CN1051399A - 钟表外壳等装饰品类的金属表层及其形成方法 - Google Patents
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Abstract
本发明涉及钟表外壳等装饰品类的金属表层及
其形成方法，该表层是由经表面预处理的装饰品成型
体底材表面上所形成的硬质透明玻璃保护层，以及进
一步在该层表面形成由硅酸烷基酯衍生的二氧化硅
层所构成。本发明涉及的金属底材装饰品完全没有
因空气中水分和二氧化碳引起的粉雾现象，很难遭致
损伤及其它污染，可以长时期地保持高质量。
Description
本发明涉及钟表外壳等装饰品类的改良金属表层及其形成方法。具体地说，本发明的目的是提供一种金属表层的形成方法及具有该表层的装饰品类，这种方法和装饰品有效地解决了在金属表层上形成的硬质玻璃保护层产生的粉雾现象。
众所周知，以前为了使钟表外壳和皮带类及其它装饰品类的金属表面具有防污性和耐裂性而在该金属表面上形成硬质保护覆膜。其典型的覆膜形成方法，如已知在表面进行珩磨或直线打磨、模压等其它预处理的金属表面上，涂覆硅酸钠和硅溶胶的水性混合液（SiO2/Na2O＝4～10），并将它在空气中加热干燥后形成保护膜的方法。然而，用该方法形成的保护膜，其中所含的Na2O，与大气中的水分或二氧化碳反应，从而在其保护膜上出现泛白物，即存在产生所谓粉雾现象的问题，这种粉雾现象很容易在保护膜的内面形成，且很难将它除去，因而使装饰品的质量显著降低，在实用上有致命的缺点。
因此，本发明的课题在于，提供一种在钟表外壳及其装饰品类的金属表面层上形成没有粉雾且具有装饰品所希望的耐擦伤，耐裂性优良的防污层的方法以及经此改善的金属表面层。
本发明者们在解决上述课题方面经多次重复试验研究，结果发现形成由较薄的硬质透明玻璃保护膜和有机硅酸酯衍生的二氧化硅层的组合层可有效地达到上述目的，且完成本发明。
即本发明提供一种钟表外壳装饰品类金属表层的形成方法，这种在表面经预处理的装饰品用的金属成形体底材表面上形成硬质透明玻璃保护层，并进一步在该层表面上形成硅酸烷基酯类衍生的二氧化硅层从而构成钟表外壳等装饰品类金属表层及其有效制造方法的特征，是将装饰品用的金属成形底材表面，经过电镀，珩磨、直线打磨、模压、渗氮或喷镀进行表面预处理并将它在空气中干燥后，在其表面上涂覆用纯水稀释成4-12倍的含SiO220-21（重量）%和Na2O3.8-4.4（重量）%胶态液，加热干燥后形成硬质透明玻璃保护薄层，然后在该表面上涂覆有机硅酸酯的部分加水分解溶液，并加热、煅烧。
本发明涉及的装饰品类，在形成透明硬质玻璃保护薄层时，其技术特征是将涂覆在金属表面的含SiO220-21（重量）%和Na2O3.8-4.4（重量）%的胶态液用纯水稀释4-12倍后再使用，这一点很重要，在用它涂覆、干燥后形成的硬质透明玻璃保护薄层的上面，涂覆硅酸烷基酯、（烷基硅酸酯）类的部分加水分解溶液，干燥后形成SiO2包覆表层。
本发明中的主要对象装饰品类是，例如钟表外壳，表带，项链，拉刀，耳环，手镯，凸耳，发夹及其它金属装饰品类，特别好的是以不锈钢，金属钛，钛合金及铜合金作为底材的物品。这些金属底材，与形成防污和防擦伤的硬质保护膜时相同，用普通已知的表面处理，例如电镀、珩磨，直线打磨、模压，渗氮或喷镀等方法进行表面预处理。这种表面预处理，根据需要，还可包括将其表面进行碱脱脂和水洗等前处理方法。在经过预处理的金属表面上再形成硬质透明玻璃保护覆膜。在这种经过表面预处理的金属成型底材表面上形成硬质透明玻璃保护覆膜时，不可按原样使用过去的硅酸钠和硅溶胶的混合胶体溶液（含有SiO220-21（重量）%和Na2O3.8-4.4（重量）%），需特别用基本上完全去除二氧化碳的纯水稀释成4-12倍的含有约1.7-5.0（重量）%SiO2和约0.3-1.0（重量）%Na2O的稀释胶体溶液涂覆。如果用纯水将硅酸钠和硅溶胶的混合胶体溶液稀释小于4倍时，膜层变厚，不能清晰地看到金属成形体底材表面形成的珩磨花纹，模压花纹，有损于外观质量。反之，如果稀释到大于12倍，则膜层变薄，功能品质显著降低，原有的功能变得没有了。脱离这种浓度比例时会发生例如产品的防粉雾性降低等情况，因而是不好的。
经过这种浓度调整的形成底层用的稀释胶体溶液可用浸渍法或喷涂法涂覆，并将它在150℃-300℃的温度下加热30分至120分钟，煅烧后形成厚度约0.5-5μm的薄膜。
其次，本发明中，在如此形成的硬质透明玻璃保护层表面上，进一步涂覆硅酸烷基酯类的部分加水分解溶液，并加热煅烧，最好形成约0.5-3μm左右的薄玻璃膜。
因此，本发明的特征是，在装饰品金属成形体底材表面上，形成较薄的硬质透明玻璃保护覆膜和由硅酸烷基酯的部分加水分解溶液形成的SiO2膜组合而成的二重膜保护层作为保护层。
用于形成最上层的处理剂，是硅酸烷基酯的部分加水分解溶液，是将下式表示的有机硅酸烷基酯类部分加水分解配制而成。
（式中，R选自低级烷基，R′是甲基或苯基，n是0、1、2或3）。作为用于形成面涂层的有机硅酸烷基酯类原料，最好是硅酸乙酯类的物质。该表层理想的膜厚约为1～3μm，与此相关，其部分加水分解溶液的浓度最好采用20-40（重量）%左右。这些形成面层用的溶液，同样可用浸渍、喷涂等普通方法涂敷，在150℃～300℃的温度下，加热30分～120分钟干燥后，使之煅烧即形成理想薄层的SiO2覆膜。这种面层的硬度为9H级，本来对防伤并不是充分有效的，但意外地发现，与底层的薄硬质玻璃膜组合成双重层时能形成不会留下伤痕的表层。
如上所述，本发明方法中，作为底涂层的硬质玻璃保护覆膜和作为面涂层由硅酸烷基酯类衍生的SiO2膜的组合是重要的。
于是，在本发明涉及的金属成形体底材表面上将硬质透明玻璃保护层和硅酸烷基酯类的部分加水分解溶液形成的SiO2层组合而成的钟表外壳等装饰品类金属表层，不会因指纹等造成污染，基本上无损伤，也不会因空气中的湿气和二氧化碳产生粉雾现象，因而能长期有效地保持装饰品的高质量。
实施例
以下通过具体实例更详细地说明本发明的特征。
有关经表面处理的金属表层的各种试验方法及其评价如下所示：
（1）耐湿性
在温度为60℃，相对湿度为95%的大气条件下保持24小时，调查其状态。
（2）耐磨损性：
用スガ试验机（NUS-ISO-1）调查。
（3）人工汗
在含下述成分的水溶液中浸渍48小时，调查其耐汗性。
（水溶液成分）
NaCl：9.9g/l，Na2S：0.8g/l，（NH2）2CO：1.7g/l，
CH3CH OH COOH：1.7g/l，以及NH4OH：0.2ml/l，
用这些方法所做的定性评价按以下记号示于表中
◎……优良 X……稍差
○……良好 △……差
实施例1
将钛合金制钟表外壳部件的表面用＃100～＃300的玻璃珠珩磨处理后，进行碱脱脂和水洗预处理。对施以这种表面预处理的面，将含有20（重量）%SiO2和4.0（重量）%Na2O的硅酸钠和硅溶胶的混合胶态液，用经过离子交换树脂除去二氧化碳的纯水稀释至6倍，浸渍上述外壳部件，使之附着在该表面上。然后，在200℃温度下干燥约60分钟，得到约2.0μm硬质透明玻璃保护覆膜。
其次，将硅酸乙酯中加水分解物为60（重量）%的溶液稀释至约30（重量）%，用它在上述硬质透明玻璃保护覆膜上进行浸渍涂覆，在约250°温度下经过约60分钟的干燥、烘干后形成厚度约2.5μm的面涂层。
用上述各种试验方法对经过表面处理的钛合金制的钟表外壳部件进行测试，其结果与评价示于后附的表1中。
实施例2
除了金属底材采用不锈钢制（SUS 304及SUS 316）的钟表用外壳部件外，其它全部与实例1相同，在底材上形成表层。试验结果与评价示于表1。
实施例3
对钟表用外壳部件（Ti材：包括Ti合金及SUS 304），用＃100～＃300的玻璃珠进行珩磨处理，然后对其进行碱脱脂和水洗处理。对这种经过表面预处理的表面，将含20（重量）%SiO2和4.0（重量）%Na2O的硅酸钠与硅溶胶的混合胶态液用经离子交换树脂除去二氧化碳的纯水稀释至约4倍，在上述外壳部件上进行喷涂使之在表面上附着。然后在约250℃温度下干燥约40分钟，得到约2.5μm的透明硬质玻璃保护覆膜。
其次，在该硬质透明玻璃保护覆膜上，将硅酸乙酯的加水分解物约60（重量）%的溶液，稀释至约30（重量）%并用喷涂方法涂覆，在200℃温度下80分钟内将硅酸乙酯进行烘干处理，结果得到厚度约1.5μm的面涂膜。
实施例4
将钟表用外壳部件（包括Ti类合金及SUS 304）用＃100-＃300玻璃珠珩磨处理，然后进行碱脱脂和水洗处理。对这种经表面预处理的表面，将含有20（重量）%SiO2和4.0（重量）%Na2O的硅酸钠和硅溶胶的混合胶态液用经离子交换树脂除去二氧化碳的纯水稀释至约8倍，喷涂在上述外壳部件上使之附着在其表面。然后，将它在约150℃温度下干燥约100分钟，即得到约1.5μm的透明硬质玻璃保护覆膜。
其次，在该硬质玻璃保护覆膜上，将硅酸乙酯的加水分解物为60（重量）%的溶液稀释至约15（重量）%后以喷涂方式涂覆，在150℃温度下经过100分钟将硅酸乙酯进行烘干处理，则得到厚度约2.5μm的面涂膜。
上述实施例3和4的结果也示于后附的表1中。
实施例5
对钟表外壳部件（Ti材：包括Ti合金及SUS 304）用＃100～＃300玻璃珠珩磨处理后，进行碱脱脂及水洗处理，将含有20（重量）%SiO2和4.0（重量）%Na2O的硅酸钠和硅溶胶的混合胶态液用经离子交换树脂除去杂质的纯水稀释约10倍，对上述外壳部件进行喷涂，使之附着在表面上。然后将它在150℃温度下干燥90分钟后则得到约1.0μm的透明硬质玻璃保护覆膜。
其次，在该硬质透明玻璃保护覆膜上，将硅酸乙酯的加水分解物为60（重量）%的溶液稀释至约30（重量）%后以喷涂方式涂覆，在150℃温度下经过100分钟将硅酸乙酯进行烘干处理，则得到厚度为2.5μm的面涂膜。
实施例6
钟表用外壳部件（包括Ti类合金和SUS 304）上，用模压等方法刻上花纹，将其面经过碱脱脂及水洗处理，将含20（重量）%SiO2和4.0（重量）%Na2O的硅酸钠和硅溶胶的混合胶态液用经离子交换树脂除去杂质的纯水稀释至约12倍，对上述外壳部件喷涂使之附着在表面上。然后将它在约150℃下干燥90分钟，得到大约为0.5μm的透明硬质玻璃保护覆膜。
其次，将硅酸乙酯类加水分解物为60（重量）%的溶液稀释至约30（重量）%后以喷涂方式涂覆，在150℃下进行100分钟的烘干处理，则得到厚度约2.5μm的面涂膜。
由于底层的硅酸钠、硅溶胶膜很薄，因此可形成清晰模压花纹。
对比例1
为了对比，在经过普通表面处理的钛合金制钟表外壳上涂覆硅酸钠和硅溶胶的水性混合液（SIO2/Na2O＝约4.8），加热干燥，煅烧形成约3μm的硬质透明玻璃保护覆膜从而得到表层，对该表层进行各种试验，其结果示于表1。
由下列表1可清楚地看出本发明之金属表层在实用方面是很好的。
本发明涉及的金属底材装饰品类，完全没有因空气中水分和二氧化碳引起的粉雾现象，很难遭损伤及其它污染，因而可以长时期地保持优良质量。
表1
| 编号 | 底材金属 | 底层厚（μm) | 面层厚(μm) | 试验项目类别号(1) (2) (3) | 综合评价 |
| 实施例1 | Ti合金 | 2.0 | 2.5 | ◎ ○ ◎ | ◎ |
| 2 | 不锈钢 | 2.0 | 2.5 | ◎ ○ ◎ | ◎ |
| 3 | Ti合金不锈钢 | 2.5 | 1.5 | ○ ○ ◎ | ◎ |
| 4 | Ti合金不锈钢 | 1.5 | 2.5 | ◎ ○ ◎ | ○ |
| 5 | Ti合金不锈钢 | 1.0 | 2.5 | ◎ △ ◎ | ○ |
| 6 | Ti合金不锈钢 | 0.5 | 2.5 | ◎ △ ◎ | ○ |
| 对比例1 | Ti合金 | 3.0 | -- | × ○ ◎ | × |
Claims (2)
1、钟表外壳等装饰品类的金属表层，该表层是由经表面预处理的装饰品用金属成形体底材表面上所形成的硬质透明玻璃保护薄层，以及进一步在该层表面形成由硅酸烷基酯衍生的二氧化硅层所构成的。
2、钟表外壳等装饰品类金属表层的形成方法，其特征在于，将装饰品用的金属成形体底材表面用电镀，珩磨，直线打磨、模压，渗氮或喷镀方法进行表面预处理，将它在空气中干燥后，在其表面上，用纯水将含有SiO220-21（重量）%和Na2O3.8-4.4（重量）%的胶体溶液稀释成4-12倍后涂覆之，加热干燥后形成硬质透明玻璃保护层，然后在该表面上涂覆有机硅酸酯的部分加水分解溶液，并加热煅烧。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP282067/88 | 1988-11-08 | ||
| JP63282067A JPH0813348B2 (ja) | 1988-11-08 | 1988-11-08 | 時計ケース等の装身具類の金属表層及びその形成方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1051399A true CN1051399A (zh) | 1991-05-15 |
| CN1020929C CN1020929C (zh) | 1993-05-26 |
Family
ID=17647715
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89108259A Expired - Fee Related CN1020929C (zh) | 1988-11-08 | 1989-10-27 | 带有保护层的装饰品类的金属制品及保护层的形成方法 |
Country Status (7)
| Country | Link |
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| US (1) | US5091224A (zh) |
| EP (1) | EP0368101B1 (zh) |
| JP (1) | JPH0813348B2 (zh) |
| KR (1) | KR940009675B1 (zh) |
| CN (1) | CN1020929C (zh) |
| DE (1) | DE68912717T2 (zh) |
| HK (1) | HK1000066A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101213497B (zh) * | 2005-06-28 | 2010-11-24 | Eta瑞士钟表制造股份有限公司 | 强化的微机械部件 |
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| US5510147A (en) * | 1995-03-03 | 1996-04-23 | International Paper Company | Sol gel barrier films |
| US5920977A (en) | 1995-12-07 | 1999-07-13 | Wyckoff; James L. | Porcelain coated substrate and process for making same |
| JP3780591B2 (ja) * | 1996-11-25 | 2006-05-31 | ソニー株式会社 | 電子機器筐体及びその製造方法 |
| GB9607090D0 (en) * | 1996-04-03 | 1996-06-05 | Bratton Graham J | Improved membrane |
| US6007925A (en) * | 1996-11-25 | 1999-12-28 | Sony Corporation | Electronic apparatus casing and electronic apparatus casing production method |
| EP1177260B1 (en) * | 1999-03-18 | 2004-12-15 | Akzo Nobel Coatings International B.V. | Primer coating of steel |
| US6358616B1 (en) | 2000-02-18 | 2002-03-19 | Dancor, Inc. | Protective coating for metals |
| US7267728B2 (en) | 2001-01-30 | 2007-09-11 | The Procter & Gamble Company | System and method for cleaning and/or treating vehicles and the surfaces of other objects |
| US6562142B2 (en) | 2001-01-30 | 2003-05-13 | The Procter & Gamble Company | System and method for cleaning and/or treating vehicles and the surfaces of other objects |
| US20020028288A1 (en) * | 2000-06-14 | 2002-03-07 | The Procter & Gamble Company | Long lasting coatings for modifying hard surfaces and processes for applying the same |
| US6869028B2 (en) | 2000-06-14 | 2005-03-22 | The Procter & Gamble Company | Spraying device |
| US6846512B2 (en) | 2001-01-30 | 2005-01-25 | The Procter & Gamble Company | System and method for cleaning and/or treating vehicles and the surfaces of other objects |
| US7381279B2 (en) | 2000-06-14 | 2008-06-03 | The Procter & Gamble Company | Article for deionization of water |
| BR0113867B1 (pt) * | 2000-09-13 | 2012-03-20 | "revestimento de aço com tinta de base". | |
| KR100802886B1 (ko) * | 2000-09-13 | 2008-02-13 | 아크조 노벨 엔.브이. | 강철의 프라이머 코팅방법 |
| BR0211639A (pt) * | 2001-08-03 | 2005-06-28 | Elisha Holding Llc | Método sem eletricidade para tratamento de um substrato, meio aquoso para uso em um processo sem eletricidade para tratamento de uma superfìcie condutora e artigo compreendendo um substrato condutor de eletricidade |
| MXPA04002292A (es) * | 2001-09-11 | 2004-06-29 | Akzo Nobel Coatings Int Bv | Composicion de revestimiento para substratos metalicos. |
| US20040188262A1 (en) * | 2002-02-05 | 2004-09-30 | Heimann Robert L. | Method for treating metallic surfaces and products formed thereby |
| WO2003066937A2 (en) * | 2002-02-05 | 2003-08-14 | Elisha Holding Llc | Method for treating metallic surfaces and products formed thereby |
| DE102004001097B4 (de) * | 2004-01-05 | 2014-06-05 | Epg (Engineered Nanoproducts Germany) Ag | Metallische Substrate mit verformbarer glasartiger Beschichtung |
| CN1955234B (zh) * | 2005-10-25 | 2010-05-12 | 樊官保 | 等同于雕刻凹版油墨的照相凹版油墨及其应用 |
| US20080014420A1 (en) * | 2006-07-11 | 2008-01-17 | Ion Technology (Hong Kong) Limited | Surface treatment for titanium or titanium-alloys |
| ITMI20122261A1 (it) * | 2012-12-28 | 2014-06-29 | Indesit Co Spa | Processo di trattamento superficiale di acciaio inox |
| US9421303B2 (en) | 2013-03-06 | 2016-08-23 | Covalent Coating Technologies, LLC | Fusion of biocompatible glass/ceramic to metal substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA856738A (en) * | 1970-11-24 | J. Burzynski Alfred | Process for the application of a further curable organopolysiloxane to metal | |
| CA661372A (en) * | 1963-04-16 | Eder Heinz | Method of rendering metallic surfaces corrosion resistant | |
| DE1291597B (de) * | 1961-07-05 | 1969-03-27 | Ritter Pfaudler Corp | Verfahren zur Herstellung eines teilweise kristallisierten Emailueberzugs auf metallischen Gegenstaenden |
| ZA795994B (en) * | 1978-11-30 | 1981-05-27 | Gen Electric | Silicone resin coating composition |
| JPS5767665A (en) * | 1980-10-16 | 1982-04-24 | Nippon Sheet Glass Co Ltd | Coating composition |
| CA1163507A (en) * | 1981-09-25 | 1984-03-13 | Daniel A. Polsinelli | Silicone resin coating composition |
| US4355135A (en) * | 1981-11-04 | 1982-10-19 | Dow Corning Corporation | Tintable abrasion resistant coatings |
| JPS5913076A (ja) * | 1982-07-13 | 1984-01-23 | Citizen Watch Co Ltd | 時計ケ−ス等装身具の表面処理方法 |
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| JPS63108082A (ja) * | 1986-10-24 | 1988-05-12 | Hitachi Chem Co Ltd | 酸化ケイ素被膜形成用塗布液 |
-
1988
- 1988-11-08 JP JP63282067A patent/JPH0813348B2/ja not_active Expired - Lifetime
-
1989
- 1989-10-14 KR KR1019890014802A patent/KR940009675B1/ko not_active IP Right Cessation
- 1989-10-19 US US07/424,059 patent/US5091224A/en not_active Expired - Lifetime
- 1989-10-27 DE DE89120027T patent/DE68912717T2/de not_active Expired - Fee Related
- 1989-10-27 CN CN89108259A patent/CN1020929C/zh not_active Expired - Fee Related
- 1989-10-27 EP EP89120027A patent/EP0368101B1/en not_active Expired - Lifetime
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101213497B (zh) * | 2005-06-28 | 2010-11-24 | Eta瑞士钟表制造股份有限公司 | 强化的微机械部件 |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1000066A1 (en) | 1997-11-07 |
| KR940009675B1 (ko) | 1994-10-15 |
| DE68912717T2 (de) | 1994-05-11 |
| KR900008063A (ko) | 1990-06-02 |
| EP0368101B1 (en) | 1994-01-26 |
| JPH0813348B2 (ja) | 1996-02-14 |
| JPH02131176A (ja) | 1990-05-18 |
| EP0368101A1 (en) | 1990-05-16 |
| CN1020929C (zh) | 1993-05-26 |
| US5091224A (en) | 1992-02-25 |
| DE68912717D1 (de) | 1994-03-10 |
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