JP2001199741A - Colorant composition and method for producing colored glass - Google Patents
Colorant composition and method for producing colored glassInfo
- Publication number
- JP2001199741A JP2001199741A JP2000006025A JP2000006025A JP2001199741A JP 2001199741 A JP2001199741 A JP 2001199741A JP 2000006025 A JP2000006025 A JP 2000006025A JP 2000006025 A JP2000006025 A JP 2000006025A JP 2001199741 A JP2001199741 A JP 2001199741A
- Authority
- JP
- Japan
- Prior art keywords
- colorant composition
- noble metal
- glass
- fine particles
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/479—Metals
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はガラス表面を着色可
能な着色剤組成物とそれを使用した着色ガラス製造方法
に係り、詳しくは、金、銀、白金、そしてパラジウムか
ら選ばれた１種以上の貴金属イオンを還元して得られ、
高分子量顔料分散剤で保護された、粒径が１〜１００ｎ
ｍの貴金属微粒子、チタン、ジルコニア、そして珪素か
ら選ばれた１種以上の有機金属化合物、および有機溶剤
から成る着色剤組成物と、この着色剤組成物をガラス表
面に塗布し、４００〜８００℃の温度条件下で焼成する
着色ガラスの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorant composition capable of coloring a glass surface and a method for producing a colored glass using the same, and more particularly, to at least one kind selected from gold, silver, platinum and palladium. Obtained by reducing the noble metal ions of
Particle size 1-100n protected with high molecular weight pigment dispersant
m, a colorant composition comprising one or more organometallic compounds selected from titanium, zirconia, and silicon, and an organic solvent; and applying the colorant composition to a glass surface at 400 to 800 ° C. The present invention relates to a method for producing a colored glass which is fired under the following temperature conditions.
【０００２】[0002]
【従来の技術】従来、ガラスの着色方法としては、エポ
キシ樹脂等に顔料を分散させた有機系塗料をガラス表面
に塗布する方法、ガラスフリット、無機顔料を主成分と
する無機系塗料をガラス表面に塗布、焼き付ける方法、
スパッタリング、蒸着等の真空製膜法により金属、或い
は金属酸化物膜をガラス表面に作製する方法、有機金属
化合物を焼き付け金属酸化物膜をガラス表面に作製する
方法、イオン交換法により銀、銅等のコロイドをガラス
表面層に形成する方法、溶融状態のガラスに金属、金属
酸化物を溶かしガラス中に金属イオン、金属コロイドを
形成する方法等がある。2. Description of the Related Art Conventionally, as a method of coloring glass, a method of applying an organic paint in which a pigment is dispersed in an epoxy resin or the like to a glass surface, a method of applying a glass frit or an inorganic paint containing an inorganic pigment as a main component to the glass surface are used. Coating and baking,
A method of forming a metal or metal oxide film on a glass surface by a vacuum film forming method such as sputtering and vapor deposition, a method of baking an organic metal compound to form a metal oxide film on a glass surface, and a method of forming silver or copper by an ion exchange method. And a method in which a metal or metal oxide is dissolved in glass in a molten state to form metal ions or a metal colloid in the glass.
【０００３】[0003]
【発明が解決しようとする課題】有機系塗料を使用する
方法は、有機系材料で構成されているため耐熱性、耐候
性が悪く、無機系塗料を使用する方法は、鉛ガラスの性
質として耐薬品性に問題がある。真空製膜法による方法
は、バッチ式の製造方法となり生産性が悪く、有機金属
化合物を焼き付ける方法は色調の自由度がなく、また、
大がかりな設備を要する。The method of using an organic paint is poor in heat resistance and weather resistance because it is made of an organic material, and the method of using an inorganic paint has a property of lead glass as a property of lead glass. There is a problem with chemical properties. The method by the vacuum film forming method is a batch type manufacturing method, and the productivity is poor, and the method of baking an organometallic compound does not have a degree of freedom in color tone,
Requires extensive equipment.
【０００４】イオン交換法による方法も色調の自由度が
なく、着色に要する時間が比較的長く生産性が悪い。ガ
ラスに金属イオン、金属コロイドを混ぜ込んだ形で着色
する方法は色毎にバッチ生産しなければならず生産性が
悪い。The ion exchange method also has no degree of freedom in color tone, and the time required for coloring is relatively long, resulting in poor productivity. The method of coloring in a form in which metal ions and metal colloids are mixed into glass has to be batch-produced for each color, resulting in poor productivity.
【０００５】本発明はこのような問題点を改善するもの
であり、貴金属微粒子、有機金属化合物、有機溶剤で構
成された着色剤組成物をガラス表面に塗布、焼成するこ
とで耐久性に優れ、様々な色調を呈する着色ガラスを、
短時間に効率よく作製することができる着色剤組成物お
よび着色ガラスの製造方法を提供することを目的とす
る。The present invention has been made to solve the above problems, and has excellent durability by applying a colorant composition composed of noble metal fine particles, an organic metal compound, and an organic solvent to a glass surface and firing it. Colored glass with various colors
It is an object of the present invention to provide a colorant composition and a method for producing a colored glass which can be efficiently produced in a short time.
【０００６】[0006]
【課題を解決するための手段】即ち、本願の請求項記載
１の発明は、（１）粒子径が１〜１００ｎｍで、金、
銀、白金、そしてパラジウムから選ばれた１種以上の貴
金属微粒子、（２）チタン、ジルコニア、そして珪素か
ら選ばれた１種以上の有機金属化合物、および（３）有
機溶媒からなる着色剤組成物にある。That is, the invention of claim 1 of the present application provides (1) a particle diameter of 1 to 100 nm, gold,
A colorant composition comprising one or more noble metal fine particles selected from silver, platinum, and palladium, (2) one or more organic metal compounds selected from titanium, zirconia, and silicon, and (3) an organic solvent. It is in.
【０００７】本願の請求項２記載の発明は、貴金属微粒
子が、貴金属イオンを還元して得られ、高分子量顔料分
散剤で保護されている着色剤組成物にある。The invention according to claim 2 of the present application resides in a colorant composition obtained by reducing noble metal ions and protecting the fine particles with a high molecular weight pigment dispersant.
【０００８】本願の請求項３記載の発明は、（１）粒子
径が１〜１００ｎｍで、金、銀、白金、そしてパラジウ
ムから選ばれた１種以上の貴金属微粒子、（２）チタ
ン、ジルコニア、そして珪素から選ばれた１種以上の有
機金属化合物、および（３）有機溶媒からなる着色剤組
成物をガラス表面に塗布し、４００〜８００°Ｃの温度
条件下で焼成する着色ガラスの製造方法にある。The invention according to claim 3 of the present application is characterized in that (1) fine particles of one or more noble metals selected from gold, silver, platinum and palladium having a particle diameter of 1 to 100 nm, (2) titanium, zirconia, A method for producing a colored glass in which a colorant composition comprising one or more organometallic compounds selected from silicon and (3) an organic solvent is applied to a glass surface and fired at a temperature of 400 to 800 ° C. It is in.
【０００９】[0009]
【発明の実施の形態】本発明で使用する貴金属微粒子
は、貴金属化合物を溶媒中に溶解した後、溶媒中の貴金
属イオンを、高分子顔料分散剤の存在下、還元させて得
られる高分子顔料分散剤で保護された、粒径が１〜１０
０ｎｍの金、銀、白金、そしてパラジウムから選ばれた
１種以上の貴金属微粒子であり、特開平１１−７６８０
０号公報に公開された発明により作製することができ
る。BEST MODE FOR CARRYING OUT THE INVENTION A noble metal fine particle used in the present invention is a polymer pigment obtained by dissolving a noble metal compound in a solvent and reducing the noble metal ion in the solvent in the presence of a polymer pigment dispersant. Particle size of 1 to 10 protected by dispersant
At least one noble metal fine particle selected from gold, silver, platinum, and palladium having a thickness of 0 nm;
It can be produced according to the invention disclosed in Japanese Patent Publication No. 0.
【００１０】ここで使用する高分子顔料分散剤は、特に
限定されないが、（１）顔料親和性基を主鎖及び／また
は複数の側鎖に有し、かつ溶剤和部分を構成する複数の
側鎖を有する櫛形構造の高分子、（２）主鎖中に顔料親
和性基からなる複数の顔料親和部分を有する高分子、
（３）主鎖の片末端に顔料親和性基からなる顔料親和部
分を有する直鎖状の高分子であり、具体的な市販品とし
て、例えばソルスパースシリーズ（ゼネカ社製）、ディ
スパービックシリーズ（ビックケミー社製）、ＥＦＫＡ
シリーズ（ＥＦＫＡケミカル社製）アジスハ−ＰＢ７１
１、アジスハ−ＰＡ１１１（味の素社製）がある。The polymer pigment dispersant used here is not particularly limited, but (1) a plurality of polymer pigment dispersants having a pigment affinity group in a main chain and / or a plurality of side chains and constituting a solvation portion. A polymer having a comb-shaped structure having a chain, (2) a polymer having a plurality of pigment-affinity portions composed of a pigment-affinity group in a main chain,
(3) A linear polymer having a pigment-affinity moiety consisting of a pigment-affinity group at one end of the main chain, and specific commercial products such as Solsperse series (manufactured by Zeneca) and Dispervic series ( Big Chemie), EFKA
Series (manufactured by EFKA Chemical Company) Addisha-PB71
1. There is Ajisha-PA111 (manufactured by Ajinomoto Co.).
【００１１】本発明に使用する有機金属化合物は、有機
チタン化合物の場合、チタンのエトキシド、プロポキシ
ド、ブトキシド等のアルコキシド類、アセチルアセトナ
ート、アミナート等のキレート類、ステアレイト等の有
機酸エステル類、その他グリコレートやアルコキシドが
重縮合化したオリゴマーが挙げられる。When the organometallic compound used in the present invention is an organotitanium compound, alkoxides such as ethoxide, propoxide and butoxide of titanium; chelates such as acetylacetonate and aminate; and organic acid esters such as stearate. And other oligomers obtained by polycondensation of glycolates and alkoxides.
【００１２】有機ジルコニア化合物の場合、有機チタン
化合物同様、アルコキシド類、キレート類、有機酸エス
テル類、グリコレート類、アルコキシドが重縮合したオ
リゴマー等が挙げられる。有機珪素化合物の場合、エト
キシド、プロポキシド、ブトキシド等のアルコキシド
類、ポリシロキサン骨格を持つ各種シリコンオイル、シ
リコンワニスを挙げることができる。In the case of the organic zirconia compound, like the organic titanium compound, alkoxides, chelates, organic acid esters, glycolates, oligomers obtained by polycondensation of alkoxide and the like can be mentioned. In the case of an organic silicon compound, alkoxides such as ethoxide, propoxide and butoxide, various silicon oils having a polysiloxane skeleton, and silicon varnish can be exemplified.
【００１３】本発明に使用する有機溶剤は、貴金属微粒
子を凝集させずに安定に分散でき、有機金属化合物を溶
解できるものであれば特に制限はなく、着色剤組成物の
塗布方法などにより適宜選択される。The organic solvent used in the present invention is not particularly limited as long as it can stably disperse the noble metal fine particles without agglomeration and can dissolve the organic metal compound, and is appropriately selected depending on the method of applying the colorant composition. Is done.
【００１４】着色剤組成物に配合する貴金属微粒子の量
は、所望する着色ガラスの色調、着色剤組成物の塗布方
法等により適宜決定されるが、同時の配合する有機金属
化合物が含有する金属原子数（Ｍ）と貴金属微粒子の貴
金属原子数（Ｎ）がＭ／Ｎ＝０．１〜１００の範囲にな
るよう配合されることが好ましい。Ｍ／Ｎが０．１より
小さくなると貴金属微粒子同士が焼結し、貴金属塊を形
成し、貴金属微粒子単体をガラス表面に塗布、焼成した
状態と変わらなくなり、本発明の目的とするコロイド発
色が得られない。逆にＭ／Ｎが１００より大きくなる
と、着色剤組成物中の貴金属微粒子数が著しく少なくな
り、有効な着色ができなく、本発明の目的を達成できな
い。The amount of the noble metal fine particles to be added to the colorant composition is appropriately determined depending on the desired color tone of the colored glass, the method of applying the colorant composition, and the like. It is preferable that the number (M) and the number of noble metal atoms (N) of the noble metal fine particles be blended in the range of M / N = 0.1 to 100. When M / N is less than 0.1, the noble metal fine particles sinter together to form a noble metal lump, which is no different from a state in which the noble metal fine particles alone are applied and baked on the glass surface, and the colloidal coloring desired by the present invention is obtained. I can't. On the other hand, when M / N is more than 100, the number of noble metal fine particles in the colorant composition is significantly reduced, and effective coloring cannot be performed, and the object of the present invention cannot be achieved.
【００１５】作製された着色剤組成物は、ガラス上にス
プレー、ディップ、ロールコ−ト、スピンコート、フレ
クソ印刷、グラビア印刷等の方法で塗布され、有機溶剤
を乾燥させた後、４００〜８００℃の炉中で１〜１０分
間焼成し、冷却を経て着色ガラスが得られる。The prepared colorant composition is applied on a glass by a method such as spraying, dipping, roll coating, spin coating, flexographic printing, gravure printing, etc., and after drying the organic solvent, the temperature is 400 to 800 ° C. In a furnace for 1 to 10 minutes, and after cooling, a colored glass is obtained.
【００１６】[0016]
【実施例】次に、本発明を具体的な実施例により更に詳
細に説明する。尚、処理液の特性と着色膜の評価方法
は、以下の通りである。Next, the present invention will be described in more detail with reference to specific examples. The properties of the treatment liquid and the method of evaluating the colored film are as follows.
【００１７】１．光学特性 分光光度計により、８００〜３００ｎｍの波長域で透過
率スペクトルを測定した。1. Optical characteristics The transmittance spectrum was measured in a wavelength range of 800 to 300 nm using a spectrophotometer.
【００１８】比較例１、実施例１ 表１に示す微粒子成分、有機金属化合物成分、有機溶剤
成分からなる添加剤を配合して着色剤組成物を得た。こ
こで使用する金微粒子は、日本ペイント社製Ａｕコロイ
ドゾル（金含有量：４０ｗｔ％）である。この着色剤組
成物を厚み３ｍｍのソーダライムガラス板上にスピンコ
ート法により塗布した。塗布量は湿潤状態で５ｇ／ｍ2
であった。Comparative Example 1, Example 1 Additives composed of a fine particle component, an organometallic compound component and an organic solvent component shown in Table 1 were blended to obtain a colorant composition. The gold fine particles used here are Au colloid sol (gold content: 40 wt%) manufactured by Nippon Paint Co., Ltd. This colorant composition was applied on a 3 mm thick soda lime glass plate by spin coating. The coating amount is 5 g / m 2 in a wet state.
Met.
【００１９】着色剤組成物を塗布後のガラス板を、１５
０℃の熱風循環式オーブンで５分間乾燥した後、６００
°Ｃのマッフル炉中で５分間焼成して試料を得た。得ら
れた試料の光学特性（透過率スペクトル）を図１に示
す。After the colorant composition has been applied, the glass plate
After drying in a hot air circulating oven at 0 ° C for 5 minutes,
A sample was obtained by baking for 5 minutes in a muffle furnace at ° C. FIG. 1 shows the optical characteristics (transmittance spectrum) of the obtained sample.
【００２０】[0020]
【表１】 [Table 1]
【００２１】比較例１は約６３０ｎｍに吸収極大を持つ
非常にブロードな吸収が見られ、目視では透過色が薄い
紺色を、反射色は金光沢を呈している。配合にチタンア
セチルアセトナートを含まないため、試料焼成段階で金
微粒子が焼結し金の薄膜が形成された。これに対し実施
例１では、約６２０ｎｍに比較的シャープな吸収が見ら
れ、目視では透過色が青色、反射色が酸化チタン薄膜の
干渉色と思われる青緑色を呈した。形成された着色膜
は、酸化チタンマトリクスの中に金微粒子が固定され、
金微粒子の表面プラズモン電子の共鳴吸収により青色に
発色している。In Comparative Example 1, a very broad absorption having an absorption maximum at about 630 nm is observed, and the transmission color is visually dark blue and the reflection color is gold gloss. Since titanium acetylacetonate was not included in the formulation, the fine gold particles were sintered during the sample firing step, and a thin gold film was formed. On the other hand, in Example 1, relatively sharp absorption was observed at about 620 nm, and the transmission color was blue and the reflection color was blue-green, which is considered to be the interference color of the titanium oxide thin film. In the formed colored film, gold fine particles are fixed in a titanium oxide matrix,
The gold particles are colored blue by resonance absorption of surface plasmon electrons.
【００２２】[0022]
【発明の効果】以上のように本願請求項によれば、金、
銀、白金、そしてパラジウムから選ばれた１種以上の貴
金属イオンを還元して得られ、高分子含量分散剤で保護
された、粒径が１〜１００ｎｍの貴金属微粒子、チタ
ン、ジルコニア、そして珪素から選ばれた１種以上の有
機金属化合物、有機溶剤から成る着色剤組成物をガラス
表面に塗布し、４００〜８００℃の温度条件下で焼成す
ることで、着色ガラスを作製することができる。As described above, according to the claims of the present application, gold,
Noble metal particles obtained by reducing one or more noble metal ions selected from silver, platinum, and palladium and protected with a polymer-containing dispersant, having a particle size of 1 to 100 nm, titanium, zirconia, and silicon A colorant composition comprising one or more selected organometallic compounds and an organic solvent is applied to the glass surface and fired at a temperature of 400 to 800 ° C. to produce a colored glass.
【図１】実施例１と比較例１に係る試料の透過率スペク
トルを示す。FIG. 1 shows transmittance spectra of samples according to Example 1 and Comparative Example 1.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G059 AA01 AC08 DA01 DA02 DA03 DB09 FA01 FB05 4J037 AA04 AA08 CB05 CB09 CB23 CB26 CC00 CC28 DD05 EE03 EE26 EE47 FF03 FF22 4J038 AA001 DL031 HA061 JA23 JC32 JC38 KA06 KA09 MA02 MA07 MA10 MA14 NA01 NA03 NA27 PA19 PC03 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4G059 AA01 AC08 DA01 DA02 DA03 DB09 FA01 FB05 4J037 AA04 AA08 CB05 CB09 CB23 CB26 CC00 CC28 DD05 EE03 EE26 EE47 FF03 FF22 4J038 AA001 DL031 HA061 MA23 MA02MA10 MA23MA02 NA03 NA27 PA19 PC03
Claims (3)
銀、白金、そしてパラジウムから選ばれた１種以上の貴
金属微粒子、（２）チタン、ジルコニア、そして珪素か
ら選ばれた１種以上の有機金属化合物、および（３）有
機溶媒からなることを特徴とする着色剤組成物。(1) a particle diameter of 1 to 100 nm;
It is characterized by comprising one or more noble metal fine particles selected from silver, platinum and palladium, (2) one or more organic metal compounds selected from titanium, zirconia and silicon, and (3) an organic solvent. Colorant composition.
て得られ、高分子量顔料分散剤で保護されている請求項
１記載の着色剤組成物。2. The colorant composition according to claim 1, wherein the noble metal fine particles are obtained by reducing a noble metal ion and protected by a high molecular weight pigment dispersant.
銀、白金、そしてパラジウムから選ばれた１種以上の貴
金属微粒子、（２）チタン、ジルコニア、そして珪素か
ら選ばれた１種以上の有機金属化合物、および（３）有
機溶媒からなる着色剤組成物をガラス表面に塗布し、４
００〜８００°Ｃの温度条件下で焼成することを特徴と
する着色ガラスの製造方法。(1) a particle size of 1 to 100 nm, gold,
A colorant composition comprising one or more noble metal fine particles selected from silver, platinum, and palladium, (2) one or more organic metal compounds selected from titanium, zirconia, and silicon, and (3) an organic solvent. Is applied to the glass surface, and 4
A method for producing a colored glass, comprising firing at a temperature of 00 to 800 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000006025A JP2001199741A (en) | 2000-01-11 | 2000-01-11 | Colorant composition and method for producing colored glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000006025A JP2001199741A (en) | 2000-01-11 | 2000-01-11 | Colorant composition and method for producing colored glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001199741A true JP2001199741A (en) | 2001-07-24 |
Family
ID=18534616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000006025A Pending JP2001199741A (en) | 2000-01-11 | 2000-01-11 | Colorant composition and method for producing colored glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001199741A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006102215A1 (en) * | 2005-03-21 | 2006-09-28 | Ppg Industries Ohio, Inc. | Metal nanostructured colorants for high redox glass composition |
| JP2007063530A (en) * | 2005-08-01 | 2007-03-15 | Saga Prefecture | Yellow coloring composite fine particle and method for producing the yellow coloring composite fine particle |
-
2000
- 2000-01-11 JP JP2000006025A patent/JP2001199741A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006102215A1 (en) * | 2005-03-21 | 2006-09-28 | Ppg Industries Ohio, Inc. | Metal nanostructured colorants for high redox glass composition |
| JP2007063530A (en) * | 2005-08-01 | 2007-03-15 | Saga Prefecture | Yellow coloring composite fine particle and method for producing the yellow coloring composite fine particle |
| JP4678736B2 (en) * | 2005-08-01 | 2011-04-27 | 佐賀県 | COMPOUND PARTICLE FOR YELLOW COLORING AND METHOD FOR PRODUCING COMPOSITE PARTICLE FOR YELLOW COLORING |
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