JP4410354B2 - Li-absorbing glass for chemical strengthening, and method for producing chemically strengthened glass using Li-absorbing glass for chemical strengthening - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、化学強化の際に母材ガラスからイオン交換によって溶融塩中に溶出するＬｉを吸収する機能を有するＬｉ吸収ガラス等に関し、特に、化学強化に適した化学強化用Ｌｉ吸収ガラス、及びこの化学強化用Ｌｉ吸収ガラスを用いた化学強化ガラスの製造方法等に関する。
【０００２】
【従来の技術】
ガラス基板等の強度を向上させる目的で、ガラス基板等の表面を化学強化処理することが知られている。詳しくは、耐衝撃性（落下に対する強度を含む）や耐振動性などの機械的強度を向上させ衝撃や振動によってガラス基板等が破損するのを防止する目的で、ガラス基板の表面に低温イオン交換法による化学強化処理を施すことが知られている。
【０００３】
化学強化処理は、例えば、Ｌｉイオンを含んだ母材ガラスをＮａイオン及び／又はＫイオンを含んだ溶融塩中に浸漬することにより、母材ガラス中のＬｉイオンを、Ｌｉイオンよりもイオン半径の大きいＮａ、Ｋイオンでイオン交換により置換して、ガラス表面層に強い圧縮応力を発生させて強度を増大させる処理である。
【０００４】
【発明が解決しようとする課題】
しかし、化学強化のイオン交換反応により、母材ガラス中のＬｉイオンが溶融塩中に溶出し、処理回数が増すごとに溶融塩中のＬｉ濃度は増加するため、化学強化のイオン交換がおこりづらくなり、所定の機械強度等が得られないという問題がある。
この問題を解決するため、特公平６−７１５２１号公報では、溶融塩中に溶出したＬｉイオンをγアルミナからなる吸着剤を用いて除去する技術が提案されているが、Ｌｉイオンを吸収できる量が限られていて、ある一定期間の後Ｌｉ濃度は上昇を始める問題がある。
また、特開昭６４−２４０５３号公報には、イオン交換による屈折率分布ガラスを製造する際に、溶融塩中に溶出したイオンを、イオン吸収ガラスで吸収する技術が開示されている。しかしながら、かかる技術は、不適切な成分を含むことによる弊害があり、また、イオン交換による屈折率分布ガラスを製造することが目的であるため、化学強化を目的としたイオン交換においてそのまま適用することはできない。
【０００５】
本発明は上述した背景の下になされたものであり、化学強化に適した化学強化用Ｌｉイオン吸収ガラス等の提供を第一の目的とする。
また、化学強化用Ｌｉイオン吸収ガラスを用いた化学強化ガラスの製造方法の提供を第二の目的とする。
さらに、イオン交換速度等の性能を向上させたＬｉイオン吸収ガラス等の提供を第三の目的とする。
【０００６】
【課題を解決するための手段】
上記目的を達成するために本発明は、以下の構成としてある。
【０００７】
（構成１）Ｌｉ2Ｏを含んだガラスを、Ｎａ2Ｏ及び／又はＫ2Ｏを含んだ溶融塩で化学強化する際、溶融塩中に溶出したＬｉイオンを吸収する目的で溶融塩中に浸漬される化学強化用Ｌｉ吸収ガラスであって、Ｎａ2Ｏを２０ｗｔ％以上含有する化学強化用Ｌｉ吸収ガラス。
【０００８】
（構成２）Ｌｉ2Ｏを含んだガラスを、Ｎａ2Ｏ及び／又はＫ2Ｏを含んだ溶融塩で化学強化する際、溶融塩中に溶出したＬｉイオンを吸収する目的で溶融塩中に浸漬される化学強化用Ｌｉ吸収ガラスであって、Ｎａ2Ｏを２０〜４０ｗｔ％、ＳｉＯ2を３０〜６０ｗｔ％主として含有する化学強化用Ｌｉ吸収ガラス。
【０００９】
（構成３）Ｌｉ2Ｏを含んだガラスを、Ｎａ2Ｏ及び／又はＫ2Ｏを含んだ溶融塩で化学強化する際、溶融塩中に溶出したＬｉイオンを吸収する目的で溶融塩中に浸漬される化学強化用Ｌｉ吸収ガラスであって、Ｎａ2Ｏを２３〜４０ｗｔ％、ＳｉＯ2を３０〜６０ｗｔ％主として含有する化学強化用Ｌｉ吸収ガラス。
【００１０】
（構成４）Ｌｉ2Ｏを含んだガラスを、Ｎａ2Ｏ及び／又はＫ2Ｏを含んだ溶融塩で化学強化する際、溶融塩中に溶出したＬｉイオンを吸収する目的で溶融塩中に浸漬される化学強化用Ｌｉ吸収ガラスであって、Ｎａ2Ｏを２５〜４０ｗｔ％、ＳｉＯ2を３０〜６０ｗｔ％、主として含有する化学強化用Ｌｉ吸収ガラス。
【００１１】
（構成５）Ｋ2Ｏを０〜１５ｗｔ％、Ｃｓ2Ｏを０〜１５ｗｔ％、ＭｇＯを０〜１５ｗｔ％、ＣａＯを０〜１５ｗｔ％、ＳｒＯを０〜１５ｗｔ％、ＺｎＯを０〜１５ｗｔ％、ＴｉＯ2を０〜１５ｗｔ％、Ｎｂ2Ｏ5を０〜１５ｗｔ％、Ｔａ2Ｏ5を０〜１５ｗｔ％、Ｌａ2Ｏ3を０〜１５ｗｔ％、Ｙ2Ｏ3を０〜１５ｗｔ％、Ｙｂ2Ｏ3を０〜１５ｗｔ％、Ｇｄ2Ｏ3を０〜１５ｗｔ％、Ａｌ2Ｏ3を０〜１５ｗｔ％、ＷＯ3を０〜１５ｗｔ％、Ｓｂ2Ｏ3を０〜１５ｗｔ％、Ａｓ2Ｏ3を０〜１５ｗｔ％、ＺｒＯ2を０〜１５ｗｔ％、ＴｅＯ2を０〜１５ｗｔ％、Ｂｉ2Ｏ3を０〜１５ｗｔ、Ｂ2Ｏ3を０〜４ｗｔ％、ＢａＯを０〜４ｗｔ％、ＰｂＯを０〜３ｗｔ％、含有することを特徴とする構成１乃至４のいずれかに記載の化学強化用Ｌｉ吸収ガラス。
【００１２】
（構成６）Ｂ2Ｏ3、ＰｂＯ、ＢａＯ及びＬｉ2Ｏのうちの一以上の成分を実質的に含まないことを特徴とする構成１乃至５のいずれかに記載の化学強化用Ｌｉ吸収ガラス。
【００１３】
（構成７）母材ガラスとして化学強化の強度が十分得られる量のＬｉイオンを含むガラスを用い、構成１乃至６のいずれかに記載の化学強化用Ｌｉ吸収ガラスを用いて、これらをＮａ2Ｏ及び／又はＫ2Ｏを含んだ溶融塩に浸漬して母材ガラスの化学強化を行うことを特徴とする化学強化ガラスの製造方法。
【００１４】
（構成８）Ｌｉ2Ｏを含んだガラスをイオン交換する際、溶融塩中に溶出したＬｉイオンを吸収する目的で溶融塩中に浸漬されるＬｉ吸収ガラスにおいて、Ｎａ2Ｏを２０ｗｔ％以上含有し、ＳｉＯ2、Ｐ2Ｏ5及びＧｅＯ2のうちのいずれかを３０〜６０ｗｔ％含有し、かつ、Ｋ2Ｏを０〜１５ｗｔ％、Ｃｓ2Ｏを０〜１５ｗｔ％、ＭｇＯを０〜１５ｗｔ％、ＣａＯを０〜１５ｗｔ％、ＳｒＯを０〜１５ｗｔ％、ＺｎＯを０〜１５ｗｔ％、ＴｉＯ2を０〜１５ｗｔ％、Ｎｂ2Ｏ5を０〜１５ｗｔ％、Ｔａ2Ｏ5を０〜１５ｗｔ％、Ｌａ2Ｏ3を０〜１５ｗｔ％、Ｙ2Ｏ3を０〜１５ｗｔ％、Ｙｂ2Ｏ3を０〜１５ｗｔ％、Ｇｄ2Ｏ3を０〜１５ｗｔ％、Ａｌ2Ｏ3を０〜１５ｗｔ％、ＷＯ3を０〜１５ｗｔ％、Ｓｂ2Ｏ3を０〜１５ｗｔ％、Ａｓ2Ｏ3を０〜１５ｗｔ％、ＺｒＯ2を０〜１５ｗｔ％、ＴｅＯ2を０〜１５ｗｔ％、Ｂｉ2Ｏ3を０〜１５ｗｔ、Ｂ2Ｏ3を０〜４ｗｔ％、ＢａＯを０〜４ｗｔ％、ＰｂＯを０〜３ｗｔ％、含有することを特徴とするＬｉ吸収ガラス。
【００１５】
（構成９）Ｂ2Ｏ3、ＰｂＯ、ＢａＯ及びＬｉ2Ｏのうちの一以上の成分を実質的に含まないことを特徴とする構成８に記載のＬｉ吸収ガラス。
【００１６】
【作用】
本発明の化学強化用Ｌｉイオン吸収ガラスは、Ｎａ2Ｏを多く含んでおり、化学強化条件下で、Ｌｉイオン吸収ガラス中のＮａ2Ｏ含有量が多くなるほど、Ｌｉイオンの吸収スピードが増し、Ｌｉイオンの吸収量が増えるので、溶融塩中のＬｉイオン濃度を常に低く保つことができ、これにより所定の機械的強度及び圧縮応力層の深さを有する化学強化ガラスが得られる。また、本発明の化学強化用Ｌｉイオン吸収ガラスは、不適切な成分を含まない、あるいは不適切な成分が少ないので、イオン交換速度や化学的耐久性等の性能を低下させることがない。
【００１７】
また、本発明の化学強化ガラスの製造方法によれば、母材ガラスとして化学強化の強度が十分得られる量のＬｉイオンを含むガラスを用い、かつ、上記本発明の化学強化用Ｌｉイオン吸収ガラスを用いているので、所定の機械的強度及び圧縮応力層の深さを有する化学強化ガラスが得られる。
また、溶融塩中のＬｉイオン濃度を上げない効果があり、Ｌｉイオン濃度が高くなった溶融塩を交換する必要がないので製造効率がよい。
【００１８】
さらに、本発明のＬｉイオン吸収ガラスによれば、不適切な成分を含まない、あるいは不適切な成分が少ないので、イオン交換速度や化学的耐久性等の性能を向上させたＬｉイオン吸収ガラスが得られる。
【００１９】
以下、本発明を詳細に説明する。
本発明の化学強化用Ｌｉイオン吸収ガラス及び本発明のＬｉイオン吸収ガラスにおける含有量の限定理由は以下のとおりである。
【００２０】
Ｎａ2Ｏはイオン交換、特に化学強化時のイオン交換の際、溶融塩中に溶出するＬｉイオンと再度イオン交換させる成分として必須成分である。Ｎａ2ＯはＬｉ吸収ガラス中の含有量が多くなるほど溶融塩中のＬｉを吸収するスピード、Ｌｉを吸収する絶対量が増加することがわかった。特に化学強化時のイオン交換の際、溶融塩中のＬｉを吸収するスピードが重要となる。これは、溶融塩中のＬｉを吸収するスピードが大きいと、溶融塩中のＬｉイオン濃度を常に低く保つことができるからである。これらのことから、Ｎａ2Ｏは２０ｗｔ％以上含有させることが好ましい。またＮａ2Ｏが４０ｗｔ％を越えるとガラス化しなくなるか、ガラスの化学的耐久性が低下しＬｉ吸収ガラス自体が溶融塩に溶けてしまう可能性がある。よって上限は４０ｗｔ％以下とすることが好ましい。より好ましいＮａ2Ｏの含有量は２３〜４０ｗｔ％で、さらに好ましくは２５〜４０ｗｔ％である。
【００２１】
ＳｉＯ2はガラス形成成分として、またＮａ2Ｏを２０〜４０ｗｔ％と多く含有してもガラス化し、かつ溶融塩に対する化学的耐久性を強くする成分として含有することが好ましい。ＳｉＯ2の好ましい含有量は３０〜６０ｗｔ％の範囲である。
ガラス形成成分としてはＳｉＯ2の代わりにＰ2Ｏ5、ＧｅＯ2を用いても構わない。Ｐ2Ｏ5、ＧｅＯ2の好ましい含有量はそれぞれ３０〜６０ｗｔ％の範囲である。
【００２２】
Ｂ2Ｏ3はガラス形成成分として添加すると溶融塩に対する化学的耐久性が悪くなり、ガラス成分が溶融塩中に溶出するため、Ｂ2Ｏ3：４ｗｔ％以下とすることが好ましく、Ｂ2Ｏ3：１ｗｔ％以下とすることがさらに好ましく、さらには、Ｂ2Ｏ3は実質的に含有しないことが最も好ましい。
【００２３】
Ｌｉ吸収ガラスにＬｉが含まれるとＬｉの吸収を阻害することから、Ｌｉ吸収ガラスはＬｉイオンを含有しないことが好ましい。特に、化学強化用Ｌｉイオン吸収ガラスにおいては、短時間で化学強化し、所定の強度及び圧縮応力層（歪み層）の深さを得るため、Ｌｉイオンを含有しないことが好ましい。
【００２４】
他の任意成分としては、Ｋ2Ｏ、Ｃｓ2Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、ＰｂＯ、ＺｎＯ、ＴｉＯ2、Ｎｂ2Ｏ5、Ｔａ2Ｏ5、Ｌａ2Ｏ3、Ｙ2Ｏ3、Ｙｂ2Ｏ3、Ｇｄ2Ｏ3、Ａｌ2Ｏ3、ＷＯ3、Ｓｂ2Ｏ3、Ａｓ2Ｏ3、ＺｒＯ2、ＴｅＯ2、Ｂｉ2Ｏ3がそれぞれ０〜１５ｗｔ％の範囲で添加可能である。
ただし、ＢａＯ、ＰｂＯはＬｉ2Ｏのイオン変換速度を低下させるため、ＢａＯ：４ｗｔ％以下、ＰｂＯ：３ｗｔ％以下とすることが好ましく、ＢａＯ：１ｗｔ％以下、ＰｂＯ：１ｗｔ％以下とすることがさらに好ましく、さらには、ＢａＯ、ＰｂＯは実質的に含有しないことが最も好ましい。
【００２５】
なお、本発明のＬｉ吸収ガラスの組成は、母材ガラスの組成とは関係がなく、Ｌｉを吸収する能力等が高く、不適切な成分を含まないガラス組成であればよい。
【００２６】
本発明の化学強化ガラスの製造方法においては、母材ガラスとして化学強化の強度が十分得られる量のＬｉイオンを含むガラスを用いることが必要である。
このような母材ガラスの組成としては、例えば、Ｌｉ2Ｏ:８〜１３ｗｔ％、ＳｉＯ2:７６〜８４ｗｔ％、Ａｌ2Ｏ3:１〜７ｗｔ％、Ｎａ2Ｏ:０〜３ｗｔ％、Ｋ2Ｏ:０〜６ｗｔ％、Ｂ2Ｏ3:０〜３ｗｔ％含有し、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、ＰｂＯ、ＺｎＯのうちの一種以上を０〜５ｗｔ％含有する母材ガラス（以下母材ガラス１と記す）等が挙げられる。
【００２７】
母材ガラスの他の組成としては、例えば、ＳｉＯ2：６２〜７５重量％、Ａｌ2Ｏ3：５〜１５重量％、Ｌｉ2Ｏ：４〜１０重量％、Ｎａ2Ｏ：４〜１２重量％、ＺｒＯ2：５．５〜１５重量％を主成分として含有するとともに、Ｎａ2Ｏ／ＺｒＯ2の重量比が０．５〜２．０、Ａｌ2Ｏ3／ＺｒＯ2の重量比が０．４〜２．５であるアルミノシリケートガラス（以下母材ガラス２と記す）等が挙げられる。
また、ＺｒＯ2の未溶解物が原因で生じるガラス基板表面の突起をなくすためには、モル％表示で、ＳｉＯ2を５７〜７４％、ＺｒＯ2を０〜２．８％、Ａｌ2Ｏ3を３〜１５％、ＬｉＯ2を７〜１６％、Ｎａ2Ｏを４〜１４％、含有するアルミノシリケートガラス（以下母材ガラス３と記す）等が好ましい。
母材ガラスのさらに他の組成としては、例えば、以下に示すガラスが挙げられる。
ｗｔ％で、ＳｉＯ2：６１〜７５％、Ａｌ2Ｏ3：１０〜２２％、Ｌｉ2Ｏ：４〜８％、Ｎａ2Ｏ：１０．１〜１５％、含有するアルミノシリケートガラス（以下母材ガラス４と記す）。
モル％で、ＳｉＯ2：３５〜７０％、Ａｌ2Ｏ3：０〜１５％、Ｌｉ2Ｏ＋Ｎａ2Ｏ：３〜３０％、ＣａＯ：１〜４５％、ＣａＯ＋ＭｇＯ：３〜４５％、ＴｉＯ2：０．１〜３０％、含有するアルミノシリケートガラス（以下母材ガラス５と記す）。
このようなアルミノシリケートガラスは、化学強化することによって、表層に生じる圧縮応力、内部に生じる引張応力、圧縮応力層の深さの三者のバランスに優れるとともに、抗折強度や、耐熱性に優れ、高温環境下であってもＮａの析出がないとともに平坦性を維持し、ヌープ硬度にも優れる。このようなアルミノシリケートガラスは、例えば、磁気記録媒体用のガラス基板として適する。
【００２８】
なお、化学強化ガラスの製造方法においては、母材ガラスとＬｉイオン吸収ガラスとは、組成が異なる。
【００２９】
本発明の化学強化ガラスの製造方法において、Ｎａ2Ｏ及び／又はＫ2Ｏを含んだ溶融塩で化学強化する際の条件としては、上記母材ガラス１の場合は、溶融塩の温度：２８０〜４９０℃、処理時間：数時間〜十数時間が好ましく、溶融塩の温度：３００〜４５０℃、処理時間：２時間〜８時間がさらに好ましい。この条件であると、強度と圧縮応力層の深さのバランスに優れる。特に、溶融塩の温度：４００℃程度、処理時間：８時間程度であると、強度が大きく、圧縮応力層の深さも深くなるので好ましい。
同様に、上記母材ガラス２〜５の場合は、溶融塩の温度：２８０℃〜歪点以下、処理時間：数分〜数十時間が好ましく、溶融塩の温度：３００〜５００℃、処理時間：数分〜十数時間がさらに好ましい。
【００３０】
【実施例】
以下、実施例に基づき本発明をさらに具体的に説明する。
（実施例１〜１５及び比較例１〜２）
表１及び表２（表１のつづき）に示す実施例１〜１５の調合組成（重量％）に従ってＬｉ吸収ガラスを作成した。調合原料は炭酸塩、硝酸塩、酸化物のいずれも使用可能で、これらの原料を所望の割合に秤取し、混合して調合原料とし、これを１１００℃〜１４５０℃に加熱した溶解炉に投入し、溶解、清澄、撹拌し、均一化してから鋳型にキャストした。
これらのＬｉ吸収ガラスを予めＬｉイオンを添加した溶融塩中に浸漬し、溶融塩中のＬｉイオン濃度を調べた。また、これらのＬｉイオン吸収ガラスと表１及び表２に示す母材ガラスを溶融塩中に浸漬し、母材ガラスの抗折強度及び圧縮応力層の深さを調べた。これらの結果を表１及び表２（表１のつづき）に示す。
【００３１】
【表１】
表１及び表２におけるＬｉイオン濃度は、上記で得られたＬｉイオン吸収ガラスを細かく粉砕して２．８ｍｍ角を通過し１ｍｍ角にとどまる大きさの粉末を試料とし、ＫＮＯ3：ＮａＮＯ3＝１：１の溶融塩中に、Ｌｉイオンを３００ｐｐｍ、Ｌｉイオン吸収ガラスを溶融塩重量に対して１０％添加して、４００℃で１０日間保持後の溶融塩中のＬｉイオン濃度を示している。
【００３３】
表１及び表２の結果より、予め溶融塩中に添加したＬｉイオンは、Ｌｉ吸収ガラスの作用により吸収され、溶融塩中のＬｉイオン濃度は大きく低下することが確認された。また、Ｌｉ吸収ガラス中のＮａ2Ｏ量が多いほど、溶融塩中のＬｉ濃度が低くなることも確認された。
【００３４】
抗折強度１及び圧縮応力層の深さは、表１及び表２に示す組成の母材ガラスからなる抗折強度試験用標準試料（大きさ４０×３ｍｍ、厚さ１ｍｍで、両面研磨したもの）を、ＫＮＯ3：ＮａＮＯ3＝１：１の溶融塩中でＬｉイオンが無い初期状態から、４００℃×８ｈｒの条件で化学強化を行ったときの抗折強度及び圧縮応力層の深さの結果である。
抗折強度２は、Ｌｉ吸収ガラスを細かく粉砕して２．８ｍｍ角を通過し１ｍｍ角にとどまる大きさの粉末を試料とし、この粉末Ｌｉ吸収ガラスを溶融塩重量に対して１０％添加して、Ｌｉイオンは化学強化により５０ｐｐｍ／ｄａｙ溶出すると仮定して、Ｌｉイオンを５０ｐｐｍ／ｄａｙ添加して４００℃×３０日後に４００℃×８ｈｒ化学強化を行い、抗折強度を測定した結果であり、抗折強度３はさらにＬｉイオンを５０ｐｐｍ／ｄａｙ添加して６０日後に４００℃×８ｈｒ化学強化を行い、抗折強度を測定した結果である。
【００３５】
表１及び表２の結果より、溶融塩中にＬｉ吸収ガラスを浸漬しない場合（比較例１）、及び、γアルミナを用いて溶融塩中のＬｉを吸着させた場合（比較例２）は、いずれの場合も抗折強度は化学強化を行うほど低下するが、実施例１〜１５のＬｉ吸収ガラスを添加することにより化学強化を行っても抗折強度の低下は少ないことが確認された。また、実施例１〜１５のＬｉ吸収ガラスを添加することにより、圧縮応力層の深さが所定範囲内にあることが確認された。さらに、抗折強度の低下の度合いはＬｉ吸収ガラス中のＮａ2Ｏ量が多いほど少ないことも確認された。
【００３６】
以上実施例をあげて本発明を説明したが、本発明は上記実施例に限定されるものではない。
【００３７】
例えば、Ｌｉ吸収ガラスの組成や形状、母材ガラスの組成や形状、化学強化条件等は実施例の範囲に限定されず、本発明の範囲内で適宜設計変更できる。
【００３８】
本発明の化学強化ガラスの製造方法によって得られた化学強化ガラスは、落下に対する強度や耐衝撃性などの機械的強度等が必要なガラス基板やガラス製品などの用途に広く使用できる。
【００３９】
【発明の効果】
以上説明したように、本発明の化学強化用Ｌｉイオン吸収ガラスは、Ｎａ2Ｏを多く含み、Ｌｉイオン吸収ガラス中のＮａ2Ｏ含有量を調整して化学強化条件下におけるＬｉイオンの吸収スピード及び吸収量を制御（大きく）でき、溶融塩中のＬｉイオン濃度を常に低く保つことができるので、所定の強度及び圧縮応力層の深さを有する化学強化ガラスが得られる。また、本発明の化学強化用Ｌｉイオン吸収ガラスは、不適切な成分を含まない、あるいは不適切な成分が少ないので、イオン交換速度や化学的耐久性等の性能を低下させることがない。
【００４０】
また、本発明の化学強化ガラスの製造方法によれば、母材ガラスとして化学強化の強度が十分得られる量のＬｉイオンを含むガラスを用い、かつ、上記本発明の化学強化用Ｌｉイオン吸収ガラスを用いているので、所定の強度及び圧縮応力層の深さを有する化学強化ガラスが得られる。
【００４１】
さらに、本発明のＬｉイオン吸収ガラスによれば、不適切な成分を含まない、あるいは不適切な成分が少ないので、イオン交換速度や化学的耐久性等の性能を向上させたＬｉイオン吸収ガラスが得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a Li-absorbing glass having a function of absorbing Li eluting into a molten salt by ion exchange from a base glass during chemical strengthening, in particular, a Li-absorbing glass for chemical strengthening suitable for chemical strengthening, and The present invention relates to a method for producing chemically strengthened glass using this chemically strengthened Li-absorbing glass.
[0002]
[Prior art]
It is known that the surface of a glass substrate or the like is chemically strengthened for the purpose of improving the strength of the glass substrate or the like. Specifically, low-temperature ion exchange is performed on the surface of glass substrates in order to improve mechanical strength such as impact resistance (including strength against dropping) and vibration resistance, and to prevent damage to glass substrates due to impact and vibration. It is known to perform chemical strengthening treatment by the law.
[0003]
The chemical strengthening treatment is performed by, for example, immersing a base glass containing Li ions in a molten salt containing Na ions and / or K ions, so that the Li ions in the base glass have an ionic radius rather than Li ions. This is a treatment for increasing the strength by generating strong compressive stress in the glass surface layer by replacing with large Na and K ions by ion exchange.
[0004]
[Problems to be solved by the invention]
However, due to the ion exchange reaction for chemical strengthening, Li ions in the base glass are eluted into the molten salt, and the Li concentration in the molten salt increases as the number of treatments increases, making it difficult for chemical strengthening ion exchange to occur. Therefore, there is a problem that a predetermined mechanical strength or the like cannot be obtained.
In order to solve this problem, Japanese Patent Publication No. 6-71521 proposes a technique for removing Li ions eluted in the molten salt using an adsorbent made of γ-alumina. However, there is a problem that the Li concentration starts to increase after a certain period.
Japanese Patent Application Laid-Open No. 64-24053 discloses a technique for absorbing ions eluted in a molten salt with an ion-absorbing glass when producing a refractive index distribution glass by ion exchange. However, this technique has an adverse effect due to the inclusion of inappropriate components, and the purpose is to produce a refractive index distribution glass by ion exchange, so it can be applied as it is in ion exchange for the purpose of chemical strengthening. I can't.
[0005]
The present invention has been made under the above-described background, and a first object is to provide a chemical strengthening Li ion absorbing glass suitable for chemical strengthening.
The second object is to provide a method for producing chemically strengthened glass using Li ion absorbing glass for chemically strengthening.
Furthermore, the third object is to provide Li ion absorbing glass and the like with improved performance such as ion exchange rate.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, the present invention has the following configuration.
[0007]
(Configuration 1) When a glass containing Li 2 O is chemically strengthened with a molten salt containing Na 2 O and / or K 2 O, it is incorporated into the molten salt for the purpose of absorbing Li ions eluted in the molten salt. A Li-absorbing glass for chemical strengthening, which is immersed, and contains 20 wt% or more of Na 2 O.
[0008]
(Configuration 2) When a glass containing Li 2 O is chemically strengthened with a molten salt containing Na 2 O and / or K 2 O, it is incorporated into the molten salt for the purpose of absorbing Li ions eluted in the molten salt. A Li-absorbing glass for chemical strengthening, which is immersed in Li-absorbing glass for chemical strengthening, and mainly contains 20 to 40 wt% Na 2 O and 30 to 60 wt% SiO 2 .
[0009]
(Configuration 3) When glass containing Li 2 O is chemically strengthened with molten salt containing Na 2 O and / or K 2 O, the molten salt is contained in the molten salt for the purpose of absorbing Li ions eluted in the molten salt. A Li-absorbing glass for chemical strengthening, which is immersed in the Li-absorbing glass for chemical strengthening, mainly containing 23 to 40 wt% of Na 2 O and 30 to 60 wt% of SiO 2 .
[0010]
(Configuration 4) When a glass containing Li 2 O is chemically strengthened with a molten salt containing Na 2 O and / or K 2 O, it is contained in the molten salt for the purpose of absorbing Li ions eluted in the molten salt. A Li-absorbing glass for chemical strengthening, which is immersed, and mainly contains 25-40 wt% Na 2 O and 30-60 wt% SiO 2 .
[0011]
(Configuration 5) 0 to 15 wt% of K 2 O, 0 to 15 wt% of Cs 2 O, 0 to 15 wt% of MgO, 0 to 15 wt% of CaO, 0 to 15 wt% of SrO, 0 to 15 wt% of ZnO, TiO 2 0-15 wt%, Nb 2 O 5 0-15 wt%, Ta 2 O 5 0-15 wt%, La 2 O 3 0-15 wt%, Y 2 O 3 0-15 wt%, Yb 2 0 to 15 wt% for O 3 , 0 to 15 wt% for Gd 2 O 3 , 0 to 15 wt% for Al 2 O 3 , 0 to 15 wt% for WO 3 , 0 to 15 wt% for Sb 2 O 3 , As 2 O 3 the 0 to 15 wt%, a ZrO 2 0 to 15 wt%, a TeO 2 0~15wt%, 0~15wt the Bi 2 O 3, B 2 O 3 and 0~4wt%, 0~4wt% of BaO, the PbO The Li absorption gas for chemical strengthening according to any one of the constitutions 1 to 4, characterized by containing 0 to 3 wt%. Nest.
[0012]
(Structure 6) The Li-absorbing glass for chemical strengthening according to any one of Structures 1 to 5, which is substantially free of one or more components of B 2 O 3 , PbO, BaO and Li 2 O. .
[0013]
(Configuration 7) using a glass containing Li ions in an amount strength chemical strengthening as a base glass is obtained sufficiently, using chemical reinforcing Li absorbing glass according to any of the first to 6, these Na 2 A method for producing chemically tempered glass, wherein the glass base material is chemically strengthened by immersing in a molten salt containing O and / or K 2 O.
[0014]
(Configuration 8) Li ion absorbing glass immersed in a molten salt for the purpose of absorbing Li ions eluted in the molten salt when ion exchange of the glass containing Li 2 O contains 20 wt% or more of Na 2 O 30 to 60 wt% of any one of SiO 2 , P 2 O 5 and GeO 2 , 0 to 15 wt% of K 2 O, 0 to 15 wt% of Cs 2 O, and 0 to 15 wt% of MgO %, CaO and 0 to 15 wt%, SrO of 0 to 15 wt%, 0 to 15 wt% of ZnO, the TiO 2 0~15wt%, Nb 2 O 5 and 0~15wt%, Ta 2 O 5 and 0 to 15 wt% La 2 O 3 0-15 wt%, Y 2 O 3 0-15 wt%, Yb 2 O 3 0-15 wt%, Gd 2 O 3 0-15 wt%, Al 2 O 3 0-15 wt% , WO 3 and 0 to 15 wt%, 0 to 15 wt% of Sb 2 O 3, As 2 3 0 to 15 wt%, a ZrO 2 0 to 15 wt%, a TeO 2 0~15wt%, 0~15wt the Bi 2 O 3, B 2 O 3 and 0~4wt%, 0~4wt% of BaO, PbO Li absorbing glass, characterized by containing 0 to 3 wt%.
[0015]
(Arrangement 9) The Li-absorbing glass according to Arrangement 8, wherein one or more components of B 2 O 3 , PbO, BaO and Li 2 O are not substantially contained.
[0016]
[Action]
Chemical strengthening for Li-ion-absorbing glass of the present invention includes a number of Na 2 O, the chemical strengthening conditions, the higher the content of Na 2 O in the Li-ion absorbing glass increases, increases the absorption speed of Li ions, Since the amount of Li ion absorption increases, the Li ion concentration in the molten salt can always be kept low, whereby a chemically strengthened glass having a predetermined mechanical strength and a compressive stress layer depth is obtained. Moreover, since the Li ion absorbing glass for chemical strengthening of the present invention does not contain an inappropriate component or has few inappropriate components, performances such as ion exchange rate and chemical durability are not deteriorated.
[0017]
In addition, according to the method for producing chemically strengthened glass of the present invention, a glass containing Li ions in an amount sufficient to obtain the strength of chemical strengthening is used as the base glass, and the Li ion absorbing glass for chemical strengthening of the present invention is used Therefore, a chemically strengthened glass having a predetermined mechanical strength and a depth of the compressive stress layer can be obtained.
In addition, there is an effect of not increasing the Li ion concentration in the molten salt, and the production efficiency is good because it is not necessary to replace the molten salt having a high Li ion concentration.
[0018]
Furthermore, according to the Li ion absorbing glass of the present invention, since there are few inappropriate components or there are few inappropriate components, the Li ion absorbing glass with improved performance such as ion exchange rate and chemical durability can be obtained. can get.
[0019]
Hereinafter, the present invention will be described in detail.
The reasons for limiting the contents in the Li ion absorbing glass for chemical strengthening of the present invention and the Li ion absorbing glass of the present invention are as follows.
[0020]
Na 2 O is an essential component as a component to be ion-exchanged again with Li ions eluted in the molten salt during ion exchange, particularly ion exchange during chemical strengthening. It has been found that the Na 2 O content increases in the Li-absorbing glass, so that the speed of absorbing Li in the molten salt and the absolute amount of absorbing Li increase. In particular, the speed of absorbing Li in the molten salt is important during ion exchange during chemical strengthening. This is because the Li ion concentration in the molten salt can always be kept low if the speed of absorbing Li in the molten salt is high. For these reasons, Na 2 O is preferably contained in an amount of 20 wt% or more. The or Na 2 O is not vitrification exceeds 40 wt%, decrease the chemical durability of the glass Li absorbing glass itself may possibly be dissolved in the molten salt. Therefore, the upper limit is preferably 40 wt% or less. The content of Na 2 O is more preferably 23 to 40 wt%, and further preferably 25 to 40 wt%.
[0021]
SiO 2 is preferably contained as a glass-forming component, or as a component that vitrifies even when Na 2 O is contained in a large amount of 20 to 40 wt% and enhances chemical durability against molten salt. The preferred content of SiO 2 is in the range of 30 to 60 wt%.
As the glass forming component, P 2 O 5 or GeO 2 may be used instead of SiO 2 . The preferred contents of P 2 O 5 and GeO 2 are each in the range of 30 to 60 wt%.
[0022]
B 2 O 3 is made poor chemical resistance to the molten salt is added as a glass-forming component, the glass component is eluted into the molten salt, B 2 O 3: preferably to 4 wt% or less, B 2 O 3 : 1 wt% or less is more preferable, and B 2 O 3 is most preferably not contained.
[0023]
When Li is contained in the Li-absorbing glass, the Li-absorbing glass is preferably inhibited from containing Li ions. In particular, in the Li ion absorbing glass for chemical strengthening, it is preferable not to contain Li ions in order to chemically strengthen in a short time and to obtain a predetermined strength and depth of the compressive stress layer (strain layer).
[0024]
Other optional components include K 2 O, Cs 2 O, MgO, CaO, SrO, BaO, PbO, ZnO, TiO 2 , Nb 2 O 5 , Ta 2 O 5 , La 2 O 3 , Y 2 O 3 , Yb 2 O 3 , Gd 2 O 3 , Al 2 O 3 , WO 3 , Sb 2 O 3 , As 2 O 3 , ZrO 2 , TeO 2 , Bi 2 O 3 can be added in the range of 0 to 15 wt%, respectively. is there.
However, since BaO and PbO decrease the ion conversion rate of Li 2 O, BaO: 4 wt% or less, PbO: 3 wt% or less are preferable, BaO: 1 wt% or less, and PbO: 1 wt% or less. More preferably, it is most preferable that BaO and PbO are not substantially contained.
[0025]
The composition of the Li-absorbing glass of the present invention is not related to the composition of the base glass, and may be any glass composition that has a high ability to absorb Li and does not contain inappropriate components.
[0026]
In the method for producing chemically strengthened glass according to the present invention, it is necessary to use a glass containing Li ions in an amount sufficient to obtain the strength of chemical strengthening as the base glass.
As a composition of such a base glass, for example, Li 2 O: 8 to 13 wt%, SiO 2 : 76 to 84 wt%, Al 2 O 3 : 1 to 7 wt%, Na 2 O: 0 to 3 wt%, K 2 O: 0 to 6 wt%, B 2 O 3 : 0 to 3 wt%, and a base glass containing 0 to 5 wt% of one or more of MgO, CaO, SrO, BaO, PbO, ZnO (hereinafter referred to as “base metal”) And the like).
[0027]
As other components of the matrix glass, for example, SiO 2: 62-75 wt%, Al 2 O 3: 5~15 wt%, Li 2 O: 4~10 wt%, Na 2 O: 4~12 weight %, ZrO 2 : 5.5 to 15% by weight as a main component, the weight ratio of Na 2 O / ZrO 2 is 0.5 to 2.0, and the weight ratio of Al 2 O 3 / ZrO 2 is 0. And aluminosilicate glass (hereinafter referred to as base material glass 2) of 4 to 2.5.
Further, in order to eliminate protrusions on the surface of the glass substrate caused by the undissolved material of ZrO 2 , SiO 2 is 57 to 74%, ZrO 2 is 0 to 2.8%, Al 2 O 3 in terms of mol%. Are preferably 3-15%, LiO 2 7-16%, Na 2 O 4-14%, aluminosilicate glass (hereinafter referred to as base glass 3).
Examples of other compositions of the base glass include the following glasses.
Aluminosilicate glass (hereinafter referred to as mother) containing wt%, SiO 2 : 61-75%, Al 2 O 3 : 10-22%, Li 2 O: 4-8%, Na 2 O: 10-15% (Referred to as material glass 4).
In mol%, SiO 2: 35~70%, Al 2 O 3: 0~15%, Li 2 O + Na 2 O: 3~30%, CaO: 1~45%, CaO + MgO: 3~45%, TiO 2: 0.1 to 30% aluminosilicate glass (hereinafter referred to as “matrix glass 5”).
Such an aluminosilicate glass is excellent in bending strength and heat resistance, as well as having a good balance between the compressive stress generated in the surface layer, the tensile stress generated in the interior, and the depth of the compressive stress layer by chemical strengthening. Even under a high temperature environment, there is no precipitation of Na, flatness is maintained, and Knoop hardness is excellent. Such an aluminosilicate glass is suitable as a glass substrate for a magnetic recording medium, for example.
[0028]
In the method for producing chemically strengthened glass, the composition of the base glass and the Li ion absorbing glass is different.
[0029]
In the method for producing chemically tempered glass according to the present invention, as a condition for chemical strengthening with a molten salt containing Na 2 O and / or K 2 O, in the case of the base glass 1, the temperature of the molten salt: 280 ˜490 ° C., treatment time: several hours to tens of hours are preferred, molten salt temperature: 300 to 450 ° C., treatment time: 2 hours to 8 hours are more preferred. Under this condition, the balance between the strength and the depth of the compressive stress layer is excellent. In particular, when the temperature of the molten salt is about 400 ° C. and the processing time is about 8 hours, the strength is large and the depth of the compressive stress layer is also preferable.
Similarly, in the case of the above-described base glass 2 to 5, the temperature of the molten salt: 280 ° C. to the strain point or less, the processing time: several minutes to several tens of hours are preferable, and the temperature of the molten salt: 300 to 500 ° C., the processing time. : Several minutes to several tens of hours are more preferable.
[0030]
【Example】
Hereinafter, the present invention will be described more specifically based on examples.
(Examples 1-15 and Comparative Examples 1-2)
Li-absorbing glasses were prepared according to the blended compositions (% by weight) of Examples 1 to 15 shown in Table 1 and Table 2 (continued in Table 1). Any of carbonate, nitrate and oxide can be used as the compounding raw material. These raw materials are weighed in a desired ratio and mixed to prepare the compounding raw material, which is put into a melting furnace heated to 1100 ° C to 1450 ° C. Then, the mixture was dissolved, clarified, stirred and homogenized, and then cast into a mold.
These Li absorption glasses were immersed in a molten salt to which Li ions had been added in advance, and the Li ion concentration in the molten salt was examined. Moreover, these Li ion absorption glasses and the base glass shown in Table 1 and Table 2 were immersed in molten salt, and the bending strength of the base glass and the depth of the compressive stress layer were examined. These results are shown in Tables 1 and 2 (continued in Table 1).
[0031]
[Table 1]
The Li ion concentration in Table 1 and Table 2 is obtained by finely pulverizing the Li ion absorbing glass obtained above, and using a powder of a size that passes through a 2.8 mm square and remains at 1 mm square as a sample. KNO 3 : NaNO 3 = The concentration of Li ions in the molten salt after 10 days of retention at 400 ° C. is shown after adding 300 ppm Li ions and 10% Li ion absorbing glass to the molten salt weight in the 1: 1 molten salt. .
[0033]
From the results of Tables 1 and 2, it was confirmed that Li ions added in advance to the molten salt were absorbed by the action of the Li absorption glass, and the Li ion concentration in the molten salt was greatly reduced. It was also confirmed that the Li concentration in the molten salt decreases as the amount of Na 2 O in the Li-absorbing glass increases.
[0034]
The bending strength 1 and the depth of the compressive stress layer are the standard samples for bending strength testing (size 40 × 3 mm, thickness 1 mm, polished on both sides) made of the base glass having the composition shown in Table 1 and Table 2. ) Of the bending strength and the depth of the compressive stress layer when chemical strengthening is performed under the condition of 400 ° C. × 8 hr from the initial state where there is no Li ion in the molten salt of KNO 3 : NaNO 3 = 1: 1. It is a result.
The bending strength 2 is obtained by finely pulverizing Li-absorbing glass and using a powder of a size that passes through 2.8 mm square and stays at 1 mm square as a sample. , Li ions were assumed to elute at 50 ppm / day by chemical strengthening, Li ions were added at 50 ppm / day, 400 ° C. × 30 hours after chemical strengthening, and the bending strength was measured. The bending strength 3 is the result of further measuring the bending strength after adding 60 ppm / day of Li ions and performing chemical strengthening at 400 ° C. for 8 hours after 60 days.
[0035]
From the results of Table 1 and Table 2, when Li absorbing glass is not immersed in the molten salt (Comparative Example 1), and when Li in the molten salt is adsorbed using γ-alumina (Comparative Example 2), In any case, the bending strength decreases as the chemical strengthening is performed. However, it was confirmed that even when the chemical strengthening is performed by adding the Li-absorbing glass of Examples 1 to 15, the bending strength is hardly decreased. Moreover, it was confirmed by adding Li absorption glass of Examples 1-15 that the depth of a compressive-stress layer exists in the predetermined range. Furthermore, it was also confirmed that the degree of decrease in the bending strength decreases as the amount of Na 2 O in the Li-absorbing glass increases.
[0036]
Although the present invention has been described with reference to the examples, the present invention is not limited to the above examples.
[0037]
For example, the composition and shape of the Li-absorbing glass, the composition and shape of the base glass, the chemical strengthening conditions, and the like are not limited to the scope of the examples, and can be appropriately changed within the scope of the present invention.
[0038]
The chemically strengthened glass obtained by the method for producing chemically strengthened glass of the present invention can be widely used for applications such as glass substrates and glass products that require mechanical strength such as strength against impact and impact resistance.
[0039]
【The invention's effect】
As described above, the chemical strengthening Li-ion-absorbing glass of the present invention, contains a large amount of Na 2 O, absorption speed of Li ions in the chemical strengthening conditions by adjusting the content of Na 2 O in the Li-ion absorbing glass Further, the amount of absorption can be controlled (increased), and the Li ion concentration in the molten salt can always be kept low, so that a chemically strengthened glass having a predetermined strength and a depth of the compressive stress layer can be obtained. Moreover, since the Li ion absorbing glass for chemical strengthening of the present invention does not contain an inappropriate component or has few inappropriate components, performances such as ion exchange rate and chemical durability are not deteriorated.
[0040]
In addition, according to the method for producing chemically strengthened glass of the present invention, a glass containing Li ions in an amount capable of sufficiently obtaining the strength of chemical strengthening is used as the base glass, and the Li ion absorbing glass for chemically strengthening of the present invention is used. Therefore, a chemically strengthened glass having a predetermined strength and a depth of the compressive stress layer can be obtained.
[0041]
Furthermore, according to the Li ion absorbing glass of the present invention, since there are few inappropriate components or there are few inappropriate components, the Li ion absorbing glass with improved performance such as ion exchange rate and chemical durability can be obtained. can get.
Claims (5)
Ｌｉ2Ｏを含んだガラスを、Ｎａ2Ｏ及び／又はＫ2Ｏを含んだ溶融塩で化学強化する際、溶融塩中に溶出したＬｉイオンを吸収する目的で溶融塩中に浸漬される化学強化用Ｌｉ吸収ガラスであって、Ｎａ2Ｏを２０ｗｔ％以上含有し、
ＳｉＯ 2 、Ｐ 2 Ｏ 5 及びＧｅＯ 2 のうちのいずれかを３０〜６０ｗｔ％含有し、かつ、
Ｋ 2 Ｏを０〜１５ｗｔ％、Ｃｓ 2 Ｏを０〜１５ｗｔ％、ＭｇＯを０〜１５ｗｔ％、ＣａＯを０〜１５ｗｔ％、ＳｒＯを０〜１５ｗｔ％、ＺｎＯを０〜１５ｗｔ％、ＴｉＯ 2 を０〜１５ｗｔ％、Ｎｂ 2 Ｏ 5 を０〜１５ｗｔ％、Ｔａ 2 Ｏ 5 を０〜１５ｗｔ％、Ｌａ 2 Ｏ 3 を０〜１５ｗｔ％、Ｙ 2 Ｏ 3 を０〜１５ｗｔ％、Ｙｂ 2 Ｏ 3 を０〜１５ｗｔ％、Ｇｄ 2 Ｏ 3 を０〜１５ｗｔ％、Ａｌ 2 Ｏ 3 を０〜１５ｗｔ％、ＷＯ 3 を０〜１５ｗｔ％、Ｓｂ 2 Ｏ 3 を０〜１５ｗｔ％、Ａｓ 2 Ｏ 3 を０〜１５ｗｔ％、ＺｒＯ 2 を０〜１５ｗｔ％、ＴｅＯ 2 を０〜１５ｗｔ％、Ｂｉ 2 Ｏ 3 を０〜１５ｗｔ、Ｂ 2 Ｏ 3 を０〜４ｗｔ％、ＢａＯを０〜４ｗｔ％、ＰｂＯを０〜３ｗｔ％、含有する化学強化用Ｌｉ吸収ガラスを用いて、
これらをＮａ2Ｏ及び／又はＫ2Ｏを含んだ溶融塩に浸漬して磁気記録媒体用ガラス基板の化学強化を行い、化学強化により抗折強度を高めることを特徴とする磁気記録媒体用ガラス基板の製造方法。Using a glass substrate for a magnetic recording medium containing an amount of Li ions sufficient to obtain sufficient strength of chemical strengthening as a base glass,
When a glass containing Li 2 O is chemically strengthened with a molten salt containing Na 2 O and / or K 2 O, the chemical is immersed in the molten salt for the purpose of absorbing Li ions eluted in the molten salt. a Li absorbing glass reinforced, contain Na 2 O or 20 wt%,
Any of SiO 2, P 2 O 5 and GeO 2 containing 30 to 60 wt%, and,
K 2 O of 0~15wt%, Cs 2 O and 0 to 15 wt%, MgO and 0 to 15 wt%, CaO and 0 to 15 wt%, SrO of 0 to 15 wt%, 0 to 15 wt% of ZnO, the TiO 2 0 ~15wt%, Nb 2 O 5 and 0~15wt%, Ta 2 O 5 and 0~15wt%, La 2 O 3 and 0 to 15 wt%, 0 to 15 wt% of Y 2 O 3, the Yb 2 O 3 0 ~15wt%, Gd 2 O 3 and 0~15wt%, Al 2 O 3 and 0 to 15 wt%, WO 3 and 0 to 15 wt%, 0 to 15 wt% of Sb 2 O 3, the As 2 O 3 0 to 15 wt %, ZrO 2 0-15 wt%, TeO 2 0-15 wt%, Bi 2 O 3 0-15 wt, B 2 O 3 0-4 wt%, BaO 0-4 wt%, PbO 0-3 wt% , using Li-absorbing glass for chemical strengthening containing,
Glass for magnetic recording media characterized in that these are immersed in a molten salt containing Na 2 O and / or K 2 O to chemically strengthen the glass substrate for magnetic recording media, and the bending strength is increased by chemical strengthening. A method for manufacturing a substrate.
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| WO2020218253A1 (en) * | 2019-04-26 | 2020-10-29 | Ａｇｃ株式会社 | Life extension method for molten salt composition, manufacturing method for chemically strengthened glass, glass auxiliary agent, and raw material for glass |
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| DE102004011218B4 (en) * | 2004-03-04 | 2006-01-19 | Schott Ag | X-ray opaque glass, process for its preparation and its use |
| US8759238B2 (en) | 2010-05-27 | 2014-06-24 | Corning Incorporated | Ion exchangeable glasses |
| CN112390539B (en) * | 2019-08-16 | 2024-01-02 | 重庆鑫景特种玻璃有限公司 | Salt bath purification additive material and method of use thereof |
| CN112645608B (en) * | 2019-10-16 | 2023-05-30 | 重庆鑫景特种玻璃有限公司 | Silicon-free salt bath purification additive material and application method thereof |
| CN112608033A (en) * | 2020-09-12 | 2021-04-06 | 重庆鑫景特种玻璃有限公司 | Chemically strengthened glass ceramics and strengthening method |
| CN116768493A (en) * | 2020-09-12 | 2023-09-19 | 重庆鑫景特种玻璃有限公司 | Boron-free and phosphorus-free ion sieve with high stability and preparation and application thereof |
| CN112125511B (en) * | 2020-09-28 | 2022-04-12 | 成都光明光电股份有限公司 | Optical glass |
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