CN102875979A - 树脂组合物 - Google Patents

树脂组合物 Download PDF

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CN102875979A
CN102875979A CN201110195783XA CN201110195783A CN102875979A CN 102875979 A CN102875979 A CN 102875979A CN 201110195783X A CN201110195783X A CN 201110195783XA CN 201110195783 A CN201110195783 A CN 201110195783A CN 102875979 A CN102875979 A CN 102875979A
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resin combination
resin
derivative
metal
crystallization
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张新倍
王君毅
李学鹏
吕明旭
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Priority to US13/327,498 priority patent/US20130017364A1/en
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Abstract

本发明提供一种树脂组合物，用于注塑于金属表面以形成金属与树脂的复合体，其包括主体树脂、结晶减缓剂和矿物填料，该主体树脂为聚对苯二甲酸乙二醇酯及其衍生物中的一种或一种以上，该树脂组合物中主体树脂的质量百分含量为40%-90%，结晶减缓剂的质量百分含量为5%-30%，矿物填料的质量百分含量为0-40%。本发明所述的树脂组合物具有较高的剪切强度、较低的结晶温度及较适宜的结晶速率，使用该树脂组合物注塑于金属表面，更有助于使树脂组合物与金属的结合紧密，机械性能更高；且该树脂组合物对加工设备的损害小。

Description

树脂组合物
技术领域
本发明涉及一种树脂组合物，尤其涉及一种用于制造金属与塑料的复合体的树脂组合物。
背景技术
金属与树脂的一体化接合技术，是指将树脂组合物注塑在经过表面处理形成有超微细凹凸粗糙结构的金属表层，从而使金属与树脂进行接合得到金属与树脂的复合体。目前应用于一体化制造技术中的树脂最常使用的是聚苯硫醚(PPS)或聚对苯二甲酸丁二醇酯 (PBT)树脂组合物，这两种组合物具有良好的力学性能及加工性能，能满足电子电器产品的强度要求。
然而，PPS树脂组合物成型温度高，成型周期长且在加工中会分解产生亚硫酸，对模具螺杆及模具损害严重。而PBT树脂组合物结晶速率太快，易在树脂熔体流入金属表层的孔洞前结晶，使得树脂与金属间的结合性能变差。聚对苯二甲酸乙二醇酯(PET)树脂及其衍生物结晶速度较慢，机械性能良好，与玻璃纤维共混后有望在树脂与金属一体化产品中应用。然而，普通PET及其衍生物加玻纤后流动性及与树脂的结合性能均不能满足一体化技术之要求，且剪切强度较低。
发明内容
有鉴于此，有必要提供一种有效解决上述问题的树脂组合物。
一种树脂组合物，其包括主体树脂、结晶减缓剂和矿物填料，该主体树脂为聚对苯二甲酸乙二醇酯及其衍生物中的一种或一种以上，该树脂组合物中主体树脂的质量百分含量为40%-90%，结晶减缓剂的质量百分含量为5%-30%，矿物填料的质量百分含量为0-40%。
相较于普通的树脂组合物，本发明所述的树脂组合物具有较低的结晶温度及较适宜的结晶速率，该树脂组合物注塑于金属表面，树脂组合物与金属的结合紧密，机械性能高；且该树脂组合物不含硫，对加工设备的损害小。
附图说明
图1为本发明较佳实施例和对比例所制备的树脂组合物的差示扫描量热分析(DSC)曲线图。
具体实施方式
本发明树脂组合物用于制造金属和塑料复合体，其包括主体树脂、结晶减缓剂及矿物填料，该树脂组合物中主体树脂的质量百分含量为40%-90%，结晶减缓剂的质量百分含量为5%-30%，矿物填料的质量百分含量为0-40%。
所述主体树脂为聚对苯二甲酸乙二醇酯(PET)及其衍生物中的一种或一种以上。
所述PET的衍生物可为聚对苯二甲酸乙二醇酯-1，4-环己烷二甲醇酯(PETG)或季戊四醇三丙烯酸酯(PETA)。
所述结晶减缓剂为聚酯、聚烯烃、苯乙烯类聚合物、聚酰胺中的一种或一种以上。所述聚酯、聚烯烃、苯乙烯类聚合物、聚酰胺或上述四种的任意组合物会影响PET及其衍生物树脂在较高温度下的结晶成核，减慢其结晶速度，使树脂组合物在较低的温度下结晶，从而使树脂在进入金属表层孔洞之前不结晶。
所述聚酯为聚对苯二甲酸丁二醇酯(PBT)及其衍生物、聚碳酸酯(PC)及其衍生物、聚甲基丙烯酸甲酯(PMMA)及其衍生物中的一种或一种以上。
所述聚烯烃为聚丙烯(PP)、聚乙烯(PE)及其接枝物中的一种或一种以上，如马来酸酐接枝聚丙烯、乙烯-丙烯酸酯-马来酸酐共聚物等。
苯乙烯类聚合物为聚苯乙烯(PS)、丙烯腈-丁二烯-苯乙烯(ABS)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、SEBS(SEBS是以聚苯乙烯为末端段，以聚丁二烯加氢得到的乙烯-丁烯共聚物为中间弹性嵌段的线性三嵌共聚物)及其接枝物中的一种或一种以上，如马来酸酐接枝SBS。
所述聚酰胺为脂肪族聚酰胺、芳香族聚酰胺、脂肪族聚酰胺和芳香族聚酰胺分子键合而成的物质中的一种或一种以上，如聚酰胺6(PA6)、聚己二酸己二胺(PA66)、聚己二酰丁二胺(PA46)等。
所述矿物填料用以增加树脂组合物的强度并降低树脂的线膨胀速率，使塑料及金属的线膨胀速率一致。所述矿物填料为玻璃纤维、碳纤维、芳纶、碳酸钙、碳酸镁、二氧化钛、二氧化硅、滑石粉、粘土及玻璃粉中的一种或一种以上。
本发明较佳实施例的树脂组合物用于注塑于金属表面以形成金属和树脂复合体较佳。所述金属可为铝合金、钛合金、铜合金、镁合金或钢铁。这些金属在制备金属和塑料复合体之前都需经过表面处理使其表面形成超微细凹凸的粗糙结构；且当金属表面被直径为10nm-1μm的孔洞覆盖时，金属与本发明所述的树脂组合物的结合更紧密。
下面通过实施例来对本发明进行具体说明。
实施例
本发明一较佳实施例的树脂组合物，其主要组分及其质量百分含量为：PET(60wt%)，PETG(5wt%)，马来酸酐接枝PP(5wt%)，玻璃纤维(30wt%)。
对比例
普通的PET树脂组合物，其主要成分及其质量百分含量为：PET(70wt%)，玻璃纤维(30wt%)。
性能测试
(1)热分析测试
图1为本实施例和对比例中所制备的树脂组合物差示扫描量热分析(DSC)曲线图，其中横坐标表示温度(单位为℃)，纵坐标表示热量且吸热朝上(单位为mW)，且图1中实线代表本实施例的树脂组合物，虚线代表对比例的树脂组合物，其中位于图1靠上的曲线为从50℃升温到300℃的DSC曲线(升温速率为10℃/min)，位于图1靠下的曲线为300℃降温到50℃的DSC曲线(降温速率为20℃/min)，靠下的曲线上出现的放热峰为结晶峰。
所以从图1可知：实施例的树脂组合物的结晶峰与对比例的树脂组合物的结晶峰相比，实施例的树脂组合物的结晶峰明显变宽且向低温方向移动。这说明实施例树脂组合物与对比例的树脂组合物相比，结晶温度降低且结晶速率变慢，这些结晶方面的适度调整有助于提高塑料与金属间的结合强度。
(2) 剪切强度测试
将本实施例和对比例的树脂组合物分别注塑于相同的铝板(铝板预先经过表面处理)上形成树脂与铝的复合体，再分别对该两个复合体进行退火处理(120℃加热1小时)后，测试树脂组合物与铝板界面处的剪切强度，测试结果如下：
本实施例的剪切强度为24MPa；对比例的剪切强度为11MPa。这说明本实施例的树脂组合物与金属的结合强度要远高于对比例的树脂组合物与金属的结合强度。
相较于普通的树脂组合物，本发明所述的树脂组合物具有较低的结晶温度及较适宜的结晶速率，该树脂组合物注塑于金属表面，树脂组合物与金属的结合紧密，机械性能高；且该树脂组合物不含硫，对加工设备的损害小。

Claims (11)

1.一种树脂组合物，其包括主体树脂和矿物填料，其特征在于：该主体树脂为聚对苯二甲酸乙二醇酯及其衍生物中的一种或一种以上，该树脂组合物还包括结晶减缓剂，该树脂组合物中主体树脂的质量百分含量为40%-90%，结晶减缓剂的质量百分含量为5%-30%，矿物填料的质量百分含量为0-40%。
2.如权利要求1所述的树脂组合物，其特征在于：该树脂组合物用于注塑于金属表面以形成金属与树脂的复合体。
3.如权利要求2所述的树脂组合物，其特征在于：所述金属为铝合金、钛合金、铜合金、镁合金或钢铁。
4.如权利要求2所述的树脂组合物，其特征在于：所述金属预先经过表面处理，其表面被直径为10nm-1μm的孔洞覆盖。
5.如权利要求1所述的树脂组合物，其特征在于：该聚对苯二甲酸乙二醇酯的衍生物为聚对苯二甲酸乙二醇酯-1，4-环己烷二甲醇酯或季戊四醇三丙烯酸酯。
6.如权利要求1所述的树脂组合物，其特征在于：该矿物填料为玻璃纤维、碳纤维、芳纶、碳酸钙、碳酸镁、二氧化钛、二氧化硅、滑石粉、粘土及玻璃粉的一种或一种以上。
7.如权利要求1所述的树脂组合物，其特征在于：该结晶减缓剂为聚酯、聚烯烃、苯乙烯类聚合物、聚酰胺中的一种或一种以上。
8.如权利要求7所述的树脂组合物，其特征在于：该聚酯为聚对苯二甲酸丁二醇酯及其衍生物、聚碳酸酯及其衍生物、聚甲基丙烯酸甲酯及其衍生物中的一种或一种以上。
9.如权利要求7所述的树脂组合物，其特征在于：该聚烯烃为聚丙烯、聚乙烯及其接枝物中的一种或一种以上。
10.如权利要求7所述的树脂组合物，其特征在于：该苯乙烯类聚合物为聚苯乙烯、丙烯腈-丁二烯-苯乙烯、苯乙烯-丁二烯-苯乙烯嵌段共聚物、SEBS及其接枝物中的一种或一种以上。
11.如权利要求7所述的树脂组合物，其特征在于：该聚酰胺为脂肪族聚酰胺、芳香族聚酰胺、脂肪族聚酰胺和芳香族聚酰胺分子键合而成的物质中的一种或一种以上。
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Cited By (2)

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CN103382297A (zh) * 2013-07-22 2013-11-06 上海电力学院 一种低翘曲碳纤增强pet/聚酯合金及其制备方法
CN114940812A (zh) * 2022-05-07 2022-08-26 东莞市盈坤电子科技有限公司 一种易成型pet片材及其制备方法

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WO2010103030A2 (en) * 2009-03-13 2010-09-16 Basf Se Stabilized blends of polyester and polyamide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103382297A (zh) * 2013-07-22 2013-11-06 上海电力学院 一种低翘曲碳纤增强pet/聚酯合金及其制备方法
CN103382297B (zh) * 2013-07-22 2015-08-12 上海电力学院 一种低翘曲碳纤增强pet/聚酯合金及其制备方法
CN114940812A (zh) * 2022-05-07 2022-08-26 东莞市盈坤电子科技有限公司 一种易成型pet片材及其制备方法

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