CN1230918A - 聚酯树脂复合模制品 - Google Patents
聚酯树脂复合模制品 Download PDFInfo
- Publication number
- CN1230918A CN1230918A CN98800921A CN98800921A CN1230918A CN 1230918 A CN1230918 A CN 1230918A CN 98800921 A CN98800921 A CN 98800921A CN 98800921 A CN98800921 A CN 98800921A CN 1230918 A CN1230918 A CN 1230918A
- Authority
- CN
- China
- Prior art keywords
- copolymer
- acid
- polyester resin
- pbt
- unsaturated carboxylic
- 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.)
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Abstract
一种由一种树脂组合物(A)和一种金属(B)组成的聚酯树脂复合模制品,其中,所述树脂组合物包含聚对苯二甲酸丁二醇酯(A1)、无机填料(A2)和一种用α、β不饱和羧酸或其酸衍生物接枝共聚所形成的改性乙烯类共聚物(A3),所述金属(B)的部分或全部涂覆了树脂组合物(A),所述接枝共聚物(A3)以分散颗粒的形式存在于构成复合模制品的树脂组合物的模塑部件中,分散颗粒的直径为1~3μm。本发明提供了一种具有优异的耐热冲击性,并在嵌件模制之类的模制周期内表现出保留稳定性的聚酯树脂复合模制品。
Description
发明详述
技术领域
本发明涉及具有出色耐久性的热塑性树脂组合物,特别是具有优良耐热冲击性的聚酯树脂复合模制品。
背景技术
聚对苯二甲酸丁二醇酯是一种具有出色的可模塑性、显示出多种优良特性如耐溶剂性的热塑性材料,可应用于各种领域,因为通过该聚合物的熔体模塑和注射成型可生产出具有良好物理性能与力学性能的模制品。
这种树脂的代表性应用的实例是电气与电子零部件、家用电器和汽车的外壳。按照近来节能和降低成本的趋势,将树脂材料与诸如金属之类的不同材料结合在一起的整体模制日益增多,而不是用树脂材料作为单独的模塑部件。在与金属整体模制的制品中,因为这种制品的非均匀结构,由室温变化所引起的膨胀与收缩就会产生热应力。
对热应力的耐久性称为耐热冲击性,对用于汽车发动机舱内的电气设备,要求能耐强烈的热冲击。树脂材料的耐热冲击性可以设法提高,方法有:如JP-A 63-3055(以下的JP-A代表“未经审查的日本专利公开”)[JP-B 5-25260(以下的JP-B代表“经审查过的日本专利公开”)]所公开的,把一种包含丙烯酸酯的接枝共聚物和一种可交联单体与环氧化合物配混起来;如JP-A 6-304963所公开的,把一种包含α-烯烃的烯烃共聚物与一种α,β-不饱和酸缩水甘油酯配混起来;以及如JP-A 6-304964所公开的,把一种乙烯-不饱和羧酸烷基酯共聚物的接枝共聚物与一种乙烯基聚合物的共聚物配混起来。
由于在上述方法中使用了一种将含有如缩水甘油基之类的环氧基的共聚物或环氧化合物配混起来的技术,在需要长模塑周期的模塑方法如嵌件模制中因粘度增加而产生一个问题:得不到基本稳定的模制品。
JP-A 55-50058(JP-B 57-59261)公开了一种提高耐冲击性的技术:把熔融态热塑性聚酯树脂与结晶度等于或小于75%、熔体指数为0.01~50的接枝改性乙烯聚合物混合,所述接枝改性乙烯聚合物是通过将α、β不饱和羧酸或其酸衍生物接枝到乙烯聚合物或乙烯-α-烯烃共聚物上所形成的。由于JP-A 55-50058中所述的技术不使用玻璃纤维,所得组合物的耐冲击性和耐热冲击性低,不足以用来制作本发明的复合模制品。
JP-A 8-253663披露,把聚酯树脂与接枝改性的乙烯-丙烯非共轭二烯共聚物配混起来,就能提高聚酯树脂的耐热冲击性,并能生产出具有出色抗冲击性的轻质树脂组合物,所述接枝改性共聚物是通过用一种含缩水甘油基的化合物与一种乙烯基单体对乙烯-丙烯-非共轭二烯共聚物进行接枝改性而获得的。
JP-A 8-283543披露,把一种聚酯树脂与一种聚丙烯树脂和一种接枝改性烯烃弹性体配混起来,就能提高聚酯树脂的耐热冲击性和焊接性,并能生产出具有刚度和耐冲击性的轻质树脂组合物,所述接枝改性烯烃弹性体是通过用一种含缩水甘油基的化合物与乙烯基单体对烯烃弹性体进行接枝改性而获得的。
在以上JP-A 8-253663和JP-A 8-283543中所述的技术利用一种把含有如缩水甘油基之类的环氧基团的共聚物配混起来的方法,因此在需要用长模塑周期的模塑方法如嵌件模制中造成粘度增高而得不到基本稳定的模制品。
发明的公开
本发明的目的是提供一种聚酯树脂复合模制品,该复合模制品具有出色的耐热冲击性以及在嵌件模制等模塑周期内有良好的保留稳定性等优点。
本发明的其他目的与优点将通过以下的描述阐明。
由于为解决上述问题而进行的深入调研的结果,本发明的发明者发现,把聚对苯二甲酸丁二酯与一种特定的改性聚烯烃树脂弹性体共混并把在复合模制品中的弹性体颗粒调节到前述颗粒直径,就能大幅度提高耐热冲击性和熔体热稳定性。
本发明包括下列组成部分:
1.一种由一种树脂组合物(A)和一种金属(B)组成的聚酯树脂复合模制品,所述树脂组合物包含一种聚对苯二甲酸丁二醇酯(A1)、一种无机填料(A2)以及一种通过α、β不饱和羧酸或其酸衍生物的接枝共聚而生产的改性乙烯共聚物(A3),其中所述金属(B)部分或全部地涂复了树脂组合物(A),所述接枝共聚物(A3)以分散颗粒的形式存在于构成复合模制品的树脂组合物的模塑部件中,分散颗粒的直径为1~3μm。
2.上一项中所述的一种聚酯树脂复合模制品,其中所述改性乙烯共聚物(A3)是一种用α、β-不饱和羧酸的酸衍生物接枝聚合的改性乙烯共聚物(A3)。
3.前面第1项中所述的一种聚酯树脂复合模制品,其中所述树脂组合物(A)包含100重量份的聚对苯二甲酸丁二醇酯(A1)、1~125重量份的无机填料(A2)和5~20重量份用α、β-不饱和羧酸的酸衍生物接枝聚合的改性乙烯共聚物(A3)。
4.前面第1项中所述的一种聚酯树脂复合模制品,其中聚对苯二甲酸丁二醇酯(A1)的特性粘度为0.5~0.9dl/g。《聚对苯二甲酸丁二醇酯》
用于本发明的聚对苯二甲酸丁二醇酯(A1)是一种用对苯二甲酸作为主要酸组分和1,4丁二醇作为主要二元醇组分所产生的聚酯。主要组分是指在总的酸组分或总的二元醇组分中其量不少于80mol%,优选地,不少于90mol%的一种组分。
可共聚酸组分的实例是指除对苯二甲酸以外的芳族二元羧酸,如间苯二甲酸、萘二甲酸、联苯二甲酸、联苯醚二甲酸、双苯氧基乙烷二甲酸和二苯酮二羧酸;脂族二羧酸,如丁二酸、己二酸和癸二酸;脂环二羧酸,如环己烷二羧酸和1,2,3,4四氢化萘二羧酸等等。
可共聚二元醇组分的实例是乙二醇、1,6-己二醇、新戊二醇、环己烷二甲醇、三环癸烷二甲醇、亚二甲苯基二甲醇、双酚A、双酚B和双羟乙氧基双酚A。
聚酯可以与一种多官能团化合物如甘油、三羟甲基丙烷、季戊四醇、偏苯三酸或1,2,4,5-苯四酸进行共聚,这些化合物的用量必须基本上不损失聚酯的模塑性,例如不超过3mol%。
在生产聚对苯二甲酸丁二醇酯中可用的其他可共聚组分的实例是羟基酸,如对羟基苯甲酸和对羟基乙氧基苯甲酸。
用于本发明的聚对苯二甲酸丁二醇酯的特性粘度(35℃,在邻氯代苯酚中)优选为0.3~1.2,尤其是0.5~0.9。《无机填料》
用于本发明的无机填料(A2)是,例如,纤维状填料如玻璃纤维、石墨纤维、二氧化硅纤维、氧化铝纤维、硼纤维、长石、钛酸钾晶须和硼酸钾晶须;箔片状填料如云母和玻璃箔片,以及粉状或粒状填料如二氧化硅、玻璃珠、玻璃球、高岭土、硅灰石、硅酸钙和碳酸钙。这些填料可单独使用,也可以二种或二种以上填料组合起来用。
从材料的力学强度、耐热性和尺寸稳定性来看,玻璃纤维是上述填料中特别优选的。无机填料可以是表面经过处理或未经处理的。用于表面处理的化合物是,例如,一种多官能团化合物如环氧化合物、异氰酸酯化合物、硅烷化合物和钛酸盐化合物。这类化合物可涂布在无机填料的表面或在材料制备中加入。
优选地,无机填料(A2)的配混量是100重量份的聚对苯二甲酸丁二醇酯(A1)中加1~125重量份填料,优选地,是树脂组合物总重量的15~45重量%。无机填料含量在上述范围内的树脂具有高的可模塑性并使模制品具有优良的力学强度。《改性的乙烯类共聚物》
用于本发明的改性乙烯类共聚物(A3)是一种将α、β不饱和羧酸或其酸衍生物接枝共聚到一种乙烯聚合物或乙烯与碳原子数为3或3以上的α-烯烃的共聚物(下面把两种聚合物统称为未改性乙烯类聚合物)上所形成的改性乙煅类聚合物。
优选的未改性乙烯类聚合物是共聚型聚合物,用作为共聚成分的α-烯烃是丙烯、丁烯-1、己烯-1、癸烯-1、4甲基丁烯-1、4甲基戊烯-1等。在上述化合物中,丙烯和丁烯-1是特别优选的。接枝共聚到未改性乙烯类聚合物上去的α、β不饱和羧酸的实例有丙烯酸、甲基丙烯酸、乙基丙烯酸、马来酸和富马酸。α、β不饱和羧酸的酸衍生物是上述酸的酯、酸酐、酰亚胺等。
优选地,改性的乙烯类共聚物(A3)是一种把α、β不饱和羧酸的酸衍生物接枝共聚到未改性乙烯类聚合物上所形成的改性乙烯类聚合物,这样可以获得较高的耐热冲击性。在α、β不饱和羧酸的酸衍生物中,马来酸酐和马来酰亚胺是优选的,而马来酸酐是特别优选的。
当接枝共聚到未改性乙烯类聚合物上去的α、β不饱和羧酸的用量太少时,很难获得高的耐热冲击性,而太多的α、β不饱和羧酸接枝会产生所获得的热塑性聚酯树脂组合物退色为黄色或红色的问题,从而使模制品外观不良。优选地,接枝量为0.05~3重量%,更优选地,为0.1~1重量%,两者均以未改性乙烯类聚合物为100重量%计。
“接枝共聚”这一术语的意思是,未改性乙烯类聚合物的一部分或全部与一种α、β不饱和羧酸或其酸衍生物的单体或聚合物发生化学键合。这种改性乙烯类聚合物很容易按传统方法制备:即把α、β不饱和羧酸或其酸的衍生物加入到未改性乙烯类聚合物中,并通常在150~300℃熔融和捏和该混合物。
通常用螺杆式挤出机进行熔融和捏和处理。不用说,为了提高接枝共聚效率,可以用有机过氧化物,如α、α’-二-叔丁基过氧-对-二异丙基苯,其用量为0.001~0.05重量%,以未改性乙烯类聚合物为100重量%计。
用作为改性乙烯类聚合物的原材料的未改性乙烯类聚合物是,例如低密度聚乙烯或由下述方法制备的共聚物:用包含一种有机铝化合物和一种诸如三氯氧化钒和四氯化钒之类的钒化合物的齐格勒-纳塔(Ziegler-Natta)催化剂将不少于50mol%,优选地,80~95mol%的乙烯与不超过50mol%,优选地,20~5mol%的α-烯烃进行共聚。
特别优选的作为未改性乙烯类聚合物的聚合物是Mitsui石油化学工业公司的商品名为Tafmer的一系列商品聚合物,例如:Tafmer A系列(乙烯-丁烯-1共聚物)如Tafmer A-4085,Tafmer A-4090和Tafmer A-20090;以及Tafmer P系列(乙烯-丙烯共聚物)如Tafmer P-0180,Tafmer P-0280,Tafmer P-0480和Tafmer P-0680。
改性乙烯类共聚物(A3)的配混量,在以100重量份聚对苯二甲酸丁二醇酯(A1)为基准时,是5~20份,优选地,以组合物总量为100重量%时,为5~10重量%。当改性乙烯类共聚物的配混量少于5重量份时,耐热冲击性得不到提高;而在超过20重量份时,刚度明显降低,因而把这种树脂作为工程塑料用就成了问题。
在本发明中,下面这一点很重要:改性乙烯类共聚物(A3)以颗粒直径为1~3μm的分散颗粒形式存在于树脂组合物的模制品中。当分散颗粒的直径小于1μm时,对提高热冲击性能没有足够的作用,而当直径超过3μm时,在模制品表面就产生了因改性乙烯类聚合物颗粒造成的不规则性,从而使实际使用成了问题。《添加剂等》
本发明的热塑性树脂组合物可以按任意比例加入多种添加剂,如阻燃剂、阻燃助剂、稳定剂、颜料和脱模剂。《金属》
用于本发明的金属(B)是一种由诸如铁、铝、铜、锌、锡、镍、钛、金、银、铂、铅、钨、镁、钒、铬、锰和钼之类的单一元素组成的金属或是通过把一种诸如硼、碳、氮、硅、磷和硫的组分加入到由上述金属组成的组合物中而形成的合金。《生产工艺》
本发明的复合模制品可优选地用以下方法生产。
为满足上述要求,必须把树脂模制品中分散颗粒的颗粒直径控制在本发明的特定范围内,必须在组合物的挤出与造粒步骤中选择适当的务件。控制分散颗粒直径的重要因素是选择挤出机和螺杆的类型,以及在生产树脂组合物的步骤中选择挤出速率Q(kg/h)与螺杆转速N(r.p.m)之比(下文称之为Q/N比)。分散颗粒的直径随Q/N比的提高而增加,随Q/N比的降低而减小。在树脂组合物的混合中,Q/N比,优选地为0.3或更高,以获得本发明的复合模制品。当Q/N比小于0.3时,因熔体混合步骤中所受到的剪切力增加而使分散颗粒直径降到1μm以下的量级。
组合物的捏合条件取决于捏合中所用的挤出机,最好适当选择挤出机,以便把模制品中分散颗粒的直径调到1μm或1μm以上至3μm或3μm以下。
混合操作可以在如转鼓式共混机或双筒混炼机之类的混炼机上进行。挤出机可用于熔体混合与造粒工艺。
在用螺杆直径为44mm的挤出机进行熔融捏和的情况下,熔融与混合最好在Q/N≥0.3的混合条件下进行。
复合模制品可以用注射成型、挤出成型和模压成型生产。
实例
本发明用下列实例和对比例作详细描述。实例中的评价方法如下所示。表2、表3中构成组合物的各组分的单位是重量份,除非特别注明。
冲击改性剂A的生产。
制备改性乙烯类聚合物(冲击改性剂A)的方法是:把100重量份的未改性乙烯-丙烯共聚物(Tafmer P-0680:Mitsui石油化学工业公司的产品)、0.025重量份溶于少量丙酮的α、α’-二-叔丁基过氧-对-二异丙基苯和0.5重量份的马来酸酐在一台汉歇尔(Henschel)混炼机中共混,用一台螺杆直径为44mm的双螺杆挤出机在230℃的料筒温度下将该共混物挤出造粒。
评价方法[流动性与保留稳定性]
除了选择的预热时间为6分钟和20分钟外,用半自动熔体指数仪(Toyo Seiki Seishaku-sho公司产品)按照JISK7210A在250℃的试验温度和2.16kgf的载荷作用下测量MFR,用20分钟和6分钟的MFR值之比评价保留稳定性。[耐热冲击试片]
如图1所示的覆盖了一种金属(SKD-11,JIS 64404)的模制品是用注射成型机进行嵌件模制而成型的,锁模压力为15吨,一次注射量为18cm3,料筒温度为260℃,模温为80℃,总周期为45秒。[耐热冲击性]
用图2所示的试验周期作为一个周期对上述试片进行反复的热冲击试验,直到上述试片中产生裂纹为止。用产生裂纹的循环次数评价耐热冲击性能。[分散颗粒直径的测量]
把构成耐热冲击性能试验所用试片中的模塑树脂部分撕下来,让烯烃组分在140℃的热二甲苯中熔解3小时,用电子显微镜拍摄断裂表面,测量颗粒直径。
试验用的电子显微镜是JMS-6100型(JEOL公司制造),照片的放大倍数为2000。用标尺测量50个分散颗粒的直径,以平均值作为分散颗粒的直径。实例1-3和对比例1-4
把特性粘度(在邻氯代苯酚中,35℃)为0.71dl/g的聚对苯二甲酸丁二醇酯(以下称之为PBT-A)与表1所示的中击改性剂按表2所示的比例预先均匀混合,用螺杆直径为44mm的双螺杆挤出机在下列条件下将混合物熔融、捏合和造粒:料筒温度为250℃,挤出速率为50kg/h,螺杆转速为120r.p.m。Q/N值为0.42。物理性能按前述方法评价,结果示于表2。表1
实例4和5以及对比例5-7
物质 | 明细 | |
冲击改性剂A | 用马来酸酐改性的乙烯-丙烯共聚物 | |
冲击改性剂B | 未改性乙烯-丙烯共聚物 | 商品名:Tafmer P0680,Mitsui石油化学工业公司 |
冲击改性剂C | 甲基丙烯酸缩水甘油酯-丙烯酸丁酯接枝聚合物 | 商品名:EXL2314,Kureha化学工业公司 |
冲击改性剂E | 乙烯-甲基丙烯酸缩水甘油酯-丙烯酸甲酯共聚物 | 与6重量%的甲基丙烯酸缩水甘油酯和30重量%的丙烯酸甲酯共聚 |
冲击改性剂F | 乙烯-丙烯酸乙酯共聚物 | 与35重量%丙烯酸乙酯共聚 |
环氧化合物 | 双酚A环氧化合物 | 商品名:EP828,Yuka Shell环氧公司 |
把特性粘度(在邻氯代苯酚中,35℃)为0.71dl/g的聚对苯二甲酸丁二醇酯(以下称之为PBT-A)、特性粘度(在邻氯代苯酚中,35℃)为0.87dl/g的聚对苯二甲酸丁二醇酯(以下称之为PBT-B)与表1中所示的冲击改性剂A按表3所示的比例(以重量份表示)预先均匀混合,然后用表4所示的挤出机在250℃的料筒温度和表3所示的条件下将混合物熔融、捏合和造粒。用制得的粒料评价物理性能,结果示于表3。表2
单位 实例1 实例2 实例3 对比例1 对比例2 对比例3 对比例4PBT-A 重量份 100 100 100 100 100 100 100冲击改性剂A 重量份 15 10 13冲击改性剂B 重量份 15冲击改性剂C 重量份 11.25冲击改性剂E 重量份 3.75 3.75冲击改性剂F 重量份 11.25环氧化物 重量份 2 2玻璃纤维 重量份 50 90 20 43 50 50 50耐热冲击性 循环 150 130 200 10 30 130 130
次数MFR(6min) g/10m 14.1 8.5 24.1 21.0 18.8 6.6 12.3MFR(20min) g/10m 15.0 9.2 26.0 22.0 19.5 2.5 3.0保留稳定性 1.06 1.08 1.08 1.05 1.03 0.37 0.24表3
单位 实例1 实例4 实例5 对比例5 对比例6 对比例7PBT-A 重量份 100 100 100 100 100PBT-B 重量份 100冲击改性剂A 重量份 15 15 15 15 15 15玻璃纤维 重量份 50 50 50 50 50 50挤出机 挤出机-A 挤出机-A 挤出机-B 挤出机-A 挤出机-B 挤出机-C挤出速率 kg/hr 50 50 100 50 260 55螺杆转速 r.p.m 120 120 220 275 220 70Q/N 0.42 0.42 0.45 0.18 1.18 0.79分散颗粒 μm 1.8 1.2 2.4 0.8 3.2 3.5直径标准偏差 μm 0.7 0.4 0.9 0.3 1.0 1.2耐热冲击性 循环 150 180 130 80 100 100
次数MFR(6min) g/10m 14.0 8.5 12.7 15.5 11.4 9.9表4挤出机 螺杆数 旋转方向 螺杆直径挤出机-A 双螺杆 同向 44Φ挤出机-B 双螺杆 同向 65Φ挤出机-C 单螺杆 65φ本发明的效果
本发明生产的聚酯复合模制品具有优异的耐热冲击性,特别适用于以与金属零件整体模压的形式制作汽车部件。
附图简述
图1是评价耐热冲击性能中所用的试片。图1-(1)是金属芯件(材料:SKD-11)的形状。图1-(2)是由金属(材料:SKD-11)和厚度为0.8mm的树脂涂层组成并用金属的嵌件模制法制备的试片。
图2是评价耐热冲击性的试验周期。
工业应用
用本发明获得的聚酯复合模制品具有优异的耐热冲击性,特别适用于以与金属件整体模压的形式制作汽车部件。
Claims (4)
1.一种由一种树脂组合物(A)和一种金属(B)组成的聚酯树脂复合模制品,所述树脂组合物(A)包含一种聚对苯二甲酸丁二醇酯(A1)、一种无机填料(A2)和一种通过α、β不饱和羧酸或其酸衍生物的接枝共聚而产生的改性乙烯共聚物(A3),其中所述金属(B)的部分或全部涂复了树脂组合物(A),组分(A3)的接枝共聚物以分散颗粒的形式存在于构成复合模制品的树脂组合物的模塑部件中,分散颗粒的直径为1~3μm。
2.权利要求1所述的聚酯树脂复合模制品,其中所述改性乙烯类共聚物(A3)是一种用α、β不饱和羧酸的酸衍生物接枝共聚的改性乙烯类共聚物(A3)。
3.权利要求1所述的聚酯树脂复合模制品,其中树脂组合物(A)包含100重量份的聚对苯二甲酸丁二醇酯(A1)、1~125重量份的无机填料(A2)和5~20重量份的用α、β不饱和羧酸的酸衍生物接枝共聚的改性乙烯类共聚物(A3)组成。
4.权利要求1所述的聚酯树脂复合模制品,其中所述的聚对苯二甲酸丁二醇酯(A1)的特性粘度为0.5~0.9dl/g。
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EP (1) | EP0916481B1 (zh) |
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Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
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US20040234791A1 (en) * | 2003-05-19 | 2004-11-25 | Ching Ta Yen | Polypropylene-graft-acrylic acid or polypropylene-graft-maleic anhydride in oxygen scavenging tie layers |
DE10359303A1 (de) * | 2003-12-17 | 2005-07-21 | Roche Diagnostics Gmbh | Kunststoff-Spritzgussteil mit eingebettetem Bauteil |
JP4799857B2 (ja) * | 2004-12-24 | 2011-10-26 | ウィンテックポリマー株式会社 | インサート成形品 |
DE102006047938A1 (de) * | 2006-10-10 | 2008-04-17 | Robert Bosch Gmbh | Gespritztes Kunststoffbauteil mit Einlegeteil |
JP4924612B2 (ja) | 2006-10-31 | 2012-04-25 | 富士通株式会社 | 電子機器用筐体及びその製造方法 |
JP5242150B2 (ja) * | 2007-12-21 | 2013-07-24 | ウィンテックポリマー株式会社 | 複合成形体 |
US9884953B2 (en) * | 2008-06-11 | 2018-02-06 | Wintech Polymer Ltd. | Polybutylene terephthalate resin composition and molded article thereof |
US8445570B2 (en) * | 2008-06-11 | 2013-05-21 | Wintech Polymer Ltd. | Method for forming an insert injection-molded article exhibiting improved resistance to heat shock utilizing a specifically defined polybutylene terephthalate composition |
CN101987913A (zh) * | 2009-07-31 | 2011-03-23 | E.I.内穆尔杜邦公司 | 增韧的聚苯二甲酸丙二醇酯树脂组合物 |
US20110274932A1 (en) * | 2010-05-05 | 2011-11-10 | Basf Se | Component comprising an insert part and plastics jacketing, and process for production of the component |
US8853304B2 (en) | 2011-11-29 | 2014-10-07 | Sabic Innovative Plastics Ip B.V. | Polyester compositions and insert-molded articles made therefrom |
JP6685081B2 (ja) * | 2014-12-26 | 2020-04-22 | ポリプラスチックス株式会社 | インサート成形用樹脂組成物及びインサート成形品 |
US11577665B2 (en) | 2020-02-27 | 2023-02-14 | Cpk Interior Products | Urethane and graphene interior trim panel |
EP3970489A1 (en) | 2020-09-18 | 2022-03-23 | CpK Interior Products Inc. | Graphene-based antiviral polymer |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6041425B2 (ja) | 1979-09-28 | 1985-09-17 | 新神戸電機株式会社 | 鉛蓄電池用陽極板の製造法 |
DE3585935D1 (de) * | 1984-02-24 | 1992-06-04 | Du Pont | Verstaerkte thermoplastische polyesterzusammensetzungen. |
US4759713A (en) * | 1985-07-25 | 1988-07-26 | Baxter Travenol Laboratories, Inc. | Disposable dental tool |
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EP0545973A4 (en) * | 1990-08-27 | 1993-09-15 | E.I. Du Pont De Nemours And Company | Toughened thermoplastic polyester compositions |
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JP2500556B2 (ja) * | 1991-11-27 | 1996-05-29 | 東洋製罐株式会社 | 耐衝撃性に優れたラミネ―ト絞り容器及びその製造法 |
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US5591518A (en) * | 1994-12-16 | 1997-01-07 | Toray Industries, Inc. | Polyester film for use of a laminate with a metal plate |
JPH08165409A (ja) | 1994-12-16 | 1996-06-25 | Teijin Ltd | 金属部材をインサートしてなる成形品 |
MY136271A (en) * | 1994-12-29 | 2008-09-30 | Toyo Kohan Co Ltd | A resin-coated metal sheet with higher vivid reflectivity having the excellent workable adhesion strength |
US6610378B1 (en) * | 1995-10-02 | 2003-08-26 | Toray Industries, Inc. | Biaxially oriented polyester film to be formed into containers |
-
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US6346320B2 (en) | 2002-02-12 |
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