JPH06157067A - Ultraviolet transmitting glass - Google Patents
Ultraviolet transmitting glassInfo
- Publication number
- JPH06157067A JPH06157067A JP43A JP32868192A JPH06157067A JP H06157067 A JPH06157067 A JP H06157067A JP 43 A JP43 A JP 43A JP 32868192 A JP32868192 A JP 32868192A JP H06157067 A JPH06157067 A JP H06157067A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- ultraviolet
- cao
- mgo
- na2o
- 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
Landscapes
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、読み出し専用記録半導
体（以下、ＥＰ−ＲＯＭという）用のアルミナセラミッ
クパッケージにおいて紫外線透過用窓として好適に用い
ることができる紫外線透過ガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet transmitting glass which can be suitably used as an ultraviolet transmitting window in an alumina ceramic package for a read-only recording semiconductor (hereinafter referred to as EP-ROM).
【０００２】[0002]
【従来の技術】アルミナセラミックスは、紫外線照射に
よるプログラムのメモリ消去が可能であるＥＰ−ＲＯＭ
用の支持体であるパッケージとして用いられ、これに
は、紫外線照射用のガラス窓が取り付けられている。2. Description of the Related Art Alumina ceramics is an EP-ROM that can erase a program memory by irradiating ultraviolet rays.
It is used as a package which is a support for a glass, and a glass window for ultraviolet irradiation is attached to the package.
【０００３】この種のガラス窓は、通常、紫外線透過率
が波長２５４ｎｍの紫外線に対しガラス厚１ｍｍにて７
０％以上の透過率を有し、しかも、支持体に対するシー
ル性との関係から熱膨張係数が０℃〜３００℃の温度範
囲で４８〜５８×１０-7／℃であること及び化学的耐久
性に優れていることが要求されている。This type of glass window normally has an ultraviolet transmittance of 7 mm at a glass thickness of 1 mm for ultraviolet rays having a wavelength of 254 nm.
It has a transmittance of 0% or more, and has a coefficient of thermal expansion of 48 to 58 × 10 -7 / ° C. in the temperature range of 0 ° C. to 300 ° C. and a chemical durability in view of the sealing property with respect to the support. It is required to have excellent properties.
【０００４】かかるガラスとして、重量％表示で ＳｉＯ2 ６１〜６７％ Ａｌ2 Ｏ3 ５〜 ８％ Ｂ2 Ｏ3 ２０〜２５％ ＭｇＯ＋ＣａＯ＋ＳｒＯ ０〜 ２％ Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ ７〜 ９％ Ｆ ０〜 ２％ からなるガラスが知られている。As such a glass, SiO 2 61 to 67% Al 2 O 3 5 to 8% B 2 O 3 20 to 25% MgO + CaO + SrO 0 to 2% Li 2 O + Na 2 O + K 2 O 7 to 9% F in terms of% by weight. Glass consisting of 0 to 2% is known.
【０００５】しかし、このガラスは気泡の含有量を少な
くすることが難しく、歩留りが低いという課題があっ
た。すなわち、従来よりガラスに不純物として混入して
いる鉄分がガラスの紫外線吸収を増大させることが知ら
れている。これは、Ｆｅ3+が紫外線域に強い吸収力をも
つことによる。However, this glass has a problem that it is difficult to reduce the content of bubbles and the yield is low. That is, it has been known that iron, which is conventionally mixed as an impurity in glass, increases ultraviolet absorption of glass. This is because Fe 3+ has a strong absorbing power in the ultraviolet region.
【０００６】このため、ガラスの紫外線吸収を減少させ
るには、鉄分の混入を減少させるほか、ガラスを還元す
ることによりＦｅ3+をＦｅ2+に変えることが必要にな
る。Therefore, in order to reduce the ultraviolet absorption of the glass, it is necessary to reduce the content of iron and to change Fe 3+ to Fe 2+ by reducing the glass.
【０００７】この際、ガラスを還元状態にするために
は、従来からバッチ中にサッカロースやカーボン粉末、
金属アルミニウム、金属シリコンなどの還元剤を加える
ことが行われてきている。At this time, in order to bring the glass into a reduced state, conventionally, sucrose, carbon powder,
It has been practiced to add reducing agents such as metallic aluminum and metallic silicon.
【０００８】しかし、これらの還元剤を用いて上記ガラ
スの溶融を行うと、還元剤とバッチとの反応により気泡
が発生し、この気泡が製品としてのガラスに残存する。However, when the glass is melted using these reducing agents, bubbles are generated due to the reaction between the reducing agent and the batch, and the bubbles remain in the glass as a product.
【０００９】このような気泡を除去しようとして溶融時
間を長くすると、還元剤の効果が次第に損なわれ、ガラ
スの還元状態が維持できなくなり、紫外線の透過率が低
下する。また、溶解温度を上昇させると、炉材の選定
等、工業的生産に困難をきたす問題がある。If the melting time is lengthened in order to remove such bubbles, the effect of the reducing agent is gradually impaired, the reduced state of the glass cannot be maintained, and the ultraviolet ray transmittance is lowered. Further, when the melting temperature is raised, there is a problem that industrial production such as selection of furnace material becomes difficult.
【００１０】[0010]
【発明が解決しようとする課題】本発明は従来の技術が
有していた上記課題を解消し、紫外線透過率、化学的耐
久性に優れ、残存する気泡の少ない紫外線透過ガラスの
提供を目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems of the prior art and to provide an ultraviolet ray transmitting glass having excellent ultraviolet ray transmittance and chemical durability and having few remaining bubbles. To do.
【００１１】[0011]
【課題を解決するための手段】本発明は、実質的に重量
％表示で ＳｉＯ2 ５５〜６０％ Ａｌ2 Ｏ3 ９〜１２％ Ｂ2 Ｏ3 ２０〜２７％ ＭｇＯ ０〜 ３％ ＣａＯ ０〜 ３％ ＭｇＯ＋ＣａＯ １〜 ３％ Ｌｉ2 Ｏ ０〜 ９％ Ｎａ2 Ｏ ０〜 ９％ Ｋ2 Ｏ ０〜 ９％ Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ ５〜 ９％ Ｆ ０〜 １％ Ｃｌ ０．１〜０．５％ からなり、０℃〜３００℃の温度範囲で４８〜５８×１
０-7／℃の熱膨張係数を有し、かつ、肉厚１ｍｍで波長
２５４ｎｍの紫外線の透過率が７０％以上である紫外線
透過ガラスを提供する。According to the present invention, substantially in terms of weight%, SiO 2 55-60% Al 2 O 3 9-12% B 2 O 3 20-27% MgO 0-3% CaO 0- 3% MgO + CaO 1 to 3% Li 2 O 0 to 9% Na 2 O 0 to 9% K 2 O 0 to 9% Li 2 O + Na 2 O + K 2 O 5 to 9% F 0 to 1% Cl 0.1 to 0 0.5%, and 48 to 58 x 1 in the temperature range of 0 to 300 ° C.
Provided is an ultraviolet-transparent glass having a thermal expansion coefficient of 0 −7 / ° C. and a transmittance of 70% or more of ultraviolet rays having a wavelength of 254 nm and a thickness of 1 mm.
【００１２】次に、本発明の紫外線透過ガラスの組成限
定理由について説明する。ＳｉＯ2＞６０％ではガラス
の溶融性が低下し、紫外線透過率が低下したり、残存す
る気泡が増加する。ＳｉＯ2 ＜５５％ではガラスの化学
的耐久性が低下する。Next, the reasons for limiting the composition of the ultraviolet transparent glass of the present invention will be explained. When SiO 2 > 60%, the melting property of glass decreases, the ultraviolet transmittance decreases, and the number of remaining bubbles increases. If SiO 2 <55%, the chemical durability of the glass decreases.
【００１３】Ａｌ2 Ｏ3 ＞１２％ではガラスの溶融性が
低下し、紫外線透過率が低下したり、残存する気泡が増
加する。Ａｌ2 Ｏ3 ＜９％ではガラスの紫外線透過率が
低下するとともに、化学的耐久性が低下する。When Al 2 O 3 > 12%, the melting property of glass is lowered, the ultraviolet transmittance is lowered, and the remaining bubbles are increased. When Al 2 O 3 <9%, the ultraviolet transmittance of the glass is lowered and the chemical durability is lowered.
【００１４】Ｂ2 Ｏ3 ＞２７％ではガラスの化学的耐久
性が低下する。Ｂ2 Ｏ3 ＜２０％ではガラスの溶融性が
低下し、紫外線透過率が減少するとともに、残存する気
泡が増加する。If B 2 O 3 > 27%, the chemical durability of the glass decreases. When B 2 O 3 <20%, the melting property of glass decreases, the ultraviolet transmittance decreases, and the remaining bubbles increase.
【００１５】ＭｇＯ、ＣａＯは単独または併用される。
ＭｇＯ＋ＣａＯ＞３％ではガラスが結晶を生じやすい。
ＭｇＯ＋ＣａＯ＜１％ではガラスの化学的耐久性が低下
する。MgO and CaO may be used alone or in combination.
If MgO + CaO> 3%, the glass tends to form crystals.
If MgO + CaO <1%, the chemical durability of the glass decreases.
【００１６】Ｌｉ2 Ｏ、Ｎａ2 Ｏ、Ｋ2 Ｏは単独または
併用される。Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ＞９％ではガ
ラスの化学的耐久性が低下し、紫外線透過率が低下する
とともに、熱膨張係数が大きくなりすぎる。Ｌｉ2 Ｏ＋
Ｎａ2 Ｏ＋Ｋ2 Ｏ＜５％ではガラスの溶解性が低下し、
紫外線透過率が低下したり残存する気泡が増加し、かつ
熱膨張係数が小さくなりすぎる。Li 2 O, Na 2 O and K 2 O may be used alone or in combination. When Li 2 O + Na 2 O + K 2 O> 9%, the chemical durability of the glass decreases, the ultraviolet transmittance decreases, and the thermal expansion coefficient becomes too large. Li 2 O +
When Na 2 O + K 2 O <5%, the solubility of glass decreases,
The ultraviolet transmittance decreases, the number of remaining bubbles increases, and the thermal expansion coefficient becomes too small.
【００１７】Ｆ＞１％ではガラスの熱膨張係数が大きく
なり、紫外線透過率が低下する。When F> 1%, the coefficient of thermal expansion of the glass becomes large, and the ultraviolet transmittance decreases.
【００１８】Ｃｌ＜０．１％では溶融性が悪くなり、紫
外線透過率が低下したり残存する気泡が増加する。Ｃｌ
＞０．５％でも、残存する気泡が増加する。Ｃｌの原料
としては、ＮａＣｌ、ＫＣｌ等が使用される。When Cl <0.1%, the meltability is deteriorated, the ultraviolet transmittance is lowered, and the remaining bubbles are increased. Cl
Even at> 0.5%, the remaining bubbles increase. As a raw material of Cl, NaCl, KCl or the like is used.
【００１９】本発明によるガラスは、例えば次のように
して製造される。目標組成になるように各原料を調合す
る。ついでこれを溶融炉に連続的に供給し、１４５０〜
１５５０℃に加熱して溶融しガラス化する。次いでこの
溶融ガラスをロールアウト法等により所定の厚さのガラ
スを製造する。The glass according to the present invention is manufactured, for example, as follows. Each raw material is compounded so as to have a target composition. Then, this was continuously supplied to the melting furnace, and 1450 ~
It is heated to 1550 ° C. to melt and vitrify. Then, this molten glass is manufactured into a glass having a predetermined thickness by a roll-out method or the like.
【００２０】[0020]
【実施例】表１の実施例（例１〜４）と比較例（例５〜
７）のガラス試料は、次のようにして製造した。EXAMPLES Examples (Examples 1 to 4) of Table 1 and Comparative Examples (Examples 5 to 5)
The glass sample of 7) was manufactured as follows.
【００２１】すなわち、表１に示す組成（単位；重量
％）になるように調合したバッチを白金ルツボに入れ、
電気炉にて１５５０℃で約４時間溶融した。溶融に際し
ては、還元剤としてサッカロースを０．４％添加した。
原料は、ガラス中の鉄分が５０ｐｐｍ以下となるように
選定した。溶融後、鉄板上に流し出し、板状試料を得
た。この板状試料を研磨により１ｍｍ厚とし、波長２５
４ｎｍの紫外線透過率（単位；％）を測定した。また、
板状試料を熱加工して４ｍｍＤ×１００ｍｍＬの棒状サ
ンプルを作製し、熱膨張係数（単位；×10-7／℃）を測
定した。これらの結果を表１に記載した。That is, a batch prepared so as to have the composition (unit:% by weight) shown in Table 1 was put in a platinum crucible,
It was melted in an electric furnace at 1550 ° C. for about 4 hours. Upon melting, 0.4% of sucrose was added as a reducing agent.
The raw materials were selected so that the iron content in the glass would be 50 ppm or less. After melting, it was poured onto an iron plate to obtain a plate-shaped sample. This plate-shaped sample was polished to a thickness of 1 mm and a wavelength of 25
The ultraviolet transmittance (unit:%) of 4 nm was measured. Also,
The plate-shaped sample was heat-processed to prepare a 4 mmD × 100 mmL rod-shaped sample, and the thermal expansion coefficient (unit: × 10 −7 / ° C.) was measured. The results are shown in Table 1.
【００２２】また、板状試料より面積が５０ｍｍ2 で厚
さが５ｍｍ程度のサンプルを切り出し、その両面を鏡面
に仕上げ、目視にて残存する気泡を数えあげた。この場
合、気泡の数が１０個以上認められたものは気泡不良と
して×印を、１０個以下のものは気泡良として○印を表
１に記載した。Further, a sample having an area of 50 mm 2 and a thickness of about 5 mm was cut out from the plate-like sample, both surfaces thereof were mirror-finished, and the remaining bubbles were counted visually. In this case, those in which the number of bubbles is 10 or more are shown in Table 1 as bad cells, and those in which 10 or less are good as bubbles and are shown in Table 1.
【００２３】化学的耐久性は、ＪＩＳ法（Ｒ−３５０
２）に準拠し、蒸留水に対するアルカリの溶出量（単
位；ｍｇ）をもって評価した。その結果も表１に記載し
た。この場合、数値が小さい方が望ましく、１ｍｇ以上
となると本用途に不適となる。The chemical durability is based on the JIS method (R-350
Based on 2), the amount of alkali dissolved in distilled water (unit: mg) was evaluated. The results are also shown in Table 1. In this case, it is desirable that the numerical value is small, and if it is 1 mg or more, it is unsuitable for this application.
【００２４】表１からわかるとおり、本発明によるガラ
スは、残存する気泡が少なく、紫外線透過率及び化学的
耐久性に優れていた。As can be seen from Table 1, the glass according to the present invention had few remaining bubbles, and was excellent in ultraviolet transmittance and chemical durability.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】以上述べたように本発明によるガラス
は、残存する気泡が少なく、紫外線透過率及びが化学的
耐久性とに優れる。したがって、ＥＰ−ＲＯＭ半導体に
おける紫外線透過用窓として好適に用いることができ
る。As described above, the glass according to the present invention has few remaining bubbles, and is excellent in ultraviolet transmittance and chemical durability. Therefore, it can be suitably used as a window for transmitting ultraviolet rays in an EP-ROM semiconductor.
Claims (1)
０-7／℃の熱膨張係数を有し、かつ、肉厚１ｍｍで波長
２５４ｎｍの紫外線の透過率が７０％以上である紫外線
透過ガラス。1. Substantially in terms of weight% SiO 2 55-60% Al 2 O 3 9-12% B 2 O 3 20-27% MgO 0-3% CaO 0-3% MgO + CaO 1-3% Li 2 O 0-9% Na 2 O 0-9% K 2 O 0-9% Li 2 O + Na 2 O + K 2 O 5-9% F 0-1% Cl 0.1-0.5%, 0 ° C 48 to 58 x 1 in the temperature range of ~ 300 ° C
An ultraviolet-transparent glass having a thermal expansion coefficient of 0 −7 / ° C. and a transmittance of 70% or more for ultraviolet rays having a wavelength of 254 nm and a thickness of 1 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32868192A JP3192013B2 (en) | 1992-11-13 | 1992-11-13 | UV transparent glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32868192A JP3192013B2 (en) | 1992-11-13 | 1992-11-13 | UV transparent glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06157067A true JPH06157067A (en) | 1994-06-03 |
| JP3192013B2 JP3192013B2 (en) | 2001-07-23 |
Family
ID=18212982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32868192A Expired - Fee Related JP3192013B2 (en) | 1992-11-13 | 1992-11-13 | UV transparent glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3192013B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005033031A1 (en) * | 2003-10-06 | 2005-04-14 | Nippon Sheet Glass Company, Limited | Ultra-violet ray transmitting glass and microplate using the same |
| JP2008280235A (en) * | 2007-04-09 | 2008-11-20 | Olympus Corp | Optical glass and optical device using the same |
| JP2015193521A (en) * | 2014-03-19 | 2015-11-05 | 日本電気硝子株式会社 | Ultraviolet transmission glass and production method |
| JP2018140928A (en) * | 2017-02-24 | 2018-09-13 | 日本電気硝子株式会社 | Optical glass |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112019007866T5 (en) | 2019-12-17 | 2022-09-01 | Yamaha Hatsudoki Kabushiki Kaisha | conveyor |
| JP7448232B2 (en) | 2021-11-11 | 2024-03-12 | 株式会社フジキカイ | Conveyance device |
-
1992
- 1992-11-13 JP JP32868192A patent/JP3192013B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005033031A1 (en) * | 2003-10-06 | 2005-04-14 | Nippon Sheet Glass Company, Limited | Ultra-violet ray transmitting glass and microplate using the same |
| JPWO2005033031A1 (en) * | 2003-10-06 | 2006-12-14 | 日本板硝子株式会社 | UV transmitting glass and microplate using the same |
| JP2008280235A (en) * | 2007-04-09 | 2008-11-20 | Olympus Corp | Optical glass and optical device using the same |
| JP2015193521A (en) * | 2014-03-19 | 2015-11-05 | 日本電気硝子株式会社 | Ultraviolet transmission glass and production method |
| JP2018197190A (en) * | 2014-03-19 | 2018-12-13 | 日本電気硝子株式会社 | Ultraviolet transmission glass |
| JP2018140928A (en) * | 2017-02-24 | 2018-09-13 | 日本電気硝子株式会社 | Optical glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3192013B2 (en) | 2001-07-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |