JP2551294B2 - Crystallized glass molded article and method for producing the same - Google Patents
Crystallized glass molded article and method for producing the sameInfo
- Publication number
- JP2551294B2 JP2551294B2 JP4069482A JP6948292A JP2551294B2 JP 2551294 B2 JP2551294 B2 JP 2551294B2 JP 4069482 A JP4069482 A JP 4069482A JP 6948292 A JP6948292 A JP 6948292A JP 2551294 B2 JP2551294 B2 JP 2551294B2
- Authority
- JP
- Japan
- Prior art keywords
- crystallized glass
- glass molded
- coating layer
- molded article
- 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.)
- Expired - Fee Related
Links
- 239000011521 glass Substances 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000011247 coating layer Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 238000003384 imaging method Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 description 14
- 239000003513 alkali Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 235000011194 food seasoning agent Nutrition 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000004278 EU approved seasoning Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000013923 monosodium glutamate Nutrition 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229940073490 sodium glutamate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- -1 sulfurous acid gas Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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)
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 material 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
O 3 -Li 2 O (silica - alumina - lithia) based crystallized glass molded article produced by the crystallized glass has a thermal expansion coefficient of a is 0~10 × 10 -7 ℃ -1, not deformed even at a high temperature ， It doesn't crack even if it is put into the water after being heated even if it is 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
The 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 component of a stove, a fireproof window, or a laser reflector. By the way, the kerosene used in the kerosene stove contains a very small amount of sulfur, and when used, a very small amount of sulfurous acid gas is generated. Also,
The top plates of electric or gas cookers come 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 or the like and react with them to generate cracks or 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 product 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−Ａｌ２Ｏ３−
Ｌｉ２Ｏ系の結晶化ガラス成形品の表面に，Ｚｒ又はＹ
の少なくとも一方の金属酸化物のコーティング層を有し
てなり，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。The present invention is directed to SiO 2 —Al 2 O 3 —
In li 2 O system crystallized surface of a glass molded article, Zr or Y
Having at least one metal oxide coating layer of
In the crystallized glass molded article, the coating layer has a thickness of 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），Ｙ（イットリウ
ム）を用いる。In the present invention, Zr (zirconium) and Y (yttrium) are used as the metal component of the metal oxide.
【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 article 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−Ａｌ２Ｏ３−Ｌｉ２Ｏ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，Ｚｒ又は
Ｙの少なくとも一方の金属アルコラートを塗布し，熱処
理することにより，上記結晶化ガラス成形品の表面に上
記金属アルコラートから生成したＺｒ又はＹの少なくと
も一方の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 crystallized glass molded product made of SiO 2 —Al 2 O 3 —Li 2 O-based crystallized glass is added with Zr or
At least one metal alcoholate of Y is applied and heat-treated to reduce the amount of Zr or Y produced from the metal alcoholate on the surface of the crystallized glass molded article.
There is a method for producing a crystallized glass molded article, which is characterized by forming a coating layer of one metal oxide.
【００１０】上記金属アルコラートとしては，前記に示
したＺｒ，Ｙの金属を用いたものがある。この金属アル
コラートは，上記金属の少なくとも一種を用いる。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 Zr and Y metals shown above. This metal alcoholate uses at least one of the above metals. A metal alcoholate is a compound in which one or more alkoxyl groups are bonded to the above metal. An 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。[0011] The metal alcoholate, have preferably those that are liquid. When using a liquid-like metal alcoholate, the crystallized glass molded article, it can be uniformly easily applied.
【００１２】金属アルコラートを結晶化ガラス成形品に
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。The method for applying the metal alcoholate to the crystallized glass molded article includes dipping, spin coating, and
There are methods such as spraying and brush painting. 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 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 may 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
品の表面に，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 [Action and Effect] The present invention, on the surface of the crystallized glass molded article has a coating layer of metal oxide. The metal oxide has excellent chemical weather resistance against acids, alkalis and the like. Therefore, the crystallized glass molded article coated with the 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の製造
方法においては，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。 The production of the crystallized glass molded article of the present invention
In the method, a metal alcoholate is applied and heat-treated to form a coating layer of a metal oxide produced from the metal alcoholate on the surface of the crystallized glass molded product . The coating layer is heat treated together with the crystallized glass molded product. As a result, the 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 having excellent chemical weather resistance to acids, alkalis and the like and excellent adhesion strength, and a method for producing the same.
【００１６】[0016]
【実施例】実施例１〜３ 本例の結晶化ガラス成形品は，ＳｉＯ２−Ａｌ２Ｏ３−
Ｌｉ２Ｏ系の結晶化ガラス成形品の表面に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−Ａｌ２Ｏ３−
Ｌｉ２Ｏ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 Examples 1 to 3 The crystallized glass molded articles of this example are SiO 2 -Al 2 O 3-.
And a coating layer of metal oxide Zr in li 2 O system crystallized surface of the glass molded article. In the above method for producing a crystallized glass molded article, SiO 2 —Al 2 O 3 —
A metal alcoholate is applied to a crystallized glass molded product made of Li 2 O-based 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
ス成形品の表面に塗布される。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 surface of the crystallized glass molded product 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結晶
化ガラス成形品につき，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
結晶化ガラス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，上記結晶化ガラス成形品は，平板を，凸型形状
に湾曲させたものである。結晶化ガラス成形品の厚さは
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. Crystals thus obtained
Of the molded glass products, those having a heat treatment temperature of 200 ° C. are referred to as Examples 1, 500 ° C. and Examples 2 and 800 ° C., respectively. Obtained by the above method
A coating layer of Zr oxide produced from Zr alcoholate was formed on the entire surface of the crystallized glass molded product. The crystallized glass molded product is a flat plate curved into a convex shape. The thickness of the crystallized glass 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，結晶化ガラス成形品の表面に，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Ｚｒ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 crystallized glass molded article coated with the coating layer has excellent chemical weather resistance against acids, alkalis and the like. The coating layer is formed by applying Zr alcoholate to a crystallized glass molded product and heat-treating it. Then, Zr alcoholate is added on the surface of the crystallized glass molded product to the above Zr.
A coating layer of Zr oxide formed from alcoholate is formed. As a result, crystallization of the Zr oxide forming the coating layer 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, 1cc of alkali is applied to the upper surface of the above-mentioned molded product.
Dropwise at intervals of 5 minutes each. As the alkali, a 50% aqueous solution of sodium organic acid (seasoning sodium glutamate) 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, Comparative Example 1 was a molded product made only of crystallized glass, and Comparative Example 2 was a molded product having a surface of crystallized glass coated with silica. 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 composed 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，コーティング層がＺｒアルコラー
トから生成したＺｒ酸化物である場合（実施例１〜３）
は，コーティング層が無い場合或いはシリカよりなる場
合（比較例１，２）よりも，化学的耐候性及び付着強度
力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 at 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. Thus, when the coating layer is a Zr oxide formed from Zr alcoholate (Example 1-3)
It is made of a case where there is no coating layer or a silica place
Than if (Comparative Examples 1 and 2), it was confirmed chemical weathering and adhesion strength strength high. Also, the higher the temperature during heat treatment, the better the chemical resistance and adhesive strength of the molded product.
【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. And about these, the same measurement as 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 alkali drops until cracking.
【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 better the chemical resistance and adhesive strength of the molded product.
【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成形品の表面に形成に作製する
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, Zr alcoholate, Zr nitrate, Zr oxychloride, and Zr acetate were used to form coating layers of crystallized glass, and the appearance was examined. The method of forming the coating layer on the surface of the crystallized glass molded product is the same as in Example 1. In this case, only when Zr alcoholate was used, a thin coating layer was formed and was well adhered 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 diagram showing a relationship between a 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 before cracking according to Example 4.
Claims (2)
晶化ガラス成形品の表面に，Ｚｒ又はＹの少なくとも一
方の金属酸化物のコーティング層を有してなり，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。1. A SiO 2 -Al 2 O 3 -Li 2 O-based imaging <br/> crystallized glass molded article surface, at least one Zr or Y
Will have a coating layer of a square metal oxide, crystallized glass molded article thickness of the coating layer, characterized in that at 1.0μm or less from the higher 0.01 [mu] m.
化ガラスにより作製された結晶化ガラス成形品に，Ｚｒ
又はＹの少なくとも一方の金属アルコラートを塗布し，
熱処理することにより，上記結晶化ガラス成形品の表面
に上記金属アルコラートから生成したＺｒ又はＹの少な
くとも一方の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 crystallized glass molded article made of SiO 2 —Al 2 O 3 —Li 2 O-based crystallized glass, comprising Zr.
Or , applying at least one metal alcoholate of Y ,
By heat treatment, a small amount of Zr or Y generated from the metal alcoholate is formed on the surface of the crystallized glass molded product.
A method for producing a crystallized glass molded article, which comprises forming a coating layer of at least one metal oxide.
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 JPH05229851A (en) | 1993-09-07 |
| JP2551294B2 true 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) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2863607B1 (en) * | 2003-12-11 | 2006-09-29 | Snc Eurokera | VITROCERAMICS WITH MODIFIED SURFACE AND THEIR PREPARATION |
| FR2873791B1 (en) * | 2004-07-30 | 2006-11-03 | Eurokera | GLASS MATERIAL PLATE FOR DEVICE TYPE INSERT OF CHIMNEY OR STOVE. |
| JP2008192455A (en) * | 2007-02-05 | 2008-08-21 | Narumi China Corp | Glass top plate for heating cooker |
| JP5328012B2 (en) * | 2008-06-20 | 2013-10-30 | 鳴海製陶株式会社 | Method for producing modified glass |
Family Cites Families (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 |
| JP2621249B2 (en) * | 1987-11-13 | 1997-06-18 | ライオン株式会社 | Dental material and method for improving adhesion of dental material to adhesive resin cement |
| JPH0354134A (en) * | 1989-07-20 | 1991-03-08 | Kubota Corp | Crystallized glass material with luster |
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1992
- 1992-02-19 JP JP4069482A patent/JP2551294B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
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| JPH05229851A (en) | 1993-09-07 |
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