CN113818258B - 合成皮 - Google Patents

合成皮 Download PDF

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CN113818258B
CN113818258B CN202110647545.1A CN202110647545A CN113818258B CN 113818258 B CN113818258 B CN 113818258B CN 202110647545 A CN202110647545 A CN 202110647545A CN 113818258 B CN113818258 B CN 113818258B
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synthetic leather
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CN113818258A (zh
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林俊伟
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Abstract

本发明涉及一种合成皮，所述合成皮包含基布、形成在该基布上的高分子层以及覆盖该高分子层的表面单元，该表面单元为功能层或功能层与印刷层的组合。该高分子层由以聚乙烯醇缩丁醛为主的组合物形成，该组合物不包括含有异氰酸酯基的交联剂。该功能层由包括主剂的材料形成，并且该主剂是聚氨酯、环氧树脂、聚丙烯酸甲酯或聚乙烯醇缩丁醛；当该主剂为聚乙烯醇缩丁醛时，该材料还包括含有异氰酸酯基的交联剂。本发明的合成皮具备耐候性、耐磨性、耐挠曲性等性质，并且表面可具有多样性的印刷图案。

Description

合成皮
技术领域
本发明涉及一种合成皮，特别是一种含有聚乙烯醇缩丁醛(polyvinyl butyral，以下简称PVB)层的合成皮。
背景技术
参考图1，中国实用新型专利第201437574号提出了一种多功能层叠物，其包含织物层100和形成在该织物层100上的第一薄膜层101。该第一薄膜层101由含有高分子组分的薄膜组合物形成，该高分子组分选自PVB。该多功能层叠物的表面为以PVB为主的第一薄膜层，在实际使用时仍可能存在以下问题：(1)在温度在30℃以上时，表面的PVB层会有粘滞感，导致触感不佳；(2)表面的耐磨性不足；(3)低温耐挠曲性不佳等。由此可知，对于合成皮及其相关的应用领域来说，以PVB为主的薄膜层不适合作为表面。
通过上述说明可知，虽然PVB能满足环保的要求，同时也可以代替聚氯乙烯(PVC)等材料，但上述所提到的合成皮所需的部分性质仍有待进一步提升。
发明内容
因此，本发明的目的为提供一种具备耐候性、耐磨性、耐挠曲性(特别是低温耐挠曲性)且表面触感良好的合成皮。
因此，本发明的合成皮包含基布、在所述基布上形成的高分子层以及覆盖所述高分子层的表面单元；所述表面单元为功能层或者功能层和印刷层的组合。所述高分子层由以聚乙烯醇缩丁醛为主的组合物形成，所述组合物不包括含有异氰酸酯基(isocyanategroup)的交联剂。所述功能层由包括主剂的材料形成，所述主剂是聚氨酯(polyurethane，PU)、环氧树脂(epoxy resin)、聚丙烯酸甲酯(polymethylacrylate，PMA)或PVB；当所述主剂为PVB时，所述材料还包括含有异氰酸酯基的交联剂。根据本发明，所述以PVB为主的组合物是指以所述组合物的总重量为基准，PVB的含量占50重量％至100重量％的组合物。
在本发明的合成皮中，所述表面单元可以为功能层。在一些实施例中，本发明的合成皮还可以进一步包含设置在功能层与高分子层之间的第二接着层。
在本发明的合成皮中，所述表面单元可以为功能层和印刷层的组合；所述印刷层覆盖高分子层，并且所述功能层覆盖所述印刷层。因此，所述合成皮的表面可以具有多样性的印刷图案。在一些实施例中，本发明的合成皮还可以进一步包含设置在印刷层与高分子层之间的第二接着层。
在本发明的合成皮中，所述表面单元可以为功能层和印刷层的组合；所述功能层覆盖高分子层，并且所述印刷层覆盖所述功能层。在一些实施例中，本发明的合成皮还可以进一步包含设置在功能层与高分子层之间的第二接着层。
在本发明的合成皮中，本发明的合成皮还可以包含在所述印刷层上形成的表面功能层。在一些实施例中，本发明的合成皮还可以进一步包含设置在所述功能层与所述高分子层之间的第二接着层。
在本发明的合成皮中，还可以包含第一接着层，所述第一接着层设置在基布与高分子层之间。
在本发明的合成皮中，当形成所述功能层的材料的主剂为聚氨酯时，所述材料还包括含有异氰酸酯基的交联剂。
本发明的功效在于：本发明的合成皮通过在由PVB为主的组合物形成的高分子层上设置表面单元，从而使得合成皮能够具备耐候性、耐磨性、耐挠曲性(特别是低温耐挠曲性)与表面触感良好等性质，并有利于后续的印刷加工作业。
附图说明
图1是现有技术的含有PVB层的层叠物的侧视示意图。
图2是实施例1的侧视示意图。
图3是实施例2的侧视示意图。
图4是实施例3的侧视示意图。
图5是实施例4的侧视示意图。
图6是实施例4进一步包含第一接着层与第二接着层的侧视示意图。
具体实施方式
本发明将就以下实施例作进一步说明，但应了解的是，所述实施例仅用于例示说明，而不应被解释为本发明实施的限制。
以下配合参考附图并结合本发明的优选实施例，进一步阐述了本发明为达成预定发明目的所采取的技术手段。
在详细描述本发明之前，应当注意，在以下的说明内容中，类似的元件以相同的编号表示。
参考图2，本发明的合成皮的实施例1包含基布1、高分子层2及表面单元3。所述高分子层2形成在所述基布1上，所述表面单元3覆盖所述高分子层2。在实施例1的合成皮中，所述表面单元3为功能层31。
所述基布1可以选用任何适合用于合成皮的布。所述基布1的型态可为织布、非织布等。制作基布1的材料可以为例如但不限于聚酯(polyester)、尼龙(Nylon)、丙烯酸树脂(acrylic resin)、聚烯烃(polyolefin)、聚氨酯、麻、棉等。基布1的厚度可以依据合成皮的实际应用进行调整。优选地，基布1的厚度范围为0.09毫米(mm)至25毫米。更优选地，基布1的厚度范围为0.18毫米至8毫米。
高分子层2由组合物形成，所述组合物以PVB为主要成份，且不包括含有异氰酸酯基的交联剂。构成高分子层2的组合物不包括含有异氰酸酯基的交联剂，以避免所述高分子层2质地过硬并可能导致可塑性降低。
优选地，高分子层2由包括PVB和可塑剂组分的组合物形成，所述可塑剂组分用于帮助所述高分子层2与基布1结合，并能增加所述高分子层2的可塑性；所述可塑剂组分为例如但不限于：乙酰柠檬酸三丁酯(acetyl tributyl citrate，ATBC)，乙酰柠檬酸三辛酯(acetyl trioctyl citrate，ATOC)，如邻苯二甲酸丁芐酯(butyl benzyl phthalate)等的烷基芐基邻苯二甲酸酯(alkyl benzyl phthalate)，烷基邻苯二甲酸酯(alkylphthalate)，吹制亚麻籽油(blown linseed oil)，蓖麻醇酸丁酯(butyl ricinoleate)，蓖麻油(castor oil)，如己二酸二己酯(dihexyl adipate)、己二酸二辛酯(dioctyladipate，DOA)等的二烷基己二酸酯(dialkyl adipate)，如邻苯二甲酸二丁酯(dibutylphthalate，DBP)、邻苯二甲酸二辛酯(dioctyl phthalate，DOP)等的二烷基邻苯二甲酸酯(dialkyl phthalate)，二异壬基环己烷-二羧酸酯(di-isononyl-cyclohexane-dicarboxylate，DINCH)，乙二醇二丁酸酯(ethylene glycol di-N-butyrate)，磷酸异癸基二苯酯(isodecyl diphenyl phosphate)，N-乙基甲苯磺酰胺(N-ethyltoluenesulfonamide)，聚乙二醇(polyethylene glycol)，磷酸叔丁基苯二苯酯(tert-butylphenyl diphenyl phosphate)，甲苯磺酰胺(toluenesulfonamide)，三芳基磷酸酯共混物(triaryl phosphate ester blend)，柠檬酸三丁酯(tributyl citrate，TBC)，磷酸三甲苯酯(tricresyl phosphate，TCP)，柠檬酸三乙酯(triethyl citrate，TEC)，三乙二醇(triethylene glycol)，三乙二醇双(2-乙基己酸酯)(triethylene glycol bis(2-ethylhexanoate))，磷酸三苯酯(triphenyl phosphate，TPP)，2-乙基己基二苯基磷酸酯(2-ethylhexyl diphenyl phosphate)或前述任一组合。
优选地，构成高分子层2的组合物可选择地包含其它成分，例如但不限于：不含有异氰酸酯基的交联剂、润滑剂、抗氧化剂、紫外线吸收剂、高分子改性剂、颜料以及填充剂。
优选地，所述润滑剂选自由下列所构成的群组：聚乙烯蜡(polyethylene wax)、硬脂酸(stearic acid)、硬脂酸锌(zinc octadecanoate)、硬脂酸钙(calciumoctadecenoate)以及前述的任一组合。
优选地，所述高分子改性剂则选自由下列所构成的群组：聚(甲基丙烯酸甲酯)(poly(methyl methacrylate)，简称为PMMA)、乙烯-醋酸乙烯酯共聚物(ethylene vinylacetate，简称为EVA)、甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(methyl methacrylate-butadiene-styrene copolymer，简称为MBS)、苯乙烯-丁二烯橡胶(styrene-butadienerubber，简称为SBR)、热塑性聚氨酯(thermoplastic polyurethane，简称为TPU)以及前述任一组合。其用于调整高分子层2的硬度、耐冲击性、耐寒性及耐挠曲性等物性。
高分子层2的厚度可依据实际需求进行调整，优选地，高分子层2的厚度范围为0.03毫米至20毫米。更优选地，高分子层2的厚度范围为0.03毫米至0.8毫米。
功能层31由包括主剂的材料形成。根据本发明，主剂是指以所述材料的总重量为基准，所述主剂的含量占50重量％至100重量％。主剂为所述材料的主要成分且可为聚氨酯、环氧树脂、聚丙烯酸甲酯或PVB。当主剂为PVB时，所述材料还包括含有异氰酸酯基的交联剂，使得所制得的功能层31的硬度高于高分子层2的硬度。优选地，功能层31的硬度为肖氏硬度(shore hardness)40A至80D；高分子层2的硬度为肖氏硬度20A至50D。
优选地，所述材料可依据所选用的主剂，选择地包括交联剂、消光剂、颜料、润滑剂等可满足合成皮所需的表面性质的试剂。所述消光剂例如但不限于二氧化硅。
功能层31的厚度可依据实际需求进行调整，优选地，功能层31的厚度范围为0.01毫米至0.8毫米。更优选地，功能层31的厚度范围为0.01毫米至0.12毫米。
形成功能层31的材料可以为例如但不限于下表1所列举的材料组成：
表1
优选地，实施例1的合成皮还可选择性地包含设置在功能层31与高分子层2之间的第二接着层(未显示于图2中)。
优选地，第二接着层的厚度范围为0.01毫米至0.08毫米。
所述第二接着层可使用如下表2的接着剂：
表2
实施例1的合成皮可以使用已知的制备方法进行制备，例如：利用涂布方式，在基布1上涂布所述组合物，然后干燥以形成高分子层2；接着依据待形成的功能层31以及主剂种类，选择使用涂布或压延贴合方式形成功能层31以覆盖所述高分子层2，其中，如果形成功能层31的材料为水性悬浮液或油性溶液，则可选用涂布方式；如果形成功能层31的材料为固体，则选用压延贴合方式。
本发明的合成皮的实施例2如图3所示，其在结构上与实施例1类似，不同之处在于：实施例2的表面单元3为层覆盖高分子层2的印刷层32和覆盖所述印刷层32的功能层31的组合。
形成印刷层32的油墨材料可选用一般水性油墨或油性油墨，且为了稳定地覆盖高分子层2，形成印刷层32的油墨也可以包含PVB，例如油墨材料可使用含有100重量份的PVB溶液、0重量份至25重量份的二氧化硅、0重量份至20重量份的聚乙烯蜡及3重量份至15重量份的油性颜料。
形成印刷层32的油墨材料可使用如下表3所列的油墨材料：
表3
优选地，实施例2的合成皮还可选择性地包含设置在印刷层32与高分子层2之间的第二接着层(未显示于图3中)。优选地，第二接着层的厚度范围为0.01毫米至0.08毫米。形成第二接着层的接着剂如实施例1所述。
本发明的合成皮的实施例3如图4所示，其在结构上与实施例1类似，不同之处在于：实施例3的表面单元3为覆盖高分子层2的功能层31和覆盖所述功能层31的印刷层32的组合。
优选地，实施例3的合成皮还可选择性地包含设置在功能层31与高分子层2之间的第二接着层(未显示于图4中)。优选地，第二接着层的厚度范围为0.01毫米至0.08毫米。形成第二接着层的接着剂如实施例1所述。
本发明的合成皮的实施例4如图5所示，其在结构上与实施例3类似，不同之处在于：实施例4的合成皮还包含形成在印刷层32上的表面功能层4。
表面功能层4与功能层31在组成、制备方法及厚度范围上类似，可参照实施例1的功能层31进行制备。
优选地，实施例4的合成皮还可选择性地包含设置在功能层31与高分子层2之间的第二接着层(未显示于图5中)。优选地，第二接着层的厚度范围为0.01毫米至0.08毫米。形成第二接着层的接着剂如实施例1所述。
在实施例1至4的合成皮中，还可选择地包含设置在基布1与高分子层2之间的第一接着层。第一接着层的厚度范围及选用的接着剂可参考上述第二接着层。以实施例4的合成皮为例，当合成皮还进一步包含第一接着层和第二接着层时，其结构如图6所示，所述合成皮包含设置在基布1与高分子层2之间的第一接着层5，以及设置在功能层31与高分子层2之间的第二接着层6。
特性分析：低温耐挠曲性
为确保特性分析的实验意义，各实施例与参考例均由相同的ASTM D6182标准方法进行分析，且实施例1-1至实施例1-4均具有如图2的叠层结构，实施例1-1至实施例1-4之间的主要差异在于功能层31的厚度。另外，参考例不具有功能层31，而是具有如图1的叠层结构。
实施例1-1至实施例1-4的基布1与参考例的织物层100：厚度为0.30毫米的针织布；
实施例1-1至实施例1-4的高分子层2与参考例的第一薄膜层101：厚度为0.45毫米的以PVB为主的层，且肖氏硬度为42A；
实施例1-1至实施例1-4的功能层31：由包含油性醚类聚氨酯和油性异氰酸酯交联剂的油性溶液涂布在高分子层2上而形成，其中，以油性醚类聚氨酯的含量为100重量份，油性异氰酸酯交联剂的含量为7重量份；所述油性溶液中的油性醚类聚氨酯的固体含量为25重量％；所述油性溶液的粘度为2500厘泊(centipoise，cps)。此外，功能层31的肖氏硬度为85A。
表4
从表4的耐挠曲性试验结果可知，由于具有功能层，实施例1-1至实施例1-4具有良好的低温耐挠曲性。
综上所述，本发明的合成皮通过在由PVB为主的组合物形成的高分子层上设置表面单元，从而使得合成皮不会产生由在温度30℃以上发生的表面粘滞感所导致的触感不佳、表面耐磨性不足以及低温耐挠曲性不佳等问题，因此确实能达成本发明的目的。
以上实施例仅是本发明的优选实施例，并非对本发明做任何形式上的限制，虽然本发明已以优选实施例描述如上，然而并非用于限定本发明，本领域技术人员在不脱离本发明技术方案的范围内均可利用上述技术内容作出些许更动或修饰为等同变化的等效实施例，但是所有未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (3)

1.一种合成皮，其包含：
基布；
高分子层，所述高分子层形成在所述基布上且由以聚乙烯醇缩丁醛为主的组合物形成，所述组合物不包括含有异氰酸酯基的交联剂；其中，所述高分子层的肖氏硬度为42A；以及
表面单元，所述表面单元覆盖所述高分子层且为功能层；
其中，所述功能层是由包含油性醚类聚氨酯和油性异氰酸酯交联剂的油性溶液涂布在所述高分子层上而形成；其中，所述油性溶液中的所述油性醚类聚氨酯的固体含量为25重量％；以所述油性醚类聚氨酯的含量为100重量份，所述油性异氰酸酯交联剂的含量为7重量份；所述功能层的肖氏硬度为85A。
2.根据权利要求1所述的合成皮，其特征在于，所述合成皮进一步包含设置在所述功能层与所述高分子层之间的第二接着层。
3.根据权利要求1或2所述的合成皮，其特征在于，所述合成皮进一步包含第一接着层，所述第一接着层设置在所述基布与所述高分子层之间。
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