以下，對本發明詳細地進行說明，但本發明並不限定於以下所說明之實施形態。再者，只要未特別申明，關於數值A及B，「A～B」之記法意指「A以上且B以下」。於該記法中，於僅對數值B附加單位之情形時，該單位亦應用於數值A。
本發明之電氣音響轉換器用振動板邊緣材係含有結晶性聚醯亞胺樹脂(A)者。又，於本發明中，電氣音響轉換器用振動板邊緣材較佳為包含結晶性聚醯亞胺樹脂(A)作為主成分。
此處所謂「主成分」係指電氣音響轉換器用振動板邊緣材所包含之結晶性聚醯亞胺樹脂(A)之比率超過50質量%。電氣音響轉換器用振動板邊緣材包含之結晶性聚醯亞胺樹脂(A)之比率重要的是超過50質量%，較佳為60質量%以上，更佳為70質量%以上，進而較佳為80質量%以上，特佳為90質量%以上，尤佳為構成電氣音響轉換器用振動板邊緣材之成分之全部(100質量%)為結晶性聚醯亞胺樹脂(A)。
又，本發明之電氣音響轉換器用振動板邊緣材較佳為包含含有結晶性聚醯亞胺樹脂(A)與聚醚醯亞胺樹脂(B)之聚醯亞胺系樹脂組合物(X)。本發明所使用之聚醯亞胺系樹脂組合物(X)之詳細情況如後文所述。
[結晶性聚醯亞胺樹脂(A)]
本發明所使用之結晶性聚醯亞胺樹脂(A)係將四羧酸成分(a-1)與二胺成分(a-2')進行聚合而獲得。
構成結晶性聚醯亞胺樹脂(A)之四羧酸成分(a-1)可例示：環丁烷-1,2,3,4-四羧酸、環戊烷-1,2,3,4-四羧酸、環己烷-1,2,4,5-四羧酸等脂環族四羧酸；3,3',4,4'-二苯基碸四羧酸、3,3',4,4'-二苯甲酮四羧酸、聯苯基四羧酸、萘-1,4,5,8-四羧酸、均苯四甲酸等。又，亦可使用該等之烷基酯體。
其中，較佳為四羧酸成分(a-1)中超過50莫耳%之成分為均苯四甲酸。藉由四羧酸成分(a-1)以均苯四甲酸作為主成分，本發明之電氣音響轉換器用振動板邊緣材及後文所述之膜、以及聚醯亞胺系樹脂組合物(X)之耐熱性、二次加工性及低吸水性優異。就該觀點而言，四羧酸成分(a-1)中，均苯四甲酸更佳為60莫耳%以上，進而較佳為80莫耳%以上，特佳為90莫耳%以上，尤佳為四羧酸成分(a-1)之全部(100莫耳%)為均苯四甲酸。
構成結晶性聚醯亞胺樹脂(A)之二胺成分(a-2')重要的是以脂肪族二胺(a-2)作為主成分。即，重要的是二胺成分(a-2')中超過50莫耳%之成分為脂肪族二胺(a-2)，更佳為60莫耳%以上，進而較佳為80莫耳%以上，特佳為90莫耳%以上，尤佳為二胺成分(a-2')之全部(100莫耳%)為脂肪族二胺(a-2)。藉此，能夠對本發明之電氣音響轉換器用振動板、及後文所述之膜及聚醯亞胺系樹脂組合物賦予耐熱性、低吸水性、成形性及二次加工性。再者，於本發明之脂肪族二胺中亦包含脂環族二胺。
作為上述二胺成分(a-2')所包含之脂肪族二胺(a-2)，並無特別限制，較佳為於烴基之兩末端具有胺基之二胺成分，又，於重視耐熱性之情形時，例如較佳為包含環狀烴之兩末端具有胺基之脂環族二胺。作為脂肪族二胺(a-2)所包含之脂環族二胺之具體例，可列舉：1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷、4,4'-二胺基二環己基甲烷、4,4'-亞甲基雙(2-甲基環己基胺)、異佛爾酮二胺、降𦯉烷二胺、雙(胺基甲基)三環癸烷等。該等之中，就能夠兼顧耐熱性及成形性、二次加工性之觀點而言，可較佳地使用1,3-雙(胺基甲基)環己烷。
另一方面，於本發明之電氣音響轉換器用振動板、及後文所述之膜及聚醯亞胺系樹脂組合物中，於重視成形性、二次加工性、或耐衝擊性、成形性、二次加工性之情形時，較佳為包含直鏈狀烴之兩末端具有胺基之直鏈狀脂肪族二胺作為上述二胺成分(a-2')包含之脂肪族二胺(a-2)。作為直鏈狀脂肪族二胺，只要為烷基之兩末端具有胺基之二胺成分，則並無特別限制，作為具體例，可列舉：乙二胺(碳數2)、丙二胺(碳數3)、丁二胺(碳數4)、戊二胺(碳數5)、己二胺(碳數6)、庚二胺(碳數7)、辛二胺(碳數8)、壬二胺(碳數9)、癸二胺(碳數10)、十一烷二胺(碳數11)、十二烷二胺(碳數12)、十三烷二胺(碳數13)、十四烷二胺(碳數14)、十五烷二胺(碳數15)、十六烷二胺(碳數16)、十七烷二胺(碳數17)、十八烷二胺(碳數18)、十九烷二胺(碳數19)、二十烷二胺(碳數20)、三十烷二胺(碳數30)、四十烷二胺(碳數40)、五十烷二胺(碳數50)等。該等之中，就成形性或二次加工性、低吸濕性優異之觀點而言，可列舉碳數4～12之直鏈狀脂肪族二胺。又，作為脂肪族二胺(a-2)，亦可為具有該等直鏈狀脂肪族二胺之碳數1～10之分枝結構之結構異構物。
作為上述二胺成分(a-2')包含之除脂肪族二胺(a-2)以外之成分，亦可包含其他二胺成分。具體而言，可列舉：1,4-苯二胺、1,3-苯二胺、2,4-甲苯二胺、4,4'-二胺基二苯醚、3,4'-二胺基二苯醚、4,4'-二胺基二苯甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、α,α'-雙(4-胺基苯基)1,4'-二異丙基苯、α,α'-雙(3-胺基苯基)-1,4-二異丙基苯、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4'-二胺基二苯基碸、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、2,6-二胺基萘、1,5-二胺基萘、對苯二甲胺、間苯二甲胺等芳香族二胺成分、矽氧烷二胺類等。
二胺成分(a-2')(即脂肪族二胺(a-2))可包含脂環族二胺與直鏈狀脂肪族二胺之任一者或兩者，就耐熱性與成形性平衡性優異之方面而言，較佳為包含脂環族二胺與直鏈狀脂肪族二胺之兩者。於包含脂環族二胺與直鏈狀脂肪族二胺兩者之情形時，各者之含量以莫耳基準計較佳為脂環族二胺：直鏈狀脂肪族二胺＝99：1～1：99之範圍，更佳為90：10～10：90，進而較佳為80：20～20：80，特佳為70：30～30：70，尤佳為60：40～40：60。二胺成分(a-2')包含之脂環族二胺與直鏈狀脂肪族二胺之比率只要為該範圍，則本發明之電氣音響轉換器用振動板邊緣材、及後文所述之膜及聚醯亞胺系樹脂組合物之耐熱性與成形性之平衡性、進而耐熱性、耐衝擊性、成形性之平衡性優異。
結晶性聚醯亞胺樹脂(A)之結晶熔解溫度較佳為260℃以上且350℃以下，更佳為270℃以上且345℃以下，進而較佳為280℃以上且340℃以下。只要結晶性聚醯亞胺樹脂(A)之結晶熔解溫度為260℃以上，則耐熱性變得充分。另一方面，只要結晶熔解溫度為350℃以下，例如於成形時能夠於相對低溫下進行成形或二次加工，因此較佳。
又，於含有結晶性聚醯亞胺樹脂(A)作為主成分之情形時，結晶性聚醯亞胺樹脂(A)之結晶熔解溫度較佳為260℃以上且340℃以下，更佳為270℃以上且335℃以下，進而較佳為280℃以上且330℃以下。只要結晶性聚醯亞胺樹脂(A)之結晶熔解溫度為260℃以上，則電氣音響轉換器用振動板邊緣材等之耐熱性變得充分。例如，可賦予能夠耐受峰值溫度為260℃之回焊步驟之耐熱性。另一方面，只要結晶熔解溫度為340℃以下，則例如於本發明之電氣音響轉換器用振動板邊緣材所使用之膜之熔融成形中使用通用之設備，能夠於相對低溫下進行二次加工，因此較佳。
[電氣音響轉換器用振動板邊緣材]
關於本發明之電氣音響轉換器用振動板邊緣材，只要為使用於揚聲器或聽筒、麥克風、耳機等電氣音響轉換器者，則能夠應用於全部，特別是可較佳地用作行動電話等之微揚聲器振動板。
電氣音響轉換器用振動板邊緣材(即，後文所述之膜)之玻璃轉移溫度(Tg)較佳為150℃以上，更佳為160℃以上，進而較佳為170℃以上。只要電氣音響轉換器用振動板邊緣材之玻璃轉移溫度為150℃以上，則能夠維持充分之耐熱性。
電氣音響轉換器用振動板邊緣材(即，後文所述之膜)之結晶熔解焓(ΔHm)較佳為25 J/g以上，更佳為30 J/g以上，進而較佳為35 J/g以上。只要結晶熔解焓(ΔHm)為25 J/g以上，則可獲得結晶性較高之膜或成形品，不僅電氣音響轉換器用振動板之耐熱性優異，而且可獲得能夠確保高音域之播放性之程度之彈性模數，因此較佳。
電氣音響轉換器用振動板邊緣材(即，後文所述之膜)之結晶熔解溫度較佳為260℃以上且340℃以下，更佳為270℃以上且335℃以下，進而較佳為280℃以上且330℃以下。只要電氣音響轉換器用振動板邊緣材之結晶熔解溫度為260℃以上，則能夠賦予充分之耐熱性。另一方面，只要電氣音響轉換器用振動板邊緣材之結晶熔解溫度為340℃以下，則熔融成形時之成形性優異。
再者，本發明之電氣音響轉換器用振動板邊緣材例如可藉由將具備以下所示之特性之本發明之膜利用後文所述之方法進行二次加工而獲得。
本發明之膜可用於上述電氣音響轉換器用振動板邊緣材，且依據JIS K7127之拉伸彈性模數為1000 MPa以上且3000 MPa以下。
膜只要拉伸彈性模數為1000 MPa以上，則具有充分之剛性。並且，於電氣音響轉換器用振動板邊緣材中可確保高溫區域之播放性，此外，具有可作為電氣音響轉換器用振動板邊緣材充分地使用之剛性(塑性)。就該觀點而言，拉伸彈性模數進而較佳為1500 MPa以上，特佳為1800 MPa以上。
又，關於拉伸彈性模數，就即便進一步提高剛性(塑性)且減薄之情形時亦確保充分之操作性之觀點而言，進而更佳為2200 MPa以上。
另一方面，若膜之拉伸彈性模數大於3000 MPa，則作為膜之柔軟性變低，於用於電氣音響轉換器用振動板邊緣材之情形時，低音之播放性等變差。
膜較佳為拉伸彈性模數未達2500 MPa。只要拉伸彈性模數未達2500 MPa，則於電氣音響轉換器用振動板、例如微揚聲器之振動板之情形時，即便使用操作性或高輸出時之耐久性等優異之厚度20～40 μm之膜，最低共振頻率(f0：f zero)亦充分低，可確保低音域之播放性，音質變得良好，因此較佳。就該觀點而言，拉伸彈性模數進而較佳為2400 MPa以下，特佳為2300 MPa以下。
關於膜，提高結晶性聚醯亞胺樹脂(A)之含有率容易降低拉伸彈性模數。即，本發明之膜例如於如上述般含有結晶性聚醯亞胺樹脂(A)作為主成分之情形時，容易將拉伸彈性模數調整至未達2500 MPa，較佳為成為2400 MPa以下，更佳為成為2300 MPa以下。
又，本發明之膜例如包含後文所述之聚醯亞胺系樹脂組合物(X)，藉由含有聚醚醯亞胺樹脂(B)，拉伸彈性模數適度地變高，例如可將拉伸彈性模數設為2200 MPa以上。
上述膜較佳為依據JIS P8115之耐折強度為1000次以上，更佳為1500次以上。只要耐折強度為該範圍，則高輸出時之耐久性優異，振動板不易產生龜裂或破損等。
上述膜較佳為依據JIS K7127之拉伸斷裂伸長率為200%以上，更佳為250%以上。只要拉伸斷裂伸長率為該範圍，則不會產生斷裂等困擾，於各種形狀例如如要求深拉拔性之形狀中均可穩定地進行二次加工。
本發明中，藉由如上述般含有結晶性聚醯亞胺樹脂(A)作為主成分，容易將膜之耐折強度及拉伸斷裂伸長率調整至上述範圍內。
進而，上述膜中亦可除上述成分以外於不超出本發明主旨之範圍內適當調配其他樹脂或填充材、各種添加劑，例如熱穩定劑、紫外線吸收劑、光穩定劑、成核劑、著色劑、潤滑劑、阻燃劑等。
作為膜之製膜方法，可採用公知之方法，例如使用T字模之擠出澆鑄法或壓光法、或流延法等，並無特別限定，就膜之生產性等方面而言，可較佳地使用利用T字模之擠出澆鑄法。
使用T字模之擠出澆鑄法中之成形溫度可根據使用之組合物之流動特性或製膜性等適當進行調整，大致為280℃以上且350℃以下。於熔融混練時，可使用通常使用之單軸擠出機、雙軸擠出機、捏合機或混合機等，並無特別限制。
於使用T字模之擠出澆鑄法之情形時，所獲得之膜可進行急冷並於非晶狀態下進行採集，亦可藉由利用流延輥進行加熱而使之結晶化，還可於非晶狀態下進行採集後實施加熱處理而於結晶化之狀態下進行採集。一般而言，由於非晶狀態之膜之耐久性或二次加工性優異、結晶化後之膜之耐熱性或剛性(塑性)優異，故而重要的是根據用途而使用最佳之結晶化狀態之膜。
於使用結晶化膜之情形時，就生產性或成本之觀點而言，較佳為利用流延輥進行加熱使之結晶化。一般而言，於利用流延輥使薄膜結晶化後進行採集之情形時，存在如下情況：由於需要加快生產線速度，膜接觸流延輥之時間較少，故而不會充分地完成結晶化，無法獲得具有所需結晶性之膜。本發明所使用之結晶性聚醯亞胺樹脂(A)由於結晶化速度極快，故而藉由利用流延輥之熱處理可獲得具有充分結晶性之薄膜。
作為用以使結晶化速度較佳之標準，將結晶性聚醯亞胺樹脂(A)以加熱速度10℃/min使用示差掃描熱量計(DSC)升溫至結晶熔解溫度以上，使結晶完全熔解，其後將以10℃/min進行降溫時之結晶化波峰之溫度設為降溫結晶化溫度，此時較佳為結晶熔解溫度與降溫結晶化溫度之差為70℃以下，較佳為60℃以下，進而較佳為50℃以下。只要降溫過程中之結晶化波峰處於該溫度範圍，則結晶化速度充分快，藉由利用流延輥之熱處理可獲得具有充分結晶性之薄膜。
上述膜之厚度並無特別限制，但作為電氣音響轉換器用振動板邊緣材，通常為1～200 μm。又，亦重要的是以膜自擠出機之行進方向(MD)及其正交方向(TD)上之物性之各向異性儘量變少之方式進行製膜。
如此獲得之膜可作為電氣音響轉換器用振動板邊緣材進一步進行二次加工。二次加工方法並無特別限定，例如於揚聲器振動板之情形時，考慮其玻璃轉移溫度或軟化溫度對該膜進行加熱，藉由壓製成形或真空成形等將其二次加工成圓頂形狀或圓錐形狀等。
本發明之電氣音響轉換器用振動板邊緣材係用於電氣音響轉換器用振動板者。電氣音響轉換器用振動板邊緣材較佳為使用於微揚聲器振動板。振動板之形狀並無特別限制，可為任意，可選擇圓形狀、橢圓形狀、卵圓形狀等。又，電氣音響轉換器用振動板一般而言具有根據電氣信號等進行振動之主體、及包圍主體周圍之邊緣。振動板之主體通常由邊緣支持。主體之形狀可為圓頂狀、圓錐狀，亦可為振動板所使用之其他形狀。
本發明之電氣音響轉換器用振動板邊緣材並無特別限定，只要為至少構成振動板之邊緣之構件即可。因此，振動板之主體及邊緣兩者可藉由電氣音響轉換器用振動板邊緣材而成形為一體，亦可僅振動板之邊緣藉由電氣音響轉換器用振動板邊緣材成形，振動板之邊緣以外之部分(例如主體)藉由其他構件成形。本發明中，即便藉由本發明之電氣音響轉換器用振動板邊緣材或膜將振動板之邊緣及主體成形為一體，亦可獲得加工性良好且具有優異之性能之電氣音響轉換器用振動板。
圖1係表示本發明之一實施形態之微揚聲器振動板1之結構的圖，且係於俯視下將圓形之微揚聲器振動板1於通過圓之中心線之面進行切斷之剖視圖。如圖1所示，微揚聲器振動板1以圓頂部(主體)1a為中心，具有安裝於音圈2之凹嵌部1b、周緣部(邊緣)1c、及於其外周貼附於框架等之外部貼附部1d。
本發明之膜由於拉伸彈性模數不會過高，故而於用於電氣音響轉換器用振動板邊緣材、尤其是小型電氣音響轉換器用振動板邊緣材之情形時，可確保低音域之播放性，音質變得良好，因此較佳。此處，作為振動板之大小，可較佳地使用最大徑為25 mm以下、較佳為20 mm以下且下限通常為5 mm左右者。再者，所謂最大徑，於振動板之形狀為圓形狀之情形時採用直徑，於楕圓形狀或卵圓形狀之情形時採用長徑。
於振動板面可適當形成所謂之被稱為切向邊緣之橫截面形狀為V字狀之槽等。圖2表示本發明之另一實施形態之微揚聲器振動板1'之俯視圖。微揚聲器振動板1'於圓形之圓頂部(主體)1a'之外周緣部具有形成有複數個切向邊緣1e之切向邊緣部1g、及形成有複數個切向邊緣1f之切向邊緣部1h。於具有切向邊緣之形態中，若膜之平均厚度較佳為3～40 μm，更佳為5～38 μm，則厚度得到充分地確保，因此操作性亦較好，於壓製成形等之平均時間之二次加工性或二次加工精度(形狀之再現性)容易提昇，因此較佳。
振動板1、振動板1'可藉由上述膜構成，亦可藉由膜與其他構件之複合材、例如後文所述之積層體構成。
又，本發明之電氣音響轉換器用振動板邊緣材亦可為於正面及背面層具有該電氣音響轉換器用振動板邊緣材、且於中間層具有阻尼效果(內部損耗)較高之黏著層的積層體。藉由設為此種積層結構，能夠賦予正面及背面層之電氣音響轉換器用振動板邊緣材具有之耐熱性、剛性、耐久性及成形性、以及中間層具有之優異之減衰特性。製作作為積層體之電氣音響轉換器用振動板邊緣材之方法並無特別限制。例如可列舉如下方法等：藉由將一對具有上述特性之膜進行二次加工而分別製作構成正面層及背面層之電氣音響轉換器用振動板邊緣材，並經由中間層所使用之黏著劑將該等接著而進行製作；或經由中間層所使用之黏著劑將一對具有上述特性之膜進行接著而製作積層膜，並利用上述方法將該積層膜進行二次加工。於此情形時，作為中間層所使用之黏著劑之種類，可列舉丙烯酸系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑、胺基甲酸酯系黏著劑等，就接著性之觀點而言，較佳為使用丙烯酸系或聚矽氧系黏著劑。又，於此情形時，正面層及背面層之厚度分別較佳為1 μm以上且30 μm以下，更佳為2 μm以上且25 μm以下，進而較佳為3 μm以上且20 μm以下。另一方面，中間層厚度較佳為3 μm以上且50 μm以下，更佳為5 μm以上且40 μm以下，進而較佳為10 μm以上且30 μm以下。中間層之材料種類或各層之厚度只要為該構成，則可獲得於維持各種機械特性或成形之狀態下減衰特性亦優異之振動板。
進而，為了實現振動板之二次加工適性或防塵性、或者音響特性之調整或設計性提昇等，亦可對本發明之電氣音響轉換器用振動板邊緣材使用之膜或已成形之振動板之表面進一步適當進行如下處理：塗佈或積層抗靜電劑或各種彈性體(例如胺基甲酸酯系、聚矽氧系、烴系、氟系等)、或蒸鍍金屬、或濺鍍、或著色(黑色或白色等)等。亦可進一步適當進行與鋁等金屬或其他膜之積層、或與不織布之複合化等。
本發明之電氣音響轉換器用振動板邊緣材於用於揚聲器振動板之情形時，高輸出時之耐久性優異。例如，於行動電話中相對於通用機種之0.3 W左右，能夠應對可應用於高輸出機種之0.6～1.0 W左右之耐輸出位準。又，含有結晶性聚醯亞胺樹脂(A)作為主成分之膜除作為揚聲器振動板、尤其是微揚聲器之振動板之基本音響特性以外，耐熱性或振動板二次加工時之成形性亦優異。
[膜]
本發明之膜如上所述，依據JIS K7127之拉伸彈性模數為1000 MPa以上且3000 MPa以下。
此種本發明之膜如上所述，為使用於電氣音響轉換器用振動板邊緣材者，亦可於電氣音響轉換器用振動板邊緣材以外使用。
本發明之膜係藉由與電氣音響轉換器用振動板邊緣材相同之材料構成。即，本發明之膜較佳為含有包含四羧酸成分(a-1)與二胺成分(a-2')之結晶性聚醯亞胺樹脂(A)者，且包含結晶性聚醯亞胺樹脂(A)作為主成分。
再者，此處所謂「主成分」係指膜所包含之結晶性聚醯亞胺樹脂(A)之比率超過50質量%。膜所包含之結晶性聚醯亞胺樹脂(A)之比率較佳為60質量%以上，更佳為70質量%以上，進而較佳為80質量%以上，特佳為90質量%以上，尤佳為構成膜之成分之全部(100質量%)為結晶性聚醯亞胺樹脂(A)。
如上所述，膜之詳細內容如電氣音響轉換器用振動板邊緣材所使用之膜所說明般，因此省略其說明。又，膜所使用之結晶性聚醯亞胺樹脂(A)之詳細內容亦與上述相同，因此省略其說明。
又，本發明之膜亦較佳為包含含有結晶性聚醯亞胺樹脂(A)及聚醚醯亞胺樹脂(B)之聚醯亞胺系樹脂組合物(X)者。本發明所使用之聚醯亞胺系樹脂組合物(X)之詳細內容如以下說明。
[聚醯亞胺系樹脂組合物(X)]
本發明亦提供一種含有結晶性聚醯亞胺樹脂(A)與聚醚醯亞胺樹脂(B)之聚醯亞胺系樹脂組合物(X)。如上所述，本發明之膜及電氣音響轉換器用振動板邊緣材分別亦較佳為包含聚醯亞胺系樹脂組合物(X)者。
於聚醯亞胺系樹脂組合物(X)中使用之結晶性聚醯亞胺樹脂(A)為含有四羧酸成分(a-1)與脂肪族二胺成分(a-2)者，其詳細情況如上所述。其中，關於聚醯亞胺系樹脂組合物(X)中使用之結晶性聚醯亞胺樹脂(A)，較佳為其結晶熔解溫度為260℃以上且350℃以下，更佳為270℃以上且345℃以下，進而較佳為280℃以上且340℃以下。只要結晶性聚醯亞胺樹脂(A)之結晶熔解溫度為260℃以上，則聚醯亞胺系樹脂組合物(X)之耐熱性變得充分。另一方面，只要結晶熔解溫度為350℃以下，則例如於使用本發明之聚醯亞胺系樹脂組合物(X)進行成形時，能夠於相對低溫下進行成形或二次加工，因此較佳。
又，於聚醯亞胺系樹脂組合物(X)中使用之結晶性聚醯亞胺樹脂(A)之玻璃轉移溫度較佳為150℃以上且300℃以下，更佳為160℃以上且290℃以下，進而較佳為170℃以上且280℃以下。只要結晶性聚醯亞胺樹脂(A)之玻璃轉移溫度為150℃以上，則聚醯亞胺系樹脂組合物(X)之耐熱性變得充分。另一方面，只要玻璃轉移溫度為300℃以下，則於使用本發明之聚醯亞胺系樹脂組合物(X)進行成形時，能夠於相對低溫下成形，因此較佳。又，於將所獲得之成形體進行二次加工之情形亦因相同之原因而較佳。
再者，於聚醯亞胺系樹脂組合物(X)中使用之結晶性聚醯亞胺樹脂(A)除結晶熔解溫度及玻璃轉移溫度以外均如上述所說明般，因此省略其記載。
＜聚醚醯亞胺樹脂(B)＞
於聚醯亞胺系樹脂組合物(X)中使用之聚醚醯亞胺樹脂(B)並無特別限定，可使用周知之化合物，其製造方法及特性例如記載於美國專利3,803,085及美國專利3,905,942。
作為於本發明中使用之聚醚醯亞胺樹脂(B)，具體而言，就耐熱性與成形性之平衡性優異之方面而言，較佳為具有下述[化1]所表示之結構。
[化1]
上述式[化1]中，n(重複數)通常為10～1,000之範圍之整數，較佳為10～500。只要n位於該範圍，則成形性與耐熱性之平衡性優異。
上述式[化1]根據鍵結形式之差異，具體而言，根據間位鍵結與對位鍵結之差異，可分類成下述[化2]及[化3]分別表示之結構。
[化2]
[化3]
上述[化2]及[化3]中，n(重複數)通常為10～1,000之範圍之整數，較佳為10～500。只要n位於該範圍，則成形性與耐熱性之平衡性優異。
作為具有此種結構之聚醚醯亞胺樹脂(B)之具體例，例如正自SABIC Innovative Plastics公司作為商品名「Ultem」系列進行市售。
聚醚醯亞胺樹脂(B)之玻璃轉移溫度較佳為160℃以上且300℃以下，更佳為170℃以上且290℃以下，進而較佳為180℃以上且280℃以下，特佳為190℃以上且270℃以下，尤佳為200℃以上且260℃以下。藉由聚醚醯亞胺樹脂(B)之玻璃轉移溫度為160℃以上，聚醯亞胺系樹脂組合物(X)之耐熱性變得充分。另一方面，藉由聚醚醯亞胺樹脂(B)之玻璃轉移溫度為300℃以下，能夠於相對低溫下進行成形或二次加工，因此於與結晶性聚醯亞胺樹脂(A)摻合時，不會引起結晶性聚醯亞胺樹脂(A)之分解、劣化。
本發明之聚醯亞胺系樹脂組合物(X)之特徵在於：上述聚醚醯亞胺樹脂(B)與上述結晶性聚醯亞胺樹脂(A)之含有比率以質量基準計為(B)/(A)＝1/99～99/1。
上述聚醚醯亞胺樹脂(B)與上述結晶性聚醯亞胺樹脂(A)之含有比率可根據所要求之用途適當調整。於本發明之聚醯亞胺系樹脂組合物(X)中，例如於重視耐熱性或剛性之情形時，較佳為上述聚醚醯亞胺樹脂(B)與上述結晶性聚醯亞胺樹脂(A)之含有比率以質量基準計為(B)/(A)＝5/95以上，更佳為10/90以上，進而較佳為15/85以上。另一方面，於重視耐衝擊性之情形時，較佳為上述聚醚醯亞胺樹脂(B)與上述結晶性聚醯亞胺樹脂(A)之含有比率以質量基準計為(B)/(A)＝80/20以下，更佳為70/30以下，進而較佳為60/40以下。
又，本發明之聚醯亞胺系樹脂組合物(X)於使用於上述電氣音響轉換器用振動板邊緣材或膜之情形時，就使耐久性良好之觀點而言，較佳為結晶性聚醯胺(A)之含量以質量基準計多於聚醚醯亞胺樹脂(B)之含量。具體而言，上述(B)/(A)特佳為40/60以下，尤佳為30/70以下。
並且，聚醯亞胺系樹脂組合物(X)於使用於電氣音響轉換器用振動板邊緣材或膜之情形時，亦較佳為如上所述般含有結晶性聚醯胺(A)作為主成分。
本發明之聚醯亞胺系樹脂組合物(X)之特徵在於存在一個損耗正切(tanδ)之峰值，該峰值係藉由JIS K7244-4記載之動態黏彈性之溫度分散測定，以應變0.1%、頻率10 Hz、升溫速度3℃/min而測得。
於本發明中，將上述損耗正切(tanδ)之峰值表示之溫度定義為玻璃轉移溫度(Tg)。又，所謂存在一個損耗正切(tanδ)之峰值，換言之，亦可認為上述玻璃轉移溫度(Tg)單一。進而，亦可陳述為於依據JISK7121以加熱速度10℃/min使用示差掃描熱量計測定玻璃轉移溫度時，僅出現1個表示玻璃轉移溫度之彎曲點。
一般而言，只要聚合物摻合組合物之玻璃轉移溫度單一，則意味著混合之樹脂處於以分子等級相溶之狀態，可確認為相溶系。又，於雖存在兩個摻合後之損耗正切(tanδ)之峰值但各波峰靠中央之情形時，具體而言，於高溫側之波峰向低溫偏移、低溫側之波峰向高溫偏移之情形時，可認為該等為部分相溶系。於摻合後亦存在兩個損耗正切(tanδ)之峰值之情形時，可認為該等為非相溶系。於部分相溶系中，由於存在一波峰不明確且難以明確地與相溶系區分之情況，故而於本發明中，除清楚地觀察到兩個以上波峰之情形以外，全部作為相溶系進行處理。
一般而言，於非相溶系之情形時，於施加拉伸或彎曲等外力時，會於界面產生剝離，引起機械物性之降低或白化。構成本發明之聚醯亞胺系樹脂組合物(X)之聚醚醯亞胺樹脂(B)及結晶性聚醯亞胺樹脂(A)由於表現相溶系，故而能夠於無損耐衝擊性之情況下進行各樹脂之改質。
如上所述，本發明之聚醯亞胺系樹脂組合物(X)為具有玻璃轉移溫度(Tg)成為單一之特徵之組合物。該玻璃轉移溫度較佳為150℃以上且300℃以下，更佳為160℃以上且290℃以下，進而較佳為170℃以上且280℃以下。只要聚醯亞胺系樹脂組合物(X)之玻璃轉移溫度為150℃以上，則聚醯亞胺系樹脂組合物(X)之耐熱性變得充分。另一方面，只要玻璃轉移溫度為300℃以下，則於使用聚醯亞胺系樹脂組合物(X)進行成形時，能夠於相對低溫下進行成形，因此較佳。又，於將所獲得之成形體進行二次加工之情形時，亦因相同之原因而較佳。
為了使製成薄膜時之操作性良好從而能夠於各種用途中適當地使用，本發明之聚醯亞胺系樹脂組合物(X)較佳為依據JIS K7127之拉伸彈性模數為2200 MPa以上且3100 MPa以下。只要拉伸彈性模數為2200 MPa以上，則使用聚醯亞胺系樹脂組合物(X)所獲得之膜具有充分之剛性，操作性優異。就該觀點而言，拉伸彈性模數進而較佳為2250 MPa以上，特佳為2300 MPa以上。另一方面，只要拉伸彈性模數為3100 MPa以下，則具有作為膜之充分之柔軟性，因此較佳。就該觀點而言，拉伸彈性模數進而較佳為3050 MPa以下，特佳為3000 MPa以下。
於將本發明之聚醯亞胺系樹脂組合物(X)使用於上述電氣音響轉換器用振動板邊緣材、及電氣音響轉換器用振動板邊緣材用之膜之情形時，拉伸彈性模數越低越佳，較佳為3000 MPa以下，更佳為未達2500 MPa，進而較佳為2400 MPa以下，特佳為2300 MPa以下。
本發明之聚醯亞胺系樹脂組合物(X)較佳為依據JIS K7127測得之拉伸斷裂伸長率為130%以上，更佳為135%以上。只要拉伸斷裂伸長率為該範圍，則於將本發明之聚醯亞胺系樹脂組合物(X)製成膜時，耐衝擊性優異。又，不會產生斷裂等困擾，能夠穩定地成形或二次加工成各種形狀。
再者，於將本發明之聚醯亞胺系樹脂組合物(X)使用於上述電氣音響轉換器用振動板邊緣材、及電氣音響轉換器用振動板邊緣材用膜之情形時，如上所述，拉伸斷裂伸長率更高為佳，進而較佳為200%以上，進而更佳為250%以上。
再者，所謂聚醯亞胺系樹脂組合物(X)之拉伸彈性模數及拉伸斷裂伸長率係於將樹脂組合物使用Φ40 mm同方向雙軸擠出機於340℃下進行混練之後，藉由T字模進行擠出，繼而利用約200℃之流延輥進行急冷，製作厚度0.1 mm之膜，並對該膜進行測定而得者。
進而，本發明之聚醯亞胺系樹脂組合物(X)除上述成分以外，於不超出本發明主旨之範圍內亦可適當調配其他樹脂或填充材、各種添加劑，例如熱穩定劑、紫外線吸收劑、光穩定劑、成核劑、著色劑、潤滑劑、阻燃劑等。
＜聚醯亞胺系樹脂組合物(X)之成形體＞
亦可藉由上述本發明之聚醯亞胺系樹脂組合物(X)而使成形體成形。作為使用本發明之聚醯亞胺系樹脂組合物(X)成形而成之成形體，由於剛性、耐衝擊性優異，故而較佳為列舉上述膜。膜之特徵如上述所說明。又，作為成形體，除膜以外例如亦可列舉具有盤、管、桿、蓋、螺栓等形狀之成形體。
作為成形體及膜之用途，可列舉汽車用構件、飛機用構件、電氣、電子用構件等要求耐熱性或剛性、耐衝擊性之用途。
又，聚醯亞胺系樹脂組合物(X)於該等用途中，亦較佳為如上所述作為電氣音響轉換器用振動板邊緣材使用。再者，如上所述，電氣音響轉換器用振動板邊緣材例如為藉由將膜進行二次加工而獲得者。此種電氣音響轉換器用振動板邊緣材之特徵如上述所說明。
＜成形體之製造方法＞
作為上述成形體之製造方法，並無特別限定，可採用公知之方法，例如擠出成形、射出成形、吹塑成形、真空成形、壓空成形、壓製成形等。
又，作為包含聚醯亞胺系樹脂組合物(X)之膜之成形(製膜)方法，並無特別限定，可採用公知之方法，例如使用T字模之擠出澆鑄法或壓光法、或流延法等，其中，就膜之生產性等方面而言，可較佳地使用利用T字模之擠出澆鑄法。再者，使用T字模之擠出澆鑄法之詳細內容如上所述，並省略其說明。
又，包含聚醯亞胺系樹脂組合物(X)之膜可為向單向或雙向實施過延伸之單軸或雙軸延伸膜，作為延伸膜之製造方法，可列舉如下方法：藉由T字模澆鑄法、壓製法、壓光法等製作作為前驅物之未延伸膜之後藉由輥延伸法、拉幅延伸法等進行延伸成形；或藉由膨脹法、管式法等一體地進行熔融擠出及延伸成形。
使用本發明之聚醯亞胺系樹脂組合物(X)成形而成之膜之厚度並無特別限制，通常為1～200 μm。又，亦重要的是以使膜自擠出機之行進方向(MD)及其正交方向(TD)上之物性之各向異性儘量變少之方式進行製膜。
如上所述，本發明提供一種將結晶性聚醯亞胺樹脂(A)使用於電氣音響轉換器用振動板邊緣材之方法。如以上所說明，本發明藉由使用結晶性聚醯亞胺樹脂(A)，能夠使電氣音響轉換器用振動板邊緣材之耐熱性、高輸出時之耐久性、自低音至高音之播放性、二次加工性等優異。
又，本發明提供一種將聚醯亞胺系樹脂組合物(X)使用於電氣音響轉換器用振動板邊緣材、或該邊緣材以外之成形體或膜的方法。本發明藉由使用聚醯亞胺系樹脂組合物(X)，能夠使電氣音響轉換器用振動板邊緣材、成形體、及膜之耐熱性、剛性、耐衝擊性等優異。
再者，一般而言，「膜」係指與長度及寬度相比厚度極小、最大厚度被任意限定之薄平的製品，通常以輥之形狀供給者(JIS K6900)，一般而言，「片材」係指於JIS之定義上較薄、其厚度相對於長度與寬度而言較小且平坦的製品。然而，片材與膜之邊界不明確，於本發明中，無需於文字上對兩者進行區分，故而於本發明中，於稱為「膜」之情形時亦包含「片材」，於稱為「片材」之情形時亦包含「膜」。
[實施例]
以下，利用實施例更詳細地進行說明，但本發明不受該等任何限制。再者，針對本說明書中所記載之原料、以及本發明之聚醯亞胺系樹脂組合物及本發明之電氣音響轉換器用振動板邊緣材所使用之膜之各種測定以如下方式進行。
(1)玻璃轉移溫度
針對各原料、原料顆粒及所獲得之膜，使用黏彈性譜儀DVA-200(IT Meter. and Control股份有限公司製造)以應變0.1%、頻率10 Hz、升溫速度3℃/min進行動態黏彈性之溫度分散測定(JIS K7244-4法之動態黏彈性測定)，將表示損耗正切(tanδ)之主分散之波峰之溫度設為玻璃轉移溫度。
(2)結晶熔解溫度、結晶熔解焓、及降溫時之結晶化溫度
針對各種原料及所獲得之膜，藉由JIS K7121以加熱速度10℃/min使用示差掃描熱量計(DSC)測定，對升溫過程中之結晶熔解溫度及結晶熔解焓進行測定。其後，針對結晶性材料，對以10℃/min降溫時之結晶化波峰(降溫結晶化溫度)之溫度進行測定，根據與結晶熔解溫度之差評價結晶化速度。
(3)拉伸彈性模數
針對所獲得之膜依據JIS K7127於溫度23℃之條件下進行測定。
(4)耐折強度
針對所獲得之膜依據JIS P8115於溫度23℃之條件下進行測定。
(5)拉伸斷裂伸長率
針對所獲得之膜依據JIS K7127於溫度23℃、試驗速度200 mm/min之條件下進行測定。
1.結晶性聚醯亞胺樹脂(A)
(A)-1：結晶性聚醯亞胺樹脂(MITSUBISHI GAS CHEMICAL股份有限公司製造；商品名：Therplim TO65S；四羧酸成分：均苯四甲酸＝100莫耳%；二胺成分：1,3-雙(胺基甲基)環己烷/八亞甲基二胺＝60/40(莫耳基準)；結晶熔解溫度：322℃；結晶熔解焓：40 J/g；玻璃轉移溫度：208℃)
2.聚醚醯亞胺樹脂(B)
(B)-1：聚醚醯亞胺(SABIC Innovative Plastics股份有限公司製造，Ultem1000，玻璃轉移溫度：232℃)
(B)-2：聚醚醯亞胺(SABIC Innovative Plastics股份有限公司製造，UltemCRS5001，玻璃轉移溫度：240℃)
(實施例1)
使用Φ40 mm單軸擠出機於340℃下將作為結晶性聚醯亞胺樹脂(A)之(A)-1進行熔融混練，其後，藉由T字模進行擠出，繼而利用約200℃之流延輥進行加熱並進行結晶化，而製作厚度25 μm之結晶化膜。對所獲得之膜進行上述(1)～(5)之測定。將結果示於表1。
(比較例1)
使用(B)-1：聚醚醯亞胺1000(SABIC Innovative Plastics股份有限公司製造，Ultem1000，非晶性樹脂，玻璃轉移溫度：232℃)代替結晶性聚醯亞胺樹脂(A)，將成形溫度設為380℃，除此以外，利用與實施例1相同之方法進行膜之製作及測定。將結果示於表1。
(比較例2)
使用(B)-2：聚醚醯亞胺5000(SABIC Innovative Plastics股份有限公司製造，UltemCRS5001，非晶性樹脂，玻璃轉移溫度：240℃)代替結晶性聚醯亞胺樹脂(A)，將成形溫度設為380℃，除此以外，利用與實施例1相同之方法進行膜之製作及測定。將結果示於表1。
[表1]
實施例1
比較例1
比較例2
結晶性聚醯亞胺樹脂(A)
(A)-1
100
聚醚醯亞胺1000
(B)-1
100
聚醚醯亞胺5000
(B)-2
100
玻璃轉移溫度
℃
208
232
240
結晶熔解焓
J/g
40
-
(非晶性)
-
(非晶性)
結晶熔解溫度
℃
322
-
(非晶性)
-
(非晶性)
結晶熔解溫度－降溫結晶化溫度
℃
47
-
(非晶性)
-
(非晶性)
拉伸彈性模數
MPa
2100
3200
3100
耐折強度
次
4000
80
130
拉伸斷裂伸長率
%
290
130
100
實施例1中，將以本發明之結晶性聚醯亞胺樹脂(A)為主成分之膜以結晶化之狀態使用。該膜由於拉伸彈性模數處於適當之範圍，故而不僅剛性(塑性)甚至操作性亦優異，而且低音域之播放性亦優異。又，通常，結晶化之膜由於韌性降低，故而存在耐折強度或拉伸斷裂伸長率之值降低之傾向，該膜即便為結晶化之狀態亦呈現出就該等之項目而言充分優異之值，甚至高輸出時之耐久性亦優異。又，由於結晶熔解焓、結晶熔解溫度、耐折強度、拉伸斷裂伸長率處於較佳之範圍，故而耐熱性或高輸出時之耐久性、二次加工性優異。進而，由於結晶熔解溫度與降溫時之結晶化溫度之差較小，故而結晶化速度充分快，藉由利用流延輥之熱處理可獲得具有充分結晶性之25 μm之膜。
另一方面，比較例1及2中使用包含作為耐熱性非晶性樹脂之聚醚醯亞胺之膜。該膜由於使用非晶性樹脂，故而不具有熔點，耐熱性較差。又，由於不僅拉伸彈性模數較高、低音之播放性較差，而且耐折強度或拉伸斷裂伸長率較低，故而高輸出時之耐久性或二次加工性亦不充分。
(實施例2)
使(B)-1、及(A)-1之混合質量比((B)/(A))以80/20之比率進行乾摻，其後，使用Φ40 mm同方向雙軸擠出機於340℃下進行混練，其後藉由T字模進行擠出，繼而利用約200℃之流延輥進行急冷，而製作厚度0.1 mm之膜。針對所獲得之膜，對玻璃轉移溫度、拉伸彈性模數、拉伸斷裂伸長率、及耐折強度進行評價。將結果示於表2。
(實施例3)
將(B)-1與(A)-1之混合質量比((B)/(A))設為60/40，除此以外，利用與實施例1相同之方法進行膜之製作、評價。將結果示於表2。
(實施例4)
將(B)-1與(A)-1之混合質量比((B)/(A))設為40/60，除此以外，利用與實施例1相同之方法進行膜之製作、評價。將結果示於表2。
(實施例5)
將(B)-1與(A)-1之混合質量比((B)/(A))設為30/70，除此以外，利用與實施例1相同之方法進行膜之製作、評價。將結果示於表2。
(實施例6)
將(B)-1與(A)-1之混合質量比((B)/(A))設為20/80，除此以外，利用與實施例1相同之方法進行膜之製作、評價。將結果示於表2。
(實施例7)
使用(B)-2代替(B)-1，除此以外，利用與實施例2相同之方法進行膜之製作、評價。將結果示於表2。
(實施例8)
使用(B)-2代替(B)-1，並將(B)-2與(A)-1之混合質量比((B)/(A))設為60/40，除此以外，利用與實施例2相同之方法進行膜之製作、評價。將結果示於表2。
(實施例9)
使用(B)-2代替(B)-1，並將(B)-2與(A)-1之混合質量比((B)/(A))設為40/60，除此以外，利用與實施例2相同之方法進行膜之製作、評價。將結果示於表2。
(實施例10)
使用(B)-2代替(B)-1，並將(B)-2與(A)-1之混合質量比((B)/(A))設為30/70，除此以外，利用與實施例2相同之方法進行膜之製作、評價。將結果示於表2。
(實施例11)
使用(B)-2代替(B)-1，並將(B)-2與(A)-1之混合質量比((B)/(A))設為20/80，除此以外，利用與實施例2相同之方法進行膜之製作、評價。將結果示於表2。
(實施例12)
單獨使用(A)-1，除此以外，利用與實施例2相同之方法進行膜之製作、評價。將結果示於表2。
(比較例3)
單獨使用(B)-1，除此以外，利用與實施例2相同之方法進行膜之製作、評價。將結果示於表2。
(比較例4)
單獨使用(B)-2，除此以外，利用與實施例2相同之方法進行膜之製作、評價。將結果示於表2。
[表2]
實施例2
實施例3
實施例4
實施例5
實施例6
實施例7
實施例8
實施例9
實施例10
實施例11
實施例12
比較例3
比較例4
結晶性聚醯亞胺樹脂(A)
(A)-1
20
40
60
70
80
20
40
60
70
80
100
聚醚醯亞胺樹脂(B)
(B)-l
80
60
40
30
20
100
(B)-2
80
60
40
30
20
100
玻璃轉移溫度
℃
228
224
222
221
220
236
234
232
231
230
208
232
240
拉伸彈性模數
MPa
3000
2800
2500
2400
2300
3000
2800
2600
2500
2400
2100
3200
3300
拉伸斷裂伸長率
%
160
190
230
245
260
140
180
210
230
250
290
120
100
耐折強度
次
175
380
835
1230
1825
260
510
1020
1430
2020
4000
80
130
實施例2～11之包含組合物之膜儘管為聚醚醯亞胺樹脂(A)與結晶性聚醯亞胺樹脂(B)之摻合物，但主分散之波峰所表示之玻璃轉移溫度均為單一，可確認為相溶系。該膜之全部物性包含於適當之範圍。又，實施例12之膜之全部物性大致包含於適當之範圍，但拉伸彈性模數相對較低，認為於以薄膜之形式使用時之操作性低於其他實施例2～11。
另一方面，比較例3及4之膜之拉伸彈性模數較高，柔軟性不充分，而且拉伸斷裂伸長率之值較低，耐衝擊性亦不充分。
Hereinafter, the present invention will be described in detail, but the present invention is not limited to the embodiments described below. In addition, unless otherwise stated, regarding the numerical values A and B, the notation of "A to B" means "more than A and less than or equal to B". In this notation, when only a unit is added to a value B, that unit also applies to a value A. The diaphragm edge material for electroacoustic transducers of the present invention contains a crystalline polyimide resin (A). Moreover, in this invention, it is preferable that the diaphragm edge material for electroacoustic transducers contains a crystalline polyimide resin (A) as a main component. The term "main component" here means that the ratio of the crystalline polyimide resin (A) contained in the diaphragm edge material for electroacoustic transducers exceeds 50 mass %. It is important that the ratio of the crystalline polyimide resin (A) contained in the diaphragm edge material for electroacoustic transducers exceeds 50 mass %, preferably 60 mass % or more, more preferably 70 mass % or more, and still more preferably 80 mass % or more, 90 mass % or more is especially preferable, and all (100 mass %) of the components constituting the diaphragm edge material for electroacoustic transducers are crystalline polyimide resin (A). Moreover, the diaphragm edge material for electroacoustic transducers of the present invention preferably includes a polyimide-based resin composition (X) containing a crystalline polyimide resin (A) and a polyetherimide resin (B). . Details of the polyimide-based resin composition (X) used in the present invention will be described later. [Crystalline Polyimide Resin (A)] The crystalline polyimide resin (A) used in the present invention is obtained by polymerizing the tetracarboxylic acid component (a-1) and the diamine component (a-2') and obtained. Examples of the tetracarboxylic acid component (a-1) constituting the crystalline polyimide resin (A) include: cyclobutane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3, Alicyclic tetracarboxylic acids such as 4-tetracarboxylic acid and cyclohexane-1,2,4,5-tetracarboxylic acid; 3,3',4,4'-diphenyltetracarboxylic acid, 3,3 ',4,4'-benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, pyromellitic acid, etc. Moreover, these alkyl ester forms can also be used. Among them, it is preferable that the component exceeding 50 mol % in the tetracarboxylic acid component (a-1) is pyromellitic acid. The tetracarboxylic acid component (a-1) contains pyromellitic acid as a main component, the diaphragm edge material for an electroacoustic transducer of the present invention, the film described later, and the polyimide-based resin composition (X ) is excellent in heat resistance, secondary processability and low water absorption. From this viewpoint, in the tetracarboxylic acid component (a-1), pyromellitic acid is more preferably 60 mol % or more, more preferably 80 mol % or more, particularly preferably 90 mol % or more, especially It is preferable that the whole (100 mol%) of the tetracarboxylic acid component (a-1) is pyromellitic acid. It is important that the diamine component (a-2') constituting the crystalline polyimide resin (A) has the aliphatic diamine (a-2) as the main component. That is, it is important that more than 50 mol % of the diamine component (a-2') is the aliphatic diamine (a-2), more preferably 60 mol % or more, and more preferably 80 mol % Above, it is especially preferable that it is 90 mol% or more, and it is especially preferable that the whole (100 mol%) of the diamine component (a-2') is aliphatic diamine (a-2). Thereby, heat resistance, low water absorption, moldability, and secondary processability can be imparted to the diaphragm for an electroacoustic transducer of the present invention, the film and the polyimide-based resin composition to be described later. In addition, alicyclic diamine is also contained in the aliphatic diamine of this invention. The aliphatic diamine (a-2) contained in the diamine component (a-2') is not particularly limited, but is preferably a diamine component having an amine group at both ends of a hydrocarbon group, and in consideration of heat resistance In the case of sex, for example, an alicyclic diamine having amine groups at both ends including a cyclic hydrocarbon is preferable. Specific examples of the alicyclic diamine contained in the aliphatic diamine (a-2) include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl) ) cyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine), isophoronediamine, noralkanediamine, Bis(aminomethyl)tricyclodecane, etc. Among them, 1,3-bis(aminomethyl)cyclohexane can be preferably used from the viewpoint of being compatible with heat resistance, moldability, and secondary processability. On the other hand, in the diaphragm for electroacoustic transducers of the present invention, and the film and polyimide-based resin composition described later, emphasis is placed on formability, secondary workability, impact resistance, and formability. , In the case of secondary processability, it is preferably a linear aliphatic diamine having an amine group at both ends of a linear hydrocarbon as the aliphatic diamine (a) contained in the above-mentioned diamine component (a-2'). -2). The linear aliphatic diamine is not particularly limited as long as it is a diamine component having amine groups at both ends of the alkyl group, and specific examples include ethylenediamine (2 carbon atoms), propylenediamine ( carbon number 3), butanediamine (carbon number 4), pentamethylenediamine (carbon number 5), hexamethylenediamine (carbon number 6), heptanediamine (carbon number 7), octanediamine (carbon number 8), Nonanediamine (carbon number 9), decanediamine (carbon number 10), undecanediamine (carbon number 11), dodecanediamine (carbon number 12), tridecanediamine (carbon number 13) , tetradecanediamine (carbon number 14), pentadecanediamine (carbon number 15), hexadecanediamine (carbon number 16), heptadecanediamine (carbon number 17), octadecanediamine (carbon number 18), nonadecanediamine (carbon number 19), eicosanediamine (carbon number 20), tridecanediamine (carbon number 30), tetradecanediamine (carbon number 40), Pentadecanediamine (carbon number 50), etc. Among these, from the viewpoint of being excellent in formability, secondary workability, and low hygroscopicity, linear aliphatic diamines having 4 to 12 carbon atoms are mentioned. Moreover, as aliphatic diamine (a-2), the structural isomer which has a C1-C10 branch structure of these linear aliphatic diamines may be sufficient. Other diamine components may be contained as components other than the aliphatic diamine (a-2) contained in the diamine component (a-2'). Specifically, 1,4-phenylenediamine, 1,3-phenylenediamine, 2,4-toluenediamine, 4,4'-diaminodiphenyl ether, and 3,4'-diamine can be mentioned. diphenyl ether, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1 ,3-bis(3-aminophenoxy)benzene, α,α'-bis(4-aminophenyl)1,4'-diisopropylbenzene, α,α'-bis(3-amine phenyl)-1,4-diisopropylbenzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminodiphenylene, Bis[4-(4-aminophenoxy)phenyl] bis[4-(3-aminophenoxy)phenyl] bis[4-(3-aminophenoxy)phenyl] bis(2,6-diaminonaphthalene, 1,5-diaminophenoxy) Aromatic diamines such as aminonaphthalene, p-xylylenediamine, m-xylylenediamine, siloxanediamines, etc. The diamine component (a-2') (ie, the aliphatic diamine (a-2)) may contain either or both of an alicyclic diamine and a linear aliphatic diamine. It is preferable to contain both of an alicyclic diamine and a linear aliphatic diamine from the point which is excellent in balance. When both alicyclic diamine and linear aliphatic diamine are included, the content of each is preferably alicyclic diamine:linear aliphatic diamine=99:1～ on a molar basis The range of 1:99 is more preferably 90:10-10:90, more preferably 80:20-20:80, particularly preferably 70:30-30:70, particularly preferably 60:40-40:60 . As long as the ratio of the alicyclic diamine and the linear aliphatic diamine contained in the diamine component (a-2') is within this range, the diaphragm edge material for electroacoustic transducers of the present invention and the following The film and the polyimide-based resin composition are excellent in the balance of heat resistance and moldability, and furthermore, the balance of heat resistance, impact resistance, and moldability. The crystal melting temperature of the crystalline polyimide resin (A) is preferably 260°C or higher and 350°C or lower, more preferably 270°C or higher and 345°C or lower, and still more preferably 280°C or higher and 340°C or lower. As long as the crystal melting temperature of the crystalline polyimide resin (A) is 260° C. or higher, the heat resistance becomes sufficient. On the other hand, as long as the crystal melting temperature is 350° C. or lower, for example, molding or secondary processing can be performed at a relatively low temperature during molding, which is preferable. In addition, when the crystalline polyimide resin (A) is contained as the main component, the crystal melting temperature of the crystalline polyimide resin (A) is preferably 260° C. or higher and 340° C. or lower, more preferably 270° C. ℃ or higher and 335°C or lower, more preferably 280°C or higher and 330°C or lower. As long as the crystal melting temperature of the crystalline polyimide resin (A) is 260° C. or higher, the heat resistance of the diaphragm edge material for an electroacoustic transducer or the like becomes sufficient. For example, heat resistance capable of withstanding a reflow step with a peak temperature of 260°C can be imparted. On the other hand, as long as the crystal melting temperature is 340° C. or lower, for example, general-purpose equipment can be used in the melt-molding of the film used for the diaphragm edge material for an electroacoustic transducer of the present invention, and secondary processing can be performed at a relatively low temperature. Therefore, it is preferable. [Vibrating plate edge material for electro-acoustic transducer] The diaphragm edge material for electro-acoustic transducer of the present invention can be applied to all electro-acoustic transducers such as speakers, earpieces, microphones, earphones, etc., especially It is preferably used as a micro-speaker vibration plate for mobile phones and the like. The glass transition temperature (Tg) of the diaphragm edge material for electroacoustic transducers (that is, the film described later) is preferably 150°C or higher, more preferably 160°C or higher, and still more preferably 170°C or higher. Sufficient heat resistance can be maintained as long as the glass transition temperature of the diaphragm edge material for electroacoustic transducers is 150° C. or higher. The crystal fusion enthalpy (ΔHm) of the diaphragm edge material for electroacoustic transducers (that is, the film described later) is preferably 25 J/g or more, more preferably 30 J/g or more, and still more preferably 35 J/g g or more. As long as the crystal melting enthalpy (ΔHm) is 25 J/g or more, a film or molded product with high crystallinity can be obtained, which not only has excellent heat resistance of the diaphragm for electroacoustic transducers, but also can ensure high-frequency range playback. degree of elasticity modulus, so it is better. The crystal melting temperature of the diaphragm edge material for an electroacoustic transducer (ie, a film to be described later) is preferably 260°C or higher and 340°C or lower, more preferably 270°C or higher and 335°C or lower, and more preferably 280°C above and below 330°C. Sufficient heat resistance can be imparted as long as the crystal melting temperature of the diaphragm edge material for an electroacoustic transducer is 260° C. or higher. On the other hand, as long as the crystal melting temperature of the edge material of the diaphragm for an electroacoustic transducer is 340° C. or lower, the moldability during melt molding is excellent. Furthermore, the diaphragm edge material for electroacoustic transducers of the present invention can be obtained, for example, by subjecting the film of the present invention having the properties shown below to secondary processing by the method described later. The film of the present invention can be used for the above-mentioned diaphragm edge material for an electroacoustic transducer, and has a tensile modulus of elasticity in accordance with JIS K7127 of 1000 MPa or more and 3000 MPa or less. The film has sufficient rigidity as long as the tensile modulus of elasticity is 1000 MPa or more. Furthermore, in the diaphragm edge material for electroacoustic transducers, reproducibility in a high temperature region can be ensured, and it has rigidity (plasticity) sufficient to be used as a diaphragm edge material for electroacoustic transducers. From this viewpoint, the tensile modulus of elasticity is more preferably 1500 MPa or more, and particularly preferably 1800 MPa or more. In addition, the tensile modulus of elasticity is more preferably 2200 MPa or more from the viewpoint of ensuring sufficient handleability even when the rigidity (plasticity) is further increased and the thickness is reduced. On the other hand, when the tensile modulus of elasticity of the film exceeds 3000 MPa, the flexibility of the film becomes low, and when used as an edge material of a diaphragm for an electro-acoustic transducer, bass reproduction properties and the like deteriorate. The film preferably has a tensile modulus of elasticity of less than 2500 MPa. As long as the tensile modulus of elasticity is less than 2500 MPa, in the case of diaphragms for electroacoustic transducers, such as diaphragms for microspeakers, even when using a thickness of 20 to 40 μm that is excellent in operability and durability at high output The lowest resonant frequency (f0: f zero) of the membrane is also sufficiently low, which can ensure the playability of the low-frequency range, and the sound quality becomes good, so it is better. From this viewpoint, the tensile modulus of elasticity is further preferably 2400 MPa or less, and particularly preferably 2300 MPa or less. Regarding the film, increasing the content of the crystalline polyimide resin (A) tends to lower the tensile modulus of elasticity. That is, when the film of the present invention contains, for example, the crystalline polyimide resin (A) as the main component as described above, the tensile modulus of elasticity can be easily adjusted to less than 2500 MPa, preferably 2400 MPa or less. , more preferably 2300 MPa or less. Moreover, the film of the present invention contains, for example, the polyimide-based resin composition (X) described later, and by containing the polyetherimide resin (B), the tensile modulus of elasticity becomes moderately high, for example, it can be The tensile modulus of elasticity is set to 2200 MPa or more. The above-mentioned film preferably has a flexural strength according to JIS P8115 of 1000 times or more, more preferably 1500 times or more. As long as the flexural strength is within this range, the durability at high output is excellent, and the vibration plate is less likely to be cracked or damaged. The above-mentioned film preferably has a tensile elongation at break based on JIS K7127 of 200% or more, more preferably 250% or more. As long as the tensile elongation at break is in this range, there is no trouble such as breakage, and secondary processing can be stably performed in various shapes such as shapes requiring deep drawability. In the present invention, by containing the crystalline polyimide resin (A) as a main component as described above, it is easy to adjust the folding strength and tensile elongation at break of the film within the above-mentioned ranges. Furthermore, other resins, fillers, and various additives, such as heat stabilizers, ultraviolet absorbers, light stabilizers, nucleating agents, and colorants, may be appropriately blended in the above-mentioned film within the scope not departing from the gist of the present invention, in addition to the above-mentioned components. , lubricants, flame retardants, etc. As the film-forming method, known methods, such as extrusion casting method using T-die, calendering method, or casting method, are not particularly limited, but in terms of film productivity, etc. Extrusion casting using a T-die is preferably used. The molding temperature in the extrusion casting method using the T-die can be appropriately adjusted according to the flow characteristics and film-forming properties of the composition to be used, and is approximately 280°C or higher and 350°C or lower. In the case of melt-kneading, a commonly used single-screw extruder, twin-screw extruder, kneader, mixer, etc. can be used without particular limitation. In the case of the extrusion casting method using a T-die, the obtained film can be quenched and collected in an amorphous state, it can also be crystallized by heating with a casting roll, or it can be in an amorphous state. After collecting in the state, a heat treatment is performed to collect in a crystallized state. Generally speaking, since the film in the amorphous state is excellent in durability and secondary workability, and the film in the crystallized state is excellent in heat resistance and rigidity (plasticity), it is important to use the film in the optimal crystallized state according to the application. membrane. When a crystallized film is used, it is preferable to crystallize it by heating with a casting roll from the viewpoint of productivity and cost. In general, when a film is collected after being crystallized by a casting roll, there are cases in which the crystallization is not sufficiently completed because the production line speed needs to be increased, and the time for the film to contact the casting roll is less. A film with the desired crystallinity is obtained. Since the crystalline polyimide resin (A) used in the present invention has an extremely fast crystallization rate, a film having sufficient crystallinity can be obtained by heat treatment using a casting roll. As a criterion for making the crystallization rate better, the crystalline polyimide resin (A) was heated at a heating rate of 10°C/min to a temperature higher than the crystal melting temperature using a differential scanning calorimeter (DSC), so that the crystals were completely melted. Then, the temperature of the crystallization peak during cooling at 10°C/min is set as the cooling crystallization temperature. At this time, the difference between the crystal melting temperature and the cooling crystallization temperature is preferably below 70°C, preferably below 60°C, More preferably, it is 50°C or lower. As long as the crystallization peak during the cooling process is in this temperature range, the crystallization speed is sufficiently fast, and a film with sufficient crystallinity can be obtained by heat treatment using a casting roll. Although the thickness of the said film is not specifically limited, It is 1-200 micrometers normally as a diaphragm edge material for electroacoustic transducers. Moreover, it is also important to form a film so that the anisotropy of physical properties in the advancing direction (MD) of the film from the extruder and its orthogonal direction (TD) is as small as possible. The film thus obtained can be further processed secondary as a diaphragm edge material for an electro-acoustic transducer. The secondary processing method is not particularly limited. For example, in the case of a speaker diaphragm, the film is heated in consideration of its glass transition temperature or softening temperature, and is secondary processed into a dome shape or a dome shape by press forming or vacuum forming. Conical shape, etc. The edge material of the diaphragm for an electroacoustic transducer of the present invention is used for the diaphragm for an electroacoustic transducer. The diaphragm edge material for electroacoustic transducers is preferably used for a microspeaker diaphragm. The shape of the vibration plate is not particularly limited, and may be arbitrary, and a circular shape, an elliptical shape, an oval shape, and the like may be selected. Moreover, the diaphragm for electroacoustic transducers generally has a main body which vibrates according to an electric signal etc., and the edge which surrounds the periphery of the main body. The body of the vibrating plate is usually supported by the edges. The shape of the main body can be a dome shape, a cone shape, or other shapes used for the vibration plate. The diaphragm edge material for electroacoustic transducers of the present invention is not particularly limited as long as it is a member constituting at least the edge of the diaphragm. Therefore, both the main body and the edge of the vibration plate may be integrally formed by the vibration plate edge material for electroacoustic transducers, or only the edge of the vibration plate may be formed by the vibration plate edge material for electroacoustic transducers, except for the edges of the vibration plate. Parts, such as the main body, are formed by other components. In the present invention, even if the edge and the main body of the diaphragm are integrally formed by the diaphragm edge material or film for an electroacoustic transducer of the present invention, a diaphragm for an electroacoustic transducer having good workability and excellent performance can be obtained. 1 is a diagram showing the structure of a microspeaker diaphragm 1 according to an embodiment of the present invention, and is a cross-sectional view of a circular microspeaker diaphragm 1 cut along a plane passing through the center line of the circle in plan view. As shown in FIG. 1, the micro-speaker diaphragm 1 has a dome (main body) 1a as the center, and has a recessed portion 1b mounted on the voice coil 2, a peripheral portion (edge) 1c, and a frame attached to the outer periphery thereof, etc. External attachment portion 1d. Since the tensile modulus of the film of the present invention is not too high, when it is used as a diaphragm edge material for an electro-acoustic transducer, especially a diaphragm edge material for a small electro-acoustic transducer, the playability in the low range can be ensured , the sound quality becomes good, so it is better. Here, as the size of the vibrating plate, the maximum diameter is preferably 25 mm or less, preferably 20 mm or less, and the lower limit is usually about 5 mm. In addition, the maximum diameter refers to the diameter when the shape of the vibrating plate is a circular shape, and the long diameter when the shape of an elliptical shape or an oval shape is used. A V-shaped groove or the like in the cross-sectional shape called a tangential edge can be appropriately formed on the surface of the vibrating plate. FIG. 2 shows a plan view of a micro-speaker diaphragm 1 ′ according to another embodiment of the present invention. The micro-speaker vibrating plate 1' has a tangential edge portion 1g formed with a plurality of tangential edges 1e and a tangential edge portion formed with a plurality of tangential edges 1f on the outer peripheral portion of the circular dome (main body) 1a' Section 1h. In the form having a tangential edge, if the average thickness of the film is preferably 3 to 40 μm, more preferably 5 to 38 μm, the thickness can be sufficiently ensured, and the workability is also good, and the average thickness of the film is good in press molding and the like. The secondary workability over time or the secondary processing accuracy (shape reproducibility) is easy to improve, so it is preferable. The vibration plate 1 and the vibration plate 1 ′ may be constituted by the above-mentioned film, or may be constituted by a composite material of the membrane and other members, for example, a laminate described later. In addition, the diaphragm edge material for an electroacoustic transducer of the present invention may be a laminate having the diaphragm edge material for an electroacoustic transducer on the front and back layers, and an adhesive layer having a high damping effect (internal loss) in the middle layer. body. By adopting such a laminated structure, it is possible to impart the heat resistance, rigidity, durability and formability of the diaphragm edge material for the electroacoustic transducer of the front and back layers, and the excellent damping properties of the intermediate layer. The method for producing the diaphragm edge material for the electroacoustic transducer as a laminated body is not particularly limited. For example, the following methods are exemplified: by secondary processing a pair of films having the above-mentioned characteristics, the diaphragm edge members for electroacoustic transducers constituting the front layer and the back layer are respectively produced, and the diaphragm edge members for electroacoustic transducers constituting the front layer and the back layer are respectively produced, and the adhesive agent used in the intermediate layer is used. These are then produced; or a pair of films having the above-mentioned characteristics are bonded through the adhesive used in the intermediate layer to produce a laminated film, and the laminated film is subjected to secondary processing by the above-mentioned method. In this case, the types of adhesives used in the intermediate layer include acrylic adhesives, rubber-based adhesives, polysiloxane-based adhesives, urethane-based adhesives, and the like. In particular, it is preferable to use an acrylic-based or polysiloxane-based adhesive. In this case, the thicknesses of the front surface layer and the back surface layer are preferably 1 μm or more and 30 μm or less, more preferably 2 μm or more and 25 μm or less, and still more preferably 3 μm or more and 20 μm or less. On the other hand, the thickness of the intermediate layer is preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 40 μm or less, and still more preferably 10 μm or more and 30 μm or less. As long as the material type of the intermediate layer and the thickness of each layer are in this configuration, a vibration plate excellent in damping properties can be obtained while maintaining various mechanical properties or molding. Furthermore, in order to realize the secondary processing suitability or dust resistance of the diaphragm, or the adjustment of the acoustic characteristics or the improvement of the design, etc., the film used for the diaphragm edge material for the electroacoustic transducer of the present invention or the surface of the formed diaphragm can also be used. Further appropriate treatment is performed as follows: coating or laminating antistatic agents or various elastomers (such as urethane-based, polysiloxane-based, hydrocarbon-based, fluorine-based, etc.), or metal vapor deposition, or sputtering, or coloring (black or white, etc.) etc. Furthermore, lamination with metals such as aluminum or other films, or compounding with non-woven fabrics, etc. may be further appropriately performed. When the diaphragm edge material for an electro-acoustic transducer of the present invention is used for a loudspeaker diaphragm, it is excellent in durability at high output. For example, in a mobile phone, compared with about 0.3 W of general-purpose models, it can cope with the output resistance level of about 0.6 to 1.0 W, which can be applied to high-output models. In addition, the film containing the crystalline polyimide resin (A) as the main component has not only the basic acoustic characteristics as a speaker diaphragm, especially the diaphragm of a micro-speaker, but also the heat resistance and the moldability of the diaphragm during secondary processing. Excellent. [Film] As described above, the film of the present invention has a tensile modulus of elasticity based on JIS K7127 of 1000 MPa or more and 3000 MPa or less. As described above, the film of the present invention is used for the diaphragm edge material for electroacoustic transducers, and may be used other than the diaphragm edge material for electroacoustic transducers. The film of the present invention is composed of the same material as the diaphragm edge material for electroacoustic transducers. That is, the film of the present invention preferably contains the crystalline polyimide resin (A) containing the tetracarboxylic acid component (a-1) and the diamine component (a-2'), and contains the crystalline polyimide resin The amine resin (A) is used as the main component. In addition, the "main component" here means that the ratio of the crystalline polyimide resin (A) contained in a film exceeds 50 mass %. The ratio of the crystalline polyimide resin (A) contained in the film is preferably 60 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more, particularly preferably 90 mass % or more, especially It is preferable that all (100 mass %) of the components constituting the film are the crystalline polyimide resin (A). As described above, the details of the film are as described for the film used for the diaphragm edge material for electroacoustic transducers, so the description is omitted. In addition, the details of the crystalline polyimide resin (A) used for the film are also the same as those described above, and therefore the description thereof is omitted. Moreover, it is also preferable that the film of this invention contains the polyimide resin composition (X) containing a crystalline polyimide resin (A) and a polyetherimide resin (B). Details of the polyimide-based resin composition (X) used in the present invention will be described below. [Polyimide-based resin composition (X)] The present invention also provides a polyimide-based resin composition (X) containing a crystalline polyimide resin (A) and a polyetherimide resin (B). ). As described above, it is also preferable that the film of the present invention and the diaphragm edge material for an electroacoustic transducer contain the polyimide-based resin composition (X). The crystalline polyimide resin (A) used in the polyimide-based resin composition (X) contains the tetracarboxylic acid component (a-1) and the aliphatic diamine component (a-2), which Details are as above. Among them, as for the crystalline polyimide resin (A) used in the polyimide-based resin composition (X), the crystal melting temperature is preferably 260°C or higher and 350°C or lower, more preferably 270°C or higher and 345°C or lower, more preferably 280°C or higher and 340°C or lower. As long as the crystal melting temperature of the crystalline polyimide resin (A) is 260° C. or higher, the heat resistance of the polyimide resin composition (X) becomes sufficient. On the other hand, as long as the crystal melting temperature is 350° C. or lower, for example, when the polyimide-based resin composition (X) of the present invention is used for molding, molding or secondary processing can be performed at a relatively low temperature, which is preferable. . Moreover, the glass transition temperature of the crystalline polyimide resin (A) used in the polyimide-based resin composition (X) is preferably 150° C. or higher and 300° C. or lower, more preferably 160° C. or higher and 290° C. °C or lower, more preferably 170°C or higher and 280°C or lower. As long as the glass transition temperature of the crystalline polyimide resin (A) is 150° C. or higher, the heat resistance of the polyimide-based resin composition (X) becomes sufficient. On the other hand, as long as the glass transition temperature is 300° C. or lower, when molding using the polyimide-based resin composition (X) of the present invention, molding can be performed at a relatively low temperature, which is preferable. In addition, it is preferable for the same reason to carry out secondary processing of the obtained molded body. In addition, the crystalline polyimide resin (A) used in the polyimide-based resin composition (X) is as described above except for the crystal melting temperature and the glass transition temperature, so descriptions thereof are omitted. <Polyetherimide resin (B)> The polyetherimide resin (B) used in the polyetherimide-based resin composition (X) is not particularly limited, and a known compound can be used, its production method and Properties are described, for example, in US Pat. No. 3,803,085 and US Pat. No. 3,905,942. Specifically, the polyetherimide resin (B) used in the present invention preferably has a structure represented by the following [Chemical 1] in terms of excellent balance between heat resistance and moldability . [hua 1] In the above formula [Chemical 1], n (the number of repetitions) is usually an integer in the range of 10 to 1,000, preferably 10 to 500. As long as n is within this range, the balance between formability and heat resistance is excellent. The above-mentioned formula [Formula 1] can be classified into the structures represented by the following [Formula 2] and [Formula 3] according to the difference in the bonding form, specifically, the difference between the meta-bonding and the para-bonding. [hua 2] [hua 3] In the above [Chemical 2] and [Chemical 3], n (the number of repetitions) is usually an integer in the range of 10 to 1,000, preferably 10 to 500. As long as n is within this range, the balance between formability and heat resistance is excellent. As a specific example of the polyetherimide resin (B) which has such a structure, it is marketed as a brand name "Ultem" series from SABIC Innovative Plastics, for example. The glass transition temperature of the polyetherimide resin (B) is preferably 160°C or higher and 300°C or lower, more preferably 170°C or higher and 290°C or lower, further preferably 180°C or higher and 280°C or lower, particularly preferably 190°C or higher and 270°C or lower, particularly preferably 200°C or higher and 260°C or lower. When the glass transition temperature of the polyetherimide resin (B) is 160° C. or higher, the heat resistance of the polyimide resin composition (X) becomes sufficient. On the other hand, since the glass transition temperature of the polyetherimide resin (B) is 300° C. or lower, molding or secondary processing can be performed at a relatively low temperature. When combined, the crystalline polyimide resin (A) will not be decomposed or deteriorated. The polyimide resin composition (X) of the present invention is characterized in that the content ratio of the polyetherimide resin (B) and the crystalline polyimide resin (A) is (B) on a mass basis. )/(A)=1/99～99/1. The content ratio of the above-mentioned polyetherimide resin (B) and the above-mentioned crystalline polyimide resin (A) can be appropriately adjusted according to the required application. In the polyimide-based resin composition (X) of the present invention, for example, when heat resistance and rigidity are important, the above-mentioned polyetherimide resin (B) and the above-mentioned crystalline polyimide resin are preferred. The content ratio of (A) is (B)/(A)=5/95 or more on a mass basis, more preferably 10/90 or more, and still more preferably 15/85 or more. On the other hand, when the impact resistance is important, the content ratio of the above-mentioned polyetherimide resin (B) and the above-mentioned crystalline polyimide resin (A) is preferably (B)/ (A)=80/20 or less, more preferably 70/30 or less, still more preferably 60/40 or less. In addition, when the polyimide-based resin composition (X) of the present invention is used for the diaphragm edge material or film for the above-mentioned electroacoustic transducer, it is preferably a crystalline polymer from the viewpoint of improving durability. The content of the amide (A) is more than the content of the polyetherimide resin (B) on a mass basis. Specifically, the above-mentioned (B)/(A) is particularly preferably 40/60 or less, particularly preferably 30/70 or less. Furthermore, when the polyimide-based resin composition (X) is used for an edge material or film of a diaphragm for an electroacoustic transducer, it is also preferable to contain crystalline polyimide (A) as a main component as described above. . The polyimide-based resin composition (X) of the present invention is characterized in that there is a peak value of loss tangent (tanδ), which is measured by the temperature dispersion of dynamic viscoelasticity described in JIS K7244-4, with a strain of 0.1% , measured at a frequency of 10 Hz and a heating rate of 3 °C/min. In the present invention, the temperature represented by the peak value of the above-mentioned loss tangent (tanδ) is defined as the glass transition temperature (Tg). In addition, it can also be considered that the above-mentioned glass transition temperature (Tg) is single when there is a single peak of the loss tangent (tan δ). Furthermore, when measuring the glass transition temperature using a differential scanning calorimeter at a heating rate of 10° C./min in accordance with JISK7121, it can also be stated that only one inflection point representing the glass transition temperature appears. Generally speaking, as long as the glass transition temperature of the polymer blend composition is single, it means that the mixed resins are in a state of being compatible at the molecular level, and it can be confirmed as a compatible system. In addition, when there are two peaks of the loss tangent (tanδ) after blending, but each peak is located in the center, specifically, the peak on the high temperature side is shifted to the low temperature, and the peak on the low temperature side is shifted to the high temperature by the difference. In such cases, these can be considered to be partially compatible systems. When there are also two peaks of loss tangent (tanδ) after blending, these can be considered as immiscible systems. In the partially compatible system, there is a case where one peak is not clear and it is difficult to clearly distinguish from the compatible system. Therefore, in the present invention, except for the case where two or more peaks are clearly observed, all are treated as compatible systems. Generally speaking, in the case of an incompatible system, when an external force such as stretching or bending is applied, peeling occurs at the interface, resulting in a decrease in mechanical properties or whitening. The polyetherimide resin (B) and the crystalline polyimide resin (A) constituting the polyimide-based resin composition (X) of the present invention are compatible with each other, so they can be used without impairing impact resistance. The modification of each resin was carried out below. As described above, the polyimide-based resin composition (X) of the present invention is a composition characterized by a single glass transition temperature (Tg). The glass transition temperature is preferably 150°C or higher and 300°C or lower, more preferably 160°C or higher and 290°C or lower, and still more preferably 170°C or higher and 280°C or lower. As long as the glass transition temperature of the polyimide-based resin composition (X) is 150° C. or higher, the heat resistance of the polyimide-based resin composition (X) will be sufficient. On the other hand, as long as the glass transition temperature is 300° C. or lower, when molding using the polyimide-based resin composition (X), molding can be performed at a relatively low temperature, which is preferable. Moreover, also in the case where the obtained molded body is subjected to secondary processing, it is preferable for the same reason. The polyimide-based resin composition (X) of the present invention preferably has a tensile modulus of elasticity of 2,200 MPa or more in accordance with JIS K7127 in order to have good handleability when it is formed into a film and to be suitably used in various applications. and below 3100 MPa. As long as the tensile elastic modulus is 2200 MPa or more, the film obtained by using the polyimide-based resin composition (X) has sufficient rigidity and is excellent in handleability. From this viewpoint, the tensile modulus of elasticity is more preferably 2250 MPa or more, and particularly preferably 2300 MPa or more. On the other hand, as long as the tensile elastic modulus is 3100 MPa or less, it has sufficient flexibility as a film, which is preferable. From this viewpoint, the tensile modulus of elasticity is further preferably 3050 MPa or less, and particularly preferably 3000 MPa or less. When the polyimide-based resin composition (X) of the present invention is used for the above-mentioned diaphragm edge material for electroacoustic transducers and films for the diaphragm edge material for electroacoustic transducers, the higher the tensile modulus of elasticity is. As low as possible, it is preferably 3000 MPa or less, more preferably less than 2500 MPa, still more preferably 2400 MPa or less, and particularly preferably 2300 MPa or less. The polyimide-based resin composition (X) of the present invention preferably has a tensile elongation at break measured in accordance with JIS K7127 of 130% or more, more preferably 135% or more. As long as the tensile elongation at break is in this range, when the polyimide-based resin composition (X) of the present invention is formed into a film, it is excellent in impact resistance. In addition, there is no trouble such as breakage, and it is possible to stably form or secondary work into various shapes. Furthermore, when the polyimide-based resin composition (X) of the present invention is used for the diaphragm edge material for electroacoustic transducers and the film for the diaphragm edge material for electroacoustic transducers, as described above, The tensile elongation at break is preferably higher, more preferably 200% or more, and still more preferably 250% or more. In addition, the so-called tensile modulus of elasticity and tensile elongation at break of the polyimide-based resin composition (X) are obtained by kneading the resin composition at 340° C. using a Φ40 mm same-direction biaxial extruder. , which was extruded through a T-die, followed by rapid cooling with a casting roll at about 200° C. to produce a film with a thickness of 0.1 mm, and the film was measured. Furthermore, the polyimide-based resin composition (X) of the present invention can be appropriately formulated with other resins, fillers, and various additives, such as heat stabilizers, ultraviolet absorbers, in the scope not exceeding the gist of the present invention, in addition to the above-mentioned components. agents, light stabilizers, nucleating agents, colorants, lubricants, flame retardants, etc. <The molded body of the polyimide-based resin composition (X)> The molded body may be molded by the above-described polyimide-based resin composition (X) of the present invention. As a molded object shape|molded using the polyimide resin composition (X) of this invention, since it is excellent in rigidity and impact resistance, the said film is mentioned preferably. The characteristics of the membrane are as described above. Moreover, as a molded object, the molded object which has shapes, such as a disk, a pipe, a rod, a cap, and a bolt, other than a film, for example can be mentioned. As the application of the formed body and the film, applications requiring heat resistance, rigidity, and impact resistance, such as automotive components, aircraft components, electrical and electronic components, and the like are exemplified. Moreover, the polyimide resin composition (X) is also preferably used as a diaphragm edge material for electroacoustic transducers as described above in these applications. In addition, as mentioned above, the diaphragm edge material for electroacoustic transducers is obtained by, for example, secondary processing a film. The characteristics of the diaphragm edge material for such an electroacoustic transducer are as described above. <Manufacturing method of molded body> The manufacturing method of the molded body is not particularly limited, and known methods such as extrusion molding, injection molding, blow molding, vacuum molding, pressure molding, and press molding can be employed. Further, the method for forming (film-forming) the film containing the polyimide-based resin composition (X) is not particularly limited, and known methods such as extrusion casting using a T-die, calendering, Or a casting method, etc., among them, the extrusion casting method using a T-die can be preferably used in terms of film productivity and the like. In addition, the details of the extrusion casting method using the T-die are as described above, and the description thereof will be omitted. In addition, the film containing the polyimide-based resin composition (X) may be a uniaxially or biaxially stretched film that is overstretched in one direction or two directions. Die casting method, pressing method, calendering method, etc. to produce an unstretched film as a precursor, and then stretching and forming by roll stretching method, tenter stretching method, etc.; or integrally melt extrusion by expansion method, tubular method, etc. out and extension. The thickness of the film formed using the polyimide-based resin composition (X) of the present invention is not particularly limited, but is usually 1 to 200 μm. Moreover, it is also important to form a film so that the anisotropy of physical properties in the advancing direction (MD) of the film from the extruder and its orthogonal direction (TD) is as small as possible. As described above, the present invention provides a method of using a crystalline polyimide resin (A) for an edge material of a diaphragm for an electroacoustic transducer. As described above, by using the crystalline polyimide resin (A) in the present invention, the heat resistance of the diaphragm edge material for electroacoustic transducers, the durability at high output, the reproducibility from bass to treble, Excellent secondary workability and the like. Furthermore, the present invention provides a method of using the polyimide-based resin composition (X) for an edge material of a diaphragm for an electroacoustic transducer, or a molded body or film other than the edge material. In the present invention, by using the polyimide-based resin composition (X), the diaphragm edge material for an electroacoustic transducer, the molded body, and the film can be excellent in heat resistance, rigidity, impact resistance, and the like. Furthermore, in general, "film" refers to a thin and flat product whose thickness is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, usually supplied in the shape of a roll (JIS K6900), and generally speaking, "sheet""Material" refers to a thin product in the definition of JIS, whose thickness is small and flat relative to the length and width. However, the boundary between the sheet and the film is not clear. In the present invention, there is no need to distinguish between the two in words. Therefore, in the present invention, the term "film" also includes "sheet". In the case of "sheet", "film" is also included. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples. In addition, various measurements about the raw material described in this specification, and the film used for the polyimide resin composition of this invention and the diaphragm edge material for electroacoustic transducers of this invention were performed as follows. (1) Glass transition temperature For each raw material, raw material particles, and the obtained film, a viscoelasticity spectrometer DVA-200 (manufactured by IT Meter. and Control Co., Ltd.) was used at a strain of 0.1%, a frequency of 10 Hz, and a heating rate of 3°C. /min The temperature dispersion measurement of dynamic viscoelasticity (dynamic viscoelasticity measurement by JIS K7244-4 method) was performed, and the temperature of the peak of the main dispersion representing the loss tangent (tanδ) was set as the glass transition temperature. (2) Crystal melting temperature, crystal melting enthalpy, and crystallization temperature during cooling With respect to various raw materials and obtained films, they were measured using a differential scanning calorimeter (DSC) at a heating rate of 10°C/min according to JIS K7121. The crystal melting temperature and crystal melting enthalpy during the process were measured. Then, with respect to the crystalline material, the temperature of the crystallization peak (cooling crystallization temperature) when the temperature was lowered at 10°C/min was measured, and the crystallization rate was evaluated based on the difference from the crystal melting temperature. (3) Tensile elastic modulus The obtained film was measured under conditions of temperature 23°C in accordance with JIS K7127. (4) Flexural strength According to JIS P8115, the obtained film was measured under the condition of a temperature of 23°C. (5) Tensile elongation at break The obtained film was measured under the conditions of a temperature of 23° C. and a test speed of 200 mm/min in accordance with JIS K7127. 1. Crystalline polyimide resin (A) (A)-1: crystalline polyimide resin (manufactured by MITSUBISHI GAS CHEMICAL Co., Ltd.; trade name: Therplim TO65S; tetracarboxylic acid component: pyromellitic acid= 100 mol%; diamine component: 1,3-bis(aminomethyl)cyclohexane/octamethylenediamine=60/40 (molar basis); crystal melting temperature: 322°C; crystal melting enthalpy : 40 J/g; glass transition temperature: 208°C) 2. Polyetherimide resin (B) (B)-1: Polyetherimide (manufactured by SABIC Innovative Plastics Co., Ltd., Ultem 1000, glass transition temperature: 232° C.) (B)-2: Polyetherimide (manufactured by SABIC Innovative Plastics Co., Ltd., Ultem CRS5001, glass transition temperature: 240° C.) (Example 1) Using a Φ40 mm uniaxial extruder at 340° C. (A)-1 as the crystalline polyimide resin (A) was melt-kneaded, then extruded through a T-die, heated with a casting roll at about 200°C, and crystallized to produce Crystallized film with a thickness of 25 μm. The measurement of the above-mentioned (1)-(5) was performed about the obtained film. The results are shown in Table 1. (Comparative Example 1) (B)-1: Polyetherimide 1000 (manufactured by SABIC Innovative Plastics Co., Ltd., Ultem1000, amorphous resin, glass transition temperature: 232° C.) was used instead of the crystalline polyimide resin ( A), except that the molding temperature was set to 380° C., the film was produced and measured by the same method as in Example 1. The results are shown in Table 1. (Comparative Example 2) (B)-2: Polyetherimide 5000 (manufactured by SABIC Innovative Plastics Co., Ltd., Ultem CRS5001, amorphous resin, glass transition temperature: 240° C.) was used instead of the crystalline polyimide resin ( A), except that the molding temperature was set to 380° C., the film was produced and measured by the same method as in Example 1. The results are shown in Table 1. [Table 1] Example 1 Comparative Example 1 Comparative Example 2
Crystalline Polyimide Resin (A) (A)-1 100
Polyetherimide 1000 (B)-1 100
Polyetherimide 5000 (B)-2 100
glass transition temperature °C 208 232 240
Crystal Melting Enthalpy J/g 40 - (amorphous) - (amorphous)
crystal melting temperature °C 322 - (amorphous) - (amorphous)
Crystal melting temperature - cooling crystallization temperature °C 47 - (amorphous) - (amorphous)
Tensile modulus of elasticity MPa 2100 3200 3100
Flexural strength Second-rate 4000 80 130
tensile elongation at break % 290 130 100
In Example 1, the film containing the crystalline polyimide resin (A) of the present invention as a main component was used in a crystallized state. Since the tensile modulus of elasticity is in an appropriate range, the film is not only excellent in rigidity (plasticity) and even in handling properties, but also in playback properties in the low-frequency range. In addition, in general, since the toughness of the crystallized film is lowered, the value of the flexural strength or tensile elongation at break tends to be lowered, and even in the crystallized state, the film is sufficiently excellent in terms of these items. value, and excellent durability even at high output. In addition, since the crystal melting enthalpy, crystal melting temperature, flexural strength, and tensile elongation at break are in a preferable range, it is excellent in heat resistance, durability at high output, and secondary workability. Furthermore, since the difference between the crystal melting temperature and the crystallization temperature during cooling is small, the crystallization rate is sufficiently fast, and a film of 25 μm having sufficient crystallinity can be obtained by heat treatment with a casting roll. On the other hand, in Comparative Examples 1 and 2, films containing polyetherimide as a heat-resistant amorphous resin were used. Since this film uses an amorphous resin, it does not have a melting point and is poor in heat resistance. In addition, since the tensile modulus of elasticity is high and the bass reproducibility is poor, the flexural strength or tensile elongation at break is low, so the durability or secondary workability at high output is also insufficient. (Example 2) The mixing mass ratio ((B)/(A)) of (B)-1 and (A)-1 was dry-blended at a ratio of 80/20, and thereafter, Φ40 mm was used in the same direction The shaft extruder was kneaded at 340° C., then extruded through a T-die, and then quenched with a casting roll at about 200° C. to produce a film with a thickness of 0.1 mm. The glass transition temperature, tensile modulus of elasticity, tensile elongation at break, and flexural strength were evaluated for the obtained film. The results are shown in Table 2. (Example 3) Film was carried out in the same manner as in Example 1, except that the mixing mass ratio ((B)/(A)) of (B)-1 and (A)-1 was set to 60/40 production and evaluation. The results are shown in Table 2. (Example 4) Film was carried out in the same manner as in Example 1, except that the mixing mass ratio ((B)/(A)) of (B)-1 and (A)-1 was set to 40/60 production and evaluation. The results are shown in Table 2. (Example 5) Film was carried out in the same manner as in Example 1, except that the mixing mass ratio ((B)/(A)) of (B)-1 and (A)-1 was set to 30/70 production and evaluation. The results are shown in Table 2. (Example 6) Film was carried out in the same manner as in Example 1, except that the mixing mass ratio ((B)/(A)) of (B)-1 and (A)-1 was 20/80 production and evaluation. The results are shown in Table 2. (Example 7) Except having used (B)-2 instead of (B)-1, the production and evaluation of a film were performed by the method similar to Example 2. The results are shown in Table 2. (Example 8) (B)-2 was used instead of (B)-1, and the mixing mass ratio ((B)/(A)) of (B)-2 and (A)-1 was set to 60/40, Except for this, film production and evaluation were performed in the same manner as in Example 2. The results are shown in Table 2. (Example 9) (B)-2 was used instead of (B)-1, and the mixing mass ratio ((B)/(A)) of (B)-2 and (A)-1 was set to 40/60, Except for this, film production and evaluation were performed in the same manner as in Example 2. The results are shown in Table 2. (Example 10) (B)-2 was used instead of (B)-1, and the mixing mass ratio ((B)/(A)) of (B)-2 and (A)-1 was set to 30/70, Except for this, film production and evaluation were performed in the same manner as in Example 2. The results are shown in Table 2. (Example 11) (B)-2 was used instead of (B)-1, and the mixing mass ratio ((B)/(A)) of (B)-2 and (A)-1 was set to 20/80, Except for this, film production and evaluation were performed in the same manner as in Example 2. The results are shown in Table 2. (Example 12) A film was produced and evaluated by the same method as in Example 2 except that (A)-1 was used alone. The results are shown in Table 2. (Comparative Example 3) A film was produced and evaluated by the same method as in Example 2 except that (B)-1 was used alone. The results are shown in Table 2. (Comparative Example 4) A film was produced and evaluated by the same method as in Example 2 except that (B)-2 was used alone. The results are shown in Table 2. [Table 2] Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 3 Comparative Example 4
Crystalline Polyimide Resin (A) (A)-1 20 40 60 70 80 20 40 60 70 80 100
Polyetherimide resin (B) (B)-l 80 60 40 30 20 100
(B)-2 80 60 40 30 20 100
glass transition temperature °C 228 224 222 221 220 236 234 232 231 230 208 232 240
Tensile modulus of elasticity MPa 3000 2800 2500 2400 2300 3000 2800 2600 2500 2400 2100 3200 3300
tensile elongation at break % 160 190 230 245 260 140 180 210 230 250 290 120 100
Flexural strength Second-rate 175 380 835 1230 1825 260 510 1020 1430 2020 4000 80 130
Although the films comprising the compositions of Examples 2 to 11 were blends of polyetherimide resin (A) and crystalline polyimide resin (B), the glass transition temperatures represented by the peaks of the main dispersion were the same. It is single, and it can be confirmed that it is a compatible system. All physical properties of the film are included in an appropriate range. In addition, all the physical properties of the film of Example 12 were generally included in the appropriate range, but the tensile modulus of elasticity was relatively low, and the workability when used in the form of a film was considered to be lower than that of the other Examples 2 to 11. On the other hand, the films of Comparative Examples 3 and 4 had high tensile modulus and insufficient flexibility, and also had low tensile elongation at break values and insufficient impact resistance.
