JPH05166423A - Manufacture of conductive film and low reflective conductive film - Google Patents
Manufacture of conductive film and low reflective conductive filmInfo
- Publication number
- JPH05166423A JPH05166423A JP35081591A JP35081591A JPH05166423A JP H05166423 A JPH05166423 A JP H05166423A JP 35081591 A JP35081591 A JP 35081591A JP 35081591 A JP35081591 A JP 35081591A JP H05166423 A JPH05166423 A JP H05166423A
- Authority
- JP
- Japan
- Prior art keywords
- conductive film
- compound
- film
- low
- solution
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はブラウン管パネル等のガ
ラス基体表面に塗布される低反射導電膜に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low reflection conductive film applied on the surface of a glass substrate such as a cathode ray tube panel.
【０００２】[0002]
【従来の技術】ブラウン管は高電圧で作動するため起動
時、或いは終了時に該表面に静電気が誘発される。この
静電気により該表面にほこりが付着しコントラスト低下
を引き起こしたり、或いは直接触れた際軽い電気ショッ
クによる不快感を生ずることが多い。2. Description of the Related Art Since a cathode ray tube operates at a high voltage, static electricity is induced on the surface of the cathode ray tube at the time of starting or ending. This static electricity often causes dust to adhere to the surface to cause a reduction in contrast, or causes discomfort due to a slight electric shock when directly touched.
【０００３】従来、上述の事柄を防止するためにブラウ
ン管パネル表面に帯電防止膜を付与する試みがかなりな
されてきた。例えば特開昭６３−７６２４７号記載の通
り、ブラウン管パネル表面を３５０℃程度に加熱し、Ｃ
ＶＤ法により酸化スズ及び酸化インジウム等の導電性酸
化物質を設ける方法が採用されてきた。しかしながらこ
の方法では装置コストがかかることに加え、ブラウン管
を高温加熱するためブラウン管内の蛍光体の脱落を生じ
たり、寸法精度が低下する等の問題があった。また、導
電層に用いる材料として酸化スズが最も一般的である
が、この場合低温処理では高性能膜が得にくい欠点があ
った。In the past, many attempts have been made to provide an antistatic film on the surface of a cathode ray tube panel in order to prevent the above-mentioned problems. For example, as described in JP-A-63-76247, the surface of the cathode ray tube panel is heated to about 350 ° C., and C
A method of providing a conductive oxide substance such as tin oxide and indium oxide by the VD method has been adopted. However, in this method, there is a problem in that in addition to the cost of the apparatus, since the CRT is heated to a high temperature, the fluorescent substance in the CRT falls off and the dimensional accuracy decreases. Further, tin oxide is the most general material used for the conductive layer, but in this case, there is a drawback that it is difficult to obtain a high performance film by low temperature treatment.
【０００４】また近年、電磁波ノイズによる電子機器へ
の電波障害が社会問題となり、それらを防止するため規
格の作成、規制が行われている。電磁波ノイズは人体に
ついて、ＣＲＴ上の静電気チャージによる皮膚ガンの恐
れ、低周波電磁界（ＥＬＦ）による胎児への影響、その
他Ｘ線、紫外線などによる害が各国で問題視されてい
る。この場合、導電性塗膜の存在により、導電性塗膜に
電磁波が当たると、塗膜中に渦電流を誘導して、この作
用で電磁波を反射する。しかしこのためには高い電界強
度に耐え得る金属並の電気特性の良導電体が必要である
が、それほどの良導電性の膜を得ることは更に困難であ
った。In recent years, radio wave interference to electronic equipment due to electromagnetic noise has become a social problem, and standards have been created and regulated to prevent them. Electromagnetic noise is considered to be a problem in various countries in the human body, such as fear of skin cancer due to electrostatic charge on the CRT, influence on the fetus due to low-frequency electromagnetic field (ELF), and harm due to X-rays and ultraviolet rays. In this case, when an electromagnetic wave hits the conductive coating film due to the presence of the conductive coating film, an eddy current is induced in the coating film and the electromagnetic wave is reflected by this action. However, for this purpose, a conductor having good electric characteristics comparable to that of a metal capable of withstanding high electric field strength is required, but it has been more difficult to obtain a film having such good conductivity.
【０００５】また低反射膜のコーティング法は、従来よ
り光学的機器においては言うまでもなく、民生用機器特
にＴＶ、コンピューター端末の陰極線管（ＣＲＴ）に関
し数多くの検討がなされてきた。Further, the coating method of the low reflection film has been hitherto examined in many cases not only in optical equipment but also in consumer equipment, particularly in cathode ray tubes (CRT) of TVs and computer terminals.
【０００６】従来の方法は例えば特開昭６１−１１８９
３１号記載の如く、ブラウン管表面に防眩効果を持たせ
るために表面に微細な凹凸を有するＳｉＯ2 層を付着さ
せたり、弗酸により表面をエッチングして凹凸を設ける
等の方法がとられてきた。しかし、これらの方法は、外
部光を散乱させるノングレア処理と呼ばれ、本質的に低
反射層を設ける手法でないため、反射率の低減には限界
があり、又ブラウン管などにおいては、解像度を低下さ
せる原因ともなっていた。A conventional method is disclosed in, for example, Japanese Patent Laid-Open No. 61-1189.
As described in No. 31, methods such as attaching a SiO 2 layer having fine irregularities to the surface of the cathode ray tube to provide an antiglare effect, or etching the surface with hydrofluoric acid to provide irregularities have been adopted. It was However, these methods are called non-glare processing that scatters external light, and there is a limit to the reduction of reflectance because it is not a method of essentially providing a low reflection layer. Also, in a cathode ray tube, etc., the resolution is lowered. It was also the cause.
【０００７】[0007]
【発明が解決しようとする課題】本発明は従来技術が有
していた前述の欠点を解消しようとするものであり、低
温熱処理が可能な高特性の低反射導電膜を新規に提供す
ることを目的とするものである。DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks of the prior art, and to provide a novel low-reflection conductive film of high characteristics which can be heat-treated at a low temperature. It is intended.
【０００８】[0008]
【課題を解決するための手段】本発明は前述の問題点を
解決すべくなされたものであり、特にブラウン管のフェ
イス面等のガラス基体に被着された酸化レニウムを含む
導電膜を基体側に、更にこの膜より低屈折率を有する膜
を空気側に配した２層からなる高性能低反射導電膜、お
よび、基体より第１層として酸化レニウム被膜よりも低
屈折率でありかつＳｉＯ2 膜よりも高屈折率を有する膜
を形成し、その上に第２層として酸化レニウムを含む導
電膜を形成し、更にその上に第３層としてＳｉＯ2 かつ
／又はＳｉＯ2 −ＭｇＦ2 を含む低屈折率膜を形成する
ことによりなる３層構造の低反射導電膜を提供するもの
である。The present invention has been made to solve the above-mentioned problems, and in particular, a conductive film containing rhenium oxide deposited on a glass substrate such as the face surface of a cathode ray tube is provided on the substrate side. And a high-performance low-reflection conductive film consisting of two layers in which a film having a lower refractive index than this film is arranged on the air side, and a SiO 2 film having a lower refractive index than the rhenium oxide film as the first layer from the substrate A film having a higher refractive index than the above, a conductive film containing rhenium oxide is formed as a second layer thereon, and a low layer containing SiO 2 and / or SiO 2 —MgF 2 is further formed thereon as a third layer. The present invention provides a low reflection conductive film having a three-layer structure formed by forming a refractive index film.
【０００９】本発明における酸化レニウムを含む導電膜
の製造方法としてレニウム化合物と水かつ／又は有機溶
媒からなる液にＳｉ化合物、Ｔｉ化合物、Ｚｒ化合物、
Ａｌ化合物、Ｓｎ化合物、Ｉｎ化合物のうち少なくとも
１種を加えた溶液を塗布し、１００〜５００℃で加熱か
つ／又は１８０〜４９０ｎｍの波長領域の紫外線を照射
して形成することを特徴とする。As a method for producing a conductive film containing rhenium oxide according to the present invention, a liquid containing a rhenium compound and water and / or an organic solvent contains a Si compound, a Ti compound, a Zr compound,
It is characterized in that it is formed by applying a solution containing at least one of an Al compound, a Sn compound and an In compound, heating it at 100 to 500 ° C. and / or irradiating it with ultraviolet rays in the wavelength region of 180 to 490 nm.
【００１０】本発明に用いるレニウム化合物としては三
塩化レニウム、四塩化レニウム、五塩化レニウム等の塩
化物、オキシ四塩化レニウム等の酸化塩化レニウム化合
物、過レニウム酸カリウム、過レニウム酸ナトリウム等
のアルカリ類との化合物、三臭化レニウム等の臭化化合
物、硼化レニウム等の硼化化合物及びその加水分解物の
うち少なくとも１種の何れも使用可能である。Examples of the rhenium compound used in the present invention include chlorides such as rhenium trichloride, rhenium tetrachloride and rhenium pentachloride, rhenium oxychloride compounds such as rhenium oxytetrachloride, and alkalis such as potassium perrhenate and sodium perrhenate. It is possible to use at least one of a compound with a class, a bromide compound such as rhenium tribromide, a boride compound such as rhenium boride, and a hydrolyzate thereof.
【００１１】親水性有機溶媒としては、メタノール、エ
タノール、プロパノール、ブタノール等のアルコール
類、エチルセルソルブ等のエーテル類が任意に使用でき
る。As the hydrophilic organic solvent, alcohols such as methanol, ethanol, propanol and butanol, and ethers such as ethyl cellosolve can be arbitrarily used.
【００１２】また本発明において用いるレニウム化合物
を含む塗布液には膜の付着強度及び硬度を向上させるた
めにバインダーとしてＳｉ（ＯＲ）y ・Ｒ´4-y （ｙ＝
３、４、Ｒ、Ｒ´：アルキル基）等のケイ素化合物また
はそれを加水分解した溶液を添加することも可能であ
る。その際加水分解の触媒としてはＨＣｌ、ＨＮＯ3 、
ＣＨ3 ＣＯＯＨ、ＨＣＯＯＨ等を用いることができる。
さらに基体との濡れ性を向上させるために種々の界面活
性剤を添加することもできる。In the coating liquid containing the rhenium compound used in the present invention, Si (OR) y · R ′ 4-y (y =) is used as a binder in order to improve the adhesion strength and hardness of the film.
It is also possible to add a silicon compound such as 3, 4, R, R ': an alkyl group) or a solution obtained by hydrolyzing the silicon compound. At that time, as the hydrolysis catalyst, HCl, HNO 3 ,
CH 3 COOH, can be used HCOOH like.
Further, various surfactants can be added to improve the wettability with the substrate.
【００１３】またさらにはＴｉ化合物、Ｚｒ化合物、Ａ
ｌ化合物、Ｓｎ化合物、Ｉｎ化合物等を添加して導電膜
の屈折率を高くすることもできる。Ｔｉ、Ｚｒ、Ａｌ、
Ｓｎ、Ｉｎの各化合物としては、加熱により、各々、Ｔ
ｉＯ2 、ＺｒＯ2 、Ａｌ2 Ｏ3 、ＳｎＯ2 、Ｉｎ2 Ｏ3
となるようなアルコキシド、金属塩および、それらの加
水分解物等、何れも使用可能である。Furthermore, Ti compound, Zr compound, A
It is also possible to increase the refractive index of the conductive film by adding an l compound, a Sn compound, an In compound or the like. Ti, Zr, Al,
Each compound of Sn and In is heated to form T
iO 2 , ZrO 2 , Al 2 O 3 , SnO 2 , In 2 O 3
Any of such alkoxides, metal salts and their hydrolysates can be used.
【００１４】レニウム化合物とケイ素化合物Ｓｉ（Ｏ
Ｒ）y ・Ｒ´4-y は任意の比で混合することができる
が、導電性の発現、膜強度を考慮に入れると、その混合
比はＲｅＯ3 ／ＳｉＯ2 換算で１／６から１０／１まで
混合することが好ましい。Rhenium compound and silicon compound Si (O
R) y · R ′ 4-y can be mixed in any ratio, but considering the development of conductivity and film strength, the mixing ratio is 1/6 to 10 in terms of ReO 3 / SiO 2. It is preferable to mix up to 1/1.
【００１５】また液中の固形分含量は０．０５〜３０．
０ｗｔ％含まれることができるがさらに好ましくは０．
３〜５．０ｗｔ％にするとよい。固形分含量があまり小
さいと、膜が薄くなるため膜の均一性や十分な導電性が
得られず、またあまり大きいと、塗布液の保存安定性が
悪くなるためかかる固形分含量が好ましい。The solid content of the liquid is 0.05 to 30.
It can be contained in an amount of 0 wt%, but more preferably, it can be 0.1%.
It is preferable to set it to 3 to 5.0 wt%. If the solid content is too small, the film becomes thin and the uniformity and sufficient conductivity of the film cannot be obtained. On the other hand, if the solid content is too large, the storage stability of the coating solution is deteriorated, and thus the solid content is preferable.
【００１６】上記で合成した塗布液の基体上への塗布方
法としては従来使用してきた方法、即ち スピンコー
ト、ディップコート、スプレーコート法等が好適に使用
できる。また、スプレーコートして表面に凹凸を形成し
防眩効果も併せて付与してもよく、その場合導電膜とな
った本発明品の上にシリカ被膜等のハードコートを設け
てもよい。As a method of applying the above-prepared coating solution onto a substrate, conventionally used methods, that is, spin coating, dip coating, spray coating and the like can be preferably used. Further, spray coating may be performed to form irregularities on the surface to impart an antiglare effect together. In that case, a hard coat such as a silica coating may be provided on the product of the present invention which has become a conductive film.
【００１７】本発明においては、導電膜の上に低屈折率
膜を形成することによって、２層構造で光の干渉を利用
して低反射導電膜を形成することができる。例えば基体
がガラス（屈折率ｎ＝１．５２）の場合、上記の導電膜
の上に、ｎ（導電膜）／ｎ（低屈折率膜）の比の値が約
１．２３となるような低屈折率膜を形成すると最も反射
率を低減できる。In the present invention, by forming the low refractive index film on the conductive film, it is possible to form the low reflection conductive film by utilizing light interference in a two-layer structure. For example, when the substrate is glass (refractive index n = 1.52), the ratio of n (conductive film) / n (low refractive index film) on the conductive film is about 1.23. The reflectance can be most reduced by forming a low refractive index film.
【００１８】３層による低反射特性を発現させる場合、
例えば基体上にＴｉアルコキサイドとＳｉアルコキサイ
ドよりなる液を塗布し、導電膜よりも低屈折率であり、
かつＳｉＯ2 膜（ｎ＝１．４６）よりも高屈折率の膜を
形成し、その上に酸化レニウムを含む導電膜を形成し、
更にその上にＳｉＯ2 かつ又はＳｉＯ2 −ＭｇＦ2 より
なる低屈折率膜を形成することにより達成される。In the case of exhibiting a low reflection property by three layers,
For example, a liquid composed of Ti alkoxide and Si alkoxide is applied on a substrate and has a lower refractive index than the conductive film,
A film having a higher refractive index than the SiO 2 film (n = 1.46) is formed, and a conductive film containing rhenium oxide is formed on the film.
Further achieved by forming the SiO 2 and or consisting SiO 2 MgF 2 low refractive index film formed thereon.
【００１９】このとき基体の屈折率を１．５４とするな
らば基体側第１層、第２層、第３層の屈折率をそれぞれ
ｎ1 、ｎ2 、ｎ3 として光学厚みをそれぞれλ／４、λ
／４、λ／４とすると ｎ2 ＝ｎ1 ｎ3 ／１．２４１ のとき最高の低反射特性が得られる。At this time, assuming that the refractive index of the substrate is 1.54, the optical thicknesses of the first layer, the second layer, and the third layer on the substrate side are n 1 , n 2 , and n 3 , respectively, and the optical thicknesses are λ / 4, λ
When / 4 and λ / 4, the highest low reflection property is obtained when n 2 = n 1 n 3 /1.241.
【００２０】又、光学厚みをそれぞれλ／４、λ／２、
λ／４、又は３／４・λ、λ／２、λ／４の構成とした
場合、ｎ1 ＝１．２４１・ｎ3 のとき低反射性が得られ
るが、この場合第２層の屈折率を高屈折率化することに
よりより一層の低反射特性が得られる。又、４層構造と
した場合基体側より低屈折率層−中屈折率層−高屈折率
層−低屈折率層で形成するとよい。The optical thicknesses are λ / 4, λ / 2, and
When λ / 4 or 3/4 · λ, λ / 2, λ / 4 is used, low reflectivity is obtained when n 1 = 1.241 · n 3 , but in this case, refraction of the second layer By making the refractive index high, further low reflection characteristics can be obtained. Further, in the case of a four-layer structure, it is preferable to form from the side of the substrate a low refractive index layer-a medium refractive index layer-a high refractive index layer-a low refractive index layer.
【００２１】かかる２層ないし３層以上の多層からなる
低反射導電膜の低屈折率膜としてはＭｇＦ2 ゾルを含む
溶液や、Ｓｉアルコキシドを含む溶液のうちから選ばれ
る少なくとも１種よりなる溶液を用いて形成する。屈折
率の面からみると該材料のうちＭｇＦ2 が最も低く反射
率低減のためにはＭｇＦ2 ゾルを含む溶液を用いること
が好ましいが、膜の硬度や耐擦傷性の点ではＳｉＯ2 を
主成分とする膜が好ましい。As the low refractive index film of the low reflection conductive film composed of two or more layers, a solution containing at least one selected from a solution containing MgF 2 sol and a solution containing Si alkoxide. It is formed by using. From the viewpoint of the refractive index, MgF 2 is the lowest of the materials, and it is preferable to use a solution containing MgF 2 sol to reduce the reflectance, but SiO 2 is mainly used in terms of film hardness and scratch resistance. Membranes of component are preferred.
【００２２】かかる低屈折率膜形成用のＳｉアルコキシ
ドを含む溶液としては種々の物が使用可能であるが、Ｓ
ｉ（ＯＲ）m Ｒ´n （ｍ＝１〜４、ｎ＝０〜３、Ｒ、Ｒ
´＝Ｃ１〜Ｃ４のアルキル基）で示されるＳｉアルコキ
シドあるいは部分加水分解物を含む液が挙げられる。例
えばシリコンエトキシド、シリコンメトキシド、シリコ
ンイソプロポキシド、シリコンブトキシドのモノマーあ
るいは重合体が好ましく使用可能である。Various materials can be used as the solution containing the Si alkoxide for forming the low refractive index film.
i (OR) m R'n ( m = 1~4, n = 0~3, R, R
A liquid containing a Si alkoxide or a partial hydrolyzate represented by ′ = C1 to C4 alkyl group). For example, a monomer or polymer of silicon ethoxide, silicon methoxide, silicon isopropoxide, silicon butoxide can be preferably used.
【００２３】シリコンアルコキシドはアルコール、エス
テル、エーテル等に溶解して用いることもでき、又前記
溶液に塩酸、硝酸、酢酸、弗酸、ギ酸あるいはアンモニ
ア水溶液を添加して加水分解して用いることもできる。
又前記Ｓｉアルコキシドは溶媒に対して、１〜３０ｗｔ
％含まれていることが好ましい。The silicon alkoxide can be used by dissolving it in alcohol, ester, ether or the like, or can be used by hydrolyzing it by adding hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid, formic acid or aqueous ammonia solution to the solution. ..
Further, the Si alkoxide is 1 to 30 wt% with respect to the solvent.
% Is preferably contained.
【００２４】又この溶液には膜の強度向上のためにバイ
ンダーとして、Ｚｒ、Ｔｉ、Ａｌ等のアルコキシドや、
これらの部分加水分解物を添加して、ＺｒＯ2 、ＴｉＯ
2 、Ａｌ2 Ｏ3 の少なくとも１種、または２種以上の複
合物をＭｇＦ2 、ＳｉＯ2 と同時に析出させてもよい。
あるいは又、基体との濡れ性を挙げるために界面活性剤
を添加してもよい。添加される界面活性剤としては、直
鎖アルキルベンゼンスルホン酸ナトリウム、アルキルエ
ーテル硫酸エステル等が挙げられる。In addition, in order to improve the strength of the film, the solution contains an alkoxide such as Zr, Ti or Al, or a binder.
By adding these partial hydrolyzates, ZrO 2 , TiO 2
At least one kind of 2 , Al 2 O 3 or a composite of two or more kinds may be simultaneously precipitated with MgF 2 and SiO 2 .
Alternatively, a surfactant may be added to improve the wettability with the substrate. Examples of the surfactant to be added include linear sodium alkylbenzene sulfonate and alkyl ether sulfate.
【００２５】本発明の導電膜及び低反射導電膜を形成す
る基体としてはブラウン管パネル、複写機用ガラス板、
計算機用パネル、クリーンルーム用ガラス、ＣＲＴ或い
はＬＣＤ等の表示装置の前面板等の各種ガラス、プラス
チック基板を用いることができる。As a substrate for forming the conductive film and the low reflective conductive film of the present invention, a cathode ray tube panel, a glass plate for a copying machine,
A computer panel, clean room glass, various kinds of glass such as a front plate of a display device such as a CRT or LCD, and a plastic substrate can be used.
【００２６】本発明におけるＲｅ化合物を含む溶液はそ
れ自体で基体上への塗布液として供し得るため、低沸点
の溶媒を用いた場合は、室温での乾燥の均一な膜が得ら
れるが、高沸点溶液を用いた場合或いは膜の強度を向上
させたい場合、塗布した基板を加熱する。加熱温度の上
限は基板に用いられるガラス、プラアスチック等の軟化
点によって決定される。この点も考慮すると好ましい温
度範囲は１００〜５００℃である。Since the solution containing the Re compound in the present invention can be provided as a coating solution on a substrate by itself, when a solvent having a low boiling point is used, a uniform film dried at room temperature can be obtained. When using a boiling point solution or when it is desired to improve the strength of the film, the coated substrate is heated. The upper limit of the heating temperature is determined by the softening point of glass, plastic or the like used for the substrate. Considering this point, the preferable temperature range is 100 to 500 ° C.
【００２７】[0027]
【作用】一般にパルス源より発生する電磁波を導電膜に
よってシールドする場合、電磁波が導電膜に入射したと
きに生成する渦電流により電界反射損失を生じさせ、電
磁波のシールドを行う。このとき電界反射損失Ｒは比導
電率をＧ、比誘磁率をμ、周波数をｆ、パルス発生源と
シールド材との距離をｒとすると Ｒ＝１０ log（Ｇ／μ・ｆ3 ・ｒ2 ）＋３５３．６ で表わされる。従って比導電率Ｇが大きなものを選択す
ることにより大きな電界反射損失を生じさせることがで
きる。In general, when the electromagnetic wave generated by the pulse source is shielded by the conductive film, the eddy current generated when the electromagnetic wave enters the conductive film causes electric field reflection loss to shield the electromagnetic wave. At this time, the electric field reflection loss R is R = 10 log (G / μ · f 3 · r 2) where G is the specific conductivity, μ is the specific magnetic susceptibility, f is the frequency, and r is the distance between the pulse generation source and the shield material. ) +353.6. Therefore, a large electric field reflection loss can be generated by selecting a material having a large specific conductivity G.
【００２８】本発明ではこれを達成するため、ＲｅＯ3
を用いた。ＲｅＯ3 においては５ｄ電子が伝導に寄与し
π反結合による伝導電子の有効質量が小さいため、金属
伝導に近い電気伝導性を有する。ため、Ｒｅ同士のバン
ド間をＲｅの５ｄ電子がキャリヤーとして動くことによ
り、伝導性を発現させるため、原子価制御タイプにおけ
る伝導性発現のためのドーパントの導入の必要がなく、
かつ、原子価制御タイプよりも高い導電性を発現するこ
とができる。In the present invention, in order to achieve this, ReO 3
Was used. In ReO 3 , since 5d electrons contribute to conduction and the effective mass of conduction electrons due to π anticoupling is small, it has electrical conductivity close to metal conduction. Therefore, since the 5d electron of Re moves as a carrier between the bands of Re to develop conductivity, it is not necessary to introduce a dopant for expressing conductivity in the valence control type,
In addition, it is possible to develop higher conductivity than the valence control type.
【００２９】[0029]
【実施例】以下に本発明の実施例を挙げ更に説明を行う
が、本発明はこれらに限定されるものではない。以下の
実施例及び比較例において、得られた膜の評価方法は次
の通りである。The present invention will be further described below with reference to examples of the present invention, but the present invention is not limited thereto. In the following examples and comparative examples, the evaluation methods of the obtained films are as follows.
【００３０】１）導電性評価 ローレスタ抵抗測定器（三菱油化製）により膜表面の表
面抵抗値を測定した。1) Conductivity evaluation The surface resistance value of the film surface was measured by a Loresta resistance measuring instrument (manufactured by Mitsubishi Yuka).
【００３１】２）耐擦傷性 １ｋｇ荷重下で（ＬＩＯＮ製５０−５０）で膜表面を２
００回往復後、その表面の傷の付きを目視で判断した。
評価基準は以下の通りとした。 ○：傷が全くつかない △：傷が多少つく ×：一部に膜剥離が生じる2) Scratch resistance Under a load of 1 kg (50-50 made by LION), the surface of the film was exposed to 2
After reciprocating 00 times, scratches on the surface were visually judged.
The evaluation criteria are as follows. ○: No scratches were found △: Some scratches were found ×: Film peeling occurred in part
【００３２】３）鉛筆硬度 １ｋｇ荷重下において、鉛筆で膜表面を走査しその後目
視により表面の傷の生じ始める鉛筆の硬度を膜の鉛筆硬
度と判断した。 ４）視感反射率 ＧＡＭＭＡ分光反射率スペクトル測定器により多層膜４
００〜７００ｎｍでの視感反射率を測定した。3) Pencil Hardness Under a load of 1 kg, the surface of the film was scanned with a pencil, and the pencil hardness at which scratches on the surface began to be visually observed was judged to be the pencil hardness of the film. 4) Luminous reflectance Multilayer film 4 by GAMMA spectral reflectance spectrum measuring device
The luminous reflectance at 00 to 700 nm was measured.
【００３３】［実施例１］ＲｅＣｌ3 をエタノールに溶
かし、液濃度をＲｅＯ3 換算で３重量％になるように調
製した。この液をＡ液とする。ケイ酸エチルをエタノー
ルに溶かし、ＨＣｌ水溶液で加水分解し、ＳｉＯ2 換算
で３重量％となるようにした。この溶液をＢ液とする。 Ｔｉ（Ｃ5 Ｈ7 Ｏ2 ）2 （ＯＣ3 Ｈ7 ）2 をＴｉＯ2 換
算で３重量％になるようにエタノールに溶かし塩酸水溶
液で加水分解し、この液をＣ液とした。[Example 1] ReCl 3 was dissolved in ethanol to prepare a solution having a concentration of 3% by weight in terms of ReO 3 . This solution is referred to as solution A. Ethyl silicate was dissolved in ethanol and hydrolyzed with an aqueous solution of HCl so as to be 3% by weight in terms of SiO 2 . This solution is referred to as solution B. Ti (C 5 H 7 O 2 ) 2 (OC 3 H 7 ) 2 was dissolved in ethanol so as to be 3% by weight in terms of TiO 2 and hydrolyzed with an aqueous hydrochloric acid solution, and this solution was designated as solution C.
【００３４】ＲｅＯ3 とＳｉＯ2 とＴｉＯ2 を種々の比
になるようにＡ液、Ｂ液、Ｃ液を混合した塗布液を７０
ｍｍφガラス板表面に２０００ｒｐｍの回転速度で５秒
間スピンコート法で塗布し、その後４５０℃で１０分間
加熱した。更にこの膜の上にＢ液を１５００ｒｐｍの回
転速度で５秒間スピンコート法で塗布し、その後４５０
℃で１０分加熱した。第１層の塗布液中の各成分の固形
分濃度、及び、Ｂ液による低屈折率膜を形成した２層か
らなる低反射導電膜の特性を表１に示す。A coating solution prepared by mixing Re liquid A, liquid B and liquid C in various ratios of ReO 3 , SiO 2 and TiO 2 was prepared.
The surface of the mmφ glass plate was applied by spin coating at a rotation speed of 2000 rpm for 5 seconds, and then heated at 450 ° C. for 10 minutes. Further, liquid B is applied onto this film by spin coating at a rotation speed of 1500 rpm for 5 seconds, and then 450
Heated at 0 ° C for 10 minutes. Table 1 shows the solid content concentration of each component in the coating liquid of the first layer and the characteristics of the two-layer low-reflection conductive film having the low-refractive index film formed of the liquid B.
【００３５】[0035]
【表１】 [Table 1]
【００３６】［実施例２］ＳｎＣｌ4 ・ｎＨ2 ＯをＳｎ
Ｏ2 換算で３重量％となるようにエタノールに溶かした
溶液をＤ液とする。実施例１におけるＣ液をＤ液に変更
する以外は実施例１と同様に行った。結果を表２に示
す。[Example 2] SnCl 4 · nH 2 O was added to Sn
A solution dissolved in ethanol so as to be 3% by weight in terms of O 2 is referred to as liquid D. The same procedure as in Example 1 was performed except that the C liquid in Example 1 was changed to the D liquid. The results are shown in Table 2.
【００３７】[0037]
【表２】 [Table 2]
【００３８】［実施例３］ＺｒＣｌ4 をＺｒＯ2 換算で
３重量％となるようにエタノールに溶かした溶液をＥ液
とする。実施例１におけるＣ液をＥ液に変更する以外は
実施例１と同様に行った。結果を表３に示す。Example 3 A solution prepared by dissolving ZrCl 4 in ethanol so as to be 3% by weight in terms of ZrO 2 was designated as solution E. The same procedure as in Example 1 was performed except that the C liquid in Example 1 was changed to the E liquid. The results are shown in Table 3.
【００３９】[0039]
【表３】 [Table 3]
【００４０】[0040]
【実施例４】Ａｌ（ＯＣ3 Ｈ7 ）2 （Ｃ6 Ｈ10 Ｏ3 ）
をＡｌ2 Ｏ3 換算で３重量％になるようにエタノールに
溶かした溶液をＦ液とする。実施例１におけるＣ液をＦ
液に変更する以外は実施例１と同様に行った。結果を表
４に示す。Example 4 Al (OC 3 H 7 ) 2 (C 6 H 10 O 3 )
Solution F is a solution prepared by dissolving 3% by weight in terms of Al 2 O 3 in ethanol. The liquid C in Example 1 was replaced with F.
The same procedure as in Example 1 was carried out except that the solution was changed. The results are shown in Table 4.
【００４１】[0041]
【表４】 [Table 4]
【００４２】［実施例５］実施例１において基体側第１
層塗布後の硬化方法を４５０℃で１０分加熱より２５４
ｎｍを主波長とする紫外線を１０分照射すると変更した
以外は実施例１と同様に行った。結果を表５に示す。[Embodiment 5] In Embodiment 1, first on the substrate side
The curing method after layer coating is 254 by heating at 450 ° C for 10 minutes.
The same procedure as in Example 1 was performed, except that the ultraviolet ray having a main wavelength of nm was irradiated for 10 minutes. The results are shown in Table 5.
【００４３】[0043]
【表５】 [Table 5]
【００４４】［実施例６］実施例５において２５４ｎｍ
の紫外線を３６５ｎｍの紫外線に変更した以外は実施例
１と同様に行った。結果を表６に示す[Embodiment 6] 254 nm in Embodiment 5
The same procedure as in Example 1 was carried out except that the ultraviolet ray of was changed to 365 nm. The results are shown in Table 6.
【００４５】[0045]
【表６】 [Table 6]
【００４６】［実施例７］実施例３において基体側第１
層塗布後の硬化方法を４５０℃で１０分加熱より３６５
ｎｍを主波長とする紫外線を１０分照射すると変更した
以外は実施例３と同様に行った。結果を表７に示す。[Embodiment 7] In Embodiment 3, first on the substrate side
After the layer is applied, the curing method is 365 minutes by heating at 450 ° C. for 10 minutes.
The same procedure as in Example 3 was performed except that irradiation with ultraviolet rays having a main wavelength of nm was performed for 10 minutes. The results are shown in Table 7.
【００４７】[0047]
【表７】 [Table 7]
【００４８】［実施例８］ＩｎＣｌ3 をＩｎ2 Ｏ3 換算
で５重量％となるようにエタノールに溶解しアセチルア
セトン／Ｉｎ＝１ｍｏｌ比となるようアセチルアセトン
を加え、１時間７０℃で還流を行った。この液を冷却後
エタノールで希釈しＩｎ2 Ｏ3 換算で３重量％となるよ
うにした（Ｇ液）。実施例１におけるＣ液をＧ液と変更
した以外は実施例１と同様に行った。結果を表８に示
す。Example 8 InCl 3 was dissolved in ethanol so as to be 5% by weight in terms of In 2 O 3 , acetylacetone was added so that the acetylacetone / In = 1 mol ratio was obtained, and the mixture was refluxed at 70 ° C. for 1 hour. .. After cooling this liquid, it was diluted with ethanol so as to be 3% by weight in terms of In 2 O 3 (liquid G). The same procedure as in Example 1 was carried out except that the C solution in Example 1 was changed to the G solution. The results are shown in Table 8.
【００４９】[0049]
【表８】 [Table 8]
【００５０】［実施例９］ＲｅＯＣｌ4 をエタノールに
溶かしＲｅＯ3 換算で３重量％となるように調製した
（Ｈ液）。実施例１におけるＡ液をＨ液と変更した以外
は実施例１と同様に行った。結果を表９に示す[Example 9] ReOCl 4 was dissolved in ethanol to prepare 3% by weight in terms of ReO 3 (solution H). The same procedure as in Example 1 was performed except that the solution A in Example 1 was changed to the solution H. The results are shown in Table 9.
【００５１】[0051]
【表９】 [Table 9]
【００５２】［実施例１０］ＭｇＣｌ3 とＢＦ3 ・Ｅｔ
ＯＨをＭｇＦ2 換算で３重量％となるようにＥｔＯＨに
溶解させ、７０℃で５時間還流を行った（Ｉ液）。Ｉ液
とＢ液をＩ液：Ｂ液＝３：７となるように混合した（Ｊ
液）。実施例１において基体側第２層構成用塗布液とし
て用いるＢ液をＪ液と変更した以外は実施例１と同様に
行った。結果を表１０に示す。Example 10 MgCl 3 and BF 3 .Et
OH was dissolved in EtOH so as to be 3% by weight in terms of MgF 2 , and refluxed at 70 ° C. for 5 hours (solution I). Solution I and solution B were mixed so that solution I: solution B was 3: 7 (J
liquid). The procedure of Example 1 was repeated, except that the solution B used as the coating solution for forming the second layer on the substrate side was changed to the solution J. The results are shown in Table 10.
【００５３】[0053]
【表１０】 [Table 10]
【００５４】［実施例１１］Ｔｉ（Ｃ5 Ｈ7 Ｏ2 ）2
（ｉｓｏ−ＯＣ3 Ｈ7 ）2 をエタノールに溶解し、ＨＣ
ｌで加水分解し、濃度を調整し３重量％となるようにし
た（Ｋ液）。Ｂ液とＫ液をＢ液：Ｋ液＝３：７となるよ
うに混合し、７０ｍｍφのガラス板表面に２３００ｒｐ
ｍの回転速度で５秒間スピンコート法で塗布し、６０℃
で５分間乾燥させた。この上にＡ液とＢ液とＣ液を種々
の混合比で混合した液を２０００ｒｐｍの回転速度で５
秒間スピンコートを行い、更に４０℃で１０分間焼成を
行った。更にこの上にＢ液を１５００ｒｐｍの回転速度
で５秒間スピンコートを行い、その後４５０℃で１０分
間加熱を行った。結果を表１１に示す。Example 11 Ti (C 5 H 7 O 2 ) 2
(Iso-OC 3 H 7 ) 2 was dissolved in ethanol and
It was hydrolyzed with 1 and the concentration was adjusted to 3% by weight (K solution). Solution B and solution K were mixed so that solution B: solution K = 3: 7, and 2300 rp was applied to the surface of a 70 mmφ glass plate.
Spin coating method for 5 seconds at a rotation speed of m, 60 ℃
And dried for 5 minutes. A liquid prepared by mixing liquid A, liquid B and liquid C at various mixing ratios was added thereto at a rotation speed of 2000 rpm for 5 minutes.
Spin coating was performed for 2 seconds, and baking was further performed at 40 ° C. for 10 minutes. Further, liquid B was spin-coated on this for 5 seconds at a rotation speed of 1500 rpm, and then heated at 450 ° C. for 10 minutes. The results are shown in Table 11.
【００５５】[0055]
【表１１】 [Table 11]
【００５６】［実施例１２］実施例１１記載の基体側第
３層構成用としてのＢ液をＪ液とした以外は実施例１１
と同様に行った。結果を表１２に示す。[Embodiment 12] Embodiment 11 is different from Embodiment 11 except that the solution B for forming the third layer on the substrate side is the solution J.
I went the same way. The results are shown in Table 12.
【００５７】[0057]
【表１２】 [Table 12]
【００５８】[0058]
【比較例】平均粒径６０ÅのＳｎＯ2 をサンドミルで４
時間粉砕した。この液を９０℃で１時間加熱解膠した
後、ケイ酸エチルを加水分解しエタノールにＳｉＯ2 換
算で３重量％添加した溶液をＳｎＯ2 ：ＳｉＯ2 ＝２：
１重量比になるように調製し、７０ｍｍφガラス板表面
に７５０ｒｐｍの回転速度で５秒間スピンコート法で塗
布し、その後４５０℃で１０分加熱した。さらにこの膜
の上にＢ液を１５００ｒｐｍの回転速度で５秒間スピン
コート法で塗布し、４５０℃で１０分加熱した。このコ
ート膜の表面抵抗値は１×１０8 （Ω／□）で、膜強度
は×、鉛筆硬度はＨＢ、視感反射率は０．８％であっ
た。[Comparative Example] SnO 2 with an average particle size of 60Å
Crushed for hours. After this solution was heated for 1 hour peptized at 90 ° C. The, SnO 2 solution was added 3 wt% in terms of SiO 2 ethyl silicate hydrolyzed to ethanol: SiO 2 = 2:
It was prepared so as to have a weight ratio of 1 and was applied on the surface of a 70 mmφ glass plate by spin coating at a rotation speed of 750 rpm for 5 seconds, and then heated at 450 ° C. for 10 minutes. Further, the liquid B was applied onto this film by spin coating at a rotation speed of 1500 rpm for 5 seconds, and heated at 450 ° C. for 10 minutes. The surface resistance of this coating film was 1 × 10 8 (Ω / □), the film strength was ×, the pencil hardness was HB, and the luminous reflectance was 0.8%.
【００５９】[0059]
【発明の効果】本発明によればスプレーまたはスピンコ
ートあるいは溶液中に基体を浸漬するなどの簡便な方法
により効率よく優れた低反射導電膜を提供することが可
能となる。本発明は生産性に優れ、かつ真空を必要とし
ないので装置も比較的安価なものでよい。特にＣＲＴの
パネルフェイス面等の大面積の基体にも充分適用でき、
量産も可能であるため工業的価値は非常に高い。EFFECTS OF THE INVENTION According to the present invention, it is possible to efficiently and excellently provide a low-reflection conductive film by a simple method such as spraying, spin coating, or immersing a substrate in a solution. Since the present invention is excellent in productivity and does not require a vacuum, the device may be relatively inexpensive. Especially, it can be applied to large area substrates such as panel face of CRT.
Since it can be mass-produced, its industrial value is very high.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｊ 29/88 9057−5Ｅ (72)発明者 平塚 和也 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 (72)発明者 竹宮 聡 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical indication location H01J 29/88 9057-5E (72) Inventor Kazuya Hiratsuka 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Satoshi Takemiya 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory
Claims (7)
含む塗布液を基体上に塗布した後、加熱かつ又は紫外線
を照射して成膜することを特徴とする酸化レニウムを含
む導電膜の製造方法。1. A method for producing a conductive film containing rhenium oxide, which comprises applying a coating solution containing a rhenium compound and another metal compound onto a substrate, and then heating and / or irradiating ultraviolet rays to form a film. ..
かつ又は紫外線照射により、それぞれＳｉＯ2 、ＺｒＯ
2 、ＴｉＯ2 、Ａｌ2 Ｏ3 、ＳｎＯ2 、Ｉｎ2 Ｏ3 とな
るＳｉ化合物、Ｚｒ化合物、Ｔｉ化合物、Ａｌ化合物、
Ｓｎ化合物、Ｉｎ化合物のうち少なくとも１種であるこ
とを特徴とする請求項１記載の導電膜の製造方法。2. A metal compound other than a rhenium compound is heated and / or irradiated with ultraviolet rays to produce SiO 2 , ZrO, respectively.
2 , Si compound, Zr compound, Ti compound, Al compound, which becomes 2 , TiO 2 , Al 2 O 3 , SnO 2 , In 2 O 3 ,
The method for producing a conductive film according to claim 1, wherein the conductive film is at least one kind of Sn compound and In compound.
化レニウムを含む導電膜を形成し、その上に、かかる導
電膜よりも低屈折率の膜を形成して、２層からなる低反
射導電膜を製造することを特徴とする低反射導電膜の製
造方法。3. A conductive film containing rhenium oxide is formed by the manufacturing method according to claim 1 or 2, and a film having a refractive index lower than that of the conductive film is formed on the conductive film to form a low reflection film composed of two layers. A method of manufacturing a low-reflection conductive film, which comprises manufacturing a conductive film.
多層からなる低反射導電膜の製造方法であって、かかる
導電膜を請求項１又は２記載の方法によって形成するこ
とを特徴とする低反射導電膜の製造方法。4. A method of manufacturing a low-reflection conductive film having a multilayer structure of three or more layers having at least one conductive film, wherein the conductive film is formed by the method according to claim 1. Method for manufacturing low-reflection conductive film.
られた低反射導電膜。5. A low-reflection conductive film obtained by the manufacturing method according to claim 3.
体上に低反射導電膜を形成したガラス製品。6. A glass product in which a low reflection conductive film is formed on a substrate by the manufacturing method according to claim 3.
極線管表面に低反射導電膜を形成した陰極線管。7. A cathode ray tube having a low reflection conductive film formed on the surface of the cathode ray tube by the manufacturing method according to claim 3 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35081591A JPH05166423A (en) | 1991-12-11 | 1991-12-11 | Manufacture of conductive film and low reflective conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35081591A JPH05166423A (en) | 1991-12-11 | 1991-12-11 | Manufacture of conductive film and low reflective conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05166423A true JPH05166423A (en) | 1993-07-02 |
Family
ID=18413070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35081591A Withdrawn JPH05166423A (en) | 1991-12-11 | 1991-12-11 | Manufacture of conductive film and low reflective conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05166423A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5853869A (en) * | 1995-08-23 | 1998-12-29 | Sumitomo Metal Mining Co., Ltd. | Transparent conductor film for electric field shielding |
| EP0941773A1 (en) * | 1998-03-13 | 1999-09-15 | Saint-Gobain Vitrage | Process for depositing metallic oxide(s) layers |
| CN1112415C (en) * | 1995-05-10 | 2003-06-25 | 三星电管株式会社 | Transparent electric-conductive coating composition |
| JP2013221171A (en) * | 2012-04-13 | 2013-10-28 | Kanagawa Univ | Recovering method of rhenium |
| JP5987244B1 (en) * | 2015-07-24 | 2016-09-07 | 学校法人神奈川大学 | Method for recovering rhenium, method for selectively recovering rhenium from a solution containing rhenium and other metals, and method for increasing the content ratio of rhenium in a solution containing rhenium and other metals |
-
1991
- 1991-12-11 JP JP35081591A patent/JPH05166423A/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112415C (en) * | 1995-05-10 | 2003-06-25 | 三星电管株式会社 | Transparent electric-conductive coating composition |
| US5853869A (en) * | 1995-08-23 | 1998-12-29 | Sumitomo Metal Mining Co., Ltd. | Transparent conductor film for electric field shielding |
| EP0941773A1 (en) * | 1998-03-13 | 1999-09-15 | Saint-Gobain Vitrage | Process for depositing metallic oxide(s) layers |
| FR2775914A1 (en) * | 1998-03-13 | 1999-09-17 | Saint Gobain Vitrage | METAL OXIDE (S) BASED LAYER DEPOSIT PROCESS |
| JPH11319547A (en) * | 1998-03-13 | 1999-11-24 | Saint Gobain Vitrage | Method for building up layer containing metallic oxide as main component |
| US6517901B1 (en) | 1998-03-13 | 2003-02-11 | Saint-Gobain Vitrage | Process for depositing layers based on metal oxide(s) |
| JP2013221171A (en) * | 2012-04-13 | 2013-10-28 | Kanagawa Univ | Recovering method of rhenium |
| JP5987244B1 (en) * | 2015-07-24 | 2016-09-07 | 学校法人神奈川大学 | Method for recovering rhenium, method for selectively recovering rhenium from a solution containing rhenium and other metals, and method for increasing the content ratio of rhenium in a solution containing rhenium and other metals |
| WO2017018364A1 (en) * | 2015-07-24 | 2017-02-02 | 学校法人神奈川大学 | Method for recovering rhenium, method for selectively recovering rhenium from solution including rhenium and other metals, and method for increasing content ratio of rhenium in solution including rhenium and other metals |
| US10480048B2 (en) | 2015-07-24 | 2019-11-19 | Kanagawa University | Method for recovering rhenium, method for selectively recovering rhenium from solution including rhenium and other metals, and method for increasing content ratio of rhenium in solution including rhenium and other metals |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19990311 |