JP2015024954A - Glass for substrate and glass substrate - Google Patents

Glass for substrate and glass substrate Download PDF

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JP2015024954A
JP2015024954A JP2014177132A JP2014177132A JP2015024954A JP 2015024954 A JP2015024954 A JP 2015024954A JP 2014177132 A JP2014177132 A JP 2014177132A JP 2014177132 A JP2014177132 A JP 2014177132A JP 2015024954 A JP2015024954 A JP 2015024954A
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JP5900560B2 (en
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遠藤 淳
Atsushi Endo
淳 遠藤
中島 哲也
Tetsuya Nakajima
哲也 中島
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AGC Inc
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Asahi Glass Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a glass for a substrate which is hardly broken and suitably made to have a high recording density.SOLUTION: A glass for a substrate contains, as represented by mole percentage based on oxides, 66-77% of SiO, 7-17% of AlO, 0-7% of BO, 0-9% of LiO, 0-8% of NaO, 0-3% of KO, 0-13% of MgO, 0-6% of CaO, 0-5% of TiO, and 0-5% of ZrO. The total content of SO, AlO, and BO, SiO+AlO+BO, is 81-92%, the total content of LiO, NaO, and KO, LiO+NaO+KO, is 3-9%, the total content of MgO and CaO, MgO+CaO, is 4-13%, the total content of NaO, KO, and CaO, NaO+KO+CaO, is 0-10%, and the total content of TiOand ZrO, TiO+ZrO, is 0-5%.

Description

本発明は、磁気ディスク(ハードディスク)などの情報記録媒体、情報記録媒体などに用いられるガラス基板およびこれら基板に用いられるガラスに関する。   The present invention relates to an information recording medium such as a magnetic disk (hard disk), a glass substrate used for an information recording medium and the like, and glass used for these substrates.

近年、ハードディスクドライブの記録容量の増大に伴い、高記録密度化がハイペースで進行している。しかし、高記録密度化に伴い、磁性粒子の微細化が熱安定性を損ない、クロストークや再生信号のSN比低下が問題となっている。そこで、光と磁気の融合技術として熱アシスト磁気記録技術が注目されている。これは、磁気記録層にレーザ光や近接場光を照射して局所的に加熱した部分の保磁力を低下させた状態で外部磁界を印加して記録し、GMR素子等で記録磁化を読み出す技術であり、高保持力媒体に記録できるため、熱安定性を保ちながら磁性粒子を微細化することが可能となる。しかし、高保持力媒体を多層膜にして成膜するには、基板を十分に加熱する必要があり、高耐熱基板が求められる。   In recent years, with the increase in recording capacity of hard disk drives, higher recording density is progressing at a high pace. However, with increasing recording density, miniaturization of magnetic particles impairs thermal stability, and crosstalk and a decrease in the S / N ratio of a reproduction signal have become problems. Therefore, heat-assisted magnetic recording technology has attracted attention as a fusion technology of light and magnetism. This is a technique in which a magnetic recording layer is irradiated with a laser beam or near-field light and recorded by applying an external magnetic field in a state where the coercive force is lowered in a locally heated portion, and the recorded magnetization is read by a GMR element or the like. In addition, since recording can be performed on a medium having a high holding force, the magnetic particles can be miniaturized while maintaining thermal stability. However, in order to form a high coercive force medium as a multilayer film, it is necessary to sufficiently heat the substrate, and a high heat resistant substrate is required.

また、垂直磁気記録方式においても高記録密度化の要求に応えるべく従来のものとは異なる磁気記録層が提案されているが、そのような磁気記録層の形成は基板を高温にして行う必要があることが多い。
ところで、先に述べた熱アシスト磁気記録技術に対応できる基板としてシリコン基板が提案されている(特許文献1参照)。
Also in the perpendicular magnetic recording system, a magnetic recording layer different from the conventional one has been proposed to meet the demand for higher recording density, but such a magnetic recording layer needs to be formed at a high temperature. There are often.
By the way, a silicon substrate has been proposed as a substrate that can cope with the heat-assisted magnetic recording technique described above (see Patent Document 1).

シリコン基板にはガラス基板に比べて一般的に強度の点で懸念がある。したがって、基板を高温にして磁気記録層を形成する磁気ディスクの製造においてもガラス基板を用いるようにすることが好ましい。   Silicon substrates are generally a concern in terms of strength compared to glass substrates. Therefore, it is preferable to use a glass substrate also in the manufacture of a magnetic disk in which the magnetic recording layer is formed at a high temperature.

情報記録媒体用基板、特に磁気ディスク用基板としてガラス基板が広く用いられており、たとえば高ヤング率のリチウム含有アルミノシリケートガラスまたはそれに化学強化処理を施したもの(特許文献2参照)、あるいは特定の組成を有するガラスを熱処理して結晶相を析出させた結晶化ガラス(特許文献3参照)が使用されている。   A glass substrate is widely used as an information recording medium substrate, particularly a magnetic disk substrate. For example, a high Young's modulus lithium-containing aluminosilicate glass or a material subjected to chemical strengthening treatment (see Patent Document 2) or a specific one. Crystallized glass (see Patent Document 3) in which a crystalline phase is precipitated by heat-treating glass having a composition is used.

特開2009−199633号公報JP 2009-199633 A 特開2001−180969号公報JP 2001-180969 A 特開2000−119042号公報JP 2000-119042 A

化学強化処理用基板ガラスは化学強化処理を効率よく施せるようにするべくその耐熱性は低くされており、前記高保持力媒体を多層膜にして成膜する際の加熱により座屈してしまうおそれがある。また、化学強化処理ガラス基板について前記加熱を行うとイオン交換処理した交換層内がその加熱により拡散してしまい強度が低下するおそれがある。また、結晶化ガラス基板を用いようとすると結晶相とバルク体との熱膨張係数の違いにより前記加熱により基板表面が歪んでしまうおそれがある。   The substrate glass for chemical strengthening treatment is low in heat resistance so that the chemical strengthening treatment can be efficiently performed, and there is a risk of buckling due to heating when forming the high coercive force medium as a multilayer film. is there. Moreover, when the said chemically strengthened glass substrate is heated, the inside of the exchange layer subjected to the ion exchange treatment may be diffused by the heating and the strength may be lowered. Further, if a crystallized glass substrate is used, the substrate surface may be distorted by the heating due to the difference in thermal expansion coefficient between the crystal phase and the bulk body.

記録媒体の回転数を高めると、記録媒体にたわみが生じ共振が大きくなり、記録媒体の表面が磁気ヘッドと衝突して読み取りエラーや磁気ヘッドがクラッシュする危険性が高くなる。したがって、現状の記録媒体では磁気ヘッドと記録媒体の距離(浮上距離)をある程度以下に小さくすることができないので、磁気記録層の記録密度増加の阻害要因となりつつある。この記録媒体のたわみと共振の問題は高弾性率基板材料の使用により解決される。   When the rotational speed of the recording medium is increased, the recording medium is deflected and resonance is increased, and the risk that the surface of the recording medium collides with the magnetic head and the reading error or the magnetic head crashes increases. Therefore, in the current recording medium, the distance (flying distance) between the magnetic head and the recording medium cannot be reduced to a certain extent, which is becoming a hindrance to increase in the recording density of the magnetic recording layer. This problem of deflection and resonance of the recording medium is solved by the use of a high modulus substrate material.

磁気ディスク基板としてガラスを用いる場合、円形加工、芯抜き、内外円周面加工など多くの加工処理が必要となる。これらの加工処理中にガラスエッジ部などに破壊基点となりうる傷が多数発生し、製造工程においてのみならずスピンドルへの装着その他取り扱い時においても形成されるわずかな傷が基板破損につながる。特に磁気ディスク回転の高速化にともなってこの問題がより重要となる。この問題はクラックの発生しにくい基板用ガラスを使用することにより解決される。   When glass is used as the magnetic disk substrate, many processing processes such as circular processing, centering, and inner and outer circumferential surface processing are required. During these processings, many scratches that can become fracture base points are generated in the glass edge portion and the like, and the slight scratches formed not only in the manufacturing process but also in the mounting to the spindle or other handling lead to the substrate damage. In particular, this problem becomes more important as the rotation speed of the magnetic disk increases. This problem can be solved by using a glass for a substrate that is less prone to cracking.

本発明は、このような要求に包括的に応えるのに好適な高い比弾性率および高いガラス転移点を有し、傷つきにくい基板用ガラスを提供することを目的とする。   It is an object of the present invention to provide a glass for a substrate that has a high specific elastic modulus and a high glass transition point that are suitable for comprehensively meeting such demands and is not easily damaged.

本発明は、下記酸化物基準のモル%表示で、SiOを66〜77%、Alを7〜17%、Bを0〜7%、LiOを2〜9%、NaOを0〜8%、KOを0〜3%、MgOを0〜13%、CaOを0〜6%、TiOを0〜5%、ZrOを0〜5%含有し、SiO、AlおよびBの含有量の合計SiO+Al+Bが81〜92%、LiO、NaOおよびKOの含有量の合計LiO+NaO+KOが3〜9%、MgOおよびCaOの含有量の合計MgO+CaOが4〜13%、NaO、KOおよびCaO含有量の合計NaO+KO+CaOが0〜10%、TiOおよびZrOの含有量の合計TiO+ZrOが0〜5%であり、上記10成分の含有量の合計が98%以上であり、ガラス転移点Tgが690℃以上であり、比弾性率が33.6MNm/kg以上であり、情報記録媒体基板に用いられる基板用ガラス(結晶化ガラスを除く)(以下、本発明のガラスという。)を提供する。なお、たとえばBを0〜7%含有するとは、Bは必須ではないが7%まで含有してもよい、の意である。 The present invention, in mol% based on the following oxides, the SiO 2 from 66 to 77%, the Al 2 O 3 7~17%, B 2 O 3 and 0 to 7%, Li 2 O 2-9% 0 to 8% Na 2 O, 0 to 3% K 2 O, 0 to 13% MgO, 0 to 6% CaO, 0 to 5% TiO 2 and 0 to 5% ZrO 2 , SiO 2 , Al 2 O 3 and B 2 O 3 total content SiO 2 + Al 2 O 3 + B 2 O 3 is 81 to 92%, Li 2 O, Na 2 O and K 2 O total content Li 2 O + Na 2 O + K 2 O is 3 to 9%, the total content of MgO and CaO is 4 to 13%, the total content of Na 2 O, K 2 O and CaO is Na 2 O + K 2 O + CaO is 0 to 10 %, the total TiO 2 + ZrO 2 content of TiO 2 and ZrO 2 0 to 5% And the total content of the above 10 components is 98% or more, the glass transition point Tg is 690 ° C. or more, the specific modulus is 33.6 MNm / kg or more, Glass (excluding crystallized glass) (hereinafter referred to as glass of the present invention) is provided. Incidentally, for example, B 2 O 3 and of containing 0-7% is, B 2 O 3 may be contained up to but not necessarily 7%, a meaning of.

また、Al含有量に対するB含有量の比B/Alが0.6以下である前記基板用ガラスを提供する。 Further, Al 2 O 3 B to the content 2 O 3 ratio of content B 2 O 3 / Al 2 O 3 provides the glass substrate is 0.6 or less.

また、NaO+KO+CaOとSiO+Al+Bの比(NaO+KO+CaO)/(SiO+Al+B)が0.125以下である前記基板用ガラスを提供する。 Further, Na 2 O + K 2 O + CaO and the ratio of SiO 2 + Al 2 O 3 + B 2 O 3 (Na 2 O + K 2 O + CaO) / for the substrate (SiO 2 + Al 2 O 3 + B 2 O 3) is less than or equal to 0.125 Provide glass.

また、NaOを含有する前記基板用ガラスを提供する。
また、Bが3%以下、NaOが4%以下、LiO+NaO+KOが3.5%以上である前記基板用ガラスを提供する。
また、(MgO+CaO)/(SiO+Al+B)が0.04〜0.16である前記基板用ガラスを提供する。
Further, to provide a glass for the substrate containing Na 2 O.
In addition, the glass for a substrate is provided wherein B 2 O 3 is 3% or less, Na 2 O is 4% or less, and Li 2 O + Na 2 O + K 2 O is 3.5% or more.
Also provides a (MgO + CaO) / the substrate glass (SiO 2 + Al 2 O 3 + B 2 O 3) is 0.04 to 0.16.

また、前記基板用ガラスからなるガラス基板を提供する。
また、情報記録媒体基板が磁気ディスク基板である前記ガラス基板を提供する。
Moreover, the glass substrate consisting of the said glass for substrates is provided.
Also provided is the glass substrate, wherein the information recording medium substrate is a magnetic disk substrate.

また、前記基板用ガラスからなるガラス板を化学強化した化学強化ガラス基板を提供する。
また、情報記録媒体基板が磁気ディスク基板である前記化学強化ガラス基板を提供する。
前記ガラス基板または前記化学強化ガラス基板の上に磁気記録層が形成されている磁気ディスクを提供する。
Moreover, the chemically strengthened glass substrate which chemically strengthened the glass plate which consists of the said glass for substrates is provided.
Also provided is the chemically strengthened glass substrate, wherein the information recording medium substrate is a magnetic disk substrate.
Provided is a magnetic disk in which a magnetic recording layer is formed on the glass substrate or the chemically strengthened glass substrate.

情報記録媒体などに用いられるガラス転移点が高い基板用ガラスを得ることができる。これにより、基板上に磁性膜を形成した後に行う熱処理温度を高くでき、記録密度の高い情報記録媒体を得ることができる。
また、情報記録媒体などに用いられる比弾性率が高い基板用ガラスを得ることができる。これにより、ドライブ回転中に反りやたわみが発生しにくくなり、高記録密度の情報記録媒体を得ることができる。
A glass for a substrate having a high glass transition point used for an information recording medium or the like can be obtained. Thereby, the heat treatment temperature performed after forming the magnetic film on the substrate can be increased, and an information recording medium having a high recording density can be obtained.
In addition, a glass for a substrate having a high specific modulus used for an information recording medium or the like can be obtained. As a result, warpage and deflection are less likely to occur during drive rotation, and an information recording medium having a high recording density can be obtained.

また、情報記録媒体などに用いられる傷つきにくい基板用ガラスを得ることができる。これにより、製造工程およびスピンドルへの装着その他取り扱い時において傷が付きにくくなり、基板割れが発生しにくくなる。   Further, it is possible to obtain a glass for a substrate that is hardly damaged and used for an information recording medium. As a result, scratches are less likely to occur during the manufacturing process, mounting to the spindle, and other handling, and substrate cracks are less likely to occur.

また、金属製のスピンドルは基板の装着に際して金属製の部材により固定されるため、これら金属製のスピンドルおよび金属製部材と基板の熱膨張係数の差が大きいと、温度変動時に応力が発生し、基板割れが発生するおそれがある。一般的にガラスの熱膨張係数は金属の熱膨張係数に比べて小さいため、基板にガラスを用いる際にはできるだけ熱膨張係数の大きい基板用ガラスを用い、金属製のスピンドルおよび金属ドライブ他部材との熱膨張マッチングを高めることが好ましい。
本発明によれば、情報記録媒体などに用いられる平均線膨張係数が大きい基板用ガラスを得ることができる。これにより、金属製のドライブ他部材との熱膨張マッチングが高くなり、温度変動時の発生応力が小さく、基板割れ等が発生しにくくなる。
In addition, since the metal spindle is fixed by a metal member when the substrate is mounted, if the difference in the coefficient of thermal expansion between the metal spindle and the metal member and the substrate is large, stress is generated at the time of temperature fluctuation, There is a risk of substrate cracking. In general, the thermal expansion coefficient of glass is smaller than the thermal expansion coefficient of metal, so when using glass for the substrate, use glass for the substrate with the largest possible thermal expansion coefficient. It is preferable to increase the thermal expansion matching.
According to the present invention, a glass for a substrate having a large average linear expansion coefficient used for an information recording medium or the like can be obtained. Thereby, the thermal expansion matching with the metal drive other member becomes high, the generated stress at the time of temperature fluctuation is small, and it becomes difficult to generate a substrate crack or the like.

以下、本発明のガラスを磁気ディスク基板に用いる場合を例にして説明するが本発明はこれに限定されない。   Hereinafter, the case where the glass of the present invention is used for a magnetic disk substrate will be described as an example, but the present invention is not limited thereto.

本発明のガラスは比弾性率E/dが32MNm/kg以上であることが好ましい。E/dが32MNm/kg未満であるとドライブ回転中に反りやたわみが発生しやすく、高記録密度の情報記録媒体を得ることが困難になるおそれがある。典型的にはE/dは40MNm/kg以下である。なお、Eはヤング率(単位:GPa)、dは密度(単位:g/cm)である。 The glass of the present invention preferably has a specific elastic modulus E / d of 32 MNm / kg or more. If E / d is less than 32 MNm / kg, warping and deflection are likely to occur during drive rotation, and it may be difficult to obtain an information recording medium having a high recording density. Typically, E / d is 40 MNm / kg or less. E is Young's modulus (unit: GPa), and d is density (unit: g / cm 3 ).

本発明のガラスのガラス転移点Tgは690℃以上であることが好ましい。690℃未満では熱により基板が変形しやすいため、磁性層形成熱処理温度を充分高くすることができず、磁性層の保磁力増加が困難になるおそれがある。より好ましくは700℃以上である。   The glass transition point Tg of the glass of the present invention is preferably 690 ° C. or higher. If the temperature is lower than 690 ° C., the substrate is likely to be deformed by heat, so that the heat treatment temperature for forming the magnetic layer cannot be sufficiently increased, and it is difficult to increase the coercivity of the magnetic layer. More preferably, it is 700 ° C. or higher.

本発明のガラスの−50〜70℃における平均線膨張係数αは典型的には20×10−7/℃〜45×10−7/℃である。金属製のドライブなど他の部材の熱膨張係数との差を小さくして温度変動時の応力発生による基板の割れなどを起こりにくくしたい場合などにはαは好ましくは32×10−7/℃以上、より好ましくは34×10−7/℃以上である。 The average linear expansion coefficient α of the glass of the present invention at −50 to 70 ° C. is typically 20 × 10 −7 / ° C. to 45 × 10 −7 / ° C. Α is preferably 32 × 10 −7 / ° C. or more when it is desired to reduce the difference from the coefficient of thermal expansion of other members such as a metal drive to make it difficult for the substrate to crack due to the occurrence of stress during temperature fluctuations. More preferably, it is 34 × 10 −7 / ° C. or more.

本発明のガラスのクラック発生確率Pは80%未満であることが好ましい。80%以上では、製造工程およびスピンドルへの装着その他取り扱い時において傷が付きにくくなり、基板割れが起こりやすくなるおそれがある。より好ましくは70%以下である。   The crack occurrence probability P of the glass of the present invention is preferably less than 80%. If it is 80% or more, scratches are less likely to occur during the manufacturing process, attachment to the spindle, and other handling, and substrate cracking may occur. More preferably, it is 70% or less.

次に、本発明のガラスの組成についてモル%表示を用いて説明する。
SiOはガラスの骨格を形成する成分であり、必須である。66%未満では、耐酸性が低下する、dが大きくなる、ガラスにキズが付きやすくなる、Tgが低下するまたは液相温度が上昇しガラスが不安定になる。好ましくは67%以上、より好ましくは68%以上である。77%超では、粘度が10dPa・sとなる温度Tおよび粘度が10dPa・sとなる温度Tが上昇しガラスの溶解、成形が困難となる、EもしくはE/dが低下する、またはαが小さくなる。好ましくは74%以下、より好ましくは72%以下、特に好ましくは70%以下である。
Next, the composition of the glass of the present invention will be described using mol% display.
SiO 2 is a component that forms a glass skeleton and is essential. If it is less than 66%, the acid resistance is lowered, d is increased, the glass is easily scratched, the Tg is lowered or the liquidus temperature is increased and the glass becomes unstable. Preferably it is 67% or more, more preferably 68% or more. In 77 percent, viscosity of 10 2 dPa · s and comprising a temperature T 2 and a viscosity of 10 4 dPa · s and the temperature T 4 is raised comprising dissolution of the glass, molding becomes difficult, decreased E or E / d Or α becomes smaller. Preferably it is 74% or less, More preferably, it is 72% or less, Most preferably, it is 70% or less.

Alは耐候性を高める効果を有し、必須である。7%未満では前記効果が小さい、またはEもしくはE/dもしくはTgが低下する。好ましくは8%以上、より好ましくは10%以上である。17%超では前記TおよびTが上昇しガラスの溶解、成形が困難となる、耐酸性が低下する、αが小さくなる、または液相温度が高くなりすぎる。好ましくは16%以下、より好ましくは15%以下、さらに好ましくは14%以下である。 Al 2 O 3 has an effect of increasing weather resistance and is essential. If it is less than 7%, the effect is small, or E or E / d or Tg is lowered. Preferably it is 8% or more, More preferably, it is 10% or more. If it exceeds 17%, the T 2 and T 4 will increase, making it difficult to melt and mold the glass, the acid resistance will decrease, α will be small, or the liquidus temperature will be too high. Preferably it is 16% or less, More preferably, it is 15% or less, More preferably, it is 14% or less.

は必須ではないが、ガラスを傷つきにくくする、もしくはガラスの溶解性を向上させる効果があるため、7%まで含有してもよい。7%超ではEもしくはE/dもしくはTgが低下する、もしくはアルカリ金属酸化物成分と共存すると非常に揮散しやすくなる。好ましくは6.5%以下である。Tgを高くしたい、もしくは揮散を抑えたい場合Bは好ましくは4%以下、より好ましくは2%以下、さらに好ましくはBを含有しない。 B 2 O 3 is not essential, but may contain up to 7% because it has the effect of making the glass difficult to damage or improving the solubility of the glass. If it exceeds 7%, E, E / d, or Tg decreases, or if it coexists with an alkali metal oxide component, it is very easy to volatilize. Preferably it is 6.5% or less. When it is desired to increase Tg or suppress volatilization, B 2 O 3 is preferably 4% or less, more preferably 2% or less, and even more preferably B 2 O 3 is not contained.

SiO、AlおよびBの含有量の合計SiO+Al+Bが81%未満ではガラスが傷つきやすくなる。92%超では前記TおよびTが上昇しガラスの溶解、成形が困難となる。好ましくは90%以下、より好ましくは88%以下である。ガラスの溶解性、成形性を高めたい場合前記合計は好ましくは86%以下である。 If the total SiO 2 + Al 2 O 3 + B 2 O 3 content of SiO 2 , Al 2 O 3 and B 2 O 3 is less than 81%, the glass tends to be damaged. If it exceeds 92%, T 2 and T 4 increase, and it becomes difficult to melt and mold the glass. Preferably it is 90% or less, More preferably, it is 88% or less. When it is desired to improve the solubility and formability of the glass, the total is preferably 86% or less.

Al含有量に対するB含有量の比B/Alは0.6以下であることが好ましい。0.6超ではEもしくはE/dが低下するおそれがある。より好ましくは0.5以下、さらに好ましくは0.4以下、特に好ましくは0.3以下、最も好ましくは0.2以下である。 Al 2 O 3 ratio of the content of B 2 O 3 with respect to the content B 2 O 3 / Al 2 O 3 is preferably 0.6 or less. If it exceeds 0.6, E or E / d may be lowered. More preferably, it is 0.5 or less, more preferably 0.4 or less, particularly preferably 0.3 or less, and most preferably 0.2 or less.

LiOは必須ではないが、E、E/dもしくはαを大きくする、またはガラスの溶解性を向上させるため、9%まで含有してもよい。9%超では耐酸性もしくは耐候性が低下する、Tgが低くなる、またはガラスが傷つきやすくなる。好ましくは7%以下である。EもしくはE/dを大きくしたい場合LiOは好ましくは3%以下、より好ましくは2%未満、さらに好ましくは1%以下、特に好ましくはLiOを含有しない。 Li 2 O is not essential, but may be contained up to 9% in order to increase E, E / d or α, or improve the solubility of the glass. If it exceeds 9%, the acid resistance or weather resistance is lowered, Tg is lowered, or the glass is easily damaged. Preferably it is 7% or less. When it is desired to increase E or E / d, Li 2 O is preferably 3% or less, more preferably less than 2%, even more preferably 1% or less, and particularly preferably Li 2 O is not contained.

NaOは必須ではないが、αを大きくする、またはガラスの溶解性を向上させる効果があるため8%まで含有してもよい。8%超では耐酸性もしくは耐候性が低下する、Tgが低くなる、またはガラスが傷つきやすくなる。好ましくは7.5%以下である。また、NaOを含有する場合、その含有量は1%以上であることが好ましい。αを大きくしたい場合NaOは好ましくは3%以上、より好ましくは4%以上、さらに好ましくは5%以上、特に好ましくは6%以上である。 Na 2 O is not essential, but may be contained up to 8% because it has an effect of increasing α or improving the solubility of glass. If it exceeds 8%, the acid resistance or weather resistance is lowered, Tg is lowered, or the glass is easily damaged. Preferably it is 7.5% or less. Further, when containing Na 2 O, its content is preferably at least 1%. When it is desired to increase α, Na 2 O is preferably at least 3%, more preferably at least 4%, even more preferably at least 5%, particularly preferably at least 6%.

Oは必須ではないが、αを大きくする、またはガラスの溶解性を向上させる効果があるため3%まで含有してもよい。3%超では耐酸性もしくは耐候性が低下する、Tgが低くなる、またはガラスが傷つきやすくなる。好ましくは2%以下、より好ましくは1%以下、さらに好ましくはKOを含有しない。 K 2 O is not essential, but may be contained up to 3% because it has the effect of increasing α or improving the solubility of glass. If it exceeds 3%, the acid resistance or weather resistance is lowered, Tg is lowered, or the glass is easily damaged. Preferably 2% or less, more preferably 1% or less, more preferably she is containing no K 2 O.

LiO、NaOおよびKOの含有量の合計ROが3%未満では、αが小さくなる、またはガラスの溶解性が低下する。好ましくは3.5%以上、より好ましくは4%以上、さらに好ましくは4.5%以上、特に好ましくは5%以上ある。ROが9%超では耐酸性もしくは耐候性が低下する、Tgが低くなる、またはガラスが傷つきやすくなる。好ましくは8.5%以下、より好ましくは8%以下、さらに好ましくは7.5%以下である。 When the total R 2 O content of Li 2 O, Na 2 O and K 2 O is less than 3%, α is small or the glass solubility is lowered. Preferably it is 3.5% or more, More preferably, it is 4% or more, More preferably, it is 4.5% or more, Most preferably, it is 5% or more. If R 2 O exceeds 9%, the acid resistance or weather resistance is lowered, Tg is lowered, or the glass is easily damaged. Preferably it is 8.5% or less, More preferably, it is 8% or less, More preferably, it is 7.5% or less.

MgOは必須ではないが、E、E/dもしくはαを大きくする、またはガラスの溶解性を向上させるため、13%まで含有してもよい。13%超ではTgが低くなる、ガラスが傷つきやすくなる、または液相温度が高くなりすぎる。好ましくは12%以下、より好ましくは11%以下、さらに好ましくは10.5%以下、特に好ましくは10%以下である。MgOを含有する場合、その含有量は4%以上であることが好ましい。EもしくはE/dを大きくしたい場合MgOは好ましくは5%以上、より好ましくは6%以上、さらに好ましくは7%以上、特に好ましくは8%以上である。   MgO is not essential, but may be contained up to 13% in order to increase E, E / d or α, or improve the solubility of the glass. If it exceeds 13%, the Tg becomes low, the glass tends to be damaged, or the liquidus temperature becomes too high. Preferably it is 12% or less, More preferably, it is 11% or less, More preferably, it is 10.5% or less, Most preferably, it is 10% or less. When MgO is contained, the content is preferably 4% or more. When it is desired to increase E or E / d, MgO is preferably at least 5%, more preferably at least 6%, even more preferably at least 7%, particularly preferably at least 8%.

CaOは必須ではないが、αを大きくする、またはガラスの溶解性を向上させるため、6%まで含有してもよい。6%超ではTgが低くなる、ガラスが傷つきやすくなる、または液相温度が高くなりすぎる。好ましくは5%以下、より好ましくは3%以下、さらに好ましくは2%以下、特に好ましくは1%以下である。   CaO is not essential, but may be contained up to 6% in order to increase α or improve the solubility of the glass. If it exceeds 6%, the Tg becomes low, the glass tends to be damaged, or the liquidus temperature becomes too high. Preferably it is 5% or less, More preferably, it is 3% or less, More preferably, it is 2% or less, Most preferably, it is 1% or less.

MgOおよびCaOの含有量の合計MgO+CaOが4%未満では、αが小さくなる、またはガラスの溶解性が低下する。好ましくは5%以上、より好ましくは6%以上、さらに好ましくは7%以上、特に好ましくは8%以上、最も好ましくは9%以上である。前記合計が13%超では耐酸性もしくは耐候性が低下する、Tgが低くなる、またはガラスが傷つきやすくなる。好ましくは12.5%以下、より好ましくは12%以下、特に好ましくは11.5%以下、最も好ましくは11%以下である。   When the total MgO + CaO content of MgO and CaO is less than 4%, α is small or glass solubility is lowered. Preferably it is 5% or more, more preferably 6% or more, still more preferably 7% or more, particularly preferably 8% or more, and most preferably 9% or more. If the total exceeds 13%, the acid resistance or weather resistance decreases, Tg decreases, or the glass tends to be damaged. It is preferably 12.5% or less, more preferably 12% or less, particularly preferably 11.5% or less, and most preferably 11% or less.

SiO+Al+Bに対するMgO+CaOの比(MgO+CaO)/(SiO+Al+B)は0.16以下であることが好ましい。0.16超では、耐酸性もしくは耐候性が低下する、Tgが低くなる、またはガラスが傷つきやすくなるおそれがある。より好ましくは0.15以下、さらに好ましくは0.14以下である。 The ratio of MgO + CaO to SiO 2 + Al 2 O 3 + B 2 O 3 (MgO + CaO) / (SiO 2 + Al 2 O 3 + B 2 O 3 ) is preferably 0.16 or less. If it exceeds 0.16, acid resistance or weather resistance may be decreased, Tg may be decreased, or the glass may be easily damaged. More preferably, it is 0.15 or less, More preferably, it is 0.14 or less.

NaO、KOおよびCaO含有量の合計NaO+KO+CaOが10%超では、耐酸性もしくは耐候性が低下する、Tgが低くなる、またはガラスが傷つきやすくなる。好ましくは9%以下である。αを大きくしたい場合などはNaO+KO+CaOは好ましくは2%以上、より好ましくは5%以上、好ましくは7%以上、特に好ましくは8%以上である。 When the total Na 2 O + K 2 O + CaO content of Na 2 O, K 2 O and CaO exceeds 10%, acid resistance or weather resistance is lowered, Tg is lowered, or glass is easily damaged. Preferably it is 9% or less. When it is desired to increase α, Na 2 O + K 2 O + CaO is preferably at least 2%, more preferably at least 5%, preferably at least 7%, particularly preferably at least 8%.

SiO+Al+Bに対するNaO+KO+CaOの比(NaO+KO+CaO)/(SiO+Al+B)は0.125以上であることが好ましい。0.125超では、耐酸性もしくは耐候性が低下する、Tgが低くなる、またはガラスが傷つきやすくなる。より好ましくは0.124以下、さらに好ましくは0.123以下、特に好ましくは0.122以下、最も好ましくは0.121以下である。 It is preferred ratio of Na 2 O + K 2 O + CaO for SiO 2 + Al 2 O 3 + B 2 O 3 (Na 2 O + K 2 O + CaO) / (SiO 2 + Al 2 O 3 + B 2 O 3) is 0.125 or more. If it exceeds 0.125, the acid resistance or weather resistance is lowered, Tg is lowered, or the glass is easily damaged. More preferably, it is 0.124 or less, More preferably, it is 0.123 or less, Especially preferably, it is 0.122 or less, Most preferably, it is 0.121 or less.

TiOは必須ではないが、耐候性を維持したままEもしくはE/dを大きくする、Tgを高くする、またはガラスの溶解性を向上させる効果があるため5%まで含有してもよい。5%超ではdが大きくなる、αが小さくなる、ガラスにキズが付きやすくなる、または分相しやすくなるおそれがある。より好ましくは3%以下、さらに好ましくは2%以下、特に好ましくは1%以下、最も好ましくはTiOを含有しない。 TiO 2 is not essential, but may be contained up to 5% because it has the effect of increasing E or E / d, increasing Tg, or improving the solubility of glass while maintaining weather resistance. If it exceeds 5%, d may be large, α may be small, glass may be easily scratched, or phase separation may be liable to occur. More preferably 3% or less, still more preferably 2% or less, particularly preferably 1% or less, and most preferably no TiO 2 is contained.

ZrOは必須ではないが、耐候性を維持したままEもしくはE/dを大きくする、Tgを高くする、またはガラスの溶解性を向上させる効果があるため5%まで含有してもよい。5%超ではdが大きくなる、αが小さくなる、ガラスにキズが付きやすくなる、または液相温度が高くなりすぎるおそれがある。より好ましくは3%以下、さらに好ましくは2%以下、特に好ましくは1%以下、最も好ましくはZrOを含有しない。 ZrO 2 is not essential, but may be contained up to 5% because it has the effect of increasing E or E / d, increasing Tg, or improving the solubility of glass while maintaining weather resistance. If it exceeds 5%, d may be large, α may be small, glass may be easily scratched, or the liquidus temperature may be too high. More preferably 3% or less, still more preferably 2% or less, particularly preferably 1% or less, and most preferably no ZrO 2 is contained.

TiOおよびZrOの含有量の合計は最大でも5%であり、典型的には3.5%以下である。5%超ではdが大きくなる、αが小さくなる、ガラスにキズが付きやすくなるおそれがある。より好ましくは3%以下、さらに好ましくは2%以下、特に好ましくは1%以下、最も好ましくはTiOおよびZrOのいずれも含有しない。 The total content of TiO 2 and ZrO 2 is at most 5%, typically 3.5% or less. If it exceeds 5%, d may increase, α may decrease, and the glass may be easily scratched. More preferably 3% or less, still more preferably 2% or less, particularly preferably 1% or less, and most preferably neither TiO 2 nor ZrO 2 is contained.

本発明のガラスは本質的に上記成分からなるが、本発明の目的を損なわない範囲でその他の成分を合計で3%未満の範囲で含有してもよい。好ましくは2%未満、典型的には1%未満である。   The glass of the present invention consists essentially of the above components, but may contain other components in a total amount of less than 3% within a range not impairing the object of the present invention. Preferably it is less than 2%, typically less than 1%.

SrOまたはBaOはdを大きくする、またはガラスにキズが付きやすくする場合があるが、耐候性を維持したままαを大きくする、またはガラスの溶解性を向上させる効果がある場合がある。その場合の含有量は合計でも2%以下であることが好ましい。より好ましくは合計で1.5%以下、さらに好ましくは1%以下である。典型的にはSrOおよびBaOを含有しない。   Although SrO or BaO may increase d or make the glass easily scratched, it may have an effect of increasing α or improving the solubility of the glass while maintaining the weather resistance. In that case, the total content is preferably 2% or less. More preferably, it is 1.5% or less in total, and more preferably 1% or less. Typically it does not contain SrO and BaO.

また、SO、Cl、As、Sb、SnO等の清澄剤を合計で2%まで含有してもよい。
また、Fe、Co、NiOなどの着色剤を合計で2%まで含有してもよい。
Further, SO 3, Cl, As 2 O 3, Sb 2 O 3, the fining agent SnO 2 or the like may be contained up to 2% in total.
Further, a total of up to 2% of colorants such as Fe 2 O 3 , Co 3 O 4 and NiO may be contained.

本発明のガラスからなる情報記録媒体用ガラス基板は通常は円形のガラス板である。
磁気ディスク用ガラス基板はノートブックパソコン等に用いられる2.5インチ基板(ガラス基板外径:65mm)やポータブルMP3プレーヤなどに用いられる1.8インチ基板(ガラス基板外径:48mm)などに広く使用され、その市場は年々拡大しており、一方で低価格での供給が求められている。このようなガラス基板に使用されるガラスは、大量生産に適したものであることが好ましい。
板ガラスの大量生産はフロート法、フュージョン法、ダウンドロー法などの連続成形法により広く行われており、本発明のガラスは先に述べたようにたとえばフロート成形が可能なガラスであるので大量生産に好適である。
The glass substrate for information recording media made of the glass of the present invention is usually a circular glass plate.
Glass substrates for magnetic disks are widely used for 2.5 inch substrates (outer diameter of glass substrate: 65 mm) used for notebook personal computers and 1.8 inch substrates (outer diameter of glass substrate: 48 mm) used for portable MP3 players, etc. The market is growing year by year, while low-cost supply is required. It is preferable that the glass used for such a glass substrate is suitable for mass production.
Mass production of sheet glass is widely performed by continuous molding methods such as the float method, fusion method, and down draw method. As described above, the glass of the present invention is a glass that can be float-molded, for example. Is preferred.

本発明のガラスおよびガラス基板の製造方法は特に限定されず、各種方法を適用できる。たとえば、通常使用される各成分の原料を目標組成となるように調合し、これをガラス溶融窯で加熱溶融する。バブリング、撹拌、清澄剤の添加等によりガラスを均質化し、周知のフロート法、プレス法、フュージョン法またダウンドロー法などの方法により所定の厚さの板ガラスに成形し、徐冷後必要に応じて研削、研磨などの加工を行った後、所定の寸法・形状のガラス基板とされる。成形法としては、特に、大量生産に適したフロート法が好適である。また、フロート法以外の連続成形法、すなわち、フュージョン法、ダウンドロー法にも好適である。   The method for producing the glass and glass substrate of the present invention is not particularly limited, and various methods can be applied. For example, the raw materials of each component normally used are prepared so as to have a target composition, and this is heated and melted in a glass melting kiln. Homogenize the glass by bubbling, stirring, adding a clarifying agent, etc., and forming it into a sheet glass of a predetermined thickness by methods such as the well-known float method, press method, fusion method or down draw method, and after slow cooling, as necessary After processing such as grinding and polishing, a glass substrate having a predetermined size and shape is obtained. As the molding method, a float method suitable for mass production is particularly suitable. It is also suitable for continuous molding methods other than the float method, that is, the fusion method and the downdraw method.

表1の例1〜8および表3の例28、29のSiOからZrOまでの欄にモル%表示で示す組成となるように各成分の原料を調合し、白金るつぼを用いて1550〜1600℃の温度で3〜5時間溶解してガラスを作製した。溶解にあたっては、白金スターラを溶融ガラス中に挿入し、2時間撹拌してガラスを均質化した。次いで溶融ガラスを流し出してほぼ板状に成形し、毎分1℃の冷却速度で室温まで徐冷し、その後所望の厚みのガラス板に加工した。表で、Si+Al+BはSiO、AlおよびBの含有量の合計(単位:モル%)、B/AlはAl含有量に対するB含有量の比、ROはLiO、NaOおよびKOの含有量の合計(単位:モル%)、Mg+CaはMgOおよびCaOの含有量の合計(単位:モル%)、MgCa/SiAlBは(MgO+CaO)/(SiO+Al+B)、Na+K+CaはNaO、KOおよびCaOの含有量の合計(単位:モル%)、NaKCa/SiAlBは(NaO+KO+CaO)/(SiO+Al+B)、Ti+ZrはTiOおよびZrOの含有量の合計(単位:モル%)をそれぞれ示している。 The raw materials of the respective components were prepared so as to have a composition represented by mol% in the columns from SiO 2 to ZrO 2 in Examples 1 to 8 in Table 1 and Examples 28 and 29 in Table 3, and the platinum crucible was used for 1550 to Glass was produced by melting at a temperature of 1600 ° C. for 3 to 5 hours. In melting, a platinum stirrer was inserted into the molten glass and stirred for 2 hours to homogenize the glass. Next, the molten glass was poured out and formed into a substantially plate shape, slowly cooled to room temperature at a cooling rate of 1 ° C. per minute, and then processed into a glass plate having a desired thickness. In the table, Si + Al + B is the total content (unit: mol%) of SiO 2 , Al 2 O 3 and B 2 O 3 , B / Al is the ratio of B 2 O 3 content to Al 2 O 3 content, R 2 O is the total content of Li 2 O, Na 2 O and K 2 O (unit: mol%), Mg + Ca is the total content of MgO and CaO (unit: mol%), and MgCa / SiAlB is (MgO + CaO) / (SiO 2 + Al 2 O 3 + B 2 O 3 ), Na + K + Ca is the total content of Na 2 O, K 2 O and CaO (unit: mol%), NaKCa / SiAlB is (Na 2 O + K 2 O + CaO) / ( SiO 2 + Al 2 O 3 + B 2 O 3 ) and Ti + Zr indicate the total content (unit: mol%) of TiO 2 and ZrO 2 , respectively.

こうして得られたガラス板について、密度d(単位:g/cm)、前記平均線膨張係数α(単位:×10−7/℃)、ヤング率E(単位:GPa)、比弾性率E/d(単位:MNm/kg)、ガラス転移点Tg(単位:℃)およびクラック発生確率P(単位:%)を以下に示す方法によって測定した。結果を表に示す。 For the glass plate thus obtained, the density d (unit: g / cm 3 ), the average linear expansion coefficient α (unit: × 10 −7 / ° C.), Young's modulus E (unit: GPa), specific elastic modulus E / d (unit: MN m / kg), glass transition point Tg (unit: ° C.) and crack occurrence probability P (unit:%) were measured by the following methods. The results are shown in the table.

d:泡のないガラス20〜50gを用い、アルキメデス法にて測定した。
α:示差熱膨張計を用いて、石英ガラスを参照試料として室温から5℃/分の割合で昇温した際のガラスの伸び率をガラスが軟化してもはや伸びが観測されなくなる温度すなわち屈伏点まで測定し、得られた熱膨張曲線から−50〜70℃における平均線膨張係数を算出した。
E:厚さが5〜10mm、大きさが3cm角のガラス板について、超音波パルス法により測定した。
d: Measured by Archimedes method using 20-50 g of glass without bubbles.
α: The temperature at which the elongation of the glass when the temperature is raised from room temperature at a rate of 5 ° C./min using a differential thermal dilatometer as a reference sample is the temperature at which the elongation of the glass is no longer observed, that is, the yield point The average coefficient of linear expansion at −50 to 70 ° C. was calculated from the obtained thermal expansion curve.
E: A glass plate having a thickness of 5 to 10 mm and a size of 3 cm square was measured by an ultrasonic pulse method.

Tg:示差熱膨張計を用いて、石英ガラスを参照試料として室温から5℃/分の割合で昇温した際のガラスの伸び率を屈伏点まで測定し、得られた熱膨張曲線における屈曲点に相当する温度をガラス転移点とした。   Tg: Using a differential thermal dilatometer, the elongation of the glass was measured up to the yield point when the temperature was raised from room temperature at a rate of 5 ° C./min using quartz glass as a reference sample, and the bending point in the obtained thermal expansion curve The temperature corresponding to was taken as the glass transition point.

P:厚さが1〜2mm、大きさが4cm×4cmのガラス板の両面をコロイダルシリカで鏡面研磨したサンプルを用いてクラック発生確率を測定した。露点−28℃〜−27℃の雰囲気中でビッカース硬度計の荷重を2kgf=19.6Nとして15点ビッカース圧子を打ち込み、圧痕の四隅に発生するクラックの本数を測定した。この発生したクラック本数をクラック発生可能本数60で除したものをクラック発生率(単位:%)とした。なお、Pの測定精度は約±10%である。   P: The crack occurrence probability was measured using a sample in which both surfaces of a glass plate having a thickness of 1 to 2 mm and a size of 4 cm × 4 cm were mirror-polished with colloidal silica. A 15-point Vickers indenter was driven with a load of a Vickers hardness meter of 2 kgf = 19.6 N in an atmosphere with a dew point of −28 ° C. to −27 ° C., and the number of cracks generated at the four corners of the indentation was measured. The crack generation rate (unit:%) was obtained by dividing the number of generated cracks by the number of possible cracks generated. The measurement accuracy of P is about ± 10%.

表1〜3の例1〜27は実施例、例28、29は比較例である。
これらの結果から、実施例のガラスは高いガラス転移点を有しながら、例28のガラスに比べて高い比弾性率を有し、例29のガラスに比べて高いクラック耐性を有することがわかる。
Examples 1 to 27 in Tables 1 to 3 are examples, and examples 28 and 29 are comparative examples.
From these results, it can be seen that the glass of the example has a high specific elastic modulus as compared with the glass of Example 28 and a high crack resistance as compared with the glass of Example 29 while having a high glass transition point.

Figure 2015024954
Figure 2015024954

Figure 2015024954
Figure 2015024954

Figure 2015024954
Figure 2015024954

本発明は磁気ディスクなどの情報記録媒体および情報記録媒体などに用いられるガラス基板の製造に利用できる。   The present invention can be used for manufacturing an information recording medium such as a magnetic disk and a glass substrate used for the information recording medium.

Claims (11)

下記酸化物基準のモル%表示で、SiOを66〜77%、Alを7〜17%、Bを0〜7%、LiOを2〜9%、NaOを0〜8%、KOを0〜3%、MgOを0〜13%、CaOを0〜6%、TiOを0〜5%、ZrOを0〜5%含有し、SiO、AlおよびBの含有量の合計SiO+Al+Bが81〜92%、LiO、NaOおよびKOの含有量の合計LiO+NaO+KOが3〜9%、MgOおよびCaOの含有量の合計MgO+CaOが4〜13%、NaO、KOおよびCaO含有量の合計NaO+KO+CaOが0〜10%、TiOおよびZrOの含有量の合計TiO+ZrOが0〜5%であり、上記10成分の含有量の合計が98%以上であり、ガラス転移点Tgが690℃以上であり、比弾性率が33.6MNm/kg以上であり、情報記録媒体基板に用いられる基板用ガラス(結晶化ガラスを除く)。 SiO 2 is 66 to 77%, Al 2 O 3 is 7 to 17%, B 2 O 3 is 0 to 7%, Li 2 O is 2 to 9%, Na 2 O, expressed in terms of mol% based on the following oxides. 0-8% of K 2 O 0 to 3% of MgO 0 to 13% Less than six% of CaO, the TiO 2 0 to 5% containing ZrO 2 0 to 5% SiO 2, Total content of Al 2 O 3 and B 2 O 3 SiO 2 + Al 2 O 3 + B 2 O 3 is 81 to 92%, total content of Li 2 O, Na 2 O and K 2 O Li 2 O + Na 2 O + K 2 O 3-9%, MgO and CaO content total MgO + CaO 4-13%, Na 2 O, K 2 O and CaO content total Na 2 O + K 2 O + CaO 0-10%, TiO 2 and the total TiO 2 + ZrO 2 in the ZrO 2 content is 0 to 5%, above Glass for substrates (crystal Excluding glass). Al含有量に対するB含有量の比B/Alが0.6以下である請求項1の基板用ガラス。 The glass for a substrate according to claim 1, wherein a ratio B 2 O 3 / Al 2 O 3 of the B 2 O 3 content to the Al 2 O 3 content is 0.6 or less. NaO+KO+CaOとSiO+Al+Bの比(NaO+KO+CaO)/(SiO+Al+B)が0.125以下である請求項1または2の基板用ガラス。 The ratio of Na 2 O + K 2 O + CaO and SiO 2 + Al 2 O 3 + B 2 O 3 (Na 2 O + K 2 O + CaO) / claims 1 or 2 (SiO 2 + Al 2 O 3 + B 2 O 3) is less than or equal to 0.125 Substrate glass. NaOを含有する請求項1、2または3の基板用ガラス。 Claim 1, 2 or 3 of the glass for a substrate contains Na 2 O. が3%以下、NaOが4%以下、LiO+NaO+KOが3.5%以上である請求項1、2または3の基板用ガラス。 The glass for a substrate according to claim 1, wherein B 2 O 3 is 3% or less, Na 2 O is 4% or less, and Li 2 O + Na 2 O + K 2 O is 3.5% or more. (MgO+CaO)/(SiO+Al+B)が0.04〜0.16である請求項5の基板用ガラス。 The glass for a substrate according to claim 5, wherein (MgO + CaO) / (SiO 2 + Al 2 O 3 + B 2 O 3 ) is 0.04 to 0.16. 請求項1〜6のいずれかの基板用ガラスからなるガラス基板。   A glass substrate made of the glass for a substrate according to claim 1. 情報記録媒体基板が磁気ディスク基板である請求項7のガラス基板。   8. The glass substrate according to claim 7, wherein the information recording medium substrate is a magnetic disk substrate. 請求項1〜6のいずれかの基板用ガラスからなるガラス板を化学強化した化学強化ガラス基板。   The chemically strengthened glass substrate which chemically strengthened the glass plate which consists of the glass for substrates in any one of Claims 1-6. 情報記録媒体基板が磁気ディスク基板である請求項9の化学強化ガラス基板。   10. The chemically strengthened glass substrate according to claim 9, wherein the information recording medium substrate is a magnetic disk substrate. 請求項8のガラス基板または請求項10の化学強化ガラス基板の上に磁気記録層が形成されている磁気ディスク。   A magnetic disk having a magnetic recording layer formed on the glass substrate of claim 8 or the chemically strengthened glass substrate of claim 10.
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