JPH01239036A - High-strength glass - Google Patents
High-strength glassInfo
- Publication number
- JPH01239036A JPH01239036A JP6297088A JP6297088A JPH01239036A JP H01239036 A JPH01239036 A JP H01239036A JP 6297088 A JP6297088 A JP 6297088A JP 6297088 A JP6297088 A JP 6297088A JP H01239036 A JPH01239036 A JP H01239036A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- strength
- substrate
- less
- chemically strengthened
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 59
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000003426 chemical strengthening reaction Methods 0.000 abstract description 10
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract description 7
- 238000005342 ion exchange Methods 0.000 abstract description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007423 decrease Effects 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 3
- 235000010333 potassium nitrate Nutrition 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- 229910011255 B2O3 Inorganic materials 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 235000010344 sodium nitrate Nutrition 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 29
- 230000003287 optical effect Effects 0.000 description 19
- 239000000463 material Substances 0.000 description 14
- 239000005345 chemically strengthened glass Substances 0.000 description 10
- 230000015654 memory Effects 0.000 description 10
- 230000005012 migration Effects 0.000 description 8
- 238000013508 migration Methods 0.000 description 8
- 230000006378 damage Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000013011 mating Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000005354 aluminosilicate glass Substances 0.000 description 4
- 239000005388 borosilicate glass Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005361 soda-lime glass Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000006103 coloring component Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 208000010392 Bone Fractures Diseases 0.000 description 2
- 206010017076 Fracture Diseases 0.000 description 2
- 206010034156 Pathological fracture Diseases 0.000 description 2
- 208000005250 Spontaneous Fractures Diseases 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 230000033458 reproduction Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910017976 MgO 4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
- Magnetic Record Carriers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、電気部品、電子部品、磁気記録・光記録・光
磁気記録装置およびそれらの再生装置、特に上記磁気・
光・光磁気装置の貯蔵素子となるメモリーディスク、す
なわち、磁気ディスク、光ディスク、光磁気ディスク用
基板等に使用する高密度記録用ディスク基板、並びに樹
脂成形体、特に眼鏡用樹脂レンズモールド(型)のよう
な強度が必要でしかも高精度の仕上げを必要とする透明
製品、および紫外線硬化型樹脂成形用の型に用いる°材
料に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to electrical parts, electronic parts, magnetic recording/optical recording/magneto-optical recording devices, and reproduction devices thereof, particularly the above-mentioned magnetic/magnetic recording devices.
High-density recording disk substrates used for memory disks serving as storage elements in optical/magnetic optical devices, i.e. substrates for magnetic disks, optical disks, magneto-optical disks, etc., as well as resin moldings, especially resin lens molds for eyeglasses. This product relates to materials used in transparent products that require strength and high-precision finishing, as well as molds for molding UV-curable resins.
高密度記録用のディスク基板としては、プラスチックお
よび無機ガラスが検討されている。しかしプラスチック
は吸湿性が高いのが最大の弱点である。従ってその欠陥
を補うため記録膜の耐湿改良および基板材料の改良が検
討課題となっている。Plastics and inorganic glasses are being considered as disk substrates for high-density recording. However, the biggest weakness of plastic is that it is highly hygroscopic. Therefore, in order to compensate for these defects, improvement of the moisture resistance of the recording film and improvement of the substrate material are being studied.
ところが経時変化に見られるように、長期の信軟性を得
るには不安定要素が多い。However, as seen in changes over time, there are many unstable factors in achieving long-term credit flexibility.
従来のソーダ石灰ガラス、ソーダアルミノ珪酸ガラス、
硼珪酸塩ガラス等を化学強化したものに見られるような
、それ自身単体使用の場合は、自然破壊の確率は低いが
、記録膜との接合によるマイグレーション(イオン移動
・拡散)によって生じる引張応力因子によって爆発的破
壊につながる確率が高い。Traditional soda lime glass, soda aluminosilicate glass,
When used alone, such as chemically strengthened borosilicate glass, the probability of natural failure is low, but the tensile stress factor caused by migration (ion movement/diffusion) due to bonding with the recording film There is a high probability that this will lead to explosive destruction.
従って合わせ条件で使用する場合は、結晶化構造を持つ
ガラスセラミックスが最適と考えられる。Therefore, when used under bonding conditions, glass ceramics with a crystallized structure are considered to be optimal.
上記自然破壊および割れ現象の内容について詳細に述べ
る。The contents of the above-mentioned natural fracture and cracking phenomena will be described in detail.
化学強化ガラスの場合、基板ガラス−化学強化層−記録
膜(無機質・有m質)の組合せは、基板ガラスに対して
化学強化層は圧縮応力強化層に対して記録膜とかその他
の合わせ材料が引張応力となるような関係が必要条件と
なる。In the case of chemically strengthened glass, the combination of substrate glass, chemically strengthened layer, and recording film (inorganic/organic) is such that the chemically strengthened layer is different from the substrate glass, and the recording film or other bonding material is different from the compressive stress strengthening layer. A necessary condition is a relationship that results in tensile stress.
正合結合的には合わせ材料としてはガラス基板よりも融
点の低いことが理怨の組合わせであるが、合わせ条件の
技術は上記のみに限られるものではなく、もちろんわず
かではあるが例外もある。In terms of proper bonding, the combination of bonding materials has a lower melting point than the glass substrate, but the techniques for bonding conditions are not limited to the above, and of course there are a few exceptions. .
化学強化されたガラスの場合、組成系によっては、特に
化学強化層が深く入り過ぎた場合、剥離現象あるいは収
縮方向に割れが生じる。又合わせる材料との複合体の場
合、ヘースとなる基板ガラスと合わせ材料との熱膨張係
数を一致させることが必要である。In the case of chemically strengthened glass, depending on the composition, especially if the chemically strengthened layer is inserted too deeply, peeling or cracking may occur in the direction of shrinkage. In addition, in the case of a composite with a mating material, it is necessary to match the thermal expansion coefficients of the base glass and the mating material.
しかしながら合わせ材料が無機質であるか有機質である
かを問わずマイグレーションなどの現象が起こり、合わ
せ面を通して何らかの形で引張応力が生じた場合、環境
条件により多少の差異はあるが、爆発的な破壊現象を起
こすことがある。However, regardless of whether the mating materials are inorganic or organic, phenomena such as migration occur, and if some form of tensile stress is generated through the mating surfaces, explosive destruction may occur, although there may be slight differences depending on the environmental conditions. may occur.
このように化学強化ガラスは、場合によって非常に危険
を伴うものであり、ガラス単体で使用する以外は不可能
な場合が多い。As described above, chemically strengthened glass is extremely dangerous in some cases, and in many cases it is impossible to use it other than as a single glass.
表面圧縮応力に対して未処理のガラス部分は、急冷強化
法、化学強化法であってっも3m/m以上の板厚を必要
とするのは常法である。Glass parts that have not been treated against surface compressive stress generally require a plate thickness of 3 m/m or more, even if the glass is strengthened by rapid cooling or chemically strengthened.
現有の高密度記録用ディスク基板の場合、板厚2 m
/ m以下の規格が多く、今後更に貰密度化されるのに
伴って板厚はますます増えるものと考えられる。In the case of the current high-density recording disk substrate, the plate thickness is 2 m.
There are many standards of less than / m, and it is thought that the plate thickness will continue to increase in the future as demand becomes even more dense.
従ってガラスの表面に一様に圧縮応力が加えられている
場合には、外部からの張力は圧縮応力を打消すために使
われるので、その分だけガラスは強化される。これが化
学強化現象であるが、マイグレーションにより化学強化
N(圧縮応力強化層)がなくなり、引張り応力が直接加
わった場合について考慮しなければならない。Therefore, when compressive stress is uniformly applied to the surface of the glass, external tension is used to cancel out the compressive stress, and the glass is strengthened by that amount. Although this is a chemical strengthening phenomenon, consideration must be given to the case where the chemically strengthened N (compressive stress reinforcing layer) disappears due to migration and tensile stress is directly applied.
[発明が解決しようとする問題点]
最近のエレクトロニクス技術、特にコンピュータに代表
される情報関連技術の進展に伴って、より本格的な情報
化社会への対応がすでに始まっている。[Problems to be Solved by the Invention] With the recent advances in electronics technology, especially information-related technology represented by computers, efforts have already begun to respond to a more full-fledged information society.
半導体レーザを用いて文書・データ・写真・TV画像等
の情報を迅速に記録再生できる光デイスクメモリーは、
従来の磁気メモリーと比較して記録密度が50〜500
倍あり、大量の情報を蓄積できる装置として追記型の光
デイスクメモリーが実用化されている。Optical disk memory uses semiconductor lasers to quickly record and reproduce information such as documents, data, photographs, and TV images.
Recording density is 50 to 500 times higher than conventional magnetic memory.
Write-once optical disk memory has been put into practical use as a device capable of storing large amounts of information.
上記光デイスクメモリーの特徴として光メモリーはCD
(コンパクトディスク)やVD(ビデオディスク)から
、CD−ROM (CD−Re a d○nly M
emory)、追記型(DRAW;Direct R
ead After Wr−iLe)ディスクと発
展し、消去再生書込み可能な光磁気型(EDRAW)
; Er a s a b I eDirect
Read After Writ、−e)ディスク
の登場も間近いものとみられている。The characteristics of the optical disk memory mentioned above are that the optical memory is a CD.
(Compact Disc) and VD (Video Disc), CD-ROM (CD-Rea d○nly M
memory), write-once type (DRAW; Direct R
Ead After Wr-iLe) disks and magneto-optical type (EDRAW) that can be erased, replayed, and written.
; Er a s a b I eDirect
The appearance of Read After Write, -e) discs is also expected to be imminent.
光デイスクメモリーの特徴としては下記の通りである。The characteristics of optical disk memory are as follows.
1、非接触で記録再生が可能である。1. Recording and playback is possible without contact.
2、ランダムアクセスが可能である。2. Random access is possible.
3、複製品が廉価である。3. Reproductions are inexpensive.
44高密度・高容量化が可能である。44 High density and high capacity are possible.
以上の様な特徴を生かしながら、光ディスクはCD、V
D等の民生用から映像ファイリング、文書ファイリング
等のオフィスオートメーション機器、情報処理機器へと
用途が拡大し、今後は電子計算機へ用途を拡大するため
に、より高い信顛性、高速転送レート、高速検索技術の
開発が課題となっている。While taking advantage of the above characteristics, optical discs are CD, V
Applications are expanding from consumer use such as D to office automation equipment such as video filing and document filing, and information processing equipment.In the future, applications will be expanded to include computers, with higher reliability, faster transfer rates, and higher speeds. The development of search technology is an issue.
これらの光ディスクの基板の材料としては、現在のとこ
ろプラスチックが圧倒的に多く使用されており、一部の
追記大型コードデータ用光ディスクには化学強化ガラス
(ソーダ石灰ガラス、ソーダアルミノ珪酸ガラス、硼珪
酸塩ガラス)がテスト使用されている。At present, plastic is overwhelmingly used as the substrate material for these optical discs, and some optical discs for additional large code data are made of chemically strengthened glass (soda lime glass, soda aluminosilicate glass, borosilicate glass). salt glass) has been tested.
しかし従来のプラスチック基板は熱による変形、複屈折
性、吸湿による反り等の欠陥があることが指摘されてい
る。また従来の化学強化ガラスは、基板自体の見掛は上
の強度は向上するが、記録膜と合わせた場合、マイグレ
ーション等の現象によって化学強化層が浸食され、強度
が低下する。更に基板ガラスに対して記録膜に引張応力
が発生した場合には爆発的に破壊が起こり、周囲の機器
に損傷を及ぼす。However, it has been pointed out that conventional plastic substrates have defects such as deformation due to heat, birefringence, and warping due to moisture absorption. Furthermore, in conventional chemically strengthened glass, although the apparent strength of the substrate itself is improved, when combined with a recording film, the chemically strengthened layer is eroded by phenomena such as migration, resulting in a decrease in strength. Further, if tensile stress is generated in the recording film relative to the substrate glass, explosive destruction occurs, causing damage to surrounding equipment.
以上のように、光デイスクメモリーの基板材料としての
プラスチックおよび化学強化ガラスは、それぞれ一長一
短があり、用途に応じた使い方がなされていくであろう
が、これから先、高性能化が要求される基板材料として
は対応しきれるものではない。As mentioned above, plastic and chemically strengthened glass as substrate materials for optical disk memories each have their advantages and disadvantages, and will likely be used depending on the application. The material is not suitable for this purpose.
光ディスク、光磁気ディスク等の基板としては、耐熱性
、機械的強度、高加工精度を有し、また複屈折性の少な
い性質を持ち、マイグレーションの少ない圧縮応力層が
緩やかに拡散しているZnOを含有していることを特徴
とする本発明の高強度ガラス製の基板が必要となる。As substrates for optical disks, magneto-optical disks, etc., we use ZnO, which has heat resistance, mechanical strength, high processing accuracy, low birefringence, and has a compressive stress layer with little migration that is gently diffused. A high-strength glass substrate of the present invention is required, which is characterized by containing:
化学強化ガラスは、強化されてはいるものの前記のよう
に割れることがあり、また高価である等の欠点が指摘さ
れている。しかし本発明の高強度ガラスは、記録膜の貼
合わせによっても高い機械的強度を示し、また記録密度
が向上することから単位メモリー当たりのコストはかえ
って割安になる。Although chemically strengthened glass is strengthened, it has been pointed out that it can break as described above and has drawbacks such as being expensive. However, the high-strength glass of the present invention exhibits high mechanical strength even when a recording film is bonded thereto, and the recording density is improved, so that the cost per unit memory is actually lower.
従って本発明の化学強化されたガラスによる基板の特徴
は下記のように表現することができる。Therefore, the characteristics of the chemically strengthened glass substrate of the present invention can be expressed as follows.
すなわち
19空気中の酸素や水分を通さないため記録膜の劣化を
防げる。In other words, since it does not allow oxygen or moisture in the air to pass through, deterioration of the recording film can be prevented.
2、複屈折がほとんどない。2. There is almost no birefringence.
3、吸湿による反りが起こらない。3. No warping due to moisture absorption.
4、剛性が高いため、回転中の変形がない。4. High rigidity prevents deformation during rotation.
5、加工精度が高く、偏心面振れが起こりにくい。5. Machining accuracy is high, and eccentric surface runout is less likely to occur.
以上のように本発明の高強度ガラスを用いた基板は、従
来の基板の欠点を克服しており、全く理想的なガラス組
成である。As described above, the substrate using the high-strength glass of the present invention overcomes the drawbacks of conventional substrates and has a completely ideal glass composition.
今後の技術動向および要求特性と本発明の高強度ガラス
の特性として、光ディスク、光磁気ディスクにおいては
、光スポツト位置の制御が電子光学的に行われるが、こ
の制御には物理的な範囲の制約があるので、ディスク基
板自体の機械的特性も十分良好でなければならない。円
周方向にうねりがあると、または素材に配向性(ガラス
成形工程による)があると、回転時の抵抗摩擦で発生す
る熱によって面振れを生し、反りが大きいとレンズ面に
接触する虞もある。Future technological trends and required characteristics, as well as the characteristics of the high-strength glass of the present invention, are that in optical disks and magneto-optical disks, the optical spot position is controlled electro-optically, but this control is limited by the physical range. Therefore, the mechanical properties of the disk substrate itself must be sufficiently good. If there are undulations in the circumferential direction, or if the material has orientation (due to the glass forming process), the heat generated by the resistance friction during rotation will cause surface deflection, and if the warpage is large, there is a risk of contact with the lens surface. There is also.
偏心が大きいと動作が不安定になる。従って基板の平坦
度、同心度が特に重要な因子となるディスク基板は記録
膜の保護も兼ねているので、基板材料は、温度、l2度
、機械的強度などの環境条件に対して強いことが望まれ
る。If the eccentricity is large, the operation will become unstable. Therefore, the flatness and concentricity of the substrate are particularly important factors.Since the disk substrate also serves to protect the recording film, the substrate material must be resistant to environmental conditions such as temperature, 12 degrees Celsius, and mechanical strength. desired.
光学的特性については、レーザー出力と媒体感度の関係
から、ガラス基板の透過率が高いほどよい。また複屈折
が大きいと、光検出器のレベル変動を生したり、レーザ
ーへの戻り光量が増してノイズが発生しやすくなる。Regarding optical properties, the higher the transmittance of the glass substrate, the better, from the relationship between laser output and medium sensitivity. Furthermore, if the birefringence is large, the level of the photodetector will fluctuate, and the amount of light returned to the laser will increase, making it easier to generate noise.
特に光磁気ディスクの場合は、光の偏波面の回転を利用
して信号を検出するので、ディスク基板の複屈折の存在
は大きな障害となる。また基板の傾きや厚さの変化は光
学的収差の原因となる。Particularly in the case of magneto-optical disks, since signals are detected using the rotation of the plane of polarization of light, the presence of birefringence in the disk substrate is a major hindrance. Also, changes in the tilt and thickness of the substrate cause optical aberrations.
いずれにしても本発明の高強度ガラスを用いた基板は、
アルミニウム類・プラスチック製の基板に比べて表面平
滑性がよく、それに加えて高強度であるため肉厚をより
薄くすることができて記録密度の向上が可能である。曲
げ強度・固さも重要なポイントであるが、従来の技術よ
りルーベル高い精度を実現し、面粗さは15〜2O人、
平坦度(5,25インチディスクの場合)2μm以下の
データを得た。In any case, the substrate using the high-strength glass of the present invention is
It has better surface smoothness than substrates made of aluminum or plastic, and in addition, it has high strength, so the wall thickness can be made thinner and recording density can be improved. Bending strength and hardness are also important points, but we have achieved higher precision than conventional technology, with a surface roughness of 15 to 20 mm.
Flatness data (for 5.25 inch disks) of 2 μm or less was obtained.
本発明は、化学強化ガラスであるにもかかわらず自然破
壊を起こさない安全性の高いガラスを提供するものであ
る。The present invention provides highly safe glass that does not spontaneously break despite being chemically strengthened glass.
すなわち本発明高強度ガラスは、重量に基づき、SiO
,60,0〜70.0%、Af、030゜5〜14.0
%、R2O(ただしRはアルカリ金属) 10.0〜3
2.0%、ZnO1,0〜15゜0%、Bz Oi 0
. 5〜14.0%から成ることを特徴とする。That is, the high-strength glass of the present invention has SiO
,60,0~70.0%,Af,030°5~14.0
%, R2O (R is an alkali metal) 10.0-3
2.0%, ZnO1.0~15°0%, Bz Oi 0
.. It is characterized by consisting of 5 to 14.0%.
また(イ)重量に基づき、Si0260.0〜70.0
%、A/!、o* 1.0〜14.0%、R2O(た
だしRはアルカリ金属)10゜0〜32゜0%、ZnO
1,0〜15.0%、B、0.0゜5〜12.0%から
成る基本成分88%以上と、(ロ)重量に基づき、Pb
O,Bad、Zro、 、Tie、 、As2O,、S
b!O,、MgO1SrOの、任意成分の中から選ばれ
た少なくとも1種の添加成分12%以下を含むことを特
徴とするもので、マイグレーションによりガラス表面に
圧縮応力を生じ、それが冷却後のガラス表面に残留する
ことによってガラスが強化される強化特性に優れた高強
度ガラスを得ることができる。(a) Based on weight, Si0260.0 to 70.0
%, A/! , o* 1.0-14.0%, R2O (where R is an alkali metal) 10°0-32°0%, ZnO
88% or more of the basic components consisting of 1.0~15.0%, B, 0.0°5~12.0%, and (b) based on weight, Pb
O,Bad,Zro, ,Tie, ,As2O,,S
b! It is characterized by containing 12% or less of at least one additive component selected from optional components such as O, MgO1SrO, which causes compressive stress on the glass surface due to migration, which causes stress on the glass surface after cooling. A high-strength glass with excellent reinforcement properties can be obtained.
上記本発明のガラスの組成は、特に厚さ3m/m以下の
薄いガラス板の化学強化に最適であり、表面をほとんど
損なうことなく応力層を緩徐に深部まで拡散し、すなわ
ち層状態ではなくイオン拡散するため、自然破壊もなく
、また化学強化後、精密研磨仕上げを行っても強化度の
変化はない。The above-mentioned composition of the glass of the present invention is particularly suitable for chemically strengthening thin glass plates with a thickness of 3 m/m or less, and allows the stress layer to be slowly diffused to the depths without substantially damaging the surface. Because it diffuses, there is no natural destruction, and even if precision polishing is performed after chemical strengthening, the degree of strengthening will not change.
化学強化は、ガラスの転移点(マイナス100℃付近)
以下の温度で、ガラス中に含まれるアルカリイオンと、
これより大きいイオン半径を持つアルカリイオンを含む
アルカリ溶融塩中にガラスを浸漬することによりイオン
交換を行う。Chemical strengthening is done at the transition point of glass (around -100℃)
At the following temperatures, the alkali ions contained in the glass,
Ion exchange is performed by immersing the glass in a molten alkali salt containing alkali ions with an ionic radius larger than this.
上記イオン交換の結果、アルカリイオンの占有容積の差
によってガラス表面に圧縮応力が発生し、その応力が冷
却後ガラスの表面に残留するため強化される。As a result of the above ion exchange, compressive stress is generated on the glass surface due to the difference in the occupied volume of the alkali ions, and this stress remains on the glass surface after cooling, so that it is strengthened.
本発明高強度ガラスの化学強化に使用する処理液には次
の3種類が適している。The following three types of treatment liquids are suitable for use in chemically strengthening the high-strength glass of the present invention.
1、KNO3100%(重量%)
2、KNOj 60%+N a Not 40%帽1%
)
(特にLixOを含有する場合に存効)3、KN○s9
9.5%十Hz S i Os 0. 5%(重量%)
上記処理液によってガラス中のLi“およびNa+イオ
ンが処理液中のNa+およびに゛イオンと交換される。1. KNO3 100% (weight%) 2. KNOj 60% + Na Not 40% Cap 1%
) (especially effective when containing LixO) 3, KN○s9
9.5% 10Hz S i Os 0. 5% (wt%) The above treatment liquid exchanges Li'' and Na+ ions in the glass with Na+ and Ni'' ions in the treatment liquid.
同時に2種類のイオン交換がおこなわれるため、優れた
強化特性を呈する。Because two types of ion exchange occur at the same time, it exhibits excellent reinforcing properties.
組成1(重量%)
Sing 64.OAlOs 8.5Na、0 8.
OK、0 7. 0ZnO2,7Lit OI
0
BaO1,OB2Oi 2.0
TfOz 1. OZrC1z 4. 5As、
030.3
組成2(重量%)
Sloz 62. 4 Affiz 0,2
.9NazO9,OK2O 9. 1
Ca0 0.I MgO2,8ZnO11,
5Bz O31,l
Ti1t 0.6 ASz ○、0.2S
bz 03 0. 3
上記組成例1および2の各側によって得られた化学強化
の処理時間と抗折強度およびシャルピー強度、応力歪層
の厚さの関係を下記表1に示す。Composition 1 (wt%) Sing 64. OAlOs 8.5Na, 0 8.
OK, 0 7. 0ZnO2,7Lit OI
0 BaO1, OB2Oi 2.0 TfOz 1. OZrC1z 4. 5As,
030.3 Composition 2 (wt%) Sloz 62. 4 Afiz 0,2
.. 9NazO9, OK2O 9. 1 Ca0 0. I MgO2,8ZnO11,
5Bz O31,l Ti1t 0.6 ASz ○, 0.2S
bz 03 0. 3 The relationship among the chemical strengthening treatment time, bending strength, Charpy strength, and stress strain layer thickness obtained by each side of Composition Examples 1 and 2 above is shown in Table 1 below.
組成例1および2の差はほとんどない。There is almost no difference between Composition Examples 1 and 2.
表1
上記2例のガラスは粉末状混合物を開口るつぼに入れ、
1450〜1500°Cに加熱溶融し、4〜12時間こ
の温度に保ち、清澄後4時間かけて徐冷したものである
。Table 1 The above two glasses were prepared by putting the powder mixture into an open crucible,
It was melted by heating to 1450 to 1500°C, kept at this temperature for 4 to 12 hours, and then slowly cooled over 4 hours after clarification.
なお構造上の均質性から、完全に除歪したのち、化学強
化処理を施すことが安定した化学強化法である。従って
構造上の不均質(歪その他)、成形上の配向性がある場
合、曲がり・ねじれ等が発生する。Note that from the viewpoint of structural homogeneity, a stable chemical strengthening method is to perform chemical strengthening treatment after completely removing strain. Therefore, if there is structural non-uniformity (such as distortion) or orientation during molding, bending, twisting, etc. will occur.
表面応力針による検査結果においては、通常のソーダ石
灰ガラス、ソーダアルミノ珪酸ガラス、硼珪酸塩ガラス
よりも化学強化層が緩徐に拡散しており自然破壊につな
がることはない。Inspection results using a surface stress needle show that the chemically strengthened layer diffuses more slowly than in ordinary soda lime glass, soda aluminosilicate glass, and borosilicate glass, and does not lead to natural failure.
本発明の課題は、前述のように記録膜との接合によって
生じるマイグレーションなどの反応現象で引張応力が起
き、自然破壊、あるいは複合時点で破壊を起こさないガ
ラス組成を得ることにあるもので、本発明高強度ガラス
(屈折率1.510〜1. 535 アツベ数63
.0〜50.0の範囲として)の基本成分中の5ift
は、全重量に基づき60.0〜70.0%必要である。As mentioned above, the object of the present invention is to obtain a glass composition that does not cause spontaneous fracture or fracture at the composite stage due to tensile stress caused by reaction phenomena such as migration caused by bonding with the recording film. Invention high-strength glass (refractive index 1.510 to 1.535, Atsbe number 63)
.. 5ift in the basic component of (as a range from 0 to 50.0)
is required in an amount of 60.0 to 70.0% based on the total weight.
この量が60.0%未満では化学的耐久性が劣化するし
、70%より多いと溶融困難となり作業性が低下する。When this amount is less than 60.0%, chemical durability deteriorates, and when it is more than 70%, it becomes difficult to melt and workability decreases.
次にAl2O,は、化学的耐久性向上および溶融ガラス
の粘性調節などのために使用されるが、この量が0.5
%未満ではこれらの効果は不十分であるし、また14.
0%より多くなると必要以上にガラスの粘性が増して取
扱いが困難になるので好ましくない。Next, Al2O is used to improve chemical durability and adjust the viscosity of molten glass, but the amount is 0.5
If the amount is less than 14.%, these effects will be insufficient.
If it exceeds 0%, the viscosity of the glass increases more than necessary, making it difficult to handle, which is not preferable.
更に、R2O(アルカリ金属酸化物例えばNag06.
0〜14.0%、Li、OO〜5.0%、K、04.O
〜13.0%)はガラスの粘性、イオン交換成分、熱膨
張係数の調節、溶融温度の低下を目的として、重量に基
づきR,Oとして10゜0〜32.0%の範囲で用いら
れる。この量が10.0%未満ではガラスが難溶性とな
り、また化学強化は不可能となる。また32%より多く
なると、ガラスの粘性低下、屈折率の低下、化学的耐久
性の劣化、ガラスの化学強化による強度に悪影響を来す
ため好ましくない。Furthermore, R2O (alkali metal oxides such as Nag06.
0-14.0%, Li, OO-5.0%, K, 04. O
~13.0%) is used in the range of 10°0 to 32.0% as R and O based on weight for the purpose of adjusting the viscosity, ion exchange component, thermal expansion coefficient, and lowering the melting temperature of the glass. If this amount is less than 10.0%, the glass becomes poorly soluble and chemical strengthening becomes impossible. Moreover, if it exceeds 32%, it is not preferable because it causes a decrease in the viscosity of the glass, a decrease in the refractive index, a deterioration in the chemical durability, and an adverse effect on the strength due to chemical strengthening of the glass.
本発明の高強度ガラスは、上記の成分に加えてZnO1
,0〜15.0%の基本成分が必要である。この成分は
化学的耐久性、屈折率の維持に必要である。また化学強
化ガラスに発生する破壊につながる現象を防止する。す
なわちイオン交換がソーダアルミノ珪酸ガラス、ソーダ
石灰ガラス、硼珪酸塩ガラス等に見られるような顕著な
強化層を示さず、イオンの拡散が緩徐に行われるため、
化学強化層は層状に明確に現れない。そのため記録膜そ
の他の合わせ材料との反応拡散によるマイグレーション
がなく、破壊につながることはない。The high-strength glass of the present invention contains ZnO1 in addition to the above components.
, 0-15.0% of the base component is required. This component is necessary for maintaining chemical durability and refractive index. It also prevents phenomena that can lead to destruction of chemically strengthened glass. In other words, ion exchange does not show a pronounced reinforcing layer as seen in soda aluminosilicate glass, soda lime glass, borosilicate glass, etc., and ion diffusion occurs slowly.
The chemically strengthened layer does not appear clearly in a layered manner. Therefore, there is no migration due to reaction and diffusion with the recording film or other mating materials, which does not lead to destruction.
本発明の高強度ガラスは、以上、の基本成分に加えて更
にB! O* 、PbO,BaO1ZrOz、Ti0z
、Lit 01Mg○、CaO1Asz Oz
、5bzOzの中から選ばれた少なくとも1種の任意成
分を含有させることができる。In addition to the above-mentioned basic components, the high-strength glass of the present invention also has B! O*, PbO, BaO1ZrOz, Ti0z
, Lit 01Mg○, CaO1Asz Oz
, 5bzOz.
これらはガラスの溶融性、泡切れ性、すなわち清澄など
を改善するために加えられるが、重量に基づきB2O,
については12.0%以下、Zr0□については4.0
%以下、PbOについては12.0%以下、BaOにつ
いては12.0%以下、TiO□については1.0%以
下、LizOについては5.0%以下、MgOについて
は4゜0%以下、CaOについては7.0%以下、As
zO3および5bzOsについては各々1.0%以下の
範囲で含有させても本発明の高強度ガラスには何らの悪
影響もない。These are added to improve glass melting properties, bubble breakability, clarification, etc., but based on weight, B2O,
12.0% or less for Zr0□, 4.0 for Zr0□
% or less, PbO 12.0% or less, BaO 12.0% or less, TiO□ 1.0% or less, LizO 5.0% or less, MgO 4°0% or less, CaO 7.0% or less for As
Even if each of zO3 and 5bzOs is contained in a range of 1.0% or less, there is no adverse effect on the high-strength glass of the present invention.
更に本発明においては、前記の基本成分または任意成分
に加えて、紫外線透過の必要のない場合(N i 01
Coo系着色剤は別)、通常の着色ガラスの製造の際に
慣用されている着色成分を含有させることができる。Furthermore, in the present invention, in addition to the above-mentioned basic components or optional components, in cases where UV transmission is not required (N i 01
In addition to Coo colorants, coloring components commonly used in the production of ordinary colored glass can be included.
このような着色成分としては、例えばSe、CU○、C
ut o、Crz 03 、Ndz O3、N 1O1
Coo、Mn0z (MnO)、Few 03(Fe
d)などの金属酸化物を挙げることができる。これらは
単独で用いてもよいし、2種以上併用してもよい。これ
らの着色成分は、その合計量が本発明高強度ガラスの全
重量当たり3%以下であれば問題は生しない。Examples of such coloring components include Se, CU○, C
ut o, Crz 03, Ndz O3, N 1O1
Coo, Mn0z (MnO), Few 03 (Fe
Metal oxides such as d) can be mentioned. These may be used alone or in combination of two or more. If the total amount of these coloring components is 3% or less based on the total weight of the high-strength glass of the present invention, no problem will arise.
下記表2に前記組成1による本発明高強度ガラスの特性
値を、表3に、その他の各種組成によって作った本発明
高強度ガラスの特性値を示す。Table 2 below shows the characteristic values of the high-strength glass of the present invention made with the composition 1, and Table 3 shows the characteristic values of the high-strength glass of the present invention made with various other compositions.
本発明高強度ガラスは、前記特許請求の範囲記載の組成
によって構成したものであるから、化学強化されたにも
かかわらず自然破壊を起こすことがなくて安全性が高く
、板厚をより薄くすることができる。従って光ディスク
、光磁気ディスク等の基板材料に適しており、本発明の
ガラスで上記記録用基板を作ると、記録膜の劣化を防げ
る、複屈折がほとんどない、吸湿による反りを生しない
、高剛性のため回転中の変形がない、加工精度が高くて
偏心面ふれが起こりにくい等の効果が得られる。Since the high-strength glass of the present invention is composed of the composition described in the claims, it does not undergo spontaneous fracture even though it has been chemically strengthened and is highly safe, and can be made thinner. be able to. Therefore, it is suitable as a substrate material for optical disks, magneto-optical disks, etc. When the recording substrate is made of the glass of the present invention, it can prevent deterioration of the recording film, has almost no birefringence, does not warp due to moisture absorption, and has high rigidity. Therefore, effects such as no deformation during rotation, high machining accuracy, and less chance of eccentric surface runout can be obtained.
(自発)手続補正書
1、 事件の表示
昭和63年特 許願第 62970号
2、 発明の名称
高強度ガラス
3、 補正をする者
事件との関係 特許出願人
名 称 株式会社 エフ・ジー・ケー4、 代理人
住所 東京都渋谷区代々木2丁目11番12号木村ビル
6階
2、特許請求の範囲
(1)重量に基づき、Sin、60.0〜70゜0%、
ADZ C)+ o、 5〜14.0%、R2O(た
だしRはアルカリ金属)10.0〜32.0%、ZnO
1,()〜15.O%、Bz O* 0.5〜14.0
%から成る高強度ガラス。(Voluntary) procedural amendment 1, Indication of the case: Patent Application No. 62970 of 1988 2, Name of the invention: High-strength glass 3, Relationship with the person making the amendment: Patent applicant name: F.G.K. Co., Ltd. 4, Agent address: 2nd floor, 6th floor, Kimura Building, 2-11-12 Yoyogi, Shibuya-ku, Tokyo Claims (1) Based on weight, Sin, 60.0-70゜0%,
ADZ C) + o, 5-14.0%, R2O (R is an alkali metal) 10.0-32.0%, ZnO
1, () ~ 15. O%, Bz O* 0.5-14.0
High strength glass consisting of %.
(2)(イ)重量に基づき、SiO260.0〜70,
0%、Ant 031.O〜14.0%、R2O(ただ
しRはアルカリ金属)10.0〜32.0%、ZnO1
,0〜15.0%、Btu30.5〜12.0%から成
る基本成分88%以上と、
(ロ)重量に基づき、PbO,BaO1ZrOz 、T
i0z 、ASZ 03、Sbz Ox、MgO,5r
O1CaOの、任意成分の中から選ばれた少なくとも1
種の添加成分12%以下を含む
高強度ガラス。(2) (a) Based on weight, SiO260.0-70,
0%, Ant 031. O~14.0%, R2O (where R is an alkali metal) 10.0~32.0%, ZnO1
,0 to 15.0%, Btu30.5 to 12.0%, and (b)Based on weight, PbO, BaO1ZrOz, T
i0z, ASZ 03, Sbz Ox, MgO, 5r
At least one selected from optional components of O1CaO
High-strength glass containing 12% or less of seed additives.
Claims (2)
、Al_2O_30.5〜14.0%、R_2O(ただ
しRはアルカリ金属)10.0〜32.0%、ZnO1
.0〜15.0%、B_2O_30.5〜14.0%か
ら成る高強度ガラス。(1) Based on weight, SiO_260.0-70.0%
, Al_2O_30.5-14.0%, R_2O (where R is an alkali metal) 10.0-32.0%, ZnO1
.. High strength glass consisting of 0-15.0% and B_2O_30.5-14.0%.
.0%、Al_2O_31.0〜14.0%、R_2O
(ただしRはアルカリ金属)10.0〜32.0%、Z
nO1.0〜15.0%、B_2O_30.5〜12.
0%から成る基本成分88%以上と、 (ロ)重量に基づき、PbO、BaO、 ZrO_2、TiO_2、As_2O_3、Sb_2O
_3、MgO、SrOの、任意成分の中から選ばれた少
なくとも1種の添加成分12%以下を含む 高強度ガラス。(2) (a) Based on weight, SiO_260.0-70
.. 0%, Al_2O_31.0-14.0%, R_2O
(R is an alkali metal) 10.0 to 32.0%, Z
nO1.0-15.0%, B_2O_30.5-12.
(b) Based on weight, PbO, BaO, ZrO_2, TiO_2, As_2O_3, Sb_2O
A high-strength glass containing 12% or less of at least one additive component selected from optional components such as _3, MgO, and SrO.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6297088A JPH01239036A (en) | 1988-03-16 | 1988-03-16 | High-strength glass |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6297088A JPH01239036A (en) | 1988-03-16 | 1988-03-16 | High-strength glass |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01239036A true JPH01239036A (en) | 1989-09-25 |
JPH0470262B2 JPH0470262B2 (en) | 1992-11-10 |
Family
ID=13215711
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6297088A Granted JPH01239036A (en) | 1988-03-16 | 1988-03-16 | High-strength glass |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01239036A (en) |
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JPS5536609A (en) * | 1978-09-02 | 1980-03-14 | Junpei Kuno | Dual stop water supply faucet |
JPS5551733A (en) * | 1978-10-06 | 1980-04-15 | Nippon Sheet Glass Co Ltd | Glass for light transmission body with superior weather resistance |
JPS57129839A (en) * | 1981-02-02 | 1982-08-12 | Seiko Epson Corp | Cover glass for watch |
JPS60260443A (en) * | 1984-06-07 | 1985-12-23 | Nippon Sheet Glass Co Ltd | Glass composition causing small degree of elution of alkaline component |
JPS6168349A (en) * | 1984-09-07 | 1986-04-08 | Toshiba Glass Co Ltd | Wear resistant glass bead |
JPS6265954A (en) * | 1985-09-18 | 1987-03-25 | Nippon Electric Glass Co Ltd | Borosilicate glass for sealing alumina |
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JPS496012A (en) * | 1972-05-10 | 1974-01-19 | ||
JPS5536609A (en) * | 1978-09-02 | 1980-03-14 | Junpei Kuno | Dual stop water supply faucet |
JPS5551733A (en) * | 1978-10-06 | 1980-04-15 | Nippon Sheet Glass Co Ltd | Glass for light transmission body with superior weather resistance |
JPS57129839A (en) * | 1981-02-02 | 1982-08-12 | Seiko Epson Corp | Cover glass for watch |
JPS60260443A (en) * | 1984-06-07 | 1985-12-23 | Nippon Sheet Glass Co Ltd | Glass composition causing small degree of elution of alkaline component |
JPS6168349A (en) * | 1984-09-07 | 1986-04-08 | Toshiba Glass Co Ltd | Wear resistant glass bead |
JPS6265954A (en) * | 1985-09-18 | 1987-03-25 | Nippon Electric Glass Co Ltd | Borosilicate glass for sealing alumina |
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JPH10167753A (en) * | 1996-12-06 | 1998-06-23 | Carl Zeiss:Fa | Lead-free crown glass |
JPH10241134A (en) * | 1996-12-26 | 1998-09-11 | Hoya Corp | Glass substrate for information-recording medium and magnetic recording medium using the same |
JPH11232627A (en) * | 1996-12-26 | 1999-08-27 | Hoya Corp | Substrate for information record medium |
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US6960399B2 (en) | 1998-03-13 | 2005-11-01 | Hoya Corporation | Crystalized glass for information recording medium, crystallized glass substrate, and information recording medium using the crystallized glass substrate |
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JPH11314931A (en) * | 1999-02-04 | 1999-11-16 | Nippon Sheet Glass Co Ltd | Glass for chemical strengthening |
JP2000322731A (en) * | 1999-05-07 | 2000-11-24 | Ishizuka Glass Co Ltd | Glass substrate for information recording medium |
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JP2001180969A (en) * | 1999-12-28 | 2001-07-03 | Central Glass Co Ltd | Manufacturing method of lithium-containing glass with high young's modulus and its glass product |
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