CN105984120A - 树脂接合体、树脂接合体的制造方法及车辆用构造体 - Google Patents

树脂接合体、树脂接合体的制造方法及车辆用构造体 Download PDF

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Publication number
CN105984120A
CN105984120A CN201610157460.4A CN201610157460A CN105984120A CN 105984120 A CN105984120 A CN 105984120A CN 201610157460 A CN201610157460 A CN 201610157460A CN 105984120 A CN105984120 A CN 105984120A
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resin
fiber
thermoplastic resin
bonded body
melting temperature
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CN201610157460.4A
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CN105984120B (zh
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岩野吉宏
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Toyota Motor Corp
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Toyota Motor Corp
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/022—Particular heating or welding methods not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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Abstract

本发明提供一种将热塑性树脂与热固性树脂固化物接合而成的树脂接合体及其制造方法以及使用了该树脂接合体的车辆用构造体。树脂接合体是利用熔敷将含有纤维的热塑性树脂与具有比所述热塑性树脂的熔解温度低的熔解温度且含有纤维的热固性树脂固化物接合而成；车辆用构造体具有所述树脂接合体；树脂接合体的制造方法包含接合工序，该接合工序利用熔敷将含有纤维的热塑性树脂与具有比所述热塑性树脂的熔解温度低的熔解温度且含有纤维的热固性树脂固化物接合。

Description

树脂接合体、树脂接合体的制造方法及车辆用构造体
技术领域
本发明涉及树脂接合体、树脂接合体的制造方法及车辆用构造体。
背景技术
可以想象，在下一代的车辆用车体中树脂制零件的使用将扩大。因此，确立树脂制零件彼此的结合方法是当务之急。
已公开了以下接合方法，即为了将纤维强化热塑性树脂彼此接合，通过配置在纤维强化热塑性树脂之间的热塑性树脂片材将纤维强化热塑性树脂彼此接合(例如，参照专利文献1。)。
另外，在使用了热固性树脂固化物的树脂制零件与使用了热塑性树脂的树脂制零件的接合中，使用了粘合剂的接合或使用了铆钉等紧固部件的固定是普遍情况。
此外，还已知含有热固性树脂和热塑性树脂的纤维强化复合材料板(例如，参照专利文献2。)。
现有技术文献
专利文献
专利文献1：日本特开2014-076565号公报
专利文献2：日本特开2008-230238号公报
发明内容
发明欲解决的技术问题
但是，专利文献1记载的技术被用在表现出可塑性的热塑性树脂彼此的接合中，在热塑性树脂与已经完成固化反应而不易塑化的热固性树脂固化物的接合中不能应用。另外，如果在使用了热固性树脂固化物的树脂制零件与使用了热塑性树脂的树脂制零件的接合中使用粘合剂或铆钉等紧固部件，则成为质量或成本的增加的原因之一，因此不优选。特别是，在使用粘合剂将热塑性树脂与热固性树脂固化物接合的情况下，粘合剂的强度决定接合部的强度，因此有时不能够发挥树脂制零件自身的材料强度。而且，专利文献2记载的技术被应用在使用了热塑性树脂和尚未固化的热固性树脂的纤维强化复合材料板的制造中，在已经完成固化反应的热固性树脂固化物与热塑性树脂的接合中不能应用。
本发明是鉴于现有技术的上述问题而完成的，其目的是提供不使用粘合剂或铆钉等紧固部件而将热塑性树脂与热固性树脂固化物接合而成的树脂接合体及其制造方法以及使用了该树脂接合体的车辆用构造体。
用于解决问题的技术手段
用于解决上述课题的具体手段如下。
(1)一种树脂接合体，其中，利用熔敷将含有纤维的热塑性树脂与具有比所述热塑性树脂的熔解温度低的熔解温度且含有纤维的热固性树脂固化物接合。
(2)根据(1)所述的树脂接合体，其中，所述热固性树脂固化物中含有的纤维是织物。
(3)根据(1)或(2)所述的树脂接合体，其中，所述热塑性树脂中含有的纤维是无纺布。
(4)根据(1)～(3)中任一项所述的树脂接合体，其中，所述热塑性树脂的熔解温度与所述热固性树脂固化物的熔解温度的差是50℃以上。
(5)一种树脂接合体的制造方法，其中，包括：接合工序，利用熔敷将含有纤维的热塑性树脂与具有比所述热塑性树脂的熔解温度低的熔解温度且含有纤维的热固性树脂固化物接合。
(6)根据(5)所述树脂接合体的制造方法，其中，所述接合工序中的熔敷是振动熔敷。
(7)一种车辆用构造体，其中，具有(1)～(4)中任一项所述的树脂接合体。
发明效果
根据本发明，提供不使用粘合剂或铆钉等紧固部件而将热塑性树脂与热固性树脂固化物接合而成的树脂接合体及其制造方法以及使用了该树脂接合体的车辆用构造体。
附图说明
图1是本实施方式涉及的树脂接合体的接合部的剖面照片的一个例子。
图2是图1中用标记了标号A的椭圆圈起的附近的放大照片。
具体实施方式
以下，针对本发明的树脂接合体、树脂接合体的制造方法及车辆用构造体的实施方式进行详细说明。
＜树脂接合体及其制造方法＞
本实施方式涉及的树脂接合体是通过熔敷将含有纤维的热塑性树脂和具有比所述热塑性树脂的熔解温度低的熔解温度且含有纤维的热固性树脂固化物接合而成的接合体。本实施方式涉及的树脂接合体不使用粘合剂或铆钉等紧固部件而通过熔敷将含有纤维的热塑性树脂和含有纤维的热固性树脂固化物接合，因此，能够抑制在对含有纤维的热塑性树脂和含有纤维的热固性树脂固化物进行接合时，因粘合剂或铆钉等紧固部件的使用而导致的质量增加。而且，不是由粘合剂的强度来决定接合部的强度，而且是能够通过选择适当的树脂来提高树脂接合体的接合强度。另外，能够扩大再利用性、高循环性优异的热塑性树脂的使用范围。
本实施方式中使用的热塑性树脂没有特别限定，能够根据目的而使用公知的各种热塑性树脂。作为本实施方式中使用的热塑性树脂，例如，可以列举：聚碳酸酯树脂、聚酰胺(PA)树脂、聚氨酯(PU)树脂、聚氯乙烯树脂、丙烯腈-丁二烯-苯乙烯共聚物(ABS)树脂和聚丙烯(PP)树脂。这些树脂中，优选PA树脂和PP树脂。
本实施方式中使用的热固性树脂固化物是使热固性树脂热固化后的固化物。在热固性树脂固化物的形成中使用的热固性树脂没有特别限定，可以根据目的而使用公知的各种热固性树脂。作为本实施方式中使用的热固性树脂，例如，可以列举：乙烯基酯树脂、不饱和聚酯树脂、酚醛树脂、环氧树脂和聚氨酯树脂。这些树脂中，优选环氧树脂。
本实施方式中使用的纤维的种类没有特别限定，能够根据目的而使用公知的各种纤维。作为本实施方式中使用的纤维种类，例如，可以列举：芳族聚酰胺纤维、纤维素纤维、尼龙纤维、维尼纶纤维、聚酯纤维、聚烯烃纤维、人造纤维等树脂纤维、碳纤维、玻璃纤维、金属纤维等。这些纤维中，优选能够实现高机械强度的碳纤维。
对于使热塑性树脂与纤维复合化的方法，没有特别限定，可以根据目的而使用公知的各种方法。例如，可以列举：使纤维中浸渍有热塑性树脂的溶液或熔液并根据需要而进行干燥并成型为片材状的方法、在使纤维与热塑性树脂膜交替层叠后进行加热加压成形的方法。对于使热固性树脂与纤维复合化的方法，也没有特别限定，能够根据目的使用公知的各种方法。也可以使热固性树脂与纤维复合化，并形成半固化片。
本实施方式中使用的纤维的状态没有特别限定，能够根据目的而使用公知的形状的纤维。作为本实施方式中使用的纤维的状态，例如，可以列举：织物和无纺布。
在本实施方式中，作为热塑性树脂中含有的纤维的含有率，优选5质量％～50质量％，更优选10质量％～50质量％。
在本实施方式中，作为热固性树脂固化物中含有的纤维的含有率，优选5质量％～50质量％，更优选10质量％～50质量％。
在本实施方式涉及的树脂接合体中，热固性树脂固化物的熔解温度低于热塑性树脂的熔解温度。热固性树脂固化物的熔解温度与热塑性树脂的熔解温度的差没有特别限定。作为热固性树脂固化物的熔解温度与热塑性树脂的熔解温度的差的下限值，例如，优选50℃以上，更优选100℃以上，进一步优选150℃以上。作为热固性树脂固化物的熔解温度与热塑性树脂的熔解温度的差的上限值，没有特别限定，但从获得树脂的容易性考虑，设定为250℃以下。
在本实施方式中，热固性树脂固化物及热塑性树脂的熔解温度的测定是，根据JISK7121-2012(塑料的转变温度测量方法)，利用差示扫描量热量法(DSC)测定的值。
此外，热固性树脂固化物中含有的纤维优选是织物。可以推测：通过使用织物来作为热固性树脂固化物中含有的纤维，从而热塑性树脂中含有的纤维容易缠结在构成织物的纤维，在热塑性树脂与热固性树脂固化物之间容易产生更大的接合强度。
另外，热塑性树脂中含有的纤维优选是无纺布。可以推测：通过使用无纺布来作为热塑性树脂中含有的纤维，热固性树脂固化物中含有的纤维与热塑性树脂中含有的纤维容易缠结，在热塑性树脂与热固性树脂固化物之间容易产生更大的接合强度。
而且，更优选热固性树脂固化物中含有的纤维是织物，且热塑性树脂中含有的纤维是无纺布。熔解温度比热塑性树脂低的热固性树脂固化物在熔敷时容易因先熔融或燃烧而消失，因此热固性树脂固化物中含有的织物容易裸露出。无纺布进入该裸露出的织物的纤维网眼，从而无纺布更容易缠绕在织物中。因此，容易产生牢固的结合。其结果，可以推测：在热塑性树脂与热固性树脂固化物之间容易产生更大的接合强度。
本实施方式涉及的树脂接合体也可以是通过包含接合工序的树脂接合体的制造方法来制造，该接合工序将含有纤维的热塑性树脂与具有比所述热塑性树脂的熔解温度低的熔解温度且含有纤维的热固性树脂固化物熔敷而接合。
在本实施方式中，由于热固性树脂固化物的熔解温度比热塑性树脂的熔解温度低，因此，在接合工序中利用熔敷对该树脂彼此进行接合时，比起热塑性树脂，热固性树脂固化物容易先因熔融或燃烧而消失。由于热固性树脂固化物先因熔融或燃烧而消失，从而热固性树脂固化物中含有的纤维被裸露出。热塑性树脂和其中含有的纤维缠绕在裸露出的热固性树脂固化物中含有的纤维中，因此在热塑性树脂与热固性树脂固化物之间产生接合强度。因此，可以推定：本实施方式涉及的树脂接合体能够不使用粘合剂或铆钉等紧固部件而将热塑性树脂与热固性树脂固化物接合。
所述接合工序中的熔敷没有特别限定，可以使用公知的各种熔敷方法。作为能够在本实施方式中使用的熔敷方法，例如，可以列举：超声波熔敷、振动熔敷、感应熔敷、高频熔敷、激光熔敷、热熔敷和旋转熔敷。这些熔敷方法中，优选超声波熔敷和振动熔敷。
图1是热固性树脂固化物中含有的纤维为织物、热塑性树脂中含有的纤维为无纺布的本实施方式涉及的树脂接合体的接合部的剖面照片的一个例子。在图1的剖面照片中，上侧是热塑性树脂，下侧是热固性树脂固化物。在下侧的热固性树脂固化物中，观察到来源于织物的有规则的纤维的剖面。图2是图1的用标注了标号A的椭圆圈出的附近的放大照片。可知在图2的熔敷面中，存在热塑性树脂(图2中标记为“热塑”者)中含有的无纺布与热固性树脂固化物(图2中标记为“热固”者)中含有的织物缠绕的部分(纤维缠结部)。
通过使用振动熔敷来作为熔敷方法，从而树脂接合体的强度进一步提高。另一方面，通过使用超声波熔敷作为熔敷方法，从而被接合的热塑性树脂和热固性树脂固化物的设计和结构的自由度变高。
在本实施方式中，作为熔敷方法，更优选使用热固性树脂固化物在熔敷时容易因熔融或燃烧而消失的振动熔敷。
振动熔敷是如下的方法：在对被熔敷的热塑性树脂和热固性树脂固化物使用压力机等施加了负荷的状态下，使热塑性树脂和热固性树脂固化物的一者相对于热塑性树脂和热固性树脂固化物的接触面在水平方向上振动，并利用由此产生的摩擦热进行熔敷。
另一方面，超声波熔敷是如下的方法：利用超声波振荡器将电能转换成振动能，并将该振动能施加到接触的状态下的热塑性树脂和热固性树脂固化物的接触面，从而利用在该接触面产生的摩擦热进行熔敷。
在使用振动熔敷作为熔敷方法的情况下，振动熔敷的各条件可以根据热塑性树脂和热固性树脂固化物的形状、熔解温度、接合面的面积等进行选择。例如，振动频率优选为100Hz～300Hz，更优选为210Hz～260HZ。另外，作为对热塑性树脂和热固性树脂固化物的负荷，优选为0.1MPa～5MPa，更优选为0.1MPa～2MPa，进一步优选为0.1MPa～1MPa。另外，振动振幅优选为0.5mm～5mm，更优选为1mm～3mm，进一步优选为1.5mm～2.5mm。
在使用超声波熔敷作为熔敷方法时，超声波熔敷的各条件可以根据热塑性树脂和热固性树脂固化物的形状、熔解温度、接合面的面积等进行选择。例如，构成发出超声波的超声波发生装置的焊头的焊头加压力优选为100N～2000N，更优选300N～1000N，进一步优选500N～800N。作为超声波振动的振幅，优选为10μm～100μm，更优选为15μm～50μm。作为对热塑性树脂和热固性树脂固化物的加压，优选为0kN～5kN，更优选0kN～3kN，进一步优选0kN～1kN。
＜车辆用构造体＞
本实施方式涉及的车辆用构造体具有上述的本实施方式涉及的树脂接合体。本实施方式涉及的车辆用构造体的种类没有特别限定，例如，可以列举：侧门、引擎盖、车顶、后车门、行李箱门、保险杠和碰撞吸能盒。
在本实施方式涉及的车辆用构造体中，含有纤维的热塑性树脂和含有纤维的热固性树脂固化物也可以分别在利用压力成形、注射成形、传递模塑等与用途相应的成形法做成为成形品的状态下通过熔敷进行接合。
一般情况下，与热塑性树脂相比，热固性树脂固化物的表面平滑性优异，因此例如在使用本实施方式涉及的树脂接合体作为车辆用构造体来形成门的情况下，优选用树脂接合体之中的热固性树脂固化物来构成门的表面侧。
根据本实施方式涉及的车辆用构造体，能够根据要求的特性，将适合每个部分的树脂材料组合，构成树脂制的车辆用构造体。因此，根据本实施方式涉及的车辆用构造体，能够实现并用多种树脂(多材料)的下一代车辆。
[实施例]
以下，列举实施例和比较例，对本实施方式进行更具体的说明，但本实施方式不限于以下的实施例。
(试验片的准备)
将碳纤维强化热塑性树脂(CFRTP、聚酰胺树脂与碳纤维(无纺布)的复合材料、熔解温度240℃)、碳纤维强化热固性树脂固化物(CFRP、环氧树脂固化物与碳纤维(织物)的复合材料、熔解温度140℃)、铝板(表面未处理)、铝板(#60砂纸打磨)和铁板(表面阳离子电沉积涂装处理)用作试验片。需要说明的是，对于CFRP，区别地使用将树脂热固化时的半固化片的模具面侧与膜面侧。试验片的大小为，长175mm、宽25mm、厚3mm。使用磨床切成上述尺寸而准备了试验片。CFRP的模具面侧和膜面侧表面、铝板的表面以及CFRTP的表面进行了脱脂处理。将试验片在控制为25±2℃的屋里保存10天以上，然后用于熔敷试验。
(振动熔敷)
作为振动熔敷机，使用Branson MICROPPL(Emerson Japan,Ltd.)。以表1所示的组合，在工件(固定侧)和工件(加振侧)安装上述试验片，并实施振动熔敷，制作树脂接合体。作为熔敷条件，振动振幅为1.8mm，加压为0.75MPa，熔深尺寸为0.3mm。
(剪切强度测定)
使用株式会社岛津制作所制造的Autograph AG-X100KN实施剪切试验。将得到的结果示于表1。需要说明的是，得到的结果是进行了2次试验的结果的平均值。
[表1]
表1中，剪切强度为“-”表示剪切强度为测定限度以下。
由表1可知，在CFRTP与CFRP之间，形成有基于熔敷的接合状态。另外，其剪切强度为19.5MPa，与将CFRTP彼此熔敷的情况(26.0MPa)相比，毫无逊色。观察在CFRTP与CFRP之间形成的接合的破断面，在CFRTP侧附着有CFRP侧的碳纤维。因此，认为在振动发热时，CFRP的环氧树脂固化物被破坏，热塑性树脂流入到被去除了环氧树脂固化物的部位，CFRP侧的碳纤维与CFRTP发生了接合。需要说明的是，在CFRP的模具面与膜面，在剪切强度上产生了差异。由于模具面与膜面的表面凹凸的差仅约10μm，因此认为，在这次评价中，表面凹凸对剪切强度的影响较少。但是，由于在模具面与膜面使用的脱模剂的种类不同，因此认为，在膜面大量残留脱模剂(熔敷前完全脱脂)而产生的影响较大。因此认为，在膜面侧，剪切强度的偏差(17.3MPa和14.0MPa)较大。另一方面，在使用铝板和铁板作为试验片的情况下，几乎未看到接合效果。认为这是，根据振动熔敷的原理，由于通过因试验片的接触面彼此的摩擦而产生的热使试验片熔敷，因此即使金属表面设置有凹凸，由于凹凸被磨平，只要不在接触面涂布树脂等，金属与热塑性树脂的接合就是困难的。另外，在表面阳离子电沉积涂装处理等树脂的膜厚极薄的情况下，因振动熔敷而该树脂被剥下的可能性较高，因此认为，为了得到剪切强度，在金属表面需要一定厚度的树脂。
(超声波熔敷)
作为超声波熔敷机，使用了Branson 2000Xdt(Emerson Japan,Ltd.)。如表2所示，设定超声波熔敷机的熔敷条件，并实施超声波熔敷试验，制作树脂接合体。另外，与基于振动熔敷的试验的情况同样，对被超声波熔敷后的试验片的剪切强度进行测定。将得到的结果示于表2。作为试验片，使用了CFRTP和CFRP。
[表2]
在表2中，1)是以焊头径φ15算出的强度，2)是以实际熔敷面积算出的强度。
根据表2，标准熔敷条件是最高强度(约50MPa)。也就是说，未发现通过按压试验片(试验片加压)而导致的强度提高。试验片加压较少者的剪切强度优异。认为这是因为，超声波熔敷利用上下移动使试验片相对于试验片的接触面震动，因此，如果对试验片彼此的推压过强，则试验片中的纤维的缠结变少。另外，通过使振幅增减约3μm(控制上约5％)，熔敷强度发生很大变化(不同)。

Claims (9)

1.一种树脂接合体，其中，
利用熔敷，将含有纤维的热塑性树脂与具有比所述热塑性树脂的熔解温度低的熔解温度且含有纤维的热固性树脂固化物接合。
2.根据权利要求1所述的树脂接合体，其中，
所述热固性树脂固化物中含有的纤维是织物。
3.根据权利要求1或2所述的树脂接合体，其中，
所述热塑性树脂中含有的纤维是无纺布。
4.根据权利要求1～3中任一项所述的树脂接合体，其中，
所述热塑性树脂的熔解温度与所述热固性树脂固化物的熔解温度的差是50℃以上。
5.根据权利要求1所述的树脂接合体，其中，
所述热塑性树脂中含有的纤维的含有率为5质量％～50质量％。
6.根据权利要求1所述的树脂接合体，其中，
所述热固性树脂固化物中含有的纤维的含有率为5质量％～50质量％。
7.一种树脂接合体的制造方法，其中，
包括接合工序，利用熔敷，将含有纤维的热塑性树脂与具有低于所述热塑性树脂的熔解温度的熔解温度且含有纤维的热固性树脂固化物接合。
8.根据权利要求7所述的树脂接合体的制造方法，其中，
所述接合工序中的熔敷是振动熔敷。
9.一种车辆用构造体，其中，具有权利要求1～6中任一项所述的树脂接合体。
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