CN102015855B - 多孔片材及其制造方法以及隔热片 - Google Patents

多孔片材及其制造方法以及隔热片 Download PDF

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CN102015855B
CN102015855B CN2009801154733A CN200980115473A CN102015855B CN 102015855 B CN102015855 B CN 102015855B CN 2009801154733 A CN2009801154733 A CN 2009801154733A CN 200980115473 A CN200980115473 A CN 200980115473A CN 102015855 B CN102015855 B CN 102015855B
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sheet
porous sheet
carbon particles
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formed body
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CN102015855A (zh
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和野隆司
樋口浩之
河边雅义
松岛良一
山本佳位
山下浩一郎
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Nitto Denko Corp
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Toyota Motor Corp
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Abstract

本发明的多孔片材的制造方法，包括：(I)准备多个含有聚四氟乙烯和碳粒子的片状成形体的工序和(II)使多个所述片状成形体叠合后进行轧制的工序。在本发明的多孔片材的制造方法中，可交替地重复进行工序(I)和工序(II)。此外，作为本发明的制造方法中使用的片状成形体，例如，可以使用将含有聚四氟乙烯和碳粒子的混合物成形为片状的母片材，也可以使用通过将多个母片材叠合后进行轧制而得到的层叠片。

Description

多孔片材及其制造方法以及隔热片
技术领域
本发明涉及多孔片材及其制造方法以及隔热片。
背景技术
隔热材料被应用于温度变化给其功能带来较大影响的精密仪器、冰箱等家电制品、洁净室的墙壁或天花板等各种制品中。以往，作为隔热材料，可以使用例如聚氨酯泡沫等聚合物的发泡体、玻璃棉。这些材料的隔热性优良，而且轻量且廉价，因此在广泛的领域中作为隔热材料使用。此外，作为高强度的隔热材料，还提出了通过使基体树脂浸渍到织物或无纺布中而形成的纤维强化塑料隔热材料(参照专利文献1)等。
但是，这些隔热材料存在产生静电的问题。因此，作为防止产生静电的隔热材料，提出了例如在隔热层之间插入了金属板的隔热材料、涂布有防静电剂的隔热材料(参照专利文献2和专利文献3)。然而，在为在隔热层之间插入了金属板的隔热材料的情况下，为了插入金属板而需要粘接工序，进而还需要强化层間的粘接强度。因此，存在制造工序数增加的问题。另一方面，在为使用了防静电剂的隔热材料的情况下，由于需要防静电剂的涂布工序，因此存在制造工序数增加的问题。此外，还存在防静电能力发生经时性变化的问题。
专利文献1：日本专利第2709371号公报
专利文献2：日本特公平3-8248号公报
专利文献3：日本特公平5-25668号公报
发明内容
如以上所述，以往难以通过简便的方法提供能够抑制静电的产生的隔热材料。
因此，本发明的目的在于，提供一种可用作能够抑制静电的产生且具有充分的隔热性的隔热材料的片材。
本发明的多孔片材的制造方法，包括：
(I)准备多个含有聚四氟乙烯(以下，记载为PTFE)和碳粒子的片状成形体的工序；和
(II)将多个所述片状成形体叠合后进行轧制的工序。
本发明的多孔片材含有PTFE和碳粒子，其在厚度方向的热导率为0.05w/mK以上且0.1w/mK以下，且在厚度方向的体积电阻率为0.5Ω·cm以上且2Ω·cm以下。
本发明还提供使用通过上述本发明的多孔片材的制造方法得到的多孔片材或使用上述本发明的多孔片材制作而成的隔热片。
发明效果
根据本发明的多孔片材的制造方法，能够得到热导率低、且具有高导电性的多孔片材。此外，本发明的多孔片材具有充分的隔热性和高导电性。因此，根据本发明，能够通过简便的方法提供可用作能够抑制静电的产生、且具有充分的隔热性的隔热材料的多孔片材。
具体实施方式
以下，对本发明的实施方式进行说明。另外，以下的记载并非是对本发明的限定。
本实施方式的多孔片材的制造方法，包括：(I)准备多个含有PTFE和碳粒子的片状成形体的工序，和(II)将多个所述片状成形体叠合后进行轧制的工序。
对工序(I)的例子进行说明。
首先，对工序(I)中准备的片状成形体的一个例子进行说明。将PTFE细粉、碳粒子和成形助剂混合，制作糊状的混合物。该混合优选在尽可能抑制PTFE的纤维化的条件下进行。具体而言，优选的是通过减小转速、缩短混合时间而不混炼地进行混合。通过如此地进行混合，以PTFE为基体的片状物的加工变得容易。碳粒子只要能够负载于PTFE基体而不发生脱落、且能够赋予所得的多孔片材充分的导电性即可，因此没有特别的限制，但优选粒径20～60nm的碳粒子。另外，这里的粒径是通过用SEM(扫描电子显微镜，Scanning ElectronMicroscope)观察任意10个位置、并测定各个位置处的10个(共计100个)粒径、从而算出平均值的方法而得到的值。作为碳粒子，可以使用例如炭黑。碳粒子的添加量为例如60～90重量％。成形助剂可以使用例如十二烷、癸烷等饱和烃。成形助剂的添加量为例如相对于固体成分的1～1.4倍(重量比)。通过挤出和轧制将这样的混合物成形为片状而得到的母片材，能够用作本发明的片状成形体(片状成形体的第一个例子)。这样得到的片状成形体的厚度为例如0.5～10mm。
此外，作为工序(I)中准备的片状成形体的另一个例子，也可以列举出通过将多个上述母片材叠合后进行轧制而得到的层叠片(片状成形体的第二个例子)。层叠片的层叠数没有特别的限制，可以考虑想要制造的多孔片材的构成层数(构成多孔片材的层的数量)而适当决定。
可像以上那样准备片状成形体。
接着，对工序(II)的例子进行说明。
工序(II)中，将工序(I)中准备的多个片状成形体叠合后进行轧制。具体而言，将工序(I)中准备的多个片状成形体层叠，对该层叠物进行轧制，从而得到层叠片。如上所述，片状成形体可以是上述母片材(第一个例子的片状成形体)，也可以是通过将多个母片材叠合后进行轧制而得到的层叠片(第二个例子的片状成形体)。工序(II)中叠合的片状成形体的数量没有特别的限制，可以为例如2～6张左右。为了实现较高的强度，优选每叠合1张片状成形体后进行轧制。
在本实施方式的多孔片材的制造方法中，可以交替地重复进行工序(I)和工序(II)。以下说明这种情况下的具体例子。
首先，准备多个(例如2～6张)母片材(工序(I))。接着，层叠多个母片材，对该层叠物进行轧制，从而得到层叠片(第一层叠片)(工序(II))。准备多个(例如2～6张)这样得到的第一层叠片，将该第一层叠片用作工序(I)中的片状成形体。接着，层叠多个(例如2～6张)第一层叠片，对该层叠物进行轧制，从而得到层叠片(第二层叠片)(工序(II))。此外，制备多个(例如2～6张)所得到的第二层叠片，将该第二层叠片用作工序(I)中的片状成形体。接着，层叠多个(例如2～6张)第二层叠片，对该层叠物进行轧制，从而得到层叠片(第三层叠片)(工序(II))。可以这样交替地重复进行工序(I)和工序(II)，直到达到作为目标的多孔片材的构成层数为止。另外，在这里说明的例子中，可以将层叠数相同的层叠片之间(第一层叠片之间、第二层叠片之间等)叠合后进行轧制，也可以将层叠数互不相同的层叠片之间叠合后进行轧制。
在重复进行工序(II)时，优选变更轧制方向。例如，在为了得到第二层叠片而进行的轧制中，可以将其轧制方向从为了得到第一层叠片而进行的轧制方向变更90度。这样通过一边改变方向一边进行轧制，PTFE的网状物向纵横延伸，能够提高片材强度和使碳粒子牢固地固定在PTFE基体上。
在用该多孔片材所含的母片材的总数表示多孔片材的构成层数时，构成层数可以为例如100～800层。为了提高片材强度，层数优选为100层以上。此外，为了实现薄膜化(例如制成1mm以下的片材)，层数优选为800层以下。构成层数越多，所得的片材的强度越高。
轧制初期(所含的母片材的总数少的阶段)难以承受强度低且高倍率的轧制，但随着片状成形体的反复层叠和轧制，轧制倍率提高，可以提高片材强度和使碳粒子牢固地固定在PTFE基体上。此外，层叠结构(构成层数)还与所得的片材的隔热性和耐压缩性有关。因此，为了得到具有充分的隔热性和耐压缩性的片材，构成层数优选为200～600层。
最终制成厚度为0.5～2mm左右的片材，然后，通过加热除去成形助剂，可以得到本发明的多孔片材。
根据本实施方式的制造方法，能够制作在厚度方向的热导率为0.05w/mK以上且0.1w/mK以下，且在厚度方向的体积电阻率为0.5Ω·cm以上且2Ω·cm以下的多孔片材。此外，根据本实施方式的制造方法，能够制作具有70～80体积％的气孔率的多孔片材。
进而，通过适当调节该多孔片材的片状成形体的层叠数等，可以使其在厚度方向的5％应变时的压缩弹性模量为0.5MPa以上且2MPa以下的范围。通常使用的隔热材料，由于压缩变形而隔热性容易降低。但是，通过本实施方式的方法制作的多孔片材，能够实现如上所述的高压缩弹性模量，因此，由压缩引起的变形小，能够抑制由于压缩变形而导致的隔热性的降低。此外，这样的多孔片材即使被压缩也具有复原力，因此即使在厚度方向施加压缩力后，热导率也不易变化。作为能够防止由于压缩引起的隔热性的降低的隔热材料，例如在日本专利第2709371号(专利文献1)中提出了通过将浸渍有基体树脂的织物或无纺布与未浸渍基体树脂的织物或无纺布交替层叠后进行加压而制成的纤维强化塑料隔热材料。但是，这样的隔热材料存在不具有导电性、以及制造工序繁杂、挠性低等问题。与此相对，通过本实施方式的方法制作的多孔片材，能够通过层叠及轧制含有PTFE和碳粒子的片状成形体而制作，因此，制造工序简便。此外，该多孔片材由于挠性高因而还具有抗弯性强的特性。
本实施方式的多孔片材还具有自粘接性，因此，例如在作为隔热片设置在机器等的预定位置时，不易发生片材偏离预定位置的问题。
如以上所述，通过本实施方式的方法制作的多孔片材，是通过使含有PTFE和碳粒子的片状成形体层叠而形成的，因此，在厚度方向的热导率、体积电阻率和压缩弹性模量能够满足上述范围。
通过本实施方式得到的多孔片材，可以作为隔热片使用。如上所述，该多孔片材具有良好的隔热性和良好的导电性，因此使用该多孔片材制作的本实施方式的隔热片，不仅具有良好的隔热性，而且还能抑制静电的产生。此外，本实施方式的隔热片还能够具有高的压缩弹性模量，因此即使在厚度方向施加压缩力，隔热性也不易降低。
实施例
以下，用实施例对本发明的多孔片材的制造方法及多孔片材进行具体地说明。
(实施例1)
用混合机将PTFE细粉(商品名“F104”，大金工业株式会社制)15质量份、乙炔黑(商品名“DENKA BLACK(粉状物)”，电气化学工业株式会社制)85质量份、作为成形助剂的饱和烃(商品名“NSCLEAN 220”，日本能源公司制)140质量份混合。混合条件为转速100rpm、温度20℃、混合时间2分钟。将混合物在压力0.3MPa下压缩而预成形。接着，在约10MPa下挤出该预成形体，成形为直径15mm的圆棒。进而使该圆棒在一对金属制轧辊(表面温度40℃)之间通过并进行轧制，得到厚5mm、宽25mm的母片材(片状成形体)。
首先，层叠2张母片材，对该层叠物进行轧制，制作成层叠片(第一层叠片)。接着，准备2张所得的第一层叠片作为片状成形体。将这2张第一层叠片叠合层叠，对该层叠物进行轧制，制作成新的层叠片(第二层叠片)。接着，准备2张所得的第二层叠片作为片状成形体。将这2张第二层叠片叠合层叠，对该层叠物进行轧制，制作成新的层叠片(第三层叠片)。这样，使用所得的层叠片作为片状成形体，将其叠合后进行轧制，重复8次上述工序，由此制作成层叠数为256层的片材。在本实施例中，重复了8次本发明的工序(II)的轧制工序，各轧制工序的轧制方向为从前一轧制工序中的轧制方向变更90度后的方向。另外，在重复轧制工序时变更轧制方向、并且其变更角度为90度这一操作，并非是对本发明的主旨的限制。最终得到的片材为厚1mm、宽250mm、长2m。接着，将该片材加热到150℃，除去成形助剂。
对于如上制成的实施例1的多孔片材，测定了热导率、体积电阻率和压缩弹性模量。测定方法如以下所述。此外，测定结果如表1所示。
<热导率的测定>
使用热线法热导率测定装置(商品名“QTM-500”，京都电子工业株式会社制)，测定厚度方向的热导率。
<体积电阻率的测定>
用四端子法进行测定。在多孔片材的厚度方向通入100mA的电流，通过测定电压，求得体积电阻率。将电极探针以0.2MPa的压力放在多孔片材上进行测定。
<压缩弹性模量的测定>
使用TENSILON万能试验机(日本爱安德株式会社制)，在厚度方向以0.5mm/分钟的速度压缩多孔片材，测定位移和应力。以20kPa应力载荷点为0位移，使用5％应变时的应力(δ)的测定值，用以下公式算出压缩弹性模量(E)。
E＝δ/0.05
(实施例2)
用混合机将PTFE细粉(商品名“F104”，大金工业株式会社制)30质量份、乙炔黑(商品名“DENKA BLACK(粉状物)”，电气化学工业株式会社制)70质量份、作为成形助剂的饱和烃(商品名“NSCLEAN 220”，日本能源公司制)100质量份混合。除此以外，使用与实施例1同样的方法，制作成实施例2的多孔片材。
对于所得的实施例2的多孔片材，采用与实施例1同样的方法测定了热导率、体积电阻率和压缩弹性模量。测定结果如表1所示。
(比较例1)
用混合机将PTFE细粉(商品名“F104”，大金工业株式会社制)15质量份、乙炔黑(商品名“DENKA BLACK(粉状物)”，电气化学工业株式会社制)85质量份、作为成形助剂的饱和烃(商品名“NSCLEAN 220”，日本能源公司制)140质量份混合。混合条件为转速100rpm、温度20℃、混合时间2分钟。将混合物在压力0.3MPa下压缩而预成形。接着，将该预成形体在约10MPa下挤出成形为厚5mm、宽30mm的板状。进而使该板状成形体在一对金属制轧辊(表面温度40℃)之间通过并在挤出方向对其进行轧制，得到厚1mm、宽50mm的片材。接着，将该片材加热到150℃，除去成形助剂。
对于所得的比较例1的多孔片材，采用与实施例1同样的方法测定了热导率、体积电阻率和压缩弹性模量。测定结果如表1所示。
表1
将实施例1的多孔片材和用与实施例1的多孔片材同样的材料比率(PTFE：15质量份，碳粒子：85质量份，成形助剂：140质量份)制成的比较例1进行比较，不具有多层结构的比较例1的多孔片材，虽然体积电阻率低(导电性高)，但是热导率高，隔热性不充分。与此相对，实施例1的多孔片材，能够同时实现低的体积电阻率(高导电性)和低的热导率(良好的隔热性)。此外，与实施例1相比虽然材料比率不同、但采用同样的方法制成的实施例2的多孔片材，与实施例1同样，也能够同时实现低的体积电阻率和低的热导率。此外，实施例1和2的多孔片材与比较例1的多孔片材相比，具有高的压缩弹性模量。
由以上的结果确认了，通过本发明的制造方法制成的多孔片材，由于导电性高因而能够抑制静电的产生，并且具有充分的隔热性。
产业上的可利用性
通过本发明得到的多孔片材，热导率低，且具有高的导电性，因此作为能够抑制静电的产生的隔热材料而优选使用于精密仪器等中。此外，通过本发明得到的多孔片材，还能够用作抑制由静电引起的噪音产生的材料、防尘用材料。

Claims (5)

1.一种多孔片材的制造方法，其包括：
(I)准备多个含有聚四氟乙烯和碳粒子的片状成形体的工序，其中，所述片状成形体的以所述聚四氟乙烯和所述碳粒子的合计重量为基准时的所述碳粒子的含量为60～90重量％；和
(II)将多个所述片状成形体叠合后进行轧制的工序，
并且，交替地重复进行所述工序(I)和所述工序(II)，
在重复进行所述工序(II)时变更轧制方向。
2.一种隔热片，其使用由权利要求1所述的方法得到的多孔片材制作而成。
3.一种多孔片材，其含有聚四氟乙烯和碳粒子，
以所述聚四氟乙烯和所述碳粒子的合计重量为基准时的所述碳粒子的含量为60～90重量％，该多孔片材在厚度方向的热导率为0.05w/mK以上且0.1w/mK以下，且在厚度方向的体积电阻率为0.5Ω·cm以上且2Ω·cm以下。
4.根据权利要求3所述的多孔片材，其在厚度方向的5％应变时的压缩弹性模量为0.5MPa以上且2MPa以下。
5.一种隔热片，其使用权利要求3所述的多孔片材制作而成。
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