CN107405890A - 热塑性树脂膜叠层体、以及包含热塑性树脂膜叠层体的成型品 - Google Patents

热塑性树脂膜叠层体、以及包含热塑性树脂膜叠层体的成型品 Download PDF

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Publication number
CN107405890A
CN107405890A CN201680015816.9A CN201680015816A CN107405890A CN 107405890 A CN107405890 A CN 107405890A CN 201680015816 A CN201680015816 A CN 201680015816A CN 107405890 A CN107405890 A CN 107405890A
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China
Prior art keywords
thermoplastic resin
resin film
molded article
welding material
film laminate
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Granted
Application number
CN201680015816.9A
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CN107405890B (zh
Inventor
黑川晴彦
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Mitsubishi Gas Chemical Co Inc
MGC Filsheet Co Ltd
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Mitsubishi Gas Chemical Co Inc
MGC Filsheet Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/53—Joining single elements to tubular articles, hollow articles or bars
    • B29C66/534—Joining single elements to open ends of tubular or hollow articles or to the ends of bars
    • B29C66/5346—Joining single elements to open ends of tubular or hollow articles or to the ends of bars said single elements being substantially flat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • 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
    • B29C65/08—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using ultrasonic vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
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    • B29C66/1222—Joint cross-sections combining only two joint-segments, i.e. one of the parts to be joined comprising only two joint-segments in the joint cross-section comprising at least a lapped joint-segment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
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    • B29C66/1224—Joint cross-sections combining only two joint-segments, i.e. one of the parts to be joined comprising only two joint-segments in the joint cross-section comprising at least a butt joint-segment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
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    • B29C66/24—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being closed or non-straight
    • B29C66/242—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being closed or non-straight said joint lines being closed, i.e. forming closed contours
    • B29C66/2424—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being closed or non-straight said joint lines being closed, i.e. forming closed contours being a closed polygonal chain
    • B29C66/24243—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being closed or non-straight said joint lines being closed, i.e. forming closed contours being a closed polygonal chain forming a quadrilateral
    • B29C66/24244—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being closed or non-straight said joint lines being closed, i.e. forming closed contours being a closed polygonal chain forming a quadrilateral forming a rectangle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
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    • B29C66/3022—Particular design of joint configurations the area to be joined comprising melt initiators said melt initiators being integral with at least one of the parts to be joined
    • B29C66/30223—Particular design of joint configurations the area to be joined comprising melt initiators said melt initiators being integral with at least one of the parts to be joined said melt initiators being rib-like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/53—Joining single elements to tubular articles, hollow articles or bars
    • B29C66/534—Joining single elements to open ends of tubular or hollow articles or to the ends of bars
    • B29C66/5346—Joining single elements to open ends of tubular or hollow articles or to the ends of bars said single elements being substantially flat
    • B29C66/53461—Joining single elements to open ends of tubular or hollow articles or to the ends of bars said single elements being substantially flat joining substantially flat covers and/or substantially flat bottoms to open ends of container bodies
    • B29C66/53462—Joining single elements to open ends of tubular or hollow articles or to the ends of bars said single elements being substantially flat joining substantially flat covers and/or substantially flat bottoms to open ends of container bodies joining substantially flat covers and substantially flat bottoms to open ends of container bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311—Thermal properties
    • B29C66/73115—Melting point
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
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    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
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    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
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    • B29C66/73117—Tg, i.e. glass transition temperature
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Abstract

通过热塑性树脂膜与热塑性树脂成型品的超声波熔接，提供具有高的熔接强度和熔接痕少的优异外观的热塑性树脂膜叠层体。该热塑性树脂叠层体通过将厚度0.4mm以下的热塑性树脂膜(A)与具有熔接料(C)的厚度0.5mm以上的热塑性树脂成型品(B)的所述熔接料(C)超声波熔接而得到，通过该熔接料(C)的高度为该热塑性树脂膜(A)的厚度的75～125％的热塑性树脂膜叠层体来解决上述课题。

Description

热塑性树脂膜叠层体、以及包含热塑性树脂膜叠层体的成 型品
技术领域
本发明涉及将薄的热塑性树脂膜与热塑性树脂成型品超声波熔接而得到的树脂叠层体等。
背景技术
近年来，对于电气电子设备的部件，制品的小型化和部件的薄壁化不断进展，所以要求更高的设计性。其中，内置有小型充电电池的电池组用的壳体，以高容量化为目的，塑料成型品的薄壁化逐步发展。由于今后构件的薄壁化也要发展，据说电池组用壳体的厚度为0.4mm以下的部分会占到成型品表面积中的40％以上。
作为得到这样的薄壁成型品的方法目前为止采用的方法，可以列举通常的注射成型法、以及专利文献1中记载的预先将薄膜设置在模具内进行注射成型的使用模内膜的注射成型法等。但是，在利用通常的注射成型方法时，存在树脂难以向薄壁部填充、制品欠注的问题，并且在以高注射压力填充时存在成型品的薄壁部翘曲的问题。另外，在利用专利文献1所记载的利用模内膜的注射成型法时，在具有开口部的成型品的情况下，由于成型品与膜的接触部和非接触部的热收缩的差异，存在覆盖开口部的膜弯曲的问题。
此外，还有利用粘接剂或双面胶带将膜与注射成型品贴合的方法等，但利用任何方法也会由于粘接部的厚度局部增加而得不到外观好的成型品。
作为成型品等的其他的接合方法，可以列举专利文献2、3所记载的利用成型品间的摩擦的超声波熔接方法。但是，关于利用超声波熔接方法的树脂间的接合，通常情况下厚壁的注射成型品彼此之间的接合是主流，在用膜和具有厚壁的注射成型品进行熔接试验的情况下，存在容易产生由于膜与成型品接触时的熔接痕所造成的外观不良的问题。
现有技术文献
专利文献
专利文献1：日本特开2013－129077号公报
专利文献2：日本特许4558374
专利文献3：日本特开昭62－54757号公报
发明内容
发明所要解决的课题
本发明的课题在于通过热塑性树脂膜与热塑性树脂成型品的超声波熔接，提供一种熔接强度高、熔接痕少且具有优异外观的热塑性树脂膜叠层体。
用于解决课题的方法
本发明的发明人为了解决上述课题反复进行了深入研究，结果，着眼于热塑性树脂膜与热塑性树脂成型品的热变形温度之差、以及设置在热塑性树脂成型品表面的熔接料(导熔线，energy director)的高度，使现有技术中难以实现的膜熔接品的良好的外观与熔接强度的兼顾成为可能。
即，本发明涉及以下所示的将热塑性树脂膜与热塑性树脂成型品进行超声波熔接而得到的热塑性树脂膜叠层体，要点如下。
[1]一种热塑性树脂膜叠层体，其是通过将厚度0.4mm以下的热塑性树脂膜(A)与具有熔接料(C)的厚度0.5mm以上的热塑性树脂成型品(B)的上述熔接料(C)进行超声波熔接而得到的热塑性树脂叠层体，该熔接料(C)的高度为热塑性树脂膜(A)的厚度的72～130％，热塑性树脂膜(A)与热塑性树脂成型品(B)的热变形温度之差在20℃以下。
[2]如[1]所述的热塑性树脂膜叠层体，其中，热塑性树脂膜(A)和热塑性树脂成型品(B)由同种树脂材料形成。
[3]如[1]或[2]中任一项所述的热塑性树脂膜叠层体，其中，热塑性树脂膜(A)的厚度为0.2mm至0.3mm。
[4]如[1]～[3]中任一项所述的热塑性树脂膜叠层体，其中，热塑性树脂成型品(B)具有至少1个以上的3cm2以上的开口部，热塑性树脂膜(A)覆盖开口部的至少一部分。
[5]一种包含上述[1]～[4]中任一项所述的热塑性树脂膜叠层体的成型品。
发明的效果
将热塑性膜与热塑性树脂成型品进行超声波熔接而得到的本发明的热塑性树脂膜叠层体具有优异的熔接强度和良好的外观。因此，本发明的热塑性树脂膜叠层体能够适合用作例如电气电子OA设备用壳体、电池组壳体、透明窗/窗框一体型成型品。
附图说明
图1是热塑性树脂膜和热塑性树脂成型品的简化的截面图。
图2是表示热塑性树脂膜覆盖热塑性树脂成型品的开口部的状态的俯视图(图2(A))以及表示沿着图2(A)中的II‐II线切断的热塑性树脂成型品的侧面形状的截面图(图2(B))。
图3是与图2不同的热塑性树脂成型品的俯视图。
图4是将图3中的热塑性树脂成型品的区域I和II放大表示的俯视图。
具体实施方式
以下，详细说明本发明。但本发明不限于以下的实施方式，能够在具有发明的效果的范围内任意变更实施。
[热塑性树脂膜(A)、热塑性树脂成型品(B)和热塑性树脂成型品的熔接料(导熔线)(C)的组成]
本发明的树脂组合物所含的热塑性树脂没有特别限制，能够从现有技术中作为成型材料使用的材料中任意选择使用。可以列举例如苯乙烯系树脂、聚苯醚系树脂、聚烯烃系树脂、聚氯乙烯系树脂、聚酰胺系树脂、聚酯系树脂、聚碳酸酯系树脂以及丙烯酸系树脂等。
作为苯乙烯系树脂，可以列举例如苯乙烯、α－甲基苯乙烯等的均聚物或它们的共聚物、或者它们与能够共聚的不饱和单体的共聚物等。具体而言，可以列举通用聚苯乙烯(GPPS)、耐冲击性聚苯乙烯(HIPS)、耐热性聚苯乙烯(例如α－甲基苯乙烯聚合物或共聚物等)、丙烯腈·丁二烯·苯乙烯共聚物(ABS)、丙烯腈·丁二烯·苯乙烯·α－甲基苯乙烯共聚物(α－甲基苯乙烯系耐热ABS)、丙烯腈·丁二烯·苯乙烯·苯基马来酰亚胺共聚物(苯基马来酰亚胺系耐热ABS)、丙烯腈－苯乙烯共聚物(AS)、丙烯腈－氯化聚苯乙烯·苯乙烯系共聚物(ACS)、丙烯腈·乙丙橡胶·苯乙烯共聚物(AES)、丙烯酸橡胶·丙烯腈·苯乙烯共聚物(AAS)或者间规聚苯乙烯(SPS)等。并且，苯乙烯系树脂可以为聚合物共混而形成的树脂。
作为聚苯醚系树脂(PPE)，可以列举例如聚(2,6－二甲基－1,4－亚苯基)醚、聚(2－甲基－6－乙基－1,4－亚苯基)醚等的均聚物，也能够使用利用苯乙烯系树脂将其改性而形成的树脂。
作为聚烯烃系树脂，代表性地可以列举乙烯、丙烯、丁烯－1、3－甲基丁烯－1、3－甲基戊烯－1、4－甲基戊烯－1等α－烯烃的均聚物或它们的共聚物、或者它们与其他能够共聚的不饱和单体的共聚物等。作为代表例，能够列举高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、直链状低密度聚乙烯、超高分子量聚乙烯、乙烯·乙酸乙烯酯共聚物、乙烯·丙烯酸乙酯共聚物、乙烯·辛烯－1共聚物等的茂金属系乙烯·α烯烃共聚物等的聚乙烯类、无规聚丙烯、间规聚丙烯、等规聚丙烯、或者丙烯·乙烯嵌段共聚物或无规共聚物等聚丙烯类、聚甲基戊烯－1等。
作为聚氯乙烯系树脂，可以列举例如氯乙烯均聚物或氯乙烯与能够共聚的不饱和单体的共聚物。具体而言，可以列举氯乙烯·丙烯酸酯共聚物、氯乙烯·甲基丙烯酸酯共聚物、氯乙烯·乙烯共聚物、氯乙烯·丙烯共聚物、氯乙烯·乙酸乙烯酯共聚物、氯乙烯·偏二氯乙烯共聚物等。并且，还可以使用将这些聚氯乙烯系树脂氯化而提高了氯含量的树脂。
作为聚酰胺系树脂(PA)，能够列举例如：将以6－尼龙(聚酰胺6)或12－尼龙等为代表的环状脂肪族内酰胺进行开环聚合而得到的树脂；将6,6－尼龙、6,10－尼龙、6,12－尼龙等的脂肪族二胺与脂肪族二羧酸缩聚而得到的树脂；或者根据情况将芳香族二胺、芳香族二羧酸共缩聚而得到的树脂等。
作为聚酯系树脂，可以列举例如使芳香族二羧酸与乙二醇、丙二醇、丁二醇等亚烷基二醇缩聚而得到的树脂。作为具体例，可以列举聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丙二醇酯(PPT)、聚对苯二甲酸丁二醇酯(PBT)等。
作为聚碳酸酯系树脂，可以列举例如4,4′－二羟基二芳基烷烃系聚碳酸酯等。作为具体例，可以列举双酚A系聚碳酸酯(PC)、改性双酚系聚碳酸酯、它们的共聚物等。
作为丙烯酸系树脂，可以列举例如甲基丙烯酸酯、丙烯酸酯均聚物或它们的共聚物、或者它们与其他能够共聚的不饱和单体的共聚物等。作为甲基丙烯酸酯、丙烯酸酯单体，可以列举甲基丙烯酸或丙烯酸的甲基、乙基、正丙基、异丙基、丁基的各酯体等。代表性地可以列举聚甲基丙烯酸(甲)酯(PMMA)。
[热塑性树脂膜(A)]
在本发明中，热塑性树脂膜(A)的厚度为0.4mm以下。这是指在热塑性树脂膜中厚度为0.4mm以下的区域的表面积为膜整体的表面积的70％以上。在热塑性树脂膜(A)的厚度大于0.4mm时，通常利用注射成型的成型容易，并且由于具有足够的厚度，所以观察不到由于导熔线的挤入而造成的外观不良，因此无法充分地发挥本发明的效果。热塑性树脂膜(A)的优选厚度为0.01mm到0.4mm以下，更优选为0.1mm到0.4mm，最优选为0.2mm到0.3mm。在热塑性树脂膜(A)的厚度小于0.01mm时，由于膜过薄，超声波熔接后得不到良好的外观，并且在作为壳体使用的情况下，会出现内部部件的保护不充分的问题。此外，本发明的热塑性树脂膜(A)可以使用由利用T模的熔融挤出法、溶剂浇铸法、吹塑成型法制得的膜。
[热塑性树脂成型品(B)]
在本发明中，热塑性树脂成型品(B)的厚度的平均值在0.5mm以上。另外，热塑性树脂成型品(B)的成型方法可以列举注射成型品、压制成型品、吹塑成型品、挤出成型品、真空成型品、压空成型品等，但从生产率的观点出发，优选使用注射成型品。
在本发明的热塑性树脂膜叠层体中，热塑性树脂成型品(B)的形状不限于平板，也可以是三维形状。作为特别有效的形状，在本发明中优选使用热塑性树脂成型品(B)具有3cm2以上的开口部的三维的成型品、例如为壳体，利用热塑性树脂膜(A)将该开口部覆盖的构成。通过利用热塑性树脂膜(A)将热塑性树脂成型品(B)的开口部覆盖，能够实现构件的轻量化、例如作为壳体的成型品(B)的内部中部件的高填充化。
[热塑性树脂成型品的熔接料(导熔线)(C)]
为了将热塑性树脂膜(A)和热塑性树脂成型品(B)接合，在热塑性树脂成型品(B)的熔接面设置有熔接料(导熔线)(C)。作为接合方法，可以使用超声波熔接。在超声波熔接时，超声波能量集中在设置于热塑性树脂成型品(B)的熔接料(导熔线)，通过因热塑性树脂成型品(B)的熔接料(C)与热塑性树脂膜(A)的摩擦所产生的放热，熔融的熔接料(导熔线)与热塑性树脂膜(A)被接合。
导熔线优选为向所接合的热塑性树脂膜(A)侧、即向上侧凸起的形状，膜厚度截面的形状优选为三角形。关于该截面的三角形，可以使用顶点的角度为40度到120度的导熔线，优选顶点的角度为50～70度，最优选为60度。即，特别优选截面形状为正三角形。这样，如果熔接料(导熔线)(C)的截面形状为三角形、特别是正三角形，则在超声波熔接时能够使超声波能量集中在上端部、即三角形的顶点，并且能够充分确保热塑性树脂成型品(B)侧、即三角形的底边侧的熔接料的区域。从这样的观点出发，优选作为熔接料(导熔线)(C)的截面形状，应当避免四边形，还要避免圆形。熔接料(导熔线)(C)的形状能够通过由注射成型或热压成型利用模具转印的方法、利用成型品的机械切削、印刷等的加工来赋予。
此外，熔接料(C)优选在热塑性树脂成型品(B)的熔接面上相连配置成列状(线状)。熔接料(C)特别优选在热塑性树脂成型品(B)的熔接面上设置成一列。这是因为在热塑性树脂成型品(B)的熔接面上设置熔接料(C)的多个列、例如平行的多个列时，超声波能量会被多个列分散的缘故。
熔接料((C)导熔线)的高度、即如图1所示从热塑性树脂成型品(B)20的熔接面20S到例如截面为三角形的熔接料24的顶点的长度24H优选为热塑性树脂膜(A)10的厚度10T的72％～130％。即，在将热塑性树脂膜(A)的厚度设为A(mm)、熔接料(C)的高度设为C(mm)时，
C(mm)/A(mm)×100(％)的值优选为72％～130％，
(1－C(mm)/A(mm))×100(％)的值优选为－28％～30％。
此外，优选熔接料24的高度24H为热塑性树脂膜(A)10的厚度10T的75～125％，更优选为80～120％，特别优选为85～115％。在熔接料(导熔线)的高度24H超过上限的情况下，虽然可以得到熔接强度，但是会出现容易由于导熔线的挤入而造成外观不良的问题。另外在熔接料(导熔线)的高度24H不足下限的情况下，虽然可以得到外观良好的叠层体，但是会出现熔接强度下降的问题。
如图1所示，在热塑性树脂膜10与热塑性树脂成型品20彼此对置的状态下，通过使它们如箭头所示熔接的超声波熔接，形成热塑性树脂膜10与热塑性树脂成型品20的叠层体。在这样得到的叠层体的热塑性树脂膜10与热塑性树脂成型品20之间，熔接料24由于超声波熔接而熔化，形成与热塑性树脂膜10熔融混合的接合部。因此，在制得的叠层体中的热塑性树脂膜10与热塑性树脂成型品20的接合区域中，这些构件的表面实质上均平滑，不会出现外观上的问题。
[热塑性树脂膜(A)、热塑性树脂成型品(B)的热变形温度]
关于本发明中的热塑性树脂膜(A)和热塑性树脂成型品(B)的热变形温度，在这些树脂为非晶性树脂的情况下为玻璃化转变温度，在这些树脂为结晶性树脂的情况下为熔点。热变形温度通过DSC(差热扫描量热分析计)测定。在非相容系的聚合物合金材料的情况下，为基体树脂的热变形温度。
热塑性树脂膜(A)和热塑性树脂成型品(B)的组合优选使用热变形温度之差在20℃以下的组合。更优选热变形温度之差在15℃以下，特别优选在10℃以下。其中，热塑性树脂膜(A)和热塑性树脂成型品(B)树脂的种类优选使用相容性高的种类、或者反应性高的种类。特别优选由同种树脂材料形成热塑性树脂膜(A)和热塑性树脂成型品(B)。这里所说的同种材料是指说明书第3页倒数第2段以下所示的树脂的类别相同的材料，更具体指具有同种化学键的热塑性树脂材料。因此，如果为具有同种分子结构的树脂材料，即使是分子量不同的材料、共聚的种类、共聚组成比、添加剂的配合量不同的材料，也定义为本发明中的同种的树脂材料。
在热塑性树脂膜(A)与热塑性树脂成型品(B)的热变形温度之差超过20℃时，在外观优先的情况下树脂熔接强度不充分，在其熔接强度优先的情况下需要更高的超声波能量，因此会出现所得到的热塑性树脂膜叠层体(成型品)的外观变差的问题。
[热塑性树脂膜叠层体的制造方法]
在本发明的热塑性树脂膜叠层体的制造方法中，使用超声波熔接。即，热塑性树脂膜叠层体通过将上述的热塑性树脂膜(A)与上述的热塑性树脂成型品(B)的熔接料(C)进行超声波熔接来制造。例如，通过在热塑性树脂成型品(B)的开口部的周围设置熔接料(C)，以覆盖开口部的方式使热塑性树脂膜(A)接合，由此得到热塑性树脂膜叠层体。
如上所述，利用调节热塑性树脂膜(A)的厚度使其达到规定范围内的值、并将规定高度的熔接料(C)设置在热塑性树脂成型品(B)的熔接表面上的制法，能够得到熔接强度和外观良好的叠层体，并且通过抑制热塑性树脂膜(A)与热塑性树脂成型品(B)的热变形温度之差，能够可靠地兼顾高熔接强度和良好的外观。
本发明中使用的热塑性树脂组合物只要不明显损害所希望的各项物性，可以根据需要含有上述成分以外的成分。作为其他成分，可以列举例如以磷酸酯、亚磷酸酯为代表的热稳定剂、以受阻酚化合物为代表的抗氧化剂、以苯并三唑系化合物为代表的紫外线吸收剂、防雾剂、抗粘连剂、流动性改良剂、冲击强度改良剂、滑动性改质剂、增塑剂、分散剂、抗菌剂、阻燃剂、玻璃纤维、碳纤维等各种树脂添加剂等。这些树脂添加剂既可以含有1种，也可以以任意的组合和比率含有2种以上。
在图2所示的本发明的一个实施方式中，对于具有开口部20H的热塑性树脂成型品20，以热塑性树脂膜10覆盖开口部20H的方式，形成热塑性树脂膜10与热塑性树脂成型品20的叠层体。此时，在热塑性树脂膜10的熔接面10S与热塑性树脂成型品20的熔接面20S(参照图1)接触的区域、即图2中边界面30S，通过超声波熔接使热塑性树脂膜10与热塑性树脂成型品20熔接。
在这样制造的作为壳体的叠层体40中，与由厚度比热塑性树脂膜10大的热塑性树脂成型品20的壁构件20W形成整个面的情况相比，能够确保更宽的内部空间40A，例如收纳电池等内部部件的空间增大。
实施例
以下，表示实施例，更具体地说明本发明。但是，本发明不限定于以下的实施例，在不脱离本发明的要点的范围内，能够任意变更实施。
＜热变形温度的测定＞
热塑性树脂的热变形温度(Tg)由差热扫描量热分析计精工电子工业株式会社制的SSC－5200(DSC)进行测定。在测定中，在氮气氛下以20℃/min升温至树脂成分熔融的温度(260℃)，骤冷至－30℃，之后再次以10℃/min升温(2nd run)。根据所得到的DSC曲线，利用起点法求出玻璃化转变温度和熔点。
＜熔接强度＞
作为超声波熔接强度的评价，将膜叠层体的熔接后的成型品的成型品开孔部，用手指从成型品侧按入将其破坏。
特别良好：没有观察到熔接部的破坏。
良好：部分观察到了熔接料处的破坏。
不良：熔接的膜发生了剥离。
＜外观评价＞
目测进行膜叠层体的超声波熔接后的成型品叠层体的外观评价。目测观察从膜侧进行。将在膜表面几乎不存在由于熔接料(导熔线)的挤入而造成的表面伤痕的特别优异的状态评价为特别良好，将表面伤痕少的良好的状态评价为良好，将表面伤痕略微显眼的评价为轻度不良，将表面伤痕大的外观差的状态评价为不良。
＜弯曲评价＞
如图3所示，在具有2个开口部、与图1和2所示的成型品形状不同的平板状的成型品上熔接膜叠层体后，目测确认成型品叠层的弯曲程度。将几乎没有弯曲的状态评价为良好，将弯曲大的状态评价为不良。
[使用材料]
＜热塑性树脂＞
聚碳酸酯树脂按照表1的配合实施混合，聚对苯二甲酸丁二醇酯使用市售的产品。
(a－1)三菱工程塑料株式会社制“Iupilon(注册商标)S－3000F”、双酚A型芳香族聚碳酸酯树脂、热变形温度(玻璃化转变温度)145℃
(a－2)三菱工程塑料株式会社制“Novaduran(注册商标)5020”、聚对苯二甲酸丁二醇酯树脂、热变形温度(熔点)224℃
(a－3)三菱工程塑料株式会社制“Novaduran(注册商标)5510S”、聚对苯二甲酸丁二醇酯树脂、热变形温度(熔点)219℃
＜阻燃剂＞
(b－1)大八化学工业株式会社制“PX－200”、芳香族缩合磷酸酯系阻燃剂、1,3－亚苯基双(二－2,6－二甲苯基磷酸酯)
[实施例1～10、比较例1～4]
＜树脂粒料的制造＞
聚碳酸酯树脂组合物的混合使用具有1个通风口的株式会社日本制钢所制双螺杆挤出机TEX30α(C18捏合块)。然后，以螺杆转速200rpm、排出量20kg/小时、转鼓温度270℃的条件，将各成分混炼，将挤出成股状的熔融树脂在水槽中骤冷，使用造粒机进行粒料化，得到聚碳酸酯树脂组合物的混合物。
＜热塑性树脂膜(A)＞
使用具备转鼓直径32mm、螺杆的L/D＝35的双螺杆挤出机的T模熔融挤出机，以排出量20kg/h、螺杆转速200rpm，形成宽度400mm的片材。关于转鼓、模头温度的设定，聚碳酸酯以260℃进行，聚对苯二甲酸丁二醇酯以235℃进行。使用膜的表面的一个面为镜面、另一个面转印有表面粗糙度Ra＝1.5μm的哑光形状的膜。膜厚度使用表1所示的厚度。关于超声波熔接试验中使用的膜的大小，为了覆盖图3所示的热塑性树脂成型品(B)，使用切成150mm×40mm的膜。
＜热塑性树脂成型品(B)＞
利用注射成型形成表1中记载的组成品的150mm×100mm×1.2mm厚平板的树脂板。通过对所得到的注射成型品进行切削加工，制造图3所示的尺寸、并且具有图1中示意性地表示的形状的熔接料(ED、导熔线)(C)24的热塑性树脂成型品(B)20。其中，图3和4中的与符号不同的数值表示各构件的尺寸(mm)。这些数值是各构件的尺寸的一例，并不能限定各构件的尺寸。
＜具有叠层体的树脂成型品＞
制作上述的热塑性树脂成型品(B)20与热塑性树脂膜(A)10一体化的熔接料一体型热塑性树脂成型品。熔接料(ED、导熔线)(C)的高度为表1所示的0.1～0.4mm的值。然后，使用具有图3所示形状的热塑性树脂成型品(B)20，以热塑性树脂膜将2个开口部20H完全覆盖的方式，使热塑性树脂膜10与热塑性树脂成型品20熔接。热塑性树脂成型品(B)20的厚度为1.0mm，长和宽的长度分别为4.0cm和15.0cm，各开口部20H的长和宽的长度分别为1.0cm和12.5cm，各开口部20H的面积为12.5cm2(参照图3)。然后，在热塑性树脂成型品(B)20的熔接面20S上，以将开口部20H的周围包围的方式，将熔接料(C)24设置在虚线所示的位置。图4中，将图3所示的熔接面20S的区域I和II放大表示。
这样一来，通过以将开口部20H的实质上全周包围的方式设置熔接料(C)24来进行超声波熔接，能够将热塑性树脂膜(A)10牢固地固定于热塑性树脂成型品(B)20。此外，在熔接面20S的区域I中，通过设置熔接料(C)24的间断的区域20D(参照图4)，设置熔接料的加工变得容易。
[表1]
＜模内膜成型＞
关于覆盖成型品开口部的膜的弯曲状态，为了进行超声波熔接品与利用模内膜的注射成型品的比较，形成利用模内膜的注射成型品。预先将与超声波熔接用成型品相同尺寸(150×40mm)的聚碳酸酯树脂膜设置在模具内，利用未雕有超声波熔接用模具的熔接料(C)的模具进行聚碳酸酯树脂的注射成型。按照以下的成型条件、即料筒温度320℃、模具温度95℃的条件进行成型。将由模内膜成型得到的结果表示在比较例4中。
[表2]
＜超声波熔接方法＞
超声波熔接使用Emerson Japan,Ltd.制的Branson 2000Xdt(20kHz2200W)，使用与成型品形状匹配的钛合金制的熔接焊头。熔接试验在热塑性树脂膜(A)的镜面侧和热塑性树脂成型品(B)的形成有熔接料的面进行，将热塑性树脂成型品(B)固定于上部焊头侧，将热塑性树脂膜(A)固定于下部焊头载台，进行熔接试验。为了保护热塑性树脂膜(A)的哑光花纹，使膜接触厚度0.03mm的聚乙烯制的保护膜进行试验。超声波熔接试验中的参数设定如下所述。即，以照射时间0.3sec(聚对苯二甲酸丁二醇酯树脂时为0.45sec)、保持时间0.3sec、气缸压力200kPa、触发压力250N和振幅100％的条件，实施超声波熔接试验。
在上述实施例1～10中，熔接强度、膜的外观和形状均在良好以上，在比较例1～4中，至少任意一项评价项目中是比实施例差的结果。由以上结果可以确认，通过以在热塑性树脂成型品的熔接面设置适当大小的熔接料、减小形成热塑性树脂膜和热塑性树脂成型品的树脂的热变形温度之差的方式调整的超声波熔接，能够制造具有比通过模内成型得到的产品更高的熔接强度和优异外观的叠层体。
符号说明
10：热塑性树脂膜；10T：热塑性树脂膜的厚度；20：热塑性树脂成型品；20H：开口部；20S：熔接面；24：熔接料；24H：熔接料的高度。

Claims (5)

1.一种热塑性树脂膜叠层体，其特征在于：
其是通过将厚度0.4mm以下的热塑性树脂膜(A)与具有熔接料(C)的厚度0.5mm以上的热塑性树脂成型品(B)的所述熔接料(C)进行超声波熔接而得到的热塑性树脂叠层体，
该熔接料(C)的高度为该热塑性树脂膜(A)的厚度的72～130％，
所述热塑性树脂膜(A)与所述热塑性树脂成型品(B)的热变形温度之差在20℃以下。
2.如权利要求1所述的热塑性树脂膜叠层体，其特征在于：
所述热塑性树脂膜(A)和所述热塑性树脂成型品(B)由同种树脂材料形成。
3.如权利要求1或2中任一项所述的热塑性树脂膜叠层体，其特征在于：
所述热塑性树脂膜(A)的厚度为0.2mm～0.3mm。
4.如权利要求1～3中任一项所述的热塑性树脂膜叠层体，其特征在于：
所述热塑性树脂成型品(B)具有至少1个以上3cm2以上的开口部，所述热塑性树脂膜(A)覆盖所述开口部的至少一部分。
5.一种包含权利要求1～4中任一项所述的热塑性树脂膜叠层体的成型品。
CN201680015816.9A 2015-03-25 2016-03-24 热塑性树脂膜叠层体、以及包含热塑性树脂膜叠层体的成型品 Active CN107405890B (zh)

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