JP2623474B2 - γ-ray irradiation prevention glass - Google Patents
γ-ray irradiation prevention glassInfo
- Publication number
- JP2623474B2 JP2623474B2 JP9923789A JP9923789A JP2623474B2 JP 2623474 B2 JP2623474 B2 JP 2623474B2 JP 9923789 A JP9923789 A JP 9923789A JP 9923789 A JP9923789 A JP 9923789A JP 2623474 B2 JP2623474 B2 JP 2623474B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- ceo
- ray irradiation
- coloring
- irradiation
- 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.)
- Expired - Fee Related
Links
- 239000011521 glass Substances 0.000 title description 28
- 230000005251 gamma ray Effects 0.000 title description 14
- 230000002265 prevention Effects 0.000 title description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000004040 coloring Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 102100027675 Guanine nucleotide exchange factor subunit RIC1 Human genes 0.000 description 1
- 101000581349 Homo sapiens Guanine nucleotide exchange factor subunit RIC1 Proteins 0.000 description 1
- 206010040925 Skin striae Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Description
【発明の詳細な説明】 〔発明の目的〕 （産業上の利用分野） 本発明は、γ線照射着色防止ガラスに係り、特に還元
雰囲気下で清澄し、少量のCeO2添加でγ線照射に対して
着色が防止できるγ線照射着色防止ガラスに関する。DETAILED DESCRIPTION OF THE INVENTION [OBJECT OF THE INVENTION] (relates) The present invention relates to γ-irradiation anti-coloring glass, especially clarified in a reducing atmosphere, the γ-ray irradiation with a small amount of CeO 2 added The present invention relates to a γ-ray irradiation coloring prevention glass capable of preventing coloring.
（従来の技術） 従来、医療用ガラスたとえば採血管は滅菌処理を施す
が、近年ガス滅菌法や高圧蒸気滅菌法に代わりγ線照射
滅菌法が普及している。ガラス製品はγ線を照射すると
材質に劣化が起こり着色する問題があった。従来から放
射線によるガラスの着色を防止するためCeO2を代表とす
る種々の添加物が使用されてきた。たとえば特公昭36−
20675号公報と特公昭60−25377号公報には陰極線管から
出るＸ線によってガラスが変色するのを防止するため
に、CeO2の有効度を一層改善する目的でCeO2とTiO2とを
共存させたことが記載されている。また特公昭42−1087
9号公報には陰極線管のガラス表面板の褐色着色防止の
ためCeO2の代わりにMnOとTiO2とを組合わせて添加する
方法が記載されている。(Prior Art) Conventionally, medical glass, for example, a blood collection tube is subjected to a sterilization treatment. In recent years, a γ-ray irradiation sterilization method has become widespread instead of a gas sterilization method or a high-pressure steam sterilization method. Irradiation of γ-rays causes glass materials to deteriorate and become colored. Conventionally, various additives typified by CeO 2 have been used to prevent coloring of glass due to radiation. For example,
Japanese Patent Publication No. 20675 and Japanese Patent Publication No. 25377/1985 coexist CeO 2 and TiO 2 for the purpose of further improving the effectiveness of CeO 2 in order to prevent the glass from being discolored by X-rays emitted from a cathode ray tube. It is described that it was done. In addition, Tokiko 42-1087
No. 9 discloses a method of adding MnO and TiO 2 in combination instead of CeO 2 to prevent brown coloration of the glass surface plate of the cathode ray tube.
一般に、医療用ガラスには着色防止のため、CeO2を1.
0wt％を越えて添加していた。Generally, CeO 2 is added to medical glass to prevent coloring.
More than 0 wt% was added.
（発明が解決しようとする問題点） 従来、医療用ガラスにγ線を照射した際の着色を防止
するためCeO2を1wt％を越えた量含有させたガラスを酸
化雰囲気で溶融する。しかし、CeO2自体がガラスを黄色
に着色するため1wt％を越えた量含有されることはCeO2
の着色防止剤としての効果が十分得られず望ましくな
い。さらにCeO2が高価であるため、これを大量に使用す
るとガラス製品のコストが高くなるという問題がある。(Problems to be Solved by the Invention) Conventionally, glass containing CeO 2 in an amount exceeding 1 wt% is melted in an oxidizing atmosphere to prevent coloring when medical glass is irradiated with γ-rays. However, the CeO 2 itself is contained amount exceeds 1 wt% to color the glass yellow CeO 2
Is not desirable because the effect as a coloring inhibitor cannot be sufficiently obtained. In addition, since CeO 2 is expensive, there is a problem that the cost of glass products increases when used in large quantities.
本発明は、上記事情を考慮してなされたものでCeO2の
含有量を1wt％以下の極限まで減らしてもγ線照射に対
する着色防止が十分なされるγ線照射着色防止ガラスを
提供することを目的とする。The present invention has been made in consideration of the above circumstances, and provides a γ-ray irradiation anti-coloring glass capable of sufficiently preventing coloration against γ-ray irradiation even when the content of CeO 2 is reduced to the limit of 1 wt% or less. Aim.
（問題を解決するための手段および作用） 本発明は、上記目的を達成するためにソーダライムガ
ラスに必須成分としてCeO2の特定量を導入した。またCe
O2の含有量を1wt％以下とするため溶融雰囲気を還元状
態に調整した。(Means and Actions for Solving the Problems) In the present invention, a specific amount of CeO 2 was introduced as an essential component into soda lime glass to achieve the above object. Also Ce
The melting atmosphere was adjusted to a reduced state in order to reduce the O 2 content to 1 wt% or less.
CeO2は溶融ガラス中でCe4+とCe3+として存在し、この
うちCe3+がγ線照射時のガラスの着色防止に有効であ
る。しかし原料から供給されるCeO2はCe4+であるから溶
融雰囲気が酸化状態の場合Ce3+の割合が小さいので着色
防止の効果を上げるため多量のCeO2を使用する必要があ
る。そこで溶融雰囲気を酸化状態から還元状態にすると
Ce4+→Ce3+の反応が進みCe3+の割合が大きくなるので少
量のCeO2を使用しても十分な着色防止効果が出る。CeO 2 exists in the molten glass as Ce 4+ and Ce 3+ , of which Ce 3+ is effective in preventing coloring of the glass during γ-ray irradiation. However, since CeO 2 supplied from the raw material is Ce 4+ , if the melting atmosphere is in an oxidized state, the proportion of Ce 3+ is small, so that it is necessary to use a large amount of CeO 2 to improve the effect of preventing coloring. Therefore, when the melting atmosphere is changed from an oxidized state to a reduced state,
Since the reaction of Ce 4+ → Ce 3+ proceeds and the ratio of Ce 3+ increases, even if a small amount of CeO 2 is used, a sufficient coloring prevention effect can be obtained.
すなわち、本発明は重量百分率で、SiO260〜〜75％，
Al2O30.5〜５％，Na2O12〜17％，K2O0〜５％CaO1〜８
％,MgO1〜６％，B2O30.1〜５％，SO30.01〜１％，CeO
20.1〜１％を含有するγ線照射着色防止ガラスである。That is, the present invention relates to SiO 2 60-75% by weight percentage,
Al 2 O 3 0.5~5%, Na 2 O12~17%, K 2 O0~5% CaO1~8
%, MgO1~6%, B 2 O 3 0.1~5%, SO 3 0.01~1%, CeO
2 It is a gamma ray irradiation prevention glass containing 0.1 to 1%.
次に上記組成範囲の数値限定理由について詳述する。 Next, the reasons for limiting the numerical values of the above composition ranges will be described in detail.
SiO2はガラス形成の必須成分の一つであるが60％未満
では膨張係数が高くなり、化学的耐久性が劣化するので
好ましくない。また75％を越えると膨張係数が低くなり
過ぎ軟化温度も高くなり環形成形が困難となる。望まし
くは65〜73％である。SiO 2 is one of the essential components for glass formation, but if it is less than 60%, the expansion coefficient becomes high, and the chemical durability is deteriorated, which is not preferable. On the other hand, if it exceeds 75%, the coefficient of expansion becomes too low, the softening temperature becomes too high, and it becomes difficult to form a ring. Desirably, it is 65 to 73%.
Al2O3は0.5％未満では化学的耐久性が劣化し、５％を
越えるとガラスが不均質となり脈理不良が増加する。望
ましくは１〜３％である。If Al 2 O 3 is less than 0.5%, the chemical durability deteriorates, and if it exceeds 5%, the glass becomes inhomogeneous and the striae failure increases. Desirably, it is 1 to 3%.
Na2Ｏが17％およびK2Ｏが５％を越えると膨張係数が
大きくなり過ぎ化学的耐久性が低下する。Na2Ｏが12％
未満であると軟化温度が高くなり環形成形が困難になる
うえ、膨張係数も低くなりすぎる。If the content of Na 2 O exceeds 17% and the content of K 2 O exceeds 5%, the expansion coefficient becomes too large and the chemical durability decreases. 12% Na 2 O
If it is less than 3, the softening temperature becomes high, the ring-forming form becomes difficult, and the expansion coefficient becomes too low.
CaOおよびMgOのアルカリ土類金属酸化物は電気絶縁性
および化学的耐久性を向上させるが、CaO1％未満および
MgO1％未満ではその効果が期待できず、CaO8％およびMg
O6％を越えるとガラスを失透させる傾向が強くなり好ま
しくない。またCaOおよびMgOは高温粘性を低下させる効
果があるが、作業温度域以下では粘性を上げるため熱加
性を悪化させるので好ましくない。Alkaline earth metal oxides of CaO and MgO improve the electrical insulation and chemical durability, but less than 1% CaO and
With less than 1% MgO, the effect cannot be expected, and CaO 8% and Mg
If O exceeds 6%, the glass tends to be devitrified, which is not preferable. Although CaO and MgO have the effect of lowering the viscosity at high temperatures, they are not preferred below the working temperature range, because they increase the viscosity and deteriorate the thermal additivity.
B2O3は溶融性を向上させ、かつ化学的耐久性も向上さ
せるが、0.1％未満ではその効果がなく５％を越えると
失透しやすいので好ましくない。SO3は0.01％未満であ
ると還元清澄の効果が得られない。また１％を越えると
ガラス溶解温度を高くするうえ、SO2ガスの発生で炉材
の損傷が激しくなるため好ましくない。B 2 O 3 improves the meltability and also the chemical durability, but if it is less than 0.1%, it has no effect, and if it exceeds 5%, it tends to be devitrified. If the content of SO 3 is less than 0.01%, the effect of reduction and fining cannot be obtained. On the other hand, if it exceeds 1%, the glass melting temperature is increased, and the furnace material is seriously damaged by the generation of SO 2 gas, which is not preferable.
CeO2はγ線照射による着色防止のための必須成分とし
て添加されるが、0.1％未満では着色防止効果がなくな
る。また１％を越えるとCe4+自体により黄色に着色され
る度合が強くなるので好ましくない。CeO 2 is added as an essential component for preventing coloration by γ-ray irradiation, but if it is less than 0.1%, the effect of preventing coloration is lost. On the other hand, if it exceeds 1%, the degree of yellowing by Ce 4+ itself increases, which is not preferable.
（実施例） 本発明の実施例を第１表に示す。No.1〜No.4が実施例
である。比較例はNo.5〜No.7でCeO2を１％を越えて含有
する従来例である。第１表のガラス組成は重量百分率で
示した。γ線照射はγ線照射装置（ラジエ工業（株）製
RIC1）により、2.5Mrad（0.24Mrad/hで10.27時間）照射
した。透過率は波長400nmにおける値である。(Examples) Table 1 shows examples of the present invention. No. 1 to No. 4 are examples. The comparative examples are No. 5 to No. 7 which are conventional examples containing more than 1% of CeO 2 . The glass compositions in Table 1 are given as weight percentages. γ-ray irradiation is performed by a γ-ray irradiation device (Rajie Industries Co., Ltd.)
RIC1) for 2.5 Mrad (0.24 Mrad / h for 10.27 hours). The transmittance is a value at a wavelength of 400 nm.
本発明の実施例ガラスを使用したγ線照射着色防止ガ
ラス、たとえば採血管はCeO2含有量が従来ガラスの約３
分の１であるのにかかわらず、γ線照射後の透過率は同
等である。The gamma-ray-irradiation-resistant glass using the glass of the embodiment of the present invention, for example, the blood collection tube has a CeO 2 content of about 3 times that of the conventional glass.
Regardless of the ratio, the transmittance after gamma ray irradiation is the same.
第１表のごとくCeO2添加量を増加させるほどγ線照射
前後の透過率の低下は少なくなる。しかし、CeO2を１％
を越えて添加するとCeO2自体により黄色に着色され、γ
線照射前の透過率が低下するので好ましくない。 As shown in Table 1, the decrease in transmittance before and after γ-ray irradiation decreases as the amount of CeO 2 added increases. However, CeO 2 is 1%
Is added, CeO 2 itself is colored yellow and γ
It is not preferable because the transmittance before the irradiation with rays is reduced.
なお、本発明はγ線照射着色防止ガラスとして記載し
たが、CeO2含有量を減少させる方法としては放射線に対
する着色防止効果を有する一般のガラス製品についても
適用できることは勿論である。Although the present invention has been described as a gamma-ray irradiation coloring prevention glass, it goes without saying that the method for reducing the CeO 2 content can be applied to general glass products having a coloring prevention effect against radiation.
以上説明したように本発明によるγ線照射着色防止ガ
ラスは還元雰囲気で清澄したため、少量のCeO2添加でγ
線照射に対する十分な着色防止効果を有する。またCeO2
添加量が少ないので、ガラスが安価に製造できる。Because was clarified by γ-irradiation anti-coloring glass according to the invention is a reducing atmosphere as described above, a small amount of CeO 2 added γ
It has a sufficient coloring prevention effect against line irradiation. Also CeO 2
Since the amount of addition is small, glass can be manufactured at low cost.
Claims (1)
５％，Na2O12〜17％，K2O0〜５％CaO1〜８％,MgO1〜６
％，B2O30.1〜５％，SO30.01〜１％，CeO20.1〜１％を
含有してなるγ線照射着色防止ガラス。In claim 1 the weight percentage, SiO 2 60~75%, Al 2 O 3 0.5~
5%, Na 2 O12~17%, K 2 O0~5% CaO1~8%, MgO1~6
%, B 2 O 3 0.1 to 5%, SO 3 0.01 to 1%, and CeO 2 0.1 to 1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9923789A JP2623474B2 (en) | 1989-04-19 | 1989-04-19 | γ-ray irradiation prevention glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9923789A JP2623474B2 (en) | 1989-04-19 | 1989-04-19 | γ-ray irradiation prevention glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02279535A JPH02279535A (en) | 1990-11-15 |
| JP2623474B2 true JP2623474B2 (en) | 1997-06-25 |
Family
ID=14242080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9923789A Expired - Fee Related JP2623474B2 (en) | 1989-04-19 | 1989-04-19 | γ-ray irradiation prevention glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2623474B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6031776B2 (en) * | 2012-02-17 | 2016-11-24 | 日本電気硝子株式会社 | Hard color change radiation shielding glass laminate |
| JP6829548B2 (en) * | 2016-04-20 | 2021-02-10 | 株式会社オハラ | Optical glass |
-
1989
- 1989-04-19 JP JP9923789A patent/JP2623474B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02279535A (en) | 1990-11-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |