CN111070811A - 一种生物可降解的合成革及其制备方法 - Google Patents

一种生物可降解的合成革及其制备方法 Download PDF

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Publication number
CN111070811A
CN111070811A CN201911080405.XA CN201911080405A CN111070811A CN 111070811 A CN111070811 A CN 111070811A CN 201911080405 A CN201911080405 A CN 201911080405A CN 111070811 A CN111070811 A CN 111070811A
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China
Prior art keywords
parts
synthetic leather
bottom layer
biodegradable
biodegradable synthetic
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CN201911080405.XA
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English (en)
Inventor
董凌凌
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Dongguan Chengyuan Leather Technology Co ltd
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Dongguan Chengyuan Leather Technology Co ltd
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Priority to CN201911080405.XA priority Critical patent/CN111070811A/zh
Publication of CN111070811A publication Critical patent/CN111070811A/zh
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Abstract

本发明提供一种生物可降解的合成革及其制备方法，合成革依次包括基布、合成革底层和合成革面层，所述基布为大豆纤维无纺布；按照重量份数比，所述合成革底层原料包括：水10‑15份；水性聚氨酯树脂60‑100份；淀粉树脂110‑120份；液体钙‑锌稳定剂2‑4份；甲基丙烯酸甲酯1‑3份；弹性体0.2‑0.5份；米糠20‑50份；降粘剂1‑2份；发泡剂5‑10份；丙烯酸丁酯的混合体1‑4份。本发明克服了现有技术中的缺点，提供了一种生物可降解的合成革及其制备方法，有利于减少环境污染，一个月后生物降解度在90％以上。

Description

一种生物可降解的合成革及其制备方法
技术领域
本发明属于合成革技术领域，具体涉及一种生物可降解的合成革及其制备方法。
背景技术
合成革是模拟天然革的组成和结构并可作为其代用材料的塑料制品。通常以经浸渍的无纺布为网状层，微孔聚氨脂层作为粒面层制得。其正、反面都与皮革十分相似，并具有一定的透气性，比普通人造革更接近天然革。广泛用于制作鞋、靴、箱包和球类等。
在传统的合成革制造中，大多数采用以100％化学合成纤维(涤纶、尼龙)的无纺布作为底基，涂覆合成树脂及各种塑料添加制成，由于化学纤维的可降解难度大，易对环境产生污染，且大多数化学纤维由于对皮肤的不可亲和性造成穿着不舒适。并且合成革制造过程中大多使用二甲基甲酰胺类有机物作为主要溶剂，这就使得传统的合成革制造中会产生大量的二甲基甲酰胺的废水以及废气，这些含有二甲基甲酰胺的废水以、废气即使是通过回收处理，还是会有一些含有排入空气中，造成工厂周边环境污染，并危害人员健康。加之近年来，生态合成革理念越来越受到人们的关注，生态合成革也日益成为皮革生产厂家以及材料科学家研究的热点，生态合成革的理念包括以下四个方面：一是在生产制造过程中不给环境带来污染，二是将其加工成革制品过程中无害；三是使用过程中对人体无害，对环境不产生污染；四是可生物降解，且降解产物不会对环境造成新的污染，大体可以概括为在生态合成革的开发中必须采用清洁的生产技术，做到低碳、低能耗、零排放或少排放。
发明内容
本发明要解决的技术问题是提供一种成本低、绿色环保一种生物可降解的合成革及其制备方法。
为了实现上述发明目的，本发明提供如下技术方案：一种生物可降解的合成革，依次包括基布、合成革底层和合成革面层，所述基布为大豆纤维无纺布；
按照重量份数比，所述合成革底层原料包括：
水10-15份
水性聚氨酯树脂60-100份
淀粉树脂110-120份
液体钙-锌稳定剂2-4份
甲基丙烯酸甲酯1-3份
弹性体0.2-0.5份
米糠20-50份
降粘剂1-2份
发泡剂5-10份
丙烯酸丁酯的混合体1-4份
按照重量份数比，所述合成革面层原料包括：
聚丙烯30～50份
淀粉13～20份
蛋白粉5～10份
保湿剂1～2份
蛋白粉3～5份
交联剂5～9份
进一步优选地，所述大豆纤维无纺布(可降解)为大豆纤维、涤纶纤维和尼龙纤维进行混棉。
进一步优选地，大豆纤维无纺布为大豆纤维、涤纶纤维和尼龙纤维以重量份数比为1： 0.1-8:0.5-10进行混棉。
进一步优选地，按照重量份数比，所述合成革底层原料包括：
水12份
水性聚氨酯树脂80份
淀粉树脂114份
液体钙-锌稳定剂3份
甲基丙烯酸甲酯2份
弹性体0.3份
米糠35份
降粘剂1.6份
发泡剂7份
丙烯酸丁酯的混合体2份
进一步优选地，按照重量份数比，所述合成革面层原料包括：
聚丙烯35份
淀粉18份
蛋白粉7份
保湿剂1.3份
蛋白粉3.5份
交联剂6份
进一步优选地，所述的水性聚氨酯树脂为脂肪族阴离子聚酯型、脂肪族阴离子聚醚型、脂肪族阴离子聚酯-聚醚型、芳香族阴离子聚酯型中的一种。
进一步优选地，所述的交联剂为海藻酸钠生物交联剂(可降解)。
进一步优选地，水性聚氨酯树脂和淀粉树脂经过改性处理，水性聚氨酯树脂和淀粉树脂的改性处理方法均为为：先经过波长为0.4-0.7μm强度为50-200Lux的光波处理2-7小时，然后加热至92-95℃持续15-20min。
进一步优选地，丙烯酸丁酯的混合体根据质量百分数分为：质量分数为15％～30％的丙烯酸丁酯、18％～36％醋酸乙烯、1.0％～10％聚乙烯醇和余量的水分。
一种生物可降解的合成革的制备方法，包括以下步骤：
1.将合成革底层的原料压延成型，得到合成革底层；
2.在基布上涂布粘合剂，并将所述合成革底层和合成革面层顺序设置于所述基布上，得到预发泡复合层；
3.对所述预发泡复合层进行发泡处理，得到所述合成革，所述发泡处理的发泡温度为 125～185℃。
本发明与现有技术的优势在于：
1、本发明克服了现有技术中的缺点，提供了一种生物可降解的合成革及其制备方法，有利于减少环境污染，一个月后生物降解度在90％以上。
2、面层不但可以提高手感和使用的舒适度，还可以提高合成革的色泽耐磨度，具有意料不到的效果。
3、本发明制备的合成革针孔抗拉强度和撕裂强度大，制备的产品结实耐用。
附图说明：图1为实施例2合成革降解曲线图。
具体实施方式
下面将结合本发明中的实施例，对分发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
以下对本发明的优选实施例进行说明，应当理解，此处所描述的优选实施例仅用于说明和解释本发明，并不用于限定本发明。
实施例1：
一种生物可降解的合成革，依次包括基布、合成革底层和合成革面层，所述基布为大豆纤维无纺布，按照重量份数比，合成革底层为：
水12份
水性聚氨酯树脂80份
淀粉树脂114份
液体钙-锌稳定剂3份
甲基丙烯酸甲酯2份
弹性体0.3份
米糠35份
降粘剂1.6份
发泡剂7份
丙烯酸丁酯的混合体2份
按照重量份数比，合成革面层为：
聚丙烯35份
淀粉18份
蛋白粉7份
保湿剂1.3份
蛋白粉3.5份
交联剂6份
水性聚氨酯树脂为脂肪族阴离子聚酯型，交联剂为海藻酸钠生物交联剂。其成分均为可降解成分，而且纳米氧化锌使其降解更充分。
实施例1合成革的制备方法，包括以下步骤：
1.将合成革底层的原料压延成型，得到合成革底层；
2.在基布上涂布粘合剂，并将所述合成革底层和合成革面层顺序设置于所述基布上，得到预发泡复合层；
3.对所述预发泡复合层进行发泡处理，得到所述合成革，所述发泡处理的发泡温度为125～185℃。
实施例2：
本实施例与实施例1的技术方案基本相同，相同之处不再赘述，其区别在于：
一种生物可降解的合成革，依次包括基布、合成革底层和合成革面层，基布为大豆纤维无纺布；
按照重量份数比，所述合成革底层为：
水14份
水性聚氨酯树脂70份
淀粉树脂117份
液体钙-锌稳定剂3份
甲基丙烯酸甲酯2份
弹性体0.3份
米糠39份
降粘剂1.6份
发泡剂6份
丙烯酸丁酯的混合体3份
按照重量份数比，所述合成革面层为：
聚丙烯42份
淀粉14份
蛋白粉6份
保湿剂1.8份
蛋白粉3.7份
交联剂8份
这种合成革面层效果柔韧性更强，同时提高了耐弯曲能力，外观质感及物理特性和舒适性方面，都能与天然皮革相媲美。
合成革面层的优势在于能实现大规模连续化生产，品质均一稳定，能按规格制造；具有接近天然皮革的结构；物理化学性能优异，在机械强度，弯曲疲劳，耐酸碱，耐水，耐油，耐候性等方面优于天然皮革，特别适合在恶劣环境和高强度，高湿度，大运动量条件下使用；花色品种具有多样性，用途广泛；革结构均一无部位差，出材率高；革面利用率高，远优于天然皮革。
生物降解是微生物(主要是细菌)的天然作用，它们在靠吃废物繁殖的过程中
将化学物质分解成更为基本的成分，可在有氧或无氧条件下进行。降解的第一步
也称作初级降解，包括吸附和裂解两个过程，在这一阶段表面活性基本丧失；第二步为达到环境可以接受程度的生物降解，降解产物不再导致污染；第三步为完
全降解，其最终产物为CO2和水等无机质和其它代谢物。
阳离子表面活性剂生物降解，一般都认为在需氧条件下进行，加之其具有抗菌性，因此降解能力较弱，甚至还会抑制其它有机物的降解。
季鏻盐、季铵盐等表面活性剂，带有正电荷，对废水中的无机和有机悬浮物具有很强的亲和力，用活性污泥处理时，发生很强的吸附作用使阳离子表面活性剂失活，使得在有氧条件下的生物降解变得容易。
试验过程中，通过每天对降解瓶中的生物合成革含量进行测定，计算其生物降解度，得到生物合成革降解度曲线。如图1合成革降解曲线图所示:
由图可以看出，生物合成革降解分为以下几个阶段：
快速降解期：第一天时，生物合成革的生物降解度即达到80％，可能是因为表面活性剂的强极性和活性污泥及微生物吸附在一起而造成；
相对稳定期：从第二天起，一直到第14天，生物降解处于相对稳定期，降解度基本保持在70％左右；
降解完成期：两周后，生物降解度上升并保持在80％以上；在第18天时，生物降解度第一次达到90％以上，之后几天，基本保持在90％以上；到第21天时，生物降解度达到96％。表明生物合成革具有良好的生物降解性能。
实施例3-8，具体原料配方为：
Figure RE-GDA0002382171990000061
Figure RE-GDA0002382171990000071
制备方法同实施例1，将实施例3、4、5、6、7、8制得的合成革进行测试，结果如下：
测试方法采用标准方法：ASTMD2209-2000(2010)
Figure RE-GDA0002382171990000081
通过以上实验数据可得出，在针孔抗拉强度的撕裂强度方面，实施例3、4、5的合成革具有较大的优势，在底层和面层为同样配方的情况下，基布材料是影响实验数据额关键；但降解方面，实施例5、6、7、8与实施例3-4相比，优势明显，这也和基本材料配方关系极大。手感方面，实施例8因没有面层而造成手感差；透气性方面，本发明实施例5、6、7的透气性高于实施例3-4。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

1.一种生物可降解的合成革，依次包括基布、合成革底层和合成革面层，所述基布为大豆纤维无纺布；按照重量份数比，所述合成革底层原料包括：水10-15份；水性聚氨酯树脂60-100份；淀粉树脂110-120份；液体钙-锌稳定剂2-4份；甲基丙烯酸甲酯1-3份；弹性体0.2-0.5份；米糠20-50份；降粘剂1-2份；发泡剂5-10份；丙烯酸丁酯的混合体1-4份；按照重量份数比，所述合成革面层原料包括：聚丙烯30～50份；淀粉13～20份；蛋白粉5～10份；保湿剂1～2份；蛋白粉3～5份；交联剂5～9份。
2.根据权利要求1所述的生物可降解的合成革，其特征在于：大豆纤维无纺布为大豆纤维、涤纶纤维和尼龙纤维进行混棉。
3.根据权利要求2所述的生物可降解的合成革，其特征在于：大豆纤维无纺布为大豆纤维、涤纶纤维和尼龙纤维以重量份数比为1：0.1-8:0.5-10进行混棉。
4.根据权利要求1所述的生物可降解的合成革，其特征在于：按照重量份数比，所述合成革底层原料包括：水12份；水性聚氨酯树脂80份；淀粉树脂114份；液体钙-锌稳定剂3份；甲基丙烯酸甲酯2份；弹性体0.3份；米糠35份；降粘剂1.6份；发泡剂7份；丙烯酸丁酯的混合体2份。
5.根据权利要求1所述的生物可降解的合成革，其特征在于：按照重量份数比，所述合成革面层原料包括：聚丙烯35份；淀粉18份；蛋白粉7份；保湿剂1.3份；蛋白粉3.5份；交联剂6份。
6.根据权利要求1所述的生物可降解的合成革，其特征在于：所述水性聚氨酯树脂为脂肪族阴离子聚酯型、脂肪族阴离子聚醚型、脂肪族阴离子聚酯-聚醚型、芳香族阴离子聚酯型中的一种。
7.根据权利要求1所述的生物可降解的合成革，其特征在于：所述的交联剂为可降解的海藻酸钠生物交联剂。
8.根据权利要求1所述的生物可降解的合成革，其特征在于：水性聚氨酯树脂和淀粉树脂经过改性处理，水性聚氨酯树脂和淀粉树脂的改性处理方法均为为：先经过波长为0.4-0.7μm强度为50-200Lux的光波处理2-7小时，然后加热至92-95℃持续15-20min。
9.根据权利要求1所述的生物可降解的合成革，其特征在于：丙烯酸丁酯的混合体根据质量百分数分为：质量分数为15％～30％的丙烯酸丁酯、18％～36％醋酸乙烯、1.0％～10％聚乙烯醇和余量的水分。
10.一种生物可降解的合成革的制备方法，其特征在于：a.根据权利要求1-9任一项所述的配方制备合成革底层和合成革面层，b.将合成革底层的原料压延成型，得到合成革底层；c.在基布上涂布粘合剂，并将所述合成革底层和合成革面层顺序设置于所述基布上，得到预发泡复合层；d.对所述预发泡复合层进行发泡处理，得到所述合成革，所述发泡处理的发泡温度为125～185℃。
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