CN102181111B - 含填充材料的氟树脂片材的制造方法及含填充材料的氟树脂片材 - Google Patents

含填充材料的氟树脂片材的制造方法及含填充材料的氟树脂片材 Download PDF

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CN102181111B
CN102181111B CN201110040362XA CN201110040362A CN102181111B CN 102181111 B CN102181111 B CN 102181111B CN 201110040362X A CN201110040362X A CN 201110040362XA CN 201110040362 A CN201110040362 A CN 201110040362A CN 102181111 B CN102181111 B CN 102181111B
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resin
sheet material
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黑河真也
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Co Walka
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Abstract

本发明的含填充材料的氟树脂片材的制造方法包含在轧辊温度为40～80℃的条件下轧制含有氟树脂、填充材料及加工助剂的片材形成用树脂组合物的工序，该加工助剂含有30质量％以上(这里，加工助剂重量为100质量％)的分馏温度为120℃以下的石油烃溶剂。通过本发明，提供即使在氟树脂的填充率低、填充材料的填充率高的情况下，高应力松弛特性和高气密特性(密封性能)也并存的含填充材料的氟树脂片材及其制造方法。

Description

含填充材料的氟树脂片材的制造方法及含填充材料的氟树脂片材
本发明专利申请是国际申请号为PCT/JP2007/055505，国际申请日为2007年3月19日，进入中国国家阶段的申请号为200780010182.9，名称为“含填充材料的氟树脂片材的制造方法及含填充材料的氟树脂片材”的发明专利申请的分案申请。
技术领域
本发明涉及含填充材料的氟树脂片材的制造方法及含填充材料的氟树脂片材，更具体地，涉及可作为密封材料等使用的含填充材料的氟树脂片材的制造方法及含填充材料的氟树脂片材。
背景技术
含填充材料的氟树脂片材是向氟树脂中填充填充材料、加工成片状的片材，除氟树脂具有的耐化学品性、耐热性、非粘着性、低摩擦性以外，还通过附加填充材料具有的固有的性能、特性，或改善作为氟树脂的缺点的耐磨损性和抗蠕变性，而多用于密封材料等。
作为密封材料，有向氟树脂中填充金属、石墨、无机填充剂等、使热传导率、耐磨损性、蠕变特性等提高的材料，用于片状垫片和压盖填料(glandpacking)的编织线等。
美国专利第3315020号说明书(专利文献1)揭示了一项技术，该技术将PTFE、填充材料和加工助剂的混合物挤出成形后，使其一次或多次通过1对轧制轧辊进行轧制，得到长片材。但是，利用该技术制成由含填充材料的氟树脂片材构成的片状垫片时，如果提高填充材料的填充率，则虽然应力松弛特性有优化的趋势，但气密性低，无法得到能满足密封材料的要求的材料。
另一方面，日本专利特开2004-323717号公报(专利文献2)揭示了一种含填充材料的氟树脂片材，该片材是将含有氟树脂、膨润性矿物、填充材料及加工助剂的组合物挤出成形后，使其通过轧制轧辊，延伸为片状而形成的。该含填充材料的氟树脂片材即使在氟树脂的填充率低、填充材料的填充率高的情况下，应力松弛率、拉伸强度等也良好。
专利文献1：美国专利第3315020号说明书
专利文献2：日本专利特开2004-323717号公报
发明的揭示
然而，专利文献2记载的含填充材料的氟树脂片材有作为将硬的粒子状的无机填充材料之间的间隙填满的粘合剂的氟树脂不足的趋势，因此可知，在密封性能这一点上还有进一步改善的余地。
本发明鉴于上述问题，其目的是提供即使在氟树脂的填充率低、填充材料的填充率高的情况下，高应力松弛性和高气密性(密封性能)也并存的含填充材料的氟树脂片材及其制造方法。
本发明者经过认真研究，结果发现通过在含填充材料的氟树脂片材制造时的轧制工序中使加工助剂逐渐挥发，可制造高应力松弛性和高气密性并存的含填充材料的氟树脂片材，从而完成了本发明。
本发明的含填充材料的氟树脂片材的制造方法的特征在于，
包含在轧辊温度为40～80℃的条件下轧制含有氟树脂、填充材料及加工助剂的片材形成用树脂组合物的工序，
该加工助剂含有30质量％以上(这里，加工助剂重量为100质量％)的分馏温度为120℃以下的石油烃溶剂。
上述组合物中的上述氟树脂和上述填充材料的质量比较好为氟树脂∶填充材料＝1∶0.1～2。
上述组合物中，较好的是相对于氟树脂和填充材料总计100重量份，含有5～50重量份的上述加工助剂。
本发明的制造方法较好的是包含将通过上述轧制工序制得的轧制片材进一步轧制的工序。
本发明的含填充材料的氟树脂片材的特征在于，通过上述本发明的含填充材料的氟树脂片材的制造方法制造。
利用本发明的制造方法，可制造尽管氟树脂的填充率低、填充材料的填充率高，高应力松弛特性和高气密性仍然并存的含填充材料的氟树脂片材。
实施发明的最佳方式
本发明的含填充材料的氟树脂片材的制造方法的特征在于，包含在轧辊温度为40～80℃的条件下轧制含有氟树脂、填充材料及加工助剂的片材形成用树脂组合物的工序，该加工助剂含有30质量％以上(这里，加工助剂重量为100质量％)的分馏温度为120℃以下的石油烃溶剂。
[片材形成用树脂组合物]
<氟树脂>
作为氟树脂，除四氟乙烯树脂(PTFE)以外，还可较好地使用改性PTFE、偏氟乙烯树脂(PVDF)、四氟乙烯-乙烯共聚物树脂(ETFE)、三氟氯乙烯树脂(PCTFE)、四氟乙烯-六氟丙烯乙烯共聚物树脂(FEP)及四氟乙烯-全氟烷基共聚物树脂(PFA)等一直以来公知的氟树脂的任一种。其中，在进行挤出成形、轧制等时的加工性方面，特好的是使用乳液聚合而得的PTFE。
作为氟树脂，可直接使用粉末状的氟树脂，也可使用将氟树脂微粒分散于水中的分散体(dispersion)。使用分散体时，只要向氟树脂分散体中添加适量的水、填充材料、加工助剂等并搅拌，即可得到含填充材料的氟树脂片材形成用组合物，通过使用该组合物，可更高效地得到含填充材料的氟树脂片材。
<填充材料>
作为填充材料，可根据目的使用石墨、炭黑、膨胀石墨、活性炭、碳纳米管等碳系填充材料；滑石、云母、粘土、碳酸钙、氧化镁等无机填充材料；或PPS等树脂的粉体等。此外，可使用由碳纤维、芳香族聚酰胺纤维、石棉等构成的纤维材料长度为10mm以下的纤维材料作为填充材料。
根据本发明，即使在氟树脂的填充率低、填充材料的填充率高的情况下，也可制造高应力松弛性和高气密性并存的含填充材料的氟树脂片材，可使上述氟树脂和上述填充材料的质量比为1∶0.1～2、较好为1∶1～1.8。
<加工助剂>
上述氟树脂片材形成用组合物中含有加工助剂。
本发明中使用的加工助剂含有30质量％以上、较好为50质量％以上的分馏温度为120℃以下(较好为110℃以下)的石油烃溶剂(这里，加工助剂重量为100质量％)，特好的是本质上仅由分馏温度为120℃以下的石油烃溶剂组成。分馏温度的下限值无特别限制，但如果分馏温度过低，则在轧制工序中加工助剂的挥发过度地加快，因此逐渐挥发、除去加工助剂会变得困难，所以可以在80℃左右。
作为分馏温度为120℃以下的石油烃溶剂，作为代表例可例举石蜡(paraffin)族溶剂等，如果是市售商品，则例如可例举Isopar C(烃系有机溶剂，分馏温度97～104℃，埃克森美孚(有))等。
以往的含填充材料的氟树脂片材的制造方法中，一般使用分馏温度高(例如180～250℃)的石油烃溶剂作为加工助剂。该加工助剂在轧制作业中溶剂不挥发、可进行稳定的轧制作业这一点上是通用的，但在后述轧制工序中即使提高轧辊温度也难以挥发。
作为加工助剂可含有的、分馏温度为120℃以下的石油烃溶剂以外的成分，可例举分馏温度超过120℃的石油烃溶剂等。作为分馏温度超过120℃的石油烃溶剂，如果是市售商品，则例如可例举Isopar G(烃系有机溶剂，分馏温度158～175℃，埃克森美孚(有))等。
理想的是在片材形成用树脂组合物中相对于氟树脂和填充材料总计100重量份含有5～50重量份、较好为10～30重量份的该加工助剂。如果以该量含有加工助剂，则在后述轧制工序的初期阶段可使氟树脂充分地膨润。
片材形成用树脂组合物本质上仅由上述氟树脂、填充材料、加工助剂组成。
要调制含有这些成分的氟树脂片材形成用树脂组合物，只要将上述各成分按任意顺序一次性、或每次少量分为多次添加至容器内，搅拌、混合等即可。
<氟树脂片材的制造方法>
一般的含填充材料的氟树脂片材的制造方法依次包含搅拌工序、预成形工序、轧制工序、干燥工序、烧成工序。
<搅拌工序>
搅拌工序中，如上所述将氟树脂、填充材料、加工助剂按任意顺序搅拌、混合。搅拌效率不佳时，可多添加加工助剂，搅拌结束后通过过滤除去多余的加工助剂。
<预成形工序>
预成形工序中，将上述氟树脂片材形成用树脂组合物挤出成形，制造预成形体(挤出成形物)。
挤出成形物(预成形体)的形状无特别限制，但如果考虑之后的片材形成效率、片材性状的均质性等，则理想的是杆状或带状。
本发明的制造方法中，在后述轧制工序中使加工助剂逐渐挥发，因此混合工序及预成形工序较好的是在低于轧制工序中的轧辊温度的温度下进行，使加工助剂不挥发。
<轧制工序>
在接着预成形工序的轧制工序中，使预成形体通过以双轴轧辊为代表的轧制轧辊之间，轧制、成形为片状。已有技术中，轧制工序在非加热下、具体的是在室温附近的10～30℃左右的温度下进行，且一般使用分馏温度高(例如180～250℃)的石油烃溶剂作为加工助剂，因此在该轧制工序中加工助剂几乎不会挥发。
该加工助剂是为使氟树脂易于膨润、纤维化而使用的。通过在搅拌工序、预成形工序、轧制工序中对片材形成用树脂组合物附加压缩力、剪切力，部分氟树脂纤维化，藉此赋予氟树脂片材由基体(matrix)的复杂化带来的片材强度、应力松弛特性。但是，如果氟树脂在被轧制的氟树脂片材的内部膨润，则该片材易柔软地变形，因此可认为即使受到双轴轧辊等的压缩，也优先发生向平面方向的变形，片材内部的致密化难以发生。另外，片材内部的致密化，是指通过轧制填补由溶剂的挥发产生的组合物内部的空孔。
本发明的制造方法中，该轧制工序是在轧辊温度为40～80℃的条件下进行的，并且使用大量含有分馏温度低(120℃以下)的石油烃溶剂的加工助剂，因此实施使用双轴轧辊等的轧制的过程中，片材形成用树脂组合物中的(预成形体中的)加工助剂逐渐挥发、被除去。因而，在轧制工序的初期阶段加工助剂大量存在，因此可使氟树脂膨润、纤维化，并且在轧制工序的后期阶段加工助剂的残存量少，所以基于加工助剂的挥发的片材内部的新空孔的形成少，因此可认为，可使片材内部的致密化优先于片材的向平面方向的变形进行。
此外，由于在比较高的温度下进行轧制，因此氟树脂的硬度稍稍下降，氟树脂片材变得更易致密化。
另一方面，如果在低于40℃的温度下进行轧制工序，则有加工助剂变得难以挥发的趋势。此外，如果在超过80℃的温度下进行轧制，则加工助剂过度地挥发，轧制工序初期时残存的加工助剂变少，因此有无法使氟树脂充分地膨润、纤维化，所得含填充材料的氟树脂片材的强度差的趋势。此外，有由组合物中的加工助剂急剧气化导致起泡现象发生，含填充材料的氟树脂片材的气密性也下降的趋势。
此外，本发明的制造方法中，较好的是包含将通过上述轧制工序制得的轧制片材进一步轧制的工序，即反复多次进行轧制工序。通过反复轧制，可使氟树脂片材内部更为致密化。另外反复进行轧制工序时，每次反复轧制，都要使轧辊间距更窄。
用双轴轧辊轧制上述预成形体、形成片材时，例如将轧辊间距离设定为0.5～20mm，使轧辊表面移动速度(片材挤出速度)为5～50mm/秒，来轧制预成形体即可。
<干燥工序>
干燥工序中，将上述轧制后的片材在常温下放置，或以氟树脂的沸点以下的温度加热，藉此除去加工助剂。
<烧成工序>
烧成工序中，以氟树脂的熔点以上的温度加热干燥后的片材使其烧结。作为加热温度，如果考虑到必需均一地烧成整个片材和在过度的高温下会产生氟系有害气体，则虽然根据氟树脂的种类多少有所不同，但例如适合的是340～370℃。
[含填充材料的氟树脂片材]
利用上述本发明的制造方法，可制造含填充材料的氟树脂片材。该含填充材料的氟树脂片材的应力松弛性和气密性都高，以JIS R3453为基准的拉伸强度为8MPa以上，且以表面压力为19.6MPa(200kgf/cm2G)、氮气内压力为0.98MPa(1.0kgf/cm2G)的条件对由该片材制成的ф48mm×ф67mm×厚度1.5mm的垫片试验片进行气密试验时的泄漏量为9×10-5Pa·m3/s以下，较好的是上述拉伸强度为10MPa以上，且泄漏量为7×10-5Pa·m3/s以下。
[实施例]
下面，通过实施例进一步就本发明的制造方法作详细说明，但本发明不限定于这些实施例。
<试验方法>
由厚度1.5mm的片材制成试验片，如下所述测定气密性及拉伸强度。
泄漏量(气密性)：
将冲裁成ф48mm×ф67mm的尺寸的垫片试验片安装在ф100mm×高度50mm、表面粗糙度Rmax＝12μm的钢法兰之间，用压缩试验机负载负荷，使表面压力为19.6MPa(200kgf/cm2G)。从设置于法兰的压力导入用的贯通孔将氮气内压力0.98MPa(1.0kgf/cm2G)负载于垫片内径侧，之后封闭压力导入配管，保持1小时。用压力传感器读取保持前后的压力变化，由压力下降求出泄漏量。
拉伸强度：
以JIS R3453为基准制成试验片，测定拉伸强度。
[实施例1]
将PTFE细粉(CD-1，旭硝子(株)制)400g、
NK-300(微粉末粘土，昭和KDE(株)制)600g及
Isopar C(烃系有机溶剂，分馏温度97～104℃，埃克森美孚(有))250g
用捏和机(kneader)混合5分钟后，在室温(25℃)下放置16小时，藉此使其熟化，调制成片材形成用组合物。
在室温(25℃)下以口模300mm×20mm的挤出机挤出该组合物，制成预成形体。
在轧辊直径700mm、轧辊间距20mm、轧辊速度6m/分、轧辊温度40℃的条件下用双轴轧辊轧制该预成形体。该轧制后立即使轧辊间距为10mm，再次轧制所得片材。接着，该轧制后立即使轧辊间距为5mm，再次轧制所得片材。最后，该轧制后立即使轧辊间距为1.5mm，再次轧制所得片材，得到厚度1.5mm的片材。
将该片材在室温(25℃)下放置24小时除去溶剂后，在电炉内以350℃烧成3小时，得到片状垫片(sheet gasket)。
该片状垫片的泄漏量(气密性)为4.0×10-5Pa·m3/s，拉伸强度为11MPa。
[实施例2]
除用Isopar C 125g及Isopar G(烃系有机溶剂，分馏温度158～175℃，埃克森美孚(有))125g代替Isopar C 250g以外，用与实施例1相同的方法制造片状垫片。
该片状垫片的泄漏量(气密性)为6.0×10-5Pa·m3/s，拉伸强度为10MPa。
[实施例3]
除将轧辊温度从40℃变更为80℃以外，用与实施例2相同的方法制造片状垫片。
该片状垫片的泄漏量(气密性)为4.0×10-5Pa·m3/s，拉伸强度为11MPa。
[比较例1]
除用Isopar G 250g代替Isopar C 250g、将轧辊温度从40℃变更为80℃以外，用与实施例1相同的方法制造片状垫片。
该片状垫片的泄漏量(气密性)为1.0×10-4Pa·m3/s，拉伸强度为11MPa。
[比较例2]
除用Isopar G 250g代替Isopar C 250g以外，用与实施例1相同的方法制造片状垫片。
该片状垫片的泄漏量(气密性)为2.0×10-4Pa·m3/s，拉伸强度为10MPa。
[比较例3]
除用Isopar M(烃系有机溶剂，分馏温度218～253℃，埃克森美孚(有))250g代替Isopar C 250g、将轧辊温度从40℃变更为80℃以外，用与实施例1相同的方法制造片状垫片。
该片状垫片的泄漏量(气密性)为8.0×10-4Pa·m3/s，拉伸强度为10MPa。
[比较例4]
除将轧辊温度从40℃变更为25℃以外，用与实施例1相同的方法制造片状垫片。
该片状垫片的泄漏量(气密性)为4.0×10-4Pa·m3/s，拉伸强度为10MPa。
[比较例5]
除将轧辊温度从40℃变更为100℃以外，用与实施例1相同的方法制造片状垫片。
该片状垫片的泄漏量(气密性)为1.0×10-3Pa·m3/s，拉伸强度为6MPa。
[表1]
Figure BSA00000436228200091

Claims (1)

1.含填充材料的氟树脂片材，其特征在于，该含填充材料的氟树脂片材是由包含如下工序的制造方法制得：
在轧辊温度为40～80℃的条件下轧制含有氟树脂、填充材料及加工助剂的片材形成用树脂组合物的工序，
该加工助剂含有30质量％以上的分馏温度为120℃以下的石油烃溶剂，这里，加工助剂重量为100质量％；
该氟树脂片材满足如下内容：
(a)以J工S R3453为基准的拉伸强度为8MPa以上；和
(b)以表面压力为19.6MPa、氮气内压力为0.98MPa的条件对由该氟树脂片材制成的φ48mm×φ67mm×厚度1.5mm的垫片试验片进行气密试验时的泄漏量为9×10-5Pa·m3/s以下。
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TW200740893A (en) 2007-11-01
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CN101405121B (zh) 2011-06-22
KR100999730B1 (ko) 2010-12-08
US9061449B2 (en) 2015-06-23
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WO2007111178A1 (ja) 2007-10-04
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