JPH11236247A - Glass product coated with conductive antireflection film - Google Patents
Glass product coated with conductive antireflection filmInfo
- Publication number
- JPH11236247A JPH11236247A JP10041542A JP4154298A JPH11236247A JP H11236247 A JPH11236247 A JP H11236247A JP 10041542 A JP10041542 A JP 10041542A JP 4154298 A JP4154298 A JP 4154298A JP H11236247 A JPH11236247 A JP H11236247A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- glass article
- thickness
- article according
- refractive index
- 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 51
- 239000010410 layer Substances 0.000 claims abstract description 146
- 239000011241 protective layer Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 17
- 238000002834 transmittance Methods 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 10
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 27
- 229910001026 inconel Inorganic materials 0.000 abstract description 9
- 238000007789 sealing Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 230000003287 optical effect Effects 0.000 description 14
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910003437 indium oxide Inorganic materials 0.000 description 7
- 230000031700 light absorption Effects 0.000 description 7
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、導電性と光吸収性
を兼ね備えた反射防止膜が被覆されたガラス物品に関
し、とりわけ陰極線管に用いられるガラス製フェースプ
レートやフェースプレートの表示部前面に樹脂又はガラ
スフリット等の接着剤で貼り合わせて用いられる導電性
反射防止ガラス板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass article coated with an antireflection film having both conductivity and light absorption, and more particularly to a glass face plate used for a cathode ray tube and a resin on the front surface of a display portion of the face plate. Also, the present invention relates to a conductive anti-reflection glass plate used by bonding with an adhesive such as glass frit.
【０００２】[0002]
【従来の技術】テレビジョンなどのように陰極線管を用
いた表示装置では、外光の表示面での反射率を低くして
表示品位を良くすることが行われている。また、この陰
極線管を用いた表示装置では、電子銃の使用により高電
圧が用いられるため、表示面は帯電が起こり、これによ
り空気中のゴミや埃を引きつけるため、表示面の帯電を
防止するために導電性にすることが行われている。その
ために、導電性反射防止膜を被覆したガラス板を陰極線
管のフェースプレートに貼り付けたり、フェースプレー
ト外表面に直接導電性反射防止膜を被覆することが行わ
れている。2. Description of the Related Art In a display device using a cathode ray tube, such as a television, it has been practiced to lower the reflectance of external light on a display surface to improve display quality. Further, in the display device using this cathode ray tube, since a high voltage is used by using an electron gun, the display surface is charged, thereby attracting dust and dirt in the air, and thus preventing the display surface from being charged. For this reason, it has been made conductive. For this purpose, a glass plate coated with a conductive anti-reflection film is attached to a face plate of a cathode ray tube, or an outer surface of the face plate is directly coated with a conductive anti-reflection film.
【０００３】上記の陰極線管の表示品を向上させる目的
で用いられる光学物品としては、特開平６−２６３４８
３号公報に、ガラス板／ＩＴＯ／チタン酸プラセオジウ
ム／フッ化マグネシウム／チタン酸プラセオジウム／フ
ッ化マグネシウムで表せる積層体が知られている。An optical article used for the purpose of improving the display quality of the above-mentioned cathode ray tube is disclosed in JP-A-6-26348.
In JP-A No. 3 (KOKAI) No. 3, there is known a laminate which can be represented by glass plate / ITO / praseodymium titanate / magnesium fluoride / praseodymium titanate / magnesium fluoride.
【０００４】また、金属層と透明酸化物層を積層して導
電性反射防止体としたものとしては、特開昭６４−７０
７０１号公報に開示されているガラス板／ステンレス／
酸化チタン／酸化珪素で表せる積層体や、特開平１−１
８０３３３号公報に開示されているガラス板／フッ化マ
グネシウム／ステンレス／酸化チタン／フッ化マグネシ
ウムで表せる積層体や、特許公報第２５６５５３８号に
開示されている、ガラス板／チタン酸プラセオジウム／
ステンレス／チタン酸プラセオジウム／フッ化マグネシ
ウムで表せる積層体がある。Japanese Patent Application Laid-Open No. Sho 64-70 discloses a conductive anti-reflective body formed by laminating a metal layer and a transparent oxide layer.
No. 701 discloses a glass plate / stainless steel /
A laminate represented by titanium oxide / silicon oxide;
No. 80333 discloses a glass plate / magnesium fluoride / stainless steel / titanium oxide / magnesium fluoride laminate, and a glass plate / praseodymium titanate / glass plate disclosed in Japanese Patent Publication No. 2565538.
There is a laminate that can be represented by stainless steel / praseodymium titanate / magnesium fluoride.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、特開平
６−２６３４８３号公報に記載の積層体は、すべての層
が透明酸化物で構成されているため光吸収性がない。し
たがって、導電性と高い透過率を有するものの、その積
層体を陰極線管前面に設けた場合、表示コントラストを
大きくして画像を見やすくするという機能はなかった。
また、この積層構成では、導電性反射防止膜の電気抵抗
の耐熱性が十分でないので、たとえばフェースプレート
表示面に直接に被覆するとファンネルとフェースプレー
トをガラスフリットで接合し電子銃ユニットを密封する
ときの加熱工程で抵抗が大きく上昇してしまい、帯電防
止の性能が著しく低下するという問題点があった。However, the laminate described in JP-A-6-263483 has no light absorbing property because all layers are made of a transparent oxide. Therefore, when the laminate is provided on the front surface of the cathode ray tube, although it has conductivity and high transmittance, there is no function of increasing the display contrast and making the image easy to see.
In addition, in this laminated structure, since the heat resistance of the electric resistance of the conductive anti-reflection film is not sufficient, for example, when directly covering the face plate display surface, the funnel and the face plate are joined with a glass frit to seal the electron gun unit. In the heating step, there is a problem that the resistance is greatly increased and the antistatic performance is significantly reduced.
【０００６】また、上記の金属層と透明酸化物層を積層
して導電性反射防止体としたものは、金属層を用いてい
るので光吸収性を有しているので表示コントラストを上
げられるが、導電性を十分に確保するには金属層の厚み
を大きくする必要があり、それにより可視光線の透過率
が低下してしまうという問題点があった。すなわち陰極
線管の表示面に被覆する反射防止膜として適した光吸収
性と高い導電性を具備する特性をいずれも有するもので
はなかった。[0006] Further, the above-mentioned conductive anti-reflective body obtained by laminating the metal layer and the transparent oxide layer has a light absorbing property because of the use of the metal layer, so that the display contrast can be increased. In order to ensure sufficient conductivity, it is necessary to increase the thickness of the metal layer, which causes a problem that the transmittance of visible light is reduced. That is, it has neither light absorbing property suitable for an anti-reflection film for coating the display surface of a cathode ray tube nor high conductivity.
【０００７】上記のように、陰極線管の手前に直接また
は間接に設けられる導電性反射防止膜は、画像の視認性
を向上させる光吸収性と、帯電を防止するための導電性
と、さらに加熱工程を受けても導電性が大きく低下しな
い（耐熱抵抗力がある）性能を併せ有するものが望まれ
ており、これを実現し提供するという課題があった。本
発明は、上記課題を解決するためになされたものであ
る。As described above, the conductive antireflection film provided directly or indirectly in front of the cathode ray tube has a light absorbing property for improving the visibility of an image, a conductive property for preventing electrification, and a heating property. It is desired to have a property that the conductivity does not greatly decrease even after undergoing the process (has a heat resistance), and there has been a problem of realizing and providing this. The present invention has been made to solve the above problems.
【０００８】[0008]
【課題を解決するための手段】本発明は、ガラス基体上
に、基体側から第１層として金属層、第２層として５５
０ｎｍの波長における屈折率が２．０〜２．４の透明高
屈折率層、第３層として酸化インジウムを主成分とする
透明導電層、第４層として５５０ｎｍの波長における屈
折率が１．３５〜１．４６の低屈折率層が順次積層され
てなる導電性反射防止膜が被覆されたガラス物品におい
て、前記第２層と第３層の間にフッ化マグネシウムまた
は二酸化珪素の保護層を介在させたことを特徴とするガ
ラス物品である。According to the present invention, a metal layer is formed as a first layer and a second layer is formed as a second layer on a glass substrate.
A transparent high refractive index layer having a refractive index of 2.0 to 2.4 at a wavelength of 0 nm, a transparent conductive layer mainly containing indium oxide as a third layer, and a refractive index of 1.35 at a wavelength of 550 nm as a fourth layer. In a glass article coated with a conductive anti-reflection film in which low refractive index layers of 1.46 to 1.46 are sequentially laminated, a protective layer of magnesium fluoride or silicon dioxide is interposed between the second and third layers. It is a glass article characterized by having been made.
【０００９】本発明の透明ガラス基体は、５５０ｎｍに
おける屈折率が１．４〜１．７の透明または着色ガラス
基体が用いられ、ガラスの組成としてはとくに限定され
るものではなく、ソーダ石灰珪酸組成、ホウ珪酸組成、
アルミノ珪酸組成、アルミノホウ珪酸組成などのガラス
を、必要により曲げ加工や風冷強化などによる加工をし
たものが用いられる。As the transparent glass substrate of the present invention, a transparent or colored glass substrate having a refractive index at 550 nm of 1.4 to 1.7 is used, and the composition of the glass is not particularly limited. , Borosilicate composition,
A glass having an aluminosilicate composition, an aluminoborosilicate composition, or the like, which is processed by bending or air-cooling if necessary, is used.
【００１０】本発明の第１層である金属層としては、イ
ンコネル、ニッケル、ニクロム、クロム、チタンなどの
金属または合金の層を用いることができる。本発明の吸
収層は、表示のコントラストを向上させるために５５０
ｎｍの波長における光吸収率を約１５〜３５％とするの
が好ましく、そのために１ｎｍ以上の厚みにすることが
好ましい。また、表示の明るさを確保するために、その
厚みは５ｎｍ以下とするのが好ましい。As the first metal layer of the present invention, a metal or alloy layer of Inconel, nickel, nichrome, chromium, titanium or the like can be used. The absorption layer according to the present invention is 550 in order to improve the contrast of the display.
The light absorption at a wavelength of nm is preferably about 15 to 35%, and for that purpose, the thickness is preferably 1 nm or more. Further, in order to secure the brightness of the display, it is preferable that the thickness is 5 nm or less.
【００１１】本発明の第２層の高屈折率の層は、波長５
５０ｎｍにおける屈折率が２．０〜２．４の透明酸化物
の層が用いられる。チタン酸プラセオジウム、二酸化チ
タニウム、酸化ジルコニウムおよび五酸化タンタルの層
が好ましく用いられ、なかでもチタン酸プラセオジウム
の層は、ＰｒＴｉＯ3を蒸発材料として酸素を導入せず
にほぼその化学量論的組成に近い組成の層を成膜するこ
とができるので、第２層を成膜するときに第１層の金属
層を酸化劣化させることがないので好ましい。第２の層
の厚みは１０〜６０ｎｍとするのが好ましい。この範囲
内とすることにより、他の層と積層されたときの光の干
渉作用により可視光線域の反射率を低くすることができ
る。The high refractive index layer of the second layer of the present invention has a wavelength of 5
A transparent oxide layer having a refractive index of 2.0 to 2.4 at 50 nm is used. A layer of praseodymium titanate, titanium dioxide, zirconium oxide and tantalum pentoxide is preferably used, in particular the layer of praseodymium titanate has a nearly stoichiometric composition without introducing oxygen using PrTiO 3 as evaporating material. Since a layer having a composition can be formed, the first metal layer is not oxidized and deteriorated when the second layer is formed, which is preferable. The thickness of the second layer is preferably set to 10 to 60 nm. Within this range, the reflectance in the visible light region can be reduced due to the interference effect of light when laminated with other layers.
【００１２】本発明の保護層は、フッ化マグネシウムま
たは二酸化珪素の層で形成される。導電性反射防止膜が
陰極線管の組立時の加熱工程を経るとき、空気中の酸素
が層内を拡散浸透し、最も空気側から遠い金属層に到達
してこれを酸化するときに光吸収性が低下する。この酸
素の拡散透過を防止するために、保護層の厚みは１０ｎ
ｍ以上とするのが好ましい。また他の層と積層されたと
きの光の干渉作用で可視光線反射率を低くする上で３０
ｎｍ以下とするのが好ましい。The protective layer of the present invention is formed of a layer of magnesium fluoride or silicon dioxide. When the conductive anti-reflection film goes through the heating process at the time of assembling the cathode ray tube, oxygen in the air diffuses and penetrates through the layer, reaches the metal layer farthest from the air side, and oxidizes it. Decrease. In order to prevent the diffusion and transmission of oxygen, the thickness of the protective layer is 10 n
m or more. In order to lower the visible light reflectance by the interference effect of light when laminated with other layers, 30
nm or less is preferable.
【００１３】チタン酸プラセオジウムの層およびフッ化
マグネシウムの層とも、酸素を導入することなく成膜す
ることができるので、これらの層は光吸収性の金属層を
その成膜中に酸化させることはない。またこの保護層
は、陰極線管のフェースプレートとファンネルとの封着
などの組立工程において熱処理を受けても、金属層が酸
化劣化するのを防止抑制する。Since both the praseodymium titanate layer and the magnesium fluoride layer can be formed without introducing oxygen, these layers do not oxidize the light-absorbing metal layer during the formation. Absent. The protective layer also prevents and suppresses the metal layer from being oxidized and deteriorated even when subjected to a heat treatment in an assembling process such as sealing the face plate of the cathode ray tube and the funnel.
【００１４】本発明においては、導電性反射防止膜の導
電性は、第１層の金属層および第３層の透明導電層によ
り維持されるが、主として第３層の透明導電層により確
保され、この層は酸化インジウムを主成分とする層で構
成される。通常酸化インジウムに酸化錫を少量含有させ
たもの（ＩＴＯ）が低い抵抗を得る上で好ましい。酸化
インジウムに対して酸化錫を３〜１５重量％含有させた
ものが、抵抗を低くするので好ましい。透明導電層の厚
みは、導電性反射防止膜のシート抵抗と光の干渉作用に
よる透過率および反射率特性から、１０〜６０ｎｍの範
囲とするのが好ましい。In the present invention, the conductivity of the conductive antireflection film is maintained by the first metal layer and the third transparent conductive layer, but is mainly ensured by the third transparent conductive layer. This layer is composed of a layer mainly containing indium oxide. Normally, indium oxide containing a small amount of tin oxide (ITO) is preferable for obtaining low resistance. It is preferable that tin oxide be contained in an amount of 3 to 15% by weight with respect to indium oxide, since the resistance is reduced. The thickness of the transparent conductive layer is preferably in the range of 10 to 60 nm in view of the transmittance and reflectance characteristics due to the sheet resistance of the conductive anti-reflection film and the interference effect of light.
【００１５】透明導電層の厚みが１０ｎｍ未満であると
抵抗が大きくなり、かつ受ける熱処理工程により抵抗値
の上昇が著しく増加するので好ましくない。また、厚み
が６０ｎｍを越えると、積層する他の層との光の干渉作
用により可視光線領域での反射率が大きくなるので好ま
しくない。本発明によればシート抵抗を５００Ω／□以
下とすることができ、かつ４５０℃の高温の熱処理を受
けても、なお５００Ω／□以下の抵抗値とすることがで
きる。[0015] If the thickness of the transparent conductive layer is less than 10 nm, the resistance is increased, and the increase in resistance value is remarkably increased by the heat treatment step, which is not preferable. On the other hand, if the thickness exceeds 60 nm, the reflectance in the visible light region increases due to the interference of light with other layers to be laminated, which is not preferable. According to the present invention, the sheet resistance can be reduced to 500 Ω / □ or less, and even when subjected to a heat treatment at a high temperature of 450 ° C., the resistance can still be 500 Ω / □ or less.
【００１６】本発明の第４層の低屈折率層は、５５０ｎ
ｍにおける屈折率が１．３５〜１．４６の可視域で透明
な低屈折率材料で構成される。この低屈折率材料として
はフッ化マグネシウムと二酸化珪素が好んで用いられ、
屈折率がより小さいフッ化マグネシウムが、反射率をよ
く低下させるのでより好ましい。The fourth low refractive index layer of the present invention has a thickness of 550n.
It is made of a transparent low-refractive-index material having a refractive index of 1.35 to 1.46 at m. Magnesium fluoride and silicon dioxide are preferably used as the low refractive index material,
Magnesium fluoride having a smaller refractive index is more preferable because it lowers the reflectance.
【００１７】本発明においては、酸化インジウムを主成
分とする透明導電層は、低屈折率層に被覆され空気に遮
断されているので、導電性反射防止膜が加熱処理を受け
ても酸素の透明導電層までの侵入が抑制され、そのシー
ト抵抗の変化が小さい。In the present invention, since the transparent conductive layer containing indium oxide as a main component is covered with the low refractive index layer and is shielded from the air, even if the conductive antireflection film is subjected to a heat treatment, the transparent conductive layer is made of oxygen. Intrusion into the conductive layer is suppressed, and the change in sheet resistance is small.
【００１８】本発明の導電性反射防止膜の各層を上記厚
みの範囲内で選定することにより、可視光線反射率を１
％以下に維持して、可視光線透過率を６５〜８５％とす
ることができ、かつ、この特性は４５０℃の熱処理を受
けても大きく変化しないようにすることができる。By selecting each layer of the conductive antireflection film of the present invention within the above-mentioned thickness range, the visible light reflectance is set to 1
%, The visible light transmittance can be 65 to 85%, and this property can be prevented from changing significantly even when subjected to a heat treatment at 450 ° C.
【００１９】上記の特性は、導電性反射防止膜を被覆し
たフェースプレートをファンネルと加熱接合して陰極線
管とする場合にとくに有用な特性である。ガラス物品と
しての光吸収性は、金属層の厚みのみによってもよく、
またガラス基体自身の着色による光吸収（ガラス自体に
着色成分を混入）と併せて行ってもよい。The above characteristics are particularly useful when a face plate coated with a conductive antireflection film is heated and joined to a funnel to form a cathode ray tube. Light absorption as a glass article may be dependent only on the thickness of the metal layer,
Alternatively, the light absorption may be performed in combination with the light absorption by coloring the glass substrate itself (mixing a coloring component into the glass itself).
【００２０】本発明の導電性反射防止膜の第３層と第４
層の間に、第２の保護層を介在させるようにして６層構
成の膜とすることにより、反射率を大きく上昇させたり
透過率を大きく低下させたりすることなく、かつ加熱処
理を受けても吸収率の低下および抵抗値の上昇を一層抑
制することができる。この目的のための第２の保護層の
材料としては、二酸化珪素の層または二酸化アルミニウ
ムの層が好ましい。The third and fourth layers of the conductive antireflection film of the present invention
By forming a six-layer film with a second protective layer interposed between the layers, the film is subjected to a heat treatment without greatly increasing the reflectivity or greatly decreasing the transmittance. Also, it is possible to further suppress the decrease in the absorption rate and the increase in the resistance value. The material of the second protective layer for this purpose is preferably a layer of silicon dioxide or a layer of aluminum dioxide.
【００２１】第２の保護層は、石英ガラスや二酸化アル
ミニウムを蒸着材料として成膜することができる。蒸着
に際しては、酸素を成膜室内に導入することなくまたは
少量導入することで蒸着材料とほぼ同じ組成の層に成膜
することができるので、第２の保護層の直前に成膜した
ＩＴＯ層を酸化させることがないので、この層のシート
抵抗を増加させることなく成膜できる。The second protective layer can be formed using quartz glass or aluminum dioxide as a deposition material. At the time of vapor deposition, by introducing oxygen into the film forming chamber without introducing or a small amount of oxygen, it is possible to form a film on a layer having almost the same composition as the vapor deposition material, so that the ITO layer formed just before the second protective layer is formed. Can be formed without increasing the sheet resistance of this layer.
【００２２】第２の保護層の厚みは１ｎｍ以上とするの
が好ましく、その厚みの上限は、積層される他の層との
光の干渉作用によって定まる反射率を低くする上で３０
ｎｍ以下とするのが好ましい。The thickness of the second protective layer is preferably 1 nm or more, and the upper limit of the thickness is 30 nm in order to reduce the reflectance determined by the interference of light with other layers to be laminated.
nm or less is preferable.
【００２３】[0023]
【発明の実施の形態】以下に本発明の実施の形態を説明
する。図１（ａ）、（ｂ）は、本発明の光学物品９の実
施例の断面図である。図１（ａ）は、ガラス板１の片面
に導電性反射防止膜８が被覆されており、図１（ｂ）は
陰極線管用のフェースプレート１の凸側表面に導電性反
射防止膜８が被覆されている。Embodiments of the present invention will be described below. FIGS. 1A and 1B are cross-sectional views of an embodiment of the optical article 9 of the present invention. FIG. 1A shows an example in which a conductive anti-reflection film 8 is coated on one surface of a glass plate 1, and FIG. 1B shows an example in which a conductive anti-reflection film 8 is coated on a convex surface of a face plate 1 for a cathode ray tube. Have been.
【００２４】図２は、導電性反射防止膜８を構成する層
の一実施例を示す一部断面図で、ガラス基体であるガラ
ス板１の片面に順次、インコネル合金層２、チタン酸プ
ラセオジウム層３、保護層であるフッ化マグネシウム層
６、錫を含有する酸化インジウム（ＩＴＯ）層４、第２
の保護層である酸化アルミニウム層７、フッ化マグネシ
ウム層５が被覆されている。FIG. 2 is a partial cross-sectional view showing an embodiment of a layer constituting the conductive anti-reflection film 8. An inconel alloy layer 2 and a praseodymium titanate layer are sequentially formed on one side of a glass plate 1 serving as a glass substrate. 3. Magnesium fluoride layer 6, which is a protective layer, tin-containing indium oxide (ITO) layer 4, second layer
Are covered with an aluminum oxide layer 7 and a magnesium fluoride layer 5 which are protective layers.
【００２５】図３、図４は、本発明の実施例５で得られ
た光学物品のそれぞれ透過率曲線、反射率曲線を示す。
Ａは熱処理前、Ｂは熱処理後（４５０℃、６０分）の曲
線である。FIGS. 3 and 4 show a transmittance curve and a reflectance curve, respectively, of the optical article obtained in Example 5 of the present invention.
A is a curve before heat treatment, and B is a curve after heat treatment (450 ° C., 60 minutes).
【００２６】ガラス板１は、所望の形状に切断され、必
要により公知の方法により曲げ加工や風冷強化されたも
のが用いられる。導電性反射防止膜の各層は、公知の真
空蒸着やイオンプーティング法により被覆される。上記
の層のうち酸化物からなる層はスパッタリングによって
も被覆することができる。The glass plate 1 is cut into a desired shape, and if necessary, bent or air-cooled by a known method is used. Each layer of the conductive anti-reflection film is coated by a known vacuum deposition or ion plating method. Of the above-mentioned layers, the layer made of an oxide can also be coated by sputtering.
【００２７】以下に本発明を実施例に基づいて説明す
る。 実施例１〜５ １００ｍｍ×１００ｍｍ×厚み３ｍｍのソーダ石灰シリ
カ組成のガラス板を真空蒸着装置にいれ、蒸着装置内に
設けられた基板加熱ヒータにより３００℃に加熱した状
態で、表１および表２に示す蒸着条件および層の構成
で、導電性反射防止膜を被覆した本発明の光学物品を作
製した。Hereinafter, the present invention will be described with reference to examples. Examples 1 to 5 A glass plate having a composition of soda-lime-silica having a size of 100 mm × 100 mm × thickness of 3 mm was placed in a vacuum evaporation apparatus and heated to 300 ° C. by a substrate heater provided in the evaporation apparatus. The optical article of the present invention coated with a conductive anti-reflection film was produced under the following deposition conditions and layer configurations.
【００２８】蒸着材料の蒸発は、電子ビーム蒸着法で行
い、蒸着るつぼからガラス板までの距離を約１００ｃｍ
とし、ガラス板を回転させながら行った。蒸着開始前の
到達真空度はいずれの層についても、油拡散ポンプで
０．００３Ｐａまで排気を行った。第３層および第２の
保護層については、その成膜は酸素ガスを外部から一定
量導入し、表１に示す酸素導入圧力で行い、金属層およ
びフッ化マグネシウム層については、酸素を導入せずに
行った。The evaporation material is evaporated by an electron beam evaporation method, and the distance from the evaporation crucible to the glass plate is about 100 cm.
This was performed while rotating the glass plate. The ultimate vacuum before the start of vapor deposition was determined for all layers using an oil diffusion pump.
Evacuation was performed up to 0.003 Pa. Regarding the third layer and the second protective layer, a certain amount of oxygen gas is introduced from the outside and the film is formed at an oxygen introduction pressure shown in Table 1, and oxygen is introduced for the metal layer and the magnesium fluoride layer. Went without.
【００２９】[0029]
【表１】 表１ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 層 蒸着材料 蒸着速度 蒸着時導入 酸素圧力 （ｎｍ／ｓｅｃ） （Ｐａ） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 第１層（光吸収性金属層） インコネル ０．０３ 酸素導入せず 第２層（高屈折率層） ＰｒＴｉＯ3 ０．２７ 酸素導入せず ＴｉＯ2 ０．２５ 酸素導入せず 第３層（透明導電層） ＩＴＯ ０．０６ ０．４０ 第４層（低屈折率層） ＭｇＦ2 ０．６６ 酸素導入せず 保護層 ＭｇＦ2 ０．６６ 酸素導入せず 第２の保護層 Ａｌ2Ｏ3 ０．２９ ０．５３ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 注）ＩＴＯ：酸化錫５重量％含有[Table 1] Table 1 =================================== Oxygen pressure (nm / sec) (Pa) --------------------------------------------------------------------------- First layer ( Light absorbing metal layer) Inconel 0.03 No oxygen introduced Second layer (high refractive index layer) PrTiO 3 0.27 No oxygen introduced TiO 2 0.25 No oxygen introduced Third layer (transparent conductive layer) ITO 0.06 0.40 Fourth layer (low refractive index layer) MgF 2 0.66 No oxygen introduced Protective layer MgF 2 0.66 No oxygen introduced Second Protective layer of Al 2 O 3 0.29 0.53 ========================================= Note ) ITO: contains 5% by weight of tin oxide
【００３０】得られた光学物品を蒸着装置から取り出
し、可視光線反射率、シート抵抗、可視光線透過率を測
定した。表１に各層の蒸着条件を、表２に導電性反射防
止膜の層構成を、表３に得られた光学物品の特性を比較
例とともに示す。The obtained optical article was taken out of the vapor deposition apparatus, and the visible light reflectance, sheet resistance, and visible light transmittance were measured. Table 1 shows the deposition conditions of each layer, Table 2 shows the layer configuration of the conductive antireflection film, and Table 3 shows the characteristics of the obtained optical article together with Comparative Examples.
【００３１】表１〜表３に示すように、本発明の実施例
１〜５の光学物品は、４５０℃の熱処理を受けても抵抗
の上昇が小さいことが分かる。また、熱処理前後での透
過率が６５〜８５％の範囲内で安定しているので、熱処
理工程を受ける陰極線管用の導電反射防止膜付き物品と
して、膜の厚みの決定が容易であるという利点を併せ有
することが分かる。As shown in Tables 1 to 3, it can be seen that the optical articles of Examples 1 to 5 of the present invention have a small increase in resistance even when subjected to heat treatment at 450 ° C. In addition, since the transmittance before and after the heat treatment is stable within the range of 65 to 85%, there is an advantage that the thickness of the film can be easily determined as an article with a conductive antireflection film for a cathode ray tube subjected to a heat treatment step. It turns out that it has both.
【００３２】比較例１〜２ 表１および表２に示す蒸着条件および層の構成で、比較
例となる光学物品のサンプルを作製した。その結果を表
３に示す。比較例１は、導電層を透明導電膜をＩＴＯの
みで構成しているので光吸収性が無い上に、熱処理によ
る抵抗の上昇が大きくなってしまうという性質があっ流
ことが分かる。比較例２は熱処理前後で低いシート抵抗
が得られないことが分かる。COMPARATIVE EXAMPLES 1-2 Samples of optical articles as comparative examples were produced under the deposition conditions and layer configurations shown in Tables 1 and 2. Table 3 shows the results. In Comparative Example 1, since the transparent conductive film is formed of only ITO as the conductive layer, there is no light absorption, and the property that the increase in resistance due to the heat treatment is increased. Comparative Example 2 shows that a low sheet resistance was not obtained before and after the heat treatment.
【００３３】[0033]
【表２】 表２ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 例 第１層 第２層 保護層 第３層 第２の 第４層 保護層 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 実施例１ インコネル PrTiO3 MgF2 ITO MgF2 ２ ２０ １５ ２０ ８６ 実施例２ インコネル PrTiO3 MgF2 ITO MgF2 ２ ２０ １５ ４０ ８６ 実施例３ インコネル PrTiO3 MgF2 ITO MgF2 ４ ３５ １０ ２０ ８１ 実施例４ インコネル TiO2 MgF2 ITO MgF2 ２ １１ １５ ２０ ８６ 実施例５ インコネル PrTiO3 MgF2 ITO Al2O3 MgF2 ２ ２０ １５ ２０ ３ ８６ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 比較例１ ITO PrTiO3 MgF2 PrTiO3 MgF2 ２３ ５ ３４ １３０ ９６ 比較例２ PrTiO3 ステンレス PrTiO3 MgF2 ６２ ４ ６２ ９８ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 層の下の数字は厚み（ｎｍ）Table 2 ==================================== Example First Layer Second Layer Protection Layer 3rd layer 2nd 4th layer Protective layer -------------------------------------------------------------------------- Examples DESCRIPTION OF SYMBOLS 1 Inconel PrTiO 3 MgF 2 ITO MgF 2 220 15 20 86 Example 2 Inconel PrTiO 3 MgF 2 ITO MgF 2 220 15 40 86 Example 3 Inconel PrTiO 3 MgF 2 ITO MgF 2 4 35 10 20 81 Example 4 Inconel TiO 2 MgF 2 ITO MgF 2 2 11 15 20 86 Example 5 Inconel PrTiO 3 MgF 2 ITO Al 2 O 3 MgF 2 220 15 20 3 86 ----------------------------------------- Comparative Example 1 ITO PrTiO 3 MgF 2 PrTiO 3 MgF 2 23 5 34 130 96 Comparative Example 2 PrTiO 3 stainless steel PrTiO 3 MgF 2 62 4 62 98 ========================= =========== The number below the layer is the thickness (nm)
【００３４】[0034]
【表３】 表３ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 例 反射率（％） シート抵抗(Ω/□)) 透過率（％） 初期 熱処理後 初期 熱処理後 初期 熱処理後 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 実施例１ 0.22 0.19 281 297 74.7 81.3 実施例２ 0.58 0.53 84 191 73.2 78.8 実施例３ 0.33 0.31 244 219 67.8 72.8 実施例４ 0.18 0.15 257 243 76.2 81.5 実施例５ 0.20 0.16 267 208 75.7 79.8 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 比較例１ 0.13 0.10 218 7024 93.0 93.1 比較例２ 0.20 0.19 923 870 65.2 69.3 ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ シート抵抗：正方形に切断したガラス板の対向する辺のエッジ部の導電性反射防 止膜表面上に、超音波を印加して電極を設け、電極間の電気抵抗を 測定。 反射率：可視光線反射率 透過率：可視光線透過率 熱処理：４５０℃に６０分維持Table 3 =================================== Example Reflectance (%) Sheet resistance (Ω / □)) Transmittance (%) Initial After heat treatment Initial After heat treatment Initial After heat treatment −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−− Example 1 0.22 0.19 281 297 74.7 81.3 Example 2 0.58 0.53 84 191 73.2 78.8 Example 3 0.33 0.31 244 219 67.8 72.8 Example 4 0.18 0.15 257 243 76.2 81.5 Example 5 0.20 0.16 267 208 75.7 79.8 --------------- 0.19 923 870 65.2 69.3 ==================================== Sheet Resistance: Glass Plate Cut to Square On the surface of the conductive anti-reflective coating at the edge of the opposite side of The electrodes are provided by applying ultrasonic waves, and the electrical resistance between the electrodes is measured. Reflectance: visible light transmittance Transmittance: visible light transmittance Heat treatment: maintained at 450 ° C. for 60 minutes
【００３５】実施例でえられた光学物品が、よい耐熱抵
抗性（熱処理を受けても電気抵抗が大きく変化しない特
性質）を有する理由は十分に明らかではないが、次のよ
うに考えられる。実施例の透明導電層は、ガラス基板上
に直接被覆されていないので、熱処理を受けてもガラス
基体表面から透明導電層への酸素侵入が無いので酸化を
受けにくく、さらに透明導電層は、真空中で成膜された
直後の清浄なフッ化マグネシウムあるいは二酸化珪素の
層の上に直接被覆されているので、結晶性がよく発達し
緻密な層になっており、このため隣接する層からの酸素
の拡散侵入が生じにくい。したがって、大気中で熱処理
を受けても層中の酸素欠陥がつぶれにくく、耐熱抵抗値
の安定性有する至ったと考えられる。The reason why the optical articles obtained in the examples have good heat resistance (characteristics in which the electric resistance does not significantly change even when subjected to heat treatment) is not sufficiently clear, but is considered as follows. Since the transparent conductive layer of the example is not directly coated on the glass substrate, there is no oxygen intrusion from the glass substrate surface to the transparent conductive layer even if it is subjected to a heat treatment, so that it is hardly oxidized. Since it is directly coated on a layer of clean magnesium fluoride or silicon dioxide immediately after being formed in the film, the crystallinity is well developed and a dense layer is formed. Difficult to infiltrate. Therefore, it is considered that the oxygen deficiency in the layer hardly collapsed even when the layer was subjected to the heat treatment in the atmosphere, and the heat resistance was stabilized.
【００３６】[0036]
【発明の効果】本発明の光学物品は、陰極線管の組立工
程において受ける加熱工程を受けても、導電性および光
吸収性が劣化（透過率が増大）することがない。本発明
においては、導電性反射防止膜の導電性は主として酸化
インジウムを主成分とする透明導電層で得られ、光吸収
性は金属層で得られる。The optical article of the present invention does not deteriorate in conductivity and light absorption (increase in transmittance) even when subjected to a heating step in a cathode ray tube assembling step. In the present invention, the conductivity of the conductive antireflection film is obtained mainly by the transparent conductive layer mainly containing indium oxide, and the light absorbing property is obtained by the metal layer.
【００３７】本発明の金属層は、酸素を導入して成膜さ
れる透明導電層の被覆に先立ち、酸素を導入せずに成膜
される高屈折率層および保護層の２つの層により酸素雰
囲気から保護されることにより一層酸化が抑制される。Prior to coating the transparent conductive layer formed by introducing oxygen, the metal layer of the present invention is formed by two layers of a high refractive index layer and a protective layer formed without introducing oxygen. Oxidation is further suppressed by being protected from the atmosphere.
【００３８】さらに、透明導電層および金属層の厚みを
それぞれ１０〜６０ｎｍ、１〜５ｎｍの範囲とすること
により、陰極線管の表示品質を向上させるのに適した透
過率である６５〜８５％の範囲内にすることができる。Further, by setting the thicknesses of the transparent conductive layer and the metal layer to 10 to 60 nm and 1 to 5 nm, respectively, a transmittance of 65 to 85%, which is suitable for improving the display quality of the cathode ray tube, is provided. It can be in the range.
【００３９】[0039]
【図１】図１は、本発明の光学物品の実施例の断面図で
ある。FIG. 1 is a sectional view of an embodiment of the optical article of the present invention.
【図２】図２は、本発明の導電性反射防止膜の積層構成
の１実施例を説明するための図である。FIG. 2 is a view for explaining one embodiment of a laminated structure of a conductive anti-reflection film of the present invention.
【図３】実施例５で得られた光学物品の熱処理前後の透
過率曲線を示す図である。FIG. 3 is a view showing transmittance curves of an optical article obtained in Example 5 before and after heat treatment.
【図４】実施例５で得られた光学物品の熱処理前後の反
射率曲線を示す図である。FIG. 4 is a graph showing reflectance curves before and after heat treatment of an optical article obtained in Example 5.
１：ガラス基体 ２：金属層 ３：透明高屈折率層、 ４：透明導電層 ５：低屈折率層 ６：保護層 ７：第２の保護層 ８：導電性反射防止膜 ９：光学物品 1: glass substrate 2: metal layer 3: transparent high refractive index layer 4: transparent conductive layer 5: low refractive index layer 6: protective layer 7: second protective layer 8: conductive antireflection film 9: optical article
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｇ０２Ｂ 1/10 Ｇ０２Ｂ 1/10 Ｚ (72)発明者 荻野 悦男 大阪府大阪市中央区道修町３丁目５番11号 日本板硝子株式会社内──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI G02B 1/10 G02B 1/10 Z (72) Inventor Etsuo Ogino 3-5-11 Doshomachi, Chuo-ku, Osaka-shi, Osaka Nippon Sheet Glass Inside the corporation
Claims (13)
金属層、第２層として５５０ｎｍの波長における屈折率
が２．０〜２．４の透明高屈折率層、第３層として酸化
インジウムを主成分とする透明導電層、第４層として５
５０ｎｍの波長における屈折率が１．３５〜１．４６の
低屈折率層が順次積層されてなる導電性反射防止膜が被
覆されたガラス物品において、前記第２層と第３層の間
にフッ化マグネシウムまたは二酸化珪素の保護層を介在
させたことを特徴とするガラス物品。1. A metal layer as a first layer, a transparent high-refractive-index layer having a refractive index of 2.0 to 2.4 at a wavelength of 550 nm as a second layer, and an oxidized layer as a third layer on a glass substrate from the substrate side. A transparent conductive layer containing indium as a main component;
In a glass article coated with a conductive antireflection film in which a low-refractive-index layer having a refractive index of 1.35 to 1.46 at a wavelength of 50 nm is sequentially laminated, a fluorine material is provided between the second layer and the third layer. A glass article having a protective layer of magnesium oxide or silicon dioxide interposed.
０ｎｍとした請求項１に記載のガラス物品。2. The thickness of the third transparent conductive layer is 10 to 6
The glass article according to claim 1, which has a thickness of 0 nm.
した請求項１または２に記載のガラス物品。3. The glass article according to claim 1, wherein the thickness of the first metal layer is 1 to 5 nm.
０ｎｍとした請求項２または３に記載のガラス物品。4. The thickness of the high refractive index layer of the second layer is 10 to 6
The glass article according to claim 2, wherein the glass article has a thickness of 0 nm.
５ｎｍとした請求項２〜４のいずれかに記載のガラス物
品。5. The low refractive index layer of the fourth layer has a thickness of 70 to 9
The glass article according to claim 2, having a thickness of 5 nm.
請求項２〜５のいずれかに記載のガラス物品。6. The glass article according to claim 2, wherein said protective layer has a thickness of 10 to 30 nm.
オジウム、二酸化チタニウム、酸化ジルコニウムおよび
五酸化タンタルからなる群から選ばれたいずれかひとつ
の層とした請求項２〜６のいずれかに記載のガラス物
品。7. The high-refractive index layer of the second layer is any one layer selected from the group consisting of praseodymium titanate, titanium dioxide, zirconium oxide and tantalum pentoxide. A glass article according to claim 1.
ウムとする請求項２〜７のいずれかに記載のガラス物
品。8. The glass article according to claim 2, wherein the low refractive index layer of the fourth layer is made of magnesium fluoride.
０Ω／□以下とした請求項１〜８のいずれかに記載のガ
ラス物品。9. The conductive antireflection film has a sheet resistance of 50.
The glass article according to any one of claims 1 to 8, wherein the glass article has a resistance of 0 Ω / □ or less.
過率を６５〜８５％とした請求項１〜９のいずれかに記
載のガラス物品。10. The glass article according to claim 1, wherein the visible light reflectance is 1% or less and the visible light transmittance is 65 to 85%.
の間に酸化アルミニウムまたは二酸化珪素の第２の保護
層を介在させたことを特徴とする請求項１〜１０のいず
れかに記載のガラス物品。11. The method according to claim 1, wherein a second protective layer of aluminum oxide or silicon dioxide is interposed between the third layer and the fourth layer of the conductive anti-reflection film. A glass article according to claim 1.
する請求項１１に記載のガラス物品。12. The glass article according to claim 11, wherein the thickness of the second protective layer is 1 nm or more.
エースプレートである請求項１〜１２のいずれかに記載
のガラス物品。13. The glass article according to claim 1, wherein the transparent substrate is a glass plate or a face plate for a cathode ray tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04154298A JP3581783B2 (en) | 1998-02-24 | 1998-02-24 | Glass article coated with conductive anti-reflective coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04154298A JP3581783B2 (en) | 1998-02-24 | 1998-02-24 | Glass article coated with conductive anti-reflective coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11236247A true JPH11236247A (en) | 1999-08-31 |
| JP3581783B2 JP3581783B2 (en) | 2004-10-27 |
Family
ID=12611317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04154298A Expired - Fee Related JP3581783B2 (en) | 1998-02-24 | 1998-02-24 | Glass article coated with conductive anti-reflective coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3581783B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001088053A1 (en) * | 2000-05-12 | 2001-11-22 | 3M Innovative Properties Company | Rigid substrate lamination adhesive |
| KR20010103321A (en) * | 2000-05-09 | 2001-11-23 | 츄, 자우-지어 | Combination Process of Vacuum Sputtering and Wet Coating for High Conductivity Anti-Reflection Coating on CRT Surface |
| JP2007271860A (en) * | 2006-03-31 | 2007-10-18 | Nidek Co Ltd | Transparent substrate with antireflection film |
| JP2012187806A (en) * | 2011-03-10 | 2012-10-04 | Toppan Printing Co Ltd | Transparent conductive layer laminated base material |
| JPWO2013172382A1 (en) * | 2012-05-15 | 2016-01-12 | Hoya株式会社 | Optical element |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909914B (en) * | 2012-10-26 | 2015-07-01 | 福建省石狮市通达电器有限公司 | Notebook shell and molding process thereof |
-
1998
- 1998-02-24 JP JP04154298A patent/JP3581783B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010103321A (en) * | 2000-05-09 | 2001-11-23 | 츄, 자우-지어 | Combination Process of Vacuum Sputtering and Wet Coating for High Conductivity Anti-Reflection Coating on CRT Surface |
| WO2001088053A1 (en) * | 2000-05-12 | 2001-11-22 | 3M Innovative Properties Company | Rigid substrate lamination adhesive |
| US6706403B1 (en) | 2000-05-12 | 2004-03-16 | 3M Innovative Properties Company | Rigid substrate lamination adhesive |
| JP2007271860A (en) * | 2006-03-31 | 2007-10-18 | Nidek Co Ltd | Transparent substrate with antireflection film |
| JP2012187806A (en) * | 2011-03-10 | 2012-10-04 | Toppan Printing Co Ltd | Transparent conductive layer laminated base material |
| JPWO2013172382A1 (en) * | 2012-05-15 | 2016-01-12 | Hoya株式会社 | Optical element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3581783B2 (en) | 2004-10-27 |
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