JPH03290335A - Glass panel - Google Patents
Glass panelInfo
- Publication number
- JPH03290335A JPH03290335A JP8998790A JP8998790A JPH03290335A JP H03290335 A JPH03290335 A JP H03290335A JP 8998790 A JP8998790 A JP 8998790A JP 8998790 A JP8998790 A JP 8998790A JP H03290335 A JPH03290335 A JP H03290335A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- glass panel
- electron beam
- weight
- surface layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 125
- 238000010894 electron beam technology Methods 0.000 claims abstract description 39
- 238000005342 ion exchange Methods 0.000 claims abstract description 17
- 239000002344 surface layer Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000003856 thermoforming Methods 0.000 claims abstract 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 18
- 238000004040 coloring Methods 0.000 claims description 15
- 229910001415 sodium ion Inorganic materials 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract 1
- 239000003456 ion exchange resin Substances 0.000 abstract 1
- 229920003303 ion-exchange polymer Polymers 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
- 238000006124 Pilkington process Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000010292 electrical insulation Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
- Gas-Filled Discharge Tubes (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は陰極線管、プラズマデイスプレィパネル等のご
とき電子線が照射される画像表示装置のガラス製パネル
、とりわけエネルギーが高い電子線がガラスに照射され
る陰極線管に好適に用いられるガラス製パネルに関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a glass panel of an image display device such as a cathode ray tube or a plasma display panel that is irradiated with electron beams, particularly when high-energy electron beams are applied to the glass. The present invention relates to a glass panel suitably used in a cathode ray tube for irradiation.
［従来の技術］
現在、陰極線管、プラズマデイスプレィを用いた表示装
置は、その輝度の向上のため、電子線の加速電圧や電流
量を上げたり、放電電流を大きくするとともに、装置を
軽量にするために、ガラス製パネルの肉厚を薄くする要
求が生じてきている。[Prior Art] Currently, in order to improve the brightness of display devices using cathode ray tubes and plasma displays, it is necessary to increase the accelerating voltage and current amount of the electron beam, increase the discharge current, and make the device lighter. Therefore, there has been a demand for reducing the thickness of glass panels.
このため、ガラス製パネルとしては、電子線が照射され
ることにより生ずるガラスの着色が少なく、かつ、ガラ
ス製パネルの肉厚が薄（でも、ガラス製パネルの強度が
大きく、かつ高電圧の印加に対しても絶縁破壊が生じに
くいという性能が必要である。一方、ガラス製パネルに
成形するためのガラス素板が大量に得られるということ
が重要である。このために、ガラスの重量を増加させる
ＰｂＯを含有しないガラス組成が種々検討されている。For this reason, as a glass panel, there is little coloring of the glass caused by irradiation with electron beams, and the wall thickness of the glass panel is thin (although the glass panel has high strength and can be used for high voltage application). On the other hand, it is important to be able to obtain large quantities of raw glass sheets for forming into glass panels. Various PbO-free glass compositions have been studied.
すなわち、ＰｂＯを含有しないガラス素板を加熱成形後
、耐電子線照射に対して着色が抑制され、かつ、ガラス
表面のナトリウムイオンをカリウムイオンに置換してガ
ラス表面に圧縮層を設けることにより機械的強度を増加
させることができるガラス素板からガラス製パネルを成
形加工することが検討されている。前記したガラス製パ
ネルにおいては、ガラス組成のとりわけＮ ａ ２０Ｓ
Ｋ２０、Ｌｉ２Ｏの含有量および、ガラス素板の粘度特
性が重要であり、特開昭６２−２８８１３４号には、ガ
ラス組成としてＳｒＯとＢａＯを含みＮａ２Ｏと
Ｋ２Ｏの含有量の比を調整したガラス製パネルが開示さ
れている。しかし、このガラス製パネルは、Ｋ２Ｏの含
有量が多いので、電気絶縁性は良好であるが、ガラスを
カリウムイオンを含む溶融塩中に漬けてガラス中のナト
リウムイオンをカリウムイオンに置換するイオン交換処
理によって機械的強度を大きくすることができず、また
耐電子線照射に対して着色を抑制するのが十分でない。In other words, after heat-forming a glass base plate that does not contain PbO, coloring is suppressed against electron beam irradiation, and the sodium ions on the glass surface are replaced with potassium ions to form a compressed layer on the glass surface. Consideration is being given to forming glass panels from glass blanks, which can increase the mechanical strength. In the glass panel described above, the glass composition is particularly N a 20S
The contents of K20 and Li2O and the viscosity characteristics of the glass base plate are important, and JP-A-62-288134 describes a glass composition containing SrO and BaO with an adjusted ratio of Na2O and K2O content. Panel is disclosed. However, this glass panel has a high content of K2O, so it has good electrical insulation properties, but it can be replaced with potassium ions by ion exchange, which involves soaking the glass in molten salt containing potassium ions and replacing the sodium ions in the glass with potassium ions. It is not possible to increase the mechanical strength by treatment, and the resistance to electron beam irradiation is insufficient to suppress coloring.
さらに、このガラス製パネルの素板は、溶融ガラス素地
をフロート法で直接平板上に成形することができず、ガ
ラスゴブをプレス成形し、さらに表面を研磨するという
工程が必要である。Furthermore, the base plate of this glass panel cannot be formed directly onto a flat plate using a float method using a molten glass base, and requires the steps of press-forming a glass gob and polishing the surface.
また、特開昭６２−１５３１４３号に開示されているガ
ラス素板は、フロート法で直接平板上に成形できるが、
このガラス素板を用いたガラス製パネルは電気絶縁性は
大きいが、イオン交換処理をおこなっても、耐電子線着
色性を良好にし、機械的強度を大きくすることができな
いという問題点がある。Furthermore, the glass base plate disclosed in JP-A-62-153143 can be directly formed onto a flat plate by the float method;
Although a glass panel using this glass base plate has high electrical insulation properties, there is a problem in that even if ion exchange treatment is performed, it is not possible to improve electron beam coloring resistance and increase mechanical strength.
また、特開昭６３−１９５１４６号に開示されているガ
ラス製パネルは、フロート法で成形された市販の窓ガラ
ス用のソーダライムンリカＨ成のガラス素板を用い、カ
リウム溶融塩中に漬けるイオン交換処理により表面にカ
リウムイオンに富む表面層を設けて耐電子線照射による
着色性と機械的強度を確保したものであるが、ガラス容
器の電気絶縁性が小さいために、ガラス製パネルの一部
分に局部的に高電圧がかかった場合に、ガラス製パネル
の絶縁破壊が生ずるという問題点があった。Furthermore, the glass panel disclosed in JP-A No. 63-195146 uses a commercially available soda lime glass base plate for window glass formed by the float method, and soaked in potassium molten salt. A surface layer rich in potassium ions is formed on the surface by ion exchange treatment to ensure coloration resistance and mechanical strength against electron beam irradiation, but due to the poor electrical insulation of the glass container, some parts of the glass panel There was a problem in that dielectric breakdown of the glass panel occurred when a high voltage was applied locally to the glass panel.
［発明が解決しようとする課題］
本発明の目的は、前記した従来の技術が有する問題点を
解決するためになされたもので、電子線照射により着色
が抑制され、かつ、イオン交換処理をしてガラスの表面
に三輪応力層を形成することにより機械的強度が確保で
き、かつガラス製パネル自体の電気絶縁性が大きく、し
たがって高電圧が印加されても電気絶縁破壊が生じにく
いガラス容器であって、さらにガラス容器に成形するた
めのガラス素板が、溶融ガラス素地から直接フロート法
で成形し得るという特徴をもつガラス製パネルを提供す
るものである。[Problems to be Solved by the Invention] The purpose of the present invention has been made to solve the problems of the conventional techniques described above. By forming a tricycle stress layer on the surface of the glass, mechanical strength can be ensured, and the glass panel itself has high electrical insulation properties, so it is a glass container that is unlikely to cause electrical breakdown even when high voltage is applied. Furthermore, the present invention provides a glass panel having the characteristic that a glass base plate for forming a glass container can be formed directly from a molten glass base by a float method.
［課題を解決するための手段］
本発明は、下記組成のガラス素板を加熱成形して得られ
るガラス製パネルであって、前記ガラス５ｆ０２
６４〜７５ 重量％Ａｌ２Ｏ３１，５〜２０
重量％
Ｍｇｏ ０〜５．０ 重量％ＣａＯ６
，５〜９．０ 重量％
Ｌ＋２０ ０．５〜２５ 重量％Ｎ８２０
７．０〜１２ 重量％Ｋ２Ｏ
１．６〜５０ 重量％ＳｒＯ＋ＢａＯ＋ＺｒＯ０〜
１０ 重■％Ｃｅ Ｏ２０〜０ 、５ 重量
％製パネルの少なくとも電子線が照射される部分の表面
層のナトリウムイオンの一部がカリウムイオンを含む溶
融塩中でのイオン交換処理によりカリウムイオンに置換
され、前記表面層のナトリウムイオンとカリウムイオン
のモル比率がＮａ２Ｏ／（Ｎａ２０＋Ｋ２Ｏ）で表して
０．３〜０．７５とした電子線照射による着色を防止し
たガラス製パネルである。本発明のガラス容器のガラス
中に含まれるＮ ａ ２０、Ｋ２Ｏ、Ｌｉ２Ｏ含有量は
、電子線＋７）［射による着色が抑制され、イオン交換
処理により圧縮応力歪が大きい表面層が形成され、かつ
ガラス製パネル全体の電気抵抗を大きくなるように定め
られている。また、同時にフロート法で直接平板状に成
形することができるように定められている。Ｎａ２Ｏ含
有量が７％以下では、カリウムイオンとのイオン交換処
理によりガラス表面近傍に発生する層の圧縮応力が小さ
くなり、ガラス製パネルの強度を大きくすることができ
ないとともに、ガラス素板を成形するに際しては粘度が
高くなりすぎ、溶融、成形が困難となる。また、Ｎ ａ
２０含膏量が、１２％以上の場合には、電子線照射に
よる着色が顕著となる。Ｎ２０含有量が１．６％以下の
場合には、電子線照射による着色が顕著になるとともに
、ガラスの電気抵抗が小さくなり、ガラス製パネルに局
部的に高電圧が印可された場合、絶縁破壊が発生しやす
くなる。また、Ｎ２０の含有量が、５％以上の場合には
、イオン交換処理によるガラス表面に発生する層の圧縮
応力を太き（することができず、したがって、ガラス製
パネルの強度を大きくすることができないとともに、ガ
ラス素板を成形するに際しては粘度が高（なりすぎ、溶
融、成形が困難となる。[Means for Solving the Problems] The present invention is a glass panel obtained by heating and forming a glass base plate having the following composition, the glass 5f02
64-75 wt% Al2O3 1.5-20
Weight% Mgo 0-5.0 Weight% CaO6
,5~9.0 weight% L+20 0.5~25 weight%N820
7.0~12 wt% K2O
1.6~50 wt% SrO+BaO+ZrO0~
Part of the sodium ions in the surface layer of the panel made of 10% by weight CeO20~0, 5% by weight at least in the part irradiated with the electron beam are replaced with potassium ions by ion exchange treatment in a molten salt containing potassium ions. This is a glass panel in which the surface layer has a molar ratio of sodium ions and potassium ions of 0.3 to 0.75 expressed as Na2O/(Na20+K2O) to prevent coloring due to electron beam irradiation. The content of Na20, K2O, and Li2O contained in the glass of the glass container of the present invention is determined by the electron beam +7) [coloring caused by radiation is suppressed, a surface layer with large compressive stress strain is formed by ion exchange treatment, and It is designed to increase the electrical resistance of the entire glass panel. At the same time, it is specified that it can be directly formed into a flat plate using the float method. If the Na2O content is 7% or less, the compressive stress in the layer generated near the glass surface due to ion exchange treatment with potassium ions becomes small, making it impossible to increase the strength of the glass panel and making it difficult to form the glass base plate. In this case, the viscosity becomes too high, making melting and molding difficult. Also, Na
When the 20% content is 12% or more, coloring due to electron beam irradiation becomes noticeable. When the N20 content is 1.6% or less, coloring due to electron beam irradiation becomes noticeable, the electrical resistance of the glass decreases, and dielectric breakdown occurs when a high voltage is locally applied to the glass panel. is more likely to occur. In addition, if the N20 content is 5% or more, the compressive stress of the layer generated on the glass surface due to ion exchange treatment cannot be increased (thus, the strength of the glass panel cannot be increased). In addition, when molding a glass base plate, the viscosity is too high (too much, making it difficult to melt and mold).
また、本発明のガラス製パネルの少な（とも電子線が照
射される部分のガラス表面には、電子線が照射され表面
から侵入する深さについて、イオン交換処理によりカリ
ウムイオンが内部のガラスより富む表面層が形成され、
前記表面層のＮ３２０とＫ２Ｏの含有比率はモル％でＮ
ａ２Ｏ／（Ｎａ２０＋Ｋ２Ｏ）で表して０．３〜０．７
５になるようにされる。上記の式で表される値が０．３
より小さいか、０．７５を越える場合は、電子線が照射
されるとＮａ２ＯやＫ２Ｏのアルカリ成分の移動がガラ
ス中で生じやすく、電子線の照射による着色を抑制する
ことができず、ガラス製パネルの光透過率が低下して、
発光を効率よく外部に取り出すことができない。In addition, the glass panel of the present invention has a small amount of potassium ions (the glass surface of the part where the electron beam is irradiated is irradiated with the electron beam, and the depth at which the electron beam penetrates from the surface is enriched with potassium ions than the inner glass due to ion exchange treatment). A surface layer is formed,
The content ratio of N320 and K2O in the surface layer is N320 and K2O in mol%.
0.3 to 0.7 expressed as a2O/(Na20+K2O)
It is made to be 5. The value expressed by the above formula is 0.3
If the value is smaller than 0.75 or exceeds 0.75, movement of alkaline components such as Na2O and K2O is likely to occur in the glass when irradiated with the electron beam, making it impossible to suppress coloring caused by the irradiation of the electron beam, and making glass The light transmittance of the panel decreases,
Luminescence cannot be efficiently extracted to the outside.
また、上記した範囲内のＮａ２ＯおよびＫ２Ｏに、Ｌｉ
２Ｏが添加されることにより、電子線照射による着色が
さらに抑制されるとともに、ガラスの電気抵抗率をｌＸ
ｌ０”Ωは以上の高い抵抗率にすることができる。Ｌｉ
２Ｏの含有量が０５％より少ないと、電子線照射による
着色を抑制する効果が小さく、２５％を越えると低温度
域（５００〜８００℃）でガラスの粘度が小さくなり、
ガラス素板を成形する上で好ましくない。In addition, Li
By adding 2O, coloring due to electron beam irradiation is further suppressed, and the electrical resistivity of the glass is increased by 1X.
10”Ω can be made to have a high resistivity of more than 10”Ω.
When the content of 2O is less than 0.5%, the effect of suppressing coloring due to electron beam irradiation is small, and when it exceeds 25%, the viscosity of the glass decreases in the low temperature range (500 to 800°C),
This is not preferable when molding a glass base plate.
５ｉ０２は、ガラス形成成分であり、含有量が６４％以
下ではガラスの粘度が小さくなりすぎ、また、７５％を
越えると粘度が高くなりすぎ、ガラス素板の溶解、成形
が困難となる。5i02 is a glass-forming component, and if the content is less than 64%, the viscosity of the glass becomes too low, and if it exceeds 75%, the viscosity becomes too high, making it difficult to melt and mold the glass base plate.
Ａｌ２Ｏ３は、含有量が１５％以下では、ガラスの化学
的耐久性が劣り、２％以上では粘度が高くなり、ガラス
素板の溶解が困難となる。If the content of Al2O3 is less than 15%, the chemical durability of the glass will be poor, and if it is more than 2%, the viscosity will increase, making it difficult to melt the glass base plate.
ＣａＯの含有量が６５％以下では、ガラスの電気抵抗が
低下し、ガラスに高電圧が印加された場合に、絶縁破壊
を起こし易くなり、また、高温での粘度が高くなり、溶
解し難くなるので好ましくない。９％以上では、ガラス
の粘度が、低温度域（５００〜８００℃）で高くなり、
高温度域（８００〜１５００℃）で低くなりすぎ、フロ
ート法で素板を成形するときに、フロートの溶融錫のバ
スでの温度分布のばらつきにより、ガラスの厚みのばら
つきが生じやすい。If the CaO content is less than 65%, the electrical resistance of the glass decreases, making it more likely to cause dielectric breakdown when a high voltage is applied to the glass, and increasing the viscosity at high temperatures, making it difficult to melt. So I don't like it. At 9% or more, the viscosity of the glass becomes high in the low temperature range (500 to 800°C),
It becomes too low in the high temperature range (800 to 1,500°C), and when a blank plate is formed by the float method, variations in the temperature distribution in the float's molten tin bath tend to cause variations in the thickness of the glass.
ＭｇＯは、ＣａＯと共に使用されるが、含有量が５％以
上では、高温域（８００〜１５００℃）での粘度を上昇
させ、ガラス素地の溶融を困難にするので好ましくない
。高い加速電圧で電子線がガラスに照射される場合には
、発生するＸ線が外部に出ないようにするために、５ｒ
Ｏ１ＢａＯ１ＺｒＯ等を、１０％を越えない範囲内でＸ
線によるガラスの着色を抑制するため、Ｃｅ Ｏ２、Ｔ
１０２を、それぞれ０５％を越えない範囲で添加して
も良い。この他に、Ｆｅ２Ｏ３等がガラス原料の不純物
としてガラス中に含まれていたり、ガラスの着色のため
、Ｎｉ０１Ｃｏｏ、Ｃｒ２Ｏ３、Ｎｄ２Ｏ３、ＭｎＯ２
等の着色成分を添加することができる。MgO is used together with CaO, but if the content is 5% or more, it is not preferable because it increases the viscosity in the high temperature range (800 to 1500°C) and makes it difficult to melt the glass base. When glass is irradiated with an electron beam at a high acceleration voltage, a 5r
O1BaO1ZrO, etc., within a range not exceeding 10%
To suppress coloring of the glass due to wires, CeO2, T
102 may be added in an amount not exceeding 0.05%. In addition, Fe2O3, etc. are contained in the glass as impurities in the glass raw materials, and Ni01Coo, Cr2O3, Nd2O3, MnO2
Coloring components such as the following can be added.
本発明のガラス製パネルをガラス素板から成形加工する
方法としては、公知の方法たとえば、特開平１−１２２
９３２号に記載された凸金型にガラス素板を載置し、周
辺部をより高温に加熱してガラス製パネルを製造する方
法を用いることができる。As a method for forming the glass panel of the present invention from a glass base plate, known methods such as Japanese Patent Application Laid-open No. 1-122
The method described in No. 932, in which a glass base plate is placed in a convex mold and the peripheral portion is heated to a higher temperature, can be used to manufacture a glass panel.
本発明のガラス製パネルは、所定形状に成形加工された
後、４３０℃ないし５１０℃のカリウムイオンを含む溶
融塩中に、浸漬し、成形加工したガラス製パネルの表面
のナトリウムイオンの一部をカリウムイオンに、イオン
交換により置換することにより得られる。イオン交換処
理温度が４３０℃より低い場合には、イオン交換に要す
る時間が長くなり、また、５１０℃より高い場合には、
イオン交換処理により生ずる表面圧縮応力が緩和し、強
化の効果が得られないので好ましくない。After the glass panel of the present invention is formed into a predetermined shape, it is immersed in a molten salt containing potassium ions at 430°C to 510°C to remove some of the sodium ions on the surface of the formed glass panel. Obtained by replacing potassium ions with ion exchange. If the ion exchange treatment temperature is lower than 430°C, the time required for ion exchange will be longer, and if it is higher than 510°C,
This is not preferable because the surface compressive stress caused by the ion exchange treatment is relaxed and no strengthening effect can be obtained.
溶融塩の陽イオンがナトリウムイオンとカリウムイオン
からなる場合、ナトリウムイオンとカリウムイオンのモ
ル比Ｎａ／Ｋ”は０．２５〜０．７５の範囲にするのが
好ましい。上記した範囲外では、イオン交換処理により
ガラス製パネルの表面層のＮａ２ＯとＫ２Ｏのモル比は
、Ｎａ２Ｏ／（Ｎａ２０＋Ｋ２Ｏ）ｒ表して０．３〜０
．７５にすることができなくなるので好ましくない。When the cations of the molten salt consist of sodium ions and potassium ions, the molar ratio Na/K'' of sodium ions and potassium ions is preferably in the range of 0.25 to 0.75. Through the exchange treatment, the molar ratio of Na2O and K2O in the surface layer of the glass panel is 0.3 to 0 expressed as Na2O/(Na20+K2O)r.
．． 75, which is not preferable.
イオン交換処理は上記した温度範囲で、温度と時間との
条件を適当に選んでおこなわれる。通常ガラス製パネル
と溶融塩との接触時間は、３０〜３００分に調整される
のが好ましい。３０分より短い場合は、ナトリウムイオ
ンとカリウムイオン交換が充分におこなわれず、３００
分より長いと上記したＮ ａ２０／ （Ｎ ａ２０ 十
Ｋ２Ｏ）で表されるガラス製パネルの表面層の組成は０
．３〜０．７５にすることが困難となる。The ion exchange treatment is carried out within the above-mentioned temperature range by appropriately selecting temperature and time conditions. Usually, the contact time between the glass panel and the molten salt is preferably adjusted to 30 to 300 minutes. If it is shorter than 30 minutes, the exchange of sodium ions and potassium ions will not be carried out sufficiently, and the
If the time is longer than 1 minute, the composition of the surface layer of the glass panel expressed as Na20/(Na20 + K2O) is 0.
．． 3 to 0.75 becomes difficult.
［作用］
本発明のガラス製パネルは、ガラス中のＮａ２Ｏ、Ｋ２
Ｏ、Ｌ１２０の含有量が調整されて、電気絶縁性が大き
くなっている。これにより、電子線が照射されてガラス
製パネルに高電圧が印加されても、ガラス製パネルは絶
縁破壊が生じにくい。また本発明のガラス製パネルは、
少なくとも電子線が照射される部分に設けられたガラス
の表面近傍には、圧縮応力歪があり、かつ、Ｎａ２Ｏと
Ｋ２Ｏの含有率が調整された表面層が設けられているの
で、電子線が照射されても着色が生じにく（、かつ、機
械的強度が大きい。[Function] The glass panel of the present invention has Na2O and K2 in the glass.
The contents of O and L120 are adjusted to improve electrical insulation. As a result, even if a high voltage is applied to the glass panel by irradiation with an electron beam, the glass panel is unlikely to suffer dielectric breakdown. Furthermore, the glass panel of the present invention has
Near the surface of the glass provided at least in the part irradiated with the electron beam, there is a surface layer with compressive stress strain and an adjusted content of Na2O and K2O, so that the electron beam irradiates It is difficult to discolor even when exposed to water (and has high mechanical strength).
し実施例］
本発明を以下に実施例に基いて説明する。第１図は、本
発明のガラス製パネルの一実施例の一部断面図である。EXAMPLES] The present invention will be described below based on Examples. FIG. 1 is a partial sectional view of an embodiment of the glass panel of the present invention.
実施例
第１表のサンプル１の欄に示すガラス組成のガラスを白
金るつぼで溶融し、溶融したガラス素地を金属板の上に
流し出し、冷却後、５ｍｍの厚みのガラス板に研磨した
。このガラス板を凸形の金型上にのせ電気炉内で周辺部
分をより高温に加熱して、画像表示部が長方形でその対
角の長さが１５偶のガラス容器の形をしたガラス製パネ
ルを製作した。このガラス製パネルについて体積抵抗率
の対数ｌｏｇρ、電子線照射後の透過率の低下量△Ｔ（
ΔＴ＝照射前の透過率−照射後の透過率）を測定した。Examples Glass having the glass composition shown in the column of Sample 1 in Table 1 was melted in a platinum crucible, the molten glass base was poured onto a metal plate, and after cooling, it was polished into a glass plate with a thickness of 5 mm. This glass plate is placed on a convex mold and the surrounding area is heated to a higher temperature in an electric furnace to create a glass container-shaped glass container with a rectangular image display area and a diagonal length of 15 mm. I made a panel. For this glass panel, the logarithm of volume resistivity logρ, the amount of decrease in transmittance after electron beam irradiation △T (
ΔT=transmittance before irradiation−transmittance after irradiation) was measured.
また、硝酸カリウム溶融塩中でのイオン交換処理をおこ
ない、その後、４５０℃で３時間熱処理をして得られた
別のガラス板について表面層の圧縮応力を測定した。結
果を第１表に示す。体積抵抗率は、１５０℃での測定値
であり、電子線照射後の透過率の低下量Δ丁は、真空中
で１０ｋｖ、４０μＡ／ｃｍ’ｉｉ子を１００時間照射
後、波長４００ｎｍでの光の透過率の低下量で示しであ
る。表面圧縮応力の測定は、偏光顕微鏡を用いて行った
。サンプル１と同じようにして、ガラス組成の異なるサ
ンプル２〜１３を製作し、その結果得られた特性をまと
めて第１表および第３表にホす。In addition, the compressive stress of the surface layer of another glass plate obtained by performing ion exchange treatment in a potassium nitrate molten salt and then heat treatment at 450° C. for 3 hours was measured. The results are shown in Table 1. The volume resistivity is a value measured at 150°C, and the amount of decrease in transmittance after electron beam irradiation, Δ, is the value measured at a wavelength of 400 nm after 100 hours of irradiation at 10 kV and 40 μA/cm'ii in vacuum. It is indicated by the amount of decrease in transmittance. Surface compressive stress was measured using a polarizing microscope. Samples 2 to 13 having different glass compositions were manufactured in the same manner as Sample 1, and the properties obtained are summarized in Tables 1 and 3.
［従来例］
実施例と同じようにして、前記した従来技術で開示され
ているガラス組成を有するガラス製パネルおよびガラス
板を製作した。得られた比較サンプルの体積抵抗率の対
数ｌｏｇρ、電子線照射後の透過率の低下量△Ｔ（△Ｔ
＝照射前の透過率照射後の透過率）硝酸カリウム溶融塩
中でのイオン交換処理により得られた表面層の圧縮応力
を測定し、結果を第２表および第４表に示した。体積抵
抗率は、１５０℃での測定値であり電子線照射後の透過
率の低下量△Ｔは、真空中で１０ｋｖ、第３表
第４表
４０μＡ／ｃｍ２電子を１００時間照射後、波長４００
ｎｍでの
透過率の低下量を示しである。表面圧縮応力の測定は、
偏光顕微鏡を用いて行った。[Conventional Example] A glass panel and a glass plate having the glass composition disclosed in the above-mentioned prior art were manufactured in the same manner as in the example. The logarithm logρ of the volume resistivity of the obtained comparison sample, the amount of decrease in transmittance after electron beam irradiation △T (△T
= Transmittance before irradiation Transmittance after irradiation) The compressive stress of the surface layer obtained by ion exchange treatment in a potassium nitrate molten salt was measured, and the results are shown in Tables 2 and 4. The volume resistivity is a value measured at 150°C, and the amount of decrease in transmittance ΔT after electron beam irradiation is 10 kV in vacuum, Table 3, Table 4, after irradiating with 40 μA/cm2 electrons for 100 hours, at a wavelength of 400
It shows the amount of decrease in transmittance in nm. Measurement of surface compressive stress is
This was done using a polarizing microscope.
以上から分かるように、本発明の実施例は、絶縁破壊が
生じない体積抵抗率の目安であるｌＸｌ０ＩｌｌΩｃｍ
より大きい電気絶縁性を有し、かつ、機械的強度が４０
ｋｇ／ｍｍ２以上と大きく、さらに電子線が照射されて
も透過率の低下量が小さいガラス製パネルであることが
分かる。従来技術のガラス製パネルより、機械的強度の
指標になる表面層の圧縮応力および耐電子線着色性が改
善されていることが分かる。As can be seen from the above, the embodiment of the present invention has a volume resistivity of 1
Has greater electrical insulation and mechanical strength of 40
It can be seen that this is a glass panel with a large size of kg/mm2 or more, and a small decrease in transmittance even when irradiated with an electron beam. It can be seen that the compressive stress and electron beam coloring resistance of the surface layer, which are indicators of mechanical strength, are improved compared to the glass panel of the prior art.
［発明の効果］
本発明のガラス製パネルは、電子線が照射される画像表
示装置に使用されるに際しては、ガラスの表面に、電子
線照射により着色が生じるのを抑制する圧縮応力層が形
成されているので、発光を外部に効率よく取り出せる。[Effects of the Invention] When the glass panel of the present invention is used in an image display device that is irradiated with electron beams, a compressive stress layer is formed on the surface of the glass to suppress coloring due to electron beam irradiation. This allows the emitted light to be efficiently extracted to the outside.
また、外部からの機械的な衝撃に対して強いので、ガラ
スの厚みを薄くすることができ、画像表示装置を軽量化
することができる。また、本発明のガラス製パネルは、
高電圧が印加されても、ガラスの体積抵抗率が大きいの
で絶縁破壊が生じにくい。また本発明のガラス製パネル
を成形加工するためのガラス素板は、フロート法により
直接溶融素地から成形できるので、大量のガラス素板を
安価に製造することができる。Furthermore, since it is strong against external mechanical impact, the thickness of the glass can be reduced, and the weight of the image display device can be reduced. Moreover, the glass panel of the present invention is
Even if a high voltage is applied, dielectric breakdown is unlikely to occur due to the high volume resistivity of glass. Moreover, since the glass base plate for forming the glass panel of the present invention can be directly molded from a molten base material by the float method, a large amount of glass base plates can be manufactured at low cost.
第１図は、本発明のガラス製パネルの一実施例の一部断
面図である。
手続補正書FIG. 1 is a partial sectional view of an embodiment of the glass panel of the present invention. Procedural amendment
Claims (1)
ネルであって、 ＳｉＯ＿２６４〜７５重量％ Ａｌ＿２Ｏ＿３１．５〜２．０重量％ ＭｇＯ０〜５．０重量％ ＣａＯ６．５〜９．０重量％ Ｌｉ＿２Ｏ０．５〜２．５重量％ Ｎａ＿２Ｏ７．０〜１２重量％ Ｋ＿２Ｏ１．６〜５．０重量％ ＳｒＯ＋ＢａＯ＋ＺｒＯ０〜１０重量％ ＣｅＯ＿２０〜０．５重量％ 前記ガラス製パネルの少なくとも電子線が照射される部
分の表面層のナトリウムイオンの一部がカリウムを含む
溶融塩中でのイオン交換処理によりカリウムイオンに置
換され、前記表面層のナトリウムイオンとカリウムイオ
ンのモル比率がＮａ＿２Ｏ／（Ｎａ＿２Ｏ＋Ｋ＿２Ｏ）
で表して０．３〜０．７５とした電子線照射による着色
を防止したガラス製パネル。[Scope of Claims] A glass panel obtained by thermoforming a glass plate having the following composition, SiO_264-75% by weight Al_2O_31.5-2.0% by weight MgO 0-5.0% by weight CaO6.5- 9.0% by weight Li_2O 0.5-2.5% by weight Na_2O 7.0-12% by weight K_2O 1.6-5.0% by weight SrO+BaO+ZrO 0-10% by weight CeO_20-0.5% by weight At least the electron beam of the glass panel A part of the sodium ions in the surface layer of the irradiated area are replaced with potassium ions by ion exchange treatment in a molten salt containing potassium, and the molar ratio of sodium ions and potassium ions in the surface layer becomes Na_2O/(Na_2O+K_2O). )
A glass panel that prevents coloring due to electron beam irradiation and has a value of 0.3 to 0.75.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2089987A JP2548423B2 (en) | 1990-04-04 | 1990-04-04 | Glass panel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2089987A JP2548423B2 (en) | 1990-04-04 | 1990-04-04 | Glass panel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03290335A true JPH03290335A (en) | 1991-12-20 |
| JP2548423B2 JP2548423B2 (en) | 1996-10-30 |
Family
ID=13985996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2089987A Expired - Fee Related JP2548423B2 (en) | 1990-04-04 | 1990-04-04 | Glass panel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2548423B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0604094A1 (en) * | 1992-12-14 | 1994-06-29 | Nippon Sheet Glass Co. Ltd. | Glass panel resistant to coloring when irradiated with electron rays |
| JPH08133778A (en) * | 1994-09-14 | 1996-05-28 | Asahi Glass Co Ltd | Glass composition and substrate for plasma display |
| EP0791563A1 (en) * | 1987-02-03 | 1997-08-27 | Nippon Sheet Glass Co. Ltd. | Glass panel resistant to coloring when irradiated with electron rays |
| WO1998001400A1 (en) * | 1995-04-14 | 1998-01-15 | Nippon Electric Glass Co., Ltd. | Substrate glass and plasma display made by using the same |
| KR100394094B1 (en) * | 1997-07-16 | 2003-09-19 | 삼성코닝 주식회사 | Substrate glass composition for plasma image display panel |
| WO2008038780A1 (en) * | 2006-09-28 | 2008-04-03 | Nippon Sheet Glass Company, Limited | Glass composition and glass article using the same |
| JP2011522770A (en) * | 2008-06-09 | 2011-08-04 | ピルキントン グループ リミテッド | Glass plate and glass composition for solar unit |
| JP2013234121A (en) * | 2007-08-03 | 2013-11-21 | Nippon Electric Glass Co Ltd | Tempered glass substrate, and method for producing the same |
| JP5456316B2 (en) * | 2006-09-28 | 2014-03-26 | 日本板硝子株式会社 | Glass composition and glass article using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104703938A (en) * | 2012-10-09 | 2015-06-10 | 旭硝子株式会社 | Cover glass for solar cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63195146A (en) * | 1987-02-04 | 1988-08-12 | Nippon Sheet Glass Co Ltd | Glass panel irradiated with electron rays and production thereof |
| JPH01203244A (en) * | 1988-02-10 | 1989-08-16 | Nippon Sheet Glass Co Ltd | Production of glass article prevented to be colored by electron beam |
-
1990
- 1990-04-04 JP JP2089987A patent/JP2548423B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63195146A (en) * | 1987-02-04 | 1988-08-12 | Nippon Sheet Glass Co Ltd | Glass panel irradiated with electron rays and production thereof |
| JPH01203244A (en) * | 1988-02-10 | 1989-08-16 | Nippon Sheet Glass Co Ltd | Production of glass article prevented to be colored by electron beam |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0791563A1 (en) * | 1987-02-03 | 1997-08-27 | Nippon Sheet Glass Co. Ltd. | Glass panel resistant to coloring when irradiated with electron rays |
| EP0604094A1 (en) * | 1992-12-14 | 1994-06-29 | Nippon Sheet Glass Co. Ltd. | Glass panel resistant to coloring when irradiated with electron rays |
| JPH08133778A (en) * | 1994-09-14 | 1996-05-28 | Asahi Glass Co Ltd | Glass composition and substrate for plasma display |
| WO1998001400A1 (en) * | 1995-04-14 | 1998-01-15 | Nippon Electric Glass Co., Ltd. | Substrate glass and plasma display made by using the same |
| KR100320628B1 (en) * | 1996-07-10 | 2002-03-08 | 모리 데쯔지 | Substrate glass and plasma display made by using the same |
| KR100394094B1 (en) * | 1997-07-16 | 2003-09-19 | 삼성코닝 주식회사 | Substrate glass composition for plasma image display panel |
| WO2008038780A1 (en) * | 2006-09-28 | 2008-04-03 | Nippon Sheet Glass Company, Limited | Glass composition and glass article using the same |
| JP5456316B2 (en) * | 2006-09-28 | 2014-03-26 | 日本板硝子株式会社 | Glass composition and glass article using the same |
| JP5456317B2 (en) * | 2006-09-28 | 2014-03-26 | 日本板硝子株式会社 | Glass composition and glass article using the same |
| JP2013234121A (en) * | 2007-08-03 | 2013-11-21 | Nippon Electric Glass Co Ltd | Tempered glass substrate, and method for producing the same |
| JP2011522770A (en) * | 2008-06-09 | 2011-08-04 | ピルキントン グループ リミテッド | Glass plate and glass composition for solar unit |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2548423B2 (en) | 1996-10-30 |
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