JP6908237B2 - Quartz glass article with ultraviolet absorption and its manufacturing method - Google Patents
Quartz glass article with ultraviolet absorption and its manufacturing method Download PDFInfo
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- JP6908237B2 JP6908237B2 JP2017033349A JP2017033349A JP6908237B2 JP 6908237 B2 JP6908237 B2 JP 6908237B2 JP 2017033349 A JP2017033349 A JP 2017033349A JP 2017033349 A JP2017033349 A JP 2017033349A JP 6908237 B2 JP6908237 B2 JP 6908237B2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 80
- 238000010521 absorption reaction Methods 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 35
- 239000005350 fused silica glass Substances 0.000 claims description 33
- 239000012535 impurity Substances 0.000 claims description 29
- 238000002834 transmittance Methods 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 230000005855 radiation Effects 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 239000010453 quartz Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 230000007847 structural defect Effects 0.000 claims description 9
- 230000007547 defect Effects 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 230000005251 gamma ray Effects 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims 2
- 230000002708 enhancing effect Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000004071 soot Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Glass Compositions (AREA)
Description
本発明は、紫外線吸収性を有する石英ガラス物品及びその製造方法に関する。 The present invention relates to a quartz glass article having ultraviolet absorption and a method for producing the same.
合成石英ガラスは、赤外から真空紫外までの広い波長範囲において透明であるばかりでなく、熱的及び化学的安定性に優れている。そのため、各種照明ランプ等の光源用窓材等として広く使用されている。しかし、その高い光透過性のため光源から発生した紫外線が直接人体に悪影響を及ぼすばかりでなく、紫外線により空気中の酸素から人体に有害なオゾンが発生する。さらには、レーザー素子が紫外線によりダメージを受け、レーザー発振効率が低下したり、光源の窓材を支持する樹脂が紫外線によりダメージを受け劣化する等の問題があった。 Synthetic quartz glass is not only transparent in a wide wavelength range from infrared to vacuum ultraviolet, but also has excellent thermal and chemical stability. Therefore, it is widely used as a window material for a light source of various lighting lamps and the like. However, due to its high light transmission, not only the ultraviolet rays generated from the light source directly adversely affect the human body, but also the ultraviolet rays generate ozone harmful to the human body from oxygen in the air. Further, there are problems that the laser element is damaged by ultraviolet rays and the laser oscillation efficiency is lowered, and the resin supporting the window material of the light source is damaged by ultraviolet rays and deteriorates.
この問題解決する手段として、本発明者は、ＯＨ基含有量が２０ｐｐｍ以下、Ｈ2分子の含有量が１×１０17個／ｃｍ3以下、Ｃｌ含有量が１０ｐｐｍ以下及び金属不純物含有量の総和が１ｐｐｍ以下であり、厚さ１０ｍｍあたりの透過率が、１８０ｎｍ以下の波長領域で５％以下かつ、２２０ｎｍ以上の波長領域で８０％以上である紫外線吸収合成石英ガラスを提供した（特許文献１）。 As a means for solving this problem, the present inventor has an OH group content of 20 ppm or less, an H 2 molecule content of 1 × 10 17 / cm 3 or less, a Cl content of 10 ppm or less, and a total of metal impurity contents. Provided is an ultraviolet absorbing synthetic quartz glass having a transmittance of 1 ppm or less and a transmittance per 10 mm thickness of 5% or less in a wavelength region of 180 nm or less and 80% or more in a wavelength region of 220 nm or more (Patent Document 1). ..
この紫外線吸収合成石英ガラスは、ガラス形成原料を、酸水素火炎中で火炎加水分解し、生成したシリカ微粒子をターゲット上に堆積させ多孔質シリカ体（スート体）を形成し、得られたスート体を、第１の熱処理としてＮＨ3ガス含有雰囲気で熱処理した後、第２の熱処理をして得られる。 This ultraviolet-absorbing synthetic quartz glass is obtained by hydrolyzing a glass-forming raw material in an acid-hydrogen flame and depositing the generated silica fine particles on a target to form a porous silica body (soo-body). Is heat-treated in an atmosphere containing NH 3 gas as the first heat treatment, and then the second heat treatment is performed.
特許文献１に記載の方法では、ＯＨ基含有量の調整のために第１の熱処理として１０００℃以上の高温にてＮＨ3ガス含有雰囲気で熱処理を行う必要がある。 In the method described in Patent Document 1, it is necessary to perform the heat treatment in an NH 3 gas-containing atmosphere at a high temperature of 1000 ° C. or higher as the first heat treatment in order to adjust the OH group content.
本発明は、このような高温でのＮＨ3ガス含有雰囲気で熱処理を要することなく紫外線吸収性を有する石英ガラス物品を製造できる新たな方法を提供することを目的とする。 An object of the present invention is to provide a new method capable of producing a quartz glass article having ultraviolet absorption in such an atmosphere containing NH 3 gas at a high temperature without requiring heat treatment.
本発明は以下の通りである。
［１］
熔融石英ガラス物品の少なくとも一部に放射線を照射することで、放射線を照射した部位の紫外線吸収性を高めることを含む、紫外線吸収性を有する石英ガラス物品の製造方法。
［２］
前記熔融石英ガラス物品は、天然石英粉を用いて調製される、［１］に記載の製造方法。
［３］
前記放射線はＸ線またはγ線である［１］又は［２］に記載の製造方法。
［４］
前記熔融石英ガラス物品の一部のみに放射線を照射して、前記物品の一部の紫外線吸収性を高める、［１］〜［３］のいずれかに記載の製造方法。
［５］
前記熔融石英ガラス物品の全部に放射線を照射して、前記物品の全体の紫外線吸収性を高める、［１］〜［３］のいずれかに記載の製造方法。
［６］
前記紫外線吸収性石英ガラス物品は、可視光線透過性である、［１］〜［５］のいずれかに記載の製造方法。
［７］
前記熔融石英ガラス物品は、アルミニウム含有量が３０ｐｐｍ以下であり、アルミニウム以外の金属不純物の含有量が２０ｐｐｍ以下であり、かつアルミニウム及びアルミニウム以外の金属不純物の合計含有量が５０ｐｐｍ以下である［１］〜［６］のいずれかに記載の製造方法。
［８］
紫外線吸収性を高めた石英ガラス物品は、厚さ１０ｍｍにおける波長２２０ｎｍの紫外光の透過率が１０％未満である、［１］〜［７］のいずれかに記載の製造方法。
［９］
アルミニウム含有量が３０ｐｐｍ以下であり、アルミニウム以外の金属不純物の含有量が２０ｐｐｍ以下であり、アルミニウム及びアルミニウム以外の金属不純物の合計含有量が５０ｐｐｍ以下であり、かつＯＨ基含有量が１００ｐｐｍ未満である熔融石英ガラス物品であって、前記物品の少なくとも一部に、厚さ１０ｍｍにおける波長２２０ｎｍの紫外光の透過率が１０％未満である紫外線吸収性を有する構造欠陥部位を有する、紫外線吸収性を有する石英ガラス物品。
［１０］
前記熔融石英ガラス物品の一部のみに紫外線吸収性を有する構造欠陥部位を有する、［９］に記載の石英ガラス物品。
［１１］
前記熔融石英ガラス物品の全部に紫外線吸収性を有する構造欠陥部位を有する、［９］に記載の石英ガラス物品。
［１２］
前記紫外線吸収性石英ガラス物品は、可視光線透過性である、［９］に記載の石英ガラス物品。
The present invention is as follows.
[1]
A method for producing a quartz glass article having ultraviolet absorption, which comprises increasing the ultraviolet absorption of the irradiated portion by irradiating at least a part of the fused silica glass article with radiation.
[2]
The production method according to [1], wherein the fused silica glass article is prepared using natural quartz powder.
[3]
The production method according to [1] or [2], wherein the radiation is an X-ray or a γ-ray.
[4]
The production method according to any one of [1] to [3], wherein only a part of the fused silica glass article is irradiated with radiation to enhance the ultraviolet absorption of the part of the article.
[5]
The production method according to any one of [1] to [3], wherein the entire fused silica glass article is irradiated with radiation to enhance the ultraviolet absorption of the entire article.
[6]
The production method according to any one of [1] to [5], wherein the ultraviolet-absorbing quartz glass article is transparent to visible light.
[7]
The fused silica glass article has an aluminum content of 30 ppm or less, a content of metal impurities other than aluminum of 20 ppm or less, and a total content of aluminum and metal impurities other than aluminum of 50 ppm or less [1]. The production method according to any one of [6].
[8]
The production method according to any one of [1] to [7], wherein the quartz glass article having improved ultraviolet absorption has a transmittance of less than 10% of ultraviolet light having a wavelength of 220 nm at a thickness of 10 mm.
[9]
The aluminum content is 30 ppm or less, the content of metal impurities other than aluminum is 20 ppm or less, the total content of aluminum and metal impurities other than aluminum is 50 ppm or less, and the OH group content is less than 100 ppm. A fused silica glass article having a structure defect portion having a structure defect portion having an ultraviolet light transmittance of less than 10% of ultraviolet light having a wavelength of 220 nm at a thickness of 10 mm in at least a part of the article. Quartz glass article.
[10]
The quartz glass article according to [9], wherein only a part of the fused silica glass article has a structural defect portion having ultraviolet absorption.
[11]
The quartz glass article according to [9], wherein all of the fused silica glass articles have a structural defect portion having ultraviolet absorption.
[12]
The quartz glass article according to [9], wherein the ultraviolet-absorbing quartz glass article is visible light transmissive.
本発明によれば、部分的又は全体に紫外線吸収性を有する石英ガラス物品を比較的容易に提供することができる。 According to the present invention, it is possible to relatively easily provide a quartz glass article having ultraviolet absorption partially or wholly.
＜紫外線吸収性石英ガラス物品の製造方法＞
本発明の紫外線吸収性石英ガラス物品の製造方法は、熔融石英ガラス物品の少なくとも一部に放射線を照射することで、放射線を照射した部位の紫外線吸収性を高めることを含む。
<Manufacturing method of UV-absorbing quartz glass articles>
The method for producing an ultraviolet-absorbing quartz glass article of the present invention includes irradiating at least a part of the fused silica glass article with radiation to enhance the ultraviolet absorption of the irradiated portion.
熔融石英ガラス物品は、天然石英粉を熔融して調製されるものであることができる。天然石英粉は、含有する不純物の種類や量に応じて、市販品から適宜選択できる。天然石英粉を用いて調製される熔融石英ガラス物品は、天然由来の不純物を含有し、特に、アルミニウム及びアルミニウム以外の金属不純物を含有する。アルミニウム以外の金属不純物は、例えば、カルシウム、マグネシウム、ナトリウム、カリウム、リチウム、鉄及び銅から成る群から選ばれる少なくとも1種の金属である。天然石英粉の熔融は、プラズマ火炎（電気熔融）にて行う。プラズマ火炎（電気熔融）による溶融は常法により実施できる。 The fused silica glass article can be prepared by melting natural quartz powder. The natural quartz powder can be appropriately selected from commercially available products according to the type and amount of impurities contained. Fused quartz glass articles prepared using natural quartz powder contain naturally occurring impurities, especially aluminum and metal impurities other than aluminum. Metal impurities other than aluminum are, for example, at least one metal selected from the group consisting of calcium, magnesium, sodium, potassium, lithium, iron and copper. The natural quartz powder is melted by a plasma flame (electric melting). Melting by plasma flame (electric melting) can be carried out by a conventional method.
天然石英粉を用いて調製される熔融石英ガラス物品は、アルミニウム含有量が３０ｐｐｍ以下であり、アルミニウム以外の金属不純物の含有量が２０ｐｐｍ以下、好ましくは１０ｐｐｍ以下、より好ましくは５ｐｐｍ以下である。アルミニウム及びアルミニウム以外の金属不純物の合計含有量は、好ましくは５０ｐｐｍ以下、より好ましくは３０ｐｐｍ以下、さらに好ましくは２０ｐｐｍ以下である。本発明においては、これらの不純物を含有する熔融石英ガラス物品に放射線照射することで、紫外線吸収性を付与することができる。 The fused silica glass article prepared using natural quartz powder has an aluminum content of 30 ppm or less, and a metal impurity content other than aluminum of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less. The total content of aluminum and metal impurities other than aluminum is preferably 50 ppm or less, more preferably 30 ppm or less, still more preferably 20 ppm or less. In the present invention, ultraviolet absorption can be imparted by irradiating a fused silica glass article containing these impurities with radiation.
熔融石英ガラス物品のアルミニウム含有量及びアルミニウム以外の金属不純物の含有量は、原料として用いる天然石英粉の不純物量を考慮して、原料として用いる天然石英粉を適宜選択することで調整できる。 The aluminum content of the fused silica glass article and the content of metal impurities other than aluminum can be adjusted by appropriately selecting the natural quartz powder used as the raw material in consideration of the impurity content of the natural quartz powder used as the raw material.
前記不純物を含有する熔融石英ガラス物品に放射線を照射することで、放射線を照射した部分の紫外線吸収性を高める。照射する放射線は、例えば、Ｘ線またはγ線とすることができる。一般に、放射線照射すると石英ガラス中に構造欠陥が生じる。具体的にはＥ′センターと呼ばれる欠陥である。欠陥の生じ方はガラスにより異なる。本発明では、不純物を含有する熔融石英ガラス物品に放射線照射すると、欠陥生成量が特に多く、紫外線吸収特性（透過率低下）に非常に優れた材料となることを見出した。欠陥生成量は放射線種にはよらず、放射線のエネルギー（波長）に依存する。従って、X線あるいはγ線等の線源の種類は限定されない。高エネルギー（低波長）の電磁波照射でも同様な効果が得られる。石英ガラス物品の組成(特に不純物組成)と照射される放射線エネルギー（波長）に依存して、紫外線吸収特性は適宜調整することができる。 By irradiating the fused silica glass article containing the impurities with radiation, the ultraviolet absorption of the irradiated portion is enhanced. The radiation to be irradiated can be, for example, X-rays or γ-rays. In general, irradiation causes structural defects in quartz glass. Specifically, it is a defect called the E'center. How defects occur depends on the glass. In the present invention, it has been found that when a fused silica glass article containing impurities is irradiated with radiation, the amount of defects generated is particularly large, and the material is extremely excellent in ultraviolet absorption characteristics (decrease in transmittance). The amount of defects generated depends on the energy (wavelength) of the radiation, not on the radiation type. Therefore, the types of radiation sources such as X-rays and γ-rays are not limited. The same effect can be obtained by irradiating high-energy (low wavelength) electromagnetic waves. The ultraviolet absorption characteristics can be appropriately adjusted depending on the composition of the quartz glass article (particularly the impurity composition) and the radiation energy (wavelength) to be irradiated.
放射線照射は、前記熔融石英ガラス物品の一部のみに行っても、全部に行っても良い。本発明の特徴は、放射線を照射した部分の紫外線吸収性を高めることができることである。また、紫外線吸収性の強弱は、熔融石英ガラス物品に含まれる不純物含有量と放射線の種類及び照射量に依存して適宜調整できる。熔融石英ガラス物品の全部に放射線を照射すれば、物品の全体の紫外線吸収性を高めることができる。 Irradiation may be performed on only a part of the fused silica glass article or all of the molten quartz glass article. A feature of the present invention is that it is possible to enhance the ultraviolet absorption of the irradiated portion. Further, the strength of the ultraviolet absorption can be appropriately adjusted depending on the impurity content contained in the fused silica glass article, the type of radiation and the irradiation amount. By irradiating the entire fused silica glass article with radiation, the overall ultraviolet absorption of the article can be enhanced.
本発明の製造方法により得られる紫外線吸収性石英ガラス物品は、２５０ｎｍ以下の紫外線に対して強い吸収を有し、好ましくは２２０ｎｍ以下の紫外線に対して強い吸収を有する。より好ましくは厚さ１０ｍｍにおける波長２２０ｎｍの紫外光の透過率が１０％未満であり、さらに好ましくは厚さ１０ｍｍにおける波長２２０ｎｍの紫外光の透過率が１％以下であり、最も好ましくは厚さ１０ｍｍにおける波長２２０ｎｍの紫外光の透過率が０．５％未満である。一方、本発明の製造方法により得られる紫外線吸収性石英ガラス物品は、４００ｎｍ以上の波長の可視光線に対して透過性を有する。好ましくは４００ｎｍ以上の波長の可視光線に対する厚さ１０ｍｍにおける透過率は８０％以上であり、好ましくは８５％以上である。 The ultraviolet-absorbing quartz glass article obtained by the production method of the present invention has strong absorption against ultraviolet rays of 250 nm or less, preferably 220 nm or less. More preferably, the transmittance of ultraviolet light having a wavelength of 220 nm at a thickness of 10 mm is less than 10%, and even more preferably, the transmittance of ultraviolet light having a wavelength of 220 nm at a thickness of 10 mm is 1% or less, and most preferably the thickness is 10 mm. The transmittance of ultraviolet light having a wavelength of 220 nm is less than 0.5%. On the other hand, the ultraviolet-absorbing quartz glass article obtained by the production method of the present invention has transparency to visible light having a wavelength of 400 nm or more. The transmittance at a thickness of 10 mm with respect to visible light having a wavelength of 400 nm or more is preferably 80% or more, preferably 85% or more.
＜紫外線吸収性石英ガラス物品＞
本発明は、上記本発明の製造方法で得られる、紫外線吸収性石英ガラス物品を包含する。本発明の紫外線吸収性石英ガラス物品は、アルミニウム含有量が３０ｐｐｍ以下であり、アルミニウム以外の金属不純物の含有量が２０ｐｐｍ以下であり、アルミニウム及びアルミニウム以外の金属不純物の合計含有量が５０ｐｐｍ以下であり、かつＯＨ基含有量が１００ｐｐｍ未満である熔融石英ガラス物品であって、前記物品の少なくとも一部に、厚さ１０ｍｍにおける波長２２０ｎｍの紫外光の透過率が１０％未満である紫外線吸収性を有する構造欠陥部位を有する。石英ガラス物品の紫外線吸収性は、好ましくは厚さ１０ｍｍにおける波長２２０ｎｍの紫外光の透過率が１％以下であり、さらに好ましくは厚さ１０ｍｍにおける波長２２０ｎｍの紫外光の透過率が０．５％未満である。
<UV-absorbing quartz glass article>
The present invention includes an ultraviolet-absorbing quartz glass article obtained by the above-mentioned production method of the present invention. The ultraviolet-absorbing quartz glass article of the present invention has an aluminum content of 30 ppm or less, a content of metal impurities other than aluminum of 20 ppm or less, and a total content of aluminum and metal impurities other than aluminum of 50 ppm or less. In addition, it is a fused silica glass article having an OH group content of less than 100 ppm, and at least a part of the article has an ultraviolet absorbency having an ultraviolet light transmittance of less than 10% at a wavelength of 220 nm at a thickness of 10 mm. It has a structural defect site. Regarding the ultraviolet absorption of the quartz glass article, the transmittance of ultraviolet light having a wavelength of 220 nm at a thickness of 10 mm is preferably 1% or less, and more preferably the transmittance of ultraviolet light having a wavelength of 220 nm at a thickness of 10 mm is 0.5%. Is less than.
石英ガラス物品のアルミニウム含有量、アルミニウム以外の金属不純物の含有量、アルミニウム及びアルミニウム以外の金属不純物の合計含有量、さらには、アルミニウム以外の金属不純物の種類などは、上記製造方法における説明と同様である。熔融石英ガラス物品のＯＨ基含有量は、原料として用いる天然石英粉のＯＨ基含有量が低く、かつ天然石英粉の熔融をプラズマ火炎（電気熔融）にて行うことから、１００ｐｐｍ未満となる。熔融石英ガラス物品のＯＨ基含有量は、好ましくは１０ｐｐｍ以下である。本発明の石英ガラス物品が、厚さ１０ｍｍにおける波長２２０ｎｍの紫外光の透過率が１０％未満である紫外線吸収性を有する構造欠陥部位を有する理由は、ＯＨ基含有量が１００ｐｐｍ未満であるためと推察される。但し、この推察に拘泥する意図はない。さらに、本発明の熔融石英ガラス物品は、ＯＨ基含有量が１００ｐｐｍ未満であるため耐熱性にも優れる。 The aluminum content of the quartz glass article, the content of metal impurities other than aluminum, the total content of aluminum and metal impurities other than aluminum, and the types of metal impurities other than aluminum are the same as those described in the above production method. be. The OH group content of the fused silica glass article is less than 100 ppm because the OH group content of the natural quartz powder used as a raw material is low and the natural quartz powder is melted by a plasma flame (electric melting). The OH group content of the fused silica glass article is preferably 10 ppm or less. The reason why the quartz glass article of the present invention has a structural defect site having ultraviolet absorption such that the transmittance of ultraviolet light having a wavelength of 220 nm at a thickness of 10 mm is less than 10% is that the OH group content is less than 100 ppm. Inferred. However, I have no intention of sticking to this speculation. Further, the fused silica glass article of the present invention has an excellent heat resistance because the OH group content is less than 100 ppm.
この紫外線吸収性石英ガラス物品は、物品全体が紫外線吸収性である場合と、物品の一部に紫外線吸収性部位を有する場合とがある。即ち、本発明の紫外線吸収性石英ガラス物品は、熔融石英ガラス物品の一部のみに紫外線吸収性を有する構造欠陥部位を有する場合と、熔融石英ガラス物品の全部に紫外線吸収性を有する構造欠陥部位を有する場合とがある。 In this ultraviolet-absorbing quartz glass article, the entire article may be ultraviolet-absorbing, or a part of the article may have an ultraviolet-absorbing portion. That is, the ultraviolet-absorbing quartz glass article of the present invention has a structural defect portion having ultraviolet absorption only in a part of the fused silica glass article and a structural defect portion having ultraviolet absorption in all of the fused silica glass article. May have.
さらに本発明の紫外線吸収性石英ガラス物品は、４００ｎｍ以上の波長の可視光線に対して透過性を有する。好ましくは４００ｎｍ以上の波長の可視光線に対する厚さ１０ｍｍにおける透過率は８０％以上であり、好ましくは８５％以上である。 Further, the ultraviolet-absorbing quartz glass article of the present invention has transparency to visible light having a wavelength of 400 nm or more. The transmittance at a thickness of 10 mm with respect to visible light having a wavelength of 400 nm or more is preferably 80% or more, preferably 85% or more.
本発明の紫外線吸収性石英ガラス物品は、各種照明ランプ等の光源用窓材等として広く使用することができる。 The ultraviolet-absorbing quartz glass article of the present invention can be widely used as a window material for a light source of various lighting lamps and the like.
以下、本発明を実施例に基づいて更に詳細に説明する。但し、実施例は本発明の例示であって、本発明は実施例に限定される意図ではない。 Hereinafter, the present invention will be described in more detail based on examples. However, the examples are examples of the present invention, and the present invention is not intended to be limited to the examples.
試料は、原料（天然石英粉、四塩化珪素、合成シリカ粉）及び熔融方法（プラズマ火炎熔融、スート合成法、酸水素バーナー火炎熔融）の異なるインゴットを製造し、厚さ10mmtの試験用試料を加工。各試料の原料及び製造方法を表１に示し、不純物含有量を表２に示す。試料１が本発明の材料である。 As samples, ingots with different raw materials (natural quartz powder, silicon tetrachloride, synthetic silica powder) and melting methods (plasma flame melting, soot synthesis method, oxyhydrogen burner flame melting) were manufactured, and a test sample with a thickness of 10 mmt was used. processing. The raw materials and manufacturing methods of each sample are shown in Table 1, and the impurity content is shown in Table 2. Sample 1 is the material of the present invention.
・試料一覧表
・不純物含有量一覧表
・試料１（本発明）
原料の天然石英粉をプラズマ火炎中に供給し熔融させた後、ターゲット上に堆積させて透明な石英ガラスインゴットを得た。このインゴットから厚さ１０ｍｍのテストピースを切り出し、試料１の評価用試料とした。試料１のＯＨ基含有量は、１０ｐｐｍ未満であった。
-Sample 1 (invention)
The raw material natural quartz powder was supplied into a plasma flame and melted, and then deposited on a target to obtain a transparent quartz glass ingot. A test piece having a thickness of 10 mm was cut out from this ingot and used as a sample for evaluation of sample 1. The OH group content of Sample 1 was less than 10 ppm.
・試料２
溶融する熱源として、プラズマ火炎の代わりに酸水素バーナー火炎を使用した以外は、試料１と同等の条件で製造した試料を試料２とした。
・ Sample 2
Sample 2 was prepared under the same conditions as Sample 1 except that an oxyhydrogen burner flame was used instead of the plasma flame as the heat source for melting.
・試料３
原料として合成シリカ粉を使用した以外は、試料１と同等の条件で製造した試料を試料３とした。
・ Sample 3
Sample 3 was prepared under the same conditions as Sample 1 except that synthetic silica powder was used as a raw material.
・試料４
原料に四塩化珪素（ＳｉＣｌ4）を使用し、スート法により合成石英ガラスインゴットを製造した。石英ガラス製バーナーの中心管から原料を供給し、バーナーの外管からＨ2ガス及びＯ2ガスを供給してスート体を合成した。このスート体を５０ｖｏｌ％Ｈ2ガス（残部Ｈｅガス）雰囲気、１２００℃で５時間熱処理を行った。その後、１００％Ｈｅガス雰囲気で１５００℃、５時間熱処理を行い透明な石英ガラスインゴットを得た。このインゴットから厚さ１０ｍｍのテストピースを切り出し、試料４の評価用試料とした。
・ Sample 4
Silicon tetrachloride (SiCl 4 ) was used as a raw material, and a synthetic quartz glass ingot was manufactured by the soot method. The raw material was supplied from the central tube of the quartz glass burner, and H 2 gas and O 2 gas were supplied from the outer tube of the burner to synthesize a suit. This suit body was heat-treated at 1200 ° C. for 5 hours in a 50 vol% H 2 gas (remaining He gas) atmosphere. Then, it was heat-treated at 1500 ° C. for 5 hours in a 100% He gas atmosphere to obtain a transparent quartz glass ingot. A test piece having a thickness of 10 mm was cut out from this ingot and used as a sample for evaluation of sample 4.
・試料５
スート体の熱処理を１０ｖｏｌ％Ｃｌ2ガス（残部Ｈｅガス）で行った以外は、試料３と同等の条件で製造した試料を試料５とした。
・ Sample 5
Sample 5 was prepared under the same conditions as Sample 3 except that the soot was heat-treated with 10 vol% Cl 2 gas (remaining He gas).
・試料６
原料にＳｉＣｌ4を使用し、直接法により合成石英ガラスインゴットを製造した。
石英ガラス製バーナーの中心管から原料を供給し、バーナーの外管からＨ2ガス及びＯ2ガスを供給し、脱水縮合反応によりシリカ微粒子を合成し、ターゲット上に堆積させると同時に透明ガラス化させ石英ガラスインゴットを得た。このインゴットから厚さ１０ｍｍのテストピースを切り出し、試料６の評価用試料とした。
・ Sample 6
Using SiCl 4 as a raw material, a synthetic quartz glass ingot was manufactured by a direct method.
Raw materials are supplied from the central tube of a quartz glass burner, H 2 gas and O 2 gas are supplied from the outer tube of the burner, silica fine particles are synthesized by a dehydration condensation reaction, deposited on a target, and at the same time transparently vitrified. A quartz glass ingot was obtained. A test piece having a thickness of 10 mm was cut out from this ingot and used as a sample for evaluation of sample 6.
・蛍光X線装置を使用して、表３に示す条件でX線を照射した。
・X線照射前後での紫外線域（220nm）及び可視域（400nm）の透過率を評価した。試料１〜６の透過率曲線を図１に示す。試料１〜６の全てが、波長４００ｎｍにおいて約９０％の透過率であったのに対して、試料１のみ波長２２０ｎｍ以下において、透過率が１％未満であった。波長２２０ｎｍ及び４００ｎｍにおける各試料の透過率を表４に示す。
-Using a fluorescent X-ray apparatus, X-rays were irradiated under the conditions shown in Table 3.
-The transmittance in the ultraviolet region (220 nm) and visible region (400 nm) before and after X-ray irradiation was evaluated. The transmittance curves of Samples 1 to 6 are shown in FIG. All of Samples 1 to 6 had a transmittance of about 90% at a wavelength of 400 nm, whereas only Sample 1 had a transmittance of less than 1% at a wavelength of 220 nm or less. Table 4 shows the transmittance of each sample at wavelengths of 220 nm and 400 nm.
・X線照射条件
・透過率測定装置
島津製 UV-3105 紫外可視近赤外分光光度計
・耐熱性は、大気中1,150℃で24時間処理した際の試料の変形の有無を、目視で観察して評価。
透過率及び耐熱性の結果を表４に示す。
・ Transmittance measuring device Shimadzu UV-3105 Ultraviolet visible near infrared spectrophotometer ・ Heat resistance is evaluated by visually observing the presence or absence of deformation of the sample when treated in the atmosphere at 1,150 ° C for 24 hours.
The results of transmittance and heat resistance are shown in Table 4.
・透過率及び耐熱性一覧表
本発明の石英ガラス物品である試料１は、X線照射後の波長２２０ｎｍにおける透過率が１％以下となり、優れた紫外線吸収性を有する物であることが分かる。 It can be seen that the sample 1 which is the quartz glass article of the present invention has an transmittance of 1% or less at a wavelength of 220 nm after X-ray irradiation, and has excellent ultraviolet absorption.
さらに本発明の石英ガラス物品である試料１は、優れた耐熱性も有する。耐熱性に優れる理由は、ＯＨ基含有量が相対的に低いからである。ＯＨ基含有量が相対的に低いのは、ＯＨ基含有量が比較的低い原料である天然石英粉をプラズマ火炎（電気溶融）により熔融して調製したためである。一方、試料２〜６は本発明以外の石英ガラス物品であり、試料２の調製のように酸水バーナー火炎を用いる方法は水蒸気雰囲気なのでＯＨ基含有量が高くなる傾向があり、試料４及び５の調製のようにスート合成法でも酸水バーナー火炎を使用するためにＯＨ基含有量が高くなる傾向がある。 Further, the sample 1 which is the quartz glass article of the present invention also has excellent heat resistance. The reason for the excellent heat resistance is that the OH group content is relatively low. The reason why the OH group content is relatively low is that the natural quartz powder, which is a raw material having a relatively low OH group content, is melted and prepared by plasma flame (electric melting). On the other hand, Samples 2 to 6 are quartz glass articles other than the present invention, and the method using an acid water burner flame as in the preparation of Sample 2 tends to increase the OH group content because of the steam atmosphere, and Samples 4 and 5 Since the acid water burner flame is used even in the soot synthesis method as in the preparation of the above, the OH group content tends to be high.
本発明は紫外線吸収性石英ガラスの製造分野に有用である。 The present invention is useful in the field of producing ultraviolet-absorbing quartz glass.
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