CN110725135B - 一种复合高分子涂层织物及其制法 - Google Patents

一种复合高分子涂层织物及其制法 Download PDF

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Publication number
CN110725135B
CN110725135B CN201911171784.3A CN201911171784A CN110725135B CN 110725135 B CN110725135 B CN 110725135B CN 201911171784 A CN201911171784 A CN 201911171784A CN 110725135 B CN110725135 B CN 110725135B
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coating
fabric
composite polymer
slurry
base material
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CN110725135A (zh
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封利苹
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Yongsheng Haeil Differential Fabric Co ltd
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Hangzhou Shengde New Material Co ltd
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Priority to CN201911171784.3A priority Critical patent/CN110725135B/zh
Priority to PCT/CN2019/122835 priority patent/WO2021103062A1/zh
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Abstract

本发明一种复合高分子涂层织物及其制法。包括织物基材层和附着在所述织物基材层至少一面的复合高分子涂层；所述复合高分子涂层织物还包括40~150μm的基材融浆层；所述基材融浆层是在生产过程中由部分的复合高分子涂层嵌入织物基材层组织内部形成的复合结构；所述复合高分子涂层的厚度为100~500μm。本发明通过对织物基材的选择、对复合高分子涂层配方的选择以及工艺参数的调整，实现了基材融浆层的生成，从而使得本发明的产品相比现有技术具有显著的优势，主要体现在贴合强度、手感、绑纱牢度等方面。

Description

一种复合高分子涂层织物及其制法
技术领域
本发明涉及一种涂层织物，尤其涉及一种复合高分子涂层织物及其制法。
背景技术
织物涂层，泛指将高分子类化合物均匀涂布在织物表面的工艺技术，它不仅能改善织物的外观和手感，还能改善织物的功能，诸如使织物具有防水、通气透湿、阻燃防污以及遮光反射等特殊功能。
现有技术中，织物涂层大约有以下几类：
1. PA（聚丙烯酸酯）
优点是：耐日光和气候牢度好，不易泛黄；透明度和共容性好，有利于生产有色涂层产品；耐洗性好；粘着力强；成本较低。缺点是：弹性差，易折皱；表面光洁度差；手感难以调节。
2. PU（聚氨酯）
优点是：涂层柔软并有弹性；涂层强度好，可用于很薄的涂层；涂层多孔性，具有透湿和通气性能；耐磨，耐湿，耐干洗。缺点是:成本较高；耐气候性差；遇水、热、碱要水解。
3. PVC（聚氯乙烯）
优点是：相对便宜，可用于雨衣箱包等。缺点是：低温柔软性差，有毒，极易产生戴奥辛类剧毒物质。
另外，还有PE（聚乙烯）、PP（聚丙烯）、PTFE（聚四氟乙烯）、聚酰氨、聚酯、合成橡胶等。
EVA材料不含卤素，符合环保标准，现有技术中，EVA通常用于制造聚合物片材，可用作夹胶玻璃的中间层。而现阶段，大量废弃的建筑物夹胶玻璃、汽车挡风玻璃等垃圾中含有可回收利用的EVA胶片。但EVA回用料相比新料在各方面性能上都有所弱化，尤其是添加一些助剂用于生产涂层织物时，在柔韧性，强度，耐磨度等各种性能都有待加强。而回用EVA来制造高分子涂层织物，仍然是本领域亟需解决的问题。
发明内容
本发明要解决上述问题，从而提供一种复合高分子涂层织物。
本发明解决上述问题的技术方案如下：
一种复合高分子涂层织物，包括织物基材层和附着在所述织物基材层至少一面的复合高分子涂层；所述织物基材层采用选自涤纶、腈纶、锦纶、维纶、氨纶、聚丙烯、植物纤维中的一种纱线或其任意配比的混纺纱线经梭织或针织工艺制成；其特征在于：所述复合高分子涂层织物还包括5~50μm的基材融浆层；所述基材融浆层是在生产过程中由部分的复合高分子涂层嵌入织物基材层组织内部形成的复合结构；所述织物基材层与基材融浆层的织物组织构成一体，所述复合高分子涂层与基材融浆层构成一体；所述复合高分子涂层的厚度为10~500μm；所述复合高分子涂层包含复合高分子组分和填料；所述的复合高分子组分以EVA为必要组分，并添加有其他组分，所述其他组分为（a）LDPE、LLDPE、PP的一种或多种和/或（b）TPU、SBS、TPR、EPDM中的一种或多种；所述复合高分子涂层包含以下质量份的组分：EVA 10~35、其他组分15~30、填料1~30。
本发明上述技术方案中，基材融浆层由织物基材的部分织物组织和所述复合高分子涂层交叉组成；具体是部分涂层嵌入到织物基材中形成的。因此，织物基材层中的织物组织与基材融浆层中的织物组织是一体的；未嵌入到织物基材中的涂层和基材融浆层也形成了一体；并且未嵌入到织物基材中的涂层还独自形成了复合高分子涂层。上述结构，由于复合高分子涂层并非仅仅附着在织物组织的表面，它还通过形成织物融浆层的形式嵌入到织物基材中；使得本发明相对于现有技术中的涂层织物具有涂层附着强度高的优点。
现有技术中的涂层织物由于没有形成基材融浆层，或者形成的基材融浆层非常薄，通常在5μm以下甚至更低，因此层间复合强度不高。
本发明上述技术方案中，基材融浆层的出现，是跟本发明织物基材的选择，跟涂层配方的选择，以及工艺参数都是密切相关的。
在织物基材的选择上，选择织造布，而非无纺布；在织造布中，尤以梭织布为佳。梭织布的微观组织结构相对硬挺，在进行涂浆时，无论是刀涂刮浆法还是辊涂法都更加容易通过施压把涂层嵌入。
在涂层配方的选择以及工艺的搭配上，尤以稍高粘度浆料一次涂胶并达到规定的涂浆量的方案为好。粘度低的浆料，相对来说需要蒸发更多的溶剂，溶剂蒸发地越多越容易发生表面变化，使得产品表面收缩，影响产品质量。除了浆料的粘度外，还跟涂浆时的压力有关，通常设置的压力要超过0.5MPa，以使形成更厚的基材融浆层，从而提高涂层的附着强度。
当其他组分中含有LDPE、LLDPE、TPE、PVA中的一种或多种时，可以显著增强复合涂层的耐摩擦强度、表面硬度、防水能力以及材料的整体强度。但会使得复合涂层在手感上变硬，质感下降；而当添加一定比例的热塑性弹性体后，可以改变这种情况，可使复合涂层变得柔韧，从而提高产品的柔韧性。
研究显示，在增加了热塑性组分后，如PP、LDPE等，能够显著提高其耐磨度和强度；但过多的添加量会使产品变硬；通常增加5%~15%的热塑性组分就能够起到良好的增强作用，且并不显著提高成膜后的表面硬度；表面硬度的提高还可以通过添加热塑性弹性体组分，如TPU、SBS、EPDM等，予以解决。虽然单独的EVA也有一定的柔韧性，强度，耐磨度，但总体上，其各种性能都有待加强，从而制得一种综合性能更佳的产品。相对单独的EVA而言，热塑性组分和热塑性弹性体的综合使用可赋予EVA产品更好的韧性，并且他们的韧性表现在不同的层次。一个层次的韧性主要表现在抗拉伸断裂，使得产品提高了拉伸强度，如使产品发生形态改变需要更大的外力作用，并且不容易被拉断，它可以提高产品的抗应力能力；另一个层次的韧性体现在恢复产品的原有形态，也即产品的弹性形变上，显著提高产品的断裂伸长率，即使外力的作用使得产品的形态发生了较大改变，在撤销该外力后，产品仍能迅速恢复到原有形态而没有变得更长或松弛。
作为上述技术方案的优选，当其他组分包含（a）和（b）时，所述其他组分中还包含有用于提高相容性的接枝改性共聚物，所述接枝改性共聚物选自PE-g-MAH、PE-g-GMA、PE-g-AA、PE-g-MMA中的一种或多种。
作为上述技术方案的优选，所述填料选自碳酸钙、滑石粉、凹凸棒黏土、硅灰石中的一种或其任意种类的组合。
作为上述技术方案的优选，当所述复合高分子涂层还包含辅料时，所述辅料包括一类辅料和二类辅料，一类辅料为丙烯酸树脂、环氧树脂、纤维素醚中的一种或多种；二类辅料为硅烷偶联剂或钛酸酯偶联剂。
作为上述技术方案的优选，所述织物基材的纱线旦数为20~4800D。
作为上述技术方案的优选，所述复合高分子涂层织物采用刮刀涂浆工艺或辊筒涂浆工艺将复合高分子浆料涂覆在所述织物基材的表面，并经过热烘使所述复合高分子浆料干化制成；所述复合高分子涂层包含以下质量份的组分：EVA 10~35、其他组分15~30、填料1~30。
本发明的另一个目的是提供上述高分子复合涂层织物的一种制造方法。
复合高分子涂层织物的制造方法，包括以下步骤：
a、选择一织物基材，进行前处理，烘干，备用；
b、在所述织物基材上进行涂浆，涂浆完成后烘干，使浆料固化不发粘，并与织物基材形成一体，得涂浆织物基材；浆料粘度为900~150000cps，总涂胶量控制在5~200g/m2；
c、涂浆完成后热烘；
所述涂浆的浆料包含以下质量份的组分：
EVA 10~35
其他组分 15~30
填料 1~30
溶剂 40~80。
作为上述技术方案的优选，所述溶剂选自乙醇和乙酸乙酯的混合液，其中乙醇的体积比为30~70vol%。
作为上述技术方案的优选，所述热烘具体为，热烘的烘道设有温度梯度，所述温度梯度从烘道入口至出口依次为：80～90℃，90～100℃，100～110℃，110～120℃；每个温度段停留2~25S。
本发明的在一个目的是提供上述的涂层织物在雨衣、雨伞、帐篷、罩子、手袋、箱包、工具袋、鞋、衣服、家具、购物袋、冰袋、 水袋、椅、沙发面料、座垫、抱枕、体育用品、书写工具、玩具、婴童用品 马衣、宠物用品等或类似物品方面的用途。
综上所述，本发明具有以下有益效果：
1、因PVC材料在降解过程中极易产生戴奥辛类剧毒物质，故本发明以代替现有PVC材料为出发点，提供一整套完整的高分子复合织物涂层技术。涂层织物的质量主要体现在涂层的表面强度、手感、屈曲后的褶皱恢复性、绑纱牢度等；表面强度主要体现在耐刮擦；手感主要体现在改变织物本来较柔软的特性，使之变硬而影响手感；绑纱牢度主要是体现在固定织物组织的能力，在对织物进行涂层后，可改变原织物易散边的特性。本发明提供的复合高分子涂层，具有良好的耐刮擦、柔韧性和抗应力作用的能力，并且由于材料不含卤素，降解过程中不产生毒性物质。
2、溶剂的选择上，乙酸乙酯是低毒溶剂，但乙酸乙酯溶解度相对略低，而且混合料在其中并不单纯地体现出溶解的特性，而是溶胀，溶胀的结果对于浆料的制备较难把控，并且也会严重影响浆料的涂层性能，如粘结性等。乙醇也是低毒溶剂，但其极性较强，其他原料在乙醇中的分散性能不佳，而乙酸乙酯的极性明显小于乙醇，其他原料在乙酸乙酯中的分散性较好。但乙酸乙酯与乙醇显然需要一个最佳的配比，乙醇偏多则其他物料的分散性不好，乙醇偏少物料的溶解度会下降并且更容易发生溶胀。经过本发明人数次试验总结，最终确定了乙酸乙酯和乙醇来制备混合溶剂的方案，并且乙醇占30~70vol%，优选40~60vol%，进一步优选1:1。这种搭配，既解决了混合物料在乙酸乙酯中的溶胀特性，也一定程度上提升了其他原料的分散性。
3、发明人进一步研究，通过复配其他树脂来增强粘结性，比如配方中使用了环氧树脂或丙烯酸树脂；通过树脂改性剂来强化粘接牢度，使得织物组织和浆料涂层在成型后成为一个整体，即使通过高压蒸汽也难以将涂层剥离。树脂改性剂的基本原理是，这类改性剂树脂能够起到一定程度的固化作用，也就是相当于交联剂的作用，显著提高涂层浆料的粘结性，也提高了对织物基材的补强强度。另外，本发明人发现通过添加一些天然的增稠物质，如纤维素醚类等，可方便调整涂层浆料的粘滞系数，使浆料适于通过辊涂或者刀涂的工艺来实施。通过填料来适当增强产品的耐刮擦性能，同时适当降低树脂的用量，但填料用量过多在提升耐刮擦的同时也容易影响产品手感，使产品变硬，一般控制在5wt%以内。偶联剂能提高浆料对于不同材质织物基材的附着性，偶联剂的选择可使用钛酸酯偶联剂和硅烷偶联剂如HK-550，HK-551等。优选钛酸酯偶联剂，钛酸酯偶联剂比硅烷偶联剂在对其他组分的分散性上更好，对各种织物基材的附着性能也更佳。上述偶联剂的使用，还能提高填料、着色剂等在浆料中的分散效果。
4、本发明采用EVA、PP、TPU等物质为主要成分，而作为本发明的EVA、PP、TPU等原料，可以是其他工业中的废料；因此，本发明可以通过回收再利用的方式，解决EVA、PP、TPU等废料的处置，并且变废为宝，产生极大的经济效益。
附图说明
图1是实施例一的刀涂设备示意图；
图中，1-放卷辊，2-织物基材，3-支撑板，4-浆料箱，5-涂刀，6-压辊组，7-热风烘箱，8-收卷辊，9-导辊。
具体实施方式
以下结合附图对本发明进行进一步的解释说明。
本具体实施方式仅仅是对本发明的解释，并不是对本发明的限制，本领域技术人员在阅读了本发明的说明书之后，所做的任何改变，只要在权利要求书的范围内，都将受到专利法的保护。
实施例一
一种复合高分子涂层织物，包括织物基材层、100μm厚的基材融浆层、以及复合高分子涂层。本实施例中，浆料粘度为5000cps，涂胶温度为室温，涂浆量为100g/m2。织物基材为PET纱线经平纹织造工艺制成。所述织物基材预先经过轧光处理，轧光车速为50m/min，轧光温度为90℃。复合高分子涂层织物是通过刀涂机将复合高分子浆料均匀涂覆在织物基材层的一个轧光处理过的表面上，然后经热烘，使涂层干化而成。在刀涂的过程中，由于压力的施加，以及织物基材层本身一定的硬度，使得复合高分子浆料部分嵌入到织物基材层中，从而形成了100μm厚的基材融浆层的复合结构。
热烘的过程既是溶剂蒸发的过程，也是浆料固化的过程。热烘参数控制如下：热烘的烘道为隧道式，并设有温度梯度，所述温度梯度从烘道入口至出口依次为：80～90℃，90～100℃，100～110℃，110～120℃；热烘时间为80s。
本实施例中，复合高分子浆料的配方包括如下质量份的组分：
EVA树脂 10
PP 7
PE-g-MAH 3
TPU 15
溶剂（乙酸乙酯：乙醇=7:3） 60
环氧树脂 5
超细碳酸钙 5
羟乙基纤维素 3
色素炭黑 1.5
偶联剂TTS 0.5。
图1所示为制作上述复合高分子涂层织物的设备，它包括放卷辊1，支撑板3，浆料箱4，涂刀5，压辊组6，热风烘箱7，收卷辊8。放卷辊1源源不断地提供PET织物基材，该基材是预先轧光过的。于支撑板处，上述浆料被放置在浆料箱4内，浆料箱4底部有开口，可以源源不断地提供上述配方的浆料，该浆料被涂刀5涂布在张紧的织物基材的上面；织物基材经过涂刀的刮浆处理，已经形成了较为均匀的尚未干化的涂层，考虑到涂层质量，本发明还在此处设置了一个压辊组，该压辊组可进一步地把尚未干化的涂层进行一道次地辊压，可以把混入其内的空气赶跑，有效地提高涂层的质量；同时还可以通过机械力的作用，把涂层部分或者全部地压入织物基材内部，从而降低整体的厚度，并强化整体的牢度。在辊压后，经过隧道式的热风烘箱7的加热作用，使浆料内部的溶剂蒸发，使涂层固化成型，最后经过收卷，得到成品的复合高分子涂层织物。需要注意的是，为了提高涂浆质量，本发明把现有技术中的涂刀的朝向进行反向设置，这样做的目的是可以提高涂浆量，然后通过压辊组的作用，把浆料压入织物基材内，降低整体厚度，这样就可以获得厚度达标，并且强化的复合高分子涂层织物。该涂层织物相比现有的具有更好的强度以及更好地结合牢度，并且在屈曲手感上也因为配方的优化而获得提升，具有良好的回弹性。
实施例二
一种复合高分子涂层织物，与实施例二不同之处仅在于涂浆的配方不同。
本实施例中，浆料的配方包括如下质量份的组分：
EVA树脂 5
HDPE 15
环氧树脂 10
超细碳酸钙 5
溶剂（乙酸乙酯：乙醇=6:4） 50
热塑性弹性体TPU 5
色素炭黑 1.0
偶联剂TTS 0.5。
实施例三
一种复合高分子涂层织物，与实施例二不同之处仅在于涂浆的配方不同。
具体的，本实施例的浆料涂层包括如下质量份的组分：
EVA树脂 15
PE-g-MAH 5
溶剂（乙酸乙酯：乙醇=1:1） 40
丙烯酸树脂 10
超细碳酸钙 5
羟丙甲纤维素 10
色素炭黑 2.5
偶联剂KH550 0.5。
实施例四
一种复合高分子涂层织物，与实施例二不同之处仅在于涂浆的配方不同。
具体的，本实施例的浆料涂层包括如下质量份的组分：
EVA树脂 20
PP 10
TPU 5
溶剂（乙酸乙酯：乙醇=0.8:1.2） 60
丙烯酸树脂 10
超细碳酸钙 2
阿拉伯树胶 5
色素炭黑 2.5
偶联剂KH550 0.5。
由于结构相同，浆料涂层在配方选择上没有本质的区别，因此，可以采用如实施例一所述的设备。
实施例五
一种复合高分子涂层织物，与实施例二不同之处仅在于涂浆的配方不同。
具体的，本实施例的浆料涂层包括如下质量份的组分：
EVA树脂 25
PE-g-GMA 5
TPU 10
溶剂（乙酸乙酯：乙醇=0.5:1.5） 40
丙烯酸树脂 10
超细碳酸钙 5
色素炭黑 2.5
偶联剂KH551 0.5。

Claims (8)

1.一种复合高分子涂层织物，所述复合高分子涂层织物包括织物基材层和附着在所述织物基材层至少一面的复合高分子涂层；所述织物基材层采用选自腈纶、维纶、氨纶、聚丙烯、植物纤维中的一种纱线或其任意配比的混纺纱线经梭织或针织工艺制成；其特征在于：所述复合高分子涂层织物还包括5~50μm的基材融浆层；所述基材融浆层是在生产过程中由部分的复合高分子涂层嵌入织物基材层组织内部形成的复合结构；所述织物基材层与基材融浆层的织物组织构成一体，所述复合高分子涂层与基材融浆层构成一体；所述复合高分子涂层的厚度为10~500μm；所述复合高分子涂层包含复合高分子组分和填料；所述的复合高分子组分以回用EVA为必要组分，并添加有其他组分，所述其他组分为（a）LDPE、LLDPE、PP的一种或多种和/或（b）TPU、SBS、TPR、EPDM中的一种或多种；所述复合高分子涂层包含以下质量份的组分：EVA 10~35、其他组分15~30、填料1~30，在形成涂浆的浆料时还加入溶剂40-80份，所述溶剂选自乙醇和乙酸乙酯的混合液，其中乙醇的体积比为30~70vol%；所述复合高分子涂层织物采用刮刀涂浆工艺将复合高分子浆料涂覆在所述织物基材的表面，并经过热烘使所述复合高分子浆料干化制成；所述热烘具体为，热烘的烘道设有温度梯度，所述温度梯度从烘道入口至出口依次为：80～90℃，90～100℃，100～110℃，110～120℃；每个温度段停留2~25S；所述复合高分子涂层织物制备采用的设备，包括放卷辊（1），支撑板（3），浆料箱（4），涂刀（5），压辊组（6），热风烘箱（7），收卷辊（8），放卷辊（1）源源不断地提供织物基材，该基材是预先轧光过的，于支撑板处，上述浆料被放置在浆料箱（4）内，浆料箱（4）底部有开口，源源不断地提供上述配方的浆料，所述涂刀反向设置，该浆料被涂刀（5）涂布在张紧的织物基材的上面；织物基材经过涂刀的刮浆处理，形成较为均匀的尚未干化的涂层，所述压辊组把尚未干化的涂层进行一道次地辊压，把混入其内的空气赶跑，有效地提高涂层的质量；同时通过机械力的作用，把涂层部分或者全部地压入织物基材内部，从而降低整体的厚度，并强化整体的牢度，在辊压后，经过隧道式的热风烘箱（7）的加热作用，使浆料内部的溶剂蒸发，使涂层固化成型，最后经过收卷，得到成品的复合高分子涂层织物。
2.根据权利要求1所述的一种复合高分子涂层织物，其特征在于：当其他组分包含（a）和（b）时，所述其他组分中还包含有用于提高相容性的接枝改性共聚物，所述接枝改性共聚物选自PE-g-MAH、PE-g-GMA、PE-g-AA、PE-g-MMA中的一种或多种。
3.根据权利要求1所述的一种复合高分子涂层织物，其特征在于：所述填料选自碳酸钙、滑石粉、凹凸棒黏土、硅灰石中的一种或其任意种类的组合。
4.根据权利要求1所述的一种复合高分子涂层织物，其特征在于：当所述复合高分子涂层还包含辅料时，所述辅料包括一类辅料和二类辅料，一类辅料为丙烯酸树脂、环氧树脂、纤维素醚中的一种或多种；二类辅料为硅烷偶联剂或钛酸酯偶联剂。
5.根据权利要求1所述的一种复合高分子涂层织物，其特征在于：所述织物基材的纱线旦数为20~4800D。
6.制造如权利要求1所述复合高分子涂层织物的方法，包括以下步骤：
a、选择一织物基材，进行前处理，烘干，备用；
b、在所述织物基材上进行涂浆，涂浆完成后烘干，使浆料固化不发粘，并与织物基材形成一体，得涂浆织物基材；浆料粘度为900~150000cps，总涂胶量控制在5~200g/m2；
c、涂浆完成后热烘；
所述涂浆的浆料包含以下质量份的组分：
EVA 10~35
其他组分 15~30
填料 1~30
溶剂 40~80。
7.根据权利要求6所述的方法，其特征在于：所述溶剂选自乙醇和乙酸乙酯的混合液，其中乙醇的体积比为30~70vol%。
8.根据权利要求1-5任一项所述的涂层织物在雨衣、雨伞、帐篷、罩子、手袋、箱包、工具袋、鞋、水袋、椅、沙发面料、座垫、抱枕、体育用品、书写工具、玩具、婴童用品、马衣、宠物用品方面的用途。
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