CN107075292A - 用于纺织品衬底的阻燃组合物 - Google Patents

用于纺织品衬底的阻燃组合物 Download PDF

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CN107075292A
CN107075292A CN201580048420.XA CN201580048420A CN107075292A CN 107075292 A CN107075292 A CN 107075292A CN 201580048420 A CN201580048420 A CN 201580048420A CN 107075292 A CN107075292 A CN 107075292A
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textile substrates
composition
fire
yarn
advantageously
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S.佐拉尔斯基
C.瓦布勒-克拉杰科
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Saint Gobain Adfors SAS
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Abstract

本发明涉及具有膨胀性质的阻燃组合物，其由丙烯酸树脂、脱水化合物、发泡剂和任选的氟碳基聚合物组成。本发明还涉及涂有上述阻燃组合物的纺织品衬底，特别是包含光学纤维和缀结纱线的发光织物。

Description

用于纺织品衬底的阻燃组合物
本发明涉及阻燃组合物，其更特别旨在施加至包含玻璃纱线和任选的合成纱线的纺织品衬底。
该阻燃组合物能够在该纺织品衬底上形成透明和柔性涂层的层，当该层暴露于热或火焰时变得膨胀。由此令该纺织品衬底更耐火。
基于玻璃纤维的织物的防火是已知的，并且通过施加包含有机树脂和膨胀化合物或阻燃添加剂（例如氢氧化物或基于磷、基于硫或基于氮的化合物）来获得。
已知的膨胀阻燃涂层主要包含三聚氰胺-甲醛树脂，其无可否认是透明的，但是其具有显著降低所述涂层的柔性的缺点。此外，这些涂层能够释放甲醛，这违背了因对生物的有害影响而禁止甲醛的现行法规。
含有阻燃添加剂的阻燃涂层能够获得所需透明度和所需柔性，但是从火灾的角度来看，它们的效力始终低于膨胀阻燃涂层的效力。
本发明所解决的技术问题在于获得一种无甲醛的膨胀阻燃组合物，其是透明的，并且其能够保留在其上施加该组合物的原始纺织品衬底的柔性性质。
根据本发明通过由丙烯酸树脂、脱水化合物、发泡剂和任选的氟碳-基聚合物组成的阻燃组合物来解决这一问题。
在本申请中，下列术语和表述具有下面的含义：
- 术语“脱水化合物”意在指在高于100℃、优选100至250℃的温度下释放强酸或能够释放强酸的强酸前体的化合物，
- 术语“发泡剂”意在指在其热降解时释放不燃性气体如二氧化碳或氨的化合物。该发泡剂是对获得膨胀效果至关重要的化合物，所述膨胀效果使其能够形成保护纺织品衬底来防火的膨胀碳基结构。该发泡剂不同于前述脱水化合物，并且
- “透明”或“透明性”性质理解为是指相对于可见光范围内的辐射。
丙烯酸树脂的功能是将纤维或纱线彼此粘合。该丙烯酸树脂可以由丙烯酸或甲基丙烯酸均聚物、或丙烯酸和/或甲基丙烯酸与烯属不饱和单体如苯乙烯的共聚物组成。优选地，该树脂由丙烯酸均聚物组成。
脱水化合物的功能是将丙烯酸树脂脱水，并且还必须能够在温度提高的作用下生成酸，所述酸与所述树脂的羟基官能反应以首先获得热稳定的酯。所述酯随后将被降解，产生构成防火保护层的碳、水和二氧化碳。
该脱水化合物选自可热降解的强酸，如磷酸、硫酸和硼酸，以及具有挥发性阳离子的这些酸的盐，并有利地为聚磷酸铵。
该发泡剂优选是胺或酰胺，有利地为尿素、三聚氰胺和胍。尿素是优选的。
作为一般规则，该丙烯酸树脂包含足够量的碳原子和能够与脱水剂反应的羟基官能以便能够形成具有良好品质的膨胀层。由此，无需向本发明的阻燃组合物中添加不同于该丙烯酸树脂的多羟基碳-基化合物，特别是多元醇如季戊四醇、糖如葡萄糖、阿拉伯糖和麦芽糖、淀粉或纤维素。
本发明的阻燃组合物为水性分散体形式。
优选地，该阻燃组合物由以下成分组成（以%固体形式）：
- 10%至60%的丙烯酸树脂，有利地为15%至50%，
- 20%至50%的脱水化合物，有利地为30%至40%，
- 5%至30%的发泡剂化合物，有利地为10%至20%，
- 0%至60%的氟碳-基聚合物，优选至少5%，有利地为10%至30%。
该阻燃组合物通常包含30重量%至80重量%的水，优选40%至60%。如下文所述，根据用于在纺织品衬底上沉积该阻燃组合物的应用模式来调节水含量。例如，当该阻燃组合物通过涂布沉积时，该水含量例如等于40%，对于通过喷涂的应用等于60%。
在该阻燃组合物中，该氟碳-基聚合物有助于改善最终的纺织品衬底在潮湿环境中的老化的耐受力。
本发明的另一主题涉及涂有上述阻燃组合物的纺织品衬底。
该纺织品衬底含有由多根矿物长丝组成的矿物纤维和/或纱线，和任选的有机纤维和/或纱线。上述矿物或有机纤维和纱线可以是连续的或短切的。
构成上述纤维和纱线的矿物材料可以是玻璃或岩石，特别是玄武岩。
上述有机纤维和纱线可以是天然纤维和纱线，特别是基于纤维素，特别是基于棉、亚麻和大麻，或是合成纤维和纱线，特别是基于聚合物，特别是聚酯，如聚(甲基丙烯酸甲酯)，或聚烯烃，如聚丙烯。
该纺织品衬底可以是非织造材料形式，例如化学或机械粘接的纤维的网或垫、织物、网幅、针织物或编织物。
优选地，该纺织品衬底是包含光学纤维和特别由玻璃制成的缀结纱线的发光织物。此类织物特别描述在专利申请WO 2005/026424、WO 2008/035010、WO 2008/062141和WO2008/087339中。
有利地，该发光织物包含光学纤维，其可以由玻璃制成，但是优选为有机纤维，以及玻璃制成的缀结纱线。
该光学纤维有利地由一种或多种聚合物材料组成。
该光学纤维和该缀结纱线可以布置在经纱中或纬纱中。该光学纤维优选布置在经纱中，该玻璃纱线优选布置在纬纱中。有利地，该发光织物包含布置在经纱中的玻璃纱线和布置在纬纱中的玻璃纱线与光学纤维的组合。
该发光织物可以包括平纹、斜纹、缎纹或提花。
根据所选的编制类型，有可能促进光学纤维在织物的一个面上的存在，同时确保该织物的良好强度。
第一有利的发光织物包含根据斜纹、有利地根据4-、6-、8-、10-或12-线束缎纹编织的至少一个部分。选择缎纹能够使纬纱或经纱在该发光织物的一个面上更可见。有利地，该发光织物在用作照明表面的面上包含纬纱效果的缎纹。
第二有利的发光织物包含根据平纹编织的至少一个部分，因为这种类型编织能够确保该织物的强度。
如前所示，该光学纤维优选是有机的，特别是由一种或多种聚合物材料组成。
作为此类聚合物材料的实例，可以提及聚(甲基丙烯酸甲酯)、聚碳酸酯、环烯烃和含氟聚合物。
护套可以覆盖该光学纤维（芯）以保护它们并获得称为核-壳的两组分结构。该护套可以具有与芯相同的性质，或具有与芯不同的性质。包含聚(甲基丙烯酸甲酯)芯与基于含氟聚合物如聚四氟乙烯的护套的纤维是优选的。
该光学纤维通常具有100至1000微米、优选200至550微米和有利地为450至550微米的直径。
在核-壳光学纤维的情况下，该护套的厚度为2至15微米，优选5至10微米。
该光学纤维具有至少5根纱线/厘米和优选为8至20根纱线/厘米的密度。
该光学纤维可以处理以形成浸润性改变，这使得能够在纤维处提取光并漫射照明该发光织物的主表面。所述浸润性改变通常为凹口或小的狭缝形式，其特别可以通过研磨工艺如喷砂、化学侵蚀或借助高强度光辐射如激光的熔融来获得。
该浸润性改变可以在其编织之前在该光学纤维上进行，或直接在该发光织物上进行。
用作缀结纱线的玻璃纱线由涂有胶料（size）的多根玻璃长丝组成，这些长丝具有5至24微米、优选6至16微米和有利地为8至13微米的直径。该玻璃纱线还具有2.8至4800tex、优选大于34 tex、并且有利地为50至800 tex的线质量密度。
布置在经纱中的玻璃纱线具有至少等于5根纱线/厘米、优选至少等于7根纱线/厘米和有利地为7至9根纱线/厘米的密度。布置在纬纱中的玻璃纱线具有至少等于5根纱线/厘米和优选8至20根纱线/厘米的密度。
该玻璃纱线可以是加捻纱线，每米的匝数为至少等于5，优选为至少20。
该玻璃纱线占该发光织物的重量的至少20%、优选至少40%。玻璃纱线在该发光织物中的比例越高，耐火性越好。
该发光织物可以包含优选施加到不用作照明表面的面上的结构涂层。该结构涂层有利地为白色和/或反射性的和/或主要基于矿物材料。
该结构涂层通常包含聚合物有机粘合剂和任选的填充材料，所述填充材料由矿物填料和/或颜料组成。该聚合物粘合剂可以是合成的，例如聚氨酯、聚(甲基)丙烯酸酯、苯乙烯-丁二烯或苯乙烯-丙烯酸共聚物，或天然聚合物，例如淀粉。
尽管更特别相对于发光织物进行描述，不能排除将该阻燃组合物施加到其它纺织品衬底上，特别是含有至少20重量%的有机材料的纺织品衬底。例如，该纺织品衬底可以是包含玻璃制成的结构和聚酯纤维的无纺布的复合物，所述无纺布占聚酯重量的50%至85%，或由天然纤维组成的织物，尤其是基于纤维素纤维、有利地为亚麻纤维的可涂饰布料。
将阻燃组合物施加至纺织品衬底可以通过本领域技术人员已知的任何方法进行，例如通过借助刮刀（任选放置在辊上）的涂覆、通过帘幕涂覆、或通过喷涂。
在涂覆阻燃组合物后进行干燥步骤，其通常在环境温度（20-25℃）下进行，但是也可以在更高的温度下进行。但是，该干燥温度应当对该纺织品衬底的纤维和纱线的性质进行调节；特别地，其不应过度接近于该阻燃组合物的成分和该纤维与纱线的成分的降解温度。
例如，含有聚合物纤维的发光织物的干燥可以在50至70℃的温度下进行至多60分钟。在这些条件下的干燥改善了该阻燃组合物层的表面光洁度。
施加到纺织品衬底上的阻燃组合物的量可以根据所需阻燃水平在大的程度上不等。通常，该阻燃组合物的量（以%固体形式）为每平方米纺织品衬底50至400克，优选为100至300克/平方米。
当该纺织品衬底是发光织物时，该阻燃组合物优选施加到用作主要照明表面的面上。
下面给出的实施例能够阐述本发明，但是不限制本发明。
在这些实施例中，在下列条件下评估该纺织品衬底的性质：
- 在标准NF EN ISO 11925-2的条件下测量耐火性。测定蔓延15厘米的距离的时间和在表面处施加或施加至样品边缘的火焰的蔓延距离。
在标准ISO 23539:2005的条件下测量亮度（以cd/m²为单位）。待检测的样品的光学纤维以几个组放置在一起并连接到光源上。
通过Lorentzen & Wettre设备在23℃和50%相对湿度下对在机器方向（相对于编织方向）上切割的矩形样品（3.8厘米×8.0厘米）测量弯曲刚度。
该样品在一端处以两个夹爪之间的最小距离垂直固定，并向自由的一段施加水平的力。测量对等于5°的弯曲角所施加的力，并根据下式计算刚度S（以mN.m为单位）：
S = 60×F×L² / π×θ×b
其中：
F是达到5°的角度的所测得的力（以mN为单位）
L是该样品的可用长度（0.05米）
θ是弯曲角（5°）
b是样品的宽度（0.038米）。
实施例1
a）纺织品衬底
所用纺织品衬底是具有8-线束缎纹编织的织物，由以下组成：
- E-玻璃缀结纱线
·在经纱中：长丝直径9微米，线质量密度68 tex，20匝/米 Z方向（EC9 68 Z20），密度7.9根纱线/厘米，
·在纬纱中：长丝直径11微米，线质量密度136 tex，28匝/米 Z方向（EC11 136 Z28），密度12根纱线/厘米，和
- 由涂有聚四氟乙烯的聚(甲基丙烯酸甲酯)芯组成的光学纤维；直径500微米，线质量密度240 tex，密度12根纱线/厘米。
该织物具有等于524 g/m²的基重，并含有43重量%的矿物材料。
通过刮刀涂覆向给发光织物的一个面（背面）上施加含有以下成分的白色结构涂层（以重量%形式）：20%的苯乙烯-丙烯酸树脂，78%的碳酸钙和2%的氧化钛。该结构涂层的量等于181 g/m²发光织物。
b）阻燃组合物
通过向含有水的容器中加入下列成分（以%固体形式）来制备阻燃组合物：
- 丙烯酸树脂（Aquaset® TF 150；Dow Chemicals） 49.0
- 聚磷酸铵（FR Cros® 484；Buddenheim） 36.0
- 尿素 15.0。
该阻燃组合物中的固含量等于60%。
获得白色的粘稠溶液。
c）耐火的纺织品衬底
通过用安装在辊上的刮刀涂覆将该组合物以不同的量施加到a）中描述的发光织物的前表面上，并随后在环境温度（20-25℃）下干燥24小时。
实施例1e的织物在施加该阻燃组合物之前经受喷砂处理。
进行本发明的实施例1a至1e的耐火性测量，并与不含有任何结构涂层和阻燃组合物的发光织物（对比例1）、不含有任何阻燃组合物的发光织物（对比例2）和其中该阻燃组合物含有三聚氰胺-甲醛树脂（FX100：Flameseal）的不具有结构涂层的发光织物（对比例3）进行比较。
在表1中给出了结果。
与对比例3相比，对于本发明的实施例1d，在发光织物表面处施加火焰和向发光织物边缘施加火焰的蔓延距离更短（并因此耐火性更好）。
实施例1a至1e的发光织物可以经受最高30°的弯曲角的手工弯曲，而不会对阻燃组合物的层造成可见的破坏。相反，对比例3的发光织物开裂和崩解，释放出粉末状残渣。
在实施例1e的发光织物（耐火织物）上测量量度，并且与喷砂之后和施加阻燃组合物之前的相同织物（不耐火织物）进行比较。结果如下：
　　　　　　　　　　　　　量度（cd/m²）
耐火织物　　　　　　　　　97.5
不耐火织物　　　　　　　　90.0。
穿过阻燃组合物层的光透射略微提高，由此表明所述层的透明性质。
实施例2和3
在实施例1的条件下进行该方法，修改在于该阻燃组合物含有（以固体%形式）：
　　　　　　　　　　　　　　　　　　　　　　例2 例3
- 丙烯酸树脂（Aquaset® TF 150；Dow Chemicals） 44.0 39.0
- 聚磷酸铵（FR Cros® 484；Buddenheim） 　　 　36.0 36.0
- 尿素　　　　　　　　　　　　　　　　　　　15.0 15.0
- 氟碳-基聚合物（Kappahob NI6；Kapp Chemie） 　5.0 10.0。
在表1中给出了结果。
实施例3的发光织物在气候室（温度：50℃，相对湿度：80%）中经受加速老化试验5天。
阻燃组合物层的外观与加速老化处理前的发光织物的外观相当。这种外观略好于实施例1a和1b的涂有阻燃组合物的发光织物。
在实施例3的发光织物中存在氟碳-基聚合物能够在耐火性和在潮湿环境中的抗老化性之间具有良好的折中。
实施例4和5
这些实施例描述了向含有有机材料的纤维或纱线的纺织品衬底施加该阻燃组合物。实施例1的阻燃组合物用于涂覆下列纺织品衬底：
- 包含在经纱方向上用玻璃纱线增强的玻璃纤维网和聚酯纱线网的复合材料（该复合材料的克重为235 g/m²），比例为150 g/m²（实施例4），
- 亚麻纱线（克重250 g/m²）的织物，比例为144 g/m²（实施例5）。
测量耐火性和弯曲刚度，并与未涂覆该阻燃组合物的相同纺织品衬底（对比例4和5）进行比较。
在表2中给出了结果。
与相应的对比例4和5相比，阻燃组合物赋予实施例4和5以改善的耐火性。
实施例4和5的弯曲刚度与不含阻燃组合物的纺织品衬底的弯曲刚度相当。
涂覆该阻燃组合物的纺织品衬底对肉眼是透明的。
表1
n.d.：未测定。

Claims (17)

1.阻燃组合物，特别用于纺织品衬底，其特征在于其由以下成分组成：
- 丙烯酸树脂，
- 脱水化合物，
- 发泡剂，和
- 任选的氟碳-基聚合物。
2.如权利要求1中所要求保护的组合物，其特征在于所述丙烯酸树脂由丙烯酸或甲基丙烯酸均聚物、或丙烯酸和/或甲基丙烯酸与烯属不饱和单体的共聚物组成。
3.如权利要求2中所要求保护的组合物，其特征在于所述丙烯酸树脂由丙烯酸均聚物组成。
4.如权利要求1至3之一中所要求保护的组合物，其特征在于所述脱水化合物选自可热降解的强酸，如磷酸、硫酸和硼酸，以及具有挥发性阳离子的这些酸的盐。
5.如权利要求4中所要求保护的组合物，其特征在于所述脱水化合物是聚磷酸铵。
6.如权利要求1至5之一中所要求保护的组合物，其特征在于所述发泡剂是胺或酰胺，优选尿素、三聚氰胺或胍，有利地为尿素。
7.如权利要求1至6之一中所要求保护的组合物，其特征在于其包含（以%固体形式）：
- 10%至60%的丙烯酸树脂，有利地为15%至50%，
- 20%至50%的脱水化合物，有利地为30%至40%，
- 5%至30%的发泡剂化合物，有利地为10%至20%，
- 0%至60%的氟碳-基聚合物，优选至少5%，有利地为10%至30%。
8.含有由多根矿物长丝组成的矿物纤维和/或纱线和任选的有机纤维和/或纱线的纺织品衬底，其特征在于其涂覆有如权利要求1至7之一中所要求保护的阻燃组合物。
9.如权利要求8中所要求保护的纺织品衬底，其特征在于所述矿物纤维和/或纱线由玻璃或岩石组成，优选由玄武岩组成。
10.如权利要求8或9中所要求保护的纺织品衬底，其特征在于所述有机纤维和/或纱线是天然的，优选基于纤维素，或合成的，优选基于聚合物。
11.如权利要求8至10之一中所要求保护的纺织品衬底，其特征在于所述矿物或有机纤维和/或纱线是连续的或短切的。
12.如权利要求8至11之一中所要求保护的纺织品衬底，其特征在于其为是非织造材料、织物、网幅、针织物或编织物的形式。
13.如权利要求8至12之一中所要求保护的纺织品衬底，其特征在于其是包含光学纤维和优选由玻璃制成的缀结纱线的发光织物。
14.如权利要求13中所要求保护的纺织品衬底，其特征在于所述光学纤维是玻璃纤维或有机纤维，优选有机纤维。
15.如权利要求13或14中所要求保护的纺织品衬底，其特征在于其包含根据斜纹、优选根据4-、6-、8-、10-或12-线束缎纹、或平纹编织的至少一个部分。
16.如权利要求13至15之一中所要求保护的纺织品衬底，其特征在于所述玻璃纱线占所述发光织物的重量的至少20%，优选至少40%。
17.如权利要求13至15之一中所要求保护的纺织品衬底，其特征在于其还包含结构涂层，所述结构涂层优选施加到不用作照明表面的面上。
CN201580048420.XA 2014-09-09 2015-09-09 用于纺织品衬底的阻燃组合物 Pending CN107075292A (zh)

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FR1458430A FR3025522B1 (fr) 2014-09-09 2014-09-09 Composition ignifugeante pour substrat textile.
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