CN108559119A - 无磷无卤的阻燃聚酯片材及其制备方法 - Google Patents

无磷无卤的阻燃聚酯片材及其制备方法 Download PDF

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CN108559119A
CN108559119A CN201810095235.1A CN201810095235A CN108559119A CN 108559119 A CN108559119 A CN 108559119A CN 201810095235 A CN201810095235 A CN 201810095235A CN 108559119 A CN108559119 A CN 108559119A
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polyester sheet
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何建平
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Suzhou Villa Electronics Technology Co Ltd
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Abstract

本发明涉及一种无磷无卤的阻燃聚酯片材，包括聚酯基材以及涂覆在所述聚酯基材表面的阻燃涂层，其特征在于：所述阻燃涂层含有11‑25%（重量百分比）的无磷无卤阻燃剂、74.5‑88%（重量百分比）的聚丙烯酸酯。所述无磷无卤阻燃剂由聚丙烯酸钠和聚碳酸丙烯酯组成。聚丙烯酸钠具有网络分子结构，能起到吸湿和保湿作用，从而一定程度上降低了聚酯片材周边环境的温度，增加了湿度，提高了聚酯片材的阻燃性；而聚碳酸丙烯酯在燃烧条件下会受热分解产生大量二氧化碳，稀释了聚酯片材周边环境中的氧浓度，达到阻燃的目的。且该阻燃剂不含卤素和磷，解决了污染环境的问题。同时采用表面涂覆的方法制备工艺更加简单，方便，有利于提高工作效率、降低生产成本。

Description

无磷无卤的阻燃聚酯片材及其制备方法
技术领域
本发明涉及聚酯片材领域，尤其涉及一种无磷无卤的阻燃聚酯片材及其制备方法。
背景技术
聚酯片材（PET）以聚对苯二甲酸乙二酯为主要原料，是一种性能比较全面的材料。其透明性好、光泽度高。相比于一般片材，聚酯片材具有更优良的机械性能。聚酯片材还具有优良的电绝缘性能、耐弱酸性和耐油性，同时还有无毒、抗化学药品稳定性好，吸水率低等优点。聚酯片材因具有诸多优点而被作为各类食品、药品、无毒无菌的包装材料；纺织品、精密仪器、电器元件的高档包装材料；录音带、录像带、电影胶片、计算机软盘、金属镀膜及感光胶片等的基材，也应用于电气绝缘材料、电容器膜、柔性印刷电路板及片材开关等电子领域和机械领域。
不过聚酯耐温性较差，比较容易燃烧，从而影响了聚酯片材的使用安全性。通常的方法是在聚酯片材中添加阻燃剂。目前常用的阻燃剂通常含有卤素或者磷。如CN201210094955.9公开了一种磷硅氟阻燃共聚酯薄膜的制备方法；CN201310005742.9公开了一种阻燃发泡型反射用聚酯薄膜，其采用的阻燃剂多含卤素或者磷。含卤素或者磷的阻燃效果明显但是对环境危害也比较大，如含卤阻燃材料在燃烧时产生二恶英，能在环境中存在多年，甚至终身累积于生物体；磷会导致水质的富营养化，严重污染水源。因此提供了一种环保、阻燃性能好、制备工艺简单的聚酯片材是本发明所要解决的问题。
发明内容
本发明克服了现有技术的不足，提供了一种环保、阻燃性能好、制备工艺简单的聚酯片材。
为达到上述目的，本发明采用的技术方案为：提供了一种无磷无卤的阻燃聚酯片材，包括聚酯基材以及涂覆在所述聚酯基材表面的阻燃涂层，其特征在于：所述阻燃涂层含有11-25%（重量百分比）的无磷无卤阻燃剂、74.5-88%（重量百分比）的聚丙烯酸酯。所述无磷无卤阻燃剂由聚丙烯酸钠和聚碳酸丙烯酯组成。
作为一种优选方案，所述无磷无卤阻燃剂的组成（重量百分比）为：聚丙烯酸钠30-70%，聚碳酸丙烯酯30-70%。
作为一种优选方案，所述无磷无卤阻燃剂的含量（重量百分比）为13-15%。
作为一种优选方案，所述阻燃涂层还含有0.5-2%（重量百分比）的MF分散剂。
作为一种更优选方案，所述聚丙烯酸钠具有网状分子结构。
作为一种更优选方案，所述聚丙烯酸酯为溶剂型聚丙烯酸酯，由甲基丙烯酸甲酯、丙烯酸丁酯以及苯乙烯聚合而成。
作为一种更优选方案，所述聚酯基材组成和含量（重量百分比）为：聚对苯二甲酸乙二酯占70-84%、聚对苯二甲酸丁二酯占9-23%、玻璃纤维占1-3%、抗氧化剂占0.5-2%、增韧剂占0.5-1.5%、抗静电剂占0.25-1.2%以及光稳定剂占0.5-2%。
作为一种更优选方案，所述抗氧化剂为抗氧化剂1010或抗氧化剂1076的一种；所述抗静电剂为三羟乙基甲基季铵甲基硫酸盐或十八烷基二甲基季铵硝酸盐的一种；所述光稳定剂为苯并三唑、二苯甲酮或水杨酸酯的一种；所述增韧剂为乙烯-醋酸乙烯共聚物。
本发明还提供了上述无磷无卤的阻燃聚酯片材的制备方法，其特征在于，包括以下步骤：
（1）将有机溶剂加入容器中，称取无磷无卤阻燃剂、聚丙烯酸酯加入有机溶剂中搅拌均匀，搅拌时间为20-40min，温度控制在17-27℃，得到涂层液；
（2）将所述涂层液采用辊涂的方式涂覆到聚酯片材的两侧，在55-90℃烘干30-70min得到无磷无卤的阻燃聚酯片材。
作为一种优选方案，所述有机溶剂为乙酸乙酯或者丙酮的一种；所述辊涂方式为：将涂层液加到聚酯片材表面，之后聚酯片材以13-23m/min恒速通过挤压辊，所述挤压辊给聚酯片材施加0.5-2.5kg的压力。
本发明的有益技术效果在于：提供了一种环保、阻燃性能好、制备工艺简单的聚酯片材。本发明提供的聚酯片材基材表面涂覆含有无磷无卤阻燃剂的涂层，无磷无卤阻燃剂由聚丙烯酸钠和聚碳酸丙烯酯组成。聚丙烯酸钠具有网络分子结构，能很好地起到吸湿和保湿作用，从而一定程度上降低了聚酯片材周边环境的温度，增加了湿度，提高了聚酯片材的阻燃性；而聚碳酸丙烯酯在燃烧条件下会受热分解产生大量二氧化碳，从而稀释了聚酯片材周边环境中的氧浓度，达到阻燃的目的。由聚丙烯酸钠和聚碳酸丙烯酯组成的阻燃剂不仅能有效的起到阻燃的作用，且不含卤素和磷，解决了污染环境的问题。同时采用表面涂覆的方法制备工艺更加简单，方便，有利于提高工作效率、降低生产成本。另外在涂层中使用聚丙烯酸酯，有效地提高了阻燃剂与聚酯基材的结合度。
具体实施方式
下面结合具体实施例对本发明作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。
实施例1
本发明提供了一种无磷无卤的阻燃聚酯片材，片材基材的组成如下（重量百分比）：
聚对苯二甲酸乙二酯占78%、聚对苯二甲酸丁二酯占18%、玻璃纤维占1%、抗氧化剂1010占1%、乙烯-醋酸乙烯共聚物占0.5%、十八烷基二甲基季铵硝酸盐占0.9%、二苯甲酮占0.6%。
聚酯片材基材表面涂覆有含无磷无卤阻燃剂的涂层，涂层含有15%（重量百分比）的无磷无卤阻燃剂、83%（重量百分比）的聚丙烯酸酯以及2%（重量百分比）的MF分散剂。其中无磷无卤阻燃剂由40%（重量百分比）的聚丙烯酸钠和60%（重量百分比）的聚碳酸丙烯酯组成，聚丙烯酸钠具有网状分子结构，有利于吸湿并包裹水分。聚丙烯酸酯为溶剂型，由甲基丙烯酸甲酯、丙烯酸丁酯以及苯乙烯聚合而成。
无磷无卤的阻燃聚酯片材按照如下方法进行制备：
（1）将丙酮乙酯加入容器中，称取无磷无卤阻燃剂、聚丙烯酸酯等原料加入其中搅拌均匀，搅拌25min，温度控制在24℃，得到涂层液；
（2）将涂层液采用辊涂的方式涂覆到聚酯片材的两侧，即将涂层液加到聚酯片材表面，之后聚酯片材以15m/min恒速通过挤压辊，所述挤压辊给聚酯片材施加2kg的压力。辊涂完成之后在65℃条件下烘干60min得到无磷无卤的阻燃聚酯片材。
实施例2
本发明提供了一种无磷无卤的阻燃聚酯片材，片材基材的组成如下（重量百分比）：
聚对苯二甲酸乙二酯占82%、聚对苯二甲酸丁二酯占12%、玻璃纤维占2%、抗氧化剂1076占1.5%、乙烯-醋酸乙烯共聚物占1%、三羟乙基甲基季铵甲基硫酸盐占0.5%、水杨酸酯占1%。
聚酯片材基材表面涂覆有含无磷无卤阻燃剂的涂层，涂层含有20%（重量百分比）的无磷无卤阻燃剂、78.5%（重量百分比）的聚丙烯酸酯以及1.5%（重量百分比）的MF分散剂。其中无磷无卤阻燃剂由30%（重量百分比）的聚丙烯酸钠和70%（重量百分比）的聚碳酸丙烯酯组成，聚丙烯酸钠具有网状分子结构，有利于吸湿并包裹水分。聚丙烯酸酯为溶剂型，由甲基丙烯酸甲酯、丙烯酸丁酯以及苯乙烯聚合而成。
无磷无卤的阻燃聚酯片材按照如下方法进行制备：
（1）将丙酮加入容器中，称取无磷无卤阻燃剂、聚丙烯酸酯等原料加入其中搅拌均匀，搅拌30min，温度控制在22℃，得到涂层液；
（2）将涂层液采用辊涂的方式涂覆到聚酯片材的两侧，即将涂层液加到聚酯片材表面，之后聚酯片材以18m/min恒速通过挤压辊，所述挤压辊给聚酯片材施加1.5kg的压力。辊涂完成之后在75℃条件下烘干50min得到无磷无卤的阻燃聚酯片材。
实施例3
本发明提供了一种无磷无卤的阻燃聚酯片材，片材基材的组成如下（重量百分比）：
聚对苯二甲酸乙二酯占80%、聚对苯二甲酸丁二酯占15%、玻璃纤维占1.5%、抗氧化剂1010占0.5%、乙烯-醋酸乙烯共聚物占1%、三羟乙基甲基季铵甲基硫酸盐占0.5%、二苯甲酮占1.5%。
聚酯片材基材表面涂覆有含无磷无卤阻燃剂的涂层，涂层含有11%（重量百分比）的无磷无卤阻燃剂、88%（重量百分比）的聚丙烯酸酯以及1%（重量百分比）的MF分散剂。其中无磷无卤阻燃剂由70%（重量百分比）的聚丙烯酸钠和30%（重量百分比）的聚碳酸丙烯酯组成，聚丙烯酸钠具有网状分子结构，有利于吸湿并包裹水分。聚丙烯酸酯为溶剂型，由甲基丙烯酸甲酯、丙烯酸丁酯以及苯乙烯聚合而成。
无磷无卤的阻燃聚酯片材按照如下方法进行制备：
（1）将乙酸乙酯加入容器中，称取无磷无卤阻燃剂、聚丙烯酸酯等原料加入其中搅拌均匀，搅拌20min，温度控制在27℃，得到涂层液；
（2）将涂层液采用辊涂的方式涂覆到聚酯片材的两侧，即将涂层液加到聚酯片材表面，之后聚酯片材以13m/min恒速通过挤压辊，所述挤压辊给聚酯片材施加2.5kg的压力。辊涂完成之后在55℃条件下烘干70min得到无磷无卤的阻燃聚酯片材。
实施例4
本发明提供了一种无磷无卤的阻燃聚酯片材，片材基材的组成如下（重量百分比）：
聚对苯二甲酸乙二酯占70%、聚对苯二甲酸丁二酯占23%、玻璃纤维占3%、抗氧化剂1076占2%、乙烯-醋酸乙烯共聚物占1.25%、三羟乙基甲基季铵甲基硫酸盐占0.25%、苯并三唑占0.5%。
聚酯片材基材表面涂覆有含无磷无卤阻燃剂的涂层，涂层含有25%（重量百分比）的无磷无卤阻燃剂、74.5%（重量百分比）的聚丙烯酸酯以及0.5%（重量百分比）的MF分散剂。其中无磷无卤阻燃剂由50%（重量百分比）的聚丙烯酸钠和50%（重量百分比）的聚碳酸丙烯酯组成，聚丙烯酸钠具有网状分子结构，有利于吸湿并包裹水分。聚丙烯酸酯为溶剂型，由甲基丙烯酸甲酯、丙烯酸丁酯以及苯乙烯聚合而成。
无磷无卤的阻燃聚酯片材按照如下方法进行制备：
（1）将丙酮加入容器中，称取无磷无卤阻燃剂、聚丙烯酸酯等原料加入其中搅拌均匀，搅拌35min，温度控制在19℃，得到涂层液；
（2）将涂层液采用辊涂的方式涂覆到聚酯片材的两侧，即将涂层液加到聚酯片材表面，之后聚酯片材以20m/min恒速通过挤压辊，所述挤压辊给聚酯片材施加0.5kg的压力。辊涂完成之后在82℃条件下烘干40min得到无磷无卤的阻燃聚酯片材。
实施例5
本发明提供了一种无磷无卤的阻燃聚酯片材，片材基材的组成如下（重量百分比）：
聚对苯二甲酸乙二酯占84%、聚对苯二甲酸丁二酯占9%、玻璃纤维占1.5%、抗氧化剂1010占0.8%、乙烯-醋酸乙烯共聚物占1.5%、十八烷基二甲基季铵硝酸盐占1.2%、苯并三唑占2%。
聚酯片材基材表面涂覆有含无磷无卤阻燃剂的涂层，涂层含有13%（重量百分比）的无磷无卤阻燃剂、85.8%（重量百分比）的聚丙烯酸酯以及1.2%（重量百分比）的MF分散剂。其中无磷无卤阻燃剂由60%（重量百分比）的聚丙烯酸钠和40%（重量百分比）的聚碳酸丙烯酯组成，聚丙烯酸钠具有网状分子结构，有利于吸湿并包裹水分。聚丙烯酸酯为溶剂型，由甲基丙烯酸甲酯、丙烯酸丁酯以及苯乙烯聚合而成。
无磷无卤的阻燃聚酯片材按照如下方法进行制备：
（1）将乙酸乙酯加入容器中，称取无磷无卤阻燃剂、聚丙烯酸酯等原料加入其中搅拌均匀，搅拌40min，温度控制在17℃，得到涂层液；
（2）将涂层液采用辊涂的方式涂覆到聚酯片材的两侧，即将涂层液加到聚酯片材表面，之后聚酯片材以23m/min恒速通过挤压辊，所述挤压辊给聚酯片材施加0.5kg的压力。辊涂完成之后在90℃条件下烘干30min得到无磷无卤的阻燃聚酯片材。
本发明提供的无磷无卤的阻燃聚酯片材，检测方法如下：
拉伸强度：按照GB/T1040-2006标准检测，测试温度为25℃；
防火等级：按照UL94防火等级评定。
测试结果如下：
表1 实施例1-5聚酯片材与普通聚酯片材力学性能和防火等级
样品 纵向拉伸强度（Mpa） 横向拉伸强度（Mpa） 防火等级
实施例1 190 193 VTM-0
实施例2 183 187 VTM-0
实施例3 193 196 VTM-1
实施例4 180 178 VTM-0
实施例5 190 192 VTM-0
普通聚酯片材 198 200 无等级
由表1结果可以看出：本发明提供的聚酯片材的阻燃等级均达到VTM-1的等级以上，表明本发明提供的聚酯片材出有良好的阻燃能力。同时由实验数据可以看出：无磷无卤阻燃剂的添加量越大，阻燃的效果越好，但是对力学性能会带来一定负面影响。无磷无卤阻燃剂的添加量在13-15%（质量百分数）所得到的聚酯片材效果最佳。
以上依据本发明的理想实施例为启示，通过上述的说明内容，相关人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定技术性范围。

Claims (10)

1.无磷无卤的阻燃聚酯片材，包括聚酯基材以及涂覆在所述聚酯基材表面的阻燃涂层，其特征在于：所述阻燃涂层含有11-25%（重量百分比）的无磷无卤阻燃剂、74.5-88%（重量百分比）的聚丙烯酸酯；所述无磷无卤阻燃剂由聚丙烯酸钠和聚碳酸丙烯酯组成。
2.根据权利要求1所述的无磷无卤的阻燃聚酯片材，其特征在于：所述无磷无卤阻燃剂的组成（重量百分比）为：聚丙烯酸钠30-70%，聚碳酸丙烯酯30-70%。
3.根据权利要求1或2所述的无磷无卤的阻燃聚酯片材，其特征在于：所述无磷无卤阻燃剂的含量（重量百分比）为13-15%。
4.根据权利要求1或2所述的无磷无卤的阻燃聚酯片材，其特征在于：所述阻燃涂层还含有0.5-2%（重量百分比）的MF分散剂。
5.根据权利要求4所述的无磷无卤的阻燃聚酯片材，其特征在于：所述聚丙烯酸钠具有网状分子结构。
6.根据权利要求4所述的无磷无卤的阻燃聚酯片材，其特征在于：所述聚丙烯酸酯为溶剂型聚丙烯酸酯，由甲基丙烯酸甲酯、丙烯酸丁酯以及苯乙烯聚合而成。
7.根据权利要求4所述的无磷无卤的阻燃聚酯片材，其特征在于：所述聚酯基材组成和含量（重量百分比）为：聚对苯二甲酸乙二酯占70-84%、聚对苯二甲酸丁二酯占9-23%、玻璃纤维占1-3%、抗氧化剂占0.5-2%、增韧剂占0.5-1.5%、抗静电剂占0.25-1.2%以及光稳定剂占0.5-2%。
8.根据权利要求7所述的无磷无卤的阻燃聚酯片材，其特征在于：所述抗氧化剂为抗氧化剂1010或抗氧化剂1076的一种；所述抗静电剂为三羟乙基甲基季铵甲基硫酸盐或十八烷基二甲基季铵硝酸盐的一种；所述光稳定剂为苯并三唑、二苯甲酮或水杨酸酯的一种；所述增韧剂为乙烯-醋酸乙烯共聚物。
9.如权利要求1所述的无磷无卤的阻燃聚酯片材的制备方法，其特征在于，包括以下步骤：
（1）将有机溶剂加入容器中，称取无磷无卤阻燃剂、聚丙烯酸酯加入有机溶剂中搅拌均匀，搅拌时间为20-40min，温度控制在17-27℃，得到涂层液；
（2）将所述涂层液采用辊涂的方式涂覆到聚酯片材的两侧，在55-90℃烘干30-70min得到无磷无卤的阻燃聚酯片材。
10.根据权利要求9所述的无磷无卤的阻燃聚酯片材的制备方法，其特征在于：所述有机溶剂为乙酸乙酯或者丙酮的一种；所述辊涂方式为：将涂层液加到聚酯片材表面，之后聚酯片材以13-23m/min恒速通过挤压辊，所述挤压辊给聚酯片材施加0.5-2.5kg的压力。
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