CN101234547B - 无粘接剂芳香族聚酰胺-聚酯叠层体及其制造方法和制造装置 - Google Patents

无粘接剂芳香族聚酰胺-聚酯叠层体及其制造方法和制造装置 Download PDF

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CN101234547B
CN101234547B CN2008100022645A CN200810002264A CN101234547B CN 101234547 B CN101234547 B CN 101234547B CN 2008100022645 A CN2008100022645 A CN 2008100022645A CN 200810002264 A CN200810002264 A CN 200810002264A CN 101234547 B CN101234547 B CN 101234547B
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中西悟
多田健一郎
与仓三好
井上哲夫
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Hitachi Engineering and Services Co Ltd
Kawamura Sangyo Co Ltd
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Abstract

本发明中，不用粘接剂将芳香族聚酰胺纸和聚酯薄膜粘接，不损害芳香族聚酰胺纸及聚酯薄膜的特性，制造环境适合型的叠层体。本发明提供无粘接剂芳香族聚酰胺-聚酯叠层体及其制造方法和制造装置。本发明的无粘接剂芳香族聚酰胺-聚酯叠层体，由芳香族聚酰胺纤维和芳香族聚酰胺浆构成，是将等离子表面处理过的芳香族聚酰胺纸和等离子表面处理过的聚酯薄膜，在室温～200℃的温度下，用加压辊直接叠层粘接而成的。

Description

无粘接剂芳香族聚酰胺-聚酯叠层体及其制造方法和制造装置
技术领域
本发明涉及作为绝缘材料等使用的片状、条状或带状的无粘接剂芳香族聚酰胺-聚酯叠体及其制造方法和制造装置。
背景技术
芳香族聚酰胺纤维，是作为诺梅克斯(ノ一メックス)(du Pont公司的注册商标)而公知的芳香族聚酰胺，有很好的电绝缘性、耐热性、耐药品性等，所以，作为电绝缘材料在很多方面被使用。
已往，将芳香族聚酰胺纤维和芳香族聚酰胺纸浆混抄制成芳香族聚酰胺纸，用粘接剂把该芳香族聚酰胺纸和聚酯薄膜或聚酯片叠层粘接起来而形成的芳香族聚酰胺-聚酯叠层体是公知的(见专利文献1～5)。
专利文献1中，揭示了将等离子处理过的芳香族聚酰胺薄膜、芳香族聚酰胺无纺布和半硬化状态的粘接剂形成为一体化的预浸成型片。专利文献2中，揭示了把m-芳香族聚酰胺纤维(ァラミドフィブリツド)及耐热性短纤维构成的芳香族聚酰胺纸和聚对苯二甲酸乙二酯系薄膜用温度220～250℃、线压50kg/cm以上的条件加压·热粘接形成的无粘接剂芳香族聚酰胺叠层体。
专利文献3中，揭示了由在芳香族聚酰胺纸中熔融含浸了聚酯的聚酯层构成的芳香族聚酰胺-聚酯叠层体的制造方法。专利文献4中，揭示了用压延加工法把m-芳香族聚酰胺纸和聚酯薄膜叠层做成叠层片的制造方法。
上述专利文献1记载的技术，由于要使用粘接剂，所以，除了存在着粘接剂的涂敷或需要粘接胶带等的问题外，还存在着对粘接剂中的溶剂挥发进行处理等各种问题。专利文献5中也同样地，虽然是使芳香族聚酰胺纤维无纺布含浸热硬化性树脂，作为预成型料，但仍然是将热硬化性作为粘接剂使用的类型。
专利文献2、3、4中，不使用粘接剂，而是将聚酯薄膜、聚酯片等与芳香族聚酰胺纤维或芳香族聚酰胺纸叠层，将聚酯熔融，使其含浸到芳香族聚酰胺纤维或芳香族聚酰胺纸中。但是，为了熔融聚酯，必须要加热到它的玻化温度以上，这样，冷却后的聚酯再次结晶化，有损其柔软性。
专利文献1：日本特开2003-246018号公报
专利文献2：日本特开平07-32549号公报
专利文献3：日本特开平07-299891号公报
专利文献4：日本特开平08-099389号公报
专利文献5：日本特开平11-209484号公报
发明内容
本发明的课题是不使用粘接剂、不损害芳香族聚酰胺纸和聚酯的特征、不损害聚酯的柔软性、容易对应环境地制造芳香族聚酰胺-聚酯叠层体。
本发明提供的无粘接剂芳香族聚酰胺-聚酯叠层体由芳香族聚酰胺纤维和芳香族聚酰胺浆构成，其特征在于，是将等离子表面处理过的芳香族聚酰胺纸和等离子表面处理过的聚酯薄膜，在室温～200℃的温度下用加压辊连续地叠层粘接而成的。本发明叠层体的特征在于，上述芳香族聚酰胺纸和聚酯薄膜不使用粘接剂，而且基本不使上述聚酯熔融，是直接叠层粘接而成的。
另外，本发明提供了无粘接剂芳香族聚酰胺-聚酯叠层体的制造方法，将等离子表面处理过的芳香族聚酰胺纸和等离子表面处理过的、由聚对苯二甲酸乙酯或聚萘二甲酸乙二酯构成的聚酯薄膜，在室温～200℃的温度下，用一对加压辊、在线压为200kg/cm以上的压力下，进行叠层粘接，所述芳香族聚酰胺纸是由芳香族聚酰胺纤维和芳香族聚酰胺浆构成的。
另外，本发明提供的无粘接剂芳香族聚酰胺-聚酯叠层体的制造装置，其特征在于，备有：抽出等离子表面处理过的芳香族聚酰胺纸的机构、抽出等离子表面处理过的聚酯薄膜的机构、对重叠的上述芳香族聚酰胺纸和聚酯薄膜施加压力的叠层粘接机构、检测·控制该叠层粘接机构的压力的机构、将叠层了的片状叠层体卷起的机构、检测·控制抽出速度和/或卷起速度的机构。
根据本发明，可以实现不使用粘接剂、不损害芳香族聚酰胺纸和聚酯的特征、不损害聚酯的柔软性、容易对应环境的环境适合型芳香族聚酰胺-聚酯叠层体及其制造方法和制造装置。
附图说明
图1是本发明实施形态的叠层·粘接装置的概念图。
图2是本发明另一实施形态的叠层·粘接装置的概念图。
图3是说明本发明实施形态中的辊弯修正的概略图。
图4是说明辊挠曲的图。
具体实施方式
上述芳香族聚酰胺纸-聚酯叠层体的粘接面，是芳香族聚酰胺纸和聚酯薄膜直接相接，用显微镜观察时，可以辨认出几nm左右的极薄交界层。即，可以认为是多孔质性的芳香族聚酰胺纸的表面层与聚酯薄膜表面层直接结合。虽然尚不明了该交界层是怎样的构造或具有怎样的功能，但可以认为这是本发明无粘接剂芳香族聚酰胺纸-聚酯叠层体的一个特征。
叠层体的芳香族聚酰胺纸及聚酯薄膜的厚度没有特别限制，但是，作为片状、带状或条状绝缘材使用时，芳香族聚酰胺纸的厚度在30～150μm、聚酯薄膜的厚度在100～200μm，是比较实用的。另外，3层的合计厚度最好为130～350μm。
上述的芳香族聚酰胺-聚酯叠层体中，上述温度最好在所用的聚酯薄膜的玻化温度以下。如果加热温度高于玻化温度，则叠层体中的聚酯冷却时再次结晶化，失去柔软性或变脆，其使用性变差，特性也降低。另外，上述叠层体，最好具有芳香族聚酰胺纸-聚酯薄膜-芳香族聚酰胺纸这样的三层构造。另外，从机械强度、柔软性、成本、绝缘性方面考虑，上述聚酯，最好是聚对苯二甲酸乙二酯(PET)或聚萘二甲酸乙二酯(PEN)。上述温度，必须在所用的聚酯薄膜的玻化温度以下。如果加热温度高于聚酯的玻化温度，则叠层体冷却时，聚酯再次结晶化，会失去其柔软性。作为PEN的具体例，有帝人·帝优博思(デュポン)(株)销售的商品名为帝奥耐克思(テオネックス)的产品，它是二轴延伸的聚萘二甲酸乙二酯。另外，PET的玻化温度约为78℃，PEN的玻化温度约为121℃。
芳香族聚酰胺纸具有电绝缘性、化学稳定性、耐热性，聚酯具有柔软性、气液不透性，所以，把芳香族聚酰胺纸配置在叠层体的两面，把聚酯作为芯材配置。如前所述，作为芯材的聚酯材料，最好是聚对苯二甲酸乙二酯或聚萘二甲酸乙二酯。
上述辊最好由刚度高的材质做成。已往通常的方法中，是将橡胶制辊和金属制辊组合使用，但是，橡胶制的辊，其加压面变形，不能对叠层体施加充分的压力。为此，采用金属等比橡胶辊刚性高的材质构成的一对加压辊，可以对叠层体施加充分的压力。
另外，上述无粘接剂芳香族聚酰胺-聚酯叠层体的制造方法中，上述辊最好备有辊弯方式的挠曲修正机构，由此调节辊的挠曲量。即使采用刚性高的金属辊，辊相对于夹着叠层体的加压面也会有一些弯曲，结果，造成不能对叠层体施加充分的压力，或者对局部施加了不均的压力。为此，为了调节挠曲量，对叠层体施加充分的加压力，最好设置辊弯方式的挠曲修正机构。其详细构造后面说明。
至少上述辊最好配置在温度可控制的环境内。为了至少将对叠层体进行加压叠层的机构保持为所需温度，例如设置备有预热·渐冷区域的温度调节装置。虽然在室温下加压也能叠层·粘接，但是，为了提高粘接速度、充分降低加压力，最好把聚酯薄膜保持在比室温高并且比聚酯薄膜的玻化温度低的温度。
另外，上述无粘接剂芳香族聚酰胺-聚酯叠层体的制造装置中，上述叠层粘接机构最好是一对辊。上述辊最好备有辊弯方式的挠曲修正机构，由此调节辊的挠曲量。另外，至少上述叠层粘接机构最好配置在温度可控制的机构内。另外，上述辊弯方式的挠曲修正机构，最好对辊左右的轴赋予独立或不同的修正量。
本发明中所说的等离子表面处理，是采用直流、交流或高频的化学等离子处理，是在真空或各种环境下进行的低温等离子法，包含电晕放电(大气压附近)、辉光放电(真空、减压下)。通过该等离子表面处理，将芳香族聚酰胺纸及聚酯薄膜或聚酯片的表面改性，在芳香族聚酰胺纸和薄膜表面形成某种官能基例如COOH、OH基。另外，上述表面改性的结果是，可以在200℃以下的低温中，将芳香族聚酰胺纸-聚酯薄膜叠层体牢固地叠层·粘接。这一特性从上述专利文献揭示的内容中推断不出，是极为特异的现象。另外，等离子处理，作为提高各种树脂粘接性的方法是公知的，所以，对于等离子处理本身的说明从略。
下面，参照附图用实施例说明本发明。图1是本发明中使用的叠层体压接装置的概念图。图中，把从芳香族聚酰胺纸的卷轴3、4抽出的芳香族聚酰胺纸5以及从聚酯薄膜的卷轴6抽出的聚酯薄膜7，重叠成为三层的夹心构造，供给到一对金属辊1、2之间。叠层体被金属辊压接，不用粘接剂地直接叠层·粘接。芳香族聚酰胺纸5的粘接面和聚酯薄膜7的两面，在叠层前预先进行了等离子表面处理。
为了检测并调节辊的加压力，设置了带控制装置的加压装置9。加压力的线压为200kgf/cm以上，最好在300kgf/cm以上。另外，设定辊的旋转速度，在辊的前后控制抽出卷轴、卷绕卷轴的旋转速度，使材料具有一定的张力。
为了更正确地控制速度，可以用检测器10计测辊上的叠层体移送速度，反馈为辊旋转速度。适合于生产性的移送速度，根据加压力及温度而变化，加压力越高，或温度越高，移送速度呈越快的倾向。根据速度的要求，为了用预热或来自辊的传热将材料提高到有效温度，也可以把预热温度或辊温度设定为玻化温度+50℃～+100℃左右。但是，要进行温度控制，使要粘接的聚酯薄膜的温度不过热，即不高于其玻化温度。叠层·粘接后的叠层体8，被卷绕在卷绕卷轴11上。
作为辊叠层·粘接装置必须具有的条件有，叠层体宽度方向的均匀荷载及辊表面温度的均匀性(宽度方向及圆周方向)。为了实现该条件，最好采用高精度的辊(圆筒度、正圆度、偏差小)、辊挠曲修正机构、表面温度均匀机构(例如热媒循环辊的使用等)。
图2是另一实施例的叠层·粘接装置的概念图。与图1中相同的标记表示相同的部件。与图1的不同点是，把辊设置在预热·渐冷区域12内。这样，可以对材料进行预热·渐冷，防止材料的急剧加热、急剧冷却，从而防止因材料的急剧加热、急剧冷却形成热膨胀时的折皱等。另外，在辊的传热方面，由于接触时间短，有时不能加热到所需的材料温度，但是，用该预热·渐冷区域将材料预热，可以补充其所需的热量，提高生产速度。另外，设置用于检测·控制预热·渐冷区域12内温度的控制装置18。图1、2中，为了清楚起见，辊加压装置9是在辊上面示出的，但实际上其是安装在辊轴的支承构造体上的。
本发明的实施形态中，一对辊最好用比橡胶辊刚性高的铁系材料构成，但是，即使如此，如图4所示，在叠层·粘接时辊的中间部也有可能会挠曲，不能对叠层体施加充分的加压力，或者不均匀地对局部施加加压力。为了解决这一问题，与辊加压装置9分开地安装辊弯修正机构13，在短时间内变更·修正或改正辊外形。图3表示其一例。图3中，对辊1、2的轴14、15施加压力F。另一方面，为了防止辊1、2及其轴14、15夹着叠层体8时如图4所示地弯曲，对叠层体8不能作用一定且充分的加压力，在与加压方向相反的方向，施加压力P。把该方法称为辊弯修正。辊弯修正，最好对左右的加压装置独立地进行。
表1-1及表1-2，表示本发明的实施形态在各种条件下得到的叠层体的性状。采用在真空中低温预先用等离子处理过的、厚度为50μm及130μm的芳香族聚酰胺纸及厚度为125μm的PEN，用图2所示的装置，形成为芳香族聚酰胺纸-PEN-芳香族聚酰胺纸这样的夹心构造，用表1-1及表1-2所示的条件，进行叠层·粘接。
得到的无粘接剂芳香族聚酰胺-聚酯叠层体，其性状如表1-1和表1-2的评价栏所示。根据粘贴评价，聚酯薄膜采用PEN时，辊温度低于玻化温度，在121℃以下，最好为110～40℃。叠层体的辊线压在300kgf/cm以上，最好在400kgf/cm以上，如果过高则不经济，所以，在1000kgf/cm左右以下是适合的。
叠层体的辊移送速度(从辊抽出的速度)，根据辊温度和线压而变化，从叠层体的生产率、成本方面等着眼决定适当的移送速度。表所示实施例中，该移送速度是0.5m/分以上，最好为1～20m/分。
根据叠层体的粘贴评价，实施例3、6～10、13～16的叠层体，显示了极好的粘贴性。这些叠层体是在适当的移送速度、适当的温度、适当的线压下叠层·粘接而成的。
Figure GSB00000300017600081
表1-1和表1-2中，加压辊温度以50～110℃示出，由于低于所用的聚酯薄膜(PEN)的玻化温度，所以，聚酯薄膜不引起玻化(特别是熔融·流动程度的变化)。在这样的条件下，芳香族聚酰胺纸与聚酯薄膜能牢固地粘接，这一点是以前没有预想到的。在这一点，本发明与使聚酯熔融粘接的专利文献2、3、4揭示的技术有本质上的不同。
如上所述，根据本发明，能得到不用粘接剂的、粘贴性好的芳香族聚酰胺-聚酯薄膜叠层体。

Claims (6)

1.无粘接剂芳香族聚酰胺-聚酯叠层体的制造方法，将等离子表面处理过的芳香族聚酰胺纸和等离子表面处理过的、由聚对苯二甲酸乙酯或聚萘二甲酸乙二酯构成的聚酯薄膜，在室温～200℃的温度下，用一对加压辊、在线压为200kg/cm以上的压力下，进行叠层粘接，所述芳香族聚酰胺纸是由芳香族聚酰胺纤维和芳香族聚酰胺浆构成的。
2.如权利要求1所述的无粘接剂芳香族聚酰胺-聚酯叠层体的制造方法，其特征在于，所述温度，在所用的聚酯薄膜的玻化温度以下。
3.如权利要求1所述的无粘接剂芳香族聚酰胺-聚酯叠层体的制造方法，其特征在于，所述叠层体，具有芳香族聚酰胺纸-聚酯薄膜-芳香族聚酰胺纸这样的三层构造。
4.如权利要求1所述的无粘接剂芳香族聚酰胺-聚酯叠层体的制造方法，其特征在于，所述辊由刚性材质做成。
5.如权利要求1所述的无粘接剂芳香族聚酰胺-聚酯叠层体的制造方法，其特征在于，所述辊备有辊弯方式的挠曲修正机构，由此调节辊的挠曲量。
6.如权利要求1所述的无粘接剂芳香族聚酰胺-聚酯叠层体的制造方法，其特征在于，至少所述辊配置在温度可控制的环境内。
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