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CN101977859A - 搪瓷 - Google Patents

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Publication number
CN101977859A
CN101977859A CN2009801095699A CN200980109569A CN101977859A CN 101977859 A CN101977859 A CN 101977859A CN 2009801095699 A CN2009801095699 A CN 2009801095699A CN 200980109569 A CN200980109569 A CN 200980109569A CN 101977859 A CN101977859 A CN 101977859A
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Prior art keywords
nanoparticles
enamel
agglomerate
ability
enamel according
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米谢勒·雷涅
奥利维耶·皮若尔
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Rolex SA
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Montres Rolex SA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/02—Designs or pictures characterised by special or unusual light effects produced by reflected light, e.g. matt surfaces, lustrous surfaces
    • B44F1/04—Designs or pictures characterised by special or unusual light effects produced by reflected light, e.g. matt surfaces, lustrous surfaces after passage through surface layers, e.g. pictures with mirrors on the back
    • B44F1/045—Designs or pictures characterised by special or unusual light effects produced by reflected light, e.g. matt surfaces, lustrous surfaces after passage through surface layers, e.g. pictures with mirrors on the back having mirrors or metallic or reflective layers at the back side
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/627—Copper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • C09C1/644—Aluminium treated with organic compounds, e.g. polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B19/00—Indicating the time by visual means
    • G04B19/06—Dials
    • G04B19/12—Selection of materials for dials or graduations markings
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Surface Treatment Of Glass (AREA)
  • Paints Or Removers (AREA)
  • Powder Metallurgy (AREA)
  • Glass Compositions (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

本发明涉及一种半透明或透明的着色搪瓷，其含有失去了自身彼此团聚倾向的金属纳米颗粒，并具有基本由光的反射产生的颜色。该纳米颗粒失去自身彼此团聚的能力是由于进行了涂覆，或因为利用静电或使用高位阻物质或使用置于其表面的亲水性物质对其进行了官能化。该纳米颗粒可为金纳米颗粒，其赋予所述搪瓷强烈的深红色。

Description

搪瓷
本发明涉及一种着色透明或半透明搪瓷。该搪瓷以置于基底上的反光层的形式存在，“着色”效果主要由表面反射、多重内反射和散射提供。
已知搪瓷(enamel)是一种由基础玻璃料得到的玻璃态化合物，在其制备过程中加入不同的助熔剂以降低其熔点。其通常沉积于例如金属的基底上以在其上形成图案，也可以将其沉积于金属晶格的“空隙”中，从而得益于搪瓷的透明性而获得特定的效果。这即被称为“pique-à-jour”搪瓷。此外，已知搪瓷的颜色是通过金属颗粒获得的。透明、半透明和不透明搪瓷的存在取决于基础玻璃料的组成。
最后，已知玻璃中的胶体金颗粒在光的传播中产生强烈的深红色。著名的例子为慕拉诺玻璃(Murano glass)，其商业秘密至今仍处于严格保密中。
本发明的目的在于获得慕拉诺型着色，也就是强烈地和深度着色，不是在玻璃上，而是在搪瓷上。搪瓷与玻璃的区别在于，后者通过在高温下熔融其组分获得，与此不同，搪瓷以称为“泥釉(slip)”的水溶液形式施加，其在大大低于玻璃熔点的温度下进行“煅烧”之前进行干燥。
还需指出玻璃基本由石英或氧化硅构成，而搪瓷通常除了石英还包括长石、高岭土和金属氧化物。
因而，本发明明确涉及一种半透明或透明搪瓷，其中含有对搪瓷着色的金属纳米颗粒从而赋予搪瓷深度和强烈着色。这基本上由光的反射产生，特别是当搪瓷沉积于基底上的层中时。
根据本发明，所述纳米颗粒通过保持隔离和彼此分离使得其在泥釉和最终的搪瓷中失去了自身彼此絮凝、聚结或团聚的倾向，并保持了他们的胶体稳定性。
的确，纳米颗粒的团聚或沉淀产生暗色或褐色，甚至完全损失红色，显而易见这与所期望的强烈的深红色相反。
在制备搪瓷过程中或在搪瓷的煅烧热处理过程中，第一种消除金属纳米颗粒团聚能力的方式为用与相对于泥釉中其它成分不活泼的物质进行涂覆，例如晶体二氧化硅，特别是专利WO2008/014623中所描述的，其涉及陶瓷而非搪瓷。
第二种消除金属纳米颗粒团聚或彼此聚集能力的方式是使其表面官能化。
可以使用多种技术进行表面官能化，例如静电排斥，借助于置于纳米颗粒表面之上的电荷载体使其彼此排斥并保持为均匀悬浮液。胶体理论提出了多种解决方案，包括已经存在于表面的官能团的离子化或离子的特定吸附。因此，可以在纳米颗粒合成过程中或向水溶液中加入例如阿拉伯树胶，其可以稳定悬浮液。
另一种物理性质的技术在于例如通过接枝或在此通过静电键在纳米颗粒表面生长物质，例如分子或离子，由此产生位阻，使得它们不再能够彼此嵌入，从而防止团聚或沉淀现象。该物质的合适例子是聚苯乙烯，其吸附于纳米颗粒表面并且看起来它们无法彼此接触。
另一种技术是使纳米颗粒表面亲水，例如也通过物质的吸附，特别是分子，由此产生的亲水纳米颗粒倾向于与溶液中的水结合，从而在泥釉干燥和搪瓷煅烧过程中彼此分离而不聚集。作为亲水性物质，有利地是使用用羧基改性的聚苯乙烯型物质，或者使用表面活性剂例如十二烷基硫酸钠。
根据本发明，所述金属纳米颗粒由贵金属构成，例如金、银或铂，或者由其它金属构成，例如铁、铬、铜、钴、镁或它们的合金。所述金属纳米颗粒也可由金属氧化物构成例如氧化锡。
考虑到日益严格的环境和公共健康标准，本发明的搪瓷的一个至关重要的优点在于，为了提供着色，不再需要加入传统的搪瓷颜料。从而可以在整个可见光谱范围内获得全部范围的着色和色调，而无需使用有毒的盐例如铅、锡、硒、铈或镉的盐。
金通常产生红色，而铬会产生绿色，其它各种物质情况类似。对于颜色，作者们彼此对于纳米颗粒尺寸、其浓度及其形状的影响的意见并不相同。
本发明还涉及分层搪瓷，其可沉积于基底、金属表面或另外的反光表面上，例如白色搪瓷。通过基底反射光的散射，强烈而深刻的“着色”效果被放大。这里需要注意，为了获得摩尔效果(moiréeffect)，或“蝴蝶翅膀(butterfly)”或“全息(hologram)”效果(即当入射光变化时产生彩虹效果、颜色变化或出现幻象)，可以制造由多层搪瓷构成的最终图案，特别是如果搪瓷层厚度非常小时，典型地小于1微米。
可以理解本发明所公开的内容适用于有关装饰的多个领域，尤其是赤陶或金属物品，特别是在珠宝和首饰领域。
本发明还发现了在钟表制造或手表制造领域用于装饰的有利应用，借助于搪瓷来装饰表壳或刻度盘。

Claims (9)

1.一种含有金属纳米颗粒的着色半透明或透明搪瓷，其特征在于：这些纳米颗粒是失去了自身易于彼此团聚的倾向的纳米颗粒。
2.根据权利要求1所述的搪瓷，其特征在于：其为置于反射性基底的层的形式，着色基本上由光的反射产生。
3.根据权利要求1所述的搪瓷，其特征在于：通过涂覆，所述纳米颗粒失去了彼此团聚的能力。
4.根据权利要求1所述的搪瓷，其特征在于：通过静电排斥，通过借助于置于其表面的电荷载体例如阿拉伯树胶进行官能化，使所述纳米颗粒失去彼此团聚的能力。
5.根据权利要求1所述的搪瓷，其特征在于：通过借助于具有高位阻的物质例如聚苯乙烯进行官能化，使所述纳米颗粒失去彼此团聚的能力。
6.根据权利要求1所述的搪瓷，其特征在于：通过借助于置于其表面的亲水性物质例如羧基改性的聚苯乙烯、或表面活性剂例如十二烷基硫酸钠进行官能化，使所述纳米颗粒失去彼此团聚的能力。
7.根据前述任一项权利要求所述的搪瓷，其特征在于：所述金属纳米颗粒为贵金属例如金、银或铂的纳米颗粒，或者为选自由铁、铬、铜、钴、镁或它们的合金所组成的组中的其它金属的纳米颗粒，或者为金属氧化物例如氧化锡的纳米颗粒。
8.一种制造如前所述任一项权利要求中搪瓷的方法，其特征在于：制备泥釉，向其中加入纳米颗粒，该纳米颗粒在泥釉中或在随后的煅烧过程中失去了彼此团聚的能力；然后干燥泥釉并煅烧获得的原料搪瓷。
9.如权利要求1-7任一项所述的搪瓷在首饰、珠宝或者钟表制造或手表制造中的应用。
CN2009801095699A 2008-03-19 2009-03-10 搪瓷 Pending CN101977859A (zh)

Applications Claiming Priority (3)

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EP08405083.0 2008-03-19
EP08405083A EP2103572A1 (fr) 2008-03-19 2008-03-19 Email
PCT/CH2009/000089 WO2009114953A1 (fr) 2008-03-19 2009-03-10 Email

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US (1) US8329779B2 (zh)
EP (2) EP2103572A1 (zh)
JP (1) JP5793072B2 (zh)
CN (1) CN101977859A (zh)
WO (1) WO2009114953A1 (zh)

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CN102515782A (zh) * 2011-12-22 2012-06-27 许昌学院 一种通过外加纳米材料在氧化气氛下烧制钧瓷的方法
CN106365452A (zh) * 2016-08-31 2017-02-01 醴陵市恒辉瓷厂 亮光砂金釉及其制备方法

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EP2305756A1 (fr) 2009-09-22 2011-04-06 Rolex Sa Materiau composite colore comprenant des nanoparticules
US20140013800A1 (en) * 2012-07-12 2014-01-16 Richline Group, Inc. Jewelry article with formed illusion plate
TWI534819B (zh) * 2014-07-31 2016-05-21 常憶科技股份有限公司 於靜態電流測試下檢測全域字元線缺陷
ITUA20163229A1 (it) * 2016-05-06 2017-11-06 Angelo Po Grandi Cucine Spa Prodotto per il rivestimento di superfici metalliche
EP4528390A1 (fr) * 2023-09-25 2025-03-26 The Swatch Group Research and Development Ltd Procédé de fabrication d'un composant horloger émaillé

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515782A (zh) * 2011-12-22 2012-06-27 许昌学院 一种通过外加纳米材料在氧化气氛下烧制钧瓷的方法
CN102515782B (zh) * 2011-12-22 2014-09-03 许昌学院 一种通过外加纳米材料在氧化气氛下烧制钧瓷的方法
CN106365452A (zh) * 2016-08-31 2017-02-01 醴陵市恒辉瓷厂 亮光砂金釉及其制备方法
CN106365452B (zh) * 2016-08-31 2019-03-12 醴陵市恒辉瓷厂 亮光砂金釉及其制备方法

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US8329779B2 (en) 2012-12-11
WO2009114953A1 (fr) 2009-09-24
JP5793072B2 (ja) 2015-10-14
US20110009525A1 (en) 2011-01-13
EP2103572A1 (fr) 2009-09-23

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