CN114426802A - 可热封橡塑复合胶布的制造方法及其制品 - Google Patents

可热封橡塑复合胶布的制造方法及其制品 Download PDF

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CN114426802A
CN114426802A CN202210124563.6A CN202210124563A CN114426802A CN 114426802 A CN114426802 A CN 114426802A CN 202210124563 A CN202210124563 A CN 202210124563A CN 114426802 A CN114426802 A CN 114426802A
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layer
chlorosulfonated polyethylene
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韩双
贾书刚
任洪利
张红霞
朱金萍
梁迎超
梁欣悦
任玮
霍晓兵
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Beijing Bangwei High Tech New Material Technology Co ltd
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Abstract

本发明为可热封橡塑复合胶布的制造方法及其制品，该制造方法包括以下步骤：(1)通过压延工艺将溴化丁基橡胶均匀压延到骨架织物上，即制成溴化丁基橡胶布；(2)再通过压延工艺将氯磺化聚乙烯橡胶均匀压延到溴化丁基橡胶布上，即制成双层橡胶复合胶布；氯磺化聚乙烯橡胶中氯磺化聚乙烯橡胶母胶与硫化体系的质量比为100：4～6；(3)将双层橡胶复合胶布共硫化工艺处理；(4)将双层橡胶复合胶布的非橡胶一面粘接在高分子膜的电晕面上，所述的胶粘剂为水性聚氨酯粘合剂，即制成所述的可热封橡塑复合胶布。

Description

可热封橡塑复合胶布的制造方法及其制品
技术领域
本发明涉及的是一种功能胶布，具体为一种橡塑复合胶布的制造方法及其制品。
背景技术
目前市面上化学防护服材料主要分为合成橡胶类和高分子膜类。其中，橡胶具有柔软、耐用性好、耐磨性好的特点，但比重大，穿着较累，且对工业化学物质(强酸、强碱及有机溶剂)的耐腐蚀性较差；橡胶的加工方式多为涂覆工艺，该方法存在成本高、效率低、污染环境的缺点。而高分子膜类具有耐腐蚀性能优异、质量轻的优点，但耐磨性差，手感硬，穿着舒适性差。
如CN 201210158136.6一种橡塑复合胶布的制备方法及其制品，采用溴化丁基橡胶/尼龙布/聚偏二氯乙烯膜/尼龙布四层结构，该橡胶布为单层橡胶加工，刮涂工艺涂覆，刮涂需要使用大量溶剂溶解橡胶再去涂覆织物，溶解周期时间较长，溶剂多为甲苯、二甲苯之类的有毒溶剂，膜在内层与橡胶一同硫化，重量高，主要用于做防护靴。由于制作化学防护服时对接缝部位的密封要求是极高的，化学防护服接缝部位采用先缝纫后贴条的方式加工，在尼龙布层贴防护胶条，穿过针眼部位的有害化学品接触内部尼龙布后通过尼龙布的芯吸作用沿四周扩散、渗透，因此尼龙布层贴条是无法起到防护作用，针对腐蚀、渗透性极强的化学品紧靠外层贴条是难以满足防护要求的，且传统橡胶贴条方式为手工刷胶冷粘贴条，生产效率较低。因此，现有的化学防护服材料已不能满足工业不断发展和生活不断进步的实际需求。
发明内容
为解决上述技术问题，本发明的目的是，提供一种可热封橡塑复合胶布的制造方法及其制品，该橡塑复合胶布主要用于制作防止化学品渗透的防护服，既具有较好的防止有害化学品渗透的性能，又具有耐磨、阻燃、质轻的特点，手感柔软，穿着舒适；防护服内外层均可实现热封贴条技术，可满足防护服的成型工艺需要及实际使用需求。该制造方法简单，生产效率高，成本低，易于工业化实施。
为实现上述目的，本发明的技术方案是：
一种可热封橡塑复合胶布的制造方法，该制造方法包括以下步骤：
(1)通过压延工艺将溴化丁基橡胶均匀压延到骨架织物上，即制成溴化丁基橡胶布；
(2)再通过压延工艺将氯磺化聚乙烯橡胶均匀压延到溴化丁基橡胶布上，即制成双层橡胶复合胶布；氯磺化聚乙烯橡胶中氯磺化聚乙烯橡胶母胶与硫化体系的质量比为100：4～6；
(3)将双层橡胶复合胶布共硫化工艺处理；
(4)将双层橡胶复合胶布的非橡胶一面粘接在高分子膜的电晕面上，所述的胶粘剂为水性聚氨酯粘合剂，即制成所述的可热封橡塑复合胶布。
步骤(4)中所述水性聚氨酯粘合剂的固含量为38％～42％，上胶量为30g/m2～50g/m2，复合辊压力为0.2MPa～0.6MPa，温度为50℃～60℃，高分子膜的单面电晕值为38dyn～43dyn；优选水性聚氨酯粘合剂的粘度为800mPa·s～1500mPa·s。
所述步骤(3)共硫化工艺为鼓式硫化机硫化，硫化温度为150℃～170℃，硫化时间为10min～15min，压力为16MPa～20MPa。
本发明还保护上述制造方法获得的可热封橡塑复合胶布，该胶布为四层结构：由外至内依次为外防护层1、外防护层2、骨架层3和内防护层4。所述的外防护层1为氯磺化聚乙烯橡胶层；所述的外防护层2为溴化丁基橡胶层；所述的骨架层3为骨架织物层；所述的内防护层4为聚氟乙烯膜、聚偏二氟乙烯膜、聚四氟乙烯膜中的至少一种；所述骨架层包括芳纶织物、阻燃平纹尼龙绸、阻燃涤纶等具备离火自熄的阻燃性能和高于1500N的强力、且克重低于130g/m2要求的骨架织物，如阻燃平纹尼龙绸克重为(100±10)g/m2，强力高于1500N。
上述氯磺化聚乙烯橡胶中氯磺化聚乙烯橡胶母胶与硫化体系的质量比为100：4～6，所述硫化体系至少包括活性氧化镁、氧化锌、季戊四醇及DPTT(四硫化双戊撑秋兰姆促进剂)四种物质。这种橡胶配方能够改变硫化橡胶表面对温度的敏感性，实现了氯磺化聚乙烯橡胶可热封成型技术，兼具良好的耐磨性，满足GB 24539-2009要求，本发明这种氯磺化聚乙烯橡胶耐介质性优异，设计在材料最外层，解决了溴化丁基橡胶遇强酸后表面发粘及橡胶材质的化学防护服成型加工慢、外观差的问题。
所述步骤(1)中溴化丁基橡胶将杂质过滤，其配方中添加了高效卤素、氧化物阻燃复配体系，溴化丁基橡胶中溴化丁基橡胶母胶与阻燃复配体系的质量配比为10:3.5～4.5，阻燃复配体系具体可为十溴联苯乙烷、三氧化二锑、氢氧化铝及氯化石蜡，溴化丁基橡胶在保证高防护、低克重的条件下实现了橡塑复合材料的协同阻燃功能。
本发明制造方法通过压延工艺先将两层橡胶复合，共硫化后再与高分子膜结合，无需溶剂，相对而言更加快速、环保，且在保证防护性能和阻燃性能的前提下使得整体质量更轻，制备的橡塑胶布重量为600g/m2～800g/m2，且显著改善材料的手感，进而有助于加工成服装，穿着舒适性更好，满足相应规定的国标要求。本发明结合了橡胶的柔软、耐腐蚀、耐磨性好等优点与防护性能更好的高分子膜并用制备，采用的是氯磺化聚乙烯橡胶/溴化丁基橡胶/骨架织物/高分子膜，其中氯磺化聚乙烯橡胶与溴化丁基橡胶均采用压延工艺复合在骨架织物上，具有生产效率高、低成本的特点。溴化丁基橡胶与高分子膜主要起防止危化品渗透的作用。
与现有技术相比，本发明的有益效果在于：
本发明制造方法工艺简单，生产效率高，无需使用甲苯等有毒溶剂溶解胶浆，加工成本低，易于工业化实施；该制造方法所制造双层橡胶结构的橡塑复合胶布，既具有较好的防止有害化学品渗透的性能，又具有耐磨、阻燃、质轻的特点，手感柔软，穿着舒适。该制造方法所制造的外层橡胶具备热封成型技术，将传统手工冷粘成型转化为机械加工，大大提高了服装的生产效率，同时也提升了防护可靠性与美观度，可满足实际需求。
附图说明
图1为本发明制造方法的工艺流程图。
图2为本发明复合胶布的结构示意图。
具体实施方式
下面结合实施例及附图进一步解释本发明，但并不以此作为对本申请保护范围的限定。
本发明设计的一种可热封橡塑复合胶布的制造方法，该胶布为四层结构：由外至内依次为外防护层1、外防护层2、骨架层3和内防护层4。所述的外防护层1为氯磺化聚乙烯橡胶层；所述的外防护层2为溴化丁基橡胶层；所述的骨架层3为芳纶布层；所述的内防护层4为聚氟乙烯膜层；该制造方法包括以下工艺：
(1)通过压延工艺将溴化丁基橡胶均匀压延到芳纶织物上，即制成溴化丁基橡胶布。所述的溴化丁基橡胶层的厚度为0.20mm～0.25mm。
所述的芳纶织物，自身具备阻燃性能，重量为(100±10)g/m2，强力大于2200N，主要提供阻燃及基本的物理机械性能指标，满足制造产品的需要。
所述的溴化丁基橡胶，具有高饱和聚异丁烯主链，结构致密，因而具有低渗透性、耐腐蚀、耐热和耐臭氧等特点。此外，溴化丁基橡胶配方中添加了高效卤素、氧化物阻燃复配体系，本发明配方中的溴化丁基橡胶母胶与阻燃复配体系的配比为10:3.5～4.5，包括但不限于10:3.5、10:3.8、10:4、10:4.2、10:4.5，溴化丁基橡胶可达到离火自熄。阻燃复配体系至少包括十溴联苯乙烷、三氧化二锑及氯化石蜡，三者的质量比为(1～1.2):(0.8～1):1，还可以包括其他种类的阻燃剂，如氢氧化铝、硼酸锌、氢氧化镁等中的至少一种，溴化丁基橡胶在保证高防护、低克重的条件下实现了橡塑复合材料的协同阻燃功能，达到防护和阻燃的平衡。压延机的加工温度是压延溴化丁基橡胶的重要工序，关键是调试合适的加工温度及配合相匹配的脱模剂。本发明优选使用三辊压延机，上辊温度70℃～80℃，中辊温度60℃～70℃，下辊温度70℃～80℃，脱模剂为PEG-4000及PA-20，避免了在压延过程中，压延机加工温度过高，溴化丁基橡胶出现粘辊现象，而温度过低，又难以控制压延厚度的弊端。
(2)再通过压延工艺将氯磺化聚乙烯橡胶均匀压延到溴化丁基橡胶布上，即制成双层橡胶复合胶布。压延温度在80℃～90℃时，能够使得第二层橡胶压延处理时不会导致第一层橡胶与骨架织物发生分离，所述的氯磺化聚乙烯橡胶的厚度设计为0.08mm～0.10mm，优选厚度为0.085mm、0.090mm、0.095mm、0.099mm等。
(3)将双层橡胶复合胶布共硫化工艺处理，鼓式硫化机硫化，硫化温度为150℃～170℃，硫化时间为10min～15min，压力为16MPa～20MPa。
本发明的双层结构橡胶复合胶布可采用鼓式硫化机共硫化处理、罐式硫化处理等，相比于罐式硫化机，鼓式硫化机硫化的橡胶布具有结构更加致密，可根据客户需求制作亚光、亮面等外观的特点。由于双层结构是不同种类的橡胶，因此硫化温度和时间要同时适合两种橡胶。本发明设计的硫化温度为150℃～170℃，优选硫化温度为155℃、160℃、165℃、168℃等，硫化时间为10min～15min，压力为16MPa～20MPa。
(4)将双层橡胶复合胶布的非橡胶一面粘接在聚氟乙烯膜电晕面上，所述的胶粘剂为水性聚氨酯粘合剂，固含量为38％～42％，粘度800mPa·s～1500mPa·s；上胶量为30g/m2～50g/m2，复合辊压力为0.2MPa～0.6MPa，温度为50℃～60℃，聚氟乙烯膜为38dyn～43dyn，即制成本发明所述的橡塑复合胶布。
本发明所述的高分子膜的厚度不超过50μm，优选高分子膜厚度为30μm～50μm，对有害化学品有很好的化学稳定性，可以有效防止有害化学品的渗透及腐蚀，尤其是对强酸、强碱、战争毒剂的防护效果显著。
本发明实施例的橡塑复合胶布厚度为0.47mm～0.52mm，重量为600g/m2～800g/m2，优选重量为620g/m2～720g/m2用于制备化学防护服，可使防护服产品对有毒有害化学品有很好的防护性能。经试验验证，本发明制造的橡塑复合胶布对GB 24539-2009中要求15种化学品及芥子气的防护时间可达到60min以上，续燃时间与阴燃时间之和＜5s，损毁长度＜2cm，且重量轻、穿着舒适、耐用性好，适于工业生产和实际生活使用。
本发明所述的水性聚氨酯粘合剂为市售飞顿科技公司12870型水性聚氨酯粘合剂、拜耳公司XP2578型等。
实施例1
(1)通过压延工艺将溴化丁基橡胶均匀压延到芳纶织物上，形成溴化丁基橡胶布。芳纶织物重量为105g/m2，溴化丁基橡胶的厚度为0.21mm。使用三辊压延机，上辊温度75℃，中辊温度65℃，下辊温度75℃。溴化丁基橡胶母胶与阻燃体系的配比为10:4，阻燃复配体系为十溴联苯乙烷、三氧化二锑及氯化石蜡三者的混合物。溴化丁基橡胶在压延前需要进行过滤处理，去掉杂质。
(2)再通过压延工艺将氯磺化聚乙烯橡胶均匀压延到溴化丁基橡胶布上，形成双层橡胶复合胶布。氯磺化聚乙烯橡胶的厚度为0.10mm。氯磺化聚乙烯橡胶中氯磺化聚乙烯橡胶母胶与硫化体系的质量比为100：5。氯磺化聚乙烯橡胶在压延前需要进行过滤处理，去掉杂质。
(3)将双层橡胶复合胶布共硫化工艺处理，鼓式硫化机硫化，硫化温度为160℃，硫化时间为13min，压力为18MPa。
(4)聚氟乙烯膜厚度为30μm，将双层橡胶复合胶布的非橡胶一面使用粘接在聚氟乙烯膜电晕面上，胶粘剂为市售飞顿科技公司12870型水性聚氨酯粘合剂，上胶量为35g/m2，复合辊压力为0.35MPa，温度为50℃，聚氟乙烯膜单面电晕值为39dyn，即制成本发明所述的橡塑复合胶布。该胶布的厚度为0.48mm，重量为642g/m2。
实施例2
(1)通过压延工艺将混炼过滤后的溴化丁基橡胶均匀压延到芳纶织物上，形成溴化丁基橡胶布。芳纶织物重量为98g/m2，溴化丁基橡胶的厚度为0.24mm。
(2)再通过压延工艺将混炼过滤后的氯磺化聚乙烯橡胶均匀压延到溴化丁基橡胶布上，形成双层橡胶复合胶布。氯磺化聚乙烯橡胶的厚度为0.08mm。
(3)将双层橡胶复合胶布共硫化工艺处理，鼓式硫化机硫化，硫化温度为168℃，硫化时间为10min，压力为20MPa。
(4)聚氟乙烯膜厚度为48μm，将双层橡胶复合胶布的非橡胶一面使用粘接在聚氟乙烯膜电晕面上，胶粘剂为水性聚氨酯粘合剂，上胶量为46g/m2，复合辊压力为0.35MPa，温度为51℃，单面电晕值为42dyn，即制成本发明所述的橡塑复合胶布。该胶布的厚度为0.51mm，重量为695g/m2。
实施例3
本实施例采用实施例1的橡塑复合胶布制作防护服，氯磺化聚乙烯橡胶配方中，氯磺化聚乙烯橡胶母胶与硫化体系(活性氧化镁、氧化锌、季戊四醇及DPTT)配比为100：5.5，鼓式硫化机硫化，硫化温度为165℃，硫化时间为10min，压力为18MPa。硫化后的氯磺化聚乙烯橡胶与实施例1获得的橡塑复合胶布的氯磺化聚乙烯橡胶表层热封贴合，形成防护服，剥离牢度为13.3N/cm。
实施例4
本实施例采用实施例1的橡塑复合胶布制作防护服，氯磺化聚乙烯橡胶配方中，氯磺化聚乙烯橡胶母胶与硫化体系(活性氧化镁、季戊四醇及DPTT)配比为100：5.5，鼓式硫化机硫化，硫化温度为165℃，硫化时间为10min，压力为18MPa。硫化后的氯磺化聚乙烯橡胶与实施例1中获得的橡塑复合胶布的氯磺化聚乙烯橡胶表层热封贴合，形成防护服，剥离牢度为11.1N/cm。
实施例5
本实施例各部分同实施例1，不同之处在于，溴化丁基橡胶母胶与阻燃复配体系的质量配比为10:3.6，阻燃复配体系为十溴联苯乙烷、三氧化二锑及氯化石蜡、氢氧化铝的混合物。四者质量相等。经测试，橡塑复合胶布的续燃与阴燃时间之和为3.4s，损毁长度为0.8cm。
实施例6
本实施例各部分同实施例1，不同之处在于，本实施例的高分子膜为聚四氟乙烯膜，厚度为30μm。
经试验验证，上述实施例制造的橡塑复合胶布对GB 24539-2009中要求15种化学品及芥子气的防护时间可达到60min以上，续燃时间与阴燃时间之和＜5s，损毁长度＜2cm，且重量轻、穿着舒适、耐用性好。
对比例1
本对比例采用实施例1的橡塑复合胶布制作防护服，氯磺化聚乙烯橡胶配方中，氯磺化聚乙烯橡胶母胶与硫化体系(由活性氧化镁、氧化锌、季戊四醇及DPTT四者构成)配比为100：2.5，鼓式硫化机硫化，硫化温度为165℃，硫化时间为10min，压力为18MPa。硫化后的氯磺化聚乙烯橡胶与实施例1获得的橡塑复合布的氯磺化聚乙烯橡胶表层热封贴合，形成防护服，剥离牢度为6.7N/cm。
对比例2
本对比例采用实施例1的橡塑复合胶布制作防护服，氯磺化聚乙烯橡胶配方中，氯磺化聚乙烯橡胶母胶与硫化体系(活性氧化镁、氧化锌、季戊四醇及DPTT)配比为100：9，鼓式硫化机硫化，硫化温度为165℃，硫化时间为10min，压力为18MPa。硫化后的氯磺化聚乙烯橡胶与实施例1获得的橡塑复合布的氯磺化聚乙烯橡胶表层热封贴合，形成防护服，剥离牢度为4.8N/cm。
对比例3
采用专利CN201210158138.5中的氯磺化聚乙烯橡胶布，使用实施例3中的硫化后的氯磺化聚乙烯橡胶与该橡塑复合胶布的氯磺化聚乙烯橡胶表层热封贴合，剥离牢度为1.5N/cm。
本发明未述及之处适用于现有技术。

Claims (10)

1.一种可热封橡塑复合胶布的制造方法，该制造方法包括以下步骤：
(1)通过压延工艺将混炼好的溴化丁基橡胶均匀压延到骨架织物上，即制成溴化丁基橡胶布；
(2)再通过压延工艺将混炼好的氯磺化聚乙烯橡胶均匀压延到溴化丁基橡胶布上，即制成双层橡胶复合胶布；混炼好的氯磺化聚乙烯橡胶中氯磺化聚乙烯橡胶与硫化体系的质量比为100：4～6；
(3)将双层橡胶复合胶布共硫化工艺处理；
(4)将双层橡胶复合胶布的非橡胶一面粘接在高分子膜的电晕面上，所述的胶粘剂为水性聚氨酯粘合剂，即制成所述的可热封橡塑复合胶布。
2.根据权利要求1所述的制造方法，其特征在于，步骤(4)中所述水性聚氨酯粘合剂的固含量为38％～42％，上胶量为30g/m2～50g/m2，复合辊压力为0.2MPa～0.6MPa，温度为50℃～60℃，高分子膜的单面电晕值为38dyn～43dyn；优选水性聚氨酯粘合剂的粘度为800mPa·s～1500mPa·s。
3.根据权利要求1所述的制造方法，其特征在于，所述步骤(3)共硫化工艺为鼓式硫化机硫化，硫化温度为150℃～170℃，硫化时间为10min～15min，压力为16MPa～20MPa。
4.根据权利要求1所述的制造方法，其特征在于，所述硫化体系至少包括活性氧化镁、氧化锌、季戊四醇及DPTT。
5.根据权利要求1所述的制造方法，其特征在于，所述混炼好的溴化丁基橡胶配方中添加了高效卤素、氧化物阻燃复配体系，溴化丁基橡胶与阻燃复配体系的质量配比为10:3.5～4.5，阻燃复配体系至少包括十溴联苯乙烷、三氧化二锑及氯化石蜡，保证防护阻燃的协同阻燃效果；步骤(1)使用三辊压延机，上辊温度70℃～80℃，中辊温度60℃～70℃，下辊温度70℃～80℃，脱模剂为PEG-4000、PA-20中的至少一种；优选地，所述阻燃复配体系还包括氢氧化铝、硼酸锌、氢氧化镁中的至少一种；十溴联苯乙烷、三氧化二锑及氯化石蜡的质量比为(1-1.2):(0.8-1):1。
6.根据权利要求1所述的制造方法，其特征在于，橡塑复合胶布厚度为0.47mm～0.52mm，重量为600g/m2～800g/m2，用于制备化学防护服，对GB 24539-2009中要求15种化学品及芥子气的防护时间能达到60min以上，续燃时间与阴燃时间之和＜5s，损毁长度＜2cm。
7.一种可热封橡塑复合胶布，采用权利要求1-6任一所述制造方法获得，其特征在于，该胶布为四层结构：由外至内依次为外防护层、外防护层、骨架层和内防护层，所述的外防护层为氯磺化聚乙烯橡胶层；所述的外防护层为溴化丁基橡胶层；所述的骨架层为骨架织物层；所述的内防护层为聚氟乙烯膜、聚偏二氟乙烯膜、聚四氟乙烯膜中的至少一种；所述骨架层为具备离火自熄的阻燃性能和高于1500N的强力、且低于130g/m2克重要求的骨架织物。
8.根据权利要求7所述的可热封橡塑复合胶布，其特征在于，所述骨架层为芳纶织物、阻燃平纹尼龙绸、阻燃涤纶；所述的氯磺化聚乙烯橡胶的厚度为0.08mm～0.10mm；所述的高分子膜厚度为30μm～50μm；溴化丁基橡胶的厚度为0.20mm～0.25mm。
9.一种制品，其特征在于，该制品采用权利要求1-6任一所述的制造方法获得的橡塑复合胶布制得，或者采用权利要求7或8所述的可热封橡塑复合胶布制得。
10.根据权利要求9所述的制品，其特征在于，所述制品为防护服，氯磺化聚乙烯橡胶中氯磺化聚乙烯橡胶母胶与硫化体系的质量比为100：4～6，采用权利要求3所述的鼓式硫化机硫化，使用氯磺化聚乙烯橡胶对防护服的氯磺化聚乙烯橡胶表层热封贴合，二者的剥离牢度为不低于7.5N/cm。
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US4190685A (en) * 1977-12-08 1980-02-26 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence Chemical resistant article
CN102642264A (zh) * 2012-05-21 2012-08-22 北京邦维高科特种纺织品有限责任公司 一种橡胶布的制造方法
CN102642351A (zh) * 2012-05-21 2012-08-22 北京邦维高科特种纺织品有限责任公司 一种橡塑复合胶布及其制备方法
US20150033801A1 (en) * 2011-07-08 2015-02-05 Mattias Finzelberg Protective Glove Having Textile Inner Lining

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190685A (en) * 1977-12-08 1980-02-26 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence Chemical resistant article
US20150033801A1 (en) * 2011-07-08 2015-02-05 Mattias Finzelberg Protective Glove Having Textile Inner Lining
CN102642264A (zh) * 2012-05-21 2012-08-22 北京邦维高科特种纺织品有限责任公司 一种橡胶布的制造方法
CN102642351A (zh) * 2012-05-21 2012-08-22 北京邦维高科特种纺织品有限责任公司 一种橡塑复合胶布及其制备方法

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