CN111778725A - 一种防护服 - Google Patents

一种防护服 Download PDF

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CN111778725A
CN111778725A CN202010450317.0A CN202010450317A CN111778725A CN 111778725 A CN111778725 A CN 111778725A CN 202010450317 A CN202010450317 A CN 202010450317A CN 111778725 A CN111778725 A CN 111778725A
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parts
finishing agent
protective clothing
protective
acrylic resin
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余也
潘跃
林晓华
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Zhejiang Ugly Duck Industry Co ltd
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Zhejiang Ugly Duck Industry Co ltd
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    • D06M13/256Sulfonated compounds esters thereof, e.g. sultones
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Abstract

本发明涉及服装的技术领域,公开了一种防护服,包括连体衣身,连体衣身表面经整理剂处理,整理剂包括如下重量份数的组分:30‑40份丙烯酸树脂;6‑8份磷酸三辛酯;2‑3份硼酸锌;2‑3份水杨酸;1‑2份表面活性剂;80‑100份去离子水。本发明具有以下优点和效果:磷酸三辛酯的添加最终可在防护服的纤维表面形成一层玻璃状保护膜,可隔绝防护服和氧的接触,起隔氧和隔热的作用,表面活性剂的添加可降低表面张力、促进丙烯酸树脂和各组分混合后成膜,提高膜的稳定性和耐久性;水杨酸具有捕获活性羟基自由基的能力,可抑制燃烧过程中的链锁反应;硼酸锌受热后可产生脱水分解,吸收大量热量,极大提升防护服的阻燃性能。

Description

一种防护服
技术领域
本发明涉及服装的技术领域,尤其是涉及一种防护服。
背景技术
许多生产车间,由于机器操作和生产条件的要求,常常处于高温状态,而许多化工产品的生产涉及到高危化学品的使用,由此化工生产车间成为了火灾和药品伤害发生的高概率区。除了必要的操作注意事项,一种更适合生产车间工人的阻燃防护服也亟待研究。
目前,公开号为CN111000302A的专利公开了一种防护服,包括防护衣和防护裤,防护衣的顶部一体裁剪有防护帽,防护衣的表面车缝连接有拉链,防护衣的袖口处均车缝连接有弹性袖口,两个弹性袖口的外表面均车缝连接有第一松紧带,防护裤的裤脚处均车缝连接有弹性裤脚;防护衣、防护裤和防护帽的原料主要为超高分子量聚乙烯纤维。
上述中的现有技术方案存在以下缺陷:防护服仅适用于普通的防护使用,对于化工生产车间中工人而言,不能实现阻燃效果,防护性能仍不完善,因此还有待改进。
发明内容
针对现有技术存在的不足,本发明的目的在于提供一种防护服,可完善化工生产车间中工人穿着的防护服的阻燃效果,优化防护服的防护性能。
为实现上述目的,本发明提供了如下技术方案:
一种防护服,包括连体衣身,所述连体衣身表面经整理剂处理,所述整理剂包括如下重量份数的组分:
30-40份丙烯酸树脂;
6-8份磷酸三辛酯;
2-3份硼酸锌;
2-3份水杨酸;
1-2份表面活性剂;
80-100份去离子水。
通过采用上述技术方案,磷酸三辛酯受热后分解成磷酸,磷酸脱水生成偏磷酸,偏磷酸聚合生成聚偏磷酸,最终聚偏磷酸覆盖在防护服的纤维表面形成一层玻璃状保护膜,可隔绝防护服和氧的接触,起隔氧和隔热的作用,从而对防护服起阻燃作用;表面活性剂的添加可降低表面张力、促进丙烯酸树脂和各组分混合后成膜,并使整理剂更易喷涂于连体衣身表面,且丙烯酸树脂的添加可提高膜的稳定性和耐久性;添加少量具有捕获活性羟基自由基能力的水杨酸,可抑制燃烧过程中活性较大的羟基自由基的链锁反应,达到阻燃目的;硼酸锌受热后可产生脱水分解,释放结晶水,吸收大量热量,从而可降低防护服表面的温度,达到较好的隔热阻燃效果,磷酸和聚偏磷酸均为强酸,又可促进硼酸锌的溶解,提高硼酸锌的分散均匀性,提升阻燃性能。
本发明在一较佳示例中可以进一步配置为:按重量份数计,所述整理剂还包括6-8份三甲基氯硅烷和0.2-0.3份过硫酸铵。
通过采用上述技术方案,在水杨酸的酸性作用下三甲基氯硅烷水解产生有机硅中间体六甲基二硅氧烷,引发剂过硫酸铵和表面活性剂的存在促使六甲基二硅氧烷和丙烯酸树脂发生聚合反应,通过该反应可得到含硅的聚合物乳液,具有互穿聚合物网络结构,可有效减小丙烯酸树脂成膜后的微观空隙,形成致密薄膜,具有极佳的稳定性,并可湿润纤维表面,降低表面张力,形成隔热和隔氧的屏障,达到较好的阻燃效果。
本发明在一较佳示例中可以进一步配置为:所述表面活性剂为马来酸酐十四醇丙磺酸钠。
通过采用上述技术方案,马来酸酐十四醇丙磺酸钠的添加有利于降低表面张力,促进成膜,也可润湿防护服的聚乙烯纤维的表面,提高整理剂成膜后在防护服上的附着力;且采用马来酸酐型表面活性剂,可有效提高固含量,同时水溶性较小的马来酸酐十四醇丙磺酸钠的添加有利于提高聚合物的聚合反应速率。
本发明在一较佳示例中可以进一步配置为:按重量份数计,所述整理剂还包括3-4份3-(甲基丙烯酰氧基)丙基三甲氧基硅烷。
通过采用上述技术方案,3-(甲基丙烯酰氧基)丙基三甲氧基硅烷可改善各组分的界面性能,显著加快乳液的混合偶联速度,促进组分成膜,并可提高稳定性以及丙烯酸树脂的固含量,从而形成稳定性好、拉伸强度高的液膜,成为隔热和隔氧的屏障,提高阻燃效果。
本发明在一较佳示例中可以进一步配置为:按重量份数计,所述整理剂还包括3-4份醋酸钙和0.1-0.2份L-脯氨酸。
通过采用上述技术方案,醋酸钙对磷化合物具有较强的吸附性,并可增加磷化合物在丙烯酸树脂的混合乳液中的分散均匀性,起提高整理剂的阻燃效果的作用;通过催化剂L-脯氨酸的作用,3-(甲基丙烯酰氧基)丙基三甲氧基硅烷具有的烯丙基活性不高,因此少量的3-(甲基丙烯酰氧基)丙基三甲氧基硅烷还可与活性较高的丙烯酸树脂产生接枝反应,一方面使整理剂组分成膜更稳定,另一方面,硅烷的接枝使整理剂组分与纤维产生亲和性,可润湿并吸附于防护服的聚乙烯纤维表面,由此,整理剂经多次水洗仍可保留大部分的有效成分,延长阻燃的防护服的使用寿命。
本发明在一较佳示例中可以进一步配置为:所述整理剂用磷酸氢钠调整pH至6-6.5。
通过采用上述技术方案,以pH值为6-6.5的整理剂整理好的防护服能经50次水洗,保留有效成分95%。
本发明在一较佳示例中可以进一步配置为:所述整理剂的制备方法如下:
S1.将表面活性剂和去离子水加入容器中,充分溶解;升温至70-80℃,加入丙烯酸树脂和磷酸三辛酯,搅拌20-25min,再加入硼酸锌和水杨酸,超声波的作用功率为200-240W,超声振荡5-8min;
S2.加入醋酸钙,搅拌5-10min,继续升温至80-120℃,加入过硫酸铵,搅拌均匀,然后在30-40min内缓慢滴加三甲基氯硅烷,继续搅拌0.5-1h;然后加入L-脯氨酸,搅拌下滴加3-(甲基丙烯酰氧基)丙基三甲氧基硅烷,在25-30min内滴加完毕,继续保温反应0.5-1h;
S3.最后用磷酸氢钠调整pH至6-6.5,70-80℃保温30-35min,再冷却至室温,得到整理剂。
通过采用上述技术方案,缓慢滴加三甲基氯硅烷,使三甲基氯硅烷可完全水解生成六甲基二硅氧烷,从而和丙烯酸树脂发生聚合反应;采用滴加方式添加3-(甲基丙烯酰氧基)丙基三甲氧基硅烷,使接枝反应更完全。
本发明在一较佳示例中可以进一步配置为:将所述整理剂通过80-120%的轧液率对连体衣身进行浸轧,再以100-120℃的温度预烘3-5min,再进行拉幅定型、预缩得到防护服。
综上所述,本发明包括以下至少一种有益技术效果:
1.磷酸三辛酯的添加最终可在防护服的纤维表面形成一层玻璃状保护膜,可隔绝防护服和氧的接触,起隔氧和隔热的作用,表面活性剂的添加可降低表面张力、促进丙烯酸树脂和各组分混合后成膜,提高膜的稳定性和耐久性;水杨酸具有捕获活性羟基自由基的能力,可抑制燃烧过程中的链锁反应;硼酸锌受热后可产生脱水分解,吸收大量热量,极大提升防护服的阻燃性能;
2.水杨酸的酸性作用下三甲基氯硅烷水解产生有机硅中间体六甲基二硅氧烷,引发剂过硫酸铵和表面活性剂的存在促使六甲基二硅氧烷和丙烯酸树脂发生聚合反应,通过该反应可得到含硅的聚合物乳液,具有互穿聚合物网络结构,可有效减小丙烯酸树脂成膜后的微观空隙,形成致密薄膜,达到较好的阻燃效果;
3.3-(甲基丙烯酰氧基)丙基三甲氧基硅烷可改善各组分的界面性能,提高稳定性以及丙烯酸树脂的固含量,形成稳定性好、拉伸强度高的液膜;通过催化剂L-脯氨酸的作用,活性不高的少量的3-(甲基丙烯酰氧基)丙基三甲氧基硅烷可与活性较高的丙烯酸树脂产生接枝反应,一方面使整理剂组分成膜更稳定,另一方面,使整理剂组分与纤维产生亲和性,可润湿并吸附于防护服的聚乙烯纤维表面,由此,整理剂经多次水洗仍可保留大部分的有效成分,延长阻燃的防护服的使用寿命;
4.马来酸酐十四醇丙磺酸钠的添加有利于降低表面张力,促进成膜,也可润湿防护服的聚乙烯纤维的表面,提高整理剂成膜后在防护服上的附着力;且采用马来酸酐型表面活性剂,可有效提高固含量,同时水溶性较小的马来酸酐十四醇丙磺酸钠的添加有利于提高聚合物的聚合反应速率;
5.醋酸钙对磷化合物具有较强的吸附性,并可增加磷化合物在丙烯酸树脂的混合乳液中的分散均匀性,起提高整理剂的阻燃效果的作用。
具体实施方式
以下对本发明作进一步详细说明。
本发明中,丙烯酸树脂购于北京恒业中远化工有限公司;3-(甲基丙烯酰氧基)丙基三甲氧基硅烷购于河南阿尔法化工有限公司;L-脯氨酸购于天津市百世化工有限公司,其余原料均为市售产品。
且本发明中,采用FT-IR对丙烯酸树脂、三甲基氯硅烷、水杨酸、过硫酸铵和马来酸酐十四醇丙磺酸钠反应后的产物进行结构表征,可以看出在1251cm-1处检测到Si-CH3的振动吸收峰,可见得到了含硅的聚合物。
利用红外谱图表征丙烯酸树脂、3-(甲基丙烯酰氧基)丙基三甲氧基硅烷和L-脯氨酸反应后的产物,在1717cm-1处有明显的羰基振动吸收峰,表明3-(甲基丙烯酰氧基)丙基三甲氧基硅烷接枝到了丙烯酸树脂上,并在1090cm-1附近有Si-O-R的伸缩振动峰,进一步显示了接枝的成功。
实施例
实施例1
本发明公开了一种防护服,包括连体衣身,连体衣身表面经整理剂处理,整理剂的制备方法如下:
S1.将表面活性剂和去离子水加入容器中,充分溶解;升温至70℃,加入丙烯酸树脂和磷酸三辛酯,搅拌20min,再加入硼酸锌和水杨酸,超声波的作用功率为200W,超声振荡5min;
S2.加入醋酸钙,搅拌5min,继续升温至80℃,加入过硫酸铵,搅拌均匀,然后在30min内缓慢滴加三甲基氯硅烷,继续搅拌0.5h;然后加入L-脯氨酸,搅拌下滴加3-(甲基丙烯酰氧基)丙基三甲氧基硅烷,在25min内滴加完毕,继续保温反应0.5h;
S3.最后用磷酸氢钠调整pH至6,70℃保温30min,再冷却至室温,得到整理剂。
将整理剂通过80%的轧液率对连体衣身进行浸轧,再以100℃的温度预烘3min,再进行拉幅定型、预缩得到防护服。
各组分含量如下表1所示。
实施例2
本发明公开了一种防护服,包括连体衣身,连体衣身表面经整理剂处理,整理剂的制备方法如下:
S1.将表面活性剂和去离子水加入容器中,充分溶解;升温至80℃,加入丙烯酸树脂和磷酸三辛酯,搅拌25min,再加入硼酸锌和水杨酸,超声波的作用功率为240W,超声振荡8min;
S2.加入醋酸钙,搅拌10min,继续升温至120℃,加入过硫酸铵,搅拌均匀,然后在40min内缓慢滴加三甲基氯硅烷,继续搅拌1h;然后加入L-脯氨酸,搅拌下滴加3-(甲基丙烯酰氧基)丙基三甲氧基硅烷,在30min内滴加完毕,继续保温反应1h;
S3.最后用磷酸氢钠调整pH至6.5,80℃保温35min,再冷却至室温,得到整理剂。
将整理剂通过120%的轧液率对连体衣身进行浸轧,再以120℃的温度预烘5min,再进行拉幅定型、预缩得到防护服。
各组分含量如下表1所示。
实施例3
本发明公开了一种防护服,包括连体衣身,连体衣身表面经整理剂处理,整理剂的制备方法如下:
S1.将表面活性剂和去离子水加入容器中,充分溶解;升温至75℃,加入丙烯酸树脂和磷酸三辛酯,搅拌24min,再加入硼酸锌和水杨酸,超声波的作用功率为220W,超声振荡6min;
S2.加入醋酸钙,搅拌8min,继续升温至100℃,加入过硫酸铵,搅拌均匀,然后在36min内缓慢滴加三甲基氯硅烷,继续搅拌1h;然后加入L-脯氨酸,搅拌下滴加3-(甲基丙烯酰氧基)丙基三甲氧基硅烷,在29min内滴加完毕,继续保温反应0.5h;
S3.最后用磷酸氢钠调整pH至6,76℃保温34min,再冷却至室温,得到整理剂。
将整理剂通过110%的轧液率对连体衣身进行浸轧,再以108℃的温度预烘4min,再进行拉幅定型、预缩得到防护服。
各组分含量如下表1所示。
对比例
对比例1
未经本发明的整理剂整理的防护服。
对比例2
与实施例1的区别在于,将丙烯酸树脂替换为聚氨酯乳液,各组分含量如下表2所示。
对比例3
与实施例1的区别在于,将表面活性剂马来酸酐十四醇丙磺酸钠替换为十二烷基硫酸钠,各组分含量如下表2所示。
对比例4
与实施例1的区别在于,将三甲基氯硅烷替换为乙烯基三甲氧基硅烷,各组分含量如下表2所示。
对比例5
与实施例1的区别在于,将3-(甲基丙烯酰氧基)丙基三甲氧基硅烷替换为三乙氧基硅烷,各组分含量如下表2所示。
对比例6
与实施例1的区别在于,不添加醋酸钙,各组分含量如下表2所示。
对比例7
与实施例1的区别在于,将L-脯氨酸替换为辛酸亚锡,各组分含量如下表2所示。
对比例8
与实施例1的区别在于,pH值为5。
对比例9
与实施例1的区别在于,pH值为7。
表1 各实施例的组分含量表
实施例1 实施例2 实施例3
丙烯酸树脂 30 40 36
磷酸三辛酯 6 8 7
硼酸锌 2 3 3
水杨酸 2 3 2
表面活性剂 1 2 1
去离子水 80 100 88
三甲基氯硅烷 6 8 7
过硫酸铵 0.2 0.3 0.2
3-(甲基丙烯酰氧基)丙基三甲氧基硅烷 3 4 3
醋酸钙 3 4 4
L-脯氨酸 0.1 0.2 0.2
表2 各对比例的组分含量表
对比例2 对比例3 对比例4 对比例5 对比例6 对比例7
丙烯酸树脂/聚氨酯乳液 30 30 30 30 30 30
磷酸三辛酯 6 6 6 6 6 6
硼酸锌 2 2 2 2 2 2
水杨酸 2 2 2 2 2 2
表面活性剂 1 1 1 1 1 1
去离子水 80 80 80 80 80 80
三甲基氯硅烷/乙烯基三甲氧基硅烷 6 6 6 6 6 6
过硫酸铵 0.2 0.2 0.2 0.2 0.2 0.2
3-(甲基丙烯酰氧基)丙基三甲氧基硅烷/三乙氧基硅烷 3 3 3 3 3 3
醋酸钙 3 3 3 3 / 3
L-脯氨酸/辛酸亚锡 0.1 0.1 0.1 0.1 0.1 0.1
性能检测试验
1.垂直燃烧性能测试:参照GB/T 5455-1997 纺织品燃烧性能测试试验标准中的垂直法进行测试,将一定尺寸的试样置于规定的燃烧器下点燃,测量材料持续无焰燃烧后的损毁长度,即炭长(被烧焦的最大长度),炭长越短,则阻燃性能越好。
2.极限氧指数测试:参照GB/T 5454-1997 纺织品燃烧性能测试试验标准中的氧指数法进行测试,将试样竖直地固定在玻璃燃烧筒中,其底座与可产生氮氧混合气流的装置相连,点燃试样的顶端,混合气流中的氧浓度将会持续下降,直至火焰熄灭,由此得到极限氧指数;极限氧指数越高,则阻燃性能越好。
以上述两组测试分别对实施例1-3和对比例1-7进行试验,测试结果如下表3所示。
表3 性能测试结果
炭长/cm 极限氧指数/%
实施例1 5.06 37.9
实施例2 5.02 38.2
实施例3 5.03 38.1
对比例1 9.11 24.7
对比例2 6.51 31.0
对比例3 6.32 32.6
对比例4 6.13 33.1
对比例5 6.12 33.4
对比例6 5.22 35.9
对比例7 5.20 36.2
3.针对实施例1-3、对比例8和对比例9做水洗测试,取20cm×20cm的防护服试样,固定在绷架上,使防护服形成无皱纹的平滑平面,然后将绷架固定在测定仪的支架上,防护服朝上,喷嘴中心对准绷架中央;将250mL、(27±1)℃的蒸馏水迅速倒入漏斗中,约在25-30s内全部淋完,测得水洗50次后的极限氧指数,以此表征防护服的阻燃寿命,测试结果如下表4所示。
表4 耐水洗性能测试结果
水洗次数 极限氧指数/%
实施例1 50 36.0
实施例2 50 36.3
实施例3 50 36.1
对比例8 50 26.8
对比例9 50 27.3
综上所述,由表3的结果可得出以下结论:
1.从实施例1-3和对比例1的对比可知,经过本发明的整理剂处理的防护服阻燃性能更好。
2.由实施例1分别和对比例2-3对比可知,丙烯酸树脂以及表面活性剂马来酸酐十四醇丙磺酸钠的添加有利于提高防护服的阻燃性能。
3.从实施例1和对比例2、4的对比可知,三甲基氯硅烷和丙烯酸树脂具有协同作用,可提高防护服的阻燃效果。
4.从实施例1和对比例2、5的对比可知,3-(甲基丙烯酰氧基)丙基三甲氧基硅烷和丙烯酸树脂的共同添加对防护服的阻燃性能具有提升作用。
5.由实施例1分别和对比例6、7对比可知,醋酸钙以及L-脯氨酸的添加有利于提高防护服的阻燃性能。
由表4的结果可得出以下结论:
当pH值为6-6.5时,经50次水洗后防护服的阻燃性能仍可维持在较高的水平。
本具体实施方式的实施例均为本发明的较佳实施例,并非依此限制本发明的保护范围,故:凡依本发明的结构、形状、原理所做的等效变化,均应涵盖于本发明的保护范围之内。

Claims (8)

1.一种防护服,包括连体衣身,其特征在于:所述连体衣身表面经整理剂处理,所述整理剂包括如下重量份数的组分:
30-40份丙烯酸树脂;
6-8份磷酸三辛酯;
2-3份硼酸锌;
2-3份水杨酸;
1-2份表面活性剂;
80-100份去离子水。
2.根据权利要求1所述的一种防护服,其特征在于:按重量份数计,所述整理剂还包括6-8份三甲基氯硅烷和0.2-0.3份过硫酸铵。
3.根据权利要求2所述的一种防护服,其特征在于:所述表面活性剂为马来酸酐十四醇丙磺酸钠。
4.根据权利要求1所述的一种防护服,其特征在于:按重量份数计,所述整理剂还包括3-4份3-(甲基丙烯酰氧基)丙基三甲氧基硅烷。
5.根据权利要求4所述的一种防护服,其特征在于:按重量份数计,所述整理剂还包括3-4份醋酸钙和0.1-0.2份L-脯氨酸。
6.根据权利要求1所述的一种防护服,其特征在于:所述整理剂用磷酸氢钠调整pH至6-6.5。
7.根据权利要求1所述的一种防护服,其特征在于:所述整理剂的制备方法如下:
S1.将表面活性剂和去离子水加入容器中,充分溶解;升温至70-80℃,加入丙烯酸树脂和磷酸三辛酯,搅拌20-25min,再加入硼酸锌和水杨酸,超声波的作用功率为200-240W,超声振荡5-8min;
S2.加入醋酸钙,搅拌5-10min,继续升温至80-120℃,加入过硫酸铵,搅拌均匀,然后在30-40min内缓慢滴加三甲基氯硅烷,继续搅拌0.5-1h;然后加入L-脯氨酸,搅拌下滴加3-(甲基丙烯酰氧基)丙基三甲氧基硅烷,在25-30min内滴加完毕,继续保温反应0.5-1h;
S3.最后用磷酸氢钠调整pH至6-6.5,70-80℃保温30-35min,再冷却至室温,得到整理剂。
8.根据权利要求1所述的一种防护服,其特征在于:将所述整理剂通过80-120%的轧液率对连体衣身进行浸轧,再以100-120℃的温度预烘3-5min,再进行拉幅定型、预缩得到防护服。
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