醯胺纖條體 之單—或混合物之水性_向造紙機送液並分散之後，進 行脫水、#水及乾燥操作，藉此作為薄片而捲取之方法較 為常見。作為造紙機，可利用長網造紙機、圓網造紙機、 傾斜型造紙機及將該等組合而成之組合造紙機等。於以組 合造紙機進行製造之情形時，可藉由使調配比率不同之浆 料進仃溥片成形並合而為一而獲得包含複數層紙層之複合 體薄片。於抄造時視需要使用分散性提高冑、消泡劑、紙 力增強劑等添加劑》 藉由㈣熱性電氣絕緣片材中添加芳族㈣胺短纖維， 可進-步提高拉伸強度。对熱性電氣絕緣片材中之芳族聚 醯胺短纖維之含量較佳為5〜50重量％之範圍，但並不限定 於該範圍，就再利用之觀點而言為3〇重量％以下，為保持 工輕強度而尤佳為5〜30重量％之範圍。 又，除此之外可添加其他纖維狀成分（例如，聚苯硫醚 纖維、聚醚醚酮纖維、纖維素系纖維、ρνΑ(ρ〇1ρ_1 alcoho卜聚乙烯醇）系纖維、聚酯纖維、芳酯纖維、液晶 聚酯纖維、聚萘二甲酸乙二酯纖維等有機纖維，玻璃纖 維、岩棉（rock wool)、石棉（asbestos)、硼纖維等無機纖維 16l777.doc 201237891 玻璃纖維）。 於本發明之耐熱性電氣絕緣片材中，芳族聚醯胺纖條體 由於作為黏合劑具有優異之特性故而可有效地補充微粒子 及其他添加成分，於本發明之耐熱性電氣絕緣片材製造中 原料良率良好，並且可於薄片内層狀地重疊，減少貫通 孔’而提高電氣絕緣性。 以此種方式獲得之耐熱性電氣絕緣片材可藉由於一對平 板間或金屬製輥間以高溫高壓進行熱壓而提高密度、機械 強度。關於熱壓之條件，例如於使用金屬製輥之情形時， 可例不溫度100〜35〇t、線學5〇〜4〇〇 kg/cm，但並不限定 於S亥等。亦可不施加加熱操作而於常溫下僅進行按壓。亦 可於熱壓時積層複數片耐熱性電氣絕緣片材。亦可以任意 之順序將上述熱壓加工進行複數次。 以下，列舉實施例對本發明進行說明。再者，該等實施 例係用於舉例說明本發明之内容者，未對本發明之内容做 任何限定。 [實施例] (測定方法） (1) 基重、厚度之測定 依據JIS C2111實施。 (2) 密度之計算 以基重+厚度計算。 (3) 長度加權平均纖維長 使用 Op Test Equipment公司製 Fiber Quality Analyzer， 16l777.doc 201237891 測定關於約4000個微粒子之長度加權平均纖維長β (4) 拉伸強度之測定 以TENSILON拉伸試驗機於寬度丨5 min、夾頭間隔50 mm '拉伸速度5〇 mm/分鐘下實施。 (5) 絕緣破壞電壓 根據ASTM D 149，於電極徑5 1 mm下藉由交流之直升壓 法而實施。 (原料製備） 使用曰本專利特開昭52_丨5621號公報中記載之以轉子與 定子之組合而構成的紙漿粒子之製造裝置（濕式沈澱機）， 製造聚間笨二甲醯間苯二胺之纖條體。以離解機、叩解機 對其進行處理而將長度加權平均纖維長調節至〇 9 。 另一方面，將杜邦公司製間芳族聚醯胺纖維（N〇mex(註 冊商標）、單紗細度為2丹尼）切割為6 mm之長度（以下記載 為「芳族聚醯胺短纖維」）而作為造紙用原料。 (經壓光加工之芳族聚醯胺紙之製造） 使製備而成之芳族聚醯胺纖條體與芳族聚醯胺短纖維各 自分散於水中製作漿料。使該等漿料以纖條體與芳族聚醯 胺短纖維成為1/1之調配比率（重量比）之方式混合以 Tappi式（標準式）手抄造紙機（剖面面積為625 cm2)製作薄片 狀物。繼而，利用金屬製壓光輥以溫度33〇<t、線壓3〇〇 kg/cm對其進行熱壓加工，獲得經壓光加工之芳族聚醯胺 紙。 (實施例1~3及對照例） 16l777.doc •12- 201237891 (微粒子原料製備） 以乾式粉碎機粉碎上述經壓光加工之芳族 備通過開孔徑3 mm之篩者與水之混合漿料，、1醯胺紙。製 解機處理該聚料並將長度加權平均纖 乂離解機、叩 之尺寸。 、長調節為表1所示 (耐熱性電氣絕緣片材之製造） 使製備而成之微粒子、製備而成之 及製備而成之芳族聚醯胺短纖維各自八、_條體、 料。使該等漿料以微粒子、纖條體 漿 .* _ 方族聚醞胺短纖維成 為表】所不之調配比率(重量比)之方式混合以 抄造紙機(剖面面積為625 cm2)製作薄片狀物。繼而，利用 金屬製Μ光親以溫度33Gt、㈣3()() kg—對其進行轨壓 加工’獲得耐熱性電氣絕緣片材。再者，對照例除不包含 微粒子以外，與實施例Μ相同地進行製作。將以此種方 式獲得之耐熱性電氣絕緣片材之主要特性值示於表】中。 實施例1 3之耐熱性電氣絕緣片材之絕緣破壞電壓亦足 夠高’進而即便以250t處理1〇分鐘亦未見外觀之變化， 故可用作耐熱性電氣絕緣片材。 I6I777.doc 13· 201237891 [表l] 表1 特性 單位 實施例1 實施例2 實施例3 對照例 原料組成 微粒子 重量％ 70 85 57 芳族聚醯胺纖條體 30 15 30 50 芳族聚醯胺短纖維 13 50 微粒子之長度加權平均纖維長 mm 0.80 0.80 0.80 基重 g/m2 41.6 40.3 44 40 厚度 μηι 58 63 64 59 密度 g/cmJ 0.72 0.64 0.69 0.68 拉伸強度 kgf/15 mm 0.97 0.57 1.37 4.3 絕緣破壞電壓 kV/mm 16 14.4 15.4 16.5 外觀(250°C、10分鐘） 無變化 無變化 無變化 無變化 (實施例4〜6) (微粒子原料製備） 以乾式粉碎機粉碎上述經壓光加工之芳族聚醯胺紙。製 備通過開孔徑3 mm之筛者、芳族聚醢胺纖條體與水之混合 漿料，以離解機、叩解機處理該漿料並將長度加權平均纖 維長調節為表2所示之尺寸。 (耐熱性電氣絕緣片材之製造） 使粉碎芳族聚醯胺紙與芳族聚醯胺纖條體之混合物而製 備之微粒子、及芳族聚醢胺短纖維各自分散於水中製作漿 料。使該等漿料以微粒子、纖條體及芳族聚醯胺短纖維成 為表2所示之調配比率（重量比）之方式混合，以Tappi式手 抄造紙機（剖面面積為625 cm2)製作薄片狀物。繼而，利用 金屬製壓光輥以溫度330°C、線壓300 kg/cm對其進行熱壓 加工，獲得耐熱性電氣絕緣片材。將以此方式獲得之耐熱 性電氣絕緣片材之主要特性值示於表2中。實施例4〜6之耐 161777.doc 14 201237891 熱性電氣絕緣片材中，由於微粒子與芳族聚醯胺纖條體之 混合漿料經粉碎，故而可以與實施例1〜3之耐熱性電氣絕 緣片材相比更短時間製備微粒子原料與芳族聚醯胺纖條 體。又，顯示與實施例1〜3大致同等或其以上之特性。 [表2] 表2 特性 單位 實施例4 實施例5 實施例6 原料組成 微粒子 重量％ 70 85 57 芳族聚醯胺纖條體 30 15 30 芳族聚醯胺短纖維 13 微粒子(芳族聚醯胺紙與芳族聚醯胺 纖條體之混合物)之長度加權平均纖維長 mm 0.70 0.70 0.70 基重 g/m^ 41 40 43 厚度 μιη 57 62 62 密度 g/cmJ 0.72 0.65 0.69 拉伸強度 kgf/15 mm 0.98 0.57 1.4 絕緣破壞電壓 kV/mm 16.2 14.8 16.0 外觀(250°C、10分鐘） 無變化 無變化 無變化 (比較例1〜4) (微粒子原料製備） 以乾式粉碎機粉碎上述經壓光加工之芳族聚酼胺紙。製 備通過開孔徑3 mm之筛者與水之混合漿料，以離解機、叩 解機處理該漿料並將長度加權平均纖維長調節為表3所示 之尺寸。 (耐熱性電氣絕緣片材之製造） 使製備而成之微粒子、製備而成之芳族聚醯胺纖條體、 及製備而成之芳族聚醯胺短纖維各自分散於水中製作漿 料。使該等漿料以微粒子、纖條體及芳族聚醯胺短纖維成 為表3所示之調配比率（重量比）之方式混合，以Tappi式手 161777.doc 15 201237891 抄造紙機（剖面面積為625 cm2)製作薄片狀物。繼而，利用 金屬製壓光輥以溫度330°C、線壓300 kg/cm對其進行熱壓 加工，獲得对熱性電氣絕緣片材。將以此種方式獲得之耐 熱性電氣絕緣片材之主要特性值示於表3中。比較例1〜4之 耐熱性電氣絕緣片材中，由於絕緣破壞電壓較低，故可認 為不足以作為耐熱性電氣絕緣片材。 [表3] 表3 特性 單位 比較例1 比較例2 比較例3 比較例4 原料組成 微粒子 重量％ 70 85 57 70 芳族聚醯胺纖條體 30 15 30 芳族聚醯胺短纖維 13 30 微粒子之長度加權平均纖維長 mm 1.2 1.2 1.2 0.80 基重 g/mz 40 40.2 44.1 43 厚度 μηι 73 78 80 80 密度 g/cm3 0.59 0.52 0.55 0.54 拉伸強度 kgf/15 mm 1.1 0.6 1.45 0.4 絕緣破壞電壓 kV/mm 9.2 8.0 8.5 8.3 外觀(25(TC、10分鐘） 無變化 無變化 無變化 無變化 161777.doc 16-Equipment manufactured by Equipment Co., Ltd., Kajaani type measuring device (Kajaani & Seika), etc. In such a machine, the fiber length and morphology of the particles passing through an optical path are individually observed, and the measured fiber length is statistically processed. When a length-weighted average fiber having a fiber length exceeding 丨 mm is used, the unevenness of the surface of the heat-resistant electrical insulating sheet becomes large, and the dielectric breakdown voltage locally decreases. Further, the detachment of the fine particles in the production of the sheet causes the occurrence of pores in the sheet, which tends to cause a decrease in the dielectric breakdown voltage and the like. The method of pulverizing the above-mentioned calendered aromatic polyamide paper is preferably a method of pulverizing and pulverizing by a dry method 'wet method or two methods. The dry method is a method in which a shredder, a crusher, a kneader or the like is used to substantially decompose the particles into a microparticle by imparting an impact to the aromatic polyamide paper. Further, the wet method is a method of reducing the particle size in an aqueous medium by giving an impact to the aromatic polyimide paper, and it is effective to carry out such a formula. Further, a high-speed disintegrator, a refiner, and a beater 4' are exemplified, but the invention is not limited thereto. 161777.doc 201237891 In the present invention, the method is as follows: in the production of fine particles, the pulverization is carried out by a dry method, and then the pulverization is carried out by a wet method, and further, when the pulverization method is used for pulverization, The body is mixed and pulverized by a wet method. By mixing with the aromatic polyamine fibrids, it is easy to homogenize the mixture, and it is easy to produce homogeneous and fine particles, and by performing wet treatment at the same time, it is also possible to omit the necessity of implementing the film for the production of the sheet. The treatment of the chitosan fibrid monomer. (Heat-resistant electrical insulating sheet) The heat-resistant electrical insulating sheet of the present invention is a sheet mainly composed of the above-mentioned fine particles and an aromatic polyamine fibrid, and generally has a range of 20 μm to 5 mm. Thick Tang. Further, the heat-resistant electrical insulating sheet generally has a basis weight in the range of 10 g/m2 to 5000 g/m2. The content of the aromatic polyamine fibrid in the thermal electrical insulating sheet is not particularly limited as long as the required electrical insulating properties are achieved, but it is preferable to maintain the engineering strength of the heat-resistant electrical insulating sheet in the production. 5 to 80% by weight, and further preferably 15% by weight, and further sufficient strength, and more preferably 3 G% by weight, in order to obtain sufficient electrical insulating properties. The content of the fine particles in the heat-resistant electrical insulating sheet is preferably. Li Ping grabbed the horse 20 to 95 weight. /. The range is not limited to this range, and in terms of reuse, (4) is 3 〇 (4) or more 'more preferably 3 〇 to 85% by weight for maintaining engineering strength, and particularly preferably 50 to 85 weight. The range of %. In general, the four thermal electrical insulating sheets are produced by a method in which the above fine particles are mixed with an aromatic polyamine fibrid and then subjected to flaking. In the form of a body, for example, a method of forming a sheet by air flow after dry-mixing the above-mentioned microparticles with an aromatic polyamine fibrid 161777.doc 201237891; and making the above-mentioned microparticles and aromatic polystyrene fibrids After dispersing and mixing in the liquid medium, it is preferably selected to use water as a medium in a liquid-permeable building body, such as a web or a belt for sheeting, a method for removing liquids, and the like. The so-called wet papermaking method. 〇 amp & method + 胄 containing at least fine particles, a single layer of aromatic polyamine fibrids or a mixture of water _ after the liquid is fed to the paper machine and dispersed, dehydration, # water and drying operations, as a sheet The method of coiling is more common. As the paper machine, a Fourdrinier paper machine, a cylinder paper machine, a tilt type paper machine, and a combination paper machine or the like which are combined can be used. In the case of manufacturing in combination with a paper machine, a composite sheet comprising a plurality of paper layers can be obtained by forming a slurry of different ratios into a sheet. In the case of papermaking, it is necessary to use an additive such as a dispersibility-enhancing enthalpy, an antifoaming agent, or a paper strength enhancer. By adding (4) an aromatic (tetra)amine short fiber to the thermal electrical insulating sheet, the tensile strength can be further increased. The content of the aromatic polyamine short fibers in the thermal insulating sheet is preferably in the range of 5 to 50% by weight, but is not limited to the above range, and is not more than 3% by weight from the viewpoint of reuse. It is particularly preferably in the range of 5 to 30% by weight in order to maintain the light strength. Further, other fibrous components (for example, polyphenylene sulfide fibers, polyetheretherketone fibers, cellulose fibers, ρνΑ(ρ〇1ρ_1 alcoho) polyvinyl alcohol) fibers, polyester fibers, or the like may be added. Organic fibers such as aryl ester fibers, liquid crystal polyester fibers, polyethylene naphthalate fibers, inorganic fibers such as glass fibers, rock wool, asbestos, and boron fibers. 16l777.doc 201237891 Glass fiber). In the heat-resistant electrical insulating sheet of the present invention, the aromatic polyamine fibrids can effectively replenish fine particles and other additive components because of their excellent properties as a binder, and are produced in the heat-resistant electrical insulating sheet of the present invention. The raw material yield is good, and it can be layered in the sheet, and the through-holes are reduced to improve electrical insulation. The heat-resistant electrically insulating sheet obtained in this manner can be increased in density and mechanical strength by hot pressing at a high temperature and a high pressure between a pair of flat plates or between metal rolls. The conditions of the hot pressing, for example, when a metal roll is used, the temperature is not limited to 100 to 35 〇t, and the line is 5 〇 to 4 〇〇 kg/cm, but is not limited to S hai. It is also possible to perform only pressing at normal temperature without applying a heating operation. It is also possible to laminate a plurality of heat-resistant electrical insulating sheets during hot pressing. The above hot press processing may be performed plural times in any order. Hereinafter, the present invention will be described by way of examples. Further, the embodiments are intended to exemplify the contents of the present invention, and the contents of the present invention are not limited in any way. [Examples] (Measurement method) (1) Measurement of basis weight and thickness According to JIS C2111. (2) Calculation of density Calculated by basis weight + thickness. (3) The length-weighted average fiber length was measured using a Fiber Quality Analyzer manufactured by Op Test Equipment, Inc., 16l777.doc 201237891. The length-weighted average fiber length of about 4000 microparticles was measured. (4) Tensile strength was measured by a TENSILON tensile tester. Width 丨 5 min, chuck spacing 50 mm 'stretching speed 5 〇 mm / min. (5) Insulation breakdown voltage is carried out according to ASTM D 149 by an AC direct voltage boosting method at an electrode diameter of 5 1 mm. (Preparation of raw materials) The apparatus for producing pulp particles (wet precipitator) which is composed of a combination of a rotor and a stator described in Japanese Laid-Open Patent Publication No. SHO 52-1561, Fibrids of diamines. The length-weighted average fiber length was adjusted to 〇 9 by treatment with a disintegrator and a disintegrator. On the other hand, DuPont intergranular aromatic polyamide fiber (N〇mex (registered trademark), single yarn fineness of 2 Danny) was cut to a length of 6 mm (hereinafter referred to as "aromatic polyamine" Fiber") is used as a raw material for papermaking. (Production of calendered aromatic polyamide paper) The prepared aromatic polyamine fibrid and aromatic polyamine short fibers were each dispersed in water to prepare a slurry. The slurry was mixed in a Tappi-type (standard) hand-held paper machine (cross-sectional area: 625 cm2) by blending the fibrids and the aromatic polyamide short fibers to a ratio of 1/1 (weight ratio). Flakes. Then, it was subjected to hot press processing using a metal calender roll at a temperature of 33 〇 < t and a linear pressure of 3 〇〇 kg / cm to obtain a calendered aromatic polyamidide paper. (Examples 1 to 3 and Comparative Example) 16l777.doc •12-201237891 (Preparation of fine particle raw material) The above-mentioned calendered aromatic preparation was passed through a dry pulverizer to pass through a mixed slurry of a sieve having a diameter of 3 mm and water. , 1 醯 amine paper. The disintegrator processes the aggregate and weights the length of the average fiber disintegrator, 叩. The length is adjusted as shown in Table 1 (manufacture of heat-resistant electrical insulating sheet). The prepared fine particles, the prepared and prepared aromatic polyamide short fibers are each a _ strip, a material. The slurry is mixed with a fine paper, a sliver slurry, a * _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Shape. Then, a heat-resistant electrically insulating sheet was obtained by using a metal calendering member at a temperature of 33 Gt and (4) 3 () () kg - for rail pressure processing. Further, the comparative example was produced in the same manner as in Example 除 except that the fine particles were not contained. The main characteristic values of the heat-resistant electrical insulating sheet obtained in this manner are shown in the table. The heat-insulating electrical insulating sheet of Example 1 was also sufficiently high in insulation breakdown voltage. Further, even if it was treated at 250 tons for 1 minute, no change in appearance was observed, so that it could be used as a heat-resistant electrical insulating sheet. I6I777.doc 13· 201237891 [Table 1] Table 1 Characteristic Unit Example 1 Example 2 Example 3 Comparative Example Raw Material Composition Microparticle Weight % 70 85 57 Aromatic Polyamide Fibrid 30 15 30 50 Aromatic Polyamide Short fiber 13 50 Length of microparticles Weighted average fiber length mm 0.80 0.80 0.80 Basis weight g/m2 41.6 40.3 44 40 Thickness μηι 58 63 64 59 Density g/cmJ 0.72 0.64 0.69 0.68 Tensile strength kgf/15 mm 0.97 0.57 1.37 4.3 Insulation Destruction voltage kV/mm 16 14.4 15.4 16.5 Appearance (250 ° C, 10 minutes) No change No change No change No change (Examples 4 to 6) (Preparation of fine particle material) The above calendered granule was pulverized by a dry pulverizer Polyamide paper. The mixture was prepared by a sieve having a pore size of 3 mm, a mixture of aromatic polyamine fibrids and water, and the slurry was treated by a disintegrator and a disintegrator to adjust the length-weighted average fiber length to the size shown in Table 2. . (Production of heat-resistant electric insulating sheet) Fine particles prepared by mixing a mixture of an agglomerated aromatic polyamide paper and an aromatic polyamidamine fiber and an aromatic polyamide short fiber are each dispersed in water to prepare a slurry. These slurries were mixed in such a manner that the fine particles, the fibrids, and the aromatic polyamide short fibers were blended at a ratio (weight ratio) shown in Table 2, and were produced in a Tappi type hand-held paper machine (sectional area: 625 cm 2 ). Flakes. Then, it was subjected to hot press working at a temperature of 330 ° C and a linear pressure of 300 kg / cm by a metal calender roll to obtain a heat-resistant electric insulating sheet. The main characteristic values of the heat-resistant electrically insulating sheet obtained in this manner are shown in Table 2. Inhibition of Examples 4 to 6 161777.doc 14 201237891 In the thermal electrical insulating sheet, since the mixed slurry of fine particles and aromatic polyamine fibrids is pulverized, it can be electrically insulated from the heat resistance of Examples 1 to 3. The microparticle raw material and the aromatic polyamine fibrid are prepared in a shorter period of time than the sheet. Further, characteristics similar to or higher than those of Examples 1 to 3 are shown. [Table 2] Table 2 Characteristic unit Example 4 Example 5 Example 6 Raw material composition Microparticle weight % 70 85 57 Aromatic polyamine fibrid 30 15 30 Aromatic polyamide short fiber 13 Microparticles (aromatic polyfluorene) Length-weighted average fiber length of a mixture of amine paper and aromatic polyamine fibrids) 0.70 0.70 0.70 basis weight g/m^ 41 40 43 Thickness μιη 57 62 62 Density g/cmJ 0.72 0.65 0.69 Tensile strength kgf/ 15 mm 0.98 0.57 1.4 Dielectric breakdown voltage kV/mm 16.2 14.8 16.0 Appearance (250 ° C, 10 minutes) No change, no change, no change (Comparative Examples 1 to 4) (Preparation of fine particle material) The above calender was pulverized by a dry pulverizer Processed aromatic polyamide paper. A slurry of a sieve having a diameter of 3 mm and a mixture of water was prepared, and the slurry was treated with a disintegrator and a disintegrator to adjust the length-weighted average fiber length to the size shown in Table 3. (Production of heat-resistant electric insulating sheet) The prepared fine particles, the prepared aromatic polyamine fibrids, and the prepared aromatic polyamide short fibers are each dispersed in water to prepare a slurry. The slurry was mixed in such a manner that the fine particles, the fibrids and the aromatic polyamide short fibers became the mixing ratio (weight ratio) shown in Table 3, and the paper machine (the cross-sectional area) was taken with a Tappi type hand 161777.doc 15 201237891 A sheet was made for 625 cm2). Then, it was subjected to hot press working at a temperature of 330 ° C and a linear pressure of 300 kg / cm by a metal calender roll to obtain a heat-conductive electrical insulating sheet. The main characteristic values of the heat-resistant electrically insulating sheet obtained in this manner are shown in Table 3. In the heat-resistant electric insulating sheets of Comparative Examples 1 to 4, since the dielectric breakdown voltage is low, it is considered to be insufficient as a heat-resistant electrical insulating sheet. [Table 3] Table 3 Characteristic unit Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Raw material composition Microparticle weight% 70 85 57 70 Aromatic polyamine fibrid 30 15 30 Aromatic polyamide short fiber 13 30 Microparticle Length-weighted average fiber length mm 1.2 1.2 1.2 0.80 basis weight g/mz 40 40.2 44.1 43 Thickness μηι 73 78 80 80 Density g/cm3 0.59 0.52 0.55 0.54 Tensile strength kgf/15 mm 1.1 0.6 1.45 0.4 Dielectric breakdown voltage kV/ Mm 9.2 8.0 8.5 8.3 Appearance (25 (TC, 10 minutes) No change No change No change No change 161777.doc 16-