TW201245073A

TW201245073A - Crystallized glass for display devices

Info

Publication number: TW201245073A
Application number: TW101107174A
Authority: TW
Inventors: Manuel Diaz Reyes; Seiki Ohara; Akio Koike; Kei Maeda; Tetsuya Nakashima
Original assignee: Asahi Glass Co Ltd
Priority date: 2011-03-04
Filing date: 2012-03-03
Publication date: 2012-11-16
Also published as: WO2012121116A1; JPWO2012121116A1

Abstract

Provided is a cover glass for display devices, which comprises a high-strength and transparent crystallized glass. A crystallized glass for display devices, which has a transmittance (T400nm) of light having a wavelength of 400 nm of more than 10% when the glass is prepared into a thickness of 1 mm, and which is produced by crystallizing a glass comprising, in mol% in terms of oxide contents, 61.5-72% of SiO2, 1-5.5% of Al2O3, 0.5-3% of P2O5, 0.5-3% of ZrO2, 20-35% of Li2O and 0-5% of K2O, wherein the total content of P2O5 and ZrO2 is 1.7-5%.

Description

201245073 六、發明說明： C ^'明所屬冬圩領2 發明領域本發明係有關於一種透明高強度結晶化玻璃，其係適用於顯示裝置，典型的係行動電話、行動資料終端機 (PDA)、附觸感測機能之輸入板個人電腦及觸控面板等之小型顯示裝置之覆蓋玻璃等。201245073 VI. INSTRUCTIONS: C ^ '明 belongs to the winter collar 2 FIELD OF THE INVENTION The present invention relates to a transparent high-strength crystallized glass, which is suitable for display devices, typically a mobile phone, mobile data terminal (PDA) The touch panel of the small display device such as a personal computer and a touch panel with a touch-sensing function.

L· J 發明背景近年來，對於行動電話、PDA等之行動式機器（可攜式資訊裝置），為了保護顯示器以及提高美觀而使用覆蓋玻璃 (保護玻璃）的情況日趨增加。另一方面，對於如所述之行動式機器，有著輕量薄型化的需求。因此，使用於顯示器保護用的覆蓋玻璃亦被要求要薄化。但是，隨著覆蓋玻璃的厚度變薄，其強度會隨之降低，會有因使用時或者是攜帶時之掉落等而造成覆蓋玻璃本身破裂的情形，而有變得無法發揮保護顯示裝置之本來的作用的問題。為了解決上述問題，而有提高覆蓋玻璃強度的需求，作為其方法而為—般所知悉的手法係使於玻璃表面形成壓縮應力層。使於玻璃表面形成壓縮應力層的代表性手法有：風冷強化法(物理強化法）’係、將已加熱至軟化點附近的玻璃板表面藉由送風冷卻等使之急速地冷卻者；及化學強作法， 201245073 其係在玻祕移點町之溫度藉由離子交換，使玻璃板表面之離子半徑小的鹼金屬離子（典型的為Li離子、Na離子）交換成離子爭徑較大的鹼離子（典型的為κ離子）者。如前所述覆蓋玻璃之厚度有著薄化的需求。然而，若對薄玻璃板應用風冷強化法的話，則會因表面與内部的溫度差難產生而難以形成壓縮應力層，且無法獲得欲達成之高強度的特性。因此，通常使用經利用後者之化學強化法所強化之覆蓋玻璃（參照專利文獻1)。化學強化玻璃雖可適用於如用於顯示裝置之覆蓋玻璃的薄玻璃，但行動電話、PDA等小型顯示裝置之覆蓋玻璃因輕量化的緣故’而需求儘可能地薄且高強度之玻璃。然而，舉例而言，即便為1mm等之通常的玻璃板厚度，因於其内部蓄積有拉伸應力’故在破裂時亦會有爆發性碎裂的情形。因此，為了於用於行動電話、行動資料終端機(pda) 等小型顯示裝置之覆蓋玻璃的時候不發生如所述之問題，而限制化學強化玻璃之強度之提案（參照專利文獻2)β即，於專利文獻2中提案有依玻璃之厚度而令拉伸應力為特定之值以下。於專利文獻2中，因拉伸應力係與玻璃表面之壓縮應力CS成正比，又，令壓縮應力層之深度為DOL，且令玻璃厚度為t，則拉伸應力與(DOL_l · t—2)成反比，因而可說其提案方向係將CS或DOL縮小。先行技術文獻專利文獻 201245073 專利文獻1 :美國專利申請公開第2008/0286548號說明書專利文獻2 :美國專利申請公開第2010/0035038號說明書【發明内容；I 發明概要發明欲解決之課題先前所述之問題為若欲增大化學強化玻璃之c s所必然會伴隨的問題且為習知之事，又，顯示拉伸應力與CS、DOL 及t之關係的式子亦為眾所周知。本發明係以提供顯示裝置之覆蓋玻璃等為目的，該顯示裝置之覆蓋玻璃係利用一種能解決化學強化玻璃之所述問題，並且為高強度、且具有透明性之結晶化玻璃者。用以欲解決課題之手段本發明係提供一種顯示裝置用結晶化玻璃（以下，有時稱之為「結晶化玻璃A」），其係將以下述氧化物為基準之莫耳％表示，含有：61.5〜72%之Si02、1〜5.5%之Al2〇3、 0.5〜3%之P2〇5、0.5〜3%之Zr02、20〜35%之Li20及0〜5% 之K20，且P2〇5及Zr02之含量合計P205 + Zr02為1.7〜5%的玻璃予以結晶化而得者。又，提供一種顯示裝置用結晶化玻璃，係厚度為1mm 時之波長400nm的光穿透率Τ4()()ηηι為超過10%者；且其係將以下述氧化物為基準之莫耳％表示，含有：61.5〜72%之 Si02、1〜5.5%之Al2〇3、0.5〜3%之P205、0.5〜3%之Zr02、 20 〜35% 之 Li20及 0 〜5% 之 K2◦，且 P205 + Zr02 為 1.7 〜5% 的玻璃予以結晶化而得者。 201245073 又’提供前述顯示裝置用結晶化玻璃，其中前述玻璃之Si02為 62〜68%、Al2〇3為 1 〜3%、P205為 0.5〜2%、Zr02 為0.5〜2%、Li2〇為25〜30%、K2O為0〜3.5°/。，且P205 + Zr02 為 1.7〜3.50/〇。提供前述顯示裝置用結晶化玻璃，其中前述玻璃之κ2ο 係0〜2.5%。提供前述顯示裝置用結晶化玻璃，其中前述玻璃之Κ20 係1 %以上。又，提供前述顯示裝置用結晶化玻璃，其中前述玻璃之 P2〇5 + Zr02 係2°/。以上。又，提供一種玻璃組成物，係藉由結晶化而形成T400nm 為超過10%之顯示裝置用結晶化玻璃者；其以下述氧化物為基準之莫耳％表示，係含有：61.5〜72%之8丨02、1〜5.5% 之Al2〇3、0.5〜3%之P2〇5、〇.5〜3%之Zr02、20〜35%之Li20 及0〜5%之K20，且P205 + Zr02為1.7〜5%，並且不含著色成分。又，提供前述不含著色成分之玻璃組成物（以下，有時以「母玻璃1」稱之），其中Si02為62〜68%、Al2〇3為1〜3%、 P205為 0.5〜2%、Zr02為 0.5〜2%、Li20為 25〜30%、K20為 0〜3.5%，且P205 + Zr02為 1.7〜3.5%。又，提供前述不含著色成分之玻璃組成物，其中K20 係1 %以上。又，提供前述不含著色成分之玻璃組成物’其中Ρ2〇5 + Zr02係2%以上。 201245073 又’提供一種玻璃組成物，係藉由結晶化而形成顯示裝置用結晶化玻璃者，且係業已使前述不含著色成分之玻璃組成物含有著色成分者（以下，有時以「母玻璃2」稱之）。又’提供一種顯示裝置用結晶化玻璃，係使前述不含著色成分之玻璃組成物、或者係業已使前述不含著色成分之玻璃組成物含有著色成分之玻璃組成物結晶化而得者。又’提供前述顯示裝置用結晶化玻璃，其析出有 Li2Si2〇5結晶。又’提供前述顯示裝置用結晶化玻璃，其中破裂韌性值Kc係1.2MPa · m丨/2以上。又’提供前述顯示裝置用結晶化玻璃，其中T400nm為超過10%者。又’提供一種顯示裝置用結晶化玻璃（以下，以「結晶化玻璃B」稱之），其係析出有Li2Si2〇5結晶，破裂韌性值Kc 為1.2MPa . 以上，且τ伽⑽為超過1〇%者。又’提供前述顯示裝置用結晶化玻璃，其係厚度為lmm 時之波長400〜800nm的光穿透率為超過1〇%者。又’提供一種顯示裝置，係具備由前述顯示裝置用結晶化玻璃所構成之覆蓋玻璃者。又，一種行動式機器，係具備前述顯示裝置者。又，提供一種結晶化玻璃之製造方法，其特徵在於：其係令含有下述組成且結晶化第2尖峰溫度乃為超過755。〇之玻璃的玻璃轉移點為Tg、並在(Tg_|_4〇°C)〜（Tg + 100。〇之溫度下保持1小時以上，之後並於(T2 —7〇。〇〜汀2_5。〇 201245073 之溫度下保持1小時以上來結晶化者；該玻璃以下述氧化物為基準之莫耳％表示，係含有：61.5〜72%之Si02、1〜5.5% 之 Al2〇3、〇_5〜3%之P2〇5、0.5〜3%之Zr02、20〜35%之〇2〇及 0〜5%之K2〇，且p2〇5 + Zr02為 1 〜5%。又’提供一種結晶化玻璃之製造方法，其特徵在於：其係令含有下述組成之玻璃的玻璃轉移點為Tg、並在(Tg + 40°C)〜（Tg+80°C)之溫度下保持1小時以上，之後並於 750〜820°C之溫度下保持1小時以上來結晶化者；該玻璃以下述氧化物為基準之莫耳％表示，係含有62〜68%之 Si〇2、1 〜3%之Al2〇3、0.5〜2%之P2〇5、〇.5〜2%之Zr02、 25〜30%之Li20及0〜2.5%之K20，且p2〇5 + Zr02為 1.5〜 3.5%。又，提供前述結晶化玻璃之製造方法，其中Tg係小於 520°C。發明效果依據本發明’能提供一種高強度且具有透明性之結晶化玻璃’且該結晶化玻璃可避免化學強化玻璃之所謂有爆發性碎裂情況的缺點。又，若欲將化學強化玻璃用於厚度為〇.4mm以下等特別薄的覆蓋玻璃，則會因内部拉伸應力變得過高，而產生無法提高表面壓縮應力，或者無法將表面壓縮層加深至預定的深度等的問題。對此’因依據本發明能將結晶化玻璃使用於顯示裝置的覆蓋玻璃’故即便使覆蓋玻璃變薄亦能維持高強度。 201245073 圖式簡單說明第1圖係以後述之例1的狀況為例，來說明結晶化第1尖峰溫度T,、結晶化第2尖峰溫度丁2的圖；横軸為溫度（單位： °C)，縱軸則為微差熱分析儀之輸出功率（單位：μν)〇另外，圖中之Tg係玻璃轉移點，ΘΝ係成核熱處理溫度，而©c則係晶體生長熱處理溫度，並將其概略溫度個別以該當之虛線來表示。第2圖係以使砂紙之磨擦面向下的方式放置於後述之例1的結晶化玻璃板上，並使質量為28g的球狀不銹鋼自 50cm之高度落下時之結晶化玻板表面的相片。第3圖係以使砂紙之磨擦面向下的方式放置於化學強化玻璃板上，並使質量為28g的球狀不銹鋼自3cm之高度落下時之化學強化玻璃板表面的相片；該化學強化玻璃板係將莫耳百分率表示組成為Si02 : 73%、A1203 : 7%、MgO : 6%及Na20 : 14%的玻璃板經予以離子交換者。【實施方式】用以實施發明之形態本發明之顯示裝置用結晶化玻璃（以下’以「本發明之結晶化玻璃」稱之）係以析出有Li2Si205結晶者為宜，而於結晶化玻璃B中係析出有Li2Si2〇5結晶。若為非析出有 LijbO5結晶者，則難成為高強度且具有透明性者。又，為析出有Li2Si205結晶之結晶化玻璃時，主要的結晶相係以Li2Si2〇5結晶為宜。所謂「主要的結晶相」，若於結晶只析出一種的情況時，係指該結晶；而若於析出有多 201245073 數之結晶的情況時，則係指結晶所占比率多之奸曰、’’0曰曰相〇通^ 常，結晶析出之有無係以X射線粉末繞射法來調杳，士曰所占比率係以體積比率來表示。且tae 本發明之結晶化玻璃，其Li2si2〇5結晶所上 1 6比率彳系以 50%以上為宜。LiJhO5結晶，係用以較能維持逯明性且同時具有高強度的結晶。前述比率較佳係6〇%以上生且同係70%以上。 t佳則同樣作為Li20-Si02系之結晶雖有㈣叫結晶但若為已析出了 Li2Si〇3結晶的情況時，職明性雖能維持=難以成為高強度。Li2Si〇3結晶之所占比率係以脚。宜，廳以下較佳，特別理想㈣實質上不存在。’ 本發明之結晶化玻璃，其刚说。結晶等之 U2〇 A1203-S咕系之結晶所占比率係以戰以下為宜。作為 LhO-AhCVSK^系結晶雖有葉長石、轉石、鐘霞石等， S已析出了其等之結晶時’則透明性與高強度之至少有一方會難以達成。前述比率係以1G%以下較佳，且實質上不存在係特_想。本發明之結晶化玻璃典型的係不析出 LiAlSi4〇i〇結晶。曰曰所占比率係、以如下方式來測定。將結晶化玻璃研磨後，混合了内部炉唯BACKGROUND OF THE INVENTION In recent years, in the case of mobile devices (portable information devices) such as mobile phones and PDAs, the use of cover glass (protective glass) has been increasing in order to protect the display and improve the appearance. On the other hand, there is a need for lightweight and thinner for the mobile machine as described. Therefore, the cover glass used for display protection is also required to be thinned. However, as the thickness of the cover glass becomes thinner, the strength thereof is lowered, and the cover glass itself may be broken due to dropping during use or when it is carried, and the display device may not be able to function. The problem of the original role. In order to solve the above problems, there is a need to improve the strength of the cover glass, and a method known as a method for forming a compressive stress layer on the surface of the glass. A representative method for forming a compressive stress layer on the surface of the glass is: an air-cooling strengthening method (physical strengthening method), wherein the surface of the glass plate heated to the vicinity of the softening point is rapidly cooled by air cooling or the like; Chemical strong practice, 201245073 The exchange of alkali metal ions (typically Li ions, Na ions) with a small ionic radius on the surface of the glass plate by ion exchange at the temperature of the glass secret point is a large ion. Alkali ions (typically kappa ions). As mentioned earlier, the thickness of the cover glass has a thinning requirement. However, when the air-cooling strengthening method is applied to a thin glass plate, it is difficult to form a compressive stress layer due to a difference in temperature between the surface and the inside, and the desired high strength property cannot be obtained. Therefore, a cover glass reinforced by the latter chemical strengthening method is usually used (see Patent Document 1). Although the chemically strengthened glass can be applied to a thin glass such as a cover glass for a display device, a cover glass of a small display device such as a mobile phone or a PDA is required to be as thin and high-strength as possible because of its weight reduction. However, for example, even if the thickness of the ordinary glass sheet of 1 mm or the like is accumulated due to the tensile stress inside, there is a case where the crack is broken at the time of cracking. Therefore, in order to cover the glass of a small display device such as a mobile phone or a mobile data terminal (pda), there is no problem as described above, and the strength of the chemically strengthened glass is limited (see Patent Document 2). Patent Document 2 proposes that the tensile stress is set to a specific value or less depending on the thickness of the glass. In Patent Document 2, since the tensile stress is proportional to the compressive stress CS of the glass surface, and the depth of the compressive stress layer is DOL, and the thickness of the glass is t, the tensile stress and (DOL_l · t-2) ) is inversely proportional, so it can be said that the direction of its proposal is to reduce CS or DOL. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 201245073 Patent Document 1: U.S. Patent Application Publication No. 2008/0286548, Patent Document 2: U.S. Patent Application Publication No. 2010/0035038, the disclosure of which is hereby incorporated by reference. The problem is that it is a matter of conventional knowledge to increase the cs of the chemically strengthened glass, and a formula showing the relationship between the tensile stress and CS, DOL, and t is also known. The present invention is for the purpose of providing a cover glass for a display device, and the cover glass of the display device utilizes a crystallized glass which is capable of solving the above problems of chemically strengthened glass and which is high in strength and transparent. Means for Solving the Problem The present invention provides a crystallized glass for a display device (hereinafter sometimes referred to as "crystallized glass A"), which is represented by mol% based on the following oxides, and contains : 61.5 to 72% of SiO 2 , 1 to 5.5% of Al 2 〇 3, 0.5 to 3% of P 2 〇 5, 0.5 to 3% of Zr02, 20 to 35% of Li 20 and 0 to 5% of K20, and P2 〇 The total content of 5 and ZrO 2 was obtained by crystallizing glass of 1.7 to 5% of P205 + Zr02. Further, there is provided a crystallized glass for a display device having a light transmittance of 4004()() ηηι of more than 10% at a wavelength of 400 nm when the thickness is 1 mm; and a molar percentage based on the following oxides Said: containing: 61.5 to 72% of SiO 2 , 1 to 5.5% of Al 2 〇 3, 0.5 to 3% of P205, 0.5 to 3% of Zr02, 20 to 35% of Li 20 and 0 to 5% of K 2 ◦, and P205 + Zr02 is obtained by crystallizing 1.7 to 5% of glass. 201245073 Further, the invention provides the crystallized glass for the display device, wherein the SiO2 of the glass is 62 to 68%, the Al2〇3 is 1 to 3%, the P205 is 0.5 to 2%, the Zr02 is 0.5 to 2%, and the Li2〇 is 25. ~30%, K2O is 0~3.5°/. , and P205 + Zr02 is 1.7~3.50/〇. The crystallized glass for the display device described above is provided, wherein the κ 2 of the glass is 0 to 2.5%. The crystallized glass for a display device described above is provided, wherein the glass is 20% or more. Further, the crystallized glass for a display device is provided, wherein the glass has a P2〇5 + ZrO 2 system of 2°/. the above. Further, a glass composition is obtained which is formed into a crystallized glass for a display device having a T400nm of more than 10% by crystallization; and is represented by mol% of the following oxides, and contains: 61.5 to 72%. 8丨02, 1~5.5% of Al2〇3, 0.5~3% of P2〇5, 〇.5~3% of Zr02, 20~35% of Li20 and 0~5% of K20, and P205 + Zr02 is 1.7 to 5%, and no coloring ingredients. Further, the glass composition containing no coloring component (hereinafter referred to as "parent glass 1") is provided, wherein SiO 2 is 62 to 68%, Al 2 〇 3 is 1 to 3%, and P205 is 0.5 to 2%. Zr02 is 0.5 to 2%, Li20 is 25 to 30%, K20 is 0 to 3.5%, and P205 + Zr02 is 1.7 to 3.5%. Further, the above-mentioned glass composition containing no coloring component is provided, wherein K20 is 1% or more. Further, the above-mentioned glass composition containing no coloring component is provided, wherein Ρ2〇5 + ZrO 2 is 2% or more. 201245073 Further, a glass composition is formed by crystallizing a crystallized glass for a display device, and the glass composition containing no coloring component contains a coloring component (hereinafter, sometimes "mother glass" 2" called it). Further, the crystallized glass for a display device is obtained by crystallizing the glass composition containing no coloring component or the glass composition containing the coloring component in the glass composition containing no coloring component. Further, the crystallized glass for a display device described above is provided, and a Li 2 Si 2 〇 5 crystal is precipitated. Further, the crystallized glass for a display device described above is provided, wherein the fracture toughness value Kc is 1.2 MPa·m丨/2 or more. Further, the crystallized glass for a display device described above is provided, wherein T400nm is more than 10%. Further, there is provided a crystallized glass for a display device (hereinafter referred to as "crystallized glass B") in which Li2Si2〇5 crystals are precipitated, and a fracture toughness value Kc is 1.2 MPa or more, and τ gamma (10) is more than 1 〇%. Further, the crystallized glass for a display device having a light transmittance of more than 1% by wavelength at a wavelength of 400 to 800 nm at a thickness of 1 mm is provided. Further, a display device is provided which is provided with a cover glass made of crystallized glass for the display device. Further, a mobile device is provided with the above display device. Moreover, a method for producing crystallized glass is provided, which is characterized in that it has the following composition and the second peak temperature of crystallization is more than 755. The glass transition point of the glass of bismuth is Tg, and is maintained at (Tg + | _4 〇 ° C) ~ (Tg + 100. 〇 at a temperature for more than 1 hour, and then at (T2 - 7 〇. 〇 ~ ting 2_5. 〇 The crystallized one is maintained at a temperature of 201245073 for 1 hour or more; the glass is represented by the following oxides: % Mo2%, 61.5 to 72% of SiO 2 , 1 to 5.5% of Al 2 〇 3, 〇 _ 5 〜 3% of P2〇5, 0.5~3% of Zr02, 20~35% of 〇2〇 and 0~5% of K2〇, and p2〇5 + Zr02 is 1~5%. Also provide a crystallized glass The manufacturing method is characterized in that the glass transition point of the glass containing the following composition is Tg and is maintained at a temperature of (Tg + 40 ° C) to (Tg + 80 ° C) for 1 hour or more, after which And crystallization is carried out at a temperature of 750 to 820 ° C for 1 hour or more; the glass is represented by the following oxides as a molar %, and contains 62 to 68% of Si 2 , 1 to 3% of Al 2 〇3, 0.5~2% of P2〇5, 〇.5~2% of Zr02, 25~30% of Li20 and 0~2.5% of K20, and p2〇5 + Zr02 is 1.5~3.5%. The method for producing the aforementioned crystallized glass, wherein the Tg system is small 520 ° C. Effect of the Invention According to the present invention, it is possible to provide a crystallized glass having high strength and transparency, and the crystallized glass can avoid the disadvantage of the so-called explosive fragmentation of the chemically strengthened glass. When the chemically strengthened glass is used for a particularly thin cover glass having a thickness of 〇.4 mm or less, the internal tensile stress becomes too high, and the surface compressive stress cannot be increased, or the surface compression layer cannot be deepened to a predetermined depth. In view of the fact that the crystallized glass can be used for the cover glass of the display device according to the present invention, the high strength can be maintained even if the cover glass is thinned. 201245073 Brief description of the drawing Fig. 1 is a later example 1 For example, the first peak temperature T of crystallization and the second peak temperature of crystallization are shown in Fig. 2; the horizontal axis is temperature (unit: °C), and the vertical axis is the output power of the differential thermal analyzer. (Unit: μν) 〇 In addition, the Tg-based glass transfer point in the figure, the nucleation nucleation heat treatment temperature, and the ©c is the crystal growth heat treatment temperature, and the approximate temperature is individually determined. In the second embodiment, the crystallized glass plate is placed on the crystallized glass plate of Example 1 to be described later, and the spherical stainless steel having a mass of 28 g is dropped from a height of 50 cm. Photograph of the surface. Fig. 3 is a photograph of the surface of the chemically strengthened glass plate when the spherical stainless steel having a mass of 28 g is placed on the chemically strengthened glass plate and the spherical stainless steel having a mass of 28 g is dropped from a height of 3 cm; The chemically strengthened glass plate is characterized by the percentage of moles expressed as SiO 2 : 73%, A1203: 7%, MgO: 6%, and Na20: 14% of the glass plate subjected to ion exchange. [Embodiment] The crystallized glass for a display device of the present invention (hereinafter referred to as "crystallized glass of the present invention") is preferably one in which crystals of Li2Si205 are precipitated, and the crystallized glass B is used. The middle system precipitates Li2Si2〇5 crystal. If it is a non-precipitated LijbO5 crystal, it is difficult to be high-strength and transparent. Further, in the case of crystallized glass in which Li2Si205 crystals are precipitated, the main crystal phase is preferably Li2Si2?5 crystal. The "main crystal phase" refers to the crystal when only one type of crystal is precipitated. If the crystal of the number of 201245073 is precipitated, it means that the ratio of crystals is too high. '0曰曰相〇通^^, the presence or absence of crystallization is determined by X-ray powder diffraction method, and the ratio of gentry is expressed by volume ratio. Further, in the crystallized glass of the present invention, it is preferable that the ratio of the ratio of the ratio of the ratio of the Li 2si 2 〇 5 crystal is 50% or more. LiJhO5 crystals are used to maintain crystal clarity and have high strength at the same time. The above ratio is preferably more than 6% by weight and is more than 70%. t is also the same as the crystal of the Li20-Si02 system. Although the crystal is called (4), if the crystal of Li2Si〇3 is precipitated, the workability can be maintained = it is difficult to become high strength. The proportion of Li2Si〇3 crystals is based on the feet. It is better to use the following, especially ideal (4) does not exist. The crystallized glass of the present invention has just been said. The ratio of crystals such as crystallization of U2〇 A1203-S lanthanide is preferably below war. When the crystals of the LhO-AhCVSK(TM) system are feldspar, turnstone, and hoaxite, and S has precipitated crystals, etc., at least one of transparency and high strength is difficult to achieve. The above ratio is preferably 1 G% or less, and substantially no such thing is present. The crystallized glass of the present invention typically does not precipitate LiAlSi4〇i〇 crystals. The ratio of 曰曰 is measured in the following manner. After crystallization of the crystallized glass, the internal furnace is mixed

知準、如預定之比率的α石英後，測定X 、;末堯射將所得之X射線粉末繞射資料使用X射線粉末繞射圖心π 5分拚敕體、例如幻gAKU公司製JADE，求取各結晶相的比率而所S胃貫質上不存在係指結晶相之比率為0的情況。 201245073 本發明之結晶化玻璃，其破裂韌性值}(^係以丨2Mpa. 以上為宜，且於結晶化玻璃3中反(；係1 2MPa . mm以上。若 Kc小於1.2MPa.mi〃，财變得容㈣裂之虞。&典型的係1.25MPa · m"2以上，較佳係丨3MPa .以上更佳係 l_5MPa . m以上，特別理想的係丨6Mpa .爪丨，2以上。另一方面，Kc係以4.0以下為宜，3·〇以下較佳。*Kc超過4〇則有切割變得極為困難之虞。After knowing the predetermined ratio of α-quartz, the X-ray is measured, and the obtained X-ray powder diffraction data is obtained by using X-ray powder diffraction pattern π 5 points, such as JADE by GYG. The ratio of each crystal phase was determined, and there was no case where the ratio of the crystal phase was 0 in the stomach. 201245073 The crystallized glass of the present invention has a fracture toughness value} (^ is preferably M2Mpa. or more, and is reversed in the crystallized glass 3; (1 2 MPa. mm or more. If Kc is less than 1.2 MPa. mi〃, The wealth becomes the (four) crack. & typical is 1.25MPa · m " 2 or more, preferably 丨 3MPa. More than the above is more than l_5MPa. m or more, particularly ideal system 丨 6Mpa. Xenopus, 2 or more. On the other hand, Kc is preferably 4.0 or less, and 3 or less is preferable. *Kc exceeding 4 〇 is extremely difficult to cut.

Kc舉例而言係以如下方式測定。即，根據JIS_R16〇7利用IF法’在乾燥氮氣體環境下使用韋氏硬度計以 2kgf=19.6N之負載壓入韋氏壓頭後，測定裂痕長度及壓痕長度，並自壓痕長度求得韋氏硬度，且由下式算出Kc。Kc is exemplified by the following method. That is, according to JIS_R16〇7, the length of the crack and the length of the indentation were measured by using the IF method 'in a dry nitrogen atmosphere using a Vickers hardness tester under a load of 2 kgf = 19.6 N, and the length of the crack was measured, and the length of the indentation was determined. Devil's hardness, and Kc is calculated from the following formula.

Kc = 0.018 X (Ε/Ην),/2 χ (P/C3/2) 此處E係楊氏模數(GPa) ’ Hv係韋氏硬度(GPa)，P係押入負載(N)，C則係裂痕長度之平均的一半。本發明之結晶化玻璃’其波長400nm的光在相當於厚度為1mm時之穿透率丁4()()11111係以超過1〇%為宜，而於結晶化玻璃B中係超過10%。若丁40〇11111為10%以下，因散射等會造成透射光變少，而使當作顯示裝置之覆蓋玻璃等來使用時難以看到影像。T_nm較佳係30%以上，更佳係50%以上，特別理想的係60%以上。另外，於本說明書中之所以將波長 400nm的光穿透率作為問題點’係因於玻璃中析出有結晶粒子之透明結晶化玻璃來說，通常其於400nm之穿透率係在 400〜800nm之可見範圍中穿透率是最低的，因此推斷其最適用於透明性之評估。 201245073 本發明之結晶化玻璃，其於厚度為1 mm時之波長400〜 800nm的光穿透率係以超過10%為宜，較佳係3〇%以上，更佳係50%以上，特別理想的則係60%以上。本發明之結晶化玻璃，其於50〜350°C中之平均線膨脹係數α係以4〇xlO-7/°C以上為宜。若α小於4〇x10_7/°C，則與包含機框之顯示器裝置構件之熱膨脹係數差大，會對顯示裝置誘發應力’而有引起變形或顯示不均勻之可能性，故宜為5〇xlO_7/°C以上。又’ α係以80><10_7/。(3以下為宜。若α 超過8〇xlO_7/°C，則與作為顯示裝置基板使用之玻璃基板之熱膨脹係數差大，而同樣會有引起變形或顯示不均勻之可能性，故宜為7〇xlO_7/°C以下。本發明之結晶化玻璃，其揚氏模數E係以lOOGPa以上為宜。若E小於lOOGPa ’則破裂韌性會變小，而有強度降低之可能性’故較佳係105GPa以上。又E係以120GPa以下為宜。若E超過120GPa，則脆度會變大而容易發生裂痕，因而有加傷強度變低之可能性，故較佳係ll〇GPa以下。本發明之結晶化玻璃，其韋氏硬度Hv係以7GPa以上為宜。若Hv小於7GPa，則有因與物體之接觸而容易產生傷痕之可能性，故較佳係7.5GPa以上。又Hv係以lOGPa以下為宜。若Hv超過lOGPa，則脆度會變大而容易發生裂痕，因而有加傷強度變低之可能性，故較佳係9GPa以下。其次，針對藉由結晶化而能獲得結晶化玻璃A的玻璃 (以下，有以「本發明之玻璃」稱之的情況，且將如所述之應結晶化之玻璃以「母玻璃」稱之）、母玻璃1及母玻璃2之 12 201245073 組成’使用莫耳百分率表示之含量來予以說明。本發明之玻璃係亦可用於本發明之結晶化玻璃之製造方法的玻璃。其玻璃轉移點Tg典型的係小於520°c，例如400〜510°c。Kc = 0.018 X (Ε/Ην), /2 χ (P/C3/2) where E is the Young's modulus (GPa) 'Hv is the Vickers hardness (GPa), P is the load (N), C It is half the average of the length of the crack. The crystallized glass of the present invention has a transmittance of light having a wavelength of 400 nm at a thickness of 1 mm, preferably 4 () () 11111 is more than 1%, and more than 10% is in the crystallized glass B. . When the temperature of the 〇40〇11111 is 10% or less, the amount of transmitted light is reduced due to scattering or the like, and it is difficult to see the image when used as a cover glass or the like of the display device. The T_nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 60% or more. In addition, in the present specification, the light transmittance of a wavelength of 400 nm is regarded as a problem because the transparent crystallized glass in which crystal particles are precipitated in the glass generally has a transmittance at 400 nm of 400 to 800 nm. The transmittance in the visible range is the lowest, so it is inferred that it is most suitable for the evaluation of transparency. 201245073 The crystallized glass of the present invention preferably has a light transmittance of more than 10% at a wavelength of 400 to 800 nm at a thickness of 1 mm, preferably more than 3% by weight, more preferably 50% or more, and particularly preferably It is more than 60%. In the crystallized glass of the present invention, the average linear expansion coefficient α at 50 to 350 ° C is preferably 4 〇 x 10 7 / ° C or more. If α is less than 4〇x10_7/°C, the difference in thermal expansion coefficient of the display device component including the frame is large, and the stress is induced on the display device, and there is a possibility of deformation or display unevenness, so it is preferably 5〇xlO_7. / °C or more. Further, the α system is 80 < 10_7/. (3 or less is preferable. If α exceeds 8〇xlO_7/°C, the difference in thermal expansion coefficient between the glass substrate used as the substrate of the display device is large, and the possibility of deformation or display unevenness is also caused, so it is preferable that 7 〇xlO_7/°C or less. The crystallized glass of the present invention preferably has a Young's modulus E of 100 GPa or more. If E is less than 100 GPa', the fracture toughness becomes small, and there is a possibility that the strength is lowered. It is preferably 105 GPa or more, and E is preferably 120 GPa or less. If E exceeds 120 GPa, the brittleness is increased and cracks are likely to occur, so that the damage strength may be lowered, so that it is preferably ll 〇 GPa or less. In the crystallized glass of the invention, the Vickers hardness Hv is preferably 7 GPa or more. When Hv is less than 7 GPa, there is a possibility that a flaw is likely to occur due to contact with an object, and therefore it is preferably 7.5 GPa or more. lOGPa or less is preferable. If Hv exceeds lOGPa, the brittleness becomes large and cracks are likely to occur, so that the damage strength is low, so it is preferably 9 GPa or less. Next, crystals can be obtained by crystallization. Glass of glass A (hereinafter, there is "this" The case of the glass of the Ming Dynasty, and the glass which should be crystallized as described above is referred to as "mother glass"), the mother glass 1 and the parent glass 2 12 201245073 are composed of the content expressed by the percentage of moles. The glass system of the present invention can also be used for the glass of the method for producing crystallized glass of the present invention, and the glass transition point Tg is typically less than 520 ° C, for example, 400 to 510 ° C.

Si〇2係61.5%以上。Si〇2係構成玻璃骨架之成分，且係作為本發明之結晶化玻璃之主要結晶相而理想的Li2Si2〇5 結晶之構成成分。若Si02小於61.5%則玻璃的黏性會降低，而使析出結晶成為微細之結晶變得困難，或是，變得易於析出LbSisO5結晶以外的結晶，而有高強度與透明性兩者並存變得困難之虞，故宜為62%以上，較佳係63%以上，特別理想的係64%以上，典型的係64.5%以上。The Si〇2 system is 61.5% or more. Si〇2 is a component of the glass skeleton and is a constituent component of the Li2Si2〇5 crystal which is a main crystal phase of the crystallized glass of the present invention. When the SiO 2 is less than 61.5%, the viscosity of the glass is lowered, and it becomes difficult to precipitate crystals into fine crystals, or it is easy to precipitate crystals other than LbSisO5 crystals, and both high strength and transparency become coexisting. After the difficulty, it is preferably 62% or more, preferably 63% or more, particularly preferably 64% or more, and the typical system is 64.5% or more.

Si〇2係72%以下。若si〇2超過72%則玻璃的黏性會增大使炼融性顯著地降低，並變得易於析出石英等之&〇2結晶’而有高強度與透明性兩者並存變得困難之虞，故宜為 70〇/〇以下，更佳係68%以下’特別理想的係67%以下，典型的係66.5%以下。The Si〇2 system is 72% or less. When si〇2 exceeds 72%, the viscosity of the glass increases, the smelting property is remarkably lowered, and it becomes easy to precipitate the crystals of quartz and the like, and it is difficult to coexist with both high strength and transparency.虞, it is preferably 70 〇 / 〇 or less, more preferably 68% or less 'Specially ideal is 67% or less, and the typical system is 66.5% or less.

Al2〇3係1 %以上，且係抑制玻璃之相分離並防止因散射所造成之透明性惡化的成分若A12 〇 3小於1 〇/。則有透明性降低之虞，故宜為1.5%以上。八12〇3係5.5%以下，若八12〇3超過5.5%會變得容易析出大量的LhO-AhOs-SiO2系結晶’而有透明性與高強度兩者並存變得困難之虞，故宜為5%以下，較佳係4%以下，典型的係3%以下。 P2〇5係0.5%以上，且係作為成核劑而有助益之成分。若1>2〇5小於〇.5%則析出結晶會難以獲得微細的結晶，而有 13 201245073 透明性降低之虞，故宜為1%以上。 P2〇5係3%以下。若ha超過3%，則結晶速率會降低，而有強度降底之虞，故宜為2_5°/〇以下，典型的係2%以下。The Al2〇3 system is 1% or more, and is a component which suppresses phase separation of the glass and prevents deterioration of transparency due to scattering. If A12 〇 3 is less than 1 〇 /. If there is a decrease in transparency, it should be 1.5% or more.八12〇3 is 5.5% or less. If 八12〇3 exceeds 5.5%, it will become easy to precipitate a large amount of LhO-AhOs-SiO2 crystals, and it is difficult to coexist with transparency and high strength. It is 5% or less, preferably 4% or less, and typically 3% or less. P2〇5 is more than 0.5% and is a useful ingredient as a nucleating agent. When 1 > 2 〇 5 is less than 〇. 5%, it is difficult to obtain fine crystals by precipitation of crystals, and it is preferable that the transparency of 13 201245073 is lowered, so it is preferably 1% or more. P2〇5 is 3% or less. If ha exceeds 3%, the crystallization rate will decrease, and if the strength is lowered, it is preferably 2_5°/〇 or less, and the typical system is 2% or less.

Zr〇2係0.5%以上。Zr〇2係以作為成核劑而有助益之成分’若小於0.5。/。則會變得難獲得微細的結晶，有透明性降低之虞。Zr〇2係宜為1%以上。Zr〇2 is 0.5% or more. Zr〇2 is a component which is useful as a nucleating agent' if it is less than 0.5. /. It becomes difficult to obtain fine crystals and there is a decrease in transparency. The Zr〇2 system is preferably 1% or more.

Zr〇2係以3%以下為宜。若Zr〇2超過3%，則會變得容易析出Zr〇2結晶，而有透明性惡化之虞，故宜為2.5%以下，較佳係2%以下，典型的係18%以下。 P205及Zr02之含量合計p2〇5 + Zr〇2係丨7%以上。雖然 P2〇5及Zr〇2皆係以作為成核劑而有助益之成分，但藉由使兩者共存’可易於獲得更微細的結晶來作為析出結晶。若其合計小於1.7%，則結晶速率會降低而難獲得所需之強度’或者是若欲升高溫度來提高結晶速率時會有無法獲得透明性之虞，故宜為2%以上。 P205 + Zr02係5%以下。若P205 + Zr02超過5%則均勻性會惡化，而有透明性惡化之虞，故宜為4.5%以下，更佳係 4%以下，典型的係3.5%以下。Zr〇2 is preferably 3% or less. When Zr 〇 2 exceeds 3%, Zr 〇 2 crystals are easily precipitated, and transparency is deteriorated. Therefore, it is preferably 2.5% or less, preferably 2% or less, and typically 18% or less. The total content of P205 and Zr02 is 7% or more in p2〇5 + Zr〇2 system. Although both P2〇5 and Zr〇2 are useful as a nucleating agent, it is easy to obtain finer crystals as precipitated crystals by coexisting both. If the total amount is less than 1.7%, the crystallization rate may be lowered to obtain the desired strength, or if the temperature is increased to increase the crystallization rate, transparency may not be obtained, so it is preferably 2% or more. P205 + Zr02 is 5% or less. If P205 + Zr02 exceeds 5%, the uniformity deteriorates and the transparency deteriorates, so it is preferably 4.5% or less, more preferably 4% or less, and typically 3.5% or less.

LhO係20%以上〇 Li2〇係作為本發明之結晶化玻璃之主要的結晶相而理想的LhSbO5結晶之構成成分，若小於 20% ’則會變得難析出LijhO5結晶，而有高強度與透明性兩者並存變得困難之虞，故宜為23%以上，特別理想的係 25%以上。LhO-based 20% or more lanthanum Li2 lanthanum is a main crystal phase of the crystallized glass of the present invention, and if the composition of the LhSbO5 crystal is preferably less than 20%, it becomes difficult to precipitate LijhO5 crystal, and has high strength and transparency. The coexistence of both sexes becomes difficult, so it is preferably 23% or more, and particularly ideally 25% or more.

LhO係35。/。以下。若ho超過35%，則玻璃的點性會降 201245073 低，使析出結晶成為微細的結晶變得困難，而有透明性空、化之虞，故宜為30%以下，典型的係28.5%以下。 K2〇係抑制白石夕石等之Si〇2結晶的析出，易於使高強产與透明性兩者並存的成分’雖非必要但為添加亦可之任擇的成分。添加K：2〇時’係以0.5%以上為宜，較佳係1%以上。而當欲使之難失透明並提升玻璃之成形性等的時候Κ2〇係以2%以上為宜，2.5%以上較佳。 Κβ即便在含有的情況下其含量亦係5%以下。若超過 5%則會變得難析出LbSbO5結晶，有高強度與透明性之並存變得困難之虞。較佳係4°/❶以下’典型的係3 5%以下。欲使強度提高等之情況時K：2〇則係以3%以下為宜，典型的係 2.5%以下。LhO is 35. /. the following. When ho exceeds 35%, the dot properties of the glass are lowered to 201245073, and it is difficult to form precipitated crystals into fine crystals, and it is preferable to have a transparency of vacancies. Therefore, it is preferably 30% or less, and a typical system is 28.5% or less. . The K2 lanthanum is a component which suppresses precipitation of Si〇2 crystals such as Shiraishi, and which is easy to cause both high-strength production and transparency to be added, although it is not necessary. When K: 2 添加 is added, the amount is preferably 0.5% or more, preferably 1% or more. When it is desired to make it difficult to be transparent and to improve the formability of the glass, etc., it is preferable to use 2% or more, and 2.5% or more is preferable. Κβ is contained in an amount of 5% or less even in the case of inclusion. When it exceeds 5%, it becomes difficult to precipitate LbSbO5 crystals, and it becomes difficult to coexist with high strength and transparency. It is preferably 4 ° / ❶ or less 'typically less than 3 5%. If the strength is to be increased, etc., K:2〇 is preferably 3% or less, and typical is 2.5% or less.

Si與Li之原子數比Si〇2/(Li2〇/2)係以ι·〇以上為宜。若該比小於1.0，則於已析出作為本發明之結晶化玻璃之主要的結晶相而理想的Li2Si2〇5結晶時之殘存玻璃相中，構成玻璃骨架之成分的Si〇2比率會變少’而有無法獲得高強度之虞，故宜為1.1以上，較佳係1.2以上。另一方面，宜為18 以下，較佳係1.6以下。若該比超過1 8，則結晶所占比率會降低，且強度會降低。The atomic ratio of Si to Li is preferably equal to or higher than Si〇2/(Li2〇/2). When the ratio is less than 1.0, the Si〇2 ratio of the constituents of the glass skeleton is reduced in the residual glass phase in the case where the Li2Si2〇5 crystal which is the main crystal phase of the crystallized glass of the present invention is precipitated. However, it is preferable to have a high strength, and therefore it is preferably 1.1 or more, preferably 1.2 or more. On the other hand, it is preferably 18 or less, preferably 1.6 or less. If the ratio exceeds 18, the ratio of crystallization will decrease and the strength will decrease.

Si與Li之原子數比與ρζ〇5 + Zr〇2的積（p2〇5 + Zr〇2)xSi〇2/(Li2〇/2)係以2.8〜3_8°/〇為宜。若該積小於2.8% 則會因結晶之析出不充分而有無法獲得高強度之虞，較佳係3.0以上，更佳係3.1以上，而若超過3 8%則玻璃會相分離而有變得無法獲得高穿透之虞，較佳係3.6%以下。 15 201245073 作為本發明之玻璃之典型的形態，可舉8丨〇2為62〜 68%、Al2〇3為 1 〜3%、p2〇5為〇.5〜2%、Zr02為 0.5〜2〇/0、 Li20為 25 〜30%、K2〇為〇〜2.5%，且卩2〇5 + 心〇2為 ι·7〜 3.5%者為例。本發明之玻璃雖本質上係由上述成分所構成，但在無損本發明之目的之範圍内亦可含有其他成分。如所述情況時含有所述成分之含量合計係宜為5。/。以下，較佳係3%以下’典型的係小於1〇/〇。舉例而言，當含有In2〇3、Ga2〇3、Sn〇2及BaO的時候係個別以1%以下、1%以下、2%以下及1%以下為宜。又當含有La2〇3時，若非為0.4%以下則會有損及本發明之目的情況。母玻璃1雖本質上係由前述成分所構成，但在無損本發明之目的之範圍内亦可含有其他以外之成分且非著色成分者。如所述情況時含有所述成分之含量合計係宜為5%以下，較佳係3%以下，典型的係小於1%。本發明中所謂「著色成分」係指作為將通常玻璃著色之成分而為人所知悉者，且係至此為止所列舉之成分以外者。舉例而言如&、州、〇 (^'(^'^^、^^、々、如及^等之過渡金屬，The product of the atomic ratio of Si to Li and ρζ〇5 + Zr〇2 (p2〇5 + Zr〇2) xSi〇2/(Li2〇/2) is preferably 2.8 to 3_8°/〇. If the product is less than 2.8%, the precipitation of the crystal may be insufficient, and high strength may not be obtained, and it is preferably 3.0 or more, more preferably 3.1 or more, and if it exceeds 38%, the glass will be phase-separated and become It is impossible to obtain a high penetration, preferably 3.6% or less. 15 201245073 As a typical form of the glass of the present invention, 8丨〇2 is 62 to 68%, Al2〇3 is 1 to 3%, p2〇5 is 〇.5 to 2%, and Zr02 is 0.5 to 2〇. /0, Li20 is 25 to 30%, K2 is 〇~2.5%, and 卩2〇5 + 〇2 is ι·7~3.5% as an example. The glass of the present invention is essentially composed of the above components, but may contain other components within the scope of the object of the present invention. The content of the component contained in the case as described above is preferably 5. /. Hereinafter, it is preferably 3% or less, and the typical system is less than 1 〇/〇. For example, when In2〇3, Ga2〇3, Sn〇2, and BaO are contained, it is preferably 1% or less, 1% or less, 2% or less, or 1% or less. Further, when La2?3 is contained, if it is not more than 0.4%, the object of the present invention may be impaired. The mother glass 1 is essentially composed of the above-mentioned components, but may contain other components and non-colored components insofar as it does not impair the purpose of the present invention. In the case described above, the total content of the components is preferably 5% or less, preferably 3% or less, and typically less than 1%. In the present invention, the term "colored component" means a component which is known as a component which colors a normal glass, and is a component other than the components enumerated hereto. For example, such as &, state, 〇 (^' (^'^^, ^^, 々, such as ^ and other transition metals,

Ce Nd Sm'Er'Tm及Pr等之稀土元素，SeACd等，或者係可舉其等之氧化物為例。典型的係選自於由Fe、Ni、Cr、 Co Cu Τι ' v ' Mn、M〇、Ce、灿、如、玢、Tm、pr、 g Au Pt、Se及Cd所構成群組中^種以上的金屬或者係選自於該群組之1種以上之金屬的氧化物。 16 201245073 母玻璃2本質上係由前述成分所構成，且係使母玻璃1 含有著色成分者。接著，將舉例就製造本發明之結晶化玻璃之方法予以說明。首先，調配玻璃原料以使成為預定之組成，並於均勻地混合後，以熔融爐來熔融玻璃原料。澄清劑係使用S03、 Sn02、Cl等眾所周知之澄清劑之至少1種以上。熔融溫度舉例而言係1200〜1780°C，欲控制設備之負荷等時則係以 1250〜1650°C為宜，而欲提高生產性等時則係以500〜 1780°C為宜，較佳係1550〜1750°C，並於該等溫度下進行熔融例如2〜24小時。另外，於熔融玻璃時亦可一邊予以減壓一邊同時進行消泡。之後進行成形、緩冷卻來作為母玻璃。另外，該母玻璃係本發明之玻璃。藉由將所得之母玻璃予以熱處理（結晶化）即獲得結晶化玻螭。熱處理係以令為晶體成核與晶體生長之2階段為宜°本發明之結晶化玻璃之製造方法係如所述者。用以晶體成核之熱處理，係令其玻璃之玻璃轉移點為 Tg ’並以在(Tg + 4(TC)〜（Tg+100°C)之溫度範圍内來進行為宜。若超過(Tg+100t)之溫度，因產生晶體生長之故，結晶會粗大化、且變得不均勻等而有造成透明性惡化之虞’典型的係(Tg+80°C)以下。若溫度低於(Tg + 4〇°c)則晶體成核會變得不充分’而有透明性與強度之兩者並存變得困難之虞。用以晶體成核之熱處理時間係以1小時以上為宜。若小 17 201245073 於1小時，則晶體成核會變得不充分，而有透明性與強度之兩者並存變得困難之虞。較佳係2小時以上或者係3小時以上。又，用以晶體成核之熱處理時間係以24小時以下為宜。若超過24小時，則晶體生長會變得不均勻等而造成有透明性惡化之虞。較佳係12小時以下。又，用以晶體成核之熱處理，係前述理想之用以晶體成核之熱處理，其係令將其玻璃經以l〇°C/分做測定時之微差熱分析之結晶化第1尖峰溫度為T,，且以（丁丨一50°C)以下之溫度下進行者較佳。本發明之結晶化玻璃，於結晶化第1 尖峰溫度所析出之結晶為Li2Si03之可能性高，且若於超過 (Τ, — 50°C)之溫度下進行熱處理的話，則會析出多量 Li2Si03 ,而有使透明性與強度之至少一方受損之可能性。用以晶體生長之熱處理，係令將其玻璃經以l〇°C/分做測定時之微差熱分析之結晶化第2尖峰溫度為丁2 5且丁2為超過755°C之情況時，以於(T2 —70°C)〜（T2-5°C)之溫度範圍内來進行為宜。若在低於(T2-70°C)之溫度下，則結晶速率會變低，有難獲得高強度之虞。又，用以晶體生長之熱處理，係以（T2 — 5°C)以下為宜。若超過(T2—5°C)則有難以獲得透明性之虞。且此時由抑制Li2Si03之析出的觀點而言， T2係宜為790°C以上，較佳係820°C以上。又，用以晶體生長之熱處理，係以於750°C〜850°C之溫度範圍下來進行為宜。若溫度低於750°C，則會析出多量 Li2Si03而有使透明性與強度之至少一方受損之可能性，較佳係770°C以上。若溫度超過850°C則結晶尺寸會變大而有 18 201245073 透明性受損之虞’較佳係830°C以下，更佳係820°C以下。用以晶體生長之熱處理時間係以1小時以上為宜。若熱處理時間少於1小時，則結晶速率會變低，而有難獲得高強度之虞，較佳係丨·5小時以上。又，用以晶體生長之熱處理時間係以24小時以下為宜。若熱處理時間超過24小時，則有變得難以獲得透明性之虞，故較佳係12小時以下，特別理想的係6小時以下。玻璃之微差熱分析之結晶化第1尖峰溫度乃及結晶化第 2尖峰溫度T2係如下述方式測定。即，研磨本發明之結晶化玻璃之母玻璃’並使用時子僅挑出粒徑可進入44μπι與53(im 之間者，並使用微差熱分析儀以升溫速度1〇。〇/分來做測定。實施例以使成為表1〜4之例1〜23、28〜39之自Si02起至 La2〇3或ΚζΟ為止的攔位中以莫耳％表示所示之組成的方式，適當地選擇氧化物、氫氧化物、碳酸鹽及硫酸鹽等一般所使用之玻璃原料，並將之予以稱量及混合以使成為 300g作為玻璃。接著，將之放入白金製坩鍋中，並投入於 1600°C之電阻加熱式電爐中，且經3小時熔融、消泡及均質化後將之倒入模具材中，並於自玻璃轉移點高3〇。〇左右的/皿度下保持1小時後，以每分鐘H的冷卻速度冷卻至室 ®即獲得4等例之玻璃^另外，表中之「p+Zr」係將 + Zr〇2予以簡記者。乂如下方式測定了該等玻璃之玻璃轉移點Tg(單位： I)、結晶化^尖峰溫度1 (單位：。〇及結晶化第2尖岭溫 201245073 度I(單位：°C)»結果示於表1〜4之該當欄位中。另外，例 10、21及22之Tg係透過計算所求得的值。Examples of rare earth elements such as Ce Nd Sm'Er'Tm and Pr, SeACd, etc., or oxides thereof can be exemplified. Typically, it is selected from the group consisting of Fe, Ni, Cr, Co Cu Τ ι ' v ' Mn, M 〇, Ce, 灿, Ru, 玢, Tm, pr, g Au Pt, Se, and Cd. The above metal is selected from the oxides of one or more metals of the group. 16 201245073 The mother glass 2 is essentially composed of the above-mentioned components, and the mother glass 1 contains a coloring component. Next, a method of producing the crystallized glass of the present invention will be described by way of example. First, the glass raw material is blended so as to have a predetermined composition, and after uniformly mixing, the glass raw material is melted in a melting furnace. As the clarifying agent, at least one of a well-known clarifying agent such as S03, Sn02 or Cl is used. The melting temperature is, for example, 1200 to 1780 ° C, and it is preferred to control the load of the equipment, such as 1250 to 1650 ° C, and to improve the productivity, etc., preferably 500 to 1780 ° C, preferably. It is 1550 to 1750 ° C and is melted at these temperatures, for example, for 2 to 24 hours. Further, in the case of melting the glass, defoaming can be simultaneously performed while reducing the pressure. Thereafter, molding is carried out, and cooling is carried out as a mother glass. Further, the mother glass is the glass of the present invention. The crystallized glass crucible is obtained by subjecting the obtained mother glass to heat treatment (crystallization). The heat treatment is preferably carried out in two stages of crystal nucleation and crystal growth. The method for producing the crystallized glass of the present invention is as described above. The heat treatment for crystal nucleation is such that the glass transition point of the glass is Tg ' and is preferably carried out in the temperature range of (Tg + 4 (TC) ~ (Tg + 100 ° C). If it exceeds (Tg At a temperature of +100 t), crystals grow coarser and become uneven, and the transparency is deteriorated. The typical system (Tg + 80 ° C) or lower. If the temperature is lower than ( Tg + 4〇°c), crystal nucleation may become insufficient, and it may be difficult to coexist both transparency and strength. The heat treatment time for crystal nucleation is preferably 1 hour or longer. Small 17 201245073 At 1 hour, crystal nucleation becomes insufficient, and it is difficult to coexist both transparency and strength. It is preferably more than 2 hours or more than 3 hours. The heat treatment time for nucleation is preferably 24 hours or less. If it exceeds 24 hours, the crystal growth becomes uneven, and the transparency is deteriorated. It is preferably 12 hours or less. Further, it is used for crystal nucleation. The heat treatment is the above-mentioned ideal heat treatment for crystal nucleation, which is to pass the glass through it. L〇°C/min The crystallization of the differential thermal analysis at the time of measurement is preferably T, and is preferably carried out at a temperature of (but not more than 50 ° C). The crystallized glass of the present invention. The crystal precipitated at the first peak temperature of crystallization is highly likely to be Li2Si03, and if heat treatment is performed at a temperature exceeding (Τ, -50 ° C), a large amount of Li2Si03 is precipitated, and transparency is improved. The possibility of damage to at least one of the strengths. The heat treatment for crystal growth is such that the second peak temperature of the crystallization of the glass is measured by differential thermal analysis at 10 ° C / min. When the temperature is more than 755 ° C, it is preferable to carry out the temperature range of (T2 - 70 ° C) to (T2 - 5 ° C). If it is lower than (T2-70 ° C) Under the crystallization rate, it is difficult to obtain high strength. Moreover, the heat treatment for crystal growth is preferably (T2 - 5 ° C) or less. If it exceeds (T2 - 5 ° C), it is difficult. In view of the fact that the precipitation of Li2Si03 is suppressed, the T2 is preferably 790 ° C or higher, preferably 820 ° C or higher. The long heat treatment is preferably carried out at a temperature ranging from 750 ° C to 850 ° C. If the temperature is lower than 750 ° C, a large amount of Li 2 Si 03 is precipitated and there is a possibility of impairing at least one of transparency and strength. Preferably, the temperature is above 770 ° C. If the temperature exceeds 850 ° C, the crystal size will become larger and there will be 18 201245073. The transparency is less than 830 ° C, more preferably 820 ° C or less. The heat treatment time for crystal growth is preferably 1 hour or more. If the heat treatment time is less than 1 hour, the crystallization rate becomes low, and it is difficult to obtain high strength, and it is preferably more than 5 hours. Further, the heat treatment time for crystal growth is preferably 24 hours or shorter. When the heat treatment time exceeds 24 hours, it becomes difficult to obtain transparency. Therefore, it is preferably 12 hours or shorter, and particularly preferably 6 hours or shorter. The first peak temperature of the crystallization of the differential thermal analysis of the glass and the second peak temperature T2 of the crystallization were measured as follows. That is, the mother glass of the crystallized glass of the present invention is ground and only the particle size can be selected to enter between 44 μm and 53 (im, and a differential thermal analyzer is used at a temperature increase rate of 1 〇. The measurement is carried out in such a manner that the composition shown in the examples 1 to 23 and 28 to 39 of Tables 1 to 4 from SiO 2 to La 2 〇 3 or ΚζΟ is expressed by mol %, suitably A glass raw material generally used such as an oxide, a hydroxide, a carbonate, or a sulfate is selected, and weighed and mixed so as to be 300 g as a glass. Then, it is placed in a white gold crucible and put into In a resistance heating electric furnace at 1600 ° C, and after 3 hours of melting, defoaming and homogenization, it is poured into the mold material, and is 3 高 high from the glass transfer point. After an hour, cool to Room® at a cooling rate of H per minute to obtain a glass of 4 cases. In addition, the "p+Zr" in the table will be a reporter for +Zr〇2. 测定The glass was measured as follows. Glass transfer point Tg (unit: I), crystallization, peak temperature 1 (unit: 〇 and crystallization The second ridge temperature 201245073 degrees I (unit: °C)»The results are shown in the fields of Tables 1 to 4. In addition, the Tg of Examples 10, 21 and 22 are calculated by the calculated values.

Tg :使用所獲得之玻璃的一部份來製作直徑5mm、長度20mm之圓柱狀試樣，並使用Bruker AXS公司製熱膨脹計 TD501 OSA以5 C/分的升溫速度來測定，而求出玻璃轉移點。 Τι、Τ'2 :研磨所獲得之玻璃的一部份，並使用篩子僅挑出粒徑能進入44μιη與53μιη之間者。將該經挑出之玻璃粉末以升溫速度1〇。〇/分，使用Bruker AXS公司製微差熱分析儀TG-DTA2020SA，讀取出結晶化第1尖峰溫度几及結晶化第2尖峰溫度丁2。另外，尖峰溫度係尖峰之最高處，即係成為最高點處的溫度。其次，將該等玻璃在表之ΘΝ所示之成核熱處理溫度（單位：°C)下保持tN所示之成核處理時間（單位：時間）後，並於0c所示之晶體生長熱處理溫度（單位：。〇下保持tc所示之晶體生長熱處理時間（單位：時間）’之後將之冷卻至室溫而製作出結晶化玻璃。熱處理時之加熱及冷卻皆係以每分鐘 10°c的速度而進行。另外，對於例31，其至^^為止係以 150C/1小時，自ΘΝ起至Θ<：為止係以15〇。〇/1小時之速度來升溫》就所獲得之結晶化玻璃，以使用CuKa線之X射線粉末繞射法來調查其析出結晶之結果為：關於例及39皆為其主要的結晶，即繞射尖峰強度最大之析出結晶係LizShO5結晶，而未見有其他之結晶的繞射尖峰。而就例 20 201245073 38而吕雖亦見到有Li2Si2〇s結晶之析出，但其主要的結晶係 LiAlSi4〇1G結晶’且未見到有其等以外之結晶的繞射尖峰。又，針對已獲得之結晶化玻璃，係以如下方式測定出破裂韌性值Kc(單位：MPa . m1，、厚度為lmm時之波長 400nm的光穿透率T4〇Qnm(單位：％)、厚度為1ιηιη時之波長 400nm〜800nm的光穿透率的最小值Tmin(單位：％)、5〇〜 350°C時之平均線膨脹係數α(單位：揚氏模數E(單位：GPa)及韋氏硬度Hv(單位：GPa)。並將結果示於表丨〜4 之§亥當棚位中。另外’例2〜5、7、9、10、14、18、19及 21〜23之Hv係透過計算而求出之值，Tg: A cylindrical sample having a diameter of 5 mm and a length of 20 mm was produced using a part of the obtained glass, and was measured at a temperature rising rate of 5 C/min using a thermal expansion meter TD501 OSA manufactured by Bruker AXS Co., Ltd. to determine a glass transition. point. Τι, Τ '2 : Grinding a part of the glass obtained, and using a sieve to pick out only the particle size can enter between 44 μm and 53 μm. The picked-out glass powder was heated at a rate of 1 Torr. 〇/min, using the differential thermal analyzer TG-DTA2020SA manufactured by Bruker AXS Co., Ltd., the first peak temperature of crystallization and the second peak temperature of crystallization were read. In addition, the peak temperature is the highest point of the peak, which is the temperature at the highest point. Next, the glass is maintained at a nucleation heat treatment temperature (unit: ° C) shown in the table, and the nucleation treatment time (unit: time) indicated by tN is maintained, and the crystal growth heat treatment temperature shown at 0c is obtained. (Unit: The crystal growth heat treatment time (unit: time) shown by tc is maintained under the armpit, and then cooled to room temperature to produce crystallized glass. Heating and cooling at the time of heat treatment are 10 ° C per minute. In addition, in Example 31, it was 150 C/1 hour, and it was 15 〇 from ΘΝ to Θ : : 升温升温升温升温升温 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Glass, the X-ray powder diffraction method using a CuKa line was used to investigate the precipitation crystallization. As a result, both of the examples and 39 are the main crystals, that is, the crystallized LizShO5 crystal having the highest diffraction peak intensity, and no The diffraction peak of other crystals. However, in the case of Example 20 201245073 38, although the precipitation of Li2Si2〇s crystals is also observed, the main crystals are LiAlSi4〇1G crystals and no crystals other than those are observed. Diffraction spikes The crystallized glass obtained was obtained by measuring the fracture toughness value Kc (unit: MPa.m1, the light transmittance of the wavelength 400 nm at a thickness of 1 mm, T4 〇 Qnm (unit: %), and the thickness of 1 ηηηη). Minimum value of light transmittance of wavelength 400 nm to 800 nm Tmin (unit: %), average linear expansion coefficient α at 5 〇 to 350 ° C (unit: Young's modulus E (unit: GPa) and Vickers hardness Hv (unit: GPa). The results are shown in Table 丨~4 §Hai Dang shed. In addition, 'H2 series of Examples 2~5, 7, 9, 10, 14, 18, 19 and 21~23 Calculated to find the value,

Kc .根據JIS-R1607 ’製作約20mmx約20mmx厚度約 1mm且上下面經鏡面加工之板狀試樣，使用韋氏硬度計以 2kgf之負載壓入韋氏壓頭’並如先前所述藉由IF法來求出破裂勒性值。 T_nm、Tmin ·製作約20mmx約20mmx厚度約1mm，且上下面經鏡面加工之板狀試樣，使用perkin Elmer公司製紫外光可見光近紅外光分光光譜儀Lambda950來取得波長400 〜800nm之分光穿透率曲線，並求出波長4〇〇nm的光之相當於1mm厚度的穿透率及該波長範圍之穿透率的最小值。另外，於任一試樣之分光穿透率曲線中，穿透率成為最小的波長皆係400nm。 α :製作直徑5mm且長度20mm之圓柱狀試樣，並使用Kc. According to JIS-R1607', a plate-like sample of about 20 mm x about 20 mm x thickness of about 1 mm and having a mirror-finished upper and lower surface was pressed, and a Weber's indenter was pressed with a load of 2 kgf using a Vickers hardness tester and as described above. The IF method is used to find the value of the fracture property. T_nm, Tmin · Approximately 20 mm x about 20 mm x thickness of about 1 mm, and the upper and lower mirror-finished plate-like samples were obtained using Perkin Elmer's ultraviolet visible near-infrared spectrophotometer Lambda 950 to obtain a spectral transmittance of 400 to 800 nm. The curve was obtained, and the transmittance corresponding to a thickness of 1 mm and the minimum value of the transmittance of the wavelength range of light having a wavelength of 4 〇〇 nm were obtained. Further, in the spectral transmittance curve of any of the samples, the wavelength at which the transmittance became the smallest was 400 nm. α : Produce a cylindrical specimen with a diameter of 5 mm and a length of 20 mm, and use

Bruker AXS公司製熱膨脹計TD5010SA，以5°C/分之升溫速度來測定，並求出50〜350°C時之平均線膨服係數。 21 201245073 以研磨以使^面里平並針對該試料利用超立製作4cmx4cm之玻璃板並予行’作成厚度為l〇mm左右之試料，波脈波法測定出揚氏模數。The TD5010SA, a thermal expansion meter manufactured by Bruker AXS, was measured at a heating rate of 5 °C/min, and the average line expansion coefficient at 50 to 350 °C was determined. 21 201245073 A sample of a thickness of about 10 mm was prepared by grinding with a glass plate of 4 cm x 4 cm for the sample, and a Young's modulus was measured by a pulse wave method.

Hv :製作約20mmx約20mmx厚度約1mm，且卜τ 上下面經鏡面加工之板狀試樣，並用韋氏硬度計以lOOgf之負栽壓人韋氏壓頭，求出韋氏硬度。例1〜23係實施例’例28〜39係比較例或參考例。例24 〜27亦係本發明之實施例，且係Kc&T_nm或Tmin為大之例，又例40係比較例。 22 201245073 [表i] 例 1 2 3 4 5 6 7 8 9 10 Si02 66.1 66.1 66.1 66.1 66.1 65.4 65.4 65.0 65.3 65.3 Al2〇3 1.9 1.9 1.9 1.9 1.9 2.5 2.5 4.7 2.5 2.5 P2O5 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 Zr02 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 hi2〇 27.6 27.6 27.6 27.6 27.6 27.6 27.6 27.6 27.6 27.5 K2〇 1.8 1.8 1.8 1.8 1.8 1.8 1.8 0 1.8 1.8 ΙΠ2〇3 0 0 0 0 0 0 0 0 0 0.2 La2〇3 0 0 0 0 0 0 0 0 0.2 0 P + Zr 2.6 2.6 2.6 2.6 2.6 2.7 2.7 2.7 2.6 2.6 "Tg 475 475 475 475 475 485 485 492 479 477 Ti 628 628 628 628 628 641 641 648 T2 847 847 847 847 847 853 853 728 Θν 537 540 537 540 495 537 536 588 606 588 tN 4 4 2 4 10 4 4 4 4 4 0C 800 790 830 790 847 800 790 800 800 800 tc 4 4 2 6 10 4 4 4 4 4 Kc 1.38 1.28 1.51 1.27 1.70 1.44 1.32 1.27 1.47 1.29 T400nm 61 61 25 60 15 63 62 33 39 48 Tmin 61 61 25 60 15 63 62 33 39 48 A 67 66 66 E 106 106 110 106 108 108 100 106 105 102 Hv 8.9 7.1 6.9 7.1 6.9 8.3 8.0 6.6 7.2 6.9 23 201245073 [表2] 例 11 12 13 14 15 16 17 18 19 20 Si02 62.0 65.6 65.3 65.3 65.1 65.1 64.8 65.4 65.3 65.3 Al2〇3 1.8 1.9 1.8 1.8 2.5 2.5 2.5 2.5 2.5 2.5 P2O5 2.0 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 Zr02 1.4 2.0 1.4 1.4 1.4 1.4 1.4 1.4 1.5 1.4 Li20 31.0 27.4 27.3 27.3 27.5 27.5 27.3 27.6 27.6 27.5 K20 1.8 1.8 3.0 3.0 1.8 1.8 1.8 1.8 1.8 1.8 Ga2〇3 0 0 0 0 0.5 0.5 0 0 0 0 Sn〇2 0 0 0 0 0 0 1.0 0 0 0 BaO 0 0 0 0 0 0 0 0 0 0.2 La2〇3 0 0 0 0 0 0 0 0.1 0 0 P + Zr 3.3 3.3 2.6 2.6 2.6 2.6 2.6 2.6 2.7 2.6 Tg 478 471 478 478 482 482 493 481 484 479 T, 598 633 647 647 626 626 649 635 642 628 T2 818 858 876 876 826 826 843 843 852 831 Θν 537 537 537 580 532 537 580 540 537 529 tN 4 4 4 1 4 4 4 4 4 4 0c 788 800 790 800 774 800 830 800 800 778 tc 4 4 4 4 4 4 4 1 2 4 Kc 1.30 1.63 1.35 1.43 1.22 1.49 1.42 1.32 1.40 1.40 丁4〇〇細 69 12 72 59 80 57 51 64 66 61 Tmin 69 12 72 59 80 57 51 64 66 61 a E 113 104 107 107 103 105 94 109 109 110 Hv 6.6 6.25 6.9 7.0 6.9 7.0 6.8 7.0 6.9 6.9 24 201245073 [表3] 例 21 22 23 24 25 26 27 28 29 30 Si02 66.5 66.5 67.3 65.3 64.3 65.0 64.0 75.0 61.0 67.0 Al2〇3 2.5 2.5 1.9 3.9 2.7 2.2 1.8 0.5 3.0 1.9 P2O5 1.3 1.3 1.3 1.3 1.5 1.3 1.5 0.5 0.5 1.3 Zr02 1.4 1.4 1.4 0.9 1.7 1.5 1.4 3.0 0.5 0 Li20 26.5 26.5 28.1 28.1 27.6 26.0 26.3 20.0 35.0 27.9 K20 1.9 1.9 0.0 0.5 2.2 4.0 5.0 1.0 0 1.9 P + Zr 2.6 2.6 2.7 2.2 3.2 2.8 2.9 3.5 1.0 1.3 Tg 490 490 486 487 471 445 430 510 464 473 Tj 651 642 631 815 657 632 T2 802 764 792 868 769 847 Θν 536 536 500 569 537 540 540 537 537 537 tN 4 4 4 3 2 4 4 4 4 4 0c 790 820 790 743 800 800 800 800 800 800 tc 4 1 4 2 4 4 4 4 4 4 Kc 1.34 1.31 1.27 1.36 1.30 1.4 1.2 1.65 T400nm 70 68 26 30 54 65 55 0.2 0.1 3 Tmin 70 68 26 30 54 65 55 0.2 0.1 3 a 65 66 E 104 104 108 108 105 118 119 115 Hv 6.8 7.0 7.1 8.3 8.1 6.7 25 201245073 [表4] 例 31 32 33 34 35 36 37 38 39 40 Si〇2 67.0 66.3 65.1 66,9 67 65.6 62.4 65.0 65.8 62.1 A1203 1.9 0.9 2.5 1.9 1.9 1.8 1.9 4.7 1.9 2.9 P205 1.3 1.3 1.3 0 1.3 2.0 1.3 1.3 3.0 0.7 Zr02 0 1.4 1.4 1.4 0 1.4 1.4 1.4 0 0.8 Li20 27.9 27.7 27.5 28.0 28.0 27.4 31.2 27.6 27.5 33.0 K20 1.9 1.9 1.8 1.9 1.9 1.8 1.8 0 1.8 0.5 La2〇3 0 0.5 0.5 0 0 0 0 0 0 0 P + Zr 1.3 2.7 2.6 1.4 1.3 3.3 2.6 2.7 3.0 1.5 Tg 472 483 481 480 473 485 477 492 475 437 T, 644 621 701 632 662 670 648 658 T2 852 842 847 856 865 728 710 〇N 700 605 606 537 537 537 606 582 540 537 tN 2 4 4 4 4 4 4 4 4 4 0c 850 800 800 800 800 826 800 706 850 807 tc 2 4 4 4 4 4 4 4 4 4 Kc 1.60 1.54 1.68 1.58 1.50 1.10 1.93 1.31 T4〇〇nm 0.2 0.4 0.2 0.3 3 3 0 84 0.2 5 Tmin 0.2 0.4 0.2 0.3 3 3 0 84 0.2 5 a 66 67 E 94 117 108 108 115 104 108 108 95 110 Hv 7.1 6.7 6.3 7.0 7.0 8.3 又，準備了大小為50mm><50mm且厚度為0.6mm之例1 的結晶化玻璃板'與化學強化玻璃板；該化學強化玻璃板係將莫耳百分率表示組成為Si02: 73%、Al2〇3: 7%、MgO : 6%、Na2〇 : 14%，且大小為 50mm><50mm，厚度為 0_6mm之玻璃板，浸潰於425°C之硝酸鉀中11小時40分鐘並進行了離子交換者。將該等結晶化玻璃板及化學強化玻璃板作為試料，進 26 201245073 行使用砂紙之如下述之落球強度測試。即，將試料載置於由花崗岩所構成之基台上’並於該試料上面以使磨擦面向下的方式’將P30(JIS R6252 : 2006年）之砂紙放置於試料上的狀態下，使直徑0.75英吋且質量為28g之不銹鏽球落下於砂紙的上面’測出破壞試料之落下高度。另外，針對結晶化玻璃板，測定其雖未破壞但於其表面產生有以目視可確認之傷痕的狀態時之落下高度。將該測定各重複10次並計算落下高度之平均後，得知相對於化學強化玻璃板破壞之落下高度係3cm，結晶化玻璃板在落下高度為43cm時雖有傷痕但未有破壞情況而顯示出有非常強的強度。另外，針對該化學強化玻璃板施行落下高度為40cm之落球強度測試，而其變成50個以上的碎片且其等飛散至約50cm四周。於第2圖中顯示在落下高度為5 0 c m之落球測試中受損之結晶化玻璃板表面之顯微照片。其存在有約675μπι之長度的微小裂痕，此雖以目視亦可確認，但未見有碎裂現象。圖中看起來為黑色的部份於第3圖中亦相同，係因各種裂痕而產生的微小空隙。相對於此，於第3圖中則顯示在落下高度3cm之落球強度測試中受損之化學強化玻璃板表面的顯微照片。可知於球之落下處發生有成為碎裂原因之長度約600μπι的深裂痕。如同所述若使用本發明之結晶化玻璃，則即便施加若為化學強化玻璃板亦會碎裂般的衝擊亦不會有碎裂的情 27 201245073 形’又亦難產生傷痕。由此點亦可知，用於保護顯示裝置之本發明之結晶化玻璃的效用。另外，前述落球強度測試之所以具有如先前所述之構成係由於以下所述之理由。使用者誤使平板顯示裝·置掉落之情況等之對覆蓋玻璃給予衝擊之狀況時’即便為經化學強化的覆蓋玻璃，亦會有以突破壓縮應力層之傷痕為起點’而產生玻璃以比較緩慢的速度碎裂之慢速裂縫的情況(以下，將如所述之玻璃的碎裂方式以「慢速裂収碎裂」稱之）。另外，該慢速裂縫式碎裂’-般而言碎裂的碎片少，且其最典型的係自破壞起點起一條裂縫延伸而造成覆蓋玻璃裂成兩半的現象。特別是，對於立起來使用的情況多的附觸感測機能之輸入板pc，其報告顯示於使歸誤___能之輸入板PC弄倒等情況，亦即對覆蓋玻璃施加通常並不會造成碎裂之程度的衝料，即便為馳㈣化之覆蓋玻璃亦有發生碎裂情況。輯卿碎裂應為慢速祕式碎裂。以使以往從未被當作問題之慢速裂縫式碎裂變成亦可評估為目的者即為前述之落球強度測試。即，前料球強度測=之想法係：輸人板PC之覆蓋玻璃之所以會因通常並不會la成碎裂之程度的衝擊而碎裂u於瀝青混凝土中所含有之◊等W形狀的東西成了破壞起點，因而設定在將於其磨U上具有與所述之砂為同樣銳角程度的研磨材之P30之砂紙放置於試料上的狀態下，來進行落球強度測試。產業上之可利用性 28 201245073 本發明之透明高強度結晶化玻璃，係可廣泛地使用於顯示裝置，典型的係行動電話、行動資料終端機(PDA)、附觸感測機能之輸入板個人電腦及觸控面板等之小型顯示裝置之覆蓋玻璃等。另外，在此援引已於2011年3月4日提出申請之日本專利申請案第2011-047828號之說明書、申請專利範圍、圖式以及摘要之全部内容，並將其納入用以作為本發明之說明書之揭示。 I：圖式簡單說明3 第1圖係以後述之例1的狀況為例，來說明結晶化第1尖峰溫度T,、結晶化第2尖峰溫度T2的圖；横軸為溫度（單位： °C)，縱軸則為微差熱分析儀之輸出功率（單位：μν)。另外，圖中之Tg係玻璃轉移點，ΘΝ係成核熱處理溫度，而0C則係晶體生長熱處理溫度’並將其概略溫度個別以該當之虛線來表示。第2圖係以使砂紙之磨擦面向下的方式放置於後述之例1的結晶化玻璃板上’並使質量為28g的球狀不錢鋼自 50cm之高度落下時之結晶化玻板表面的相片。第3圖係以使砂紙之磨擦面向下的方式放置於化學強化玻璃板上，並使質量為28g的球狀不銹鋼自3cm之高度落下時之化學強化玻璃板表面的相片；該化學強化玻璃板係將莫耳百分率表示組成為Si02 : 73%、Α1Λ : 7%、MgO : 6°/〇及NaaO : 14%的玻璃板經予以離子交換者。【主要元件符號說明】 29 201245073Hv: A plate-like sample of about 20 mm x about 20 mm x thickness of about 1 mm and having a mirror-finished upper and lower surface was prepared, and a Vickers hardness was measured by a Vickers hardness tester at a pressure of 100 gf. Examples 1 to 23 are examples. Examples 28 to 39 are comparative examples or reference examples. Examples 24 to 27 are also examples of the present invention, and Kc & T_nm or Tmin is a large example, and Example 40 is a comparative example. 22 201245073 [Table i] Example 1 2 3 4 5 6 7 8 9 10 Si02 66.1 66.1 66.1 66.1 66.1 65.4 65.4 65.0 65.3 65.3 Al2〇3 1.9 1.9 1.9 1.9 1.9 2.5 2.5 4.7 2.5 2.5 P2O5 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 Zr02 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 hi2〇27.6 27.6 27.6 27.6 27.6 27.6 27.6 27.6 27.6 27.5 K2〇1.8 1.8 1.8 1.8 1.8 1.8 1.8 0 1.8 1.8 ΙΠ2〇3 0 0 0 0 0 0 0 0 0 0.2 La2〇3 0 0 0 0 0 0 0 0 0.2 0 P + Zr 2.6 2.6 2.6 2.6 2.6 2.7 2.7 2.7 2.6 2.6 "Tg 475 475 475 475 475 485 485 492 479 477 Ti 628 628 628 628 628 641 641 648 T2 847 847 847 847 847 853 853 728 Θν 537 540 537 540 495 537 536 588 606 588 tN 4 4 2 4 10 4 4 4 4 4 0C 800 790 830 790 847 800 790 800 800 800 tc 4 4 2 6 10 4 4 4 4 4 Kc 1.38 1.28 1.51 1.27 1.70 1.44 1.32 1.27 1.47 1.29 T400nm 61 61 25 60 15 63 62 33 39 48 Tmin 61 61 25 60 15 63 62 33 39 48 A 67 66 66 E 106 106 110 106 108 108 100 106 105 102 Hv 8.9 7.1 6.9 7.1 6.9 8.3 8.0 6.6 7.2 6.9 23 201245073 [Table 2] Example 11 12 13 14 15 16 1 7 18 19 20 Si02 62.0 65.6 65.3 65.3 65.1 65.1 64.8 65.4 65.3 65.3 Al2〇3 1.8 1.9 1.8 1.8 2.5 2.5 2.5 2.5 2.5 2.5 P2O5 2.0 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 Zr02 1.4 2.0 1.4 1.4 1.4 1.4 1.4 1.4 1.5 1.4 Li20 31.0 27.4 27.3 27.3 27.5 27.5 27.3 27.6 27.6 27.5 K20 1.8 1.8 3.0 3.0 1.8 1.8 1.8 1.8 1.8 1.8 Ga2〇3 0 0 0 0 0.5 0.5 0 0 0 0 Sn〇2 0 0 0 0 0 0 1.0 0 0 0 BaO 0 0 0 0 0 0 0 0 0 0.2 La2〇3 0 0 0 0 0 0 0 0.1 0 0 P + Zr 3.3 3.3 2.6 2.6 2.6 2.6 2.6 2.6 2.7 2.6 Tg 478 471 478 478 482 482 493 481 484 479 T, 598 633 647 647 626 626 649 635 642 628 T2 818 858 876 876 826 826 843 843 852 831 Θν 537 537 537 580 532 537 580 540 537 529 tN 4 4 4 1 4 4 4 4 4 4 0c 788 800 790 800 774 800 830 800 800 778 tc 4 4 4 4 4 4 4 1 2 4 Kc 1.30 1.63 1.35 1.43 1.22 1.49 1.42 1.32 1.40 1.40 D 4 〇〇 69 12 72 59 80 57 51 64 66 61 Tmin 69 12 72 59 80 57 51 64 66 61 a E 113 104 107 107 103 105 94 109 109 110 Hv 6.6 6.25 6.9 7.0 6.9 7.0 6.8 7.0 6.9 6.9 24 201245073 [Table 3] Example 21 22 23 24 25 26 27 28 29 30 Si02 66.5 66.5 67.3 65.3 64.3 65.0 64.0 75.0 61.0 67.0 Al2〇3 2.5 2.5 1.9 3.9 2.7 2.2 1.8 0.5 3.0 1.9 P2O5 1.3 1.3 1.3 1.3 1.5 1.3 1.5 0.5 0.5 1.3 Zr02 1.4 1.4 1.4 0.9 1.7 1.5 1.4 3.0 0.5 0 Li20 26.5 26.5 28.1 28.1 27.6 26.0 26.3 20.0 35.0 27.9 K20 1.9 1.9 0.0 0.5 2.2 4.0 5.0 1.0 0 1.9 P + Zr 2.6 2.6 2.7 2.2 3.2 2.8 2.9 3.5 1.0 1.3 Tg 490 490 486 487 471 445 430 510 464 473 473 Tj 651 642 631 815 657 632 T2 802 764 792 868 769 847 Θν 536 536 500 569 537 540 540 537 537 537 tN 4 4 4 3 2 4 4 4 4 4 0c 790 820 790 743 800 800 800 800 800 800 tc 4 1 4 2 4 4 4 4 4 4 Kc 1.34 1.31 1.27 1.36 1.30 1.4 1.2 1.65 T400nm 70 68 26 30 54 65 55 0.2 0.1 3 Tmin 70 68 26 30 54 65 55 0.2 0.1 3 a 65 66 E 104 104 108 108 105 118 119 115 Hv 6.8 7.0 7.1 8.3 8.1 6.7 25 201245073 [Table 4] Example 31 32 33 34 35 36 37 38 39 40 Si〇2 67.0 66.3 65.1 66,9 67 65.6 62.4 65.0 65.8 62.1 A1203 1.9 0.9 2.5 1.9 1.9 1.8 1.9 4.7 1.9 2.9 P205 1.3 1. 3 1.3 0 1.3 2.0 1.3 1.3 3.0 0.7 Zr02 0 1.4 1.4 1.4 0 1.4 1.4 1.4 0 0.8 Li20 27.9 27.7 27.5 28.0 28.0 27.4 31.2 27.6 27.5 33.0 K20 1.9 1.9 1.8 1.9 1.9 1.8 1.8 0 1.8 0.5 La2〇3 0 0.5 0.5 0 0 0 0 0 0 0 P + Zr 1.3 2.7 2.6 1.4 1.3 3.3 2.6 2.7 3.0 1.5 Tg 472 483 481 480 473 485 477 492 475 437 T, 644 621 701 632 662 670 648 658 T2 852 842 847 856 865 728 710 〇N 700 605 606 537 537 537 606 582 540 537 tN 2 4 4 4 4 4 4 4 4 4 0c 850 800 800 800 800 826 800 706 850 807 tc 2 4 4 4 4 4 4 4 4 4 Kc 1.60 1.54 1.68 1.58 1.50 1.10 1.93 1.31 T4〇〇nm 0.2 0.4 0.2 0.3 3 3 0 84 0.2 5 Tmin 0.2 0.4 0.2 0.3 3 3 0 84 0.2 5 a 66 67 E 94 117 108 108 115 104 108 108 95 110 Hv 7.1 6.7 6.3 7.0 7.0 8.3 Again, ready A crystallized glass plate of Example 1 having a size of 50 mm > 50 mm and a thickness of 0.6 mm and a chemically strengthened glass plate; the chemically strengthened glass plate is represented by a percentage of the molar composition as SiO 2 : 73%, Al 2 〇 3: 7%, MgO: 6%, Na2〇: 14%, and size 50mm><50mm, thickness 0_6mm The glass plate was immersed in potassium nitrate at 425 ° C for 11 hours and 40 minutes and subjected to an ion exchanger. These crystallized glass plates and chemically strengthened glass plates were used as samples, and the falling ball strength test using sandpaper as follows was carried out in the line 20122445073. In other words, the sample was placed on a base made of granite and placed on the sample in such a manner that the surface of the sample was placed on the sample so that the surface of the sample was placed on the sample to make the diameter of the paper (PIS (JIS R6252: 2006)) A 0.75 inch stainless steel rust ball of 28 g was dropped on the top of the sandpaper to measure the falling height of the damaged sample. Further, the crystallized glass plate was measured for the drop height when it was not broken but had a visually identifiable flaw on its surface. After the measurement was repeated 10 times and the average of the drop height was calculated, it was found that the height of the drop of the chemically strengthened glass plate was 3 cm, and the crystallized glass plate showed a scratch but no damage when the drop height was 43 cm. It has a very strong strength. Further, the chemically strengthened glass plate was subjected to a falling ball strength test having a drop height of 40 cm, which became 50 or more pieces and was scattered to about 50 cm. A photomicrograph of the surface of the crystallized glass plate damaged in the falling ball test with a drop height of 50 m is shown in Fig. 2. There was a microcrack of about 675 μm, which was confirmed by visual observation, but no cracking was observed. The portion that appears black in the figure is the same in Figure 3, which is a small gap due to various cracks. On the other hand, in Fig. 3, a photomicrograph of the surface of the chemically strengthened glass plate damaged in the falling ball strength test at a drop height of 3 cm is shown. It can be seen that a deep crack having a length of about 600 μm which is a cause of chipping occurs at the falling point of the ball. As described above, if the crystallized glass of the present invention is used, even if a chemically strengthened glass sheet is applied, the impact will be broken without breaking. 27 201245073 The shape is also hard to cause scratches. From this point of view, the effect of the crystallized glass of the present invention for protecting a display device is also known. Further, the aforementioned falling ball strength test has the constitution as described above for the reasons described below. When the user mistakenly causes the flat panel display device to be placed or dropped, the impact on the cover glass is caused. Even if the chemically strengthened cover glass is used, the glass may be generated by breaking the damage layer of the compressive stress layer. The case of a slow crack with a slower rate of fragmentation (hereinafter, the fragmentation of the glass as described is referred to as "slow cracking"). In addition, the slow crack cracking is generally less fragmented, and the most typical one is a crack extending from the fracture starting point to cause the cover glass to split into two halves. In particular, for the input panel pc of the touch sensing function, which is often used upright, the report is displayed on the input panel PC that causes the faulty ___, that is, the application of the cover glass is usually not A material that will cause a degree of fragmentation, even if it is a cover glass that has been broken. The compilation of the crack should be slow and secret. In order to make the slow crack cracking which has never been regarded as a problem in the past, it is also possible to evaluate the falling ball strength test. That is, the idea of the strength of the front ball is that the cover glass of the input plate PC is broken by the impact of the degree of cracking, and the shape of the W is contained in the asphalt concrete. The thing which becomes the origin of destruction is set in the state which puts the sandpaper of the P30 of the grinding|polishing material which has the same acute angle as the sand on the grinding|polishing U on the sample, and the ball strength test was carried out. Industrial Applicability 28 201245073 The transparent high-strength crystallized glass of the present invention can be widely used in display devices, and is typically a mobile phone, a mobile data terminal (PDA), and a touch-sensing input tablet. Cover glass for small display devices such as computers and touch panels. In addition, the entire contents of the specification, application, and drawings of Japanese Patent Application No. 2011-047828, filed on March 4, 2011, the entire contents of The disclosure of the specification. I. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a state in which the first peak temperature T is crystallized and a second peak temperature T2 of crystallization, and the horizontal axis is temperature (unit: °). C), the vertical axis is the output power of the differential thermal analyzer (unit: μν). Further, in the figure, the Tg-based glass transition point, the lanthanide nucleation heat treatment temperature, and the 0C is the crystal growth heat treatment temperature', and the approximate temperature thereof is individually indicated by the dotted line. Fig. 2 is a view showing the surface of the crystallized glass plate when the spherical steel of the mass of 28 g is dropped from the height of 50 cm by placing the rubbing surface of the sandpaper downward on the crystallized glass plate of Example 1 to be described later. photo. Figure 3 is a photograph of the surface of a chemically strengthened glass plate placed on a chemically strengthened glass plate with the rubbing surface of the sandpaper facing downward and the spherical stainless steel having a mass of 28 g dropped from a height of 3 cm; the chemically strengthened glass plate The composition of the molar percentage is expressed as SiO 2 : 73%, Α 1 Λ : 7%, MgO: 6 ° / 〇 and NaaO : 14% of the glass plate is ion exchanged. [Main component symbol description] 29 201245073

Claims

201245073 VII. Patent application scope: 1. A crystallized glass for a display device, having a wavelength of 1 mm, a wavelength of 400 nm, a light transmittance τ, and an nm of more than 1 伤. /. And it is represented by the following oxides: SiO2 of 61.5 to 72%, Al2〇3 of 1 to 5.5%, P205 of 0.5 to 3%, Zr02 of 0.5 to 3%, 20 to 35°/. Li2〇 and 〇~5% of K20, and the total content of P205 and Zr02 (P2〇5 + Zr02) is 1.7 to 5% of the glass is crystallized. 2. The crystallized glass for a display device according to claim 1, wherein the SiO2 of the glass is 62 to 68. /. Al2〇3 is 1 to 3%, P205 is 0.5 to 2%, 21"〇2 is 0.5 to 2%, Li20 is 25 to 30%, K20 is 0 to 3.5%', and P205 + Zr02 is 1.5 to 3.50/ Hey. 3. The crystallized glass for a display device according to claim 1 or 2, wherein the K20 of the glass is 0 to 2.5%. 4. The crystallized glass for a display device according to the first, second or third aspect of the patent application, wherein the glass of the glass is 1% or more. 5. The crystallized glass for a display device according to any one of claims 1 to 4, wherein the P205 + ZrO 2 of the glass is 2% or more. 6. A glass composition is formed by crystallizing to form a crystal having a light transmittance of 400 nm at a wavelength of inm and having a light transmittance of T4 () () nm of more than 10% for crystallization of a display device; The object is the base of the ear. /. The method comprises: 61.5 to 72% of SiO 2 , 1 to 5.5% of Al 2 〇 3, 0.5 to 3% of P205, 0.5 to 3% of Zr02, 20 to 35% of Li 20 and 0 to 5% of K20, and The total content of P205 and ZrO 2 (p2〇5 + Zr02) was 1.7 to 5%, and no coloring component was contained. 31 201245073 7. The glass composition of claim 6 of the patent scope, wherein SiO 2 is 62 to 68%, Al 2 〇 3 is 1 to 3%, P 2 〇 5 is 0.5 to 2%, Zr02 is 0.5 to 2%, Li 20 It is 25 to 30%, K20 is 0 to 3.5%, and P205 + Zr02 is L7 to 3.5%. 8. For the glass composition of claim 6 or 7, wherein K20 is more than 1%. 9. For the glass composition of claim 6, 7 or 8, wherein Ρ205 + Zr02 is more than 2%. 10. A glass composition which is formed by crystallization to form a crystallized glass for a display device, and which has a coloring component as a glass composition according to any one of claims 6 to 9. A crystallized glass for a display device obtained by crystallizing a glass composition according to any one of claims 6 to 10. 12. A crystallized glass for a display device according to the first, second, third, fourth, fifth or eleventh aspect of the patent application, wherein a crystal of Li2Si205 is precipitated. 13. The crystallized glass for a display device of claim 1, 2, 3, 4, 5, 11 or 12, wherein the fracture toughness value Kc is 1.2 MPa_m1/2 or more. 14. For crystallized glass for display devices according to the scope of claims 1, 2, 3, 4, 5, 11, 12 or 13 of the patent application, the light transmittance of the wavelength of 400 to 800 nm when the thickness is 1 mm exceeds 50. %By. 15. For the crystallized glass for display devices of claim 1, 2, 3, 4, 5, 11, 12, 13 or 14 of the patent application, the light transmittance at a wavelength of 400 nm when the thickness is 1 mm is more than 50 %By. A display device comprising a cover glass comprising crystallized glass for a display device according to any one of claims 1 to 5 or 32 201245073 11 to 15. 17. An action type machine comprising the display device of the "Scope of Application". 18. A method for producing a crystallized glass, characterized in that the system has the following composition and crystallized the second peak. The temperature of diced 2 is more than 755. The glass transition point of the glass of bismuth is Tg, and it is maintained at (Dg + 100 〇 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 一一一一一〇 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ~5.5% of Al2〇3, 0.5~3% of p2〇5, 0.5~3% of Zr〇2, 20~35% of Li20 and 0~5% of K2〇, ap2〇5 and Zr〇2 A total of (P2〇5 + Zr〇2) is 1 to 5%. 〇 19. A method for producing crystallized glass, which is characterized in that the glass transition point of the glass having the following composition is Tg and (Tg) + 40»c) maintained at a temperature of ~(Tg+80 °C) for more than 1 hour, and then maintained at a temperature of 75 ° to 820 ° C for 1 hour or more to crystallize; the glass is as follows The molar percentage of the compound is 62% to 68% of SiO 2 , 1 to 3% of A12 〇 3, 〇 .5 〜 2 ° /. P2 〇 5, 0.5 〜 2% of Zr02, 25 to 30 20/〇 Li20 and 〇~2.5°/. K20, and the total content of P205 and Zr02 (P205 + Zr02) is 1.5 to 3.5%. 20. Manufacture of crystallized glass according to claim 18 or 19. Method wherein the Tg system is less than 520 ° C. 33