CN111093932A - 金属树脂复合成型品及其制造方法 - Google Patents

金属树脂复合成型品及其制造方法 Download PDF

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Publication number
CN111093932A
CN111093932A CN201880060255.3A CN201880060255A CN111093932A CN 111093932 A CN111093932 A CN 111093932A CN 201880060255 A CN201880060255 A CN 201880060255A CN 111093932 A CN111093932 A CN 111093932A
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China
Prior art keywords
metal plate
metal
resin
molded article
groove
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Granted
Application number
CN201880060255.3A
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English (en)
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CN111093932B (zh
Inventor
近藤秀水
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Yamase Electric Co ltd
Polyplastics Co Ltd
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Yamase Electric Co ltd
Polyplastics Co Ltd
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Publication of CN111093932A publication Critical patent/CN111093932A/zh
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    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
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Abstract

本发明的目的在于，对于利用激光在金属板的表面形成槽来提高金属板与树脂的密合性的技术而言，提供即使金属板变薄也能够抑制由激光加工导致的变形的金属树脂复合成型品。本发明的目的通过下述金属树脂复合成型品来实现，所述金属树脂复合成型品是对金属板嵌入成型树脂组合物而得到的，该金属板的厚度H为500μm以下，在该金属板的要嵌入该树脂组合物的表面形成有槽，该槽的宽度Y为30～300μm、深度X为该金属板的厚度H的24％以下、该深度X相对于该宽度Y的比例X/Y为0.1～2.5。

Description

金属树脂复合成型品及其制造方法
技术领域
本发明涉及与树脂接合的金属板的制造方法和具备利用该制造方法制造的金属板和树脂的金属树脂复合成型品。
背景技术
由金属、合金等构成的金属板与由热塑性树脂组合物构成的树脂成型品经复合化而成的金属树脂复合成型品一直以来被用于仪器面板周围的控制箱等汽车的内饰构件、发动机周围构件、内饰构件、数码相机或便携电话等电子设备的壳体部、接口连接部、电源端子部等与外界接触的构件。
作为对金属板与树脂成型品进行复合化的方法，有如下方法等：预先在金属板侧的接合面形成微小的凹凸，利用锚固效应进行接合的方法；使用粘接剂、双面胶进行粘接的方法；对金属板和/或树脂成型品设置折叠片、钩等固定构件，并使用该固定构件将两者固定的方法；使用螺丝等进行接合的方法等。这些之中，对金属板形成微小凹凸的方法、使用粘接剂的方法在设置金属树脂复合成型品的形状自由度方面是有效的。
尤其是，将金属板的表面进行加工而形成微小凹凸的方法在不使用昂贵的粘接剂方面、不需要粘接剂的涂布和固化的工序方面是有利的。作为对金属板的表面进行加工而形成微小的凹凸的方法，可列举出例如专利文献1中记载的方法。
现有技术文献
专利文献
专利文献1：日本特开2014-117724号公报
发明内容
发明要解决的问题
上述专利文献1中记载的方法利用激光在金属板的表面形成槽，因此，能够在上述表面的期望范围形成槽，作业也简便，是一个有效的方法。
然而，在对金属板进行激光加工时，在金属板的加工点处存在局部的发热，有时因金属板的热膨胀而发生变形。如果是热膨胀小的金属或者容易发生热扩散之类的形态的金属板，则能够在某种程度上抑制这种变形，但板厚小于500μm那样的薄壁金属板难以利用金属板自身的刚性来确保结构强度，因此，该变形增大至无法忽视的程度。
对于最近的智能手机的壳体那样的寻求薄型的金属板而言，抑制该变形成为课题。
此外，如拉带成型的嵌入端子那样将金属卷绕成卷状来使用的情况下，金属板过厚时无法卷绕成卷状，即便能够卷绕也会产生如下问题：若强行将厚的金属板进行卷绕，则此时施加于金属板的负载也会以内部应变的形式而残留，发生金属板的强度降低、变形，作为嵌入成型品的接合强度、气密性降低，因此，在这种用途中，从卷取性的方面出发，也需要厚度为500μm以下左右的金属薄板，抑制这种薄壁的金属板在激光加工时的变形成为课题。
本发明的目的在于，对于利用激光在金属板的表面形成槽来提高金属板与树脂的密合性的技术而言，提供即使金属板变薄也能够抑制由激光加工导致的变形的金属树脂复合成型品。
用于解决问题的方案
本发明通过下述方案来实现。
(1)一种金属树脂复合成型品，其是对金属板嵌入成型树脂组合物而得到的金属树脂复合成型品，该金属板的厚度H为500μm以下，在该金属板的要嵌入该树脂组合物的表面形成有槽，该槽的宽度Y为30～300μm、深度X为该金属板的厚度H的24％以下、该深度X相对于该宽度Y的比例X/Y为0.1～2.5。
(2)一种金属树脂复合成型品的制造方法，其是对厚度H为500μm以下的金属板嵌入成型树脂组合物而制造金属树脂复合成型品的方法，所述方法具有：在该金属板的表面形成用于嵌入该树脂组合物的槽的工序，将该槽的宽度Y设为30～300μm、深度X设为该金属板的厚度H的24％以下、该深度X相对于该宽度Y的比例X/Y设为0.1～2.5。
发明的效果
本发明的金属树脂复合成型品尽管金属板为薄膜，由激光加工导致的变形也被抑制得较小。
附图说明
图1是示出对金属表面照射激光的照射图案的例子的图。
图2是示出用于气密性试验的成型品的确保气密性的方向Z的图。
图3是示意性地示出实施例和比较例中使用的金属树脂复合成型品试验片(金属板的厚度t的嵌入成型品)的图，(a)是俯视图，对背面实施了金属板的加工。(b)是分解的立体图，对下方实施了金属板的加工。(c)是A-A’的截面图。
图4是示出实施例所使用的树脂部与金属板之间的气密试验机E的图。
图5是实施例和比较例的标绘图。
具体实施方式
以下，针对本发明的实施方式进行说明。需要说明的是，本发明不限定于以下的实施方式。
<金属树脂复合成型品>
本发明的金属树脂复合成型品的特征在于，其是对金属板嵌入成型树脂组合物而得到的金属树脂复合成型品，该金属板的厚度H为500μm以下，在该金属板的要嵌入该树脂组合物的表面形成有槽，该槽的宽度Y为30～300μm、深度X为该金属板的厚度H的24％以下、该深度X相对于该宽度Y的比例X/Y为0.1～2.5。
《金属板》
作为本发明中使用的金属板，可例示出铝、镁、不锈钢、铜、钛等。此外，金属板可以由金属合金构成。此外，可以对金属材料的表面进行了阳极氧化处理等表面处理、涂装。从轻量、强度的方面出发，优选为铝、镁、铜、钛，在端子等需要导电性的用途中，更优选为铝、铜，特别优选为铜。此外，在便携终端壳体等要求薄壁且刚性的用途中，优选为镁、钛，特别优选为钛。
本发明中，金属板的厚度H为500μm以下时是有用的。金属板的厚度H的下限在强度上优选为100μm以上。
《槽的形状》
本发明中，在金属板的表面形成的槽以宽度Y为30～300μm、深度X为该金属板的厚度H的24％以下、该深度X相对于该宽度Y的比例X/Y为0.1～2.5的方式来形成。
如果金属板的厚度H超过500μm，则槽的深度与接合强度基本相关，通过增加槽的深度而能够获得期望的接合强度，但金属板的厚度H为500μm以下时，首先，因为薄而在形成槽时，金属板容易发生变形，此外，在槽的深度深的情况下，金属板在槽部进一步变薄，因此，有时无法在保证金属板的强度的同时确保充分的槽深度，需要除了深度之外还获得接合强度的技术手段。本发明发现：通过槽形状的调整而能够实现该目的。
本发明的槽的深度X和宽度Y采用使用激光显微镜而测得的值。此外，在如激光光束交叉那样地进行照射而存在交叉部分的情况下，针对交叉部分之外的部分，利用上述方法来测定深度。
本发明中，宽度Y为30～300μm，从变形与接合强度的平衡的方面出发，优选为50～200μm。
如果深度X不设为金属板的厚度H的24％以下，则难以抑制变形。为了进一步抑制变形且获得接合强度，优选为5～23％。作为X，优选为20～100μm。
深度X相对于宽度Y的比例X/Y为0.1～2.5的情况，从变形与接合强度的平衡的方面出发是必要的。优选为0.2～2，更优选为0.25～1。
《槽的形成方法》
本发明的槽利用激光而形成。具体而言，通过照射激光对金属表面进行槽加工并使其熔融而再凝固的条件来形成槽。具体而言，以照射脉冲波的激光光束的情况为例进行说明。图1记载对金属表面照射激光光束的照射图案的例子。在金属表面上的照射过激光的部分形成槽。需要说明的是，图1中的白底箭头表示激光的扫描方向。
此外，图1的(a)表示用于以排列的方式形成槽的激光照射方法。在图1的(a)中记载的照射方法的情况下，两个槽大致平行地排列。槽的排列方向上的脉冲的中心距为相邻的槽的间隔(本说明书中，有时将相邻的槽的间隔称为“影线宽度(hatching width)”W)。在图1的(a)所示的情况下，影线宽度是恒定的，本发明中，优选以影线宽度为槽的宽度Y的0.1～5.0倍的范围的方式进行调整。
若影线宽度小于上述范围，则槽与槽之间存在的金属部的宽度变窄，该部分的强度降低，由此有时接合强度、气密性变得不利，若影线宽度大于上述范围，则槽与槽的间隔变大，能够在同一处理面积内设置的槽的条数变少，因此有时接合强度、气密性降低。
需要说明的是，如图1的(b)所示那样，可以不大致平行地照射激光。在图1的(b)所示那样的情况下，影线宽度不是恒定的，但优选影线宽度的至少一部分为槽的宽度Y的0.1～5.0倍的范围。此外，如图1的(c)所示那样，可以不线性地照射激光光束。
此外，槽的数量也没有特别限定。在槽的数量为3以上的情况下，任意相邻的槽的影线宽度的至少一部分优选为槽的宽度Y的0.1～5.0倍的范围。此外，只要如上所述地以排列的方式形成槽，则如图1的(d)所示那样，多条槽彼此可以交叉。
如上所述，对金属板表面照射激光光束，但本发明中，如图1的(e)所示那样，为了提高接合部的强度而更优选的照射方法是如下方法：以沿着特定方向排列的方式形成的槽与沿着不同于上述特定方向的方向排列的槽相交叉的方式照射激光光束。最优选的照射方法是上述交叉角度大致成为90°的照射方法。
本发明中，如图2所示那样，为了提高接合部的气密性而优选的照射方法是以槽阻断想要确保气密性的方向Z的方式照射激光光束的方法。最优选的照射方法是相对于想要确保气密性的方向大致垂直地形成多条上述槽，且以它们互不相连的方式照射激光光束的方法。此外，激光光束的光斑直径(图1所示那样的激光光束的照射范围为圆的情况，表示照射范围的圆的直径)优选为300μm以下，更优选为30～100μm。
本发明中的激光的照射方法可列举出如下方法：对于照射过一次激光光束的位置重复照射二次、三次激光光束(调整扫描次数)，或者调节激光光束的光斑直径，或者调节激光光束的输出，或者调节激光光束的频率，或者调节激光光束的扫描速度。针对具体的条件，根据构成金属板的金属材料的种类等而异，根据金属材料的种类等而适当采用优选的条件。
使用根据用途等而成型为期望形状的金属板。例如，通过向期望形状的模具中流入熔融的金属等，能够获得期望形状的金属板。此外，为了将金属板成型为期望形状，可以使用基于工作机械等的切削加工等。
尤其是，本发明那样的薄壁金属板有时在卷绕成卷状的状态下供给至拉带成型，但在这种情况下，可以在从卷绕金属板而成的卷供给至成型机的过程中的阶段照射激光光束来形成槽，也可以将预先照射激光光束而形成有槽的金属板卷绕成卷状。
在如上那样得到的金属板的表面使用激光来形成槽。形成槽的位置、槽的范围的大小考虑要形成树脂的位置等来确定。
《树脂组合物》
本发明所使用的树脂组合物没有特别限定，可以使用包含现有公知的热塑性树脂的热塑性组合物。
作为热塑性树脂，可列举出例如聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、丙烯腈/苯乙烯树脂(AS)、丙烯腈/丁二烯/苯乙烯树脂(ABS)、甲基丙烯酸类树脂(PMMA)、聚氯乙烯(PVC)，作为热塑性树脂(通用工程树脂)，可列举出例如聚酰胺(PA)、聚缩醛(POM)、超高分子量聚乙烯(UHPE)、聚对苯二甲酸丁二醇酯(PBT)、GF增强聚对苯二甲酸乙二醇酯(GF-PET)、聚甲基戊烯(TPX)、聚碳酸酯(PC)、改性聚苯醚(PPE)，作为热塑性树脂(超级工程树脂)，可列举出例如聚苯硫醚(PPS)、聚醚醚酮(PEEK)、液晶性树脂(LCP)、聚四氟乙烯(PTFE)、聚醚酰亚胺(PEI)、聚芳酯(PAR)、聚砜(PSF)、聚醚砜(PES)、聚酰胺酰亚胺(PAI)，作为热固化性树脂，可列举出例如酚醛树脂、脲树脂、三聚氰胺树脂、不饱和聚酯、醇酸树脂、环氧树脂、苯二甲酸二烯丙酯，作为弹性体，可列举出例如热塑性弹性体、橡胶、例如苯乙烯/丁二烯系、聚烯烃系、氨基甲酸酯系、聚酯系、聚酰胺系、1,2-聚丁二烯、聚氯乙烯系、离聚物。进而，也可以列举出向热塑性树脂中添加有玻璃纤维的物质、聚合物合金等。
此外，在不明显损害本发明效果的范围内，为了赋予期望的物性，可以添加玻璃纤维所代表的无机填充剂、有机填充剂、阻燃剂、紫外线吸收剂、热稳定剂、光稳定剂、着色剂、脱模剂、增塑剂等添加剂。
热塑性树脂组合物之中，为了获得更良好的密合性，优选使用以热塑性树脂的熔点+20℃以上且热塑性树脂的熔点+30℃以下的温度测得的、剪切速度1000/秒时的熔融粘度为500Pa·s以下的热塑性树脂组合物。
从上述观点出发，聚缩醛(POM)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、聚苯硫醚(PPS)、聚醚醚酮(PEEK)、液晶性树脂(LCP)等是优选的热塑性树脂，特别优选使用聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、聚苯硫醚(PPS)、液晶性树脂(LCP)。
<金属树脂复合成型品的制造方法>
本发明的金属树脂复合成型品具备上述金属板和在金属板表面的至少一部分形成的树脂组合物。
金属树脂复合成型品的制造方法的具体工序没有特别限定，只要通过使已熔融的热塑性树脂组合物进入至槽的凹凸而使树脂与金属板复合化即可。
例如可列举出如下方法：将形成有槽的金属板配置在注射成型用模具内，并将熔融状态的热塑性树脂组合物注射至注射成型用模具内，从而制造树脂与金属板的金属树脂复合成型品。注射成型的条件没有特别限定，可根据热塑性树脂组合物的物性等来适当设定优选的条件。此外，使用传递成型、压缩成型等的方法也是形成由树脂与金属板复合化而成的金属树脂复合成型品的有效方法。
作为其它例，可列举出如下方法：预先利用注射成型法等一般的成型方法来制造树脂，使形成有槽的金属板与上述树脂在期望的接合位置处抵接，并对抵接面施加热，由此使树脂的抵接面附近熔融来制造树脂与金属板的金属树脂复合成型品。
<金属树脂复合成型品的特性>
如上所述，由于树脂与薄壁金属板的密合性优异、且即使在高温环境下、低温环境下也长期稳定地持续密合性这一长期耐久性也优异，因此本发明的金属树脂复合成型品可适宜地用于要求在高温环境下长期稳定且密合性优异的用途。
例如，本发明的金属树脂复合成型品可以用于如下散热结构体：其具备导电性发热部、绝缘部和导电性散热部，且从导电性发热部借助绝缘部向导电性散热部传递热而进行散热。
此处，本发明的金属树脂复合成型品中的树脂和金属板分别对应于散热结构体中的绝缘部和导电性散热部，作为导电性发热部，可列举出例如电子部件等。尤其是，本发明的金属树脂复合成型品使用了薄壁的金属板，因此能够利用将其以卷状的形式供给的拉带成型来有效地制造，从这点出发，可适宜地用于要求气密性的电子部件、其端子保持结构体。
更具体而言，对于本发明的金属树脂复合成型品，内部具备树脂制的凸台、保持构件等的壳体中收纳的具备导电性发热部的电气/电子设备中作为散热结构体的一部分是有用的。此处，作为电气/电子设备，可列举出便携电话、照相机、摄像复合型照相机、数码相机等便携用影像电子设备、笔记本型个人电脑、便携式计算机、计算器、电子记事本、PDC、PHS、便携电话等便携用信息或通信终端、MD、盒式立体声耳机、收音机等便携用音响电子设备、液晶TV/监测器、电话、传真、手持式扫描仪等家庭用电化机器等。此外，作为要求气密性的电子部件，可列举出连接器、传感器、冷凝器、电容器、电池、LED封装体等。
实施例
以下，示出实施例和比较例，具体说明本发明，但本发明不限定于这些实施例。
<嵌入成型品的制造方法>
将实施例和比较例中使用的金属树脂复合成型品(嵌入成型品)的示意图示于图3。(a)为俯视图，(b)为立体图，(c)为截面图。(b)的上部为金属板，下部为嵌入树脂。
利用下述方法制造该嵌入成型品。需要说明的是，图中的尺寸的单位为mm。
作为构成树脂部的热塑性树脂组合物，使用了聚苯硫醚系树脂组合物(包含35质量％的玻璃纤维作为填充材料，在310℃下测得的剪切速度为1000/秒时的熔融粘度为260Pa·s的树脂组合物、宝理塑料株式会社制、“DURAFIDE(注册商标)1135ML1”)。
[熔融粘度]
使用东洋精机株式会社制的Capillograph，作为毛细管而使用
Figure BDA0002414095410000091
/平模，测定特定的滚筒温度、剪切速度1000/秒时的熔融粘度。上述机筒温度设定为310℃。
作为金属板，使用由铜(C1100P、厚度H记载在表中)构成且如下所示那样形成有槽的外径为
Figure BDA0002414095410000092
的圆板状物。这些金属板在图3的(a)的槽部周围、具体而言在自圆板的中心部起
Figure BDA0002414095410000093
的外侧区域、即
Figure BDA0002414095410000094
的圆板的外周侧5mm宽的区域具有接合预定面。
<槽的形成>
使用激光标识器MD-V9900(Keyence Corporation制、激光类型：YVO4激光、振荡波长：1064nm、最大额定输出：13W(平均))，在输出为90％、频率为40kHz、扫描速度为1000mm/秒的条件下，在接合预定面的金属表面，以表1和表2所示的深度和宽度、按照成为图3的(b)所示那样的同心圆状的方式形成槽。需要说明的是，激光光束的光斑直径和扫描次数根据槽的深度和宽度来适当调整。例如，在宽度为50μm、深度为70μm的情况下，将光斑直径调整至50μm，将扫描次数设为300次。
此处，槽的根数以如下方式设定：在图3所示的试验片中，为了树脂与金属接触的区域(接合预定面)的面积之中形成槽的凹凸的凹部与凸部的投影面积分别同等的方式，而按照凹部的宽度与凸部的宽度为等间隔(影线宽度为槽的宽度Y的2倍)的方式进行设定。即，在树脂与金属接触的区域的外周(直径为30mm)的半径15mm与内周(直径为20mm)的半径10mm之间的5mm宽度中所形成的槽的根数大致为5mm÷(宽度Y×2)。
此外，使用激光显微镜(基恩士株式会社制、“VK-9510”)测定形成槽的凹凸的深度X和宽度Y。将深度X、宽度Y和比值X/Y的测定结果示于表1和表2。
将这些金属板分别配置于模具中，进行复合化工序。成型条件如下所示。金属树脂复合成型品的形状如图3所示那样。
[成型条件]
成型机：SODICK TR-40VR(立式注射成型机)
料筒温度：320℃
模具温度：150℃
注射速度：100mm/秒
保压力：49MPa×5秒
<评价>
针对利用上述方法而制作的金属树脂复合成型品，评价接合部分的接合强度和剥离后的破坏形态。具体的评价方法如下所示。
[变形]
通过目视来观察激光照射后的金属板，将观察到翘曲等显著变形的情况评价为×、除此之外评价为○。将结果示于表1和表2。
[接合性(气密性)]
接合性的评价针对利用上述方法而制作的金属树脂复合成型体5，利用下述方法来测定气密性。图4是示出使用了气密试验机E的气密性评价的方法的纵向截面图。气密试验机E具备气密试验机主体7和气密试验机盖6。借助O形环5将金属树脂复合成型体试验片2安装于气密试验机主体7，将金属树脂复合成型体试验片2的下部密封。其后，将气密试验机盖6载置在金属树脂复合成型体试验片2的树脂构件4上并固定。
向金属树脂复合成型体试验片2上注入蒸馏水10，将金属树脂复合成型体试验片2完全浸渍在蒸馏水10中。借助线路9来送入空气，对气密试验机主体内部7施加6分钟的0.1MPa压力，通过目视来观察气泡是否从金属板3与树脂构件4的界面泄露。将上述试验实施3次，并将基于下述基准的气密性评价结果示于表1和表2。
○：1次也未确认到气泡泄露时，评价为气密性良好。
△：确认到1～2次气泡泄露时，气密性评价为中等程度。
×：3次均确认到泄露时，气密性评价为不良。
[卷取性]
设想其用于拉带成型的情况，将实施例和比较例中使用的各厚度的金属板以进行激光照射前的状态裁切成20mm×50mm的板状，以长度方向成为圆周方向的方式卷绕于曲率半径40mm的圆柱，并保持10秒钟，然后在保持时将成为外侧的面朝下载置在平板上，通过目视来确认因应变而发生的翘曲。
针对观察翘曲的样品，由于可认为将金属板卷绕成卷状时需要过大的力而难以卷绕或者因应变而强度降低、发生变形，因此，将观察到显著翘曲的情况评价为×，除此之外评价为○。将结果示于表1和表2。
[表1]
Figure BDA0002414095410000121
[表2]
Figure BDA0002414095410000122
如表1和表2所示那样，在本发明的范围中，能够以变形少的状态来显著提高树脂部与金属板的接合强度。
图5中，针对使用了厚度400μm的金属板的情况，用阴影线框表示满足权利要求1的各数值规定的范围，示出了符合板厚400μm的实施例和比较例。
附图标记说明
Z 用于气密性试验的成型品的确保气密性的方向
W 影线宽度
1 利用激光对金属板形成的槽
2 金属板用树脂组合物进行了嵌入成型的试验片
3 进行了激光加工的金属板
4 由树脂组合物形成的成型体＝树脂构件
5 O形环
6 气密试验机盖
7 气密试验机主体
8 压力
9 线路
10 蒸馏水
E 气密试验机
a、c、d 接合(气密性)不良发生区域
b 变形发生区域

Claims (2)

1.一种金属树脂复合成型品，其是对金属板嵌入成型树脂组合物而得到的金属树脂复合成型品，该金属板的厚度H为500μm以下，在该金属板的要嵌入该树脂组合物的表面形成有槽，该槽的宽度Y为30～300μm、深度X为该金属板的厚度H的24％以下、该深度X相对于该宽度Y的比例X/Y为0.1～2.5。
2.一种金属树脂复合成型品的制造方法，其是对厚度H为500μm以下的金属板嵌入成型树脂组合物而制造金属树脂复合成型品的方法，所述方法具有：在该金属板的表面形成用于嵌入该树脂组合物的槽的工序，将该槽的宽度Y设为30～300μm、将深度X设为该金属板的厚度H的24％以下、将该深度X相对于该宽度Y的比例X/Y设为0.1～2.5。
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