CN102108485A - 塑胶表面抗菌镀层的制备方法 - Google Patents
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Abstract
塑胶表面抗菌镀层的制备方法，涉及一种塑胶材料。提供一种抗菌效果较好的塑胶表面抗菌镀层的制备方法。将塑胶基材放入PVD真空设备中抽真空，进行活化处理；将活化后的塑胶基材表面真空镀抗菌金属膜；对所得的真空镀抗菌金属膜的样品喷镀抗菌中间涂层，即完成塑胶表面的抗菌镀层，所述抗菌中间涂层为添加有机抗菌剂或无机抗菌剂的漆层。利用PVD真空镀的金属抗菌膜层来弥补有机抗菌涂层抗菌时效，使得具有双层抗菌层产品在使用周期都具有优异的抗菌抑菌效果，抗菌效果不仅长期有效，而且抗菌与抑菌效率高，抗菌率在99％以上，产品功能优异且外观优良，非常适用于卫浴、电子、家电与汽车等行业。
Description
技术领域
本发明涉及一种塑胶材料，尤其是涉及一种塑胶表面抗菌镀层的制备方法。
背景技术
进入21世纪以来，塑料制品已成为人们的日常生活中必不可少的一部分，其广泛应用于我们生活的每一个细节，例如在人们日常接触的各种家用电器(电话、洗衣机、电脑、电器开关等)当中已经大量采用了塑料制品。另一方面，由于环境污染等原因的影响，这些人们日常接触的塑料制品的表面往往会带有大量的细菌，成为细菌污染源和疾病传播源。据统计，全世界每年的死亡人数中大约有1700万人是因细菌传染而引起的。那么发展和研究具有抗菌性能的新型镀层制品，对于改善人们的生活环境、减少疾病发生率、保护人类身体健康等方面都具有十分重要的现实意义。
从2003年SARS病毒全球泛滥到H1N1流感的全球性爆发，让消费者对食品安全和环境中存在各种病原菌的担心加剧。抗菌剂在塑料中的应用日益广泛，以满足人们对公共卫生和日常生活的需要，据统计，全世界的抗菌剂在塑料中应用的年增长率约为3.5％～4％。北美是使用抗菌剂(包括生物抑制剂)最多的地区，占全球总用量的约40％，日本约占20％。而日本的人均抗菌剂使用量最大，远超北美和欧洲。根据世界知名的民意调查公司Gallup poll最近发布的一项调查显示，绝大多数的消费者表示愿意购买有抗菌保护的抗菌产品，75％的消费者偏爱选择具有抗菌保护的产品。调查中，10人有7人以上透露有用到超过6样抗菌产品。消费者感觉在用途和环境方面有必要使用抗菌加工的制品。
中国专利200420071581公开一种表面抗菌耐磨制品，其基材是金属制品、无机材料制品、高分子材料制品，通过物理气相沉积技术在上述基材表面上镀有含银或铜或银铜复合物的硬质膜。但是该发明的镀层的耐磨性不够好，抗菌性持续效果较差。
发明内容
本发明的目的在于针对现有的塑胶表面抗菌有机涂层存在耐磨性较差，抗菌抑菌的时效性不够长等缺点，提供一种抗菌效果较好的塑胶表面抗菌镀层的制备方法。
本发明包括以下步骤：
1)将塑胶基材放入PVD真空设备中抽真空，进行活化处理；
在步骤1)中，所述塑胶基材可采用热塑性塑胶或热固性塑胶等，所述热塑性塑胶可选自ABS、PC/ABS、HIPS、PC、PPO、PP、PERT、HDPE、PA6、PA66、ABS/TPU、玻纤增强PA6和玻纤增强PP等热塑性塑胶，所述热固性塑胶可选自BMC等；所述活化处理的工艺条件可为离子源电流0.3～0.8A，偏压80～300V，占空比50％～80％，氩气流速10～200SCCM，氧气流速50～300SCCM，炉内真空压力0.1～0.8Pa，活化时间5～15min，以达到清洁及活化塑胶基材表面的目的，以提高底层金属膜与基材间的结合力。
2)将活化后的塑胶基材表面真空镀抗菌金属膜；
在步骤2)中，所述将活化后的塑胶基材表面真空镀抗菌金属膜可采用电弧法或中频溅射法，所述电弧法的工艺条件可为：靶电源电流50～120A，偏压80～200V，氩气流速20～100SCCM，氮气流速20～100SCCM，炉内真空压力0.1～0.8Pa，镀膜时间5～60min；所述中频溅射法的工艺条件可为：中频电源功率5～9kW，偏压80～200V，氩气流速20～100SCCM，氮气流速20～100SCCM，炉内真空压力0.1～0.8Pa，镀膜时间5～60min；所述抗菌金属膜的靶材可选自Cu，Cr，Ag，Zn，Cu0.5-Zn0.5，Cr0.98-Ag0.2合金靶材等中的至少一种。
3)对步骤2)所得的真空镀抗菌金属膜的样品喷镀抗菌中间涂层，即完成塑胶表面的抗菌镀层，所述抗菌中间涂层为添加有机抗菌剂或无机抗菌剂的漆层。
在步骤3)中，所述有机抗菌剂可选自罗门哈斯公司vinyzene的二氯十辛基异噻唑啉酮(Dichlorooctylisothiazolinone，DCOIT)、美国道康宁公司的3-(三甲氧甲硅烷基)丙基十八烷基二甲基氯化铵，DC5700、托洛伊公司(Troy Corporation)的10，10’-氧代双吩恶砒(OBPA)、聚合化学合金公司(PolyChem Alloy)的磷酸酯复合物，PolySept L型抗菌剂的抗菌剂等中的至少一种。所述无机抗菌剂可选自纳米银、纳米铜等中的至少一种；所述漆层为UV(光固化)漆、烤(热固化)漆、电泳漆、静电粉末漆等中的至少一种；所述UV(光固化)漆的喷涂工艺包含以下程序：(1)喷镀一层添加1％～10％抗菌剂的UV漆，漆层厚度可为10～30μm；(2)塑胶件送入红外线烘炉，进行喷漆膜层流平、烘干，烘干的温度可为50～70℃，烘干的时间可为3～10min；(3)流平后喷漆膜层在紫外线光固化炉内接受照射固化交联10～45s；所述电泳漆的喷涂工艺包含以下程序：(1)在样品表面电泳沉积厚度为10～30μm电泳漆；(2)电泳漆层在烘箱内固化，固化温度可为140℃，固化时间可为20min；所述静电粉末漆的喷涂工艺包含以下程序：(1)在上述样品表面喷涂一层粉末漆，其厚度为10～30μm；(2)塑胶件送入红外线烘炉，进行喷漆膜层流平、固化，固化温度可为50～70℃，固化时间可为30～40min。
与现有的塑胶表面抗菌有机涂层相比，本发明的突出优点是：
本发明利用PVD真空镀金属抗菌膜层来提高在有机涂层的抗菌效果不佳时起到很好的抗菌补充效果，达到抗菌的时效性与产品的使用寿命周期都有很好的抗菌效果。这种具有双层抗菌层的塑胶制品表面具有持久的抗菌、抑菌效果。也就是说，利用PVD真空镀的金属抗菌膜层来弥补有机抗菌涂层抗菌时效，使得具有双层抗菌层产品在使用周期都具有优异的抗菌抑菌效果，抗菌效果不仅长期有效，而且抗菌与抑菌效率高，抗菌率在99％以上，产品功能优异且外观优良，非常适用于卫浴、电子、家电与汽车等行业。
附图说明
图1为本发明实施例1的大肠杆菌测试结果图。在图1中，(a)为空白样上存活的大肠杆菌(稀释100倍)，(b)为抗菌样上存活的大肠杆菌。
图2为本发明实施例1的金黄色葡萄球菌测试结果图。在图2中，(a)为空白样上存活的金黄色葡萄球菌(稀释100倍)，(b)为抗菌样上存活的金黄色葡萄球菌。
具体实施方式
实施例1
一种PC/ABS镜壳镀双层抗菌镀层示例，其工艺流程如下：
(1)将PC/ABS注塑成型坯件放入PVD真空设备中，进行抽真空，当真空度达到10-2时，对基材实施清洗与活化(等离子辉光)，其工艺条件为离子源电流0.3A，偏压150V，占空比80％，氩气流速100SCCM，氧气流速200SCCM，炉内真空压力0.4Pa，活化时间10min，以达到清洁及化活化基体表面之目的，提高金属抗菌膜与基材间的结合力。
(2)对将PC/ABS注塑成型坯件表面真空镀金属底膜，对基材表面真空镀抗菌金属膜，同时沉积铜铬银3种金属抗菌膜，铬银两种纯金属靶材采用电弧靶材，纯铜靶材采用频溅用的圆柱形靶材，其工艺条件：铬靶电源电流60A，银靶电源电流80A，铜靶中频电源功率5kW，偏压120V，氩气流速50SCCM，氮气流速80SCCM炉内真空压力0.15Pa，镀膜时间5min。
(3)对已镀PVD金属底层的样品喷镀抗菌中间涂层为添加无机抗菌剂的UV涂层其工艺包含以下程序，依次：
a.喷镀一层添加1％纳米银抗菌剂的UV漆，漆层厚约30μm。
c.塑胶件送入红外线烘炉，进行喷漆膜层流平、烘干，烘干温度为50℃，烘干时间为10min。
d.流平后喷漆膜层在紫外线光固化炉内接受照射固化交联，交联时间为45s。
样品依据JIS Z2801：2000 Antimicrobial～Test for antimicrobial activity and efficacy标准进行检测，检测结果如表1所示，抗菌的效果照片如图1和图2所示。
表1
实施例2
在玻纤增强PPO塑胶基材镀双层抗菌镀层应用示例，其工艺流程如下：
(1)将玻纤增强PPO塑胶基体放入PVD真空设备中，进行抽真空，当真空度达到10-2时，对基材实施清洗与活化(等离子辉光)，其工艺条件为离子源电流0.8A，偏压200V，占空比50％，氩气流速10SCCM，氧气流速300SCCM，炉内真空压力0.5Pa，活化时间15min，以达到清洁及化活化基体表面之目的，提高抗菌膜层与基材间的结合力。
(2)对玻纤增强PPO塑胶基材表面真空镀金属底膜，其工艺条件为中频溅射法工艺条件：中频电源功率6kW，偏压80V，氩气流速20SCCM，偏压200V，氩气流速100SCCM，氮气流速50SCCM炉内真空压力0.2Pa，镀膜时间50min。抗菌膜层所采用的靶材为：Cr0.98-Ag0.2合金靶材。
(3)对已镀PVD金属底层的样品喷镀抗菌中间涂层为添加无机抗菌剂的UV涂层其工艺包含以下程序，依次：
a.喷镀一层添加10％纳米铜抗菌剂的UV漆，漆层厚约10μm。
c.塑胶件送入红外线烘炉，进行喷漆膜层流平、烘干，烘干温度为70℃，烘干时间为3min。
d.流平后喷漆膜层在紫外线光固化炉内接受照射固化交联，交联时间为10s。
实施例3
一种PA6加玻纤矿粉(增强型PA6)镀双层抗菌镀层水龙头示例，其工艺流程如下：
(1)将PA6加玻纤矿粉(增强型PA6)胶件基体放入PVD真空设备中，进行抽真空，当真空度达到10～2时，对基材实施清洗与活化(等离子辉光)，其工艺条件为离子源电流0.6A，偏压100V，占空比70％，氩气流速50SCCM，氧气流速100SCCM，炉内真空压力0.3Pa，活化时间8min，以达到清洁及化活化基体表面之目的，提高抗菌除氯膜与基材间的结合力。
(2)对PA6加玻纤矿粉(增强型PA6)胶件基材表面真空镀金属底膜，对基材表面真空镀抗菌金属膜，同时沉积铜锌银3种金属抗菌膜，纯银金属靶材采用电弧靶材，Cu0.5-Zn0.5合金靶采用频溅用的圆柱形靶材，其工艺条件：银靶电源电流70A，Cu0.5-Zn0.5合金靶中频电源功率9kW，偏压200V，氩气流速100SCCM，氮气流速10SCCM，炉内真空压力0.2Pa，镀膜时间30min。
(3)对已镀PVD金属底层的样品喷镀抗菌中间涂层为添加有机抗菌剂的UV。其工艺包含以下程序，依次：
a.喷镀一层添加3％罗门哈斯公司的DCOIT抗菌剂的UV漆，漆层厚约20μm。
c.塑胶件送入红外线烘炉，进行喷漆膜层流平、烘干，烘干温度为70℃，烘干时间为8min。
d.流平后喷漆膜层在紫外线光固化炉内接受照射固化交联，交联时间为30s。
实施例4
一种BMC热固性塑胶坯件镀双层抗菌镀层冰箱把手示例，其工艺如下：
(1)将BMC热固性塑胶坯件基体放入PVD真空设备中，进行抽真空，当真空度达到10-2时，对基材实施清洗与活化(等离子辉光)，其工艺条件为离子源电流0.3A，偏压80V，占空比60％，氩气流速100SCCM，氧气流速300SCCM，炉内真空压力0.7Pa，活化时间10min，以达到清洁及化活化基体表面之目的，提高抗菌膜与基材间的结合力。
(2)对BMC热固性塑胶坯件基材表面真空镀金属底膜，对基材表面真空镀抗菌金属膜，同时沉积铜铬锌3种金属抗菌膜，铜锌两种纯金属靶材采用电弧靶材，纯银靶材采用频溅用的圆柱形靶材，其工艺条件：铜靶电源电流80A，锌靶电源电流50A，纯银靶中频电源功率5kW，偏压150V，氩气流速100SCCM，氮气流速20SCCM，炉内真空压力0.21Pa，镀膜时间15min。
(3)对已镀PVD金属底层的样品喷镀抗菌中间涂层为添加有机抗菌剂的UV。其工艺包含以下程序，依次：
a.喷镀一层添加6％托洛伊公司的10，10’-氧代双吩恶砒(OBPA)抗菌剂的UV漆，漆层厚约15μm。
c.塑胶件送入红外线烘炉，进行喷漆膜层流平、烘干，烘干温度为62℃，烘干时间为9min。
d.流平后喷漆膜层在紫外线光固化炉内接受照射固化交联，交联时间为25s。
实施例5
一种ABS镜框镀双层抗菌镀层生产示例，其工艺流程如下：
(1).将ABS镜框胶件基体放入PVD真空设备中，进行抽真空，当真空度达到10-2时，对基材实施清洗与活化(等离子辉光)，其工艺条件为离子源电流0.8A，偏压120V，占空比60％，氩气流速80SCCM，氧气流速120SCCM，炉内真空压力0.2Pa，活化时间5min，以达到清洁及化活化基体表面之目的，提高抗菌除氯膜与基材间的结合力。
(2).对ABS镜框胶件基材表面真空镀金属底膜，对基材表面真空镀抗菌金属膜，同时沉积铜锌铬银四种金属抗菌膜，铬银两种纯金属靶材采用电弧靶材，Cu0.5-Zn0.5合金靶采用频溅用的圆柱形靶材，其工艺条件：铬靶电源电流60A，银靶电源电流50A，Cu0.5-Zn0.5合金靶中频电源功率8kW，偏压100V，氩气流速50SCCM，氮气流速50SCCM，炉内真空压力0.25Pa，镀膜时间25min。
(3).对已镀PVD金属底层的样品喷镀抗菌中间涂层为添加有机抗菌剂的UV。其工艺包含以下程序，依次：
a.喷镀一层添加10％聚合化学合金公司的“PolySept”抗菌剂的UV漆，漆层厚约10μm。
c.塑胶件送入红外线烘炉，进行喷漆膜层流平、烘干，烘干温度为55℃，烘干时间为10min。
d.流平后喷漆膜层在紫外线光固化炉内接受照射固化交联，交联时间为10s。
Claims (10)
1.塑胶表面抗菌镀层的制备方法，其特征在于包括以下步骤：
1)将塑胶基材放入PVD真空设备中抽真空，进行活化处理；
2)将活化后的塑胶基材表面真空镀抗菌金属膜；
3)对步骤2)所得的真空镀抗菌金属膜的样品喷镀抗菌中间涂层，即完成塑胶表面的抗菌镀层，所述抗菌中间涂层为添加有机抗菌剂或无机抗菌剂的漆层。
2.如权利要求1所述的塑胶表面抗菌镀层的制备方法，其特征在于在步骤1)中，所述塑胶基材选自热塑性塑胶或热固性塑胶；所述热塑性塑胶选自ABS、PC/ABS、HIPS、PC、PPO、PP、PERT、HDPE、PA6、PA66、ABS/TPU、玻纤增强PA6和玻纤增强PP热塑性塑胶；所述热固性塑胶选自BMC。
3.如权利要求1所述的塑胶表面抗菌镀层的制备方法，其特征在于在步骤1)中，所述活化处理的工艺条件为离子源电流0.3～0.8A，偏压80～300V，占空比50％～80％，氩气流速10～200SCCM，氧气流速50～300SCCM，炉内真空压力0.1～0.8Pa，活化时间5～15min。
4.如权利要求1所述的塑胶表面抗菌镀层的制备方法，其特征在于在步骤2)中，所述将活化后的塑胶基材表面真空镀抗菌金属膜采用电弧法或中频溅射法。
5.如权利要求4所述的塑胶表面抗菌镀层的制备方法，其特征在于所述电弧法的工艺条件为：靶电源电流50～120A，偏压80～200V，氩气流速20～100SCCM，氮气流速20～100SCCM，炉内真空压力0.1～0.8Pa，镀膜时间5～60min；所述中频溅射法的工艺条件为：中频电源功率5～9kW，偏压80～200V，氩气流速20～100SCCM，氮气流速20～100SCCM，炉内真空压力0.1～0.8Pa，镀膜时间5～60min。
6.如权利要求1所述的塑胶表面抗菌镀层的制备方法，其特征在于在步骤2)中，所述抗菌金属膜的靶材选自Cu，Cr，Ag，Zn，Cu0.5-Zn0.5，Cr0.98-Ag0.2合金靶材中的至少一种。
7.如权利要求1所述的塑胶表面抗菌镀层的制备方法，其特征在于在步骤3)中，所述有机抗菌剂选自二氯十辛基异噻唑啉酮、3-(三甲氧甲硅烷基)丙基十八烷基二甲基氯化铵、DC5700、10，10’-氧代双吩恶砒、磷酸酯复合物、PolySeptL型抗菌剂的抗菌剂中的至少一种。
8.如权利要求1所述的塑胶表面抗菌镀层的制备方法，其特征在于在步骤3)中，所述无机抗菌剂选自纳米银、纳米铜中的至少一种。
9.如权利要求1所述的塑胶表面抗菌镀层的制备方法，其特征在于在步骤3)中，所述漆层为UV漆、烤漆、电泳漆、静电粉末漆中的至少一种。
10.如权利要求9所述的塑胶表面抗菌镀层的制备方法，其特征在于，
所述UV漆的喷涂工艺包含以下程序：(1)喷镀一层添加1％～10％抗菌剂的UV漆，漆层厚度为10～30μm；(2)塑胶件送入红外线烘炉，进行喷漆膜层流平、烘干，烘干的温度为50～70℃，烘干的时间为3～10min；(3)流平后喷漆膜层在紫外线光固化炉内接受照射固化交联10～45s；
所述电泳漆的喷涂工艺包含以下程序：(1)在样品表面电泳沉积厚度为10～30μm电泳漆；(2)电泳漆层在烘箱内固化，固化温度为140℃，固化时间为20min；
所述静电粉末漆的喷涂工艺包含以下程序：(1)在上述样品表面喷涂一层粉末漆，其厚度为10～30μm；(2)塑胶件送入红外线烘炉，进行喷漆膜层流平、固化，固化温度为50～70℃，固化时间为30～40min。
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| CN102851666A (zh) * | 2012-09-27 | 2013-01-02 | 厦门建霖工业有限公司 | 一种镀有铜层基材上的复合抗菌镀层的表面处理方法 |
| CN103574121A (zh) * | 2013-11-14 | 2014-02-12 | 厦门建霖工业有限公司 | 一种无重金属污染的金属龙头及其制备方法 |
| CN104674168A (zh) * | 2015-03-03 | 2015-06-03 | 温州职业技术学院 | 一种聚合物高分子材料等离子体表面改性工艺 |
| CN105504661A (zh) * | 2016-01-29 | 2016-04-20 | 青岛海信电器股份有限公司 | 一种具有抗菌功能的遥控器外壳材料及制备方法 |
| WO2019212092A1 (ko) * | 2018-05-02 | 2019-11-07 | 21세기메디칼 주식회사 | 생활용품의 표면처리방법 |
| CN111903682A (zh) * | 2020-07-03 | 2020-11-10 | 东莞捷尔信实业有限公司 | 一种新型的抗菌、抗病毒组合物及其处理工艺 |
| US11665956B2 (en) | 2016-09-08 | 2023-05-30 | Boe Technology Group Co., Ltd. | Flexible substrate and fabrication method thereof, and flexible display apparatus |
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| US20160168688A1 (en) * | 2014-12-15 | 2016-06-16 | Cheng-Shang Tsao | Method for preparation of composite composition |
| US10064273B2 (en) | 2015-10-20 | 2018-08-28 | MR Label Company | Antimicrobial copper sheet overlays and related methods for making and using |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851666A (zh) * | 2012-09-27 | 2013-01-02 | 厦门建霖工业有限公司 | 一种镀有铜层基材上的复合抗菌镀层的表面处理方法 |
| CN102851666B (zh) * | 2012-09-27 | 2014-05-07 | 厦门建霖工业有限公司 | 一种镀有铜层基材上的复合抗菌镀层的表面处理方法 |
| CN103574121A (zh) * | 2013-11-14 | 2014-02-12 | 厦门建霖工业有限公司 | 一种无重金属污染的金属龙头及其制备方法 |
| CN103574121B (zh) * | 2013-11-14 | 2016-05-25 | 厦门建霖工业有限公司 | 一种无重金属污染的金属龙头制备方法 |
| CN104674168A (zh) * | 2015-03-03 | 2015-06-03 | 温州职业技术学院 | 一种聚合物高分子材料等离子体表面改性工艺 |
| CN104674168B (zh) * | 2015-03-03 | 2016-11-30 | 温州职业技术学院 | 一种聚合物高分子材料等离子体表面改性工艺 |
| CN105504661A (zh) * | 2016-01-29 | 2016-04-20 | 青岛海信电器股份有限公司 | 一种具有抗菌功能的遥控器外壳材料及制备方法 |
| US11665956B2 (en) | 2016-09-08 | 2023-05-30 | Boe Technology Group Co., Ltd. | Flexible substrate and fabrication method thereof, and flexible display apparatus |
| WO2019212092A1 (ko) * | 2018-05-02 | 2019-11-07 | 21세기메디칼 주식회사 | 생활용품의 표면처리방법 |
| KR20190126661A (ko) * | 2018-05-02 | 2019-11-12 | 김민호 | 생활용품의 표면처리방법 |
| KR102103403B1 (ko) * | 2018-05-02 | 2020-04-23 | 김민호 | 생활용품의 표면처리방법 |
| CN111903682A (zh) * | 2020-07-03 | 2020-11-10 | 东莞捷尔信实业有限公司 | 一种新型的抗菌、抗病毒组合物及其处理工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20120193232A1 (en) | 2012-08-02 |
| CN102108485B (zh) | 2012-03-28 |
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