CN115593034A - 高剥离性辐射交联聚烯烃弹性体人造革 - Google Patents

高剥离性辐射交联聚烯烃弹性体人造革 Download PDF

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CN115593034A
CN115593034A CN202110774241.1A CN202110774241A CN115593034A CN 115593034 A CN115593034 A CN 115593034A CN 202110774241 A CN202110774241 A CN 202110774241A CN 115593034 A CN115593034 A CN 115593034A
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polyolefin elastomer
radiation
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李民
蔡相成
许桥
李庆北
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Shanghai HIUV Applied Materials Technology Co Ltd
Shanghai HIUV New Materials Co Ltd
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    • B32—LAYERED PRODUCTS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]

Abstract

本发明公开了一种高剥离性辐射交联聚烯烃弹性体人造革，所述的人造革在聚烯烃弹性体层与基布层的中间增加了一层聚烯烃弹性体粘合层，并且该粘合层经过辐射交联。该粘合层提升了聚烯烃弹性体层与基布层的粘合力。该人造革可广泛用于鞋面革、箱包革、沙发革、家装内饰革或汽车内饰革等领域。

Description

高剥离性辐射交联聚烯烃弹性体人造革
技术领域
本发明涉及人造革技术领域，尤其涉及一种高剥离性辐射交联聚烯烃弹性体人造革。
背景技术
随着人们生活水平的日益提高，人们对生活用品提出越来越高的质量要求。皮革，作为生活用品，其近年来不仅市场需求量越来越大，同时对满足客户的各项要求(包括环保性能、内在的物理强度要求、耐久性要求、耐溶剂要求等)也越来越高。由于真皮在制造过程中会产生大量污染，同时生产成本较高、耐久性相对较差、表面物性相对较低，保养困难等先天不足，已不能够满足人们高质量的潜在需求。以聚氨酯(PU)为主体合成革从开始发展到现在，因为其相对优异的性能，相对较低的成本等优势，已大量使用于鞋、箱包、沙发、服装等领域的制造，合成革产业已成为轻工行业的支柱产业。
目前，整个合成革的结构都是建立在聚氨酯(PU)或者聚氯乙烯(PVC)为主体的基层上，生产过程中大量使用有机溶剂、增塑剂，如二甲基甲酰胺、甲乙酮、丙酮、甲苯、乙酸乙酯、邻苯类增塑剂等，这些材料对人体或环境都有危害的极大性。
在我司的前期专利中提出以EVA为基材结构的合成革，具有良好的回弹性、柔顺性、耐老化等性能，且对环境友好，工艺简单，成本低廉等优点。但其自身醋酸的气味限制了其使用范围。
聚烯烃弹性体的气味低，具有优异的耐老化性能，目前已经有使用聚烯烃弹性体作为人造革基材的报道。但其由于是非极性材料，其本身没有粘性，与基布的粘结需要使用胶水。常用的胶水与聚烯烃不是同类材料，一般用丙烯酸酯类、聚氨酯类、环氧等，其含溶剂而在生产过程中产生污染。如果使用粘结性树脂，尽管其可以粘结聚烯烃弹性体和基布，但其融点低影响该类合成革的使用温度范围。如何既满足环保要求，又使聚烯烃弹性体与基布的粘合力在适当的温度范围中均能满足合成革的粘结性要求，需要有合适的解决办法。
发明内容
本发明的目的是克服了上述现有技术的缺点，提供了一种高剥离性辐射交联聚烯烃弹性体人造革。所述的人造革在聚烯烃弹性体层与基布层的中间增加了一层聚烯烃弹性体粘合层，并且该粘合层经过辐射交联。按重量份数计，所述的聚烯烃弹性体粘合层由以下成分组成(聚烯烃弹性体与接枝改性聚烯烃弹性体的总和为100份)：聚烯烃弹性体0～100份；接枝改性聚烯烃弹性体0～100份；增粘树脂0.5～40份；助交联剂1～10份及其它助剂和填料。
较佳地，所述的聚烯烃弹性体为乙烯-α烯烃共聚物弹性体。
较佳地，所述基布为针织弹力起毛布、平织起毛布、针织平布、机织涤纶布、尼龙布、超纤基布、涤纶长丝弹力布、无纺布、各种其它无纺布中的任意一种。
优选地，所述的聚烯烃弹性体粘合层，其特征在于，按重量份数计，由以下成分组成(聚烯烃弹性体与接枝改性聚烯烃弹性体的总和为100份)：聚烯烃弹性体60～100份；接枝改性聚烯烃弹性体0～40份；增粘树脂4～20份；助交联剂2～8份及其它助剂和填料。
较佳地，所述的接枝改性聚烯烃弹性体的接枝基团为丙烯酸(AA)、马来酸酐(MAH)、甲基丙烯酸缩水甘油酯(GMA)、丙烯酸甲酯(MA)、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸盐单体中的任意一种或多种。
优选地，所述的接枝改性聚烯烃弹性体的接枝基团为马来酸酐(MAH)。
较佳地，所述的增粘树脂包括松香(脂松香、妥尔油松香、木松香)、松香衍生物(氢化松香、歧化松香、聚合松香、酯化松香、马来酸化松香)和萜烯树脂(α－萜烯树脂、β－萜烯树脂、萜烯酚醛树脂)；合成系列树脂包括聚合树脂[C5，C9和C5/C9石油树脂、二环戊二烯(DCPD)树脂、古马隆－茚树脂、苯乙烯系列树脂]和缩合树脂(烷基酚醛树脂、二甲苯树脂)中的任意一种或多种。
优选地，所述的增粘树脂为萜烯树脂。
较佳地，所述的增粘树脂的软化点≤120℃。
较佳地，所述的辐射采用高能电子束、γ射线或X射线，辐射剂量为5～200KGY。
较佳地，聚烯烃弹性体粘合层辐照后的交联度为1％～90％。
具体实施方式
为了能够更清楚地描述本发明的技术内容，下面结合具体实施例来进行进一步的描述。
本发明提供了一种高剥离性辐射交联聚烯烃弹性体人造革，所述的人造革在聚烯烃弹性体层与基布层的中间增加了一层聚烯烃弹性体粘合层，并且该粘合层经过辐射交联。该粘合层提升了聚烯烃弹性体层与基布层的粘合力，剥离强度明显提升。聚烯烃弹性体粘合层的配方和辐射剂量如表一所示，其中实施例1增粘树脂为C5石油树脂。实施例2接枝聚烯烃弹性体的接枝基团为甲基丙烯酸缩水甘油酯(GMA)，增粘树脂为松香。实施例3接枝聚烯烃弹性体的接枝基团为丙烯酸甲酯(MA)，增粘树脂为萜烯树脂(T100)。实施例4接枝聚烯烃弹性体的接枝基团为丙烯酸(AA)，增粘树脂为C5石油树脂。实施例5接枝聚烯烃弹性体的接枝基团为甲基丙烯酸缩水甘油酯(GMA)，增粘树脂为松香。实施例6接枝聚烯烃弹性体的接枝基团为马来酸酐(MAH)，增粘树脂为萜烯树脂(T100)。实施例7接枝聚烯烃弹性体的接枝基团为马来酸酐(MAH)，增粘树脂为萜烯树脂(T90)。实施例8接枝聚烯烃弹性体的接枝基团为马来酸酐(MAH)，增粘树脂为萜烯树脂(T100)。实施例9接枝聚烯烃弹性体的接枝基团为马来酸酐(MAH)，增粘树脂为萜烯树脂(T110)。实施例10接枝聚烯烃弹性体的接枝基团为马来酸酐(MAH)，增粘树脂为萜烯树脂(T120)实施例11接枝聚烯烃弹性体的接枝基团为马来酸酐(MAH)，增粘树脂为沙林树脂。
表一 聚烯烃弹性体粘合层各组分重量份数表
Figure BDA0003153868560000031
实施例1～11和比较例1～2制得的高剥离性聚烯烃弹性体人造革中聚烯烃弹性体粘合层的交联度及聚烯烃弹性体粘合层与基布层的层间剥离强度数据如下表二所示：按照GB/T 29848-2018-5.5.3中二甲苯萃取法测试聚烯烃弹性体粘合层的交联度，层间粘合力按照GB/T 14905-2009测试。
表2高粘结性辐射交联聚烯烃弹性体合成革的性能参数表
Figure BDA0003153868560000032
Figure BDA0003153868560000041
从表2数据可以看出，采用了该发明中的高剥离性辐射交联聚烯烃弹性体人造革，在聚烯烃弹性体层与基布层的中间增加了一层聚烯烃弹性体粘合层，且经过辐射交联处理，提升了聚烯烃弹性体层与基布层的粘合力，制造工艺简单。
在此说明书中，本发明已参照其特定的实施例作了描述。但是，很显然仍可以作出各种修改和变换而不背离本发明的精神和范围。因此，说明书被认为是说明性的而非限制性的。

Claims (6)

1.一种高剥离性辐射交联聚烯烃弹性体人造革，其特征在于，所述的人造革在聚烯烃弹性体层与基布层的中间增加了一层聚烯烃弹性体粘合层，并且该粘合层经过辐射交联。按重量份数计，所述的聚烯烃弹性体粘合层由以下成分组成：聚烯烃弹性体0～100份；接枝改性聚烯烃弹性体0～100份(聚烯烃弹性体与接枝改性聚烯烃弹性体的总和为100份)；增粘树脂0.5～40份；助交联剂1～10份及其它助剂和填料。
2.根据权利要求1所述的高剥离性辐射交联聚烯烃弹性体人造革，其特征在于，所述的接枝改性聚烯烃弹性体的接枝基团为丙烯酸(AA)、马来酸酐(MAH)、甲基丙烯酸缩水甘油酯(GMA)、丙烯酸甲酯(MA)、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)等(甲基)丙烯酸单体及(甲基)丙烯酸钠、(甲基)丙烯酸锂、(甲基)丙烯酸锌等(甲基)丙烯盐中的任意一种或多种。
3.根据权利要求1所述的高剥离性辐射交联聚烯烃弹性体人造革，其特征在于，所述的增粘树脂包括松香、沙林树脂、松香衍生物、萜烯树脂、C5，C9和C5/C9石油树脂、二环戊二烯(DCPD)树脂中的任意一种或多种。
4.根据权利要求1所述的高剥离性辐射交联聚烯烃弹性体人造革，其特征在于，所述的增粘树脂的软化点≤120℃。
5.根据权利要求1所述的高粘结性辐射交联聚烯烃弹性体人造革，其特征在于，所述的辐射采用高能电子束、γ射线或X射线。
6.根据权利要求1所述的高粘结性辐射交联聚烯烃弹性体人造革，其特征在于，聚烯烃弹性体粘合层辐照后的交联度为1％～90％。
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