TWI784350B - 複合材料之製造方法 - Google Patents

複合材料之製造方法 Download PDF

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TWI784350B
TWI784350B TW109139897A TW109139897A TWI784350B TW I784350 B TWI784350 B TW I784350B TW 109139897 A TW109139897 A TW 109139897A TW 109139897 A TW109139897 A TW 109139897A TW I784350 B TWI784350 B TW I784350B
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fluororesin
mentioned
melt
composite material
carbon fiber
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村上眞司
湯川宏和
羽儀圭祐
金森尚哲
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日商大金工業股份有限公司
日商福美化學工業股份有限公司
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Abstract

本發明提供一種於製作預浸體時氟樹脂膜不易在寬度方向收縮之氟樹脂/碳纖維複合材料之製造方法。本發明係一種複合材料之製造方法，該複合材料含有碳纖維與可熔融加工之氟樹脂，且該製造方法包括下述步驟：步驟（1），其將經開纖之碳纖維、與將逆張力設為3.0 N/cm2 以下之可熔融加工之氟樹脂的膜進行重疊，於該重疊之狀態加熱至上述氟樹脂之熔點以上之溫度並進行加壓，藉此獲得預浸體；及步驟（2），其將上述預浸體在厚度方向重疊1片以上，於該重疊狀態加熱至上述氟樹脂之熔點以上並進行加壓，藉此獲得上述複合材料。

Description

複合材料之製造方法
本發明係關於一種複合材料之製造方法。
近年來，開發且市售有多種纖維強化之複合材料，其係於合成樹脂等基質中混入或夾入作為強化材料之碳纖維或玻璃纖維、芳香族聚醯胺纖維等而成者。該等纖維強化複合材料可依基質與強化材料之選擇而於強度、耐熱性、耐蝕性、電特性、輕量性等諸方面獲得符合目的之優異性能，故用於航太、陸上運輸、船舶、建築、土木、工業用零件、運動用品等廣泛領域，具有廣大社會需求。
作為強化纖維之使用形態，有將複數根長絲排列成所需寬度而成之形態、將長絲切割為特定尺寸而成之形態、梭織物等製成布狀之形態等。作為複合材料，可列舉：利用基質使該等強化纖維直接複合化而成之複合材料；或使長絲有規律地排列而形成片材或梭織物等，使合成樹脂含浸至該片材或梭織物等中而製造出被稱為預浸體之半成品，視需要將該預浸體重疊適當片數，並利用高壓釜等裝置製成目標最終製品而成之複合材料等。
該等強化纖維係以進行併線並利用上漿劑進行結合而成之複絲之形態提供，若為加工時之黏度較高之熱塑性樹脂，則不易使樹脂充分地含浸至強化纖維束中，因此業界正在研究對強化纖維進行開纖而容易使樹脂含浸之技術（例如參照專利文獻1）。
又，專利文獻2及3中記載有一種纖維強化熱塑性樹脂片，其使用了經開纖之碳纖維、及尼龍、聚丙烯等非氟系基質樹脂。 先前技術文獻 專利文獻
專利文獻1：國際公開第97/41285號 專利文獻2：日本特開2003-165851號公報 專利文獻3：日本特開2012-148568號公報
[發明所欲解決之課題]
本發明之目的在於提供一種於製作預浸體時氟樹脂膜不易在寬度方向收縮之氟樹脂/碳纖維複合材料之製造方法。 [解決課題之技術手段]
本發明係關於一種複合材料之製造方法，該複合材料含有碳纖維與可熔融加工之氟樹脂；且該製造方法包括下述步驟： 步驟（1），其將經開纖之碳纖維、與將逆張力設為3.0 N/cm2 以下之可熔融加工之氟樹脂的膜進行重疊，於該重疊之狀態加熱至上述氟樹脂之熔點以上之溫度並進行加壓，藉此獲得預浸體；及 步驟（2），其將上述預浸體在厚度方向重疊1片以上，於該重疊狀態加熱至上述氟樹脂之熔點以上並進行加壓，藉此獲得上述複合材料。
上述可熔融加工之氟樹脂較佳為選自由四氟乙烯/全氟(烷基乙烯基醚)共聚物、四氟乙烯/六氟丙烯共聚物、乙烯/四氟乙烯共聚物、聚氯三氟乙烯及聚偏二氟乙烯所組成之群中至少一種。
上述可熔融加工之氟樹脂較佳為，熔體流動速率為0.1～100 g/10分鐘，熔點為272～323℃。
上述可熔融加工之氟樹脂較佳為四氟乙烯/全氟(烷基乙烯基醚)共聚物。 [發明之效果]
根據本發明，可提供一種於製作預浸體時氟樹脂膜不易在寬度方向收縮之氟樹脂/碳纖維複合材料之製造方法。
氟樹脂具有耐熱性、耐化學品性、滑動性、低介電常數等多種優異之特性，而可用於汽車、飛機、半導體、電氣、電子、化學等眾多領域，但與其他樹脂相比，亦存在強度較低，線膨脹係數較大等課題。作為其解決方法之一，可例舉與碳纖維等強化纖維之複合化，但若與使用尼龍等非氟系基質樹脂時以相同之條件製作預浸體，則會產生氟樹脂膜在寬度方向收縮之問題。本發明人等進行了努力研究，結果發現，氟樹脂之彈性模數較低，若以與非氟系樹脂相同之逆張力陸續拉出氟樹脂膜，則氟樹脂膜會因逆張力及熱而在寬度方向收縮。並且發現，藉由將逆張力控制於特定之範圍內，可解決上述收縮問題。 以下，對本發明進行具體說明。
本發明係關於一種複合材料之製造方法，該複合材料含有碳纖維與可熔融加工之氟樹脂；且該製造方法包括下述步驟： 步驟（1），其將經開纖之碳纖維、與將逆張力設為3.0 N/cm2 以下之可熔融加工之氟樹脂之膜進行重疊，於該重疊之狀態加熱至上述氟樹脂之熔點以上並進行加壓，藉此獲得獲得預浸體；及步驟（2），其將上述預浸體在厚度方向重疊1片以上，於該重疊狀態加熱至上述氟樹脂之熔點以上之溫度並進行加壓、藉此獲得上述複合材料。 關於本發明之製造方法，於製作預浸體之步驟（1）中，上述可熔融加工之氟樹脂之膜不易在寬度方向收縮。其結果為，可提昇連續生產上述複合材料時之品質的穩定性。
步驟（1）中所使用之碳纖維被開纖。藉此，上述氟樹脂充分地含浸至上述碳纖維中。 開纖之方法並無特別限制，可採用：交替地通過凹凸輥之方法；使用鼓型輥之方法；對軸向振動施加張力變動之方法；利用進行垂直往返運動之2個摩擦體使碳纖維束之張力發生變動之方法；向碳纖維束吹送空氣之方法等。又，亦可採用日本專利第3064019號公報及日本專利第3146200號公報中所記載之開纖方法。
上述碳纖維較佳為單位面積重量為100 g/m2 以下，更佳為80 g/m2 以下，進而較佳為50 g/m2 以下，又，較佳為10 g/m2 以上。單位面積重量越低，則越易使氟樹脂含浸至碳纖維中。又，上述單位面積重量亦可為30 g/m2 以上。
作為上述碳纖維，可列舉：聚丙烯腈系、瀝青系、嫘縈系、纖維素系、木質素系、酚系、氣相生長系等。其中，較佳為聚丙烯腈系、瀝青系或嫘縈系碳纖維，更佳為聚丙烯腈系碳纖維。
上述碳纖維可進行表面處理，可使用處理劑，亦可使用上漿劑。
步驟（1）中所使用之氟樹脂可熔融加工。於本說明書中，所謂可熔融加工，意指可使用擠出機及射出成形機等習知之加工機器使聚合物熔融而進行加工。 上述可進行熔融加工之氟樹脂較佳為熔體流動速率（MFR）為0.1～100 g/10分鐘，更佳為0.5～50 g/10分鐘。 於本說明書中，MFR係依據ASTM D1238，使用熔融指數測定儀，於根據氟樹脂之種類而決定之測定溫度（例如，於PFA或FEP之情形時為372℃，於ETFE之情形時為297℃）、負重（例如，於PFA、FEP及ETFE之情形時為5 kg）時，以自內徑2 mm、長度8 mm之噴嘴每10分鐘流出之聚合物之質量（g/10分鐘）之方式獲得之值。
上述氟樹脂較佳為熔點為150～323℃，更佳為200～323℃，進而較佳為250～323℃，進而更佳為272℃～323℃，尤佳為280～320℃。 上述熔點係與使用示差掃描熱量計[DSC]以10℃/分鐘之速度升溫時之熔融熱曲線中之極大值對應之溫度。
作為上述氟樹脂，較佳為選自由四氟乙烯[TFE]/全氟(烷基乙烯基醚)[PAVE]共聚物[PFA]、TFE/六氟丙烯[HFP]共聚物[FEP]、乙烯[Et]/TFE共聚物[ETFE]、聚氯三氟乙烯[PCTFE]、及聚偏二氟乙烯[PVDF]所組成之群中至少一種，更佳為選自由PFA、FEP及ETFE所組成之群中至少一種，進而較佳為PFA。
上述PFA具有基於四氟乙烯（TFE）之聚合單位（TFE單位）及基於全氟(烷基乙烯基醚)（PAVE）之聚合單位（PAVE單位）。
作為上述PAVE，並無特別限制，例如可列舉下述通式（1）： CF2 =CF-ORf1 （1） （式中，Rf1 表示碳數1～10、較佳為碳數1～5之全氟烷基）所表示者，其中，較佳為全氟(甲基乙烯基醚)[PMVE]、全氟(乙基乙烯醚)[PEVE]、全氟(丙基乙烯基醚)[PPVE]。
作為上述PFA，並無特別限制，較佳為相對於TFE單位與PAVE單位之合計的TFE單位之比率為70莫耳%以上且未達99.5莫耳%之共聚物，更佳為TFE單位之比率為70莫耳%以上且98.9莫耳%以下之共聚物，進而較佳為TFE單位之比率為80莫耳%以上且98.7莫耳%以下之共聚物。上述PFA可為僅由TFE單位及PAVE單位所構成之共聚物，亦較佳為以下共聚物，即，相對於總單體單位，來自可與TFE及PAVE進行共聚之單體的單體單位為0.1～10莫耳%，且TFE單位及PAVE單位合計為90～99.9莫耳%。作為可與TFE及PAVE進行共聚之單體，可列舉：HFP、CZ1 Z2 =CZ3 (CF2 )nZ4 （式中，Z1 、Z2 及Z3 可相同或不同，且表示氫原子或氟原子，Z4 表示氫原子、氟原子或氯原子，n表示整數2～10）所表示之乙烯基單體、及CF2 =CF-OCH2 -Rf11 （式中，Rf11 表示碳數1～5之全氟烷基）所表示之烷基全氟乙烯醚衍生物等。
於本說明書中，構成PFA之各單體單位之含量可藉由根據單體之種類將NMR、FT-IR、元素分析、螢光X射線分析加以適當組合而算出。
上述可進行熔融加工之氟樹脂的膜較佳厚度為0.01～2 mm，更佳為0.01～1 mm。
於步驟（1）中，將上述碳纖維與上述氟樹脂之膜進行重疊時，將上述膜之逆張力設為3.0 N/cm2 以下。藉由使逆張力處於上述範圍內，可於製作預浸體時抑制上述膜在寬度方向收縮。 上述逆張力較佳為2.5 N/cm2 以下，更佳為2.0 N/cm2 以下，進而較佳為1.0 N/cm2 以下，尤佳為0.8 N/cm2 以下，又，較佳為0.05 N/cm2 以上，更佳為0.1 N/cm2 以上。 上述逆張力係在「與上述膜之搬送方向相反之方向」對上述膜施加之張力，可藉由控制機器之輸出而進行調整。作為控制機器，例如可列舉三菱電機製造之ZKB-0.6AM/YK等。
於步驟（1）中，較佳為將上述碳纖維及上述氟樹脂之膜連續地搬送。
於步驟（1）中，將上述碳纖維、與將逆張力設為上述範圍內之上述膜進行重疊，於該重疊之狀態加熱至上述氟樹脂之熔點以上之溫度並進行加壓，藉此獲得預浸體。藉由進行加熱、加壓，而使上述氟樹脂含浸至上述碳纖維中。 上述加熱之溫度只要為上述氟樹脂之熔點以上即可，較佳為310℃以上，更佳為340℃以上，又，較佳為400℃以下。 上述加壓之壓力較佳為0.01～5.0 MPa，更佳為0.1～1.0 MPa。 上述加熱及加壓較佳為藉由以下方式而實施，即，利用被加熱至上述氟樹脂之熔點以上之溫度的輥來施加壓力。
上述預浸體可為對上述碳纖維與上述氟樹脂進行熱熔接而成者。上述預浸體較佳為上述氟樹脂含浸至上述碳纖維中。
上述預浸體較佳為，相對於上述碳纖維與上述氟樹脂之合計量，上述碳纖維為5～70體積%。上述碳纖維更佳為10體積%以上，進而較佳為15體積%以上，又，更佳為60體積%以下，進而較佳為50體積%以下。
本發明之製造方法可進而包括以下步驟：藉由切割步驟（1）中所獲得之預浸體而獲得短切材。可將上述短切材用作步驟（2）中之預浸體。 上述短切材可於二維方向無規地配向而積層，因此可使碳纖維類等向性地配向，從而使所獲得之複合材料之「由方向導致之強度差」變少。又，亦可容易地成形為複雜形狀。
本發明之製造方法亦可進而包括以下步驟：將使2片以上之上述短切材在厚度方向進行重疊，於該重疊狀態進行加熱，藉此獲得短切片。亦可將上述短切片用作步驟（2）中之預浸體。
於步驟（2）中，將上述預浸體在厚度方向重疊1片以上，於該重疊狀態加熱至上述氟樹脂之熔點以上並進行加壓，藉此獲得含有碳纖維與可熔融加工之氟樹脂的複合材料。
於步驟（2）中，較佳為將上述預浸體在厚度方向重疊2片以上。於該情形時，構成各預浸體之碳纖維之配向可相同，亦可不同。於重疊之預浸體為上述短切材之情形時，較佳為在二維方向上無規地配向。
步驟（2）中之加熱之溫度只要為上述氟樹脂之熔點以上即可，較佳為310℃以上，更佳為340℃以上，又，較佳為400℃以下。
步驟（2）中之加壓之壓力較佳為0.05～10 MPa，更佳為2～5 MPa。
於步驟（2）中，可同時進行成形而獲得含上述碳纖維及上述氟樹脂之複合成形品。於該情形時，例如只要使用壓縮成形機進行上述加熱及加壓即可。
關於藉由本發明之製造方法而獲得之複合材料，於由2片以上之上述預浸體而獲得之情形時，上述複合材料較佳為2片以上之上述預浸體被一體化。此處，所謂一體化意指上述預浸體彼此熱熔接而構成一種材料。經熱熔接之上述預浸體彼此之界面可不必明確。
上述複合材料較佳為，相對於上述碳纖維與上述氟樹脂之合計量，上述碳纖維為5～70體積%。上述碳纖維更佳為10體積%以上，進而較佳為15體積%以上，又，更佳為60體積%以下，進而較佳為50體積%以下。
上述複合材料可藉由壓縮成形等公知之成形方法進行成形而製成成形品。又，如上所述，亦可於步驟（2）中進行成形。
上述複合材料可用於航太、陸上運輸、船舶、建築、土木、工業用零件、運動用品等廣泛領域。其中，可較佳地用於半導體洗淨裝置用構件。 實施例
以下，列舉實施例來進一步詳細地說明本發明，但本發明非僅限於該等實施例。
實施例之各數值係藉由以下方法而測定。 （1）MFR 依據ASTM D3307，於測定溫度372℃、負重5 kg測定自噴嘴每10分鐘流出之聚合物之質量。
實施例1 ＜UD片（預浸體）之製作＞ 使用以下材料製作UD片。 碳纖維束（東麗公司製造之T700SC-12000-60E） PFA膜（MFR 14 g/10分鐘，熔點306℃，厚度0.05 mm） 使用公知之開纖方法將5根上述碳纖維束分別開纖為寬度42 mm，在寬度方向排列並製成片狀，從而製作寬度210 mm之開纖碳纖維片（單位面積重量38.1 g/m2 ）。藉由將控制機器（三菱電機製造之ZKB-0.6AM/YK）之輸出設為5%以下而將上述PFA膜之逆張力設為0.6 N/cm2 ，對該開纖碳纖維片與上述PFA膜進行積層，使其在被設定為360℃之加熱溫度之加熱加壓輥間移行（線速度：10 m/min）而製作UD片。可於上述PFA膜不在寬度方向收縮之狀態下獲得Vf（碳纖維體積含有率）29.7%、厚度0.072 mm之UD片。
實施例2 將PFA膜之厚度設為0.025 mm，將逆張力設為0.25 N/cm2 ，除此以外，藉由與實施例1相同之方式製作UD片。可於上述PFA膜不在寬度方向收縮之狀態下獲得Vf 45.8%、厚度0.046 mm之UD片。
實施例3 將PFA膜之厚度設為0.050 mm，將逆張力設為2.5 N/cm2 ，除此以外，藉由與實施例1相同之方式製作UD片。儘管上述PFA膜在寬度方向收縮了2～3 mm左右，但仍可獲得Vf 29.7%、厚度0.072 mm之UD片。
實施例4 將3根上述碳纖維束分別開纖為寬度75 mm，在寬度方向排列並製成片狀，從而製作225 mm之開纖碳纖維片（單位面積重量26.7 g/m2 ），除此以外，藉由與實施例1相同之方式製作UD片。儘管上述PFA膜在寬度方向收縮了2～3 mm左右，但仍可獲得Vf 22.7%、厚度0.064 mm之UD片。
＜短切材之製作＞ 使用上述UD片，藉由公知之供給機構及切割機構沿著纖維方向將其切割成寬度5 mm，且沿著與纖維方向正交之方向切割成長度20 mm而製作短切材。
＜短切片之製作＞ 使用上述UD片，藉由日本特開2016-27956號公報所記載之方法而製作短切片。於該方法中，使用UD片切割機構、短切材搬送機構、片材一體化機構、片材捲取機構。 首先，利用UD片切割機構沿著纖維方向將UD片切割成寬度5 mm，沿著與纖維方向正交之方向切割成長度20 mm而製作短切材。 其次，使所獲得之寬度5 mm×長度20 mm之短切材自然掉落於搬送帶上並使其分散。在帶上重疊之短切材係在厚度方向重疊2片以上者。 其次，利用被設定為360℃之加熱溫度之加熱輥使短切材熔融一體化（線速度：0.6 m/min）而製作短切片。所獲得之短切片之單位面積重量為500 g/m2 ，厚度為0.6 mm。
＜複合材料之製作＞ 使用公知之加壓成形機由上述UD片、短切材、短切片分別製作複合材料。 關於由UD片來製作複合材料之情況，係以成為寬度298 mm×長度298 mm之方式將UD片加以組合，積層940片，將模具設定為360℃之加熱溫度，於5 MPa之壓力進行5分鐘加熱加壓，以使成形品厚度成為40 mm。然後，將模具設定為30℃之溫度，於7 MPa之壓力進行20分鐘加壓。
比較例1 將上述PFA膜之逆張力設為5.0 N/cm2 並積層上述開纖碳纖維片與上述PFA膜，除此以外，藉由與實施例2相同之方式製作UD片，但使其在加熱加壓輥之間移行時，上述PFA膜在長度方向延伸，由於在寬度方向收縮20 mm以上，且厚度亦發生變化，因此無法獲得所設定之規格的UD片。
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Claims (5)

  1. 一種複合材料之製造方法，該複合材料含有碳纖維與可熔融加工之氟樹脂；且該製造方法包括下述步驟：步驟(1)，其將經開纖之碳纖維、與將逆張力設為3.0N/cm2以下之可熔融加工之氟樹脂的膜進行重疊，於該重疊之狀態加熱至上述氟樹脂之熔點以上之溫度並進行加壓，藉此獲得預浸體；及步驟(2)，其將上述預浸體在厚度方向重疊1片以上，於該重疊狀態加熱至上述氟樹脂之熔點以上並進行加壓，藉此獲得上述複合材料。
  2. 如請求項1之製造方法，其中，上述可熔融加工之氟樹脂為選自由四氟乙烯/全氟(烷基乙烯基醚)共聚物、四氟乙烯/六氟丙烯共聚物、乙烯/四氟乙烯共聚物、聚氯三氟乙烯及聚偏二氟乙烯所組成之群中至少一種。
  3. 如請求項1或2之製造方法，其中，上述可熔融加工之氟樹脂的熔體流動速率為0.1~100g/10分鐘，熔點為272~323℃。
  4. 如請求項1或2之製造方法，其中，上述可熔融加工之氟樹脂為四氟乙烯/全氟(烷基乙烯基醚)共聚物。
  5. 如請求項3之製造方法，其中，上述可熔融加工之氟樹脂為四氟乙烯/全氟(烷基乙烯基醚)共聚物。
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