JPH07223844A - Production of glass - Google Patents
Production of glassInfo
- Publication number
- JPH07223844A JPH07223844A JP1801294A JP1801294A JPH07223844A JP H07223844 A JPH07223844 A JP H07223844A JP 1801294 A JP1801294 A JP 1801294A JP 1801294 A JP1801294 A JP 1801294A JP H07223844 A JPH07223844 A JP H07223844A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- molten salt
- over over
- nitrate
- mixed molten
- 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
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]
【産業上の利用分野】本発明は、化学的耐候性が改善さ
れたガラスを製造する方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing glass having improved chemical weathering resistance.
【０００２】[0002]
【従来の技術】従来、安価なガラスとして入手できるガ
ラスとしては、窓ガラス等の用途に大量に製造されてい
るソーダライムシリカ組成のフロートガラスが知られて
いる。しかしながら、このガラスは、ガラス中にアルカ
リ成分としてナトリウムイオンを多量に含んでいるの
で、化学的耐久性が十分でなく、とりわけ高温高湿の雰
囲気下ではガラス中のアルカリイオンが表面に溶出して
生じるヤケと呼ばれる欠点が生じ易い。したがってガラ
ス板上に金属膜を被覆した磁気記録媒体や光記録媒体の
非磁性支持体として用いるには、さらに、耐候性を向上
させることが望まれていた。2. Description of the Related Art Conventionally, as a glass available as an inexpensive glass, a float glass having a soda lime silica composition which is produced in large quantities for use as a window glass is known. However, since this glass contains a large amount of sodium ions as an alkali component in the glass, its chemical durability is not sufficient, and in particular in a high temperature and high humidity atmosphere, alkali ions in the glass are eluted on the surface. A defect called "burning" is likely to occur. Therefore, in order to use it as a non-magnetic support of a magnetic recording medium or an optical recording medium in which a glass plate is coated with a metal film, further improvement in weather resistance has been desired.
【０００３】一方、ガラス中にナトリウム成分が多く含
まれないアルミノ珪酸塩系のガラス、無アルカリ系のガ
ラス、ジルコニアを多量に含むガラスを用いることは、
経済的に問題があった。On the other hand, the use of aluminosilicate type glass which does not contain much sodium in the glass, alkali-free type glass, and glass which contains a large amount of zirconia are
There was an economic problem.
【０００４】また、ガラスを硝酸亜鉛水溶液に漬けて硝
酸亜鉛の被膜をガラス表面に形成する簡便な方法は、十
分な化学的耐久性が得られないという問題点があった。Further, the simple method of forming a coating film of zinc nitrate on the glass surface by immersing the glass in an aqueous solution of zinc nitrate has a problem that sufficient chemical durability cannot be obtained.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記の問題
点を解決するためになされたものであって、アルカリ成
分としてナトリウムイオンを含むガラスを用いて化学的
耐久性が改善されたガラスを製造する方法を提供するこ
とを目的とする。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems and provides a glass having improved chemical durability by using a glass containing sodium ions as an alkali component. It is intended to provide a method for manufacturing.
【０００６】[0006]
【課題を解決するための手段】本発明の第１は、アルカ
リ成分としてナトリウムイオンを含有するガラスを、硝
酸亜鉛がモル濃度で０．０１〜０．５％含有する硝酸亜
鉛と硝酸カリウムからなる混合溶融塩に漬け、前記ガラ
ス表面に亜鉛イオンを含むアルカリ溶出防止層を形成し
たガラスを製造する方法である。硝酸亜鉛は単独で存在
する場合はその分解温度は３５０℃であるが、硝酸カリ
ウム中に上限値として０．５モル％までの量で含まれる
ときは、その分解温度以上であっても安定して存在する
ことを見い出した。とりわけ３３０℃〜４５０℃の範囲
でガラスを漬けることは、溶融塩の安定性確保と処理時
間の短縮化の両面から好ましい。The first aspect of the present invention is to mix a glass containing sodium ions as an alkaline component with zinc nitrate containing 0.01 to 0.5% by mole of zinc nitrate and potassium nitrate. It is a method of producing glass in which an alkali elution preventing layer containing zinc ions is formed on the surface of the glass by immersing it in a molten salt. When zinc nitrate is present alone, its decomposition temperature is 350 ° C., but when it is contained in potassium nitrate in an amount of up to 0.5 mol%, it is stable even at or above its decomposition temperature. I found out that it exists. In particular, it is preferable to immerse the glass in the range of 330 ° C. to 450 ° C. from the viewpoint of ensuring the stability of the molten salt and shortening the processing time.
【０００７】本発明の第２は、アルカリ成分としてナト
リウムイオンを含有するガラスを、硝酸リチウムがモル
濃度で２０〜５０％含有する硝酸亜鉛と硝酸カリウムか
らなる混合溶融塩に漬け、前記ガラス表面近傍に亜鉛イ
オンを含むアルカリ溶出防止層を形成したガラスを製造
する方法である。上記組成範囲の混合溶融塩を用いると
硝酸リチウムと硝酸亜鉛の系が有する共融点近傍の低い
温度で処理することができる。混合溶融塩の温度を混合
溶融塩の共融点以上３５０℃以下の比較的低温度域で行
うのが好ましい。In the second aspect of the present invention, a glass containing sodium ions as an alkaline component is dipped in a mixed molten salt of zinc nitrate and potassium nitrate containing 20 to 50% of lithium nitrate in a molar concentration, and the glass is placed near the surface of the glass. This is a method for producing a glass having an alkali elution preventive layer containing zinc ions. When the mixed molten salt having the above composition range is used, the treatment can be performed at a low temperature near the eutectic point of the system of lithium nitrate and zinc nitrate. It is preferable to perform the temperature of the mixed molten salt in a relatively low temperature range from the eutectic point of the mixed molten salt to 350 ° C.
【０００８】本発明の第３は、アルカリ成分としてナト
リウムイオンを含有するガラスを、硝酸カルシウムがモ
ル濃度で１０〜４０％含有する硝酸カルシウムと硝酸カ
リウムからなる混合溶融塩に漬け、前記ガラス表面近傍
にアルカリ溶出防止層を形成したガラスを製造する方法
である。そして混合溶融塩の温度は３５０℃〜４７０℃
とするのが好ましい。In a third aspect of the present invention, a glass containing sodium ions as an alkali component is dipped in a mixed molten salt of calcium nitrate and potassium nitrate containing 10 to 40% of calcium nitrate in a molar concentration, and the glass is brought into the vicinity of the glass surface. This is a method for producing a glass having an alkali elution preventive layer formed thereon. The temperature of the mixed molten salt is 350 ° C to 470 ° C.
Is preferred.
【０００９】本発明の第４は、アルカリ成分としてナト
リウムイオンを含有するガラスを、硝酸リチウムがモル
濃度で１〜３０％含有する硝酸リチウムと硝酸カリウム
からなる混合溶融塩に漬け、前記ガラス表面近傍にリチ
ウムイオンを含有するアルカリ溶出防止層を形成したガ
ラスを製造する方法である。混合溶融塩の温度は３３０
℃〜４５０℃とするのが好ましい。In a fourth aspect of the present invention, a glass containing sodium ions as an alkali component is dipped in a mixed molten salt of lithium nitrate and potassium nitrate containing lithium nitrate in a molar concentration of 1 to 30%, and the glass is brought into the vicinity of the glass surface. It is a method for producing glass on which an alkali elution preventing layer containing lithium ions is formed. The temperature of the mixed molten salt is 330
C. to 450.degree. C. is preferable.
【００１０】[0010]
【作用】本発明の第１においては、溶融した硝酸カリウ
ムと硝酸亜鉛との混合塩中にアルカリ成分としてナトリ
ウムイオンを含むガラスを漬けると、ガラス中のナトリ
ウムイオンと溶融塩中の亜鉛イオンがイオン交換により
置換し、表面近傍に亜鉛を含む層が形成され、この層に
より高耐湿性が付与される。In the first aspect of the present invention, when a glass containing sodium ions as an alkali component is immersed in a mixed salt of molten potassium nitrate and zinc nitrate, sodium ions in the glass and zinc ions in the molten salt are ion-exchanged. To form a layer containing zinc in the vicinity of the surface, and this layer imparts high moisture resistance.
【００１１】本発明の第２においては、混合塩の共融点
近傍の低い温度で、表面近傍に亜鉛を含む層を形成する
ことができ、この層により高耐湿性が付与される。In the second aspect of the present invention, a layer containing zinc can be formed near the surface at a low temperature near the eutectic point of the mixed salt, and this layer imparts high humidity resistance.
【００１２】本発明の第３においては、ガラス表面近傍
にアルカリがガラス内部よりも減少した層が形成され、
この層により高耐湿性が付与される。In the third aspect of the present invention, a layer in which alkali is reduced in the vicinity of the glass surface is formed in the vicinity of the glass surface,
High moisture resistance is provided by this layer.
【００１３】本発明の第４においては、ガラス中のナト
リウムイオンと溶融塩中のリチウムイオンがイオン交換
により置換し、表面近傍にリチウムを含む層が形成さ
れ、この層により高耐湿性が付与される。In a fourth aspect of the present invention, sodium ions in the glass and lithium ions in the molten salt are replaced by ion exchange to form a layer containing lithium near the surface, and this layer imparts high humidity resistance. It
【００１４】[0014]
【実施例】以下に実施例により本発明を説明する。 実施例１ 表１に示す３種類の調合割合の硝酸亜鉛６水和物Ｚｎ
（ＮＯ3）2・６Ｈ2Ｏと硝酸カリウムＫＮＯ3をステンレ
ス容器（ＳＵＳ３１４）に入れ、３６０℃に加熱して溶
融塩とした。結晶水の蒸発による泡の発生が止まった
ら、塩の使用が可能である。縦５ｃｍ横５ｃｍ厚み２ｍ
ｍのソーダライムシリカ組成のフロートガラス（アルカ
リ成分として約Ｎ2Ｏ１３重量％、約Ｋ2Ｏ０．９重量％
含む）を表１の３種類の溶融塩に１時間漬けてその後徐
冷した。表１の３種の塩で処理したガラスと比較のため
に処理しなかったガラス（未処理）を、温度８０℃、相
対湿度８０％の雰囲気下に５日間放置した。その後ガラ
ス表面を水で洗い流すことで、発生したヤケを純水中に
補集し、ガラス表面に析出したＮａ2Ｏ量を測定した。
その結果を表２に示す。硝酸亜鉛濃度が０．０１〜０．
５％でヤケの発生が抑制されていることが分かる。EXAMPLES The present invention will be described below with reference to examples. Example 1 Zinc nitrate hexahydrate Zn in three types of mixing ratios shown in Table 1
(NO 3) Put 2 · 6H 2 O and potassium nitrate KNO 3 stainless steel vessel (SUS314), and the molten salt is heated to 360 ° C.. Salt can be used once the generation of bubbles due to evaporation of water of crystallization has stopped. Vertical 5 cm Horizontal 5 cm Thickness 2 m
m of soda lime silica composition of float glass (about N 2 O13 wt% as alkaline component, about K 2 O0.9 wt%
Was included in the three types of molten salts shown in Table 1 for 1 hour and then gradually cooled. For comparison, the glasses treated with the three kinds of salts in Table 1 and untreated glass (untreated) were left in an atmosphere of a temperature of 80 ° C. and a relative humidity of 80% for 5 days. After that, the glass surface was washed off with water to collect the generated burns in pure water, and the amount of Na 2 O deposited on the glass surface was measured.
The results are shown in Table 2. The zinc nitrate concentration is 0.01 to 0.
It can be seen that the occurrence of burns is suppressed at 5%.
【００１５】 表１ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 硝酸亜鉛濃度（％） ＫＮＯ3（ｇ） Ｚｎ（ＮＯ3）2・６Ｈ2Ｏ（ｇ） ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー ０．００５ ５００ ０．０７４ ０．０１ ５００ ０．１５ ０．５ ５００ ７．４ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 溶融塩に漬ける温度と時間は、温度が４５０℃であれ
ば、３０分、３５０℃であれば４時間でほぼ析出量が４
分の１以下になる。Table 1 ----------- Zinc nitrate concentration (%) KNO 3 (g) Zn (NO 3) 2 · 6H 2 O (g) over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over 0.005 500 0.074 0.01 500 0.15 0.5 500 7.4 ------------------ -The temperature and time for soaking in molten salt is 30 minutes if the temperature is 450 ° C, and 4 hours if the temperature is 350 ° C, the precipitation amount is approximately 4
It is less than one-third.
【００１６】 表２ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 硝酸亜鉛濃度（％） Ｎａ2Ｏ析出量（μｇ／ｃｍ2） ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 未処理 ０．５５ ０．００５ ０．３４ ０．０１ ０．１３ ０．５ ０．０６ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 実施例２実施例１で用いたのと同じガラスを４００℃の
雰囲気中で１０分間予熱した後、４５０℃の溶融硝酸カ
リウム溶融塩中に１０時間漬け化学強化を施した。次
に、硝酸亜鉛をモルで０．５％含む硝酸亜鉛と硝酸カリ
ウムの混合塩の３８０℃に加熱されたものの中に５時間
漬けた。比較のために混合溶融塩に漬けない化学強化処
理のみをしたもの（表３で未処理として表示）と併せて
実施例１と同じ用にして耐湿性を評価した。このガラス
のアルカリ金属析出量を実施例１と同様に評価した。た
だし、この場合、析出する成分は、主に、化学強化にて
ガラス表面層に侵入しているカリウムであるので測定対
象はＫ2Ｏとした。表３から、本発明により耐湿性が向
上していることが分かる。Table 2 --------------- Zinc nitrate concentration (%) Na 2 O precipitation amount (Μg / cm 2 ) ------------------ Untreated 0.55 0.005 0. 34 0.01 0.13 0.5 0.06 ------------------ Example 2 The same glass as used in Example 1 was preheated in an atmosphere of 400 ° C. for 10 minutes, and then immersed in a molten potassium nitrate molten salt at 450 ° C. for 10 hours for chemical strengthening. Next, it was immersed in a mixed salt of zinc nitrate and potassium nitrate containing 0.5% by mole of zinc nitrate heated to 380 ° C. for 5 hours. For comparison, moisture resistance was evaluated in the same manner as in Example 1 together with a sample that was only chemically strengthened without being immersed in a mixed molten salt (shown as untreated in Table 3). The amount of alkali metal deposited on this glass was evaluated in the same manner as in Example 1. However, in this case, the component to be precipitated is mainly potassium that has penetrated into the glass surface layer due to chemical strengthening, so the measurement target was K 2 O. From Table 3, it can be seen that the present invention improves the moisture resistance.
【００１７】 表３ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 混合溶融塩 Ｋ2Ｏ析出量（μｇ／ｃｍ2） ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 未処理 ０．６９ 処理 ０．０８ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 実施例３ 表４に示す２種類の調合割合の硝酸亜鉛６水和物Ｚｎ
（ＮＯ3）2・６Ｈ2Ｏと硝酸カリウムＫＮＯ3をステンレ
ス容器（ＳＵＳ３１４）に入れ、３２０℃に加熱して溶
融塩とした。結晶水の蒸発による泡の発生が止まった
ら、塩の使用が可能である。実施例で用いたのと同じガ
ラスを表４の２種の塩で３２０℃で２時間漬けた。比較
のために混合溶融塩で処理しなかったガラス（未処理）
と併せて、温度８０℃、相対湿度８０％の雰囲気下に５
日間放置した。その後実施例１で行 表４ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 硝酸亜鉛濃度（％） ＫＮＯ3（ｇ） Ｚｎ（ＮＯ3）2・６Ｈ2Ｏ（ｇ） ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー ３０ ３００ ３７８ ５０ ２００ ５８９ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー ったのと同じ測定法によりガラスの耐久性を評価した。
結果を表５に示す。Table 3 ----------------------- Mixed molten salt K 2 O precipitation amount (μg / cm 2 ) ---------------------- Untreated 0.69 Treated 0.08 ------- Example 3 Zinc nitrate hexahydrate Zn with two blending ratios shown in Table 4 Example 3
(NO 3) Put 2 · 6H 2 O and potassium nitrate KNO 3 stainless steel vessel (SUS314), and the molten salt is heated to 320 ° C.. Salt can be used once the generation of bubbles due to evaporation of water of crystallization has stopped. The same glass used in the examples was soaked with the two salts in Table 4 at 320 ° C. for 2 hours. Glass not treated with mixed molten salt for comparison (untreated)
In addition, 5 in an atmosphere with a temperature of 80 ° C and a relative humidity of 80%
Left for days. After that, in Example 1, the table 4 --- --- --- --- --- ------- Zinc nitrate concentration (%) KNO 3 (g) Zn (NO 3) 2 · 6H 2 O (g) over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over 30 300 378 50 50 200 589 ----------------------- The durability was evaluated.
The results are shown in Table 5.
【００１８】 表５ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 硝酸亜鉛濃度（％） Ｎａ2Ｏ析出量（μｇ／ｃｍ2） ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 未処理 ０．５５ ３０ ０．０９ ５０ ０．０６ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 実施例４ 硝酸カルシウム４水和物Ｃａ（ＮＯ3）2・４Ｈ2Ｏをス
テンレス容器（ＳＵＳ３１４）に入れ加熱して結晶水を
蒸発させ、２５０℃に５時間保持して脱水した。すべて
が固形状態になってから硝酸カリウムを加え３５０℃に
加熱して混合溶融塩とした。混合溶融塩は表６に示す５
種類を作成した。実施例１で用いたガラスと同じガラス
を表６の５種の塩で処理した。比較のために処理しなか
ったガラス（未処理）とともに、温度８０℃、相対湿度
８０％の雰囲気下に５日間放置した。その後ガラス表面
を水で洗い流すことで、発生したヤケを純水中に補集
し、 表６ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 硝酸カルシウム濃度（％）ＫＮＯ3（ｇ） Ｃａ（ＮＯ3）2・４Ｈ2Ｏ（ｇ） ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー １ ５００ １１．８ ５ ５００ ６１．５ １０ ５００ １２９．７ ２０ ４００ ２３３．５ ３０ ３４０ ３４０．３ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー ガラス表面に析出したＮａ2Ｏ量を測定した。その結果
を表７に示す。Table 5 --------------- Zinc nitrate concentration (%) Na 2 O precipitation amount (Μg / cm 2 ) ---------------- Untreated 0.55 30 0.09 50 0.06 ---------- Example 4 Calcium nitrate tetrahydrate Ca (NO 3 ) the 2 · 4H 2 O was heated placed in a stainless steel container (SUS314) evaporating the water of crystallization, and dehydrated by 5 hours to 250 ° C.. After everything became solid, potassium nitrate was added and heated to 350 ° C. to obtain a mixed molten salt. The mixed molten salt is shown in Table 6 as 5
Created a type. The same glasses used in Example 1 were treated with the five salts in Table 6. For comparison, the glass was left untreated (untreated) for 5 days in an atmosphere at a temperature of 80 ° C. and a relative humidity of 80%. After that, the glass surface is washed away with water to collect the generated burns in pure water, and Table 6 ------------------ chromatography over over over over over over over over calcium nitrate concentration (%) KNO 3 (g) Ca (NO 3) 2 · 4H 2 O (g) over over over over over over over over over over over over over over over over over ---------- 1 500 11.8 5 500 61.5 10 500 129.7 20 400 233.5 30 340 340.3 ----- ---------- The amount of Na 2 O deposited on the glass surface was measured. The results are shown in Table 7.
【００１９】 表７ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 硝酸カルシウム濃度（％） Ｎａ2Ｏ析出量（μｇ／ｃｍ2） ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 未処理 ０．５５ １ ０．３８ ５ ０．１５ １０ ０．０７ ２０ ０．０５ ３０ ０．０３ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 表７に示すように硝酸カルシウムが１０％以上含有する
ときにアルカリ溶出量は、未処理のものに比較して約８
分の１に低下した。Table 7 --------------- Calcium nitrate concentration (%) Na 2 O precipitation amount (Μg / cm 2 ) ------------------ Untreated 0.55 1 0.38 5 0.15 10 0.07 20 0.05 30 30 0.03 ----------------------- Table As shown in 7, when the amount of calcium nitrate contained is 10% or more, the amount of alkali elution is about 8 as compared with the untreated one.
It has decreased to one-half.
【００２０】実施例５ 実施例１で用いたのと同じガラスを４００℃の雰囲気中
で10分間予熱した後、４５０℃の溶融硝酸カリウムに１
０時間浸漬して化学強化した。次に、硝酸カルシウムを
１０モル％含む硝酸カルシウムと硝酸カリウムの４００
℃に加熱された混合溶融塩に５時間漬け、その後取り出
して塩から取り出して徐冷をした。一方、比較のための
未処理ガラスとして、硝酸カリウム溶融塩に漬け化学強
化をしたのみのガラスとともにし実施例２と同様にガラ
ス耐久性の評価を行った。結果を表８に示す。Example 5 The same glass as used in Example 1 was preheated in an atmosphere of 400 ° C. for 10 minutes, and then heated to 450 ° C. in molten potassium nitrate.
It was immersed for 0 hours to chemically strengthen it. Next, 400% of calcium nitrate and potassium nitrate containing 10 mol% of calcium nitrate.
It was soaked in the mixed molten salt heated to 0 ° C. for 5 hours, then taken out, taken out from the salt and gradually cooled. On the other hand, as an untreated glass for comparison, the glass durability was evaluated in the same manner as in Example 2 except that the glass was only soaked in a molten salt of potassium nitrate and chemically strengthened. The results are shown in Table 8.
【００２１】 表８ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 硝酸亜鉛濃度（％） Ｋ2Ｏ析出量（μｇ／ｃｍ2） ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 未処理 ０．６９ １０ ０．０５ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 本発明においては、溶融塩の温度は４７０℃以下が望ま
しい。処理の時間は、温度に依存して定められる。４７
０℃であれば４時間以下、４３０℃なら１２時間以下が
好ましい。また、処理時間は処理効果を得る上で４７０
℃であれば１０分以上、４３０℃であれば３０分以上が
望ましい。このように、温度を低くすることは時間を長
くすることで補えるが、その下限は３５０℃以上が好ま
しい。また、硝酸カルシウムの濃度は１％以上で本発明
の効果が現われるが、１０％〜４０％が好ましい。硝酸
カルシウム濃度が４０％より大きいと、塩の溶解混合時
に結晶水の蒸発が多く作業性が低下し、かつ融点が高く
なるので好ましくない。Table 8 ------------------ Zinc nitrate concentration (%) K 2 O precipitation Amount (μg / cm 2 ) ------------------ Untreated 0.69 10 0.0. 05 ------------- In the present invention, the temperature of the molten salt is 470 ° C or lower. desirable. The treatment time is determined depending on the temperature. 47
It is preferably 4 hours or less at 0 ° C and 12 hours or less at 430 ° C. Also, the processing time is 470 to obtain the processing effect.
It is desirable that the temperature is 10 minutes or longer at ℃, and the time is 30 minutes or longer at 430 ° C. Thus, lowering the temperature can be supplemented by lengthening the time, but the lower limit is preferably 350 ° C. or higher. Further, the effect of the present invention appears when the concentration of calcium nitrate is 1% or more, but 10% to 40% is preferable. A calcium nitrate concentration of more than 40% is not preferable because the amount of crystal water is largely evaporated when the salt is dissolved and mixed, the workability is lowered, and the melting point is increased.
【００２２】実施例６ 表９に示す４種類の調合割合の硝酸リチウムＬｉＮＯ3
と硝酸カリウムＫＮＯ3をステンレス容器（ＳＵＳ３１
４）に入れ、３５０℃に加熱して混合溶融塩を用意し
た。実施例１で用いたのと同じガラスを表９の４種類の
溶融塩に漬けてその後徐冷した。表９の塩で処理したガ
ラスと比較のために処理しなかったガラス（未処理）
を、温度８０℃、相対湿度８０％の雰囲気下に５日間放
置した。その後ガラス表面を水で洗い流すことで、発生
したヤケを純水中に補集し、ガラス表面に析出したＬｉ
2Ｏ量、Ｋ2ＯとＮａ2Ｏの合計量を測定した。その結果
を表１０に示す。同時にガラスの硬さを測定した。硝酸
リチウム濃度が１〜３０％でヤケの発生が抑制されてい
ることが分かる。さらに、１０〜３０％のときに、ガラ 表９ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 硝酸リチウム濃度（％） ＫＮＯ3（ｇ） ＬｉＮＯ3（ｇ） ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー １ ５００ １１．８ １０ ５００ １２９．７ ３０ ３４０ ３４０．３ ５０ ３４０ ３４０．３ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー ス表面の硬度を低下させずにアルカリ溶出量を低下させ
ることができることが分かる。 表１０ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 硝酸リチウム濃度 Ｌｉ2Ｏ Ｎａ2Ｏ＋Ｋ2Ｏ ビッカース硬度 （％） （μｇ／ｃｍ2） （μｇ／ｃｍ2） ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 未処理 ０ ０．７８ ２５０ １ ０．０２ ０．３８ ２３０ １０ ０．０２ ０．０４ ２１０ ３０ ０．０４ ０．０２ １９０ ４０ ０．０８ ０．０３ １２０ ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー 硝酸リチウムの濃度１０％の時、溶融塩温度が４４０℃
であれば１５分〜２時間の範囲がよく、３８０℃であれ
ば１時間〜５時間の範囲が好ましい。Example 6 Lithium nitrate LiNO 3 having four kinds of mixing ratios shown in Table 9
And potassium nitrate KNO 3 in a stainless steel container (SUS31
4) and heated to 350 ° C. to prepare a mixed molten salt. The same glass used in Example 1 was dipped in the four types of molten salts shown in Table 9 and then annealed. Glass treated with salt in Table 9 and untreated for comparison (untreated)
Was left under an atmosphere of a temperature of 80 ° C. and a relative humidity of 80% for 5 days. After that, the glass surface was washed off with water to collect the generated burns in pure water, and Li deposited on the glass surface
The amount of 2 O and the total amount of K 2 O and Na 2 O were measured. The results are shown in Table 10. At the same time, the hardness of the glass was measured. It can be seen that the occurrence of burns is suppressed when the lithium nitrate concentration is 1 to 30%. In addition, when the content is 10 to 30%, the amount of lithium table 9 ---------------------------- Lithium nitrate concentration (%) KNO 3 (g) LiNO 3 (g) over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over over 1 500 11.8 10 500 129.7 30 340 340 340.3 50 340 340.3 ----- ----- ----- ----- ----- ----- It is understood that the alkali elution amount can be reduced without reducing the hardness of the surface. Table 10 ------------------ Lithium nitrate concentration Li 2 O Na 2 O + K 2 O Vickers hardness (%) (Μg / cm 2 ) (μg / cm 2 ) ------------------------ Untreated 0 0.78 250 1 0.02 0.38 230 10 0.02 0.04 210 30 0.04 0.02 190 40 0.08 0.03 120 -------- ------------- When the concentration of lithium nitrate is 10%, the molten salt temperature is 440 ° C.
If so, the range of 15 minutes to 2 hours is preferable, and if 380 ° C., the range of 1 hour to 5 hours is preferable.
【００２３】[0023]
【発明の効果】本発明により、高温高湿雰囲気下におい
てもガラス表面から溶出するアルカリ量が抑制された高
化学的耐久性を有するガラスを得ることができる。According to the present invention, it is possible to obtain a glass having high chemical durability in which the amount of alkali eluted from the glass surface is suppressed even in a high temperature and high humidity atmosphere.
【図１】本発明で得られるガラスの一部断面図である。FIG. 1 is a partial cross-sectional view of glass obtained by the present invention.
１・・・ガラス、２・・・アルカリ溶出防止層 1 ... glass, 2 ... alkali elution prevention layer
Claims (9)
有するガラスを、硝酸亜鉛がモル濃度で０．０１〜０．
５％含有する硝酸亜鉛と硝酸カリウムからなる混合溶融
塩に漬け、前記ガラス表面近傍に亜鉛イオンを含むアル
カリ溶出防止層を形成したガラスの製造方法。1. A glass containing sodium ions as an alkaline component is used to prepare zinc nitrate having a molar concentration of 0.01 to 0.
A method for producing glass, which comprises soaking in a mixed molten salt of 5% zinc nitrate and potassium nitrate to form an alkali elution preventive layer containing zinc ions near the surface of the glass.
℃としたことを特徴とする請求項１に記載のガラスの製
造方法。2. The temperature of the mixed molten salt is 330 ° C. to 450 ° C.
The temperature is set to ° C. The method for producing glass according to claim 1, wherein the glass is manufactured.
有するガラスを、硝酸亜鉛がモル濃度で２０〜５０％含
有する硝酸亜鉛と硝酸カリウムからなる混合溶融塩に漬
け、前記ガラス表面近傍に亜鉛イオンを含むアルカリ溶
出防止層を形成したガラスの製造方法。3. A glass containing sodium ions as an alkaline component is dipped in a mixed molten salt consisting of zinc nitrate and potassium nitrate containing 20 to 50% of zinc nitrate in a molar concentration, and an alkali containing zinc ions in the vicinity of the glass surface. A method for producing glass having an elution preventive layer formed thereon.
点以上３５０℃以下としたことを特徴とする請求項３に
記載のガラスの製造方法。4. The method for producing glass according to claim 3, wherein the temperature of the mixed molten salt is set to not less than the eutectic point of the mixed molten salt and not more than 350 ° C.
有するガラスを、硝酸カルシウムがモル濃度で１０〜４
０％含有する硝酸カルシウムと硝酸カリウムからなる混
合溶融塩に漬け、前記ガラス表面近傍にガラス内部より
も少ないアルカリ成分を含むアルカリ溶出防止層を形成
したガラスの製造方法。5. A glass containing sodium ions as an alkaline component, calcium nitrate having a molar concentration of 10 to 4
A method for producing glass, which comprises immersing it in a mixed molten salt containing 0% of calcium nitrate and potassium nitrate to form an alkali elution preventive layer containing an alkali component less in the glass near the glass surface.
℃としたことを特徴とする請求項５に記載のガラスの製
造方法。6. The temperature of the mixed molten salt is 350 ° C. to 470.
6. The method for producing glass according to claim 5, wherein the temperature is set to be ° C.
有するガラスを、硝酸リチウムがモル濃度で１〜３０％
含有する硝酸リチウムと硝酸カリウムからなる混合溶融
塩に漬け、前記ガラス表面近傍にリチウムイオンを含有
するアルカリ溶出防止層を形成したガラスの製造方法。7. A glass containing sodium ions as an alkaline component is used, and lithium nitrate has a molar concentration of 1 to 30%.
A method for producing glass, which comprises immersing it in a mixed molten salt containing lithium nitrate and potassium nitrate, and forming an alkali elution preventing layer containing lithium ions in the vicinity of the glass surface.
℃としたことを特徴とする請求項７に記載のガラスの製
造方法。8. The temperature of the mixed molten salt is 330 ° C. to 450 ° C.
8. The glass manufacturing method according to claim 7, wherein the temperature is set to be ° C.
リウムのみからなる溶融塩に漬けてその溶融塩中のカリ
ウムイオンとガラス中のナトリウムイオンとをイオン交
換する請求項１乃至８のいずれかの項に記載の化学強化
ガラスの製造方法。9. The method according to claim 1, wherein prior to the dipping in the mixed molten salt, the potassium ion in the molten salt and the sodium ion in the glass are ion-exchanged by dipping in the molten salt containing only potassium nitrate. A method for producing the chemically strengthened glass according to item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01801294A JP3166470B2 (en) | 1994-02-15 | 1994-02-15 | Glass manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01801294A JP3166470B2 (en) | 1994-02-15 | 1994-02-15 | Glass manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07223844A true JPH07223844A (en) | 1995-08-22 |
| JP3166470B2 JP3166470B2 (en) | 2001-05-14 |
Family
ID=11959766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01801294A Expired - Lifetime JP3166470B2 (en) | 1994-02-15 | 1994-02-15 | Glass manufacturing method |
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| Country | Link |
|---|---|
| JP (1) | JP3166470B2 (en) |
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| JP2011529438A (en) * | 2008-07-29 | 2011-12-08 | コーニング インコーポレイテッド | Two-stage ion exchange for chemical strengthening of glass |
| US8499583B2 (en) | 2005-03-31 | 2013-08-06 | Hoya Corporation | Method of manufacturing magnetic-disk glass substrate and method of manufacturing magnetic disk |
| US8613206B2 (en) * | 2006-03-24 | 2013-12-24 | Hoya Corporation | Method for manufacturing glass substrate for magnetic disk and method for manufacturing magnetic disk |
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1994
- 1994-02-15 JP JP01801294A patent/JP3166470B2/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8499583B2 (en) | 2005-03-31 | 2013-08-06 | Hoya Corporation | Method of manufacturing magnetic-disk glass substrate and method of manufacturing magnetic disk |
| JP2007284338A (en) * | 2006-03-24 | 2007-11-01 | Hoya Corp | Method for producing magnetic disk glass substrate and method for producing magnetic disk |
| US8613206B2 (en) * | 2006-03-24 | 2013-12-24 | Hoya Corporation | Method for manufacturing glass substrate for magnetic disk and method for manufacturing magnetic disk |
| KR100659558B1 (en) * | 2006-09-04 | 2006-12-20 | (주)한국나노글라스 | Tempered glass manufacturing apparatus of display window |
| JP2011529438A (en) * | 2008-07-29 | 2011-12-08 | コーニング インコーポレイテッド | Two-stage ion exchange for chemical strengthening of glass |
| JP2010275130A (en) * | 2009-05-27 | 2010-12-09 | Hoya Corp | Method for producing lithium ion conductive glass |
| JP2011134367A (en) * | 2009-12-22 | 2011-07-07 | Asahi Glass Co Ltd | Method for manufacturing glass substrate for data storage medium and glass substrate |
| WO2015049888A1 (en) * | 2012-10-05 | 2015-04-09 | Asahi Glass Company, Limited | Strengthened glass and methods for making the same by using differential chemistry |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3166470B2 (en) | 2001-05-14 |
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