CN105647027A - Tpv热塑性弹性体复合片材、tpv热塑性弹性体复合片材的制作方法 - Google Patents

Tpv热塑性弹性体复合片材、tpv热塑性弹性体复合片材的制作方法 Download PDF

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CN105647027A
CN105647027A CN201610012809.5A CN201610012809A CN105647027A CN 105647027 A CN105647027 A CN 105647027A CN 201610012809 A CN201610012809 A CN 201610012809A CN 105647027 A CN105647027 A CN 105647027A
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毛丛敏
林咸雄
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ZHEJIANG IMIN NEW MATERIAL TECHNOLOGY Co Ltd
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Abstract

本发明针对现有技术材质的扬声器易老化，使扬声器寿命低，且复卷时易粘连的不足，提供一种不易老化，且复卷时不易粘连的TPV热塑性弹性体复合片材、TPV热塑性弹性体复合片材的制作方法，在TPV热塑性弹性体复合片材中，中间层由三元乙丙胶40％-63％、软化剂20％-45％、聚丙烯10％-30％、硫化剂2％-5％、黑色母0％-5％、滑石粉3％-10％组成，表面层由三元乙丙胶43％-65％、软化剂7.5％-30％、聚丙烯23％-45％、硫化剂2％-5％、黑色母0％-5％、防老剂0％-2％、防粘连剂0.5％～1％组成，由于防粘连剂的加入，使得复合片材在复卷时不易粘连，由于TPV采用的是复合片材的表面层原料，所以，也具用防粘连的性能。

Description

TPV热塑性弹性体复合片材、TPV热塑性弹性体复合片材的制作方法
本申请是对申请号为CN201310187851申请日为2013.05.17，名称为“TPV、TPV热塑性弹性体复合片材、TPV热塑性弹性体复合片材的制作方法”的专利申请的分案申请。
技术领域
本发明涉及一种TPV热塑性弹性体复合片材、TPV热塑性弹性体复合片材的制作方法。
背景技术
目前市场上的扬声器材料多以橡胶或PVC橡胶为主，这种材质的扬声器容易老化，因老化而产生惰性变形和龟纹，影响扬声器的音色和品质，从而影响扬声器使用，另外采用上述材质的片材复卷以后容易粘连。
发明内容
本发明的目的是，针对现有技术材质的扬声器易老化，使扬声器寿命低，且复卷时易粘连的不足，提供一种不易老化，且复卷时不易粘连的TPV热塑性弹性体复合片材、TPV热塑性弹性体复合片材的制作方法。
本发明的目的是通过下述技术方案实现的：
一种TPV热塑性弹性体复合片材，包括中间层、位于中间层上表面和下表面的表面层，其特征在于，按质量百分比计，所述的中间层由三元乙丙胶40％-63％、软化剂20％-45％、聚丙烯10％-30％、硫化剂2％-5％、黑色母0％-5％、滑石粉3％-10％组成，所述的表面层由三元乙丙胶43％-65％、软化剂7.5％-30％、聚丙烯23％-45％、硫化剂2％-5％、黑色母0％-5％、防老剂0％-2％、防粘连剂0.5％～1％组成；
按质量百分比计，所述的中间层由三元乙丙胶40-50％、软化剂20-31％、聚丙烯16-21％、硫化剂3-4％、黑色母0％-2％、滑石粉5％-10％组成，所述的表面层由三元乙丙胶50-60％、软化剂9.2-20％、聚丙烯25-35％、硫化剂2.4-3.0％、黑色母2-2.5％、防老剂0.1-1％、防粘连剂0.8％～1％组成；
所述的硫化剂为双马来酰亚胺、辛基酚醛树脂和二叔丁基过氧化异丙基苯的混合物，三者的质量配比为双马来酰亚胺20-40％，辛基酚醛树脂15-35％，二叔丁基过氧化异丙基苯25-65％；
所述的防粘连剂为有机硅聚合物或甲基丙烯酸酯的聚合物。
TPV热塑性弹性体复合片材的制作方法，包括如下步骤：A、造粒：采用上述中间层的质量配比，先取三元乙丙胶和软化剂塑炼，再加入聚丙烯、硫化剂、黑色母、滑石粉进行预分散得到中间层混合料，将中间层混合料加入造粒机中进行硫化，挤出成中间层颗粒；采用上述表面层的质量配比，取三元乙丙胶和软化剂塑炼，再加入聚丙烯、硫化剂、黑色母、防老剂进行预分散得到表面层混合料，将表面层混合料加入造粒机中进行动态硫化挤出成表面层混合颗粒，将表面层混合颗粒与防粘连剂混合搅拌，进行二次改性造粒制成表面层颗粒；B、片材复合挤出，将上述挤出制成的中间层颗粒和表面层颗粒分别加入除湿干燥箱，进行干燥，将干燥完毕的颗粒用两台挤出机同一口模共同挤出，将表面层涂覆于中间层，制得复合片材；
所述造粒机的主机转速在35-45转/分，喂料转速30-33转/分，熔体压力在5-8MPa；所述干燥的时间为60-100分钟，烘干温度为80-100度；片材挤出温度为170-205度；
所述挤出机的上、中、下三辊温度为50～65度。
采用本发明组份的TPV热塑性弹性体复合片材，由于在表面层加入了有机硅聚合物或甲基丙烯酸酯的聚合物，且中间层和表面层的主要成份均为三元乙丙胶和聚丙烯，且中间层的三元乙丙胶的含量与表面层的三元乙丙胶的含量基本相同，而聚丙烯的含量小于表面层的含量，所以片材不仅具有环保无毒、耐磨、耐屈挠、耐低温、耐油、耐酸、防霉抗菌的特性，且片材表面干爽，不粘连，含油量少，易吸塑成型，低分子不容易挥发到片材表面。
采用本发明方法制造的TPV热塑性弹性体复合片材，表面层颗粒是分两步制得的，先用造粒机制得表面层混合颗粒，再将表面层混合颗粒与防粘剂混合搅拌形成表面层颗粒，所以当片材挤出成型后进行吸塑成型时，在拉伸力的作用下制品底部变得很薄形成薄膜，有机硅聚合物或甲基丙烯酸酯的聚合物在薄膜表面上形成平均高度为60～600nm的突出物，从而可起到防止薄膜粘连的作用，采用三层共挤工艺，使吸塑成型优越，使得用该材料制成的电子产品具有不易老化、耐久、密度低，耐热性持久的特点；它以高延伸率、高抗撕裂强度改性TPV弹性体为基材，提高了产品弹性比率。
上述配方和工艺特别适用于生产超薄TPV热塑性弹性体吸塑成型专用材料，该材料特别适用于制作高性能电声制品。
具体实施方式
下面结合具体实施例对本发明作进一步地描述：
本发明的防老剂和软化剂市场内有销售，本发明的实施例中采用市售的德国拜耳产的防老剂264，防老剂采用河北宇鹏橡塑软化剂研究中心EPDM专用石蜡油。硫化剂可为双马来酰亚胺、辛基酚醛树脂和二叔丁基过氧化异丙基苯的一种或两种以上的混合物，最好是三者的混合物，其组份的质量配比为：双马来酰亚胺20-40％，辛基酚醛树脂15-35％，二叔丁基过氧化异丙基苯25-65％。采用该组份的硫化剂，硫化速度快，在剪切力作用下经硫化的EPDM三元乙丙橡胶被分散成微小粒子，从而形成具有“海一岛”结构的PP/EPDM复合材料。
当片材对遮光性能要求不高时，可不加入黑色母。本发明的片材中加入黑色母的目的是提高片材的遮光性能，防止片材吸塑成载带后底角透光。原因是片材完成挤出成型后需进行吸塑成型，片材经吸塑拉伸后底部变得很薄，而加入黑色母可使片材具有良好的遮光性能。
本发明的实施例的复合片材的制作方法是优选的方案，当然，在进行片材造粒时可以同时加入三元乙丙胶、软化剂、聚丙烯、硫化剂、黑色母、滑石粉直接搅拌均匀后用造粒机造粒，形成中间层颗粒。
加工TPV时，需注意为了达到好的防粘连性能，进行造粒时，应先将三元乙丙胶和软化剂塑炼，而后再加入聚丙烯、硫化剂、黑色母、防老剂，进行预分散得到表面层混合料，将表面层混合料加入双螺杆造粒机中进行动态硫化挤出成表面层混合颗粒，将表面层混合颗粒与防粘连剂混合搅拌，进行二次改性造粒制成表面层颗粒，这样，作为防粘剂的有机硅聚合物或甲基丙烯酸酯的聚合物在薄膜表面上形成平均高度为60～600nm的突出物，从而可起到防止薄膜粘连的作用。其余步骤采用现有的片材挤出加工工艺即可。
在对三元乙丙胶进行塑练时，采用常规的三元乙丙胶塑练工艺即可。
采用本发明方法制造复合片材，可制得超薄片材，挤出后片材的厚度最薄可达到0.2-0.5mm。通过调整挤出机两辊间距来设定片材的厚度。
造粒时，可使用普通造粒机，最好用双螺杆造粒机。本发明的实施例均采用双螺杆造粒机，由于当给定了材料的组份和步骤后，采用造粒机进行造粒普技术人员都熟知，所以本发明不再一一进行举例说明。
实施例1
1)中间层质量百分比组份由三元乙丙胶40％、软化剂31％、聚丙烯16％、硫化剂3％、黑色母0％、滑石粉10％组成；表面层质量百分比组份：由三元乙丙胶50％、软化剂9.2％、聚丙烯35％、硫化剂2.4％、黑色母2.5％、防老剂0.1％、防粘连剂0.8％组成；
2)造粒：按中间层配比，先取三元乙丙胶和软化剂进行塑炼，再加入聚丙烯、硫化剂、黑色母、滑石粉进行预分散得到中间层混合料，将中间层混合料加入双螺杆造粒机中进行动态硫化，挤出成中间层颗粒，造粒机主机转速在35转/分，喂料转速33转/分，熔体压力在5MPa之间；按表面层的质量配比，取三元乙丙胶和软化剂塑炼，再加入聚丙烯、硫化剂、黑色母、防老剂进行预分散得到表面层混合料，将表面层混合料加入造粒机中进行动态硫化挤出成表面层混合颗粒，将表面层混合颗粒与防粘连剂混合搅拌，进行二次改性造粒制成表面层颗粒，主机转速在40转/分，喂料转速33转/分，熔体压力在7MPa之间；
B、片材复合挤出，将上述挤出制成中间层颗粒加入除湿干燥箱，干燥时间在60分钟，烘干温度100度；将上述挤出制成的表面层颗粒加入除湿干燥箱，干燥时间60分钟，烘干温度在80度，片材通过两台挤出机同一口模共同挤出，将表面层涂覆于中间层两侧。基材层片材挤出温度设在170度挤出制得的片材厚度为0.25mm；
采用硫化剂的质量百分比组份为：双马来酰亚胺20％，辛基酚醛树脂15，二叔丁基过氧化异丙基苯65％。防粘连剂采用有机硅聚合物。
实施例1′
中间层、表面层组份及工艺参数见表一，其余同实施例1。
实施例2
中间层、表面层组份及工艺参数见表一，采用硫化剂的质量百分比组份为：双马来酰亚胺40％，辛基酚醛树脂35％，二叔丁基过氧化异丙基苯25。防粘连剂采用甲基丙烯酸酯的聚合物；其余同实施例1。制得的片材厚度为0.5mm
实施例3
中间层、表面层组份及工艺参数见表一，采用硫化剂的质量百分比组份为：双马来酰亚胺30％，辛基酚醛树脂20％，二叔丁基过氧化异丙基苯50％，防粘连剂采用甲基丙烯酸酯的聚合物；其余同实施例1。制得的片材厚度为0.4mm
实施例4
中间层、表面层组份及工艺参数见表一，采用硫化剂的质量百分比组份为：双马来酰亚胺25％，辛基酚醛树脂29％，二叔丁基过氧化异丙基苯56％，防粘连剂采用有机硅聚合物；其余同实施例1。
实施例5
中间层、表面层组份及工艺参数见表一，采用硫化剂的质量百分比组份为：双马来酰亚胺37％，辛基酚醛树脂18％，二叔丁基过氧化异丙基苯55％，防粘连剂采用有机硅聚合物；其余同实施例1。
实施例6
中间层、表面层组份及工艺参数见表一，采用硫化剂的质量百分比组份为：双马来酰亚胺25％，辛基酚醛树脂15％，二叔丁基过氧化异丙基苯60％，防粘连剂采用甲基丙烯酸酯的聚合物；其余同实实施例1。
实施例7
1)片材质量百分比组份：由三元乙丙胶50％，软化剂9.2％，聚丙烯35％，硫化剂2.4％，黑色母2.5％，防老剂0.1％，防粘连剂0.8％组成；
2)造粒：取三元乙丙胶和软化剂塑炼，再加入聚丙烯、硫化剂、黑色母、防老剂进行预分散得到表面层混合料，将表面层混合料加入造粒机中进行动态硫化挤出成表成表面层混合颗粒，将表面层混合颗粒与防粘连剂混合搅拌，进行二次改性造粒制成表面层颗粒，主机转速在40转/分，喂料转速33转/分，熔体压力在7MPa之间；
B、片材复合挤出，将上述挤出制成的颗粒加入除湿干燥箱，干燥60分钟，烘干温度100度；片材通过双螺杆挤出机挤出。片材挤出温度170度，挤出制得的片材厚度为0.25mm；
采用硫化剂的质量百分比组份为：双马来酰亚胺20％，辛基酚醛树脂15，二叔丁基过氧化异丙基苯65％。防粘连剂采用有机硅聚合物。
实施例8
组份及工艺参数见表二，采用硫化剂的质量百分比组份为：双马来酰亚胺40％，辛基酚醛树脂35％，二叔丁基过氧化异丙基苯25。防粘连剂采用甲基丙烯酸酯的聚合物；其余同实施例7。挤出制得的片材厚度为0.5mm。
实施例9
组份及工艺参数见表二。采用硫化剂的质量百分比组份为：双马来酰亚胺30％，辛基酚醛树脂20％，二叔丁基过氧化异丙基苯50％，防粘连剂采用甲基丙烯酸酯的聚合物；其余同实施例1。挤出制得的片材厚度为0.4mm。
实施例10
组份及工艺参数见表二，采用硫化剂的质量百分比组份为：双马来酰亚胺25％，辛基酚醛树脂29％，二叔丁基过氧化异丙基苯56％，防粘连剂采用有机硅聚合物；其余同实施例1。
实施例11
组份及工艺参数见表二，采用硫化剂的质量百分比组份为：双马来酰亚胺37％，辛基酚醛树脂18％，二叔丁基过氧化异丙基苯55％，防粘连剂采用有机硅聚合物；其余同实施例1。
实施例12
组份及工艺参数见表二，采用硫化剂的质量百分比组份为：双马来酰亚胺25％，辛基酚醛树脂15％，二叔丁基过氧化异丙基苯60％，防粘连剂采用甲基丙烯酸酯的聚合物；其余同实施7。
表一、TPV热塑性弹性体复合片材组份配比及加工参数
表二、TPV片材组份及工艺参数
表三、超薄TPV热塑性弹性体片材性能表
说明：拉伸强度、断裂伸长率、100％定伸强度延流动方向测试，撕裂强度延与流动方向垂直的方向测试。
表四、TPV片材性能表
说明：拉伸强度、断裂伸长率、100％定伸强度延流动方向测试，撕裂强度延与流动方向垂直的方向测试。
表五、现有技术中耐老化扬声器材料耐老化性与本产品综合耐老化性对照表

Claims (6)

1.一种TPV热塑性弹性体复合片材，包括中间层、位于中间层上表面和下表面的表面层，其特征在于，按质量百分比计，所述的中间层由三元乙丙胶40％-63％、软化剂20％-45％、聚丙烯10％-30％、硫化剂2％-5％、黑色母0％-5％、滑石粉3％-10％组成，所述的表面层由三元乙丙胶43％-65％、软化剂7.5％-30％、聚丙烯23％-45％、硫化剂2％-5％、黑色母0％-5％、防老剂0％-2％、防粘连剂0.5％～1％组成，所述的防粘连剂为有机硅聚合物或甲基丙烯酸酯的聚合物。
2.如权利要求1所述的TPV热塑性弹性体复合片材，其特征在于，按质量百分比计，所述的中间层由三元乙丙胶40-50％、软化剂20-31％、聚丙烯16-21％、硫化剂3-4％、黑色母0％-2％、滑石粉5％-10％组成，所述的表面层由三元乙丙胶50-60％、软化剂9.2-20％、聚丙烯23-35％、硫化剂2.4-3.0％、黑色母2-2.5％、防老剂0.1-1％、防粘连剂0.8％～1％组成。
3.如权利要求1或2所述的TPV热塑性弹性体复合片材，其特征在于，所述的硫化剂为双马来酰亚胺、辛基酚醛树脂和二叔丁基过氧化异丙基苯的混合物，三者的质量配比为双马来酰亚胺20-40％，辛基酚醛树脂15-35％，二叔丁基过氧化异丙基苯25-65％。
4.TPV热塑性弹性体复合片材的制作方法，其特征在于，包括如下步骤：
A、造粒：采用权利要求1-3任一项中间层的质量配比，先取三元乙丙胶和软化剂塑炼，再加入聚丙烯、硫化剂、黑色母、滑石粉进行预分散得到中间层混合料，将中间层混合料加入造粒机中进行硫化，挤出成中间层颗粒；采用权利要求1-3任一项所述的表面层的质量配比，取三元乙丙胶和软化剂塑炼，再加入聚丙烯、硫化剂、黑色母、防老剂进行预分散得到表面层混合料，将表面层混合料加入造粒机中进行动态硫化挤出成表面层混合颗粒，将表面层混合颗粒与防粘连剂混合搅拌，进行二次改性造粒制成表面层颗粒；
B、片材复合挤出，将上述挤出制成的中间层颗粒和表面层颗粒分别加入除湿干燥箱，进行干燥，将干燥完毕的颗粒用两台挤出机同一口模共同挤出，将表面层涂覆于中间层，制得复合片材。
5.如权利要求4所述的TPV热塑性弹性体复合片材的制作方法，其特征在于，所述造粒机的主机转速在35-45转/分，喂料转速30-33转/分，熔体压力在5-8MPa；所述干燥的时间为60-100分钟，烘干温度为80-100度；片材挤出温度为170-205度。
6.如权利要求5所述的TPV热塑性弹性体复合片材的制作方法，其特征在于，所述挤出机的上、中、下三辊温度为50～65度。
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