JPH10203848A - Colored glass - Google Patents
Colored glassInfo
- Publication number
- JPH10203848A JPH10203848A JP9007983A JP798397A JPH10203848A JP H10203848 A JPH10203848 A JP H10203848A JP 9007983 A JP9007983 A JP 9007983A JP 798397 A JP798397 A JP 798397A JP H10203848 A JPH10203848 A JP H10203848A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- type thin
- glass
- liquid
- colored glass
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガラス表面の一部
あるいは全面に着色被膜が形成された着色ガラスに関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored glass having a colored film formed on a part or the entire surface of the glass.
【０００２】[0002]
【従来の技術】従来より、着色ガラスに対しては、好み
の色調や色濃度で着色可能であること、あるいは耐熱性
が高いこと、そしてコストも低いことなどが求められて
いる。そして、基体となるガラス表面に被膜を形成して
着色するタイプの着色ガラスにおいても、これらの要求
を満たすため、様々な方法が開発されている。そのよう
なガラス表面着色法の主なものとして、たとえば次の方
法などが知られている。2. Description of the Related Art Conventionally, colored glass has been required to be colored with a desired color tone and color density, to have high heat resistance, and to have low cost. In order to satisfy these requirements, various methods have also been developed for colored glass of a type in which a film is formed on the surface of a glass serving as a substrate and colored. As the main glass surface coloring method, for example, the following method is known.
【０００３】（１）ソルダーガラスを主成分とするエナ
メル塗料を、ガラス表面に塗布し焼き付ける方法（エナ
メル法）。(1) A method in which an enamel paint mainly composed of solder glass is applied to a glass surface and baked (enamel method).
【０００４】（２）化学的あるいは物理的蒸着により、
高屈折率の薄膜と低屈折率の薄膜との多層膜をガラス表
面に形成する方法（蒸着法） （３）銀や銅などの貴金属化合物を含むペーストをガラ
ス表面に塗布し加熱して、ガラス表面のアルカリ金属イ
オンを、貴金属イオンと交換することにより着色する方
法（ステイニング法）。(2) By chemical or physical vapor deposition,
Method of forming a multilayer film of a high-refractive-index thin film and a low-refractive-index thin film on a glass surface (evaporation method) (3) A paste containing a noble metal compound such as silver or copper is applied to the glass surface and heated to form a glass. A method of coloring by exchanging alkali metal ions on the surface with precious metal ions (staining method).
【０００５】（４）有機金属化合物と貴金属化合物を含
む溶液をガラス表面に塗布し加熱して、金属酸化物中に
貴金属コロイドを生成させた薄膜をガラス表面に形成す
る方法（ラスター法）。(4) A method in which a solution containing an organometallic compound and a noble metal compound is applied to a glass surface and heated to form a thin film in which a noble metal colloid is formed in a metal oxide on the glass surface (raster method).
【０００６】（５）有機金属化合物として金属アルコキ
シドを含む溶液（さらに有機顔料や有機染料、金属塩な
どを添加する場合もある）をガラス表面に塗布し、焼成
して有色の金属酸化物の被膜を形成する方法（ゾルゲル
法）。(5) A solution containing a metal alkoxide as an organometallic compound (an organic pigment, an organic dye, a metal salt, or the like may be added in some cases) is applied to the glass surface and baked to form a colored metal oxide film. (Sol-gel method).
【０００７】[0007]
【発明が解決しようとする課題】しかしながら上記した
従来の各着色法には、得られる薄膜の色調選択性が限ら
れたり、色濃度の濃いものが得難かったり、あるいは耐
熱性が劣る、コストが高いなどの短所や問題点がそれぞ
れあり、着色法としてのすべての要求を満たすような方
法は未だ得られていない。そのため、着色ガラスの用途
に合わせ要求のいくつかは妥協して、次善の無難な方法
を選択しているのが現状である。However, in the above-mentioned conventional coloring methods, the color tone selectivity of the obtained thin film is limited, a color having a high color density is difficult to obtain, the heat resistance is poor, and the cost is low. There are disadvantages and problems such as high cost, and a method that satisfies all requirements as a coloring method has not yet been obtained. Therefore, at present, some of the requirements are compromised according to the use of the colored glass, and the next best safe method is selected.
【０００８】以下に上記方法が有する主な問題点をあげ
る。The main problems of the above method are described below.
【０００９】（１）エナメル法は、熱膨脹係数の関係か
らも硬質ガラスは基体として使えない。また、エナメル
自体の耐熱性があまり大きくないので、電球や車の部品
などのように耐熱性が必要な場合には用いることができ
ない。さらに、エナメル中にカドミウムなどの人体に有
害な元素を含有する場合もあって、環境保護の面からあ
まり好ましくなく、得られる着色ガラスの製膜後の外観
も、ブツブツが残るなどして美観が損なわれることも多
い。(1) In the enamel method, hard glass cannot be used as a substrate because of the coefficient of thermal expansion. Further, since the heat resistance of the enamel itself is not so large, it cannot be used when heat resistance is required, such as a light bulb or a car part. Furthermore, the enamel may contain elements that are harmful to the human body such as cadmium, which is not very desirable from the viewpoint of environmental protection. Often damaged.
【００１０】（２）蒸着により多層膜を形成する方法の
場合には、蒸着機などの高価な装置が必要で排気処理に
時間がかかる上、１回の処理量も少なくコストは非常に
高いものとなる。また、平面状の基体表面には良好に製
膜可能であるが、電球やキャップのような曲面部を均一
に被覆し製膜することは難しい。(2) In the case of a method of forming a multilayer film by vapor deposition, an expensive apparatus such as a vapor deposition machine is required, and it takes a long time to perform an exhaust process. Becomes In addition, although a film can be satisfactorily formed on a flat substrate surface, it is difficult to uniformly coat a curved surface portion such as a light bulb or a cap to form a film.
【００１１】（３）ステイニング法により得られる色調
はガラス基体の組成により決められるが、ほとんどの場
合銀か銅の着色によるものであるため、色調選択の幅が
狭く、黄緑〜黄〜かっ色〜赤という範囲にとどまる。(3) The color tone obtained by the staining method is determined by the composition of the glass substrate. In most cases, the color tone is determined by coloring silver or copper. It stays in the range of color to red.
【００１２】（４）ラスター法は、貴金属を使用するた
め材料費が非常に高くなるばかりでなく、有色透明な着
色の場合１回の処理では得られる色濃度が薄いため、必
要な濃さになるまで重ね塗りをしなくてはならない。そ
の結果コスト高になる。(4) In the raster method, not only the material cost is extremely high because of using a noble metal, but also in the case of colored and transparent coloring, the color density obtained by one treatment is low, so that the required density can be reduced. I have to re-coat until it is. As a result, costs increase.
【００１３】（５）ゾルゲル法を用い無機化合物を含有
させて着色する場合は、やはり色濃度が薄いため重ね塗
りを必要とする。ゾルゲル法により重ね塗りをして多層
膜を形成する場合には、溶液の厳密な管理を必要とし、
また、１層ごとに乾燥と焼成とを繰返すため層を重ねる
につれコスト高になるばかりでなく、膜にクラックも生
じ易くなる。一方、有機化合物を着色剤として添加する
場合には、１回塗りでかなりの濃さの色濃度が得られる
ものの、熱により色素・染料が分解して色が消えてしま
うため、耐熱性が非常に小さい。(5) In the case of coloring by incorporating an inorganic compound by using the sol-gel method, the color density is too low, so that recoating is required. When forming a multilayer film by overcoating by the sol-gel method, strict control of the solution is required,
Further, since drying and baking are repeated for each layer, not only the cost increases as the layers are stacked, but also cracks are easily generated in the film. On the other hand, when an organic compound is added as a coloring agent, although a considerably high color density can be obtained by a single application, heat and heat are used to decompose the dyes and dyes, causing the color to disappear. Small.
【００１４】次の表１に各方法の長所・短所をまとめて
示す。表中○印はその項目にすぐれていること、×印は
劣っていること、そして△印はその中間であることを表
している。The following Table 1 summarizes the advantages and disadvantages of each method. In the table, a circle indicates that the item is superior, a cross indicates that the item is inferior, and a triangle indicates that the item is intermediate.
【００１５】[0015]
【表１】 本発明は上記事情を考慮してなされたもので、従来の着
色ガラスの短所を補い長所を生かしたすぐれた着色ガラ
スを提供すること、すなわちゾルゲル法により製造も容
易であって、耐熱性が大きく色濃度や色調の選択性の幅
も広い着色ガラスを提供することを、その目的としてい
る。[Table 1] The present invention has been made in consideration of the above circumstances, and provides an excellent colored glass that compensates for the disadvantages of the conventional colored glass and takes advantage of the advantages.In other words, the production is easy by the sol-gel method, and the heat resistance is large. It is an object of the present invention to provide a colored glass having a wide range of color density and color tone selectivity.
【００１６】[0016]
【課題を解決するための手段】本発明は、上記目的を達
成するために鋭意研究を進め、屈折率の異なったガラス
体薄膜がゾルゲル法により得られることを見出だして成
されたものであり、屈折率の異なった薄膜の少なくとも
一方に着色剤となる物質を添加して基体となるガラス表
面に積層させ、色の濃い着色ガラスが容易に得られるよ
うにしたものである。Means for Solving the Problems The present invention has been made to achieve the above object, and has been made by discovering that glass thin films having different refractive indices can be obtained by a sol-gel method. In addition, a substance serving as a coloring agent is added to at least one of the thin films having different refractive indices and laminated on a glass surface serving as a base so that a colored glass having a strong color can be easily obtained.
【００１７】すなわち本発明は、ガラス基体表面の少な
くとも一部に、屈折率ｎ1 の第１種の薄膜と屈折率ｎ2
（ただしｎ1 ＞ｎ2 ）の第２種の薄膜とが積層してなる
多層膜が形成され、前記第１種の薄膜および前記第２種
の薄膜の少なくとも一方が有色であることを、特徴とし
ている。そして、前記第１種の薄膜および前記第２種の
薄膜の各層が、有機金属化合物を主成分として含む溶液
を塗布の後１５０〜７００℃の温度で焼成することによ
り形成され、金属酸化物を主体としてなる膜厚１０〜１
０００ｎｍの薄膜であることを、さらなる特徴としてい
る。[0017] The present invention, at least a portion of the glass substrate surface, the refractive first type of thin film and the refractive index of the index n 1 n 2
(Where n 1 > n 2 ), wherein a multilayer film is formed by laminating a second type thin film, and at least one of the first type thin film and the second type thin film is colored. And Each layer of the first type thin film and the second type thin film is formed by applying a solution containing an organometallic compound as a main component and then baking the solution at a temperature of 150 to 700 ° C. to form a metal oxide. Main thickness 10-1
It is a further feature that it is a thin film of 000 nm.
【００１８】本発明において、基体として使用可能なガ
ラスの種類は、軟質、硬質、あるいは半硬質ガラスのい
ずれでもよく、ガラスの膨脹係数を問うものではない。
また、鉛ガラス、リン酸塩ガラス、ソーダライムなどガ
ラスの組成にもよらず、どのような組成のものであって
も適用可能である。またその形状は、平面の板状のもの
に限定されず、曲面でも可能である。しかも、表、裏の
同時被覆ができるので、より少ない製膜操作で濃く着色
し得る。片面だけ被覆することが可能なことはもちろん
である。In the present invention, the kind of glass usable as the substrate may be any of soft, hard and semi-hard glass, and does not matter the expansion coefficient of the glass.
In addition, regardless of the composition of the glass, such as lead glass, phosphate glass, and soda lime, any composition can be applied. The shape is not limited to a flat plate-like shape, but may be a curved surface. In addition, since the front and back surfaces can be coated at the same time, the color can be deeply colored with less film forming operation. Of course, it is possible to cover only one side.
【００１９】本発明において、第１種の薄膜および第２
種の薄膜をゾルゲル法により形成するためには、主成分
となる溶質として有機金属化合物を含む溶液を、基体と
なるガラス表面に塗布するようにする。有機金属化合物
としては金属アルコキシド｛一般式 Ｍ（ＯＲ）n で表
され、金属アルコラートともいう。Ｍは金属元素、Ｒは
アルキル基を表す｝が、溶液化してさまざまな添加物を
含有させ易く塗布時の膜厚の調整も容易であるため、好
適に使用可能である。しかしながら、本発明は金属アル
コキシドに限定されるものではなく、焼成時に分解・酸
化して金属酸化物となり、かつ金属の種類を選択するこ
とによって金属酸化物の屈折率の差別化が可能であれ
ば、どのような有機金属化合物であっても使用すること
は可能である。In the present invention, the first type thin film and the second type thin film
In order to form a seed thin film by the sol-gel method, a solution containing an organometallic compound as a solute as a main component is applied to a glass surface as a substrate. The organometallic compound is represented by a metal alkoxide {general formula M (OR) n and is also called a metal alcoholate. M represents a metal element, and R represents an alkyl group. However, it can be suitably used because it is easy to be in a solution to contain various additives and the film thickness at the time of coating is easily adjusted. However, the present invention is not limited to metal alkoxides, as long as it can be decomposed and oxidized during firing to form a metal oxide, and the refractive index of the metal oxide can be differentiated by selecting the type of metal. It is possible to use any organometallic compound.
【００２０】本発明において、屈折率ｎ1 の第１の薄膜
（高屈折率薄膜）の形成のために塗布される溶液に主成
分として含まれる金属アルコキシドとしては、たとえば
チタニウムテトラエトキシド（あるいはテトラエチルチ
タネートともいう）、チタニウムテトライソプロポキシ
ド、チタニウムテトラノルマルブトキシドなどのＴｉの
アルコキシドが好ましいが、たとえばジルコニウムテト
ラエトキシド、ジルコニウムテトライソプロポキシドな
どのＺｒのアルコキシド、あるいはタンタルペンタエト
キシド、タンタルペンタイソプロポキシド、タンタルペ
ンタノルマルブトキシドなどのＴａのアルコキシド、あ
るいはアンチモントリエトキシド、アンチモントリノル
マルブトキシドなどのＳｂのアルコキシドなど、焼成し
て酸化すると屈折率が高くなる金属アルコキシドが好適
に使用可能である。また、２種類以上のアルコキシドを
組み合わせて使用してもよい。In the present invention, as a metal alkoxide contained as a main component in a solution applied for forming a first thin film (high refractive index thin film) having a refractive index of n 1 , for example, titanium tetraethoxide (or tetraethyl) Ti alkoxides such as titanate), titanium tetraisopropoxide and titanium tetranormal butoxide are preferable, and for example, alkoxides of Zr such as zirconium tetraethoxide and zirconium tetraisopropoxide, or tantalum pentaethoxide and tantalum pentaisod Refraction when fired and oxidized, such as Ta alkoxide such as propoxide and tantalum pentanormal butoxide, or Sb alkoxide such as antimony triethoxide and antimony trinormal butoxide Metal alkoxide is higher can be suitably used. Also, two or more alkoxides may be used in combination.
【００２１】本発明において、屈折率ｎ2 （ただしｎ1
＞ｎ2 ）の第２の薄膜（低屈折率薄膜）の形成のために
塗布される溶液に主成分として含まれる金属アルコキシ
ドとしては、たとえばシリコンテトラエトキシド（ある
いはテトラエトキシシラン、テトラエチルシリケートと
もいう）、シリコンテトライソプロポキシド（テトライ
ソプロポキシシラン）、シリコンテトラノルマルブトキ
シドなどのＳｉのアルコキシド、あるいはアルミニウム
トリエトキシド、アルミニウムトリイソプロポキシド、
アルミニウムトリノルマルブトキシドなどのＡｌのアル
コキシドなどが好適に使用可能である。やはり、２種類
以上のアルコキシドを組み合わせて使用してもよい。In the present invention, the refractive index n 2 (where n 1
As a metal alkoxide contained as a main component in a solution applied for forming a second thin film (low-refractive-index thin film) of> n 2 ), for example, silicon tetraethoxide (or also referred to as tetraethoxysilane or tetraethylsilicate) ), Silicon tetraisopropoxide (tetraisopropoxysilane), silicon alkoxide such as silicon tetranormal butoxide, or aluminum triethoxide, aluminum triisopropoxide,
Al alkoxides such as aluminum trinormal butoxide can be suitably used. Again, two or more alkoxides may be used in combination.
【００２２】なお、本発明において第１の薄膜の屈折率
ｎ1 は、１．５〜２．６の範囲、第２の薄膜の屈折率ｎ
2 は、１．２〜１．９の範囲にあることが望ましい。In the present invention, the refractive index n 1 of the first thin film is in the range of 1.5 to 2.6, and the refractive index n
2 is desirably in the range of 1.2 to 1.9.
【００２３】本発明において、薄膜形成にあたって上記
アルコキシドを主成分として含む溶液を調製する場合、
溶媒としてはたとえばエチルアルコール、イソプロピル
アルコール、ブチルアルコールなどのアルコール類や、
酢酸メチル、酢酸エチルなどのエステル類、アセチルア
セトンなどのキレート剤、加水分解速度を調整するため
の酢酸や塩酸、水など、ゾルゲル法において使用可能な
溶媒を必要に応じて組み合わせて用いることができる。In the present invention, when preparing a solution containing the above alkoxide as a main component in forming a thin film,
Examples of the solvent include alcohols such as ethyl alcohol, isopropyl alcohol, and butyl alcohol,
Solvents that can be used in the sol-gel method, such as esters such as methyl acetate and ethyl acetate, chelating agents such as acetylacetone, and acetic acid, hydrochloric acid, and water for adjusting the hydrolysis rate, can be used in combination as needed.
【００２４】本発明において、薄膜に含有させることが
可能な着色剤としては、たとえば塩化コバルト、塩化
銅、塩化鉄、塩化セリウム、塩化鉛、塩化ニッケル、塩
化ビスマス、塩化ネオジム、塩化タングステン、塩化イ
ンジウム、塩化マンガンなどの塩化物、たとえば硝酸
銅、硝酸クロム、硝酸ニッケル、硝酸コバルト、硝酸
鉄、硝酸鉛、硝酸ビスマス、硝酸マンガンなどの硝酸
塩、たとえば水酸化銅、水酸化鉄などの水酸化塩、硫酸
銅、硫酸鉄、硫酸セリウムなどの硫酸塩などで代表され
る無機金属化合物が使用可能である。これら着色剤は上
記アルコキシド溶液中に溶解させることにより薄膜中に
容易に取り込まれ、焼成によって有色の酸化物となって
薄膜を着色することができる。In the present invention, examples of the coloring agent that can be contained in the thin film include cobalt chloride, copper chloride, iron chloride, cerium chloride, lead chloride, nickel chloride, bismuth chloride, neodymium chloride, tungsten chloride, and indium chloride. , Chlorides such as manganese chloride, such as copper nitrate, chromium nitrate, nickel nitrate, cobalt nitrate, nitrate such as iron nitrate, lead nitrate, bismuth nitrate, manganese nitrate, such as copper hydroxide, hydroxide such as iron hydroxide, Inorganic metal compounds represented by sulfates such as copper sulfate, iron sulfate and cerium sulfate can be used. These colorants are easily taken into the thin film by dissolving in the alkoxide solution, and can be turned into a colored oxide by firing to color the thin film.
【００２５】また、本発明においては、上記したように
焼成によって有色の酸化物となって薄膜を着色するタイ
プの無機金属化合物の着色剤の他に、たとえば酸化コバ
ルト、酸化セリウム、酸化銅、酸化鉛、酸化鉄、酸化ニ
ッケル、酸化ビスマス、酸化プラセオジム、酸化ネオジ
ム、酸化チタン、酸化タングステン、酸化インジウム、
酸化ホルミウム、酸化マンガン、あるいは酸化ユーロピ
ウムなどの有色の金属酸化物も使用可能である。これら
金属酸化物は上記溶液に難溶のため、微粒子の状態で溶
液中に分散させて使用することが望ましい。Further, in the present invention, in addition to the coloring agent of the inorganic metal compound of the type which forms a colored oxide upon firing to color the thin film, for example, cobalt oxide, cerium oxide, copper oxide, Lead, iron oxide, nickel oxide, bismuth oxide, praseodymium oxide, neodymium oxide, titanium oxide, tungsten oxide, indium oxide,
Colored metal oxides such as holmium oxide, manganese oxide, or europium oxide can also be used. Since these metal oxides are hardly soluble in the above solution, it is desirable to use them in the form of fine particles dispersed in the solution.
【００２６】本発明において薄膜に含有させることが可
能な着色剤としては、上記した無機化合物の他に、たと
えばローダミンやカーミン類など、ほとんどの有機染料
や有機顔料を有機着色剤として用いることかできる。In the present invention, as a coloring agent that can be contained in the thin film, most organic dyes and organic pigments such as rhodamine and carmine can be used as the organic coloring agent in addition to the above-mentioned inorganic compounds. .
【００２７】本発明において薄膜形成にあたり、上記溶
液を塗布する方法としては、たとえばディッピング法
（浸漬塗布法）、スプレー法、あるいはスピンコート法
などが使用可能であるが、これらのうちではディッピン
グ法は、引上げ速度の調節などによって膜厚を管理し易
いことから、とくに好適である。In forming a thin film in the present invention, as a method of applying the above solution, for example, a dipping method (dip coating method), a spray method, a spin coating method, or the like can be used. It is particularly preferable because the film thickness can be easily controlled by adjusting the pulling speed.
【００２８】本発明の薄膜を形成するにあたっては、基
体となるガラス表面に上記溶液を塗布し、その後に溶媒
を蒸発させて被膜を乾燥させたのち焼成を行う。このよ
うな操作によって、ガラス表面においてアルコキシドの
ような有機金属化合物の加水分解と縮重合とが起こり、
金属酸化物を主体として成る乾燥ゲル体被膜がガラス体
被膜へと変化する。In forming the thin film of the present invention, the above solution is applied to the surface of glass as a substrate, and then the solvent is evaporated to dry the film, followed by baking. By such an operation, hydrolysis and polycondensation of an organometallic compound such as an alkoxide occur on the glass surface,
The dried gel coating mainly composed of a metal oxide changes to a glass coating.
【００２９】焼成時の温度は１５０℃以上７００℃以下
の範囲が好ましいが、形成されたガラス体からなる被膜
を焼きしめて硬度を大きくするためには、３００℃以上
ガラス変型温度以下の範囲がより好ましい。ただし、有
機染料・顔料を着色剤として用いる場合は、その分解温
度以下で行うようにする。The firing temperature is preferably in the range of 150 ° C. or more and 700 ° C. or less, but in order to bake the formed glass body and increase the hardness, the temperature range of 300 ° C. or more and the glass deformation temperature is more preferable. preferable. However, when an organic dye / pigment is used as a colorant, it is performed at a temperature lower than its decomposition temperature.
【００３０】上記操作で形成される薄膜の各１層の膜厚
は、１０〜１０００ｎｍの範囲が好ましく、より好まし
くは２０〜５００ｎｍの範囲である。１０ｎｍより薄い
場合には、着色剤を含有させても必要な色濃度が得難
く、一方１０００ｎｍより厚い場合には、クラックが入
ったり白濁が生じたりするので、どちらも好ましくな
い。The thickness of each layer of the thin film formed by the above operation is preferably in the range of 10 to 1000 nm, more preferably in the range of 20 to 500 nm. When the thickness is less than 10 nm, it is difficult to obtain a required color density even if a coloring agent is contained. On the other hand, when the thickness is more than 1000 nm, cracks or cloudiness may occur.
【００３１】本発明の着色ガラスを得るにあたって、上
記操作で形成され積層される薄膜の層数は、第１種の薄
膜および第２種の薄膜の１層ずつ以上からなり少なくと
も２層であることが好ましい。そして、上記２種類の薄
膜をさらに交互に積層することにより色濃度を濃くする
ことができるが、多くとも１５層であることが好まし
い。層数が１５層を越えて多くなるとクラックを生じ易
くなるだけでなく、工程が増えることによりコスト高と
なるので、好ましくない。In obtaining the colored glass of the present invention, the number of layers of the thin films formed and laminated by the above-mentioned operation is at least two, each of at least one of the first type thin film and the second type thin film. Is preferred. The color density can be increased by alternately laminating the above two types of thin films, but preferably at most 15 layers. If the number of layers exceeds 15 layers, cracks are likely to occur, and the number of steps increases the cost, which is not preferable.
【００３２】本発明において、相対的に屈折率の高い第
１種の薄膜と屈折率の低い第２種の薄膜とを積層させ、
光の吸収と屈折の両方の現象を利用することにより、少
ない層数で濃い色濃度の有色多層膜を得ることができ
る。また、着色剤として有色の金属酸化物微粉末、ある
いは焼成により有色の金属酸化物となる無機金属化合物
を含有させることによって、発色がよく耐熱性が大きく
硬度が高い有色多層膜とすることができる。ゾルゲル法
にしたがい１種類の溶液の塗布により多層膜を形成する
場合に比較して、溶液の管理も容易であり少ない層数で
濃い色濃度が得られ、その調整も容易である。In the present invention, a first type thin film having a relatively high refractive index and a second type thin film having a low refractive index are laminated,
By utilizing both phenomena of light absorption and refraction, a colored multilayer film with a high color density can be obtained with a small number of layers. Further, by containing a colored metal oxide fine powder as a coloring agent, or an inorganic metal compound which becomes a colored metal oxide by firing, a colored multilayer film having good color development, high heat resistance and high hardness can be obtained. . Compared to the case of forming a multilayer film by applying one type of solution according to the sol-gel method, the solution can be easily managed, a deep color density can be obtained with a small number of layers, and the adjustment can be easily performed.
【００３３】[0033]
【発明の実施の形態】以下本発明を実施例にしたがって
詳しく説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to embodiments.
【００３４】＜実施例１＞図１に断面を示す着色ガラス
の製造に先立ち、まず薄膜形成のための溶液を調製し
た。金属アルコキシドとしてチタニウムテトラノルマル
ブトキシド５０ｇ、溶媒としてエチルアルコール３００
ｇ、アセチルアセトン２０ｇ、酢酸２０ｇを混合した液
に、着色剤として硝酸クロム九水和物５０ｇを加え、２
時間撹拌した。その後２４時間放置し、さらに酢酸エチ
ル１００ｇを加えて、第１種の薄膜（高屈折率薄膜）形
成のための第１液を得た。Example 1 Prior to the production of a colored glass having a cross section shown in FIG. 1, first, a solution for forming a thin film was prepared. 50 g of titanium tetranormal butoxide as a metal alkoxide and 300 parts of ethyl alcohol as a solvent
g, 20 g of acetylacetone, and 20 g of acetic acid, and 50 g of chromium nitrate nonahydrate as a colorant was added.
Stirred for hours. Then, the mixture was left for 24 hours, and 100 g of ethyl acetate was further added to obtain a first liquid for forming a first type thin film (high refractive index thin film).
【００３５】一方、金属アルコキシドとしてテトラエト
キシシラン１００ｇ、溶媒としてイソプロピルアルコー
ル２００ｇ、エチルアルコール２５０ｇ、０．１規定塩
酸５０ｇを混合した液に、着色剤として硝酸セリウム
（III)六水和物１５ｇを加え、２時間撹拌した。その後
２４時間放置し、さらに酢酸エチル１００ｇを加えて、
第２種の薄膜（低屈折率薄膜）形成のための第２液を得
た。On the other hand, to a mixture of 100 g of tetraethoxysilane as a metal alkoxide, 200 g of isopropyl alcohol, 250 g of ethyl alcohol and 50 g of 0.1 N hydrochloric acid as a solvent, 15 g of cerium (III) nitrate hexahydrate as a coloring agent was added. And stirred for 2 hours. After that, it was left for 24 hours, and 100 g of ethyl acetate was further added.
A second liquid for forming a second type thin film (low refractive index thin film) was obtained.
【００３６】次いで、基体としての厚さ１ｍｍの板状の
スライドガラス１を第１液に浸漬し、１１０ｍｍ／ｍｉ
ｎの速度で引き上げた。そして１５０℃で１０分間乾燥
後、５００℃で１０分間焼成して第１種の薄膜２を形成
した。冷却後、第２液に浸漬し、２０ｍｍ／ｍｉｎの速
度で引き上げたのち、同様の焼成処理により第２種の薄
膜３を形成した。さらに同様の操作を繰り返して、図１
に断面を示すようにガラス１の両面に、それぞれ第１種
の薄膜２、第２種の薄膜３、第１種の薄膜２、第２種の
薄膜３、そして第１種の薄膜２の順に計５層を積層させ
た多層膜を形成した。Next, a plate-shaped slide glass 1 having a thickness of 1 mm as a substrate is immersed in the first liquid, and is immersed in the first liquid at 110 mm / mi.
It was raised at a speed of n. After drying at 150 ° C. for 10 minutes, it was baked at 500 ° C. for 10 minutes to form a first type thin film 2. After cooling, the film was immersed in the second liquid and pulled up at a speed of 20 mm / min, and then a second type thin film 3 was formed by the same baking treatment. Further, by repeating the same operation, FIG.
As shown in the cross section, the first type thin film 2, the second type thin film 3, the first type thin film 2, the second type thin film 3, and the first type thin film 2 are formed on both surfaces of the glass 1 in this order. A multilayer film was formed by laminating a total of five layers.
【００３７】得られた着色ガラスの第１種の薄膜２の各
層の厚さは９．１×１０-2μｍ、第２種の薄膜３の各層
の厚さは５．４×１０-2μｍであった。第１種の薄膜２
は酸化チタニウムを主体とし酸化クロム４が着色剤とし
て含まれて成り、第２種の薄膜３は酸化ケイ素を主体と
し酸化セリウム５が着色剤として含まれて成っている。
このガラスの色度をトプコン社製色度計ＢＭ−５を用い
て測定すると、Ａ光源でｘ＝０．４７６８、ｙ＝０．４
５０５の黄緑色を呈した。The thickness of each layer of the first type thin film 2 of the obtained colored glass is 9.1 × 10 −2 μm, and the thickness of each layer of the second type thin film 3 is 5.4 × 10 −2 μm. Met. First type thin film 2
Is composed mainly of titanium oxide and contains chromium oxide 4 as a colorant, and the second type thin film 3 is composed mainly of silicon oxide and contains cerium oxide 5 as a colorant.
When the chromaticity of this glass was measured using a chromaticity meter BM-5 manufactured by Topcon, x = 0.4768 and y = 0.4 with the A light source.
505 yellow-green color was exhibited.
【００３８】＜実施例２＞第１液の主成分をチタニウム
テトライソプロポキシド４５ｇとし着色剤を含まないよ
うにして、第２液の着色剤を硝酸コバルト（II）六水和
物３０ｇに変えた他は実施例１と同様にして、第１液と
第２液を調製した。<Example 2> The main component of the first liquid was changed to 45 g of titanium tetraisopropoxide without using a colorant, and the colorant of the second liquid was changed to 30 g of cobalt (II) nitrate hexahydrate. Other than the above, a first liquid and a second liquid were prepared in the same manner as in Example 1.
【００３９】次いで、この第１液と第２液を用いて、ス
ライドガラス表面に第１種の薄膜、第２種の薄膜および
第１種の薄膜をこの順に積層させ、３層からなる多層膜
をガラス両面に形成して、水色の着色ガラスを得た。薄
膜形成にあたって乾燥・焼成条件などは、第１液からの
引き上げ速度を１２０ｍｍ／ｍｉｎ、第２液からの引き
上げ速度を１３０ｍｍ／ｍｉｎとした他は実施例１と同
様にして行った。得られた着色ガラスの第１種の薄膜の
各層の厚さは８．４×１０-2μｍ、第２種の薄膜の各層
の厚さは１３．２×１０-2μｍであった。Next, using the first liquid and the second liquid, a first type thin film, a second type thin film and a first type thin film are laminated in this order on the surface of a slide glass, and a three-layer multilayer film is formed. Was formed on both sides of the glass to obtain a light blue colored glass. The conditions for drying and baking in forming the thin film were the same as in Example 1 except that the pulling speed from the first liquid was 120 mm / min and the pulling speed from the second liquid was 130 mm / min. The thickness of each layer of the first type thin film of the obtained colored glass was 8.4 × 10 −2 μm, and the thickness of each layer of the second type thin film was 13.2 × 10 −2 μm.
【００４０】＜実施例３＞第１液の着色剤を硝酸セリウ
ム３５ｇに変え、第２液が着色剤を含まないようにした
他は実施例１と同様にして、第１液と第２液を調製し
た。Example 3 A first liquid and a second liquid were prepared in the same manner as in Example 1 except that the colorant of the first liquid was changed to 35 g of cerium nitrate and the second liquid did not contain a colorant. Was prepared.
【００４１】次いで、この第１液と第２液を用いて、ス
ライドガラス表面に第１種の薄膜、第２種の薄膜および
第１種の薄膜をこの順に積層させ、３層からなる多層膜
をガラス両面に形成して、紫色の着色ガラスを得た。薄
膜形成にあたって乾燥・焼成条件は、第１液からの引き
上げ速度を７０ｍｍ／ｍｉｎ、第２液からの引き上げ速
度を８０ｍｍ／ｍｉｎとした他は実施例１と同様にして
行った。得られた着色ガラスの第１種の薄膜の各層の厚
さは７．８×１０-2μｍ、第２種の薄膜の各層の厚さは
８．５×１０-2μｍであった。Next, using the first liquid and the second liquid, a first type thin film, a second type thin film, and a first type thin film are laminated in this order on the surface of a slide glass, and a three-layer multilayer film is formed. Was formed on both sides of the glass to obtain a purple colored glass. Drying and firing conditions for forming the thin film were the same as in Example 1 except that the pulling speed from the first liquid was 70 mm / min and the pulling speed from the second liquid was 80 mm / min. The thickness of each layer of the first type thin film of the obtained colored glass was 7.8 × 10 −2 μm, and the thickness of each layer of the second type thin film was 8.5 × 10 −2 μm.
【００４２】＜実施例４＞第１液は着色剤を含まないよ
うにし、第２液の着色剤を硝酸鉄２５ｇに変えた他は実
施例１と同様にして、第１液と第２液を調製した。<Example 4> The first liquid and the second liquid were prepared in the same manner as in Example 1 except that the first liquid did not contain a colorant, and the colorant of the second liquid was changed to 25 g of iron nitrate. Was prepared.
【００４３】次いで、この第１液と第２液を用いて、ス
ライドガラス表面に第１種の薄膜、第２種の薄膜、第１
種の薄膜、および第２種の薄膜をこの順に積層させ、４
層からなる多層膜を両面に形成して、アンバー色の着色
ガラスを得た。薄膜形成にあたって乾燥・焼成条件は、
第１液からの引き上げ速度を４０ｍｍ／ｍｉｎ、第２液
からの引き上げ速度を１２０ｍｍ／ｍｉｎとした他は実
施例１と同様にして行った。得られた着色ガラスの第１
種の薄膜の各層の厚さは６．０×１０-2μｍ、第２種の
薄膜の各層の厚さは１１．８×１０-2μｍであった。Next, using the first liquid and the second liquid, a first type of thin film, a second type of thin film,
And a second kind of thin film in this order,
A multilayer film composed of layers was formed on both sides to obtain an amber colored glass. Drying and firing conditions for thin film formation are as follows:
The procedure was performed in the same manner as in Example 1 except that the lifting speed from the first liquid was 40 mm / min and the lifting speed from the second liquid was 120 mm / min. First of the obtained colored glass
The thickness of each layer of the kind thin film was 6.0 × 10 −2 μm, and the thickness of each layer of the second kind thin film was 11.8 × 10 −2 μm.
【００４４】＜実施例５＞第１液は着色剤を含まないよ
うにし、第２液の着色剤を酸化タングステン微粒子１５
ｇに変えた他は実施例１と同様にして、第１液と第２液
を調製した。<Embodiment 5> The first liquid does not contain a coloring agent, and the coloring agent of the second liquid is replaced with tungsten oxide fine particles 15.
A first liquid and a second liquid were prepared in the same manner as in Example 1 except that g was changed to g.
【００４５】次いで、この第１液と第２液を用いて、第
１液からの引き上げ速度を１２０ｍｍ／ｍｉｎ、第２液
からの引き上げ速度を１００ｍｍ／ｍｉｎとした他は実
施例１と同様にして、５層からなる多層膜を両面に形成
して、黄色の着色ガラスを得た。得られた着色ガラスの
第１種の薄膜の各層の厚さは８．６×１０-2μｍ、第２
種の薄膜の各層の厚さは１０．１×１０-2μｍであっ
た。Next, using the first liquid and the second liquid, the pulling speed from the first liquid was set to 120 mm / min, and the pulling speed from the second liquid was set to 100 mm / min. Then, a multilayer film composed of five layers was formed on both sides to obtain a yellow colored glass. The thickness of each layer of the first type thin film of the obtained colored glass is 8.6 × 10 −2 μm,
The thickness of each layer of the seed thin film was 10.1 × 10 −2 μm.
【００４６】＜実施例６＞第１液および第２液の着色剤
をコバルトブルー（ＣｏＯ・ｎＡｌ2 Ｏ3 ）の微粒子２
０ｇに変えた他は実施例１と同様にして、第１液と第２
液を調製した。<Example 6> Cobalt blue (CoO.nAl 2 O 3 ) fine particles 2 were used as the colorants of the first liquid and the second liquid.
The first liquid and the second liquid were prepared in the same manner as in Example 1 except that the amount was changed to 0 g.
A liquid was prepared.
【００４７】次いで、この第１液と第２液を用いて、ス
ライドガラス表面に第１種の薄膜および第２種の薄膜を
この順に積層させ、２層からなる多層膜を両面に形成し
て、青色の着色ガラスを得た。薄膜形成にあたって乾燥
・焼成条件は、第１液からの引き上げ速度を１２０ｍｍ
／ｍｉｎ、第２液からの引き上げ速度を１３０ｍｍ／ｍ
ｉｎとした他は実施例１と同様にして行った。得られた
着色ガラスの第１種の薄膜の厚さは９．５×１０-2μ
ｍ、第２種の薄膜の厚さは１０．６×１０-2μｍであっ
た。Next, using the first liquid and the second liquid, a first-type thin film and a second-type thin film are laminated in this order on the surface of a slide glass, and a multilayer film composed of two layers is formed on both surfaces. To obtain a blue colored glass. The drying and baking conditions for forming the thin film are as follows: the lifting speed from the first liquid is 120 mm.
/ Min, the lifting speed from the second liquid is 130 mm / m
The procedure was carried out in the same manner as in Example 1 except that "in" was set. The thickness of the first type thin film of the obtained colored glass is 9.5 × 10 −2 μm.
m, the thickness of the second type thin film was 10.6 × 10 −2 μm.
【００４８】＜実施例７＞第１液の着色剤をセリウムの
アルコラート（セリウムトリイソプロポキシド）２０ｇ
に変え、第２液の着色剤を酸化ビスマスの微粒子２５ｇ
に変えた他は実施例１と同様にして、第１液と第２液を
調製した。<Example 7> 20 g of cerium alcoholate (cerium triisopropoxide) was used as the colorant of the first liquid.
And the coloring agent of the second liquid is 25 g of bismuth oxide fine particles.
A first liquid and a second liquid were prepared in the same manner as in Example 1 except for changing to.
【００４９】次いで、この第１液と第２液を用いて、ス
ライドガラス表面に第１種の薄膜、第２種の薄膜および
第１種の薄膜をこの順に積層させ３層からなる多層膜を
両面に形成して、黄色の着色ガラスを得た。薄膜形成に
あたって乾燥・焼成条件は、第１液からの引き上げ速度
を１２０ｍｍ／ｍｉｎ、第２液からの引き上げ速度を２
０ｍｍ／ｍｉｎとした他は実施例１と同様にして行っ
た。得られた着色ガラスの第１種の薄膜の各層の厚さは
９．５×１０-2μｍ、第２種の薄膜の各層の厚さは５．
０×１０-2μｍであった。Next, using the first liquid and the second liquid, a first-type thin film, a second-type thin film, and a first-type thin film are laminated in this order on a slide glass surface to form a three-layer multilayer film. Formed on both sides, a yellow colored glass was obtained. In forming the thin film, the drying and baking conditions are as follows: the pulling speed from the first liquid is 120 mm / min, and the pulling speed from the second liquid is 2 mm.
The procedure was performed in the same manner as in Example 1 except that 0 mm / min was set. The thickness of each layer of the first type thin film of the obtained colored glass is 9.5 × 10 −2 μm, and the thickness of each layer of the second type thin film is 5.
It was 0 × 10 −2 μm.
【００５０】＜実施例８＞第２液の着色剤をローダミン
１２３の５０ｇに変えた他は実施例１と同様にして、第
１液と第２液を調製した。Example 8 A first liquid and a second liquid were prepared in the same manner as in Example 1 except that the colorant of the second liquid was changed to 50 g of rhodamine 123.
【００５１】次いで、第１液からの引き上げ速度を１２
０ｍｍ／ｍｉｎ、第２液からの引き上げ速度を１００ｍ
ｍ／ｍｉｎとし、第１種の薄膜の焼成条件を５００℃で
１０分、第２種の薄膜の焼成条件を３００℃で１０分と
した他は実施例１と同様にして、黄色の着色ガラスを得
た。得られた着色ガラスの第１種の薄膜の各層の厚さは
９．０×１０-2μｍ、第２種の薄膜の各層の厚さは９．
３×１０-2μｍであった。Next, the pulling speed from the first liquid is set to 12
0 mm / min, 100 m lifting speed from the second liquid
m / min, the first type thin film was fired at 500 ° C. for 10 minutes, and the second type thin film was fired at 300 ° C. for 10 minutes. I got The thickness of each layer of the first-type thin film of the obtained colored glass is 9.0 × 10 −2 μm, and the thickness of each layer of the second-type thin film is 9.
It was 3 × 10 −2 μm.
【００５２】＜比較例１＞第１液および第２液ともに着
色剤を含まないようにした他は実施例１と同様にして、
第１液と第２液を調製した。<Comparative Example 1> The procedure of Example 1 was repeated except that the first and second liquids did not contain a coloring agent.
A first liquid and a second liquid were prepared.
【００５３】次いで、この第１液と第２液を用いて、実
施例１の着色ガラスの色濃度と同じ濃さになるまで第１
種の薄膜と第２種の薄膜とを積層させたところ、両側に
９層の積層を必要とした。Next, using the first liquid and the second liquid, the first liquid is used until the color density of the colored glass of Example 1 becomes the same.
When the seed thin film and the second kind thin film were stacked, nine layers were required on both sides.
【００５４】なお、本発明の実施例の着色ガラスの透過
率曲線を、図２に示した。測定にあたっては、日立製分
光光度計Ｕ３２００を用いた。図２からも明らかなよう
に、本発明によれば、さまざまな色調で発色がよい着色
ガラスが得られた。FIG. 2 shows a transmittance curve of the colored glass of the example of the present invention. In the measurement, a spectrophotometer U3200 manufactured by Hitachi was used. As is clear from FIG. 2, according to the present invention, colored glass having various colors and good color development was obtained.
【００５５】[0055]
【発明の効果】以上説明したように本発明によれば、耐
熱性が大きく色濃度が濃く発色もよく、しかも従来の着
色ガラスに比較して製造コストも低いすぐれた着色ガラ
スが提供される。As described above, according to the present invention, there is provided an excellent colored glass having high heat resistance, high color density, good color development, and low production cost as compared with conventional colored glass.
【図１】本発明の実施例１の着色ガラスの断面構造を示
す概略図である。FIG. 1 is a schematic diagram showing a cross-sectional structure of a colored glass of Example 1 of the present invention.
【図２】実施例１〜８の着色ガラスの分光透過率曲線を
示す図である。FIG. 2 is a view showing a spectral transmittance curve of the colored glasses of Examples 1 to 8.
１………ガラス基体 ２………酸化チタニウムを主体とする第１種の薄膜 ３………酸化ケイ素を主体とする第２種の薄膜 ４………酸化クロム ５………酸化セリウ
ムDESCRIPTION OF SYMBOLS 1 ... Glass base material 2 ... 1st kind thin film mainly consisting of titanium oxide 3 ... 2nd kind thin film mainly consisting of silicon oxide 4 ... Chromium oxide 5 ... Cerium oxide
Claims (7)
折率ｎ1 の第１種の薄膜と屈折率ｎ2 （ただしｎ1 ＞ｎ
2 ）の第２種の薄膜とが積層してなる多層膜が形成さ
れ、前記第１種の薄膜および前記第２種の薄膜の少なく
とも一方が有色であることを特徴とする着色ガラス。At least a portion of a glass substrate surface is provided with a first type thin film having a refractive index of n 1 and a refractive index of n 2 (where n 1 > n).
2 ) A colored glass, wherein a multilayer film formed by laminating the second type thin film is formed, and at least one of the first type thin film and the second type thin film is colored.
膜の各層が、有機金属化合物を主成分として含む溶液を
塗布の後１５０〜７００℃の温度で焼成することにより
形成され、金属酸化物を主体としてなる膜厚１０〜１０
００ｎｍの薄膜であることを特徴とする特許請求の範囲
請求項１記載の着色ガラス。2. The method according to claim 1, wherein each of the first type thin film and the second type thin film is formed by applying a solution containing an organometallic compound as a main component and then baking the solution at a temperature of 150 to 700 ° C. Oxide-based film thickness of 10 to 10
The colored glass according to claim 1, wherein the colored glass is a thin film having a thickness of 00 nm.
る溶液に主成分として含まれる有機金属化合物が、Ｔ
ｉ、Ｚｒ、Ｔａ、およびＳｂの群から選ばれた少なくと
も１種の金属のアルコキシドであることを特徴とする特
許請求の範囲請求項２記載の着色ガラス。3. An organometallic compound contained as a main component in a solution applied for forming the first type thin film,
3. The colored glass according to claim 2, wherein the glass is an alkoxide of at least one metal selected from the group consisting of i, Zr, Ta, and Sb.
る溶液に主成分として含まれる有機金属化合物が、Ｓｉ
およびＡｌから選ばれた少なくとも１種の金属のアルコ
キシドであることを特徴とする特許請求の範囲請求項２
あるいは３記載の着色ガラス。4. The method according to claim 1, wherein the organometallic compound contained as a main component in the solution applied for forming the second type thin film is Si.
3. An alkoxide of at least one metal selected from Al and Al.
Alternatively, the colored glass according to 3.
膜の少なくとも一方に、着色剤が添加されていることを
特徴とする特許請求の範囲請求項１、２、３、あるいは
４記載の着色ガラス。5. The color filter according to claim 1, wherein a colorant is added to at least one of the first type thin film and the second type thin film. Colored glass.
ことを特徴とする特許請求の範囲請求項５記載の着色ガ
ラス。6. The colored glass according to claim 5, wherein the coloring agent is a colored metal oxide.
料であることを特徴とする特許請求の範囲請求項５記載
の着色ガラス。7. The colored glass according to claim 5, wherein the colorant is an organic pigment or an organic dye.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9007983A JPH10203848A (en) | 1997-01-20 | 1997-01-20 | Colored glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9007983A JPH10203848A (en) | 1997-01-20 | 1997-01-20 | Colored glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10203848A true JPH10203848A (en) | 1998-08-04 |
Family
ID=11680680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9007983A Pending JPH10203848A (en) | 1997-01-20 | 1997-01-20 | Colored glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10203848A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005102954A1 (en) * | 2004-04-26 | 2005-11-03 | Koa Glass Co., Ltd | Multicolor development glass vessel and process for producing the same |
| FR2885995A1 (en) * | 2005-05-20 | 2006-11-24 | Eurokera | Vitroceramic plate with a coating incorporating at least two contrasting zones with matt or reflective finishes, for covering or receiving heating elements notably for cookers |
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| JPH0782527A (en) * | 1993-06-30 | 1995-03-28 | Asahi Glass Co Ltd | Colored film-forming liquid coating, colored film, and production thereof |
| JPH07330379A (en) * | 1994-05-31 | 1995-12-19 | Asahi Glass Co Ltd | Colored transparent material |
| JPH08104545A (en) * | 1994-09-30 | 1996-04-23 | Nippon Sheet Glass Co Ltd | Ultraviolet absorbing glass |
| JPH09235141A (en) * | 1995-12-26 | 1997-09-09 | Nippon Sheet Glass Co Ltd | Uv rays absorbing colored film-coated glass article |
| JPH10162756A (en) * | 1996-12-03 | 1998-06-19 | Hitachi Ltd | High-precision cathode-ray tube and manufacture thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6433538U (en) * | 1987-08-25 | 1989-03-01 | ||
| JPH06103931A (en) * | 1992-09-17 | 1994-04-15 | Hitachi Ltd | Cathode-ray tube |
| JPH06234940A (en) * | 1993-02-10 | 1994-08-23 | Sumitomo Cement Co Ltd | Coating material for forming antistatic high-refractive-index film, transparent laminate having antistatic reflection-preventing film, and cathode ray tube |
| JPH0782527A (en) * | 1993-06-30 | 1995-03-28 | Asahi Glass Co Ltd | Colored film-forming liquid coating, colored film, and production thereof |
| JPH07330379A (en) * | 1994-05-31 | 1995-12-19 | Asahi Glass Co Ltd | Colored transparent material |
| JPH08104545A (en) * | 1994-09-30 | 1996-04-23 | Nippon Sheet Glass Co Ltd | Ultraviolet absorbing glass |
| JPH09235141A (en) * | 1995-12-26 | 1997-09-09 | Nippon Sheet Glass Co Ltd | Uv rays absorbing colored film-coated glass article |
| JPH10162756A (en) * | 1996-12-03 | 1998-06-19 | Hitachi Ltd | High-precision cathode-ray tube and manufacture thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005102954A1 (en) * | 2004-04-26 | 2005-11-03 | Koa Glass Co., Ltd | Multicolor development glass vessel and process for producing the same |
| US7851035B2 (en) | 2004-04-26 | 2010-12-14 | Koa Glass Co., Ltd. | Multicolor glass vessel |
| FR2885995A1 (en) * | 2005-05-20 | 2006-11-24 | Eurokera | Vitroceramic plate with a coating incorporating at least two contrasting zones with matt or reflective finishes, for covering or receiving heating elements notably for cookers |
| WO2007000532A3 (en) * | 2005-05-20 | 2007-08-16 | Eurokera | Glass-ceramic plate and method for the production thereof |
| US8168925B2 (en) | 2005-05-20 | 2012-05-01 | Eurokera S.N.C. | Glass-ceramic plate and method for the production thereof |
| US9051212B2 (en) | 2005-05-20 | 2015-06-09 | Eurokera S.N.C. | Glass-ceramic plate and method for producing same |
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