JP3125312B2 - Transparent plate and method for producing transparent plate - Google Patents
Transparent plate and method for producing transparent plateInfo
- Publication number
- JP3125312B2 JP3125312B2 JP03054371A JP5437191A JP3125312B2 JP 3125312 B2 JP3125312 B2 JP 3125312B2 JP 03054371 A JP03054371 A JP 03054371A JP 5437191 A JP5437191 A JP 5437191A JP 3125312 B2 JP3125312 B2 JP 3125312B2
- Authority
- JP
- Japan
- Prior art keywords
- ultrafine
- film
- ultrafine particles
- particle
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Surface Treatment Of Optical Elements (AREA)
- Formation Of Various Coating Films On Cathode Ray Tubes And Lamps (AREA)
- Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は透明板とその製造方法、
並びにこれを応用した画面表示面板及びブラウン管（陰
極管）等とこれらの製造方法に係り、特に画像表示板の
帯電、反射防止膜として有効に機能し得る超微粒子を利
用した透明板とその製造方法、並びにこれを応用した画
面表示面板及びブラウン管（陰極管）等とこれらの製造
方法に関する。The present invention relates to a transparent plate and a method for producing the same,
Also, the present invention relates to a screen display surface plate, a cathode ray tube (cathode tube), etc. to which these are applied, and a method for producing the same, and in particular, a transparent plate utilizing ultrafine particles which can effectively function as an anti-reflection film for charging an image display plate and a method for producing the same The present invention also relates to a screen display surface plate, a cathode ray tube (cathode tube), etc. to which this is applied, and a method for producing these.
【０００２】[0002]
【従来の技術】透明性板表面の反射率を低減する膜（反
射防止膜）は古くから研究されておりカメラ、メガネな
どのレンズに利用されてきた。現在は、ＶＤＴ（ビジュ
アル・デイスプレイ・タ−ミナル）の反射光を低減する
ための反射防止フィルタなどに用いられている。反射防
止膜には様々なものが考えられているが、現在利用され
ているものは主に多層膜と不均一膜である。2. Description of the Related Art A film (antireflection film) for reducing the reflectance on the surface of a transparent plate has been studied for a long time and has been used for lenses of cameras, glasses and the like. At present, it is used as an anti-reflection filter for reducing reflected light of a VDT (Visual Display Terminal). Various antireflection films have been considered, but currently used ones are mainly multilayer films and nonuniform films.
【０００３】多層膜は透明性板表面に低屈折率物質と高
屈折率物質とを交互に少なくとも三層積層した構造であ
り、その反射防止効果は各層感での光学的干渉作用の総
合効果である。多層膜に関してはフィジックス・オブ・
シン・フィルムの２号（１９６４年）２４３頁〜２８４
頁（Ｐｈｉｙｓｉｃｓ ｏｆ Ｔｈｉｎ Ｆｉｌｍｓ
２，（１９６４）ｐ．２４３〜２８４）に論じられてい
る。A multilayer film has a structure in which at least three layers of a low-refractive index substance and a high-refractive index substance are alternately laminated on the surface of a transparent plate, and the antireflection effect is a total effect of optical interference effect in each layer. is there. Physics of Multilayer
Shin Film No. 2 (1964) pp. 243-284
Page (Physics of Thin Films)
2, (1964) p. 243-284).
【０００４】また、膜厚方向に屈折率分布を持つ不均質
膜は、膜の平均屈折率が基板ガラスよりも低い場合に反
射防止膜となる。不均質膜は透明性板表面を多孔質化し
たものが一般的である。A heterogeneous film having a refractive index distribution in the thickness direction becomes an antireflection film when the average refractive index of the film is lower than that of the substrate glass. The heterogeneous film generally has a transparent plate surface made porous.
【０００５】ガラス表面に島上の金属蒸着膜を形成後、
スパッタエッチングにより微細な凹凸を形成して不均質
膜を作り、反射率を低減する方法がアプライド・フィジ
ックス・レタ−３６号（１９８０）の７２７頁から７３
０頁（Ａｐｌ．Ｐｈｙｓ．Ｌｅｔｔ，３６（１９８０）
ｐ．７２７〜ｐ．７３０）において論じられている。ま
たソ−ダムガラスをＳｉＯ2過飽和のＨ2ＳｉＦ6溶液に
浸漬し、表面を多孔質化して反射率を低減する方法がソ
−ラ・エネルギ−，６号（１９８０年）の２８頁から３
４頁（Ｓｏｌａｒ Ｅｎｅｒｇｙ ６ （１９８０）
ｐ．２８〜ｐ．３４）において論じられている。After forming a metal deposition film on the island on the glass surface,
A method for forming a non-uniform film by forming fine irregularities by sputter etching and reducing the reflectance is described in Applied Physics Letterer No. 36 (1980), pp. 727-73.
Page 0 (Apl. Phys. Lett, 36 (1980))
p. 727-p. 730). Further, a method of immersing Sodam glass in a supersaturated SiO 2 H 2 SiF 6 solution to make the surface porous and reduce the reflectance is disclosed in Solar Energy, No. 6, page 1980 (page 28).
4 pages (Solar Energy 6 (1980))
p. 28 to p. 34).
【０００６】一方、陰極管においてはガラス面の帯電防
止のために導電性膜を形成するとともに反射防止の工夫
も要求されている。On the other hand, in the cathode ray tube, it is required to form a conductive film in order to prevent the glass surface from being charged, and to take measures to prevent reflection.
【０００７】ところで、ブラウン管などの陰極管の全面
パネル表面（画像表示版）が帯電することが知られてい
るが、その理由は図４に示すごとく、通常ブラウン管４
１の内面４２に塗布されている螢光体４３の上に薄く均
一なアルミニウムを蒸着しているがそのアルミニウム膜
４４に高電圧が印加されると、その印加時及び遮断時に
ブラウン管前面パネル４５に静電誘導により帯電現象を
起こすことによる。It is known that the entire panel surface (image display plate) of a cathode ray tube such as a cathode ray tube is charged. The reason for this is as shown in FIG.
Although a thin and uniform aluminum is deposited on the phosphor 43 coated on the inner surface 42 of the CRT 1, when a high voltage is applied to the aluminum film 44, the CRT front panel 45 is applied when the voltage is applied and cut off. It is caused by charging phenomenon caused by electrostatic induction.
【０００８】このような表示管表面での帯電防止にさら
に反射防止をかねて帯電、反射防止膜を形成させる方法
特開昭６１−５１１０１号公報に開示されている。この
場合にはまずガラス基板に真空蒸着法、スパッタリング
法などの物理的気相法あるいは化学的気相法などによ
り、導電性膜を形成し、その上に反射防止膜を形成する
ようになっていた。A method of forming a charge and antireflection film while also preventing reflection on the display tube surface is disclosed in JP-A-61-51101. In this case, a conductive film is first formed on a glass substrate by a physical vapor method such as a vacuum deposition method or a sputtering method or a chemical vapor method, and an antireflection film is formed thereon. Was.
【０００９】[0009]
【発明が解決しようとする課題】上記従来技術は形成方
法がスパッタリング、真空蒸着法に限られ、かつ膜厚の
高精度制御が必要であるため、コストが高く大面積の基
板への適用が困難であるという問題があった。In the above prior art, since the forming method is limited to the sputtering and vacuum deposition methods, and high-precision control of the film thickness is required, it is difficult to apply the method to a substrate having a large cost and a large area. There was a problem that is.
【００１０】特に従来技術は、導電性膜と反射防止膜を
それぞれ形成する２層構造であり、生産性、価格の点で
問題があった。また膜焼成温度が低温に限定されるブラ
ウン管などの表示管表面に膜形成する場合には膜強度、
反射特性に問題があった。In particular, the prior art has a two-layer structure in which a conductive film and an anti-reflection film are respectively formed, and has problems in productivity and cost. Also, when a film is formed on the surface of a display tube such as a CRT where the film firing temperature is limited to a low temperature, the film strength,
There was a problem with the reflection characteristics.
【００１１】また超微粒子を利用した反射膜の場合は、
超微粒子が高密度に規則正しく基板上に配列されたとき
に最も小さな反射率が得られる。In the case of a reflective film using ultrafine particles,
The smallest reflectance is obtained when the ultrafine particles are regularly arranged on the substrate at high density.
【００１２】図５は超微粒子が整然と規則正しく透明性
板基板上に塗布された場合の断面模式図を示す。４６は
超微粒子、４７は樹脂層、４８は基板である。この場
合、ｎ0は空気の屈折率、ｎ1は空気側の超微粒子ｄａ層
の屈折率、ｎ2はｄａ層の超微粒子側の屈折率、ｎSは超
微粒子とバインダ−とで形成される層の屈折率、ｎGは
透明性板の屈折率とするとｄａ層の反射率Ｒａは式（数
１）で、ｄｂ層の屈折率Ｒｂは式（数２）でそれぞれ示
すことができる。FIG. 5 is a schematic sectional view showing a case where ultrafine particles are applied to a transparent plate substrate in an orderly and regular manner. 46 is ultrafine particles, 47 is a resin layer, and 48 is a substrate. In this case, n 0 is the refractive index of air, n 1 is the refractive index of the air side of the ultrafine da layer, n 2 is the refractive index of the ultrafine particles side of da layer, n S is the ultrafine particles and a binder - are formed by city Assuming that the refractive index of the layer is n and the refractive index n G is the refractive index of the transparent plate, the reflectance Ra of the da layer can be expressed by the equation (Equation 1), and the refractive index Rb of the db layer can be expressed by the equation (Equation 2).
【００１３】[0013]
【数１】 (Equation 1)
【００１４】[0014]
【数２】 (Equation 2)
【００１５】また超微粒子の存在しない部分の反射率を
Ｒｃとしたとき、合計の反射率Ｒは超微粒子の存在しな
い部分の面積比をαとして式（数３）で示すことができ
る。When the reflectance of the portion where no ultrafine particles are present is represented by Rc, the total reflectance R can be expressed by the following equation (3), where α is the area ratio of the portion where no ultrafine particles are present.
【００１６】 Ｒ＝（１−α）（Ｒａ＋Ｒｂ）＋αＲｃ …………（数３） 通常、ガラス体と同様のバインダを用いた場合にはＲｃ
は４．２％である。R = (1−α) (Ra + Rb) + αRc (Equation 3) Normally, when a binder similar to a glass body is used, Rc
Is 4.2%.
【００１７】Ｒａは、ｎ0＝１．０、ｎ1＝１．１０、ｎ
2＝１．３８、ｎS＝１．４７と仮定すると、λ＝５５０
ｎｍで約０．１９％となる。またＲｂは透明性板をガラ
スとすると、ｎG＝１．５３、他の屈折率はＲａの場合
と同一と仮定すると、λ＝５５０ｎｍで約０．０４％と
なる。Ra is n 0 = 1.0, n 1 = 1.10, n
Assuming that 2 = 1.38 and n s = 1.47, λ = 550
It is about 0.19% in nm. Further, Rb is about 0.04% at λ = 550 nm, assuming that n G = 1.53 when the transparent plate is made of glass and other refractive indices are the same as those of Ra.
【００１８】従って（Ｒａ＋Ｒｂ）≪Ｒｃであり、αが
小さいほど反射率は小さくなることがわかる。言い替え
ると超微粒子を規則正しく緻密に塗布した場合に最も反
射率が小さくなることになる。Therefore, it is understood that (Ra + Rb) ≪Rc, and the smaller α is, the smaller the reflectance is. In other words, when the ultrafine particles are applied regularly and densely, the reflectance becomes the smallest.
【００１９】本発明者等は、先に超微粒子を反射防止膜
に適用することを提案したが、更に鋭意検討した結果、
塗布液を基板表面上を一定速度で上昇あるいは下降する
ことにより塗布液に混合されている超微粒子が基板上に
規則正しく配列、塗布され、理論値に近い低反射率が得
られることを見出した。The present inventors have previously proposed applying ultrafine particles to an antireflection film, but as a result of further intensive studies,
It has been found that by raising or lowering the coating solution on the substrate surface at a constant speed, the ultrafine particles mixed with the coating solution are regularly arranged and coated on the substrate, and a low reflectance close to the theoretical value is obtained.
【００２０】またこの場合、反射防止用超微粒子の粒径
に対して１／１０以下の粒径を持つ帯電防止用超微粒子
を塗布溶液に同時に混合することにより、反射防止用超
微粒子間の間隙に帯電防止用超微粒子が網目状に配列さ
れて導電性膜になることを見出した。In this case, the antistatic ultrafine particles having a particle size of 1/10 or less of the particle size of the antireflective ultrafine particles are simultaneously mixed with the coating solution, so that the gaps between the antireflective ultrafine particles are reduced. It has been found that antistatic ultrafine particles are arranged in a network to form a conductive film.
【００２１】本発明の目的は低コストでかつ大面積に適
用できる帯電、反射防止膜とこれを適用した画像表示板
を提供することにある。It is an object of the present invention to provide a charge and antireflection film which can be applied to a large area at low cost and an image display panel using the same.
【００２２】[0022]
【課題を解決するための手段】上記目的は、超微粒子が
均一に分散された塗布溶液を、基板表面側に設置された
浴槽内に充たした後、一定速度で引き抜くかあるいは一
定速度で浴槽内に充たしていくことにより達成される。An object of the present invention is to fill a coating solution in which ultrafine particles are uniformly dispersed in a bath provided on the surface of a substrate and then withdraw the coating solution at a constant speed, or to fill the bath at a constant speed. Is achieved by allocating
【００２３】本発明の透明板の製造方法は、超微粒子群
と各超微粒子間隙を充填するバインダ−とによる超微粒
子膜を透明基板上に形成するに際して、超微粒子膜を形
成すべき基板を容器に立てかけ、超微粒子とバインダ−
とを含む混合塗布溶液をこの容器内に導入し一定速度で
基板表面上に上昇あるいは下降させて基板表面に超微粒
子膜を形成することを特徴とする。According to the method for producing a transparent plate of the present invention, when forming an ultrafine particle film on a transparent substrate by a group of ultrafine particles and a binder filling each ultrafine particle gap, the substrate on which the ultrafine particle film is to be formed is placed in a container. , Ultra-fine particles and binder
Is introduced into the container and raised or lowered at a constant speed on the substrate surface to form an ultrafine particle film on the substrate surface.
【００２４】本発明の透明板は、超微粒子群と各超微粒
子間隙を充填するバインダ−とによる超微粒子膜を透明
基板上に形成した透明板において、基板材に対する官能
基を有するカップリング剤を前記超微粒子膜内に混在さ
せ及び／又は超微粒子膜と透明基板との界面に存在させ
ること、及び／又は超微粒子の塗膜のさらにその上にケ
イ酸エチルを主成分とする塗布液を塗布することを特徴
とする。In the transparent plate of the present invention, a coupling agent having a functional group to a substrate material is used in a transparent plate having an ultrafine particle film formed by ultrafine particles and a binder filling each ultrafine particle gap formed on the transparent substrate. Coating it in the ultrafine particle film and / or present it at the interface between the ultrafine particle film and the transparent substrate, and / or applying a coating liquid containing ethyl silicate as a main component on the ultrafine particle coating film It is characterized by doing.
【００２５】本発明の画像表示板や画像表示板保護板
は、上記要領で作成した透明板をその透明基板の表面に
適用し、或いは直接画像表示板の表面に上記要領で超微
粒子膜を形成したことを特徴とする。In the image display plate and the image display plate protection plate of the present invention, the transparent plate prepared as described above is applied to the surface of the transparent substrate, or the ultrafine particle film is formed directly on the surface of the image display plate as described above. It is characterized by having done.
【００２６】本発明のブラウン管は上記画像表示板や画
像表示板保護板を備えてなることを特徴とする。尚、本
発明は同じ要領にて他の陰極線管や液晶表示装置、自動
車用窓ガラス、各種透明保護体、メガネレンズなど種々
の応用品に適用できる。A CRT according to the present invention comprises the above-mentioned image display plate and image display plate protection plate. The present invention can be applied to various applied products such as other cathode ray tubes, liquid crystal display devices, window glasses for automobiles, various transparent protective bodies, and spectacle lenses in the same manner.
【００２７】本発明のブラウン管の製造方法は、容器側
面の開口部から該容器内にブラウン管の透明基板面を露
出させ、超微粒子とバインダ−とを含む混合塗布溶液を
前記容器内に導入し一定速度で該基板表面上に上昇ある
いは下降させて該基板表面に超微粒子膜を形成すること
を特徴とする。In the method of manufacturing a cathode ray tube according to the present invention, the transparent substrate surface of the cathode ray tube is exposed in the container from the opening on the side of the container, and a mixed coating solution containing ultrafine particles and a binder is introduced into the container and fixed. The method is characterized in that an ultra-fine particle film is formed on the substrate surface by moving up or down on the substrate surface at a speed.
【００２８】本発明の自動車用窓ガラスの製造方法は、
容器側面の開口部から該容器内に自動車用窓ガラスの透
明基板面を露出させ、超微粒子とバインダ−とを含む混
合塗布溶液を前記容器内に導入し一定速度で該基板表面
上に上昇あるいは下降させて該基板表面に超微粒子膜を
形成することを特徴とする。The method for manufacturing a window glass for an automobile according to the present invention comprises:
The transparent substrate surface of the automotive window glass is exposed in the container from the opening on the side surface of the container, and a mixed coating solution containing ultrafine particles and a binder is introduced into the container and is raised at a constant speed onto the substrate surface. It is characterized in that it is lowered to form an ultrafine particle film on the substrate surface.
【００２９】[0029]
【作用】一般に超微粒子を混合していない塗布溶液を用
いて、ディッピング法により膜形成を行った場合、膜厚
ｔと引上げ速度ｖとの間には次の式（数４）が成り立つ
ことが知られている。In general, when a film is formed by a dipping method using a coating solution containing no ultrafine particles, the following equation (Equation 4) is established between the film thickness t and the pulling speed v. Are known.
【００３０】ｔ＝Ｋ（ηｖ／ｐｇ）05………（数４） ここにηは溶液の粘度、ｐは溶液の密度、ｇは重力加速
度、Ｋは定数である。T = K (ηv / pg) 05 (Equation 4) where η is the viscosity of the solution, p is the density of the solution, g is the gravitational acceleration, and K is a constant.
【００３１】一方、本発明者等は、超微粒子混合塗布液
を一定速度で基板表面上を上昇あるいは下降させた場
合、図６に示すようにある引上げ速度までは超微粒子が
一層配列された膜となり、それ以上では二層乃至三層構
造の膜となることを見出した。したがって反射防止機能
用超微粒子として粒径Ｄ2の超微粒子を混合した場合一
層配列の速度範囲内では見かけの膜厚はＤ2となる。こ
の時の臨界速度は１０ｍｍ／ｓ程度である。On the other hand, the present inventors have found that when the ultrafine particle mixed coating liquid is raised or lowered on the substrate surface at a constant speed, a film in which the ultrafine particles are arranged in a single layer until a certain pulling speed as shown in FIG. It was found that a film having a two-layer structure or a three-layer structure was formed above this. Thus the apparent thickness in the speed range of more sequences when mixed ultrafine particles having a particle diameter D 2 as an anti-reflection function for ultrafine particles becomes D 2. The critical speed at this time is about 10 mm / s.
【００３２】またブラウン管の様に複雑な形状をした基
板表面に通常のディッピング法により膜を塗布すること
は非常に困難であるが、本発明法ではブラウン管表面に
塗布液が入る浴槽を設け、この浴槽内で塗布液を一定速
度で上昇あるいは下降させることにより塗膜を簡便に形
成することができる。Further, it is very difficult to apply a film on a substrate having a complicated shape such as a cathode ray tube by a usual dipping method. The coating film can be easily formed by raising or lowering the coating solution at a constant speed in the bathtub.
【００３３】混合超微粒子により膜を形成すると、それ
ぞれの超微粒子はそれぞれの機能を発揮する。例えば多
量成分の超微粒子を反射防止機能成分とすれば主に表面
の粗さが功を奏して低反射機能を発揮する。またもう一
方の少量超微粒子が、反射防止機能超微粒子の粒径に対
して１／１０以下の粒径を持つ導電性機能成分とすれば
網目状に凝集する効果により導電性を発揮する。このよ
うにして本発明の方法によって反射と帯電とを防止する
二つの特性を有する膜が一回の塗布により得られる。When a film is formed from the mixed ultrafine particles, each ultrafine particle exerts its function. For example, if ultra-fine particles containing a large amount of components are used as the antireflection function component, the surface roughness is mainly effective, and the low reflection function is exhibited. Further, when the other small amount of ultrafine particles is a conductive functional component having a particle size of 1/10 or less of the particle size of the antireflection function ultrafine particles, conductivity is exerted by an effect of agglomerating in a network. In this way, a film having two properties for preventing reflection and charging can be obtained by a single application by the method of the present invention.
【００３４】さらにこの混合塗布液に多量成分超微粒子
の粒径に対して２〜３倍の粒径を持つ超微粒子を加える
と、この超微粒子が島状に配列される。この状態はこの
比較的大きな超微粒子があたかも反射防止機能超微粒子
の海の中に転々と存在する如くである。Further, when ultrafine particles having a particle diameter that is two to three times the particle diameter of the large amount of ultrafine particles are added to the mixed coating solution, the ultrafine particles are arranged in an island shape. In this state, it is as if these relatively large ultrafine particles are present in the sea of antireflection function ultrafine particles.
【００３５】この間隔は約１〜２μｍ程度であるので、
この膜が機械的な摩擦力を受けた時にはこの大きな超微
粒子に点接触し、反射防止機能超微粒子には接触しない
ため光学的特性は全く変化しない。換言すれば摩擦力に
対する膜の光学的強度が著しく向上する。また同様の理
由により、油等の汚れに対する落ち易さも向上する。Since this interval is about 1-2 μm,
When this film receives mechanical frictional force, it comes into point contact with the large ultrafine particles and does not contact the antireflection function ultrafine particles, so that the optical characteristics do not change at all. In other words, the optical strength of the film against the frictional force is significantly improved. Further, for the same reason, the easiness of falling off of dirt such as oil is also improved.
【００３６】通常、サブミクロンオ−ダ−の凹凸表面に
人間が手で触れた場合、指紋が膜に転写され、アルコ−
ルなどで洗浄してもなかなか落ちないが、この比較的大
きな超微粒子を混合して島状に配列することにより、指
紋が膜に転写されにくくなると同時に、仮に転写された
場合でも簡単に拭い去ることができる。Normally, when a human touches the uneven surface of submicron order, a fingerprint is transferred to the film, and the
Although it does not fall off easily even when washed with a tool, it is difficult to transfer fingerprints to the film by mixing these relatively large ultrafine particles and arranging them in an island shape, and at the same time, even if they are transferred, they can be easily wiped off be able to.
【００３７】[0037]
【実施例】以下、本発明の実施例につき図面に従って説
明する。先ず本発明の構成要件につき分説する。Embodiments of the present invention will be described below with reference to the drawings. First, the components of the present invention will be described separately.
【００３８】（超微粒子）超微粒子の機能は透明性、透
光性に支障のない限り特に限定はされないが、平均粒径
としては０．１μｍ以下のものをいう。代表的な機能は
帯電防止、反射防止及び／又は赤外線反射である。(Ultra-fine particles) The function of the ultra-fine particles is not particularly limited as long as it does not affect the transparency and the light-transmitting property, but the average particle diameter is 0.1 μm or less. Typical functions are antistatic, antireflective and / or infrared reflection.
【００３９】帯電防止超微粒子はＳｎＯ2（酸化ス
ズ），ＳｎＯ2＋Ｓｂ2Ｏ3（酸化アンチモン），Ｉｎ2Ｏ
3（酸化インジウム），Ｉｎ2Ｏ3＋Ｓｂ2Ｏ3の群から選
ばれることが望ましい。反射防止超微粒子はＳｉＯ
2（二酸化ケイ素），ＭｇＦ2（フッ化マグネシウム）の
群から選ばれることが望ましい。また赤外線反射超微粒
子はＳｎＯ2，ＳｎＯ2＋Ｓｂ2Ｏ3，Ｉｎ2Ｏ3，Ｉｎ2Ｏ3
＋Ｓｂ2Ｏ3，ＴｉＯ2（酸化チタン），ＺｒＯ2（酸化ジ
ルコニウム）の群から選ばれることが好ましい。The antistatic ultrafine particles are SnO 2 (tin oxide), SnO 2 + Sb 2 O 3 (antimony oxide), In 2 O
3 (indium oxide), is preferably selected from the group consisting of In 2 O 3 + Sb 2 O 3. Antireflection ultrafine particles are SiO
2 (silicon dioxide) and MgF 2 (magnesium fluoride). The infrared reflective ultrafine particles are SnO 2 , SnO 2 + Sb 2 O 3 , In 2 O 3 , In 2 O 3
It is preferable to be selected from the group of + Sb 2 O 3 , TiO 2 (titanium oxide), and ZrO 2 (zirconium oxide).
【００４０】上記反射防止用超微粒子の平均粒径は１０
０〜１５０ｎｍが望ましい。ＳｉＯ2等は１００ｎｍよ
り小さな粒径では形成された膜の最外表面が平坦になり
すぎて充分な反射防止効果が得られない恐れがあり、一
方１５０ｎｍより大きな粒径では反射防止効果は充分得
られるが、拡散反射が大きくなり、その結果白濁すると
同時に解像度が低下する恐れがあるからである。従って
反射防止用超微粒子の粒径は１００〜１５０ｎｍが好ま
しい。尚、ＳｉＯ2やＭｇＦ2等の反射防止用超微粒子材
料はいずれもその屈折率が１．５０以下である。The average particle size of the antireflection ultrafine particles is 10
0 to 150 nm is desirable. If the particle size of SiO 2 or the like is smaller than 100 nm, the outermost surface of the formed film may be too flat to obtain a sufficient antireflection effect, while if the particle size is larger than 150 nm, the antireflection effect may be sufficiently obtained. However, this is because diffuse reflection becomes large, and as a result, there is a possibility that the resolution becomes lower at the same time as the cloudiness. Therefore, the particle diameter of the antireflection ultrafine particles is preferably 100 to 150 nm. Incidentally, the refractive index of each of the antireflection ultra-fine particle materials such as SiO 2 and MgF 2 is 1.50 or less.
【００４１】帯電防止用超微粒子の平均粒径は１０ｎｍ
以下が望ましい。また、帯電防止用超微粒子は２種以上
併用してもよい。反射防止用超微粒子と併用する場合の
帯電防止用超微粒子の粒径は、反射防止用超微粒子の粒
径に対して１／１０以下が望ましい。すなわち粒径の異
なる２種類の微粒子を混合した溶液を塗布した場合、粒
径比が１／１０以内では比較的良く分散されるが、１／
１０以上では分散されずに粒径の小さな微粒子は網目状
に凝集するからである。The average particle size of the antistatic ultrafine particles is 10 nm.
The following is desirable. Further, two or more kinds of antistatic ultrafine particles may be used in combination. When used in combination with the antireflection ultrafine particles, the particle diameter of the antistatic ultrafine particles is preferably 1/10 or less of the particle size of the antireflection ultrafine particles. That is, when a solution in which two kinds of fine particles having different particle diameters are mixed is applied, the particles are relatively well dispersed when the particle diameter ratio is within 1/10.
This is because when the particle size is 10 or more, the fine particles having a small particle size without being dispersed are aggregated in a network.
【００４２】このことから帯電防止用超微粒子の粒径が
反射防止用超微粒子粒径の１／１０以内では、導電性が
なくなる程度まで良く分散されてしまい、その結果帯電
防止機能を発揮しない。一方、その粒径比が１／１０以
上では網目状に凝集するので導電性膜となり、帯電防止
機能を良く発揮する。本発明の場合、反射防止用超微粒
子の適正粒径は１００〜１５０ｎｍであるので、このこ
とから帯電防止用超微粒子の適正粒径は１０ｎｍ以下が
望ましい。From this, if the particle diameter of the antistatic ultrafine particles is within 1/10 of the particle diameter of the antireflective ultrafine particles, the particles are sufficiently dispersed to the extent that conductivity is lost, and as a result, the antistatic function is not exhibited. On the other hand, when the particle size ratio is 1/10 or more, the particles are aggregated in a network form, so that the film becomes a conductive film and exhibits an antistatic function well. In the case of the present invention, since the appropriate particle size of the antireflection ultrafine particles is 100 to 150 nm, the appropriate particle size of the antistatic ultrafine particles is preferably 10 nm or less.
【００４３】また反射防止用超微粒子と帯電防止用超微
粒子との構成割合は、帯電防止用超微粒子が全超微粒子
量の１０％以上であることが好ましい。尚、この量が５
０％以上になると反射防止機能の低下をきたす恐れがあ
り、５０％以下に調整する必要がある。The composition ratio of the antireflection ultrafine particles and the antistatic ultrafine particles is preferably 10% or more of the total ultrafine particles. This amount is 5
If it is 0% or more, the antireflection function may be deteriorated, and it is necessary to adjust it to 50% or less.
【００４４】また同様の理由により、反射防止用超微粒
子の粒径に対して２〜３倍の粒径を持つ超微粒子を少な
くとも全超微粒子量の２０重量％以下混合させることが
望ましい。For the same reason, it is desirable to mix ultrafine particles having a particle diameter that is two to three times the particle diameter of the antireflection ultrafine particles at least not more than 20% by weight of the total ultrafine particles.
【００４５】赤外線反射機能或いは電磁遮断機能或いは
透明導電性機能を有する超微粒子としては、ＴｉＯ2，
ＺｒＯ2，ＳｎＯ2，Ｉｎ2Ｏ3などの金属酸化物或いはこ
れらの混合物などが挙げられる。この中でＳｎＯ2＋１
０重量％Ｓｂ2Ｏ3、或いはＩｎ2Ｏ3＋５重量％ＳｎＯ2
は導電特性と赤外線反射特性が優れているので好まし
い。膜厚は０．２〜０．５μｍ、粒径は０．０１〜０．
０５μｍが望ましい。Ultrafine particles having an infrared reflecting function, an electromagnetic shielding function or a transparent conductive function include TiO 2 ,
Examples include metal oxides such as ZrO 2 , SnO 2 , and In 2 O 3, and mixtures thereof. Among them, SnO 2 +1
0% by weight Sb 2 O 3 or In 2 O 3 + 5% by weight SnO 2
Is preferred because of its excellent conductive properties and infrared reflection properties. The film thickness is 0.2-0.5 μm, and the particle size is 0.01-0.
05 μm is desirable.
【００４６】（透光性基板）透光性基板としてはガラス
板でもプラスチック板でも差し支えない。プラスチック
板としては主成分が例えば、ポリエチレン、ポリプロピ
レン、ウレタン、アクリル、フェノ−ル、エポキシ、メ
ラミン、ナイロン、ポリイミド、ポリカ−ボネ−ト、ブ
チル、エポキシフェノ−ル、塩化ビニル、ポリエステル
等のものが挙げられる。尚、基板の超微粒子形成面は平
板状はもちろんのこと、ブラウン管のように曲率を有し
ていても良い。また超微粒子形成面は片面でも両面でも
差し支えない。(Translucent Substrate) The transparent substrate may be a glass plate or a plastic plate. The main components of the plastic plate include, for example, polyethylene, polypropylene, urethane, acrylic, phenol, epoxy, melamine, nylon, polyimide, polycarbonate, butyl, epoxy phenol, vinyl chloride, polyester, and the like. No. The surface of the substrate on which the ultrafine particles are formed may have not only a flat plate shape but also a curvature like a cathode ray tube. The surface on which the ultrafine particles are formed may be one side or both sides.
【００４７】（前処理）基板との濡れ性を考慮するなら
ば、アルカリ処理やフッ素処理等の前処理が好ましい。(Pretreatment) In consideration of wettability with the substrate, pretreatment such as alkali treatment or fluorine treatment is preferable.
【００４８】（塗布方法）塗布液の上昇あるいは下降速
度は１０ｍｍ／ｓ以下が望ましい。基板は容器内に立て
かけるか、或いはこれに代えて容器の側面部にあけた穴
から基板面を露出させてもよい。後者の方法はブラウン
管など製品形状がほぼ出来上がったものに超微粒子膜を
形成するのに特に適している。(Coating Method) The rising or falling speed of the coating solution is preferably 10 mm / s or less. The substrate may be leaned against the inside of the container, or alternatively, the surface of the substrate may be exposed through a hole formed in the side surface of the container. The latter method is particularly suitable for forming an ultrafine particle film on an almost finished product such as a cathode ray tube.
【００４９】塗布面の加熱処理としては炉中で５０〜２
００℃焼成するのが実用的であるが高圧水銀灯等を用い
て紫外線により短時間に焼成しても良い。As the heat treatment of the coating surface, 50 to 2
Although it is practical to bake at 00 ° C., baking may be performed in a short time by ultraviolet rays using a high-pressure mercury lamp or the like.
【００５０】以上はディッピング方法の１例で説明した
が、プラスチック基板への塗布方法や膜表面の均質さを
問わないなら、このディッピング法に限らず他のディッ
ピング法やスピニング法、スプレ−法、或いはこれらの
組合せやこれらとディッピング法との組合せも有効であ
る。The above description has been made with reference to one example of the dipping method. However, if the coating method on a plastic substrate or the uniformity of the film surface is not limited, the dipping method is not limited to this dipping method, and other methods such as spinning, spraying, Alternatively, a combination of these or a combination of these with a dipping method is also effective.
【００５１】更に超微粒子の塗膜の上にケイ酸エチルを
主成分とする塗布液を塗布することも有効である。層の
数は１層でも必要により２層以上でも良い。It is also effective to apply a coating solution containing ethyl silicate as a main component on the coating film of ultrafine particles. The number of layers may be one or two or more if necessary.
【００５２】（塗布溶液）本発明の超微粒子膜の形成に
は、所定の超微粒子にバインダ−や必要に応じてカップ
リング剤、その他添加物を加えた塗布溶液を用いる。(Coating Solution) In forming the ultrafine particle film of the present invention, a coating solution obtained by adding a binder, a coupling agent as needed, and other additives to predetermined ultrafine particles is used.
【００５３】透光性板がガラス体のときはバインダとし
てＳｉ（ＯＲ）4（但しＲはアルキル基）を使用するこ
とが好ましく、透光性板がプラスチックのときはバイン
ダとしてＳｉ（ＯＲ）X（Ｘ＝２〜４、特に好ましくは
３）を使用することが好ましい。更に透光性板がプラス
チックのときはこのプラスチック材に対する官能基を有
するカップリング剤を併用することが望ましい。When the translucent plate is a glass body, it is preferable to use Si (OR) 4 (where R is an alkyl group) as a binder, and when the translucent plate is plastic, Si (OR) x as a binder. (X = 2 to 4, particularly preferably 3) is preferably used. Further, when the translucent plate is made of plastic, it is desirable to use a coupling agent having a functional group for this plastic material.
【００５４】透光性板がガラス体の場合にはＳｉ（Ｏ
Ｒ）4（但しＲはアルキル基）を溶解したアルコ−ル溶
液に、透光性板がプラスチックの場合にはこの高分子体
と容易に反応する官能基とＳｉ（ＯＲ）X（Ｘ＝２〜
４、特に好ましくは３）を保有するシランカップリング
剤、或いは上記Ｓｉ（ＯＲ）4とシランカップリング剤
との混合溶液を溶解したアルコ−ル溶液に超微粒子を分
散させる。When the translucent plate is a glass body, Si (O
R) 4 (where R is an alkyl group) is dissolved in an alcohol solution. When the translucent plate is made of plastic, a functional group which easily reacts with this polymer and Si (OR) x (X = 2 ~
Ultrafine particles are dispersed in an alcohol solution in which a silane coupling agent containing 4 and particularly preferably 3) or a mixed solution of the above Si (OR) 4 and the silane coupling agent is dissolved.
【００５５】この溶液を透光性板上に前記方法により塗
布した後、この塗布面を加熱（或いは焼成）して膜形成
を行う。この加熱処理により前記Ｓｉ（ＯＲ）4或いは
シランカップリング剤は分解してＳｉＯ2等夫々超微粒
子と基板との接着剤としての役目を果たす。After this solution is applied on a light-transmitting plate by the above method, the applied surface is heated (or baked) to form a film. By this heat treatment, the Si (OR) 4 or the silane coupling agent is decomposed to serve as an adhesive between the ultrafine particles such as SiO 2 and the substrate, respectively.
【００５６】Ｓｉ（ＯＲ）4のＲとしては一般に炭素数
１〜５のアルキル基が好ましい。一方シランカップリン
グ剤は透光性板の高分子材料によって適宜選択する必要
がある。In general, R in Si (OR) 4 is preferably an alkyl group having 1 to 5 carbon atoms. On the other hand, the silane coupling agent needs to be appropriately selected depending on the polymer material of the light-transmitting plate.
【００５７】例えば主成分がポリエチレン、ポリプロピ
レン、ウレタン、アクリル等の場合にはビニルトリエト
キシシラン、γ−メタクリルオキシプロピルトリメトキ
シシランなどのシランカップリング剤が有効である。ま
たフェノ−ル、エポキシ、メラミン、ナイロン、ポリイ
ミド、ポリカ−ボネ−トの場合にはγ−アミノプロピル
トリエトキシシラン、γ−グリシドオキシプロピルトリ
メトキシシランなどのシランカップリング剤が有効であ
る。更にブチル、エポキシフェノ−ル、塩化ビニル、ポ
リエステルの場合にはβ，３，４−エポキシシクロヘキ
シルエチルトリメトキシシラン、γ−グリシドオキシプ
ロピルトリメトキシシランなどのシランカップリング剤
が有効である。For example, when the main component is polyethylene, polypropylene, urethane, acrylic or the like, a silane coupling agent such as vinyltriethoxysilane or γ-methacryloxypropyltrimethoxysilane is effective. In the case of phenol, epoxy, melamine, nylon, polyimide and polycarbonate, silane coupling agents such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane are effective. Further, in the case of butyl, epoxyphenol, vinyl chloride, and polyester, a silane coupling agent such as β, 3,4-epoxycyclohexylethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane is effective.
【００５８】またＳｉ（ＯＲ）4アルイハシランカップ
リング剤を溶解させるためのアルコ−ルは、上記Ｒの炭
素数の増加と共に混合アルコ−ル溶液の粘性が高くなる
ので作業性を考慮して粘性が高くなりすぎないように適
宜アルコ−ルを選択すれば良い。一般に使用可能なアル
コ−ルとしては炭素数が１乃至５のアルコ−ルが挙げら
れる。In the alcohol for dissolving the Si (OR) 4 alihasilane coupling agent, the viscosity of the mixed alcohol solution increases as the number of carbon atoms of R increases. An alcohol may be appropriately selected so that the viscosity does not become too high. Alcohols that can be generally used include alcohols having 1 to 5 carbon atoms.
【００５９】さらに上記の膜には、帯電防止効果を付与
するために周期律表第II族、第III族金属の塩を添加し
て使用しても良い。代表的な例としてはアルミニウムの
塩酸塩や硝酸塩、硫酸塩及びカルボン酸塩が挙げられ
る。Further, a salt of a metal of Group II or III of the periodic table may be added to the above-mentioned film in order to impart an antistatic effect. Representative examples include hydrochloride, nitrate, sulfate and carboxylate of aluminum.
【００６０】更にＳｉ（ＯＲ）4が分解するために水及
び触媒として鉱酸、例えば硝酸などを加えて塗膜用溶液
を調整しても良い。Further, in order to decompose Si (OR) 4 , a coating solution may be prepared by adding water and a mineral acid such as nitric acid as a catalyst.
【００６１】以下、本発明をブラウン管の前面パネル表
面に（ガラス面板）に適用した例を示す。Hereinafter, an example in which the present invention is applied to a front panel surface (glass face plate) of a cathode ray tube will be described.
【００６２】図１は本発明の装置例を示す。図１におい
て１１はブラウン管、１２は塗布浴槽、１３は塗布溶
液、１４は加圧調整用バルブ、１５はオ−バ−フロ−用
のバルブ、１６は溶液タンク、１７は溶液供給加圧バル
ブ、１８はリ−ク用バルブである。FIG. 1 shows an example of the apparatus of the present invention. In FIG. 1, 11 is a cathode ray tube, 12 is a coating bath, 13 is a coating solution, 14 is a pressure adjusting valve, 15 is an overflow valve, 16 is a solution tank, 17 is a solution supply pressure valve, Reference numeral 18 denotes a leak valve.
【００６３】かかる構成において、ブラウン管１１に塗
布浴槽１２を取り付けた。この場合塗布浴槽１２の取付
け面には、塗布過程で塗布液及び加圧ガスが漏れないよ
うにパッキンあるいはＯリングが施されており、かつ作
業性を考慮してブラウン管を挿入するだけでシ−ルでき
るようになっている。In such a configuration, the coating bath 12 was attached to the cathode ray tube 11. In this case, the mounting surface of the coating bath 12 is provided with a packing or an O-ring so that the coating liquid and the pressurized gas do not leak during the coating process. Can be used.
【００６４】次に超微粒子が混合された塗布溶液を塗布
浴槽１２とブラウン管表面との間に形成された空間に導
入した。この塗布液の導入は、まずオ−バ−フロ−用バ
ルブ１５及び溶液供給加圧バルブ１７を開にした。Next, the coating solution containing the ultrafine particles was introduced into a space formed between the coating bath 12 and the surface of the cathode ray tube. For the introduction of this coating solution, first, the overflow valve 15 and the solution supply pressure valve 17 were opened.
【００６５】この操作により溶液タンク１６に充填され
ている塗布溶液１３を加圧してブラウン管表面上に満た
し、一部をオ−バ−フロ−バルブ１５から予備タンクに
入れた。このことによりブラウン管表面上あるいは経路
上に付着しているゴミ等をオ−バ−フロ−させた溶液と
共に予備タンクに排出することができた。By this operation, the coating solution 13 filled in the solution tank 16 was pressurized and filled on the surface of the cathode ray tube, and a part thereof was put into the spare tank from the overflow valve 15. As a result, dust or the like adhering on the surface of the cathode ray tube or on the path could be discharged to the spare tank together with the overflowed solution.
【００６６】次にオ−バ−フロ−用バルブ１５及び溶液
供給加圧バルブ１７を閉にした後、加圧調製用バルブ１
４とリ−ク用バルブ１８を開にするとブラウン管表面に
満たされている塗布溶液１３は溶液タンク１６に戻され
た。この場合、加圧調製用バルブ１４に加えるガス圧力
とリ−ク用バルブ１８の開閉度とによって、塗布溶液１
３がブラウン管表面上を一定速度で下降する速度を調製
することができた。Next, after the overflow valve 15 and the solution supply pressure valve 17 are closed, the pressure control valve 1 is closed.
When the leak valve 4 and the leak valve 18 were opened, the coating solution 13 filling the surface of the cathode ray tube was returned to the solution tank 16. In this case, the coating solution 1 is controlled by the gas pressure applied to the pressure adjusting valve 14 and the opening / closing degree of the leaking valve 18.
It was possible to adjust the speed at which the sample No. 3 descended on the surface of the cathode ray tube at a constant speed.
【００６７】次にこの塗布溶液の混合方法について述べ
る。まずエチルシリケ−ト〔Ｓｉ（ＯＣ2Ｈ5）4〕をエ
タノ−ルに溶解し、さらに加水分解のためのＨ2Ｏと、
触媒としてのＨＮＯ3とを添加した溶液を作り、この溶
液に粒径１２０ｎｍのほぼ球形のＳｉＯ2超微粒子を重
量％で１０％と、粒径６ｎｍのＳｎＯ2超微粒子を重量
％で２％添加する。このとき充分分散するように溶液の
ＰＨを調製する。Next, a method of mixing the coating solution will be described. First Echirushirike - bets [Si (OC 2 H 5) 4] ethanol - dissolved in Le, and more of H 2 O for hydrolysis,
A solution to which HNO 3 as a catalyst is added is prepared. To this solution, approximately spherical SiO 2 ultrafine particles having a particle diameter of 120 nm are added by 10% by weight and SnO 2 ultrafine particles having a particle diameter of 6 nm are added by 2% by weight. I do. At this time, the pH of the solution is adjusted so as to be sufficiently dispersed.
【００６８】次にこの溶液を上記方法によりブラウン管
表面に満たし、１．０ｍｍ／ｓの速度で塗布液を降下し
て塗布を行った。その後、１５０℃で３０分間空気中で
焼成し、エチルシリケ−ト〔Ｓｉ（ＯＣ2Ｈ5）4〕を分
解した。溶液に添加したＳｉＯ2超微粒子は、分解して
出来たＳｉＯ2がバインダの役目を果たすので、お互い
に強固に接着されると同時に、ブラウン管表面とも強固
に接着、固定される。この方法により、ブラウン管表面
には超微粒子による均一な連続した凹凸を形成すること
ができた。Next, the solution was filled on the surface of the cathode ray tube by the above method, and the coating solution was dropped at a speed of 1.0 mm / s to perform coating. Thereafter, the mixture was calcined at 150 ° C. for 30 minutes in air to decompose ethyl silicate [Si (OC 2 H 5 ) 4 ]. The ultrafine particles of SiO 2 added to the solution are firmly adhered to each other and simultaneously firmly adhered and fixed to the surface of the cathode ray tube, because the SiO 2 formed by decomposition serves as a binder. By this method, uniform continuous irregularities due to ultrafine particles could be formed on the surface of the cathode ray tube.
【００６９】この膜を形成したブラウン管表面に入射角
５°で光を入射させ、反射率を測定した結果、図２に示
すように波長５５０ｎｍにおいて０．０８％の低反射率
が得られた。Light was incident on the surface of the cathode ray tube on which this film was formed at an incident angle of 5 °, and the reflectance was measured. As a result, a low reflectance of 0.08% was obtained at a wavelength of 550 nm as shown in FIG.
【００７０】一方、この膜の表面抵抗値を測定した結果
約１０6Ω／□であり、この帯電特性は図３に示す如く
であって、参考として示した従来の特性と比較してほと
んど帯電しないことが判った。On the other hand, the surface resistance of this film was measured to be about 10 6 Ω / □. The charging characteristics are as shown in FIG. 3, which is almost the same as the conventional characteristics shown for reference. Turned out not to.
【００７１】次に、本発明実施例の帯電防止低反射膜を
消しゴム（ライオン社製、５０−３０タイプ）を用いて
１Ｋｇの荷重で５０回擦った結果、反射率は０．１％程
度変化しただけで、膜品質上は全く問題がなかった。Next, as a result of rubbing the antistatic low-reflection film of the embodiment of the present invention 50 times with a load of 1 kg using an eraser (Lion, 50-30 type), the reflectance changed by about 0.1%. There was no problem in film quality at all.
【００７２】また上記溶液に、粒径３００ｎｍの超微粒
子を全超微粒子含有量の１０ｗｔ％を混合させ、同様の
方法により塗布した結果、反射防止及び帯電防止効果は
全く変わらなかったが、消しゴムテスト前後の反射率の
変化は０．０２％となり、機械的摩耗に対して強い膜が
得られた。これは膜中に島状に分散した大きな超微粒子
がバリアの役目を果たすことによる。Further, ultrafine particles having a particle diameter of 300 nm were mixed with the above solution at 10 wt% of the total ultrafine particle content, and the mixture was applied in the same manner. As a result, the antireflection and antistatic effects were not changed at all, but the eraser test was performed. The change in reflectance before and after was 0.02%, and a film strong against mechanical wear was obtained. This is because large ultrafine particles dispersed like islands in the film function as a barrier.
【００７３】このような帯電、反射防止膜を形成するプ
ロセスでは、完成したブラウン管に直接膜を形成するこ
とができ、また既存のＳｉ（ＯＲ）4アルコ−ル溶液に
ＳｉＯ2超微粒子とＳｎＯ2超微粒子とを混合して塗布、
焼成するだけでよく、フッ酸などの有害な薬品の使用は
は一切なく、品質一定でしかも低コストで製造すること
ができる。In the process of forming such a charging and anti-reflection film, a film can be formed directly on the completed cathode ray tube, and ultra-fine particles of SiO 2 and SnO 2 can be added to an existing Si (OR) 4 alcohol solution. Mix with ultrafine particles and apply,
It is only necessary to bake, there is no use of harmful chemicals such as hydrofluoric acid, and it can be manufactured with constant quality and at low cost.
【００７４】また上記実施例では、Ｓｉ（ＯＲ）4とし
てＲがエチル基の例を示したが、前述のとおりＲ＝Ｃn
Ｈm（ｍ＝２ｎ＋１）としたとき、ｎ＝１〜５の範囲で
実施可能でありｎが大きくなる場合、溶液の粘性が少し
高くなるので溶媒としては作業性を考慮してそれに応じ
たアルコ−ルを選択すればよい。Further, in the above embodiment, the example where R is an ethyl group as Si (OR) 4 is shown, but as described above, R = C n
When Hm (m = 2n + 1), it can be carried out in the range of n = 1 to 5. When n becomes large, the viscosity of the solution becomes slightly high. You may select
【００７５】以上のように、本実施例によれば、反射防
止効果に優れ、かつ帯電防止機能を有する膜を形成した
画像表示板が一回の塗布工程で形成することができる。
しかも、本発明のこの面板は、フッ酸などの有害な処理
薬品を使用せず、簡単で安全なプロセスで製造でき、量
産性に好適で、耐汚染性にも優れている。As described above, according to this embodiment, an image display plate having a film having an excellent antireflection effect and having an antistatic function can be formed in a single coating step.
Moreover, this face plate of the present invention can be manufactured by a simple and safe process without using harmful treatment chemicals such as hydrofluoric acid, is suitable for mass production, and has excellent stain resistance.
【００７６】他の実施例につき図７を用いて説明する。Another embodiment will be described with reference to FIG.
【００７７】図７は本発明の装置例を示す。図７におい
て５１は透明基板で複数枚を治具５２に立てかけ塗布浴
槽１２内に納めている。第１実施例のブラウン管の透明
基板がガラス板であったのに対し、透明基板５１はプラ
スチック板である。FIG. 7 shows an example of the apparatus of the present invention. In FIG. 7, reference numeral 51 denotes a transparent substrate, a plurality of which are placed on the jig 52 and placed in the coating bath 12. The transparent substrate of the cathode ray tube of the first embodiment is a glass plate, whereas the transparent substrate 51 is a plastic plate.
【００７８】この場合塗布浴槽１２の取付け面には、塗
布過程で塗布液及び加圧ガスが漏れないようにパッキン
あるいはＯリングが施されている。In this case, the mounting surface of the coating bath 12 is provided with a packing or an O-ring so that the coating liquid and the pressurized gas do not leak during the coating process.
【００７９】次に超微粒子が混合された塗布溶液を塗布
浴槽１２の空間に導入した。この塗布液の導入は、まず
オ−バ−フロ−用バルブ１５及び溶液供給加圧バルブ１
７を開にした。この操作により溶液タンク１６に充填さ
れている塗布溶液１３を加圧して塗布浴槽１２内に満た
し、一部をオ−バ−フロ−バルブ１５から予備タンクに
入れた。Next, the coating solution containing the ultrafine particles was introduced into the space of the coating bath 12. The introduction of the coating solution is performed by firstly, an overflow valve 15 and a solution supply pressure valve 1.
7 was opened. By this operation, the coating solution 13 filled in the solution tank 16 was pressurized and filled in the coating bath 12, and a part of the solution was put into the spare tank from the overflow valve 15.
【００８０】次にオ−バ−フロ−用バルブ１５及び溶液
供給加圧バルブ１７を閉にした後、加圧調製用バルブ１
４とリ−ク用バルブ１８を開にすると塗布浴槽１２に満
たされている塗布溶液１３は溶液タンク１６に戻され
た。この場合、加圧調製用バルブ１４に加えるガス圧力
とリ−ク用バルブ１８の開閉度とによって、塗布溶液１
３が複数枚の透明基板５１の各両面上を一定速度で下降
する速度を調製することができた。Next, after the overflow valve 15 and the solution supply pressure valve 17 are closed, the pressure control valve 1
When the valve 4 and the leak valve 18 were opened, the coating solution 13 filled in the coating bath 12 was returned to the solution tank 16. In this case, the coating solution 1 is controlled by the gas pressure applied to the pressure adjusting valve 14 and the opening / closing degree of the leaking valve 18.
3 was able to adjust the speed at which the lower surface of each of the plurality of transparent substrates 51 was lowered at a constant speed.
【００８１】次にこの塗布溶液の混合方法について述べ
る。まずγ−メタクリルオキシプロピルトリメトキシシ
ランを含むエチルシリケ−ト〔Ｓｉ（ＯＣ2Ｈ5）3〕を
エタノ−ルに溶解し、さらに加水分解のためのＨ2Ｏ
と、触媒としてのＨＮＯ3とを添加した溶液を作り、こ
の溶液に粒径１２０ｎｍのほぼ球形のＳｉＯ2超微粒子
を重量％で１０％と、粒径６ｎｍのＳｎＯ2超微粒子を
重量％で２％添加し、充分分散するように溶液のＰＨを
調製した。Next, a method of mixing the coating solution will be described. First, ethyl silicate [Si (OC 2 H 5 ) 3 ] containing γ-methacryloxypropyltrimethoxysilane is dissolved in ethanol, and H 2 O for hydrolysis is further dissolved.
And HNO 3 as a catalyst were added to the solution, and approximately spherical SiO 2 ultrafine particles having a particle diameter of 120 nm were added to the solution by 10% by weight and SnO 2 ultrafine particles having a particle diameter of 6 nm to 2% by weight. %, And the pH of the solution was adjusted so as to be sufficiently dispersed.
【００８２】次にこの溶液を上記方法により塗布浴槽１
２内に満たし、１．０ｍｍ／ｓの速度で塗布液を降下し
て塗布を行った。その後、１５０℃で３０分間空気中で
焼成し、エチルシリケ−トを分解した。溶液に添加した
ＳｉＯ2超微粒子は、分解して出来たＳｉＯ2がバインダ
の役目を果たすので、お互いに強固に接着されると同時
に、ブラウン管表面とも強固に接着、固定される。この
方法により、ブラウン管表面には超微粒子による均一な
連続した凹凸を形成することができた。Next, this solution was applied to the coating bath 1 by the above method.
2, and the coating liquid was dropped at a speed of 1.0 mm / s to perform coating. Thereafter, the mixture was calcined at 150 ° C. for 30 minutes in the air to decompose the ethyl silicate. The ultrafine particles of SiO 2 added to the solution are firmly adhered to each other and simultaneously firmly adhered and fixed to the surface of the cathode ray tube, because the SiO 2 formed by decomposition serves as a binder. By this method, uniform continuous irregularities due to ultrafine particles could be formed on the surface of the cathode ray tube.
【００８３】[0083]
【発明の効果】本発明によれば、超微粒子による微小凹
凸を簡単な塗布方法で形成できるため帯電、反射防止膜
を低コストで製造できる。According to the present invention, since fine irregularities due to ultrafine particles can be formed by a simple coating method, a charge and antireflection film can be manufactured at low cost.
【図１】本発明の一実施例に係る装置の配置図である。FIG. 1 is a layout view of an apparatus according to an embodiment of the present invention.
【図２】本発明の超微粒子膜を反射防止膜に適用した場
合の反射率特性図である。FIG. 2 is a reflectance characteristic diagram when the ultrafine particle film of the present invention is applied to an antireflection film.
【図３】本発明の超微粒子膜を帯電防止膜に適用した場
合の帯電特性図である。FIG. 3 is a charging characteristic diagram when the ultrafine particle film of the present invention is applied to an antistatic film.
【図４】本発明の適用対象例である陰極管の一般的な断
面図である。FIG. 4 is a general sectional view of a cathode ray tube which is an application example of the present invention.
【図５】本発明の一実施例に係る超微粒子膜の断面模式
図である。FIG. 5 is a schematic sectional view of an ultrafine particle film according to one embodiment of the present invention.
【図６】本発明の一実施例に係る超微粒子膜の膜厚特性
図である。FIG. 6 is a diagram showing a film thickness characteristic of an ultrafine particle film according to one example of the present invention.
【図７】本発明の他の実施例に係る装置の配置図であ
る。FIG. 7 is a layout view of an apparatus according to another embodiment of the present invention.
１１…ブラウン管、１２…塗布浴槽、１３…塗布溶液、
１４…加圧調整用バルブ、１５…オ−バ−フロ−用バル
ブ、１６…溶液タンク、１７…溶液供給加圧バルブ、１
８…リ−ク用バルブ。11 ... CRT, 12 ... Coating bath, 13 ... Coating solution,
14 ... Pressure adjustment valve, 15 ... Overflow valve, 16 ... Solution tank, 17 ... Solution supply pressurization valve, 1
8. Valve for leakage.
フロントページの続き (72)発明者 河村 孝男 千葉県茂原市早野3300番地 株式会社 日立製作所 茂原工場内 (72)発明者 河村 啓溢 千葉県茂原市早野3300番地 株式会社 日立製作所 茂原工場内 (72)発明者 小原 克美 千葉県茂原市早野3300番地 株式会社 日立製作所 茂原工場内 (56)参考文献 特開 平２−175601（ＪＰ，Ａ) 特開 平１−312501（ＪＰ，Ａ) 特開 平３−21678（ＪＰ，Ａ) 特開 昭60−127250（ＪＰ，Ａ) 実開 昭63−92328（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) G02B 1/11 H01J 29/88 Continued on the front page (72) Inventor Takao Kawamura 3300 Hayano Mobara-shi, Chiba Pref.Hitachi, Ltd.Mobara Plant, Hitachi, Ltd. Inventor Katsumi Ohara 3300 Hayano Mobara-shi, Chiba Pref. Hitachi, Ltd. Mobara Factory (56) References JP-A-2-175601 (JP, A) JP-A-1-312501 (JP, A) JP-A-3-3 21678 (JP, A) JP-A-60-127250 (JP, A) JP-A-63-92328 (JP, U) (58) Fields investigated (Int. Cl. 7 , DB name) G02B 1/11 H01J 29 / 88
Claims (4)
インダーとによる超微粒子膜を透明基板上に形成した透
明板において、 超微粒子群は帯電防止超微粒子と反射防止超微粒子との
混合したものであり、前記基板材に前記超微粒子の塗布
膜を形成した上に、ケイ酸エチルを主成分とする層を形
成したことを特徴とする透明板。1. A transparent plate having an ultrafine particle film formed of an ultrafine particle group and a binder filling each ultrafine particle interval on a transparent substrate, wherein the ultrafine particle group is a mixture of antistatic ultrafine particles and antireflection ultrafine particles. ones, and the on the formation of the coating film of the ultrafine particles to the substrate material, Akiraban permeable and characterized by forming a layer mainly composed of ethyl silicate.
防止用超微粒子の粒径Ｄ1と前記反射防止用超微粒子の
粒径Ｄ2との比Ｄ1／Ｄ2が少なくとも１／１０以下であ
ることを特徴とする透明板。2. The transparent plate according to claim 1, wherein the ratio D 1 / D 2 of the particle diameter D 1 of said antistatic ultrafine particles to the particle diameter D 2 of said antireflective ultrafine particles is at least 1/10. Akiraban permeable to equal to or less than.
インダーとによる超微粒子膜を透明基板上に形成する透
明板の製造方法において、 前記超微粒子群は粒径Ｄ1の帯電防止超微粒子と粒径Ｄ2
の反射防止超微粒子とを混合比Ｄ1／Ｄ2が１／１０以下
となるように混合したものであり、前記超微粒子を形成
すべき基板を容器内に立てかけ、前記超微粒子群とバイ
ンダーとを含む混合塗布溶液を前記容器内に、１０ｍｍ
／ｓ以下の一定速度で導入、排出して透明超微粒子膜を
形成することを特徴とする透明板の製造方法。3. A method for producing a transparent plate, comprising forming an ultrafine particle film on a transparent substrate by using an ultrafine particle group and a binder filling each ultrafine particle interval, wherein the ultrafine particle group has an antistatic ultrafine particle having a particle diameter D 1. And particle size D 2
Are mixed so that the mixing ratio D 1 / D 2 is 1/10 or less, and the substrate on which the ultra fine particles are to be formed is placed in a container, and the ultra fine particles and the binder are mixed with each other. A mixed coating solution containing 10 mm
A method for producing a transparent plate, comprising introducing and discharging at a constant speed of not more than / s to form a transparent ultrafine particle film.
＋Ｓｂ 2 Ｏ3、Ｉｎ2Ｏ3、Ｉｎ2Ｏ3＋Ｓｂ 2Ｏ3の群から選
ばれ、前記反射防止超微粒子はＳｉＯ2、ＭｇＦ2の群か
ら選ばれことを特徴とする請求項３記載の透明板の製造
方法。4. The antistatic ultrafine particles are composed of SnO 2 , SnO 2
+ Sb 2 O 3, In 2 O 3, In 2 O 3 + is selected from S b 2 groups of O 3, claim 3, wherein the antireflection ultrafine particles, characterized in that selected from SiO 2, MgF 2 groups Method for producing a transparent plate.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03054371A JP3125312B2 (en) | 1991-03-19 | 1991-03-19 | Transparent plate and method for producing transparent plate |
| US08/062,747 US5707685A (en) | 1991-03-19 | 1993-05-18 | Process for forming ultrafine particle film, transparent plate and image display plate |
| US08/230,252 US5742118A (en) | 1988-09-09 | 1994-04-20 | Ultrafine particle film, process for producing the same, transparent plate and image display plate |
| US08/341,946 US5612128A (en) | 1988-09-09 | 1994-11-16 | Ultra fine particles having uneven surfaces and treatment plate using same |
| US08/413,447 US5665422A (en) | 1991-03-19 | 1995-03-30 | Process for formation of an ultra fine particle film |
| US08/818,428 US5880557A (en) | 1988-09-09 | 1997-03-17 | Transparent plate, process for the production thereof and their applied screen display plate, and cathode ray tube and process for the production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03054371A JP3125312B2 (en) | 1991-03-19 | 1991-03-19 | Transparent plate and method for producing transparent plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04289801A JPH04289801A (en) | 1992-10-14 |
| JP3125312B2 true JP3125312B2 (en) | 2001-01-15 |
Family
ID=12968812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03054371A Expired - Lifetime JP3125312B2 (en) | 1988-09-09 | 1991-03-19 | Transparent plate and method for producing transparent plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3125312B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002014421A (en) | 2000-06-28 | 2002-01-18 | Seiko Epson Corp | Optoelectronic device and projector |
-
1991
- 1991-03-19 JP JP03054371A patent/JP3125312B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04289801A (en) | 1992-10-14 |
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