JPH05229851A - Molded article of crystallized glass and its production - Google Patents
Molded article of crystallized glass and its productionInfo
- Publication number
- JPH05229851A JPH05229851A JP6948292A JP6948292A JPH05229851A JP H05229851 A JPH05229851 A JP H05229851A JP 6948292 A JP6948292 A JP 6948292A JP 6948292 A JP6948292 A JP 6948292A JP H05229851 A JPH05229851 A JP H05229851A
- Authority
- JP
- Japan
- Prior art keywords
- crystallized glass
- coating layer
- molded article
- alcoholate
- molded product
- 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.)
- Granted
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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
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)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は，化学的耐候性に優れた
結晶化ガラス成形品及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystallized glass molded article excellent in chemical weather resistance and a method for producing the same.
【０００２】[0002]
【従来技術】温度変化による伸び縮みの大きいガラスほ
ど急熱急冷，即ち熱衝撃により割れやすい。そして，こ
の温度変化による物質の伸び縮みの程度は，熱膨張係数
で表される。ところで，結晶化ガラスの中には熱膨張係
数が非常に小さいものがある。特に，ＳｉＯ2 −Ａｌ2
Ｏ3 −Ｌｉ2 Ｏ（シリカ−アルミナ−リチア）系結晶化
ガラスにより作製された結晶化ガラス成形品は，熱膨張
係数が０〜１０×１０-7℃-1であり，高温でも変形せ
ず，直火にかけても赤熱後水中に投入しても割れること
はない。2. Description of the Related Art Glass having a larger expansion and contraction due to temperature change is more likely to be broken by rapid heating, that is, thermal shock. The degree of expansion and contraction of the substance due to this temperature change is represented by the coefficient of thermal expansion. By the way, some crystallized glasses have a very small coefficient of thermal expansion. In particular, SiO 2 -Al 2
A crystallized glass molded product made of O 3 -Li 2 O (silica-alumina-lithia) -based crystallized glass has a coefficient of thermal expansion of 0 to 10 × 10 -7 ℃ -1 , and does not deform even at high temperatures. ， It doesn't crack even if it is put into the water after it has been red-hot, even if it is put into an open flame.
【０００３】そのため，このＳｉＯ2 −Ａｌ2 Ｏ3 −Ｌ
ｉ2 Ｏ系結晶化ガラスは，鍋或いはコーヒー沸かしのよ
うな超耐熱高級食器として使われている。また，電気又
はガス調理器のトッププレート等の種々の熱器具にも使
用され，ストーブの熱線透過部品や防火窓或いはレーザ
ーの反射鏡としても使われている。ところで，灯油スト
ーブに用いられる灯油中には，微量の硫黄が含まれてお
り，使用時には，微量の亜硫酸ガスが発生する。また，
電気又はガス調理器のトッププレートは，調味料や煮汁
及びこれらの炭化物と接触する。Therefore, this SiO 2 --Al 2 O 3 --L
i 2 O-based crystallized glass is used as super heat-resistant high-grade tableware such as pots or coffee brewers. It is also used in various heat appliances such as the top plate of electric or gas cookers, and is also used as a heat ray transmitting part of a stove, a fireproof window or a reflector of a laser. By the way, the kerosene used in the kerosene stove contains a small amount of sulfur, and a small amount of sulfurous acid gas is generated during use. Also,
The top plate of an electric or gas cooker comes into contact with seasonings, broth and their charcoal.
【０００４】[0004]
【解決しようとする課題】しかしながら，上記ＳｉＯ2
−Ａｌ2 Ｏ3 −Ｌｉ2 Ｏ系結晶化ガラス成形品は，上記
亜硫酸ガス，調味料，煮汁中の有機酸，果汁等の酸，或
いは，調味料中のグルタミン酸ナトリウム及びその分解
物である酸化ナトリウムなどのアルカリに弱い。そのた
め，上記結晶化ガラス成形品は，灯油ストーブ及び調理
器に用いる場合，亜硫酸ガス又は調味料等と接触し，こ
れらと反応し，クラック等を生じることがある。そし
て，その部分は，２，３か月の短期間で上記結晶化ガラ
ス成形品の破壊へと進行する。[Problems to be Solved] However, the above-mentioned SiO 2
The -Al 2 O 3 -Li 2 O-based crystallized glass molded article is an oxidation product of the above-mentioned sulfurous acid gas, seasoning, organic acid in broth, acid such as fruit juice, or sodium glutamate and its decomposition product in seasoning. Weak against alkali such as sodium. Therefore, when the above-mentioned crystallized glass molded product is used in a kerosene stove and a cooking device, it may come into contact with sulfurous acid gas, seasonings, etc., and react with them to cause cracks and the like. Then, that portion progresses to the destruction of the crystallized glass molded product in a short period of a few months.
【０００５】そこで，上記結晶化ガラス成形品の表面を
シリカ（ＳｉＯ2 ）によりコーティングしたものがあ
る。このものは，亜硫酸ガス等の酸には，耐性がある
が，有機酸ナトリウム分解物等のアルカリについては耐
性がない。したがって，シリカコーティングが施された
結晶化ガラス成形品は，必ずしもアルカリに対する耐性
があるとは言えない。そこで，本発明はかかる問題点に
鑑み，酸，アルカリ等の化学的耐候性に優れた結晶化ガ
ラス成形品及びその製造方法を提供しようとするもので
ある。Therefore, there is a crystallized glass molded article whose surface is coated with silica (SiO 2 ). This product is resistant to acids such as sulfurous acid gas, but is not resistant to alkali such as organic acid sodium decomposition products. Therefore, it cannot be said that the crystallized glass molded article coated with silica is necessarily resistant to alkali. Therefore, in view of such problems, the present invention intends to provide a crystallized glass molded article excellent in chemical weather resistance against acids, alkalis and the like, and a method for producing the same.
【０００６】[0006]
【課題の解決手段】本発明は，ＳｉＯ2 −Ａｌ2 Ｏ3 −
Ｌｉ2 Ｏ系結晶化ガラスの表面に，Ｚｒ，Ｌｉ，Ｎａ，
Ｋ，Ｍｇ，Ｃａ，Ｓｒ，Ｂａ，Ａｌ，Ｉｎ，Ｇｅ，Ｂ
ｉ，Ｆｅ，Ｃｕ，Ｙ，Ｔａの金属酸化物のコーティング
層を有し，該コーティング層の厚みは０．０１μｍ以上
から１．０μｍ以下であることを特徴とする結晶化ガラ
ス成形品にある。According to the present invention, SiO 2 --Al 2 O 3-
On the surface of the Li 2 O-based crystallized glass, Zr, Li, Na,
K, Mg, Ca, Sr, Ba, Al, In, Ge, B
A crystallized glass molded article is characterized in that it has a coating layer of a metal oxide of i, Fe, Cu, Y, and Ta, and the thickness of the coating layer is 0.01 μm or more and 1.0 μm or less.
【０００７】本発明において，上記金属酸化物の金属成
分としては，Ｚｒ（ジルコニウム），Ｌｉ（リチウ
ム），Ｎａ（ナトリウム），Ｋ（カリウム），Ｍｇ（マ
グネシウム），Ｃａ（カルシウム），Ｓｒ（ストロンチ
ウム），Ｂａ（バリウム），Ａｌ（アルミニウム），Ｉ
ｎ（インジウム），Ｇｅ（ゲルマニウム），Ｂｉ（ビス
マス），Ｆｅ（鉄），Ｃｕ（銅），Ｙ（イットリウ
ム），Ｔａ（タンタル）を用いる。In the present invention, as the metal component of the above metal oxide, Zr (zirconium), Li (lithium), Na (sodium), K (potassium), Mg (magnesium), Ca (calcium), Sr (strontium) are used. ), Ba (barium), Al (aluminum), I
n (indium), Ge (germanium), Bi (bismuth), Fe (iron), Cu (copper), Y (yttrium), Ta (tantalum) are used.
【０００８】上記金属酸化物のコーティング層の形成方
法としては，後述する金属アルコラートを被覆し，熱処
理する方法がある。コーティング層の厚みは，０．０１
μｍ以上から１．０μｍ以下である。コーティング層の
厚みが０．０１μｍ未満では，結晶化ガラス成形品の化
学的耐候性が低く，本発明の目的を達成できない。コー
ティング層の厚みが１．０μｍを越えた場合，熱膨張差
でコーティング層にクラックが生じる，或いは熱線透過
率が低下する等の問題がある。As a method of forming the above-mentioned metal oxide coating layer, there is a method of coating a metal alcoholate, which will be described later, and heat treatment. The thickness of the coating layer is 0.01
It is from μm to 1.0 μm. When the thickness of the coating layer is less than 0.01 μm, the chemical weather resistance of the crystallized glass molded product is low, and the object of the present invention cannot be achieved. When the thickness of the coating layer exceeds 1.0 μm, there is a problem that the coating layer is cracked due to a difference in thermal expansion or the heat ray transmittance is lowered.
【０００９】次に，上記結晶化ガラス成形品の製造方法
としては，ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｌｉ2 Ｏ系結晶化ガ
ラスにより作製された結晶化ガラス成形品に，金属アル
コラートを塗布し，熱処理することにより，成形品の表
面に上記金属アルコラートから生成した金属酸化物のコ
ーティング層を形成することを特徴とする結晶化ガラス
成形品の製造方法がある。Next, as a method for producing the above-mentioned crystallized glass molded product, a metal alcoholate is applied to a crystallized glass molded product made of SiO 2 --Al 2 O 3 --Li 2 O type crystallized glass, There is a method for producing a crystallized glass molded product, which comprises forming a coating layer of a metal oxide produced from the metal alcoholate on the surface of the molded product by heat treatment.
【００１０】上記金属アルコラートとしては，前記に示
したＺｒ，Ｌｉ，Ｙ，Ｔａ等の金属を用いたものがあ
る。この金属アルコラートは，上記金属の一種又は二種
以上を用いる。金属アルコラートは，上記金属に１つも
しくはそれ以上のアルコキシル基が結合した化合物であ
る。アルコキシル基とは，アルキル基に酸素原子が１つ
付与した基である。かかる金属アルコラートは，アルコ
ールの水酸基の水素を金属で置換することにより得られ
る。As the above-mentioned metal alcoholate, there is one using the above-mentioned metals such as Zr, Li, Y and Ta. As the metal alcoholate, one or more of the above metals are used. A metal alcoholate is a compound in which one or more alkoxyl groups are bonded to the above metal. The alkoxyl group is a group in which one oxygen atom is added to an alkyl group. Such a metal alcoholate can be obtained by substituting the hydrogen of the hydroxyl group of alcohol with a metal.
【００１１】上記金属アルコラートは，液体状であるも
のが好ましい。液体状の金属アルコラートとしては，Ｚ
ｒ，Ａｌ，Ｉｎ，Ｇｅ，Ｆｅ，Ｔａの金属に１つもしく
はそれ以上のアルコキシル基が結合した化合物がある。
液体状の金属アルコラートを用いる場合には，結晶化ガ
ラス成形品に，均一に容易に塗布することができる。The metal alcoholate is preferably in the liquid state. As a liquid metal alcoholate, Z
There are compounds in which one or more alkoxyl groups are bonded to the metal of r, Al, In, Ge, Fe, Ta.
When a liquid metal alcoholate is used, it can be uniformly and easily applied to a crystallized glass molded product.
【００１２】金属アルコラートを結晶化ガラスに塗布す
る方法としては，ディッピング，スピンコート，スプレ
ー，刷毛塗り等の方法がある。そして，金属アルコラー
トは，塗布しやすい形態にするために，酢酸ブチル等の
溶媒と混合して塗布することが好ましい。As a method of applying the metal alcoholate to the crystallized glass, there are methods such as dipping, spin coating, spraying and brush coating. Then, the metal alcoholate is preferably mixed and applied with a solvent such as butyl acetate in order to make the form easy to apply.
【００１３】上記塗布後の熱処理は，乾燥状態で，１０
０〜１０００℃の温度にて行う。１００℃未満の場合，
温度が低すぎて，熱処理としての効果がない。一方，１
０００℃を越えた場合，コーティング層の結晶化が進行
しすぎて，コーティング層が剥がれてしまうおそれがあ
る。The heat treatment after the above-mentioned application is 10
It is carried out at a temperature of 0 to 1000 ° C. If the temperature is below 100 ° C,
The temperature is too low to be effective as a heat treatment. On the other hand, 1
If the temperature exceeds 000 ° C, the crystallization of the coating layer will proceed too much, and the coating layer may peel off.
【００１４】[0014]
【作用及び効果】本発明においては，結晶化ガラス成形
品に，金属酸化物のコーティング層を有している。上記
金属酸化物は，酸，アルカリ等に対する化学的耐候性に
優れるものである。それ故，上記コーティング層で被覆
された結晶化ガラスの成形品は，酸，アルカリ等に対す
る化学的耐候性に優れている。In the present invention, the crystallized glass molded article has a metal oxide coating layer. The metal oxide has excellent chemical weather resistance against acids, alkalis and the like. Therefore, the molded product of crystallized glass coated with the above-mentioned coating layer has excellent chemical weather resistance against acids, alkalis and the like.
【００１５】また，本発明の結晶化ガラス成形品は，金
属アルコラートを塗布し，熱処理することにより，結晶
化ガラスの表面に，上記金属アルコラートから生成した
金属酸化物のコーティング層を形成している。コーティ
ング層は，結晶化ガラス成形品と共に，熱処理が施され
ている。これにより，コーティング層を形成している金
属酸化物の結晶化が進行する。そのため，上記コーティ
ング層は，付着強度に優れている。以上の如く，本発明
によれば，酸，アルカリ等に対する化学的耐候性及び付
着強度に優れた結晶化ガラス成形品及びその製造方法を
提供することができる。In the crystallized glass molded article of the present invention, a coating layer of a metal oxide produced from the above-mentioned metal alcoholate is formed on the surface of the crystallized glass by applying a metal alcoholate and heat-treating it. .. The coating layer is heat treated together with the crystallized glass molded product. As a result, crystallization of the metal oxide forming the coating layer proceeds. Therefore, the coating layer has excellent adhesion strength. As described above, according to the present invention, it is possible to provide a crystallized glass molded article which is excellent in chemical weather resistance and adhesion strength against acids, alkalis and the like, and a manufacturing method thereof.
【００１６】[0016]
実施例１〜３ 本例の結晶化ガラス成形品は，ＳｉＯ2 −Ａｌ2 Ｏ3 −
Ｌｉ2 Ｏ系結晶化ガラスの表面にＺｒの金属酸化物のコ
ーティング層を有している。上記結晶化ガラス成形品の
製造方法においては，ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｌｉ2 Ｏ
系結晶化ガラスにより作製された結晶化ガラス成形品
に，金属アルコラートを塗布し，熱処理する。Examples 1 to 3 The crystallized glass molded articles of this example are SiO 2 —Al 2 O 3 —
A coating layer of Zr metal oxide is provided on the surface of Li 2 O-based crystallized glass. In the above method for producing a crystallized glass molded article, SiO 2 —Al 2 O 3 —Li 2 O
A metal alcoholate is applied to a crystallized glass molded product made of a system crystallized glass and heat-treated.
【００１７】上記金属アルコラートとしては，Ｚｒ（ジ
ルコニウム）アルコラートを用いる。上記Ｚｒアルコラ
ートは液体である。Ｚｒアルコラートは，酢酸ブチルよ
りなる溶媒と混合し，５重量％酢酸ブチル溶液とする。
上記金属アルコラートはディッピングにより結晶化ガラ
スに塗布される。Zr (zirconium) alcoholate is used as the metal alcoholate. The Zr alcoholate is a liquid. Zr alcoholate is mixed with a solvent consisting of butyl acetate to prepare a 5 wt% butyl acetate solution.
The metal alcoholate is applied to the crystallized glass by dipping.
【００１８】上記熱処理は，乾燥状態で，２００，５０
０，８００℃にて行った。このようにして得られた成形
品につき，熱処理の温度が２００℃のものを実施例１，
５００℃のものを実施例２，８００℃のものを実施例３
とする。上記のごとき方法により得られた成形品の全表
面には，Ｚｒアルコラートから生成したＺｒ酸化物のコ
ーティング層が形成されていた。尚，上記成形品は，平
板を，凸型形状に湾曲させたものである。成形品におけ
る結晶化ガラスの厚さは３ｍｍ，コーティング層の厚さ
は約０．１μｍである。The above heat treatment is performed in a dry state at 200, 50
It was carried out at 0,800 ° C. Of the molded products thus obtained, those having a heat treatment temperature of 200 ° C. were used in Example 1,
One having a temperature of 500 ° C. is Example 2 and one having a temperature of 800 ° C. is Example 3
And A coating layer of Zr oxide produced from Zr alcoholate was formed on the entire surface of the molded article obtained by the above method. The molded product is a flat plate curved in a convex shape. The thickness of the crystallized glass in the molded product is 3 mm, and the thickness of the coating layer is about 0.1 μm.
【００１９】本例において，Ｚｒ酸化物は，酸，アルカ
リ等に対する化学的耐候性に優れるものである。それ
故，上記コーティング層で被覆された結晶化ガラスの成
形品は，酸，アルカリ等に対する化学的耐候性に優れて
いる。コーティング層は，結晶化ガラス成形品に，Ｚｒ
アルコラートを塗布し，熱処理している。そして，Ｚｒ
アルコラートは，結晶化ガラスの表面に，上記Ｚｒアル
コラートから生成したＺｒ酸化物のコーティング層を形
成する。これにより，コーティング層を形成しているＺ
ｒ酸化物の結晶化が進行する。そのため，上記コーティ
ング層は，付着強度に優れている。In this example, the Zr oxide has excellent chemical weather resistance against acids, alkalis and the like. Therefore, the molded product of crystallized glass coated with the above-mentioned coating layer has excellent chemical weather resistance against acids, alkalis and the like. The coating layer is Zr
Alcolate is applied and heat treated. And Zr
The alcoholate forms a coating layer of Zr oxide produced from the Zr alcoholate on the surface of the crystallized glass. As a result, Z forming the coating layer
Crystallization of the r oxide proceeds. Therefore, the coating layer has excellent adhesion strength.
【００２０】次に，上記実施例１〜３の成形品の化学的
耐候性及び付着強度について評価した。その評価方法に
つき，以下に説明する。上記成形品の下面をガスバーナ
ーにより加熱する。ガスバーナーの温度は，約５００℃
である。一方，上記成形品の上面に，アルカリを１ｃｃ
ずつ５分間の間隔で滴下する。アルカリとしては，有機
酸ナトリウム（調味料グルタミン酸ソーダ）５０％水溶
液を用いた。このテストにおいては，滴下１０回毎に，
上記成形品を冷却し，次いでナイロンたわしにより成形
品の表面を研磨した。そして，アルカリを滴下する度
に，成形品の外観検査を行った。なお，上記テストにお
ける同種成形品試料数は５つである。Next, the chemical weather resistance and the adhesive strength of the molded articles of Examples 1 to 3 were evaluated. The evaluation method will be described below. The lower surface of the molded product is heated with a gas burner. The temperature of the gas burner is about 500 ℃
Is. On the other hand, 1 cc of alkali is applied to the upper surface of the molded product.
Dropwise at intervals of 5 minutes each. As the alkali, a 50% aqueous solution of sodium organic acid (sodium glutamate seasoning) was used. In this test, every 10 drops,
The above molded product was cooled, and then the surface of the molded product was polished with a nylon scrubber. Every time the alkali was dropped, the appearance of the molded product was inspected. The number of samples of the same type of molded product in the above test was five.
【００２１】また，比較のため，結晶化ガラスのみから
なる成形品を比較例１，結晶化ガラスの表面にシリカよ
りなるコーティング層を施してなる成形品を比較例２と
した。比較例１，２の形状及び評価方法は，実施例１〜
３と同様である。実施例１〜３及び比較例１，２の化学
的耐候性及び付着強度の評価結果の平均値を図１に示
す。図１の横軸には，及び実施例１，２，３及び比較例
１，２からなる評価対象物を配列させた。その縦軸に
は，クラックが発生するまでのアルカリの滴下回数を示
した。For comparison, a molded product made only of crystallized glass was designated as Comparative Example 1, and a molded product made by coating the surface of the crystallized glass with a coating layer made of silica was designated as Comparative Example 2. The shapes and evaluation methods of Comparative Examples 1 and 2 are described in Examples 1 to 1.
Same as 3. The average values of the evaluation results of the chemical weather resistance and the adhesion strength of Examples 1 to 3 and Comparative Examples 1 and 2 are shown in FIG. On the horizontal axis of FIG. 1, evaluation objects made of Examples 1, 2, 3 and Comparative Examples 1, 2 were arranged. The vertical axis shows the number of alkali drops before cracking.
【００２２】図１より知られるごとく，実施例１，２，
３の成形品は，アルカリ滴下平均６０，６３，８２回目
でマイクロクラックが発生した。一方，比較例１，２の
成形品は，共に，平均５５回目でマイクロクラックが発
生した。このように，成形品の表面にＺｒアルコラート
から生成したＺｒ酸化物のコーティング層が被覆してい
る結晶化ガラス（実施例１〜３）は，コーティング層が
ない或いはシリカよりなるコーティング層が被覆してい
る結晶化ガラス（比較例１，２）よりも，化学的耐候性
及び付着強度が高いことが確認された。また，熱処理時
の温度が高い程，成形品は化学的耐候性及び付着強度に
優れるものとなった。As is known from FIG. 1, Embodiments 1, 2,
In the molded product of No. 3, microcracks were generated on the average 60, 63, and 82 times of alkali dropping. On the other hand, in the molded products of Comparative Examples 1 and 2, microcracks occurred on average 55 times. As described above, the crystallized glass (Examples 1 to 3) in which the surface of the molded article is coated with the coating layer of Zr oxide generated from Zr alcoholate has no coating layer or is coated with the coating layer of silica. It was confirmed that the chemical weather resistance and the adhesion strength were higher than those of the crystallized glass (Comparative Examples 1 and 2) which are present. Also, the higher the temperature during heat treatment, the more excellent the molded article was in chemical weather resistance and bond strength.
【００２３】実施例４ 実施例１と同様にして結晶化ガラス成形品の表面にＺｒ
アルコラートを用いて熱処理し，種々の厚みの金属酸化
物のコーティング層を形成した。熱処理温度は８００℃
である。そして，これらにつき，実施例１と同様の測定
を行った。その結果を図２に示す。図２は，横軸にコー
ティング層の厚みを，縦軸にクラック発生までのアルカ
リ滴下回数を示す。Example 4 In the same manner as in Example 1, Zr was formed on the surface of the crystallized glass molded product.
Heat treatment was performed using alcoholate to form metal oxide coating layers of various thicknesses. Heat treatment temperature is 800 ℃
Is. Then, for these, the same measurement as in Example 1 was performed. The result is shown in FIG. In FIG. 2, the horizontal axis shows the thickness of the coating layer, and the vertical axis shows the number of times the alkali is dropped until cracks occur.
【００２４】図２より知られるごとく，コーティング層
の厚みが，０．００７，０．０１，０．１，０．５，
１．０，１．２μｍの成形品は，アルカリ滴下平均５
５，５８，８２，６５，５８，５５回目でマイクロクラ
ックが発生した。このように，０．０１μｍ以上１．０
μｍ以下の厚みを有するコーティング層が被覆された結
晶化ガラス成形品は，化学的耐候性及び付着強度が高い
ことが確認された。また，熱処理時の温度が高い程，成
形品は化学的耐候性及び付着強度に優れるものとなっ
た。As is known from FIG. 2, the thickness of the coating layer is 0.007, 0.01, 0.1, 0.5,
Alkali dripping average is 5 for molded products of 1.0 and 1.2 μm
Microcracks occurred at the 5th, 58th, 82nd, 65th, 58th and 55th times. Thus, 0.01 μm or more and 1.0
It was confirmed that the crystallized glass molded article coated with the coating layer having a thickness of μm or less has high chemical weather resistance and high adhesive strength. Also, the higher the temperature during heat treatment, the more excellent the molded article was in chemical weather resistance and bond strength.
【００２５】比較実験例 本実験においては，Ｚｒアルコラート，硝酸Ｚｒ，オキ
シ塩化Ｚｒ，酢酸Ｚｒを用いて，各々結晶化ガラスのコ
ーティング層を作製し，その外観検査を行った。コーテ
ィング層を結晶化ガラスに作製する方法は実施例１と同
様である。この場合，Ｚｒアルコラートを用いた場合の
みについて，薄層のコーティング層が形成され，結晶化
ガラス成形品の表面に良く密着していた。一方，その他
のコーティング層については，コーティング層が形成さ
れず，ボイドが発生していた。そのため，化学的耐候性
が劣っていた。Comparative Experimental Example In this experiment, a coating layer of crystallized glass was prepared using Zr alcoholate, Zr nitrate, Zr oxychloride and Zr acetate, and the appearance was inspected. The method for producing the coating layer on the crystallized glass is the same as in Example 1. In this case, only when Zr alcoholate was used, a thin coating layer was formed, and it adhered well to the surface of the crystallized glass molded product. On the other hand, with respect to the other coating layers, the coating layers were not formed and voids were generated. Therefore, the chemical weather resistance was poor.
【図１】実施例１ないし３及び比較例にかかる，コーテ
ィング層とクラックが発生するまでのアルカリ滴下回数
との関係を示す線図。FIG. 1 is a graph showing the relationship between the coating layer and the number of alkali drops until a crack is generated according to Examples 1 to 3 and Comparative Example.
【図２】実施例４にかかる，コーティング層の厚みとク
ラックが発生するまでのアルカリ滴下回数との関係を示
す線図。FIG. 2 is a graph showing the relationship between the thickness of a coating layer and the number of alkali drops until a crack is generated according to Example 4.
Claims (2)
化ガラスの表面に，Ｚｒ，Ｌｉ，Ｎａ，Ｋ，Ｍｇ，Ｃ
ａ，Ｓｒ，Ｂａ，Ａｌ，Ｉｎ，Ｇｅ，Ｂｉ，Ｆｅ，Ｃ
ｕ，Ｙ，Ｔａの金属酸化物のコーティング層を有し，該
コーティング層の厚みは０．０１μｍ以上から１．０μ
ｍ以下であることを特徴とする結晶化ガラス成形品。1. Zr, Li, Na, K, Mg, C is formed on the surface of SiO 2 —Al 2 O 3 —Li 2 O type crystallized glass.
a, Sr, Ba, Al, In, Ge, Bi, Fe, C
It has a coating layer of u, Y, Ta metal oxide, and the thickness of the coating layer is from 0.01 μm to 1.0 μm.
A crystallized glass molded article characterized by being m or less.
化ガラスにより作製された結晶化ガラス成形品に，金属
アルコラートを塗布し，熱処理することにより，成形品
の表面に上記金属アルコラートから生成した金属酸化物
のコーティング層を形成することを特徴とする結晶化ガ
ラス成形品の製造方法。2. A metalized alcoholate is applied to a crystallized glass molded product made of SiO 2 —Al 2 O 3 —Li 2 O-based crystallized glass and heat-treated to form the metal alcoholate on the surface of the molded product. A method for producing a crystallized glass molded article, which comprises forming a coating layer of a metal oxide produced from the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4069482A JP2551294B2 (en) | 1992-02-19 | 1992-02-19 | Crystallized glass molded article and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4069482A JP2551294B2 (en) | 1992-02-19 | 1992-02-19 | Crystallized glass molded article and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05229851A true JPH05229851A (en) | 1993-09-07 |
| JP2551294B2 JP2551294B2 (en) | 1996-11-06 |
Family
ID=13403971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4069482A Expired - Fee Related JP2551294B2 (en) | 1992-02-19 | 1992-02-19 | Crystallized glass molded article and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2551294B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005058768A1 (en) | 2003-12-11 | 2005-06-30 | Eurokera Snc | Surface-modified glass-ceramics and their preparation |
| JP2008508173A (en) * | 2004-07-30 | 2008-03-21 | ユーロケラ ソシエテ オン ノーム コレクティフ | Plate made of glass material for fireplace inserts or stove-type equipment |
| JP2008192455A (en) * | 2007-02-05 | 2008-08-21 | Narumi China Corp | Glass top plate for heating cooker |
| JP2010001183A (en) * | 2008-06-20 | 2010-01-07 | Narumi China Corp | Method for producing modified glass |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5845138A (en) * | 1981-09-14 | 1983-03-16 | Nippon Electric Glass Co Ltd | Window of combustion apparatus |
| JPS5935032A (en) * | 1982-08-20 | 1984-02-25 | Nippon Electric Glass Co Ltd | Preparation of crystallized glass having low expansibility and high strength |
| JPH01131040A (en) * | 1987-11-13 | 1989-05-23 | Lion Corp | Crystallized glass having treated surface |
| JPH0354134A (en) * | 1989-07-20 | 1991-03-08 | Kubota Corp | Crystallized glass material having luster |
-
1992
- 1992-02-19 JP JP4069482A patent/JP2551294B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5845138A (en) * | 1981-09-14 | 1983-03-16 | Nippon Electric Glass Co Ltd | Window of combustion apparatus |
| JPS5935032A (en) * | 1982-08-20 | 1984-02-25 | Nippon Electric Glass Co Ltd | Preparation of crystallized glass having low expansibility and high strength |
| JPH01131040A (en) * | 1987-11-13 | 1989-05-23 | Lion Corp | Crystallized glass having treated surface |
| JPH0354134A (en) * | 1989-07-20 | 1991-03-08 | Kubota Corp | Crystallized glass material having luster |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005058768A1 (en) | 2003-12-11 | 2005-06-30 | Eurokera Snc | Surface-modified glass-ceramics and their preparation |
| JP2007513860A (en) * | 2003-12-11 | 2007-05-31 | ユーロケラ | Surface-modified glass ceramic and its preparation |
| KR101030606B1 (en) * | 2003-12-11 | 2011-04-20 | 유로케라 | Surface-modified glass-ceramics and their preparation |
| JP2012229156A (en) * | 2003-12-11 | 2012-11-22 | Eurokera Snc | Surface-modified glass-ceramics and their preparation |
| JP2008508173A (en) * | 2004-07-30 | 2008-03-21 | ユーロケラ ソシエテ オン ノーム コレクティフ | Plate made of glass material for fireplace inserts or stove-type equipment |
| JP2008192455A (en) * | 2007-02-05 | 2008-08-21 | Narumi China Corp | Glass top plate for heating cooker |
| JP2010001183A (en) * | 2008-06-20 | 2010-01-07 | Narumi China Corp | Method for producing modified glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2551294B2 (en) | 1996-11-06 |
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