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CN101654003A - 具有三层结构的塑料复合材料模塑品 - Google Patents

具有三层结构的塑料复合材料模塑品 Download PDF

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Publication number
CN101654003A
CN101654003A CN200910165984A CN200910165984A CN101654003A CN 101654003 A CN101654003 A CN 101654003A CN 200910165984 A CN200910165984 A CN 200910165984A CN 200910165984 A CN200910165984 A CN 200910165984A CN 101654003 A CN101654003 A CN 101654003A
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CN
China
Prior art keywords
layer
plastic composite
composite moulding
layer plastic
thermoplastic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN200910165984A
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English (en)
Other versions
CN101654003B (zh
Inventor
W·德鲁比
J·哈蒂格
G·沃斯特
W·奥米勒
U·斯滕格林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PTS PLASTIC TECHNOLOGIE SERVIC (DE)
Covestro Deutschland AG
Original Assignee
PTS PLASTIC TECHNOLOGIE SERVIC (DE)
Bayer MaterialScience AG
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Publication of CN101654003A publication Critical patent/CN101654003A/zh
Application granted granted Critical
Publication of CN101654003B publication Critical patent/CN101654003B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

本发明涉及尤其适用于汽车内装饰的具有三层结构的塑料复合材料模塑品,所述三层结构包含非发泡支持元件和表面层以及置于支持元件与表面层之间的胶粘改进功能层。

Description

具有三层结构的塑料复合材料模塑品
相关申请
本申请要求2008年8月20日提交的德国专利申请号102008038522.0的权益,为所有适用目的,该文献全文引于此供参考。
发明背景
本发明涉及尤其适用于汽车内装饰的具有三层结构的塑料复合材料模塑品,所述三层结构包含非发泡载体元件和表面层以及置于载体元件与表面层之间的胶粘改进功能层。
关于技术背景,参考DE-A 2416694,该文献描述用来生产具有光滑表面和由含发泡剂热塑性塑料所形成发泡芯的模塑品的设备,该设备包含2个对合半模和呼吸装置,利用该呼吸装置可改变起始或注射体积。尺寸的变化或增加一般称做“呼吸”。
按照DE 2416694A1,为从含发泡剂的热塑性塑料生产模塑品,先要合模。然后,经由注塑机的喷嘴注射进规定注射量的已加热到发泡温度的塑化塑料。在注射操作期间,维持超过发泡剂气压的锁模压力,使已注进塑料组合物不发泡。
在压力下的塑料组合物表面已冷却成光滑表面层之后,以规定方式开模并因此增加体积尺寸。已注进塑料组合物的压力因尺寸增加而降低,因而仍然温热的流体塑料组合物能膨胀。冷却而凝固的表面层定位在扩大的模腔壁上,同时形成发泡芯。
进一步参考DEA 4304751,该文献涉及生产塑料零件的方法,在该塑料零件上要涂布带热塑性弹性体外表皮的发泡塑料表面层。
按照DE 4304751A1,为生产复合材料零件,要把塑料零件安排在注塑模内,使拟涂布表面层的一侧留有空间。然后,在该空间内注射进热塑性弹性体和发泡剂的可发泡组合物,并在组合物发泡时,空间尺寸增大。
用DE 4304751A1所建议的方法,大大简化了包含具有发泡塑料表面层的塑料零件的塑料复合材料模塑品的生产方法。
按照EP-B 0907484,为生产注塑零件,要把插件安排在模腔内,然后,通过从注射料筒注射进至少一种硬塑料组分和接着至少一种软塑料组分的组合层,包封该插件。据说,该硬组分既形成产生干把手的较硬外表皮又保证与插件粘结。另一方面,据说,被硬组分所包封的软组分产生柔软把手。这类舒适的压触感,也称做理想的压韧性,是靠软组分的7~40邵氏A的硬度实现的。
EP-B 0907484中所述的生产结构零件的方法是特殊的复合材料注塑法(多组分法),即所谓的夹心注塑法。在该方法中,2种材料(表面和功能层)被同时经由浇口注射进模腔。在充模操作期间,先引进表面层材料,之后形成所谓的表皮组分,然后在其流体中心充进功能层材料(芯组分)。表皮组分(表面层材料)沉积在模壁上,从而复制构件的表面。也可以在夹心法中的注射之前,预先定位作为插件的载体元件,然后使夹层材料流过其表面,这样,其表皮组分,即表面层,就与载体元件粘结,形成包封材料。为实现舒适的压触感,同时具有耐刮擦表面,把邵氏A硬度远高于功能层的热塑性弹性体用于表面层。
EP-B-0907484中所述的方法,在生产在其表面上进行注塑的结构零件时,遇到了限制。在模塑品的注塑过程中,作为规则,在材料围绕凹穴/插件流动时,出现材料的影响,即所谓流线。因此,在夹心法中,这类流线常由表皮组分材料(即较硬的表面层)组成。在成品结构零件上,流线区内的表面呈现不同的压触感,即层结构的硬度因缺少底下的功能层(芯组分)而大大增加了。
但是,在实践中,结构零件的用户不接受这类不规则的压触感。由于EP-B 0907484中所述的夹心法在充模操作期间按位移原理起作用,在流径末端(结构零件边界)还会形成仅包含表面层材料的区域。这些区域的特征同样是高得多的不合格硬度,因此与朝向模塑品中心的区域相比,有完全不同的压触感。
EP-B-0970484中还公开,由于软功能层被硬表面层包封,所以插入的(inserted)载体上覆盖有一薄层硬组分。这样就保证了载体一方与其它层另一方之间的粘结性,而按照EP-B 0907484,载体与软组分之间的粘结性不足。按EP-B 0907484所必要的各层顺序使结构零件昂贵且对缺陷敏感。
DE-A 102004033139描述了类似的三层结构。在该情况下,用泡沫注塑法把产生压触感的软层引到表面层与载体元件之间。据说,称做功能层的该组分具有胶粘改进性,但文中未加详述。软热塑性塑料被称为功能层材料,关于热塑性材料的性质和形态及硬度无详细规定。作为规则,软热塑性塑料是所有TPE材料(热塑性弹性体),包括硬度最高达72邵氏D的材料。因此可以把三层结构定义为包含载体元件、功能层和表面层,对于所提及的后两项,可能是同类材料并具有相同硬度。例如,如果所形成的层结构具有硬度为90邵氏A的TPU表面层和硬度也为90邵氏A的软热塑性塑料,则因硬度相同而变得在压力下不易弯曲(压触感)且无回弹性。
三层结构的生产方法已描述在DE-A 102005024776中,而且在复杂性、避免修剪废料和壁厚质量方面都得到了改进。
在DE 3414794C2中描述了用泡沫体作为载体的类似多层结构。
DE-A 10005862对生产载体和泡沫双层结构的方法要求权利。所述泡沫可以是SBS(苯乙烯/丁二烯/苯乙烯嵌段共聚物)、SEBS(苯乙烯/乙烯/丁烯/苯乙烯嵌段共聚物)、PU(聚氨酯)、PP-EPDM(聚丙烯/乙烯/丙烯/二烯单体嵌段共聚物)、聚酯弹性体或生物基材料。为了在载体与泡沫之间产生更好的粘结性,用了并未详述的增容剂。泡沫上可涂布装饰材料。
在要求双层结构权利的US-A 5472782中,为改进热塑性聚氨酯与硬塑料之间的粘结性,描述了SBS(苯乙烯/丁二烯/苯乙烯嵌段共聚物)或SIS(苯乙烯/异戊二烯/苯乙烯嵌段共聚物)及其特定氢化形式与热塑性聚氨酯的复合物,热塑性聚氨酯的含量为50~97wt%。
原则上,需要实现具有三层结构的塑料复合材料模塑品,其中各层对塑料复合材料模塑品的性能都作出特定贡献。
尤其是,迄今已有可能解决多层的只有靠复杂工艺才能解决的或令人不满的各材料之间的粘结问题。此外,在目前已有的多层结构中,很多塑料复合材料模塑品都因它们由多类材料组成而无法回收。
因此本申请的目标是提供具有三层结构的塑料复合材料模塑品,它易生产而实现最可能的价格/性能比,而且在其中,多层彼此间的粘结很好并形成包封材料(closed material)。
已可能用特定的胶粘改进功能层来实现该目标。
发明的实施方案
本发明的实施方案是包含非发泡载体元件、表面层和置于所述非发泡载体元件与所述表面层之间的胶粘改进功能层的三层塑料复合材料模塑品,其中所述胶粘改进功能层包含
a)选自氢化苯乙烯嵌段共聚物(HSBC)类的热塑性弹性体;
b)选自如下一组的胶粘改进剂:热塑性聚醚嵌段酰胺(TPE-A)、热塑性聚酯弹性体(TPE-E)和热塑性聚氨酯(TPU),对于每100重量份弹性体a)和,如果存在,增容剂d)之和,其用量是60~100重量份;
c)增塑剂;和
d)任选地,增容剂。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述热塑性弹性体a)选自如下一组:苯乙烯/乙烯/丙烯/苯乙烯嵌段共聚物(SEPS)、苯乙烯/乙烯/乙烯/丙烯/苯乙烯嵌段共聚物(SEEPS)、苯乙烯/乙烯/丁烯/苯乙烯嵌段共聚物(SEBS)和它们的组合。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述增容剂d)选自如下一组:苯乙烯/丁二烯/苯乙烯嵌段共聚物(SBS)、苯乙烯/SBS共聚物和由极性接枝法官能化的热塑性聚合物。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述以极性接枝法官能化的热塑性聚合物选自如下一组:氢化苯乙烯嵌段共聚物(HSBC)、聚丙烯(PP)、乙烯/丙烯/二烯单体嵌段共聚物(EPDM)、聚烯烃、甲基丙烯酸酯/丁二烯/苯乙烯嵌段共聚物(MBS,芯-壳改性剂)、聚苯乙烯和离聚物。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述以极性接枝法官能化的热塑性聚合物是以极性接枝法官能化的氢化苯乙烯嵌段共聚物(HSBC)。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中使所述以极性接枝法官能化的热塑性聚合物实现官能化的方法是接枝上包含极性基团的有机化合物。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中对于功能层的每100重量份热塑性弹性体a),所述增容剂d)的优选存在量是1~100重量份。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述增塑剂包含石蜡油。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述增塑剂c)包含白色矿物油(white mineral oil)。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中对于每100重量份弹性体a)和,如果存在,增容剂d)之和,所述增塑剂c)的优选存在量是1~300重量份。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述胶粘改进功能层的硬度低于46邵氏A。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述胶粘改进功能层在发泡态的壁厚为2~15mm。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述胶粘改进功能层是发泡或非发泡层。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述非发泡载体元件包含选自如下一组的热塑性塑料:聚酰胺(PA)、聚丙烯(PP)、玻纤增强PP、聚甲醛(POM)、聚苯醚(PPO)、聚对苯二甲酸丁二酯(PBT)、聚苯乙烯(PS)、丙烯腈/丁二烯/苯乙烯共聚物(ABS)、聚碳酸酯(PC)/ABS共混物、PS/PP共混物、苯乙烯/马来酸酐共聚物(SMA)/ABS共混物、ABS/PA共混物、PBT/PC共混物和PBT/丙烯腈/苯乙烯/丙烯酸酯(ASA)共混物。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述表面层包含注塑膜(film)或表皮或搪瓷表皮(slush skin)。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述注塑膜包含增塑的聚氯乙烯(PVC)、热塑性聚醚嵌段酰胺(TPE-A)、热塑性聚酯弹性体(TPE-E)、热塑性聚烯烃(TPE-O)或热塑性聚氨酯(TPU)。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述表面层的厚度为0.5~2mm。
本发明的另一个实施方案是上述三层塑料复合材料模塑品,其中所述表面层具有压纹化(grained)或结构化表面。
本发明的还有一个实施方案是包含上述三层塑料复合材料模塑品的车辆的仪表板、车门内衬、行李架、把手、操作钮或屏幕。
发明详述
本发明提供包含非发泡载体元件和表面层以及置于载体元件与表面层之间的胶粘改进功能层的塑料复合材料模塑品,其特征在于胶粘改进功能层包含
a)至少一种选自氢化苯乙烯嵌段共聚物(HSBC)类的热塑性弹性体;
b)至少一种选自如下一组的胶粘改进剂:热塑性聚醚嵌段酰胺(TPE-A)、热塑性聚酯弹性体(TPE-E)和热塑性聚氨酯(TPU),对于每100重量份弹性体a)和,任选地,增容剂d)之和,其用量是60~100重量份,特别优选60~95重量份,非常优选60~90重量份;
c)至少一种增塑剂;和
d)任选地,增容剂。
用按照本发明的功能层组合物,能实现特定质量的,尤其光学和触感性能(压触感)的调节,同时,一方面在表面层与功能层之间,另一方面在功能层与载体之间,都有很好的粘结性,而且生产成本低。进一步,就塑料复合材料模塑品的可回收性而言,满足欧盟报废汽车指令2005/53/EC的要求。所以纯热塑性三层结构因能再熔化而能被再利用。
非发泡载体元件能用注塑技术生产并优选包含结构材料类中的热塑性塑料。优选的材料是,例如,聚酰胺(PA)、聚丙烯(PP)-任选地,经玻纤增强-、聚甲醛(POM)、聚苯醚(PPO)、聚对苯二甲酸丁二酯(PBT)、聚苯乙烯(PS)、丙烯腈/丁二烯/苯乙烯共聚物(ABS)、聚碳酸酯(PC)/ABS共混物、PS/PP共混物、SMA(苯乙烯/马来酸酐共聚物)/ABS共混物、ABS/PA共混物、PBT/PC共混物和PBT/丙烯腈/苯乙烯/丙烯酸酯(ASA)共混物,以及特别优选ABS、ABS/PA共混物和PC/ABS共混物。
当注塑在表面上时,胶粘改进功能层与所述载体元件紧密结合地(cohesively)粘结地很好。从结构观点看,可提供加强筋(reinforcing rib)来增加载体元件的刚度。
优选用塑料膜,尤其装饰膜,作为表面层。优选表面层已被压纹化或结构化,并优选厚度为约0.5~2mm。该膜可以从,例如,增塑聚氯乙烯(PVC)或从热塑性弹性体(TPE),如热塑性聚醚嵌段酰胺(TPE-A)、热塑性聚酯弹性体(TPE-E)、热塑性聚烯烃(TPE-O)或热塑性聚氨酯(TPU)生产。在本申请中,优选热塑性聚氨酯,尤其优选脂肪族TPU,因为后者的光稳定性特别好。在热塑性弹性体中,TPU还具有很好的耐磨性和耐刮擦性,因此特别适用于表面层。
热塑性聚氨酯(TPU)因它们良好的弹性体性能和热塑可加工性而具有重要的工业意义,而且是涂饰非极性塑料的适用伴侣。关于TPU的制备、性能和应用的综述已在,例如,Kunststoff Handbuch[G.Becker,D.Braun],Vo1.7,“Polyurethane(聚氨酯)”,Munich,Vienna,Carl HanserVerlag,1983中给出。
原则上,所有的TPU都能用来生产按照本发明的三层结构。尤其优选用下列基础单元制成的TPU:六亚甲基二异氰酸酯、4,4’-二苯基甲烷-二异氰酸酯、聚酯多元醇、聚醚多元醇、1,4-丁二醇和1,6-己二醇。
对于较少暴露于UV的或深色的表面层,除脂肪族TPU外,也可以用芳族TPU或聚酯弹性体(TPE-E)或TPU与另一种热塑性弹性体的共混物。
优选用作表面层的膜可用搪瓷技术或用注塑技术以压实(compact)或泡沫注塑法生产。优选它们是注塑膜,因为在这种情况下,尤其用TPU时,能实现无可见流线(flow line)的表面。
优选用TPU膜而不经表面处理和不经表面涂布。如果对耐磨性和耐刮擦性的要求很高,则可对膜作进一步表面处理或涂布。膜还可具有压纹化或结构化表面。
所述胶粘改进功能层优选具有低于46邵氏A,尤其优选低于41邵氏A的较低硬度。功能层包含a)选自氢化苯乙烯嵌段共聚物(HSBC)类的热塑性弹性体,如苯乙烯/乙烯/丙烯/苯乙烯嵌段共聚物(SEPS)、苯乙烯/乙烯/乙烯/丙烯/苯乙烯嵌段共聚物(SEEPS)和苯乙烯/乙烯/丁烯/苯乙烯嵌段共聚物(SEBS)及它们的组合。此外,功能层还包含选自如下一组的聚合物作为胶粘改进剂b):热塑性聚醚嵌段酰胺(TPE-A)、热塑性聚酯弹性体(TPE-E)和热塑性聚氨酯(TPU),如前所述。功能层还包含增塑剂c),优选石蜡油、尤其优选所谓的白色矿物油,和任选地,选自如下一组的增容剂d):SBS、苯乙烯/SBS共聚物(如来自BASF SE的Styroflex
Figure G2009101659848D00071
)以及以极性接枝法官能化的热塑性聚合物。功能层可以呈发泡或非发泡形式。
当在表面层如注塑膜或表皮或搪瓷表皮之后注塑时,胶粘改进功能层与表面层具有良好的粘结性,所以能用注塑法形成粘合性(cohesive)复合材料。
优选用上述热塑性聚氨酯(TPU)作为功能层内的胶粘改进剂b)。对于功能层中每100重量份热塑性弹性体a)和,如果存在,增容剂d)之和,该胶粘改进剂的存在量优选是60~95重量份,尤其非常优选60~90重量份。
在特别优选的实施方案中,功能层包含增容剂。
能用于热塑性弹性体与胶粘改进剂之间的增容剂是SBS、苯乙烯/SBS共聚物(如来自BASF SE的Styroflex
Figure G2009101659848D00081
)或已用极性接枝法官能化的热塑性聚合物,如氢化苯乙烯嵌段共聚物(HSBC)、聚丙烯(PP)、乙烯/丙烯/二烯单体嵌段共聚物(EPDM)、聚烯烃、甲基丙烯酸酯/丁二烯/苯乙烯嵌段共聚物(MBS,芯-壳改性剂)、聚苯乙烯和/或离聚物(如来自杜邦的Surlyn
Figure G2009101659848D00082
)。使所述热塑性聚合物实现官能化的方法是,例如,通过接枝上含极性基团如酸酐(如马来酸酐(MA))、丙烯酸酯、环氧化物和/或酸基的有机化合物。优选用接枝上极性基团的上述热塑性聚合物之一作为增容剂,特别优选功能化HSBC。优选对于功能层的每100重量份的热塑性弹体a),增容剂的存在量是0~100重量份,优选1~100重量份。
优选用石蜡油作为增塑剂,尤其优选所谓白色矿物油。对于功能层的每100重量份热塑性弹性体a)和,任选地,增容剂d)之和,其优选存在量是1~300重量份。
胶粘改进功能层优选具有数毫米,尤其约2~15mm的壁厚,并包含上述成分。功能层能用化学或物理发泡剂或两者的组合进行发泡,然后能在,例如,开模放气工艺(mould breathing process)中形成泡沫层。
塑料复合材料模塑品在注塑模内生产,所述注塑模包含2个围合成模腔的半模和任选的滑块(slide)。
塑料复合材料模塑品优选通过在注塑工艺中先分别形成载体元件和表面层来生产。然后把由此形成的载体元件和由此形成的表面层放在注塑模内,使在两者之间留有空间(hollow space),然后在另一个注塑工艺步骤中把功能层引进其中。
功能层内的泡沫结构对实现柔软压触感有利。这种泡沫结构是通过在注塑加工过种中已知的TFC工艺(TFC=热塑性泡沫浇注,按Saechtling,Kunststofftaschenbuch,第30版)结合开模放气工艺而获得。优选用基于微球(=在热作用下膨胀的空心珠(hollow bead),如来自Plastic TechnologieService的THERMOCEL-Master 180/65)的物理发泡剂来实现这种泡沫结构。在注塑之前,优选按相对于功能层的重量2~6wt%的剂量混合它们。
通过开模放气法(注射后按规定发泡量(foam lift)开模(opening ofthe cavity)),微球发泡剂在功能层内能发挥其最佳作用并产生细孔泡沫结构。
按照本发明的塑料复合材料模塑品的显著特征是舒适的压触感,即模塑表面的柔软可压缩性,和良好的耐磨性。
在生产按照本发明的塑料复合材料模塑品中,无需后加工,如切削或冲孔(如仪表板上的无线电舱(radio compartment)、通风器管口(ventilator nozzles))或除去飞边。也不必为了使塑料复合材料模塑品表面耐磨和耐刮擦而进行后处理。所述方法使模塑品可以具有高度综合的多功能并降低生产成本。
塑料复合材料模塑品优选应用在车辆内部,如仪表板、车门内衬、行李架、把手、操纵钮、屏幕等。
本发明将利用下列实施例作更详细的解释。
为所有的应用目的,上述所有参考资料都全文引于此供参考。
虽然已给出并描述了利用本发明的某些特定结构,但本领域的技术人员将看到,可以在不偏离隐含在本发明概念下的精神和范围内作各种修正和重排,而且它们也不限于本文所示和所述的特定形式。
实施例
前述PC+ABS共混物,商品名为BAYBLEND
Figure G2009101659848D00091
T85,和TPUDesmopan
Figure G2009101659848D00092
DP85092A,是Bayer Material Science AG(Leverkusen,Germany)的商品。
功能层材料在常用于混合塑料的双螺杆挤出机(TSE,双螺杆挤出机)内在热作用下以混合方法制得。把对应于配方构分(参考表1)的原材料的预混物经由计量设备喂进双螺杆挤出机并在热(140℃~250℃)和剪切力作用下塑化和均化。在塑化的塑料组合物排离双螺杆挤出机时,使之通过开孔板和水下造粒设备(water granulating device),使功能层材料呈颗粒状。
表1:功能层内材料的说明
功能层 配方构分  硬度[邵氏A]
聚合物颗粒1   25phr SEEPS/30%苯乙烯含量a)50phr SEPS/10%苯乙烯含量a)25phr SEBS-MA d)60phr石蜡油c)32.5phr醚基TPU邵氏A 70b)17.5phr酯基TPU邵氏A 86b) 34
聚合物颗粒2   25phr SEEPS/30%苯乙烯含量50phr SEPS/10%苯乙烯含量25phr SEBS-MA60phr石蜡油45.5phr醚基TPU邵氏A 7024.5phr酯基TPU邵氏A 86 35
聚合物颗粒3   25phr SEEPS/30%苯乙烯含量50phr SEPS/10%苯乙烯含量25phr SEBS-MA60phr石蜡油52phr醚基TPU邵氏A 7028phr酯基TPU邵氏A 86 38
聚合物颗粒4   25phr SEEPS/30%苯乙烯含量50phr SEPS/10%苯乙烯含量25phr SEBS-MA60phr石蜡油65phr醚基TPU邵氏A 7034phr酯基TPU邵氏A 86 40
聚合物颗粒5   25phr SEEPS/30%苯乙烯含量50phr SEPS/10%苯乙烯含量25phr SEBS-MA60phr石蜡油110.5phr醚基TPU邵氏A 7059.5phr酯基TPU邵氏A 86 48
邵氏硬度按ISO 868测定。
″phr″是指″相对于每100份的份数″;份数是指重量份。
所述三层结构按时间顺序地通过注塑法形成。首先把分别用注塑法形成的载体元件层和表面层铺放在注塑模内,使它们之间留有空间。然后在另一个注塑工艺步骤中使功能层材料经由载体元件上的一个或多个开孔或穿破口(break-through)引进该空间。也就是说,通过注射使表面层与载体元件之间的空间完全充满功能层。
为实现柔软的压触感,结合已知的TFC工艺(TFC=热塑性泡沫浇注,按Saechtling,Kunststofftaschenbuch,第30版)和开模放气工艺来生产功能层中的泡沫结构。在该方法中,在把功能层注射进模腔内载体元件与表面层之间时,首先使该空间在体积上充满功能层材料,而没有其后的保压。为此,在注射压力终点和达到体积充满后,就立即靠合模时的垂直溢料面(vertical flash face)经由抽芯机(core puller)或滑块产生相对于起始模腔厚度约20~50%的规定发泡量,从而使预先加进注塑机料斗内的其量为功能层重量4~6wt%的物理发泡剂抵抗大气压膨胀,所述发泡剂是来自Plastic Technologie Service的THERMOCEL-Master180/65。该发泡剂由所谓微球即被塑料壳包围的气泡组成,并在热的作用下在聚合物熔体内膨胀到规定程度。
鉴于实践中无法对成品三层结构测定,一方面,表面层与功能层之间的粘结性和,另一方面,功能层与载体元件之间的粘结性,所以,为测量粘结性,在所有情况下都制备仅由2层构成的试样。
测定硬和软组分之间粘结强度的测量方法
第一组分(载体元件或表面层)与软组分(功能层)之间粘结强度的基本试验按标准试验法,即按DIN EN 1464的辊式剥离试验进行。该试验方法描述“高强粘结键抗剥离性的测量”并与金属的粘结键相关。由于试样的尺寸,对DIN EN 1464中所述的加进拉伸试验机的辊式剥离试验设备的辊长度略作改变(延长至103mm),以定位试样。而且不用标准中所规定的试样几何形状。复合材料试样与标准试样之间的差别包含几何形状略有不同和两组分之间的连接区(joining zone)较短。由于该测量属相对比较性测量,所以试样与标准试样的差别对评价影响不大。按DIN EN 1464,软组分以与复合材料表面成90°地剥离。
本试验中的试样从包含表层或载体层(第1组分)的外形尺寸为130×100×3mm的框架构建。框架三边的宽度为25mm,第四边的宽度为45mm。在框的表面上较宽边侧注射面积达45mm×35mm的功能层材料(软组分或第2组分)。软组分是壁厚为2mm,长为115mm和宽为35mm的凸缘(lip)。软组分的中心浇口是穿过第1组分材料的镗孔(bore)。由此导致对称流径。试样用2部件模具以退芯法(core retraction process)制成,以为粘结强度创造良好条件。更详细的内容参考DE-A 102004047200。
试样在多组分注塑机(Arburg Allrounder,420V 1000-350/150型,Arburg.D72290 Loβburg制造)上,按表2给出的参数,以1,000kN锁模力(clamping force)进行生产。
把按DIN EN 1464从90°辊式剥离试验得到的粘结强度的特征值作为抗剥离性,单位为[N/mm]。
  抗剥离性[N/mm]=剥离力[N]/试样宽度[mm]
测定最小剥离力Fmin、最大剥离力Fmax和平均剥离力Fave的值。
平均剥离力示于表3a和3b,而且是评价粘结强度的量度。平均抗剥离性按平均剥离力值除以软组分的宽度(35mm)进行计算。
表2:制备试样所用的注塑参数
Figure G2009101659848D00131
Figure G2009101659848D00141
表3a:载体/功能层粘结性研究
Figure G2009101659848D00151
实施例1和5是对比实施例。
表3b:表面层/功能层粘结性研究
Figure G2009101659848D00152
实施例1和5是对比实施例。
粘结因子编号的意义:
  1   无粘结   无粘附,不能作为复合材料零件脱模
  2   粘附   略粘结,软组分与硬组分不能保持粘结
3   粘结-粘聚(cohesion)   粘结良好,软组分与硬组分牢固粘结(粘聚),有间隙
4 粘聚   粘结很好,软组分与硬组分在整个面积上牢固粘结,剥离断裂发生在软组分内部
5   粘聚强度>材料强度(C>MS)   粘结强度大于材料强度,粘结处不能分离,不再能剥离,在剥离开始前软组分撕裂
如从表3a和3b可见,从实施例2~4可以证明:如果正确选择功能层的各组分,则可使结构零件实现各个层彼此间的良好粘结,同时还具有良好压触感所必要的硬度。

Claims (19)

1.包含非发泡载体元件、表面层和置于所述非发泡载体元件与所述表面层之间的胶粘改进功能层的三层塑料复合材料模塑品,其中所述胶粘改进功能层包含
a)选自氢化苯乙烯嵌段共聚物(HSBC)类的热塑性弹性体;
b)选自如下一组的胶粘改进剂:热塑性聚醚嵌段酰胺(TPE-A)、热塑性聚酯弹性体(TPE-E)和热塑性聚氨酯(TPU),对于每100重量份弹性体a)和,任选地,增容剂d)之和,其用量是60~100重量份;
c)增塑剂;和
d)任选地,增容剂。
2.权利要求1的三层塑料复合材料模塑品,其中所述热塑性弹性体a)选自如下一组:苯乙烯/乙烯/丙烯/苯乙烯嵌段共聚物(SEPS)、苯乙烯/乙烯/乙烯/丙烯/苯乙烯嵌段共聚物(SEEPS)、苯乙烯/乙烯/丁烯/苯乙烯嵌段共聚物(SEBS)和它们的组合。
3.权利要求1的三层塑料复合材料模塑品,其中所述增容剂d)选自如下一组:苯乙烯/丁二烯/苯乙烯嵌段共聚物(SBS)、苯乙烯/SBS共聚物和由极性接枝法官能化的热塑性聚合物。
4.权利要求3的三层塑料复合材料模塑品,其中所述由极性接枝法官能化的热塑性聚合物选自如下一组:氢化苯乙烯嵌段共聚物(HSBC)、聚丙烯(PP)、乙烯/丙烯/二烯单体嵌段共聚物(EPDM)、聚烯烃、甲基丙烯酸酯/丁二烯/苯乙烯嵌段共聚物(MBS,芯-壳改性剂)、聚苯乙烯和离聚物。
5.权利要求3的三层塑料复合材料模塑品,其中由极性接枝法官能化的热塑性聚合物是由极性接枝法官能化的氢化苯乙烯嵌段共聚物。
6.权利要求3的三层塑料复合材料模塑品,其中,使所述由极性接枝法官能化的热塑性聚合物实现官能化的方法是接枝上包含极性基团的有机化合物。
7.权利要求1的三层塑料复合材料模塑品,其中对于功能层的每100重量份的热塑性弹性体a),所述增容剂d)的存在量是1~100重量份。
8.权利要求1的三层塑料复合材料模塑品,其中所述增塑剂c)包含石蜡油。
9.权利要求1的三层塑料复合材料模塑品,其中所述增塑剂c)包含白色矿物油。
10.权利要求1的三层塑料复合材料模塑品,其中对于每100重量份弹性体a)和,任选地,增容剂d)之和,所述增塑剂c)的存在量是1~300重量份。
11.权利要求1的三层塑料复合材料模塑品,其中所述胶粘改进功能层的硬度小于46邵氏A。
12.权利要求1的三层塑料复合材料模塑品,其中所述胶粘改进功能层在发泡态的壁厚为2~15mm。
13.权利要求1的三层塑料复合材料模塑品,其中所述胶粘改进功能层是发泡或非发泡层。
14.权利要求1的三层塑料复合材料模塑品,其中所述非发泡载体元件包含选自如下一组的热塑性塑料:聚酰胺(PA)、聚丙烯(PP)、玻纤增强PP、聚甲醛(POM)、聚苯醚(PPO)、聚对苯二甲酸丁二酯(PBT)、聚苯乙烯(PS)、丙烯腈/丁二烯/苯乙烯共聚物(ABS)、聚碳酸酯(PC)/ABS共混物、PS/PP共混物、苯乙烯/马来酸酐共聚物(SMA)/ABS共混物、ABS/PA共混物、PBT/PC共混物和PBT/丙烯腈/苯乙烯/丙烯酸酯(ASA)共混物。
15.权利要求1的三层塑料复合材料模塑品,其中所述表面层包含注塑膜或表皮或搪瓷表皮。
16.权利要求15的三层塑料复合材料模塑品,其中所述注塑膜包含增塑聚氯乙烯(PVC)、热塑性聚醚嵌段酰胺(TPE-A)、热塑性聚酯弹性体(TPE-E)、热塑性聚烯烃(TPE-O)或热塑性聚氨酯(TPU)。
17.权利要求1的三层塑料复合材料模塑品,其中所述表面层的厚度为0.5~2mm。
18.权利要求1的三层塑料复合材料模塑品,其中所述表面层具有压纹化或结构化表面。
19.包含权利要求1~18的三层塑料复合材料模塑品的车辆的仪表板、车门内衬、行李架、把手、操纵旋钮或屏幕。
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CN103249557A (zh) * 2010-12-17 2013-08-14 Sika技术股份公司 减少增塑剂迁移的pvc膜
CN106536183A (zh) * 2014-07-17 2017-03-22 贝内克-凯利科股份公司 用于气囊应用的箔片
CN107075208A (zh) * 2014-09-11 2017-08-18 爱彼思塑胶有限公司 粘性经改变的烯属热塑性弹性体,特别是tpe‑v、tpe‑o
CN107778753A (zh) * 2016-08-25 2018-03-09 现代自动车株式会社 制备具有皮‑芯结构的内侧门把手的树脂组合物、使用其制备内侧门把手的方法、及其制品
CN107215350A (zh) * 2017-07-17 2017-09-29 苏州迪迈塑胶有限公司 一种高铁行李架用聚酯板及其制备方法
CN107698962A (zh) * 2017-10-16 2018-02-16 广西南宁英凡达科技有限公司 计算机外壳及其制造方法
CN107674402A (zh) * 2017-10-16 2018-02-09 广西南宁英凡达科技有限公司 电器外壳材料及其制备方法
CN107556503A (zh) * 2017-10-16 2018-01-09 广西南宁英凡达科技有限公司 电子产品外壳及其制作方法
CN113573948A (zh) * 2019-02-08 2021-10-29 泰佛产品服务与创新公司 用于机动车辆发动机舱的隔音屏
CN112026279A (zh) * 2020-08-27 2020-12-04 江苏宏宇车业有限公司 一种高强度抗延展车用内饰塑料件
CN112026279B (zh) * 2020-08-27 2022-07-01 江苏宏宇车业有限公司 一种高强度抗延展车用内饰塑料件
CN112239633A (zh) * 2020-10-15 2021-01-19 青岛未来塑胶有限公司 房屋户外用含asa膜的修复材料及制备工艺和覆膜方法
CN112874094A (zh) * 2021-01-28 2021-06-01 上海万硕油墨有限公司 一种家具边缘装饰条
CN113459618A (zh) * 2021-06-04 2021-10-01 苏州瑞赛科物流科技股份有限公司 一种防静电内衬材料及其制备方法
CN115556445A (zh) * 2021-07-01 2023-01-03 三芳化学工业股份有限公司 复合式热可塑性膜及其制造方法

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