CN104772965B - 镜面精加工层的表面处理 - Google Patents
镜面精加工层的表面处理 Download PDFInfo
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- CN104772965B CN104772965B CN201510005854.3A CN201510005854A CN104772965B CN 104772965 B CN104772965 B CN 104772965B CN 201510005854 A CN201510005854 A CN 201510005854A CN 104772965 B CN104772965 B CN 104772965B
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- 238000004381 surface treatment Methods 0.000 title description 2
- 239000000758 substrate Substances 0.000 claims abstract description 98
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- 239000000243 solution Substances 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 27
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 20
- 238000011282 treatment Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
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- 239000003795 chemical substances by application Substances 0.000 claims description 13
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- 239000000126 substance Substances 0.000 claims description 10
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
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- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 3
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
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- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000006533 methyl amino methyl group Chemical group [H]N(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明开发了处理金属或者塑料衬底以形成镜面精加工层的方法。在改性衬底表面情况的几个预处理步骤之后，不管是金属还是塑料材料，为了增强上述涂层的粘附性，将使用示出有金属外观且光滑的具有装饰功能的镜面精加工层。涂覆可变外涂层，以保护下面的镜面精加工层并实现色彩丰富的装饰。所有材料和处理步骤都是环保的，且不包括昂贵的设备。
Description
相关申请的交叉参考
本申请要求于2014年1月30日提交的美国临时专利申请序列号61/965,421、2014年1月30日提交的美国临时专利申请序列号61/965,417、2014年1月30日提交的美国临时专利申请序列号61/965,420、2014年1月9日提交的美国临时专利申请序列号61/964,586、2014年1月9日提交的美国临时专利申请61/964,584的权益，并将其公开通过参考并入本文。
技术领域
本发明涉及一种形成在衬底上的镜面精加工层，尤其涉及一种在衬底上形成镜面精加工层的预处理方法。
背景技术
金属或者塑料衬底上的镜面精加工层是通过若干传统的方法(诸如电镀、真空沉积和热蒸发)来实现的。除了保护衬底和金属感装饰功能外，该镜面精加工层还可以提供其它性能或特性，诸如电或热传导性。然而，这些传统的处理具有它们自身的缺点。
电镀，工业中最常用的表面处理，由于大量有毒的副产品和废料而对环境有害。由于复杂的后处理工序，因此整个过程将以高成本操作。这限制并阻碍了电镀工业的进一步发展。越来越多的国家通过许多政策禁止或限制电镀工业。
真空沉积和热蒸发使用不能连续生产的昂贵的设备。该批量生产可使产量降低并使产品不稳定。在没有执行产品预处理和后处理的其它辅助方法的情况下，利用上述方法的涂覆产品(尤其是塑料产品)的性能可能不够好，诸如粘附性。
US20060135281公开了一种包括通过电化(电镀)形成的细粒金属层的涂层，其展示了高硬度。US20060135282教导了具有2nm至5,000nm大小的小金属材料晶粒的涂层。中国专利申请CN1944710A公开了通过硝酸银溶液与氨水和氢氧化钠的反应形成的镜面状涂层。之后该涂层用硼氢化物显影。CN101469427A教导了通过喷硝酸银和酒石酸钾以及氢氧化钠的溶液形成的银镜面。该涂层用亚硫酸钠进行后处理。
在上述专利申请中，电镀方法仍用于这两个美国发明，其不能解决废料的高成本和环境污染的问题。另外两个发明仅仅报导了在没有特殊改性情况下银的传统镜面状反应，这会导致银镜面状涂层的不良粘附性和银涂层的氧化问题。
因此，存在还未得到满足的对在衬底上形成具有良好粘附特性和低成本的镜面精加工层的需要。另外，可以以有效且环保的方式制造这种镜面精加工层。
发明内容
本发明开发了一种处理金属或者塑料衬底以形成镜面精加工层的方法。在改性衬底表面情况的几个预处理步骤之后，不管是金属还是塑料材料，为了增加上面涂层的粘附性，将使用示出有金属外观且光滑的具有装饰功能的镜面精加工层。将涂覆可变外涂层，以保护下面的镜面精加工层并实现色彩丰富的装饰。所有涂层材料和处理步骤都是环保的，且无需昂贵的设备。在没有较大改变的情况下可以使用普通喷涂系统，这能实现连续生产以得到更多一致且稳定的涂层产品，并增加产量。
因此，本发明的第一方面在于给衬底提供多步预处理方法以形成镜面精加工层。
根据本发明的实施方式，一种用于预处理用于形成镜面精加工层的衬底的方法包括：将第一材料放置在衬底上，其中第一材料包括第一环氧树脂、第一流平剂、丁醇、丙酮、双丙酮醇、第一固化剂和2,4,6-三(二甲氨基甲基)苯酚；固化该第一材料；将第二材料放置在固化的第一材料上，其中第二材料包括第二环氧树脂、第二流平剂、2-甲基苯基缩水甘油醚、双丙酮醇、丁醇、第二固化剂和2,4,6-三(二甲氨基甲基)苯酚；固化该第二材料；和在固化的第二材料上涂覆镜面精加工层。
优选地，该方法还包括用混合溶剂冲洗固化的第二材料。
优选地，该方法还包括用氯化锡(II)和盐酸的混合溶液处理固化的第二材料。
优选地，该衬底为金属衬底或者塑料衬底。
优选地，该方法还包括通过将后处理材料放置在镜面精加工层上来后处理镜面精加工层。
本发明的第二方面在于提供一种在用本发明的方法制备的塑料或金属衬底上形成的镜面精加工层。
附图说明
参考附图，在下文中将更加详细地描述本发明的实施方式，其中：
图1是示出根据本发明实施方式的在金属/塑料衬底上制备镜面精加工涂层的方法步骤的流程图。
具体实施方式
在下面的描述中，作为优选实例提出了形成在金属/塑料衬底上的镜面精加工层和衬底的预处理方法的对应实施方式。对于本领域技术人员显而易见的是，在不背离本发明的范围和精神的情况下可以进行包括附加和/或替换的修改。可以省略具体细节以免使本发明模糊不清；然而，该公开被撰写成使本领域的技术人员在没有过多实验的情况下能够实践本文的教导。
在该发明中，提供了处理塑料或金属衬底以实现镜面精加工层的整个过程，它不仅能用于批量生产，例如浸渍，而且还能用于连续生产，例如自动化生产线中的喷涂。
图1是示出根据本发明实施方式的在金属/塑料衬底上制备镜面精加工涂层的方法步骤的流程图。在步骤11中，首先通过初始预处理预先处理衬底。对于金属衬底，用砂纸抛光该金属衬底。之后，用水、洗洁精、丙酮和乙醇清洗该抛光的金属衬底。对于塑料衬底，可以使用等离子体处理、化学处理和/或物理处理来预处理该塑料衬底。在步骤12中，用第一材料改性预处理衬底的表面以改善该衬底的粘附性。通过浸渍或喷涂将第一材料放置在预处理衬底上，之后在烤箱中固化。该第一材料包括环氧树脂(诸如E-51)、流平剂(诸如BYK-361N、丁醇、丙酮、双丙酮醇)、固化剂(诸如TZ-550和2,4,6-三(二甲氨基甲基)苯酚)。在步骤13中，用第二材料改性预处理衬底的表面以改善镜面精加工层的粘附性。通过浸渍或喷涂将第二材料放置在固化的第一材料上，之后在烤箱中固化。该第二材料包括环氧树脂(诸如E-51)、流平剂(诸如BYK-361N、2-甲基苯基缩水甘油醚(CGE)、双丙酮醇、丁醇)、固化剂(诸如TZ-550和2,4,6-三(二甲氨基甲基)苯酚)。在步骤14中，用第三材料改性预处理衬底的表面以增强镜面精加工层的形成。用第三材料冲洗第二材料处理的预处理衬底的表面。该第三材料是包含混合溶剂(诸如1：1(体积比)的丙酮和乙醇)的一种溶液。在步骤15中，用第四材料改性预处理衬底的表面以增强镜面精加工层的形成。将第四材料应用在用第三材料处理的预处理衬底的表面上，之后在室温下使其干燥。该第四材料是包含氮化锡(II)和酸的混合物的一种溶液。在步骤16中，在该预处理衬底的表面上涂覆镜面精加工层。在步骤17中，实施用于镜面精加工层的后处理。
优选地，塑料衬底包括丙烯腈丁二烯苯乙烯(ABS)、聚苯烯(PP)或聚碳酸酯(PC)，且金属衬底包括铁、锌、铝、镁或它们的合金。
优选地，将执行在镜面精加工层上放置透明或可变色材料(后处理材料)的步骤以保护它或增加一些特殊功能，其可以通过浸渍或喷涂来产生，之后在烤箱中进行热处理。
因此，虽然金属和塑料两种衬底的表面具有不同特性，但是可将本发明的衬底预处理方法应用于这两种衬底。该预处理方法能够增强衬底和镜面精加工层之间的粘附性。在本发明中没有使用有害且不环保的化学品。另外，用本发明的该方法制备的镜面精加工层提供了高的膜硬度、抗划伤性和耐冲击性。
实例
涂覆金属和塑料衬底的过程主要包括预处理、放置功能涂覆和后处理。
1.衬底的多步预处理
由于两种类型衬底的表面特性不同，因此对于金属和塑料衬底，衬底的预处理也是不同的。
1)处理金属衬底的主要步骤如下示出：
(1)表面抛光：分别用#240、#360和#800的砂纸抛光该金属衬底。也可以使用振动研磨机或者滚筒研磨机以用适当的研磨石抛光相同衬底。对于软金属，诸如Al或Mg合金，如果抛光不适宜，则可以跳过该步骤。
(2)衬底清洗：将该(抛光的)衬底浸入到DI水和洗洁精的混合物中。声波降解衬底超过30分钟。使用流动的DI水逐一地冲洗样品。再次通过超声降解在1：1(体积)的丙酮和乙醇中清洗衬底超过30分钟。用流动的乙醇冲洗衬底。在空气中干燥它们。
(3)用材料1改性表面：通过浸渍或者喷涂将材料1放置在预处理衬底上，之后在烤箱中固化。固化温度可以根据衬底在80～150℃的温度范围内变化至少10分钟。通常，低温适合塑料衬底，高温适合金属衬底。材料1将用于改性衬底表面以实现上面涂层的良好粘附性。
材料1的实例是约10g E-51、0.1g BYK-361N、6g丁醇、1g丙酮、10g双丙酮醇、2gTZ-550和1g 2,4,6-三(二甲氨基甲基)苯酚。通过在室温中搅拌超过30分钟将这些化学品加入并混合在一起。如果必要，在超声波浴中声波降解混合物3分钟。准备好之后，应将材料1保存在室温或者诸如5～10℃的低温中。然而，一旦加入固化剂TZ-550，材料1在室温中应该在2小时内用完。
(4)用材料2改性表面：通过浸渍或者喷涂将材料2放置在涂有材料1的衬底上，之后在烤箱中固化。固化温度可以根据衬底在80～150℃的温度范围变化至少10分钟。通常，低温适合塑料衬底，高温适合金属衬底。该材料2将用于改性表面特性以实现上面涂层的良好粘附性。
材料2的实例是约22g E-51、0.2g BYK-361N、2g GGE、12g双丙酮醇、8g丁醇、5gTZ-550和1g 2,4,6-三(二甲氨基甲基)苯酚。通过在室温中搅拌超过30分钟将这些化学品加入并混合在一起。如果必要，在超声波浴中声波降解混合物3分钟。准备好之后，应将涂层材料2保存在室温或者诸如5～10℃的低温中。然而，一旦加入固化剂TZ-550，材料2在室温中应该在1小时内用完。
2)处理塑料衬底的主要步骤如下示出：
(1)等离子体处理：将等离子体衬底放入等离子室中，并使用等离子清洗机以高水平处理它们至少20分钟。
(2)化学处理：使用不同的化学品处理不同的塑料材料。实例是浓酸对ABS处理5～7分钟，或者高锰酸钾的强氧化剂对PP在70℃处理24小时。
(3)物理处理：如果必要，可以在3.2巴的条件下使用喷沙物理处理超过1分钟。
(4)用材料1改性表面：通过浸渍或者喷涂将材料1放置在预处理衬底上，之后在烤箱中进行热处理。热处理温度可以根据衬底在80～150℃的温度范围内变化至少10分钟。通常，低温适合塑料衬底，高温适合金属衬底。材料1将用于改性衬底表面以实现上面涂层的良好粘附性。
材料1的实例是约10g E-51、0.1g BYK-361N、6g丁醇、1g丙酮、10g双丙酮醇、2gTZ-550和1g 2,4,6-三(二甲氨基甲基)苯酚。通过在室温中搅拌超过30分钟将这些化学品加入并混合在一起。如果必要，在超声波浴中声波降解混合物3分钟。准备好之后，应将材料1保存在室温或者诸如5～10℃的低温中。然而，一旦加入成分TZ-550，材料1在室温中应该在2小时内用完。
(5)用材料2改性表面：通过浸渍或者喷涂将材料2放置在涂有材料1的衬底上，之后在烤箱中进行热处理。热处理温度可以根据衬底在80～150℃的温度范围变化至少10分钟。通常，低温适合塑料衬底，高温适合金属衬底。材料2将用于改性表面特性以实现上面涂层的良好粘附性。
材料2的实例是约22g E-51、0.2g BYK-361N、2g GGE、12g双丙酮醇、8g丁醇、5gTZ-550和1g 2,4,6-三(二甲氨基甲基)苯酚。通过在室温中搅拌超过30分钟将这些化学品加入并混合在一起。如果必要，在超声波浴中声波降解混合物3分钟。准备好之后，应将材料2保存在室温或者诸如5～10℃的低温中。然而，一旦加入成分TZ-550，材料2在室温中应该在1小时内用完。
(6)用材料3改性表面：用流动的混合溶剂(诸如1：1(体积比)的丙酮和乙醇)冲洗用以上材料处理的表面。这可以通过使用洗涤瓶来实现。此后，用流动的DI水冲洗表面。在室温中干燥表面。准备好之后，可以用能长时间(数天或数周)保持有效的密封盖将混合溶剂保存在室温中。该步骤处理将使表面粗糙，以增强上面涂层的粘附性。
(7)用材料4改性表面：材料4是能通过浸渍或者喷涂使用的一种溶液。处理之后，将在室温中干燥衬底。
材料4的实例是约2g氯化锡(II)和2mL盐酸(37％)。以约60℃的温度加热该溶液约10分钟，直到形成清液。此后，在室温中加入400mL的DI水，并彻底打转溶液。在使用之前，使溶液在室温中用盖密封至少4小时以使其老化。将溶液保存在室温中并用盖密封。准备好之后，该溶液应该保持有效1-2周。该步骤处理可在下面衬底的表面上形成一些活性位置，之后使形成镜面精加工层的反应变得更容易。
2.在经上述步骤处理之后的衬底上准备镜面精加工层
通过浸渍或者喷涂将2种溶液放置在经上述步骤处理之后的衬底上，之后在烤箱中固化。当浸渍时，立即将2种溶液混合物并应用在衬底上。如果使用喷涂，在2个独立容器中具有2种溶液的双头喷枪或者2个同时工作的单头喷枪是必须的。固化温度可以根据衬底在80～150℃的温度范围变化至少10分钟。通常，低温适合塑料衬底，高温适合金属衬底。该涂层将实现镜面精加工层。
制备2种溶液的实例如下所示：
2-1)用于镜面精加工层的溶液1(其应在使用时制备并且不应长时间保存)的制备如下：。
1)将20mL的DI水加入到空玻璃烧杯中；
2)将6g氢氧化钠慢慢地加入到上述玻璃烧杯中；
3)在室温中小心地搅拌上述溶液直到所有固体被溶解；
4)将10g硝酸银加入到空玻璃瓶中；
5)将100mL的DI水加入到上述玻璃瓶中；
6)在室温中搅拌上述溶液直到所有固体被溶解；
7)将溶液3)倒入溶液6)中；
8)彻底搅拌上述溶液(将形成棕色沉淀物)；
9)将20mL的28％氨水加入到另一空玻璃烧杯中；
10)将50mL的DI水加入到上述玻璃烧杯中；
11)彻底搅拌上述溶液；
12)将溶液11)滴入溶液8)中，直到所有棕色沉淀物正好被再溶解(将使用大约60mL的氨溶液)并形成清液；
13)用DI水将清液稀释成总容量为1000mL的溶液；
2-2)将如下制备用于镜面精加工层的溶液2，且将其保存在室温中并用盖密封。准备好之后，该溶液将保持数月有效。
1)将8g葡萄糖加入空玻璃瓶中；
2)加入0.5g柠檬酸；
3)加入20mL乙醇；
4)加入980mL的DI水；
5)彻底搅拌该溶液，直到所有固体都被溶解；
3.涂覆镜面精加工层之后的后处理
将在镜面精加工层上执行放置透明或者可变色材料(后处理材料)的步骤，以保护它或者增加一些特殊功能，其可以通过浸渍或者喷涂来实施，之后在烤箱中进行热处理。热处理温度可以根据衬底在80～150℃的温度范围变化至少10分钟。通常，低温适合塑料衬底，高温适合金属衬底。该后处理在改变整个外观的不同颜色或者提供其它特殊功能的同时，还将保护镜面精加工的下面涂层。
后处理材料的实例是约15g甲基三乙氧基硅烷(MTES)、2g γ-巯基丙基三甲氧基硅烷(A189)、6g乙醇、0.5g乙酸、5g丙酮、5g DI水、2g HS-30硅胶和15g双丙酮醇。通过在室温中搅拌超过30分钟将这些化学品加入并混合在一起。如果必要，在超声波浴中声波降解混合物45分钟，直到获得透明溶液。此后，在烤箱中以70℃加热后处理材料18小时，之后冷却至室温并保持24小时。应将后处理材料保存在室温或者诸如5～10℃的低温中。
调整后处理材料颜色的实例是首先使用聚四氟乙烯(PTFE)过滤器(450nm孔径大小)过滤上述无色外涂层溶液。将50g的经过滤的无色后处理材料与11mg结晶紫混合以得到均匀溶液。
特性和性能试验
实施根据本发明上述实例的关于丙烯腈丁二烯苯乙烯(ABS)和聚苯烯(PP)衬底的镜面精加工层的各种性能试验。
实施关于标准ASTM D3363-05/ISO 15184:1998(ISO 15184:2012)的膜硬度试验。在提供750g重荷的条件下，试验结果示出了没有明显变化的4H和没有被损坏的6H。用市场中销售的常规镜面涂层实施相同试验，试验结果仅为2H。
实施关于标准ASTM D3359-02/ISO 2409:2007的胶带试验的粘附性。在具有交叉纹路的条件下，试验结果示出了5B(100％没有脱落)。用市场中销售的常规镜面涂层实施相同试验，试验结果示出了100/100脱落。
实施关于标准ISO 1518-1:2011的抗划伤性试验。通过电机使以面板支撑物固定的试验面板相对于尖笔移动。尖笔移动的速度是(35±5)mm/s。选择具有(0.50±0.01)mm半径的半球形硬金属尖的划痕型尖笔，以用于该试验。试验结果示出了对于ABS，表面涂层通过了150g试验，对于PP，表面涂层通过了81g试验。
实施关于API导线的REACH试验。在高度关注物质(SVHC)的候选列表中的155个衬底中没有任何一个被检测出。
实施关于标准ASTM F2357-04的抗磨损性试验。在具有100个循环的磨损之后，用ABS衬底的镜面精加工层的损耗是3.3mg，用PP衬底的镜面精加工层的损耗是2.1mg。
为了示例和说明，提供了本发明的前面的描述。其并不意指彻底全面或者将该发明限制为所公开的精确形式。对于本领域的技术人员而言，许多修改和变更将是显而易见的。
为了最好地解释本发明的精神和它的实际应用，选择并描述了这些实施方式，从而使该领域的技术人员能够理解该发明的各种实施方式以及适合特殊用途的各种变更。本发明的范围旨在由所附权利要求及其等效物限定。
Claims (10)
1.一种用于形成镜面精加工层的预处理衬底的方法，包括：
将第一材料放置在衬底上，其中第一材料包括第一环氧树脂、第一流平剂、丁醇、丙酮、双丙酮醇、第一固化剂和2,4,6-三(二甲氨基甲基)苯酚；
固化该第一材料；
将第二材料放置在固化的第一材料上，其中第二材料包括第二环氧树脂、第二流平剂、2-甲基苯基缩水甘油醚、双丙酮醇、丁醇、第二固化剂和2,4,6-三(二甲氨基甲基)苯酚；
固化该第二材料；和
在固化的第二材料上涂覆镜面精加工层；
其中衬底为塑料衬底，其中固化第一材料和固化第二材料的步骤在80至150℃的温度范围内执行。
2.根据权利要求1所述的方法，还包括：
用混合溶剂冲洗固化的第二材料。
3.根据权利要求1所述的方法，还包括：
用氯化锡(II)和盐酸的溶液混合物处理固化的第二材料。
4.根据权利要求1所述的方法，还包括：
在将第一材料放置在衬底上的步骤之前，利用初始处理预处理该塑料衬底。
5.根据权利要求4所述的方法，其中初始处理是等离子体处理、化学处理或者物理处理。
6.根据权利要求1所述的方法，其中将第一材料放置在衬底上的步骤通过浸渍或者喷涂来执行。
7.根据权利要求1所述的方法，其中将第二材料放置在固化的第一材料上的步骤通过浸渍或者喷涂来执行。
8.根据权利要求2所述的方法，其中该混合溶剂包括体积比为1比1的丙酮和乙醇。
9.根据权利要求1所述的方法，还包括：
通过将后处理材料放置在镜面精加工层上来后处理镜面精加工层，其中该后处理材料包括甲基三乙氧基硅烷、γ-巯基丙基三甲氧基硅烷、乙醇、乙酸、丙酮、DI水、硅胶和双丙酮醇；和
固化该后处理材料。
10.一种在用权利要求1的方法制备的衬底上形成的镜面精加工层。
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| US20150140340A1 (en) * | 2013-11-21 | 2015-05-21 | Nano And Advanced Materials Institute Limited | Thermal resistant mirror-like coating |
| CN106944322A (zh) * | 2016-01-07 | 2017-07-14 | 泗通贸易有限公司 | 基底的无电镀涂层 |
| CN109290736A (zh) * | 2017-07-24 | 2019-02-01 | 嘉瑞科技（惠州）有限公司 | 一种具有原色高光质感的镁合金工件加工方法 |
| TWI762785B (zh) * | 2019-05-31 | 2022-05-01 | 高鼎實業股份有限公司 | 無銅製程之鏡面背塗層組成物及其形成方法 |
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