CN112375345B - 一种激光打标遮光增强pbt组合物及其制备方法和应用 - Google Patents

一种激光打标遮光增强pbt组合物及其制备方法和应用 Download PDF

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CN112375345B
CN112375345B CN202011182810.5A CN202011182810A CN112375345B CN 112375345 B CN112375345 B CN 112375345B CN 202011182810 A CN202011182810 A CN 202011182810A CN 112375345 B CN112375345 B CN 112375345B
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莫文杰
黄险波
叶南飚
朱文
龚德君
冯健
付学俊
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Kingfa Science and Technology Co Ltd
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Abstract

本发明提供一种激光打标遮光增强PBT组合物，包括如下重量份的的组分：PBT树脂50～80份；遮光剂6～20份；玻璃纤维15～30份；抗氧剂0.1～0.5份，炭黑为所述遮光剂重量的0.0033％～0.033％。本发明在不使用价格高昂的激光打标剂，只是采用遮光剂和微量炭黑复配的情况下，该组合物具有白度值大于90和小于3mm厚度的遮光以及激光打标前后的色差值大于15的性能，因此，该组合物可以应用于制备照明行业的灯杯外壳、电容器、连接器或继电器制品领域中。

Description

一种激光打标遮光增强PBT组合物及其制备方法和应用
技术领域
本发明涉及工程塑料技术领域，更具体地，涉及一种照明行业使用的激光打标遮光增强PBT组合物及其制备方法和应用。
背景技术
聚对苯二甲酸丁二醇酯(PBT)是一种半透明到不透明的乳白色结晶热塑性聚酯，五大工程塑料的重要成员之一，PBT常用于照明行业中的灯杯外壳。灯杯外壳的性能要求通常包括阻燃、冷热冲击循环、遮光、激光打标、耐热等。目前解决遮光性能的方法主要是加入大量遮光剂，解决激光打标性能的方法主要是加入激光打标剂，但是激光打标剂价格昂贵，难以制得价廉的兼具良好的遮光性能和激光打标性能的材料。
中国专利(CN107201011A)公开了一种可激光打标的高遮光LED用聚酯复合材料，具体公开了聚酯、玻璃纤维、抗氧剂、遮光剂和激光打标粉，但是该专利的激光打标粉为锡氧化物、锑氧化物和钕氧化物中的至少一种，价格昂贵，不利于工业化大规模生产。
因此，目前的激光打标材料昂贵，不能大规模工业生产，急需开发一种价格低廉，且激光打标效果好的复合材料。
发明内容
本发明的目的是克服现有技术激光打标材料昂贵、不能大规模生产的缺陷，提供一种激光打标遮光增强PBT组合物，所述PBT组合物兼具激光打标和遮光效果。
本发明的另一目的在于提供所述激光打标遮光增强PBT组合物的制备方法。
本发明的另一目的在于提供所述激光打标遮光增强PBT组合物的应用。
本发明的目的通过以下技术方案实现：
一种激光打标遮光增强PBT组合物，包括如下重量份的组分：
Figure BDA0002750634990000011
Figure BDA0002750634990000021
本发明通过遮光剂和炭黑的复配，改善了PBT组合物的激光打标效果。遮光剂在组合物中起到反射光的作用，而炭黑在吸收激光的同时使得树脂碳化，形成碳化层起到打标剂的效果。但是炭黑同时是一种色素，添加量过大容易改变底色，添加量过小，对比度不足，又无法起到打标的效果。本发明的遮光剂能进一步提高对比度，使得激光打标更清晰，实现了白度值大于90和3mm以下厚度的遮光效果并且激光打标前后的色差值可达到15以上。
优选地，所述组合物包括如下重量份的组分：
Figure BDA0002750634990000022
优选地，所述遮光剂为钛白粉、硫化锌、锑白的一种或几种。
优选地，所述遮光剂为钛白粉。
遮光剂的加入不仅仅是提高树脂的遮光性能，还能够与微量炭黑协同作用，提高激光达标的效果。
优选地，所述炭黑为乙炔炭黑或导电炭黑；若炭黑的用量超过遮光剂重量的0.033％，则材料的颜色太深，白度值低于90，不能实现“白打黑”(即：于浅色的聚合物上显示出深色的标记)的功能；而炭黑的重量也不能少于遮光剂重量的0.0033％，过少会导致碳化层变浅，本底部分与激光打标部分的对比度下降，不能达到激光打标效果，另外，炭黑还能够与遮光剂协同作用提高遮光效果。
所述炭黑的含量测量方法：S1.固定遮光剂用量，加入不同含量的炭黑，测定组合物的白度值，建立标准曲线，得到标准方程；S2.用ICP-AES电感耦合原子发射光谱仪测定不同遮光剂用量的组合物中的遮光剂含量，S3.通过已知遮光剂的含量和白度值来计算炭黑的含量。
优选地，所述玻璃纤维是直径为7～17μm，长度为3～5mm的无碱玻璃纤维。
玻纤的直径越小，相同重量的玻纤，玻纤的数量越多，材料的力学性能越好。当玻纤的直径小于7μm，其制造成本会较高；当玻纤的直径大于17μm，材料的力学性能下降。
优选地，所述抗氧剂是受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫代酯类抗氧剂中的一种或几种。
更优选地，所述抗氧剂是受阻酚类抗氧剂。
所述受阻酚类抗氧剂为RIANOX 1010或SONOX 1010；
所述亚磷酸酯类抗氧剂为RIANOX 168或SONOX 168；
所述硫代酯类抗氧剂为RIANOX 412S。
本发明还提供了一种激光打标遮光增强PBT组合物的制备方法，包括如下步骤：
S1：将烘干的PBT树脂，玻璃纤维，遮光剂，炭黑，抗氧剂混合均匀，将混合物投入双螺杆挤出机的主喂料斗中；
S2：将玻璃纤维投入到双螺杆挤出机的侧喂料斗中；
S3：设置双螺杆挤出机各区的温度为220～250℃，喂料量为300～500kg/h，主机转速为300～400rpm；
S4：熔体经挤出机挤出后，加工得到激光打标遮光增强PBT组合物。
所述加工为过水槽冷却，风冷吹干，切粒、包装。
所述激光打标遮光增强PBT组合物在制备灯杯外壳制品、电容器、连接器、继电器制品中的应用。
与现有技术相比，本发明的有益效果是：
本发明提供一种激光打标遮光增强PBT组合物，发明人意外发现遮光剂与炭黑的协同作用，大大地提高了组合物的激光打标性能和遮光效果，且炭黑的含量在遮光剂重量的0.0033％～0.033％范围内得到的激光打标遮光增强PBT组合物能够达到厚度为3mm以下的遮光效果；激光打标前后的色差值可达到15以上；白度值大于90，由于本发明不含有激光打标剂，可大幅降低材料的成本，提高经济实用性，该组合物可以应用于制备照明行业的灯杯外壳、电容器、连接器或继电器制品领域中。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，但本发明的实施方式不限于此。
以下实施例及对比例中采用的原料如下：
A.PBT树脂：1200-211M，中国台湾长春；
B.遮光剂：钛白粉TR-33(上海颜钛实业有限公司)；
C.炭黑：乙炔炭黑DENKA BLACK(上海华仲荣)；
D.玻璃纤维：无碱玻璃纤维ECS13-3.0-T436W(玻纤直径13μm，长度3.0mm，泰山玻璃纤维有限公司)；
E.抗氧剂：选用受阻酚类抗氧剂RIANOX 1010(利安隆)。
下面实施例和对比例均通过以下方法制备PBT树脂，均按照表1-5的重量份数称取各组分；具体步骤如下：
S1：将烘干的PBT树脂，玻璃纤维，遮光剂，炭黑，抗氧剂混合均匀，将混合物投入双螺杆挤出机的主喂料斗中；
S2：将玻璃纤维投入到双螺杆挤出机的侧喂料斗中；
S3：设置双螺杆挤出机各区的温度为220-250℃，喂料量为300-500kg/h，主机转速为300～400rpm；
S4：熔体经挤出机挤出后，加工得到激光打标遮光增强PBT组合物。
所述炭黑的用量为所述遮光剂重量的0.0033％～0.033％。
表1实施例1～4PBT组合物各组分含量
Figure BDA0002750634990000041
表2实施例5～8PBT组合物各组分含量
Figure BDA0002750634990000042
表3实施例9～12PBT组合物各组分含量
Figure BDA0002750634990000051
表4实施例13～15PBT组合物各组分含量
Figure BDA0002750634990000052
表5对比例1～5PBT组合物各组分含量
Figure BDA0002750634990000053
对比例1～3与实施例2对比，其中对比例1不加入遮光剂和炭黑；对比例2 不加入炭黑；对比例3不加入遮光剂，但是炭黑的含量为遮光剂的0.0005％；对比例4和对比例5中的炭黑含量分别为遮光剂的0.0005％和0.1％。
注塑不同厚度的100*100mm的方板，厚度分别为0.8、1.0、1.5、2.0、2.5 和3.0mm。
(1)开启手机灯贴紧不同厚度的方板，观察方板是否完全遮光，以评估其遮光厚度h。
(2)用分光光度色差仪测定方板的白度值L。
(3)用激光打标机对方板进行激光打标，用分光光度色差仪测定激光打标前后的方板的色差△E。所用激光打标机型号为TFL-M20(深圳市泰德激光科技有限公司)，打标参数为：功率为额定功率的60％，频率20KHz，速度1500mm/s。
表6性能测试数据表
遮光厚度h(mm) 白度值L 色差(△E)
实施例1 0.8 93.12 36.12
实施例2 0.8 92.78 35.56
实施例3 0.8 92.47 34.13
实施例4 0.8 92.03 32.98
实施例5 2.5 94.12 17.5
实施例6 1.5 90.23 24.75
实施例7 2.0 95.11 18.71
实施例8 1.0 90.48 29.85
实施例9 1.5 95.32 30.46
实施例10 0.8 90.33 42.05
实施例11 1.0 96.78 32.89
实施例12 0.8 90.58 48.12
实施例13 0.8 92.54 36.88
实施例14 0.8 92.40 34.66
实施例15 0.8 92.30 33.12
对比例1 >3.0 91.45 10.13
对比例2 1.5 97.96 13.55
对比例3 >3.0 89.54 11.22
对比例4 1.5 97.57 13.88
对比例5 0.8 83.15 14.55
本发明各实施例中白度值大于90和3mm以下厚度的遮光效果并且激光打标前后的色差值可达到15以上。其中，从实施例5～12可以看出，遮光厚度和白度值受遮光剂和炭黑两者含量的影响，总体来讲，炭黑的加入会提高遮光厚度，降低白度值，遮光剂的加入提高白度值和遮光厚度；当遮光剂和炭黑复配时，能大幅度提高激光打标效果，其中当遮光剂的优选含量为15～20之间时，其激光打标效果要优于实施例5～8的激光打标效果，而对比例1在不加入遮光剂和炭黑的条件下，其遮光厚度和色差值都远差于各实施例；对比例2在不加入炭黑的情况下，其激光打标效果不好；对比例3在不加入遮光剂的情况下，激光打标效果不如实施例，且遮光厚度大于3mm。从对比例4和对比例5可以看出，当炭黑的量不在遮光剂0.0033％～0.033％之间，激光打标的色差值低于各实施例。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (7)

1.一种激光打标遮光增强PBT组合物，其特征在于，包括如下重量份的组分：
Figure FDA0003623343970000011
乙炔炭黑为所述钛白粉重量的0.0033％～0.033％。
2.如权利要求1所述激光打标遮光增强PBT组合物，其特征在于，包括如下重量份的组分：
Figure FDA0003623343970000012
乙炔炭黑为所述钛白粉重量的0.0033％～0.033％。
3.如权利要求2所述激光打标遮光增强PBT组合物，其特征在于，所述玻璃纤维是直径为7～17μm，长度为3～5mm的无碱玻璃纤维。
4.如权利要求2所述激光打标遮光增强PBT组合物，其特征在于，所述抗氧剂是受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫代酯类抗氧剂中的一种或几种。
5.如权利要求4所述激光打标遮光增强PBT组合物，其特征在于，所述抗氧剂是受阻酚类抗氧剂。
6.如权利要求1～5任一项所述激光打标遮光增强PBT组合物的制备方法，其特征在于，包括如下步骤：
S1.将烘干的PBT树脂、玻璃纤维、钛白粉、乙炔炭黑、抗氧剂混合均匀，将混合物投入双螺杆挤出机的主喂料斗中；
S2.将玻璃纤维投入到双螺杆挤出机的侧喂料斗中；
S3.设置双螺杆挤出机的温度为220～250℃，喂料量为300～500kg/h，主机转速为300～400rpm；
S4.熔体经挤出机挤出后，加工得到激光打标遮光增强PBT组合物。
7.权利要求1～5任一项所述激光打标遮光增强PBT组合物在制备灯杯外壳、电容器、连接器或继电器制品中的应用。
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