CN115478440B - 水性油漆及由其制备而成的抗菌皮革 - Google Patents
水性油漆及由其制备而成的抗菌皮革 Download PDFInfo
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- CN115478440B CN115478440B CN202110660475.3A CN202110660475A CN115478440B CN 115478440 B CN115478440 B CN 115478440B CN 202110660475 A CN202110660475 A CN 202110660475A CN 115478440 B CN115478440 B CN 115478440B
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- aqueous
- paint
- antibacterial agent
- organic polymer
- ion
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- 239000003973 paint Substances 0.000 title claims abstract description 94
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- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 49
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 48
- 229920000620 organic polymer Polymers 0.000 claims abstract description 45
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
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Abstract
本发明揭示了一种水性油漆及由其制备而成的抗菌皮革。所述抗菌皮革包括表皮层和油漆层。所述表皮层可以是真皮、PVC表皮层、TPO表皮层、PU表皮层等。所述油漆层由所述水性油漆制备而成，所述水性油漆包含有机聚合物和负载于所述有机聚合物上的抗菌剂，所述抗菌剂为金属和/或金属离子和/或金属氧化物。本发明通过将抗菌剂金属和/或金属离子和/或金属氧化物负载于有机聚合物上，意外的发现，不仅有助于提高由所述水性油漆制备而成的抗菌皮革的抗菌性能，还可以保证所述抗菌皮革的耐磨性和耐噪音性能。
Description
【技术领域】
本发明涉及一种水性油漆及由其制备而成的抗菌皮革，所述水性油漆和抗菌皮革可以应用于汽车领域。
【背景技术】
皮革作为一种表面装饰材料被广泛应用于汽车、家装等很多领域，常见的皮革有真皮、极性人造革例如聚氯乙烯(下称PVC)人造革、非极性人造革例如热塑性聚烯烃弹性体(TPO)人造革等，其中，PVC人造革是指以聚氯乙烯为树脂原料制成的人造革，TPO人造革是指以热塑性聚烯烃为树脂原料制成的人造革。
以汽车领域为例，皮革被广泛应用汽车的门板、仪表板、扶手、头枕和座椅，而经过长时间的使用，皮革上会出现很多细菌，尤其是头枕和座椅，严重影响驾乘者的健康和安全。因此，抗菌皮革的开发一直是皮革领域比较重要的一块，特别是近年来，随着经济的不断发展以及人们生活水平的不断提高，人们对于汽车这一第三生活空间的品质的要求越来越高，因而对于抗菌皮革的关注也随之更甚，然而，市场上的皮革均难以满足人们对于优异抗菌性能的要求。
所以，希望提出一种新的技术方案以解决上述技术问题。
【发明内容】
本发明所要解决的技术问题在于：提供一种水性油漆及由其制备而成的抗菌皮革，所述抗菌皮革的抗菌性能较好，且耐磨性和耐噪音性能也能够保证。
为解决上述技术问题，本发明可采用如下技术方案：一种用于制备皮革的水性油漆，其包含有机聚合物和负载于所述有机聚合物上的抗菌剂，所述抗菌剂为金属和/或金属离子和/或金属氧化物。
申请人通过大量的实验意外的发现，通过将所述抗菌剂金属和/或金属离子和/或金属氧化物负载于有机聚合物上，所述有机聚合物可以使得所述抗菌剂在所述水性油漆中均匀分散、不会发生絮凝和沉降，也可以保证所述抗菌剂在由所述水性油漆制备而成的油漆层内缓慢释放，有效的提高由所述水性油漆制备而成的皮革的抗菌性能，同时，还可以保证所述皮革的耐磨性和耐噪音性能。所述皮革可以是真皮、PVC人造革、TPO人造革、PU人造革等。
在本发明中，所述有机聚合物作为有机物载体可以为聚氨酯树脂、丙烯酸树脂和环氧树脂中的一种、两种或者三种。所述有机聚合物的粒径优选为50nm-500nm，更优选440nm-500nm。倘若所述有机聚合物的粒径太大，较大粒径的有机聚合物本身的分散性较差，且所述抗菌剂容易被较大粒径的有机聚合物的分子链包裹住，从而降低抗菌性能；倘若所述有机聚合物的粒径太小，所述水性油漆成膜后的强度会降低。本发明中的所述有机聚合物可以为Permutex EVO-WF-3649/A或者Permutex WF-43-005，均购自斯塔尔精细涂料(苏州)有限公司，中国苏州。
在本发明中，所述抗菌剂为银、银离子、银的氧化物、锌、锌离子、锌的氧化物、铜、铜离子、铜的氧化物、镍、镍离子、镍的氧化物、钴、钴离子、钴的氧化物、铅、铅离子和铅的氧化物中的一种、两种或者多种。所述抗菌剂优选为银及其离子、锌及其离子和铜及其离子，其中，银及其离子的杀菌效果最好且最安全。当所述抗菌剂为锌离子时，以所述水性油漆的总重量为基础计，所述水性油漆优选包含的所述抗菌剂。当所述抗菌剂为银离子时，以所述水性油漆的总重量为基础计，所述水性油漆包含/>的所述抗菌剂，例如 或者这些数值中任意两者之间范围内的所述抗菌剂，优选/>的所述抗菌剂，更优选/>的所述抗菌剂。
在本发明中，负载是指通过一定的处理工艺将所述抗菌剂固定于所述有机聚合物上，使得所述抗菌剂在所述水性油漆中难以与所述有机聚合物分离，本领域普通技术人员可以选择常规的处理工艺处理。
在本发明中，所述有机聚合物和所述抗菌剂制备成抗菌剂水溶液后再制备所述水性油漆，当所述抗菌剂为银离子时，以所述抗菌剂水溶液的总重量为基础计，所述抗菌剂水溶液包含0.1-3％的抗菌剂、1-30％的有机聚合物和69-98.5％的水。进一步地，以所述水性油漆的总重量为基础计，所述水性油漆包含50-98％的水性树脂、2-15％的所述抗菌剂水溶液、1-10％的固化剂、0-25％的助剂；更优选地，所述水性油漆包含60-95％的所述水性树脂、2-10％的所述抗菌剂水溶液、1-10％的所述固化剂、0-25％的所述助剂。
在本发明中，所述水性树脂是指树脂和水的混合物，所述水性树脂可以为水性聚氨酯树脂、水性丙烯酸树脂、水性环氧树脂中的一种、两种或者三种。所述水性树脂的粒径优选为50-900nm。所述水性树脂的固含量为15-55％，例如15％、20％、25％、30％、35％、40％、45％、50％、55％或者这些数值中任意两者之间范围内，更优选为15-30％。本领域技术人员根据实际需要和应用场合，知晓如何选择合适的水性树脂来制备本发明的水性油漆，例如，适用于本发明的水性树脂可以为Permutex EVO-WF-3649/A或者Permutex WF-43-005，均购自斯塔尔精细涂料(苏州)有限公司，中国苏州。
在本发明中，所述固化剂可以是适用于制备水性油漆的任何合适的固化剂，本领域技术人员根据具体的应用场合和要求，知晓如何选择合适的固化剂，例如聚异氰酸酯类固化剂、聚碳化二亚胺固化剂和噁唑啉类固化剂，这些固化剂可以单独使用或组合使用。例如，适用于本发明的固化剂可以为Aquolin 166异氰酸酯固化剂，购自万华化学集团股份有限公司，中国烟台。
在本发明中，所述助剂可以是消泡剂、流平剂、增稠剂、手感剂和稳定剂等，本领域技术人员知晓如何根据实际需要选择添加何种助剂。
所述消泡剂可以是适用于制造水性油漆的任何合适的消泡剂。本领域技术人员根据具体的应用场合和要求，知晓如何选择合适的消泡剂。适用于本发明的消泡剂可以为有机硅消泡剂、聚醚消泡剂、矿物油消泡剂等。例如，适用于本发明的消泡剂可以为购自德国BYK Additives&Instruments的BYK093，购自德国Evonik Industries AG的Tego Airex902W等。
所述流平剂可以是适用于制造水性油漆的任何合适的流平剂。本领域技术人员根据具体的应用场合和要求，知晓如何选择合适的流平剂。适用于本发明的流平剂可以选自丙烯酸类流平剂、有机硅类流平剂和氟碳化合物类流平剂。有机硅类流平剂还可以选自例如硅油、聚二甲基硅氧烷、聚醚聚酯改性有机硅氧烷、烷基改性有机硅氧烷、端基改性有机硅、反应型的流平剂等。例如，适用于本发明的流平剂可以为购自德国BYK Additives&Instruments的BYK333和BYK306。
所述增稠剂可以是适用于制备水性油漆的任何合适的增稠剂。本领域技术人员根据具体的应用场合和要求，知晓如何选择合适的增稠剂。本发明的增稠剂可以为聚氨酯增稠剂或甲基丙烯酸和丙烯酸酯共聚物。例如，适用于本发明的增稠剂可以为PUR 48水性聚氨酯增稠剂，购自德国明凌。
所述手感剂可以是适用于制备水性油漆的任何合适的手感剂。本领域技术人员根据具体的应用场合和要求，知晓如何选择合适的手感剂。例如，聚硅醚，再例如，蜡粉，型号：920，购自BYK Additives&Instruments。
所述稳定剂用于防止氧化变色，增加水性油漆的耐老化性能。本领域技术人员根据具体的应用场合和要求，知晓如何选择合适的稳定剂。本发明的稳定剂可以选自受阻胺类稳定剂、受阻酚类抗氧剂、硫代酯、亚磷酸酯、硫醚中的一种、两种或者多种。
为解决上述技术问题，本发明还可采用如下技术方案：一种抗菌皮革，其包括油漆层，所述油漆层由前面所述的水性油漆制备而成。
为解决上述技术问题，本发明还可采用如下技术方案：一种抗菌皮革，其包括表皮层和油漆层，所述油漆层包括有机聚合物和负载于所述有机聚合物上的抗菌剂，所述抗菌剂为金属和/或金属离子和/或金属氧化物。
在本发明中，所述表皮层为真皮、PVC表皮层、TPO表皮层或者PU表皮层。
在本发明中，所述有机聚合物作为有机物载体可以为聚氨酯树脂、丙烯酸树脂和环氧树脂中的一种、两种或者三种。所述有机聚合物的粒径优选为50nm-500nm，更优选440nm-500nm。倘若所述有机聚合物的粒径太大，一方面，较大粒径的有机聚合物本身的分散性较差，另一方面，所述抗菌剂容易被较大粒径的有机聚合物的分子链包裹住，从而降低抗菌性能；倘若所述有机聚合物的粒径太小，所述水性油漆成膜后的强度会降低。
在本发明中，所述抗菌剂为银、银离子、银的氧化物、锌、锌离子、锌的氧化物、铜、铜离子、铜的氧化物、镍、镍离子、镍的氧化物、钴、钴离子、钴的氧化物、铅、铅离子和铅的氧化物中的一种、两种或者多种。所述抗菌剂优选为银及其离子、锌及其离子和铜及其离子，其中，银及其离子的杀菌效果最好且最安全。
在本发明中，负载是指通过一定的处理工艺将所述抗菌剂固定于所述有机聚合物上，使得所述抗菌剂在所述水性油漆中难以与所述有机聚合物分离，本领域普通技术人员可以选择常规的处理工艺处理。
与现有技术相比，本发明具有如下有益效果：本发明通过将抗菌剂金属和/或金属离子和/或金属氧化物负载于有机聚合物上，由包含所述抗菌剂和有机聚合物的水性油漆制备抗菌皮革，意外的发现，不仅有助于提高所述抗菌皮革的抗菌性能，还可以保证所述抗菌皮革的耐磨性和耐噪音性能。
【具体实施方式】
下面通过实施例和对比例进一步说明本发明。
实施例1
本实施例为一种PVC人造革的制备，本实施例采用的PVC人造革的制备方法为本领域常规的方法，本领域技术人员能够清楚的知道如何选择具体的设备、工艺步骤和条件，因此，以下制备工艺的描述仅涉及其中一种制备方法的关键步骤和条件。
步骤一，混料
PVC致密层浆料的制备：选择PVC粉50份、邻苯类增塑剂45份、钙锌复合稳定剂2份、氢氧化铝助剂1份、受阻胺类光稳定剂1份、受阻酚类抗氧剂1份和颜料3份作为原料，投放到混料罐中，然后进行机械搅拌，并抽真空，直至混合均匀，即获得PVC致密层浆料。
PVC发泡层浆料的制备：选择PVC粉50粉、发泡剂2份、邻苯类增塑剂45份、钙锌复合稳定剂2份、氢氧化铝助剂1份、受阻胺类光稳定剂1份、受阻酚类抗氧剂1份和颜料1份作为原料，投放到混料罐中，然后进行机械搅拌，并抽真空，直至混合均匀，即获得PVC发泡层浆料。
PVC胶水层浆料的制备：选择PVC粉50份、邻苯类增塑剂45份、钙锌复合稳定剂2份、氢氧化铝助剂1份、受阻胺类光稳定剂1份和受阻酚类抗氧剂1份作为原料，投放到混料罐中，然后进行机械搅拌，并抽真空，直至混合均匀，即获得PVC胶水层浆料。
步骤二、PVC表皮层的制备和基布的复合
采用间接涂布法，先将PVC致密层浆料涂覆在离型纸上，送入第一段烘箱塑化定型。接着在塑化定型的PVC致密层上，涂覆PVC发泡层浆料，继续送入第二段烘箱塑化定型，即获得PVC表皮层。
在塑化定型的PVC发泡层上辊涂PVC胶水层浆料，再复合涤纶经编布，送入第三段烘箱进行最终定型，得到PVC人造革涂布材料。出烘箱后，将PVC人造革涂布材料与离型纸分离，各自进行收卷。收卷的PVC人造革涂布材料送至印刷阶段。
步骤三、水性聚氨酯油漆的制备
按照表1-1中的实施例1的水性聚氨酯油漆的配方，将水性聚氨酯油漆原料投放到油漆桶内，进行机械搅拌，直至混合均匀，即获得水性聚氨酯油漆。
步骤四、印刷
将步骤二收卷的PVC人造革涂布材料放卷后，在PVC人造革涂布材料的PVC致密层上印刷步骤三制备的水性聚氨酯油漆。通过印刷机印刷3层水性聚氨酯油漆后，送入烘箱烘干，然后冷却收卷，获得收卷的PVC人造革的印刷半成品。将该PVC人造革的印刷半成品送至压花阶段。
步骤五、压花
将上述收卷的PVC人造革的印刷半成品放卷。经过加热使该PVC人造革的印刷半成品表面软化后，使用压花辊将压花辊表面的花纹通过压力赋予到PVC人造革的印刷半成品上位于PVC致密层的一侧。冷却后，即得到表面具有花纹的PVC人造革。
实施例2-9
实施例2-9同样是PVC人造革的制备，其PVC人造革的制备工艺、PVC致密层的组分和含量、PVC发泡层的组分和含量、PVC胶水层的组分和含量以及基布层的选择均与实施例1完全相同，不同点仅在于油漆层的配方，具体参表1-1、表1-2和表1-3。
对比例1-8
对比例1-8同样是PVC人造革的制备，其PVC人造革的制备工艺、PVC致密层的组分和含量、PVC发泡层的组分和含量、PVC胶水层的组分和含量以及基布层的选择均与实施例1完全相同，不同点仅在于油漆层的配方，具体参表1-1、表1-2和表1-3。
表1-1
表1-2
表1-3
备注：表1-1、表1-2和表1-3中的份数是指重量份，基准份数均相同。
性能测试
耐噪音测试
按照行业标准VDA230-206对实施例1-9和对比例1-8制备的PVC人造革进行表面耐噪音测试，测试结果见表2-1、表2-2、表2-3和表2-4。
耐磨测试
按照通用汽车企业标准GMW3208，选择负荷1000克、测试次数1000次对实施例1-9和对比例1-8制备的PVC人造革进行表面耐磨测试，测试结果见表2-1、表2-2、表2-3和表2-4。
抗菌性能测试
原始样的抗菌性能测试：按照国家标准GB/T31402-2015，对实施例1-9和对比例1-8制备的PVC人造革进行原始样的表面抗菌性能测试，测试结果见表2-1、表2-2、表2-3和表2-4。
热老化后的抗菌性能测试：按照通用汽车企业标准GMW14122，将原始样放置于120℃的烘箱中21天，对实施例1-9和对比例1-8制备的PVC人造革进行热老化后的表面抗菌性能测试，测试结果见表2-1、表2-2、表2-3和表2-4。
马丁代尔耐磨后的抗菌性能测试：按照国家标准GB/T19089-2003，选择磨20000次，对实施例1-9和对比例1-8制备的PVC人造革进行摩擦后的表面抗菌性能测试，测试结果见表2-1、表2-2、表2-3和表2-4。
光照测试
按照大众汽车企业标准PV1303，将原始样放置于测试设备中光照5个循环，对实施例1-9和对比例1-8制备的PVC人造革进行光照测试，测试结果见表2-1、表2-2、表2-3和表2-4。
耐胺测试
按照大众汽车企业标准PV3944，对实施例1-9和对比例1-8制备的PVC人造革进行耐胺测试，测试结果见表2-1、表2-2、表2-3和表2-4。
表2-1
表2-2
表2-3
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表2-4
由实施例2、实施例4、实施例5和对比例7的测试结果可以看出，在水性油漆中添加抗菌剂银离子、锌离子或者氧化锌，且将抗菌剂负载到有机聚合物聚氨酯树脂上，可以显著提高由其制备的PVC人造革的抗菌性能，且PVC人造革的耐噪音性能和耐磨性能仍可以达标。基于此，本领域技术人员可以合理获知金属、金属离子及金属氧化物均可以负载到有机聚合物上，并获得相似的技术效果。
由实施例2、实施例4、实施例5和对比例8的测试结果可以看出，将抗菌剂负载到有机聚合物上与将抗菌剂负载到无机载体上相比，PVC人造革表面的抗菌性能、耐噪音性能和耐磨性能均有显著的提升，取得了意料不到的技术效果。
由实施例1-3和对比例1-2的测试结果可以看出，银离子在水性油漆内的含量对于由该水性油漆制备而成的抗菌皮革的抗菌性能、耐噪音性能和耐磨性能均有影响。倘若银离子的含量太小，例如，对比例1，仅含有0.08‰，其抗菌性能的各项指标均较差；倘若银离子的含量太大，例如，对比例2，含有3.5‰，虽然其部分抗菌性能达标(原始样≥99.9％，热老化后的样≥99.9％)，但是其耐噪音、耐磨和马丁代尔耐磨后的样的抗菌性能均较差。由实施例1-3的测试结果还可以看出，当银离子的含量在一定范围内时，银离子的含量的变化对于抗菌性能、光照性能和耐胺性能的影响不明显，但是对于耐噪音性能和耐磨性能的影响却比较明显，三个实施例中，实施例1的综合性能最好。
由实施例2、实施例6-7和对比例3-4的测试结果可以看出，水性油漆中的主树脂水性聚氨酯树脂的固含量对于由该水性油漆制备而成的抗菌皮革的抗菌性能有一定的影响。倘若主树脂水性聚氨酯树脂的固含量太小，例如，对比例3，由该水性油漆制备而成的油漆层较薄，虽然原始样和热老化后的样的抗菌性能可以达标，但是马丁代尔耐磨后的样的抗菌性能不能达标；倘若主树脂水性聚氨酯树脂的固含量太大，例如，对比例4，由该水性油漆制备而成的油漆层较厚，抗菌皮革各方面的抗菌性能均无法达标。
由实施例2、实施例8-9和对比例5-6的测试结果可以看出，水性油漆中的载体水性聚氨酯树脂的粒径对于由该水性油漆制备而成的抗菌皮革的抗菌性能、耐噪音性能和耐磨性能均有影响。倘若载体水性聚氨酯树脂的粒径太小，例如，对比例5，抗菌皮革各方面的抗菌性能和耐磨性能均不达标；倘若载体水性聚氨酯树脂的粒径太大，例如，对比例6，抗菌皮革各方面的抗菌性能均不达标。由实施例2和实施例8-9的测试结果还可以看出，当载体水性聚氨酯树脂的粒径在一定的范围内，载体聚氨酯树脂的粒径对于抗菌性能、光照性能和耐胺性能的影响不明显，但是对于耐噪音性能和耐磨性能的影响却比较明显，三个实施例中，实施例9的综合性能最好。
实施例1-9均为PVC人造革，基于此，本领域技术人员可以合理获知，上述水性聚氨酯油漆也可以应用于真皮、TPO人造革、PU人造革等以获得相似的技术效果。
可以理解的是，本发明的上述实施例在不冲突的情况下，可以相互结合来获得更多的实施例。在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。
以上实施例仅为本发明的优选实施例，并非全部实施例。可以理解的是，所属领域普通技术人员在不背离本发明的实质精神和范围下，可以对本发明的技术方案进行许多合理的变化，这些合理的变化都是本发明的保护范围。
Claims (16)
1.一种用于制备皮革的水性油漆，其特征在于：所述水性油漆包含水性树脂、作为有机物载体的有机聚合物和负载于所述有机聚合物上的抗菌剂，所述水性树脂为水性聚氨酯树脂，所述有机聚合物为聚氨酯树脂，所述有机聚合物和所述抗菌剂制备成抗菌剂水溶液后再制备所述水性油漆，以所述水性油漆的总重量为基础计，所述水性油漆包含50-98％的所述水性树脂和2-15％的所述抗菌剂水溶液，所述水性树脂的固含量为15-55％，以所述抗菌剂水溶液的总重量为基础计，所述抗菌剂水溶液包含0.1-3％的所述抗菌剂、1-30％的所述有机聚合物和69-98.5％的水，所述抗菌剂为金属和/或金属离子和/或金属氧化物，所述有机聚合物的粒径为300nm-500nm。
2.如权利要求1所述的水性油漆，其特征在于：所述有机聚合物的粒径为440nm-500nm。
3.如权利要求1所述的水性油漆，其特征在于：所述抗菌剂为银、银离子、银的氧化物、锌、锌离子、锌的氧化物、铜、铜离子、铜的氧化物、镍、镍离子、镍的氧化物、钴、钴离子、钴的氧化物、铅、铅离子和铅的氧化物中的一种、两种或者多种。
4.如权利要求1至3中任意一项所述的水性油漆，其特征在于：所述抗菌剂为锌离子，以所述水性油漆的总重量为基础计，所述水性油漆包含的所述抗菌剂。
5.如权利要求1至3中任意一项所述的水性油漆，其特征在于：所述抗菌剂为银离子，以所述水性油漆的总重量为基础计，所述水性油漆包含的所述抗菌剂。
6.如权利要求5所述的水性油漆，其特征在于：以所述水性油漆的总重量为基础计，所述水性油漆包含的所述抗菌剂。
7.如权利要求6所述的水性油漆，其特征在于：以所述水性油漆的总重量为基础计，所述水性油漆包含的所述抗菌剂、1-10％的固化剂、0-25％的助剂。
8.如权利要求7所述的水性油漆，其特征在于：所述水性油漆包含60-95％的所述水性树脂、2-10％的所述抗菌剂水溶液、1-10％的所述固化剂、0-25％的所述助剂。
9.如权利要求7所述的水性油漆，其特征在于：所述水性树脂的粒径为50-900nm。
10.如权利要求7所述的水性油漆，其特征在于：所述水性树脂的固含量为15-30％。
11.一种抗菌皮革，其包括油漆层，其特征在于：所述油漆层由权利要求1至10中任意一项所述的水性油漆制备而成。
12.一种抗菌皮革，其包括表皮层和油漆层，其特征在于：所述油漆层包括水性树脂、作为有机物载体的有机聚合物和负载于所述有机聚合物上的抗菌剂，所述抗菌剂为金属和/或金属离子和/或金属氧化物，所述有机聚合物的粒径为300nm-500nm。
13.如权利要求12所述的抗菌皮革，其特征在于：所述有机聚合物为聚氨酯树脂、丙烯酸树脂和环氧树脂中的一种、两种或者三种。
14.如权利要求12所述的抗菌皮革，其特征在于：所述有机聚合物的粒径为440nm-500nm。
15.如权利要求12所述的抗菌皮革，其特征在于：所述抗菌剂为银、银离子、银的氧化物、锌、锌离子、锌的氧化物、铜、铜离子、铜的氧化物、镍、镍离子、镍的氧化物、钴、钴离子、钴的氧化物、铅、铅离子和铅的氧化物中的一种、两种或者多种。
16.如权利要求12所述的抗菌皮革，其特征在于：所述表皮层为真皮、PVC表皮层、TPO表皮层或者PU表皮层。
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