JPH05105486A - Smooth glass base plate and its production - Google Patents
Smooth glass base plate and its productionInfo
- Publication number
- JPH05105486A JPH05105486A JP27294491A JP27294491A JPH05105486A JP H05105486 A JPH05105486 A JP H05105486A JP 27294491 A JP27294491 A JP 27294491A JP 27294491 A JP27294491 A JP 27294491A JP H05105486 A JPH05105486 A JP H05105486A
- Authority
- JP
- Japan
- Prior art keywords
- glass substrate
- silica
- film
- coating
- base plate
- 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
Landscapes
- Liquid Crystal (AREA)
- Surface Treatment Of Glass (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は、液晶表示素子、プラズマ
ディスプレイ、光ディスク、磁気ディスク等に用いられ
ている平滑ガラス基板およびその製造方法に関し、さら
に詳しくは、膜形成時の収縮ストレスに基づくクラック
の発生がなく、しかも塗布液組成物の分解による被膜の
ボイドがなく、緻密なシリカ系被膜が、表面の平滑化膜
として表面上に形成されたガラス基板、およびこの平滑
ガラス基板の製造方法に関する。本発明は、さらに、こ
のような平滑ガラス基板を用いて形成された透明電極基
板を有する液晶表示装置にも関する。TECHNICAL FIELD The present invention relates to a smooth glass substrate used for a liquid crystal display device, a plasma display, an optical disk, a magnetic disk and the like, and a method for manufacturing the same, and more specifically, to a crack caused by shrinkage stress during film formation. The present invention relates to a glass substrate on which a dense silica-based coating is formed on the surface as a smoothing film on the surface without generation of voids due to decomposition of the coating liquid composition, and a method for producing the smooth glass substrate. The present invention also relates to a liquid crystal display device having a transparent electrode substrate formed using such a smooth glass substrate.
【０００２】[0002]
【発明の技術的背景】液晶表示素子、プラズマディスプ
レイ、光ディスク、磁気ディスク等の基板としてガラス
基板等が用いられている。BACKGROUND OF THE INVENTION Glass substrates and the like are used as substrates for liquid crystal display devices, plasma displays, optical disks, magnetic disks and the like.
【０００３】このような基板としてガラス基板を用いた
場合、ガラス表面の微細なうねりや凹凸が、表示素子や
記録素子の形成時に悪影響を及ぼすことがあった。この
ためガラス基板の表面を平滑にする必要があり、平滑化
の方法として、ガラス表面を物理的、化学的に研磨する
方法が知られている。When a glass substrate is used as such a substrate, fine undulations and irregularities on the glass surface may adversely affect the formation of display elements and recording elements. Therefore, it is necessary to smooth the surface of the glass substrate, and as a smoothing method, a method of physically or chemically polishing the glass surface is known.
【０００４】しかしながら、これらの研磨法によりガラ
ス表面を平滑化すると、コストが高くなり、また、生産
効率が悪くなるという問題点がある。このため、ガラス
表面に塗布液を塗布することによって被膜を形成し、ガ
ラス表面を平滑にする方法が望まれているが、満足な平
滑表面を形成し得るような塗布液は得られていない。However, if the glass surface is smoothed by these polishing methods, there are problems that the cost is increased and the production efficiency is deteriorated. Therefore, there is a demand for a method of forming a film by applying a coating solution to the glass surface to smooth the glass surface, but a coating solution capable of forming a satisfactory smooth surface has not been obtained.
【０００５】[0005]
【発明の目的】本発明は、上記のような従来技術におけ
る問題点を解決しようとするものであって、ボイド、ピ
ンホール、クラック等のない緻密なシリカ系被膜で表面
が平滑化された平滑ガラス基板を提供することを目的と
し、またこのような平滑ガラス基板の製造方法を提供す
ることを目的としている。SUMMARY OF THE INVENTION The present invention is intended to solve the above problems in the prior art, and the surface is smoothed with a dense silica-based coating free from voids, pinholes, cracks and the like. An object is to provide a glass substrate, and an object is to provide a method for producing such a smooth glass substrate.
【０００６】[0006]
【発明の概要】本発明に係る平滑ガラス基板は、下記一
般式（Ｉ）SUMMARY OF THE INVENTION A smooth glass substrate according to the present invention has the following general formula (I).
【０００７】[0007]
【化３】 [Chemical 3]
【０００８】（ただし、Ｒ1 、Ｒ2 およびＲ3 は、それ
ぞれ独立して水素原子または炭素原子数１〜８のアルキ
ル基である。）で表わされる繰り返し単位を有するポリ
シラザンの１種または２種以上を含む塗布液から形成さ
れたシリカ系被膜で、ガラス基板の表面が被覆されるこ
とを特徴としている。(However, R 1 , R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) One or two polysilazanes having a repeating unit. It is characterized in that the surface of the glass substrate is coated with a silica-based coating formed from the coating liquid containing the above.
【０００９】またこのような平滑ガラス基板は、前記塗
布液をガラス基板に塗布したのち、得られた塗膜を酸化
雰囲気中での加熱および／または酸化雰囲気中での紫外
線照射により硬化して、シリカ系被膜をガラス基板上に
形成する工程を含んで製造される。Further, such a smooth glass substrate is obtained by applying the coating solution onto a glass substrate and then curing the resulting coating film by heating in an oxidizing atmosphere and / or ultraviolet irradiation in an oxidizing atmosphere. It is manufactured including a step of forming a silica-based coating on a glass substrate.
【００１０】[0010]
【発明の具体的説明】以下本発明に係る平滑ガラス基板
およびその製造方法について、具体的に説明する。DETAILED DESCRIPTION OF THE INVENTION The smooth glass substrate and the method for producing the same according to the present invention will be specifically described below.
【００１１】本発明に係る平滑ガラス基板は、ガラス基
板の表面が、In the smooth glass substrate according to the present invention, the surface of the glass substrate is
【００１２】[0012]
【化４】 [Chemical 4]
【００１３】（ただし、Ｒ1 、Ｒ2 およびＲ3 は、それ
ぞれ独立して水素原子または炭素原子数１〜８のアルキ
ル基である。）で表わされる繰り返し単位を有するポリ
シラザンの１種または２種以上を含む塗布液から形成さ
れたシリカ系被膜で被覆されている。(However, R 1 , R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) One or two polysilazanes having a repeating unit. It is covered with a silica-based coating formed from a coating liquid containing the above.
【００１４】ガラス基板を形成するガラスとしては、特
に制限はなく用いられ、具体的には、ソーダライムガラ
ス、アルミノシリケートガラス、ボロシリケートガラ
ス、ホウ珪酸ガラス、結晶化ガラスなどが例示される。The glass forming the glass substrate is not particularly limited, and specific examples thereof include soda lime glass, aluminosilicate glass, borosilicate glass, borosilicate glass and crystallized glass.
【００１５】本発明の平滑ガラス基板では、通常ガラス
基板の片面が上記のようなシリカ系被膜で被覆されてい
るが、両面が上記のようなシリカ系被膜で被覆されてい
てもよい。In the smooth glass substrate of the present invention, one surface of the glass substrate is usually coated with the above silica-based coating, but both surfaces may be coated with the above-described silica-based coating.
【００１６】前記式（１）においてＲ1 、Ｒ2 およびＲ
3 がアルキル基である場合、アルキル基としてはメチル
基、エチル基およびプロピル基から選ばれる１種が好ま
しい。特にＲ1 、Ｒ2 およびＲ3 がいずれも水素原子で
ある場合が好ましく、この場合には、加熱時に分解する
アルキル基がなく、膜収縮が少なく、このため膜形成時
の収縮ストレスに基づくクラックが生じることが少なく
なり、クラックのほとんどない平滑ガラス基板が得られ
る。In the above formula (1), R 1 , R 2 and R
When 3 is an alkyl group, the alkyl group is preferably one selected from a methyl group, an ethyl group and a propyl group. In particular, it is preferable that all of R 1 , R 2 and R 3 are hydrogen atoms. In this case, there is no alkyl group that decomposes during heating, and the film shrinkage is small. Therefore, cracks due to shrinkage stress during film formation are caused. Is less likely to occur, and a smooth glass substrate with almost no cracks can be obtained.
【００１７】また、上記式（１）で表わされる繰り返し
単位を有するポリシラザンは、直鎖状であっても、環状
であってもよく、直鎖状のポリシラザンと環状のポリシ
ラザンの両者が含まれていてもよい。The polysilazane having the repeating unit represented by the above formula (1) may be linear or cyclic, and includes both linear polysilazane and cyclic polysilazane. May be.
【００１８】さらに、このようなポリシラザンの重量平
均分子量は、５００〜１０，０００、好ましくは１，０
００〜４，０００の範囲にあることが望ましい。重量平
均分子量が５００未満では、加熱硬化時に低分子量のポ
リシラザンが揮発し、得られたシリカ系被膜が多孔質に
なりやすく、また、分子量が１０，０００を越えると、
塗布液の流動性が低下し、被膜の平滑性が悪くなるとい
う傾向がある。Further, the weight average molecular weight of such polysilazane is 500 to 10,000, preferably 1,0.
It is preferably in the range of 00 to 4,000. If the weight average molecular weight is less than 500, the low molecular weight polysilazane volatilizes during heat curing, and the resulting silica-based coating tends to become porous, and if the molecular weight exceeds 10,000,
The fluidity of the coating solution tends to decrease, and the smoothness of the coating tends to deteriorate.
【００１９】本発明において用いられる被膜形成用塗布
液は、通常、有機溶媒中に上記ポリシラザンを溶解して
形成される。このような有機溶媒としては、ポリシラザ
ンを溶解し、塗布液に流動性を付与するものであれば特
に制限はなく、具体的には、シクロヘキサン、トルエ
ン、キシレン、ヘキシレン等の炭化水素、塩化メチレ
ン、塩化エチレン、トリクロロエタン等のハロゲン化炭
化水素、エチルブチルエーテル、ジブチルエーテル、ジ
オキサン、テトラヒドロフラン等のエーテル類等が挙げ
られる。これらの有機溶媒は、単独もしくは２種以上を
混合して用いることができる。The coating solution for forming a film used in the present invention is usually formed by dissolving the above polysilazane in an organic solvent. Such an organic solvent is not particularly limited as long as it dissolves polysilazane and imparts fluidity to the coating liquid, and specifically, hydrocarbons such as cyclohexane, toluene, xylene and hexylene, methylene chloride, Examples thereof include halogenated hydrocarbons such as ethylene chloride and trichloroethane, ethers such as ethyl butyl ether, dibutyl ether, dioxane and tetrahydrofuran. These organic solvents can be used alone or in combination of two or more.
【００２０】また、被膜形成用塗布液中のポリシラザン
の濃度は、３〜３５重量％であることが望ましい。本発
明に係る平滑ガラス基板の製造方法では、上記塗布液を
ガラス基板上に塗布し、得られた塗膜を酸化雰囲気中で
加熱するか、または得られた塗膜を酸化雰囲気中で紫外
線照射するか、あるいは得られた塗膜を酸化雰囲気中で
加熱および紫外線照射することにより、塗膜を硬化させ
てシリカ系被膜が形成される。The concentration of polysilazane in the coating solution for forming a film is preferably 3 to 35% by weight. In the method for producing a smooth glass substrate according to the present invention, the above coating solution is applied onto a glass substrate and the obtained coating film is heated in an oxidizing atmosphere, or the obtained coating film is irradiated with ultraviolet rays in an oxidizing atmosphere. Alternatively, the obtained coating film is heated in an oxidizing atmosphere and irradiated with ultraviolet rays to cure the coating film to form a silica-based coating film.
【００２１】上記の製造方法において、塗膜を加熱およ
び紫外線照射するとは、塗膜を加熱しながら紫外線照射
すること、または塗膜を加熱後紫外線照射すること、あ
るいは塗膜を紫外線照射後加熱することなどを意味す
る。In the above-mentioned manufacturing method, heating and irradiating the coating film means that the coating film is irradiated with ultraviolet rays while being heated, or that the coating film is heated and then irradiated with ultraviolet rays, or the coating film is irradiated and irradiated with ultraviolet rays. Means things.
【００２２】ここで塗布液をガラス基板上に塗布して塗
膜を形成する際には、スプレー法、スピンコート法、デ
ィップコート法、ロールコート法、スクリーン印刷法、
転写印刷法などの塗布方法を用いることができる。Here, when the coating liquid is applied onto the glass substrate to form a coating film, a spray method, a spin coating method, a dip coating method, a roll coating method, a screen printing method,
A coating method such as a transfer printing method can be used.
【００２３】上記のような酸化雰囲気としては、たとえ
ば、酸素含有ガス、水蒸気含有ガス、オゾン含有ガスな
どが挙げられる。平滑ガラス基板の製造方法における塗
膜の硬化方法について具体的に説明すると、酸化雰囲気
中での塗膜の加熱は、１５０℃〜８００℃好ましくは３
５０℃〜８００℃の温度で行われることが望ましい。Examples of the oxidizing atmosphere include oxygen-containing gas, water vapor-containing gas, ozone-containing gas and the like. The method for curing the coating film in the method for producing a smooth glass substrate will be specifically described. The heating of the coating film in an oxidizing atmosphere is performed at 150 ° C to 800 ° C, preferably 3 ° C.
It is desirable to be performed at a temperature of 50 ° C to 800 ° C.
【００２４】また塗膜を酸化雰囲気中で紫外線を照射
し、その後、１５０℃〜４５０℃で加熱して、塗膜を硬
化することもできる。さらに塗膜を酸化雰囲気中で紫外
線照射することによって硬化させることもできる。It is also possible to cure the coating film by irradiating the coating film with ultraviolet rays in an oxidizing atmosphere and then heating at 150 ° C. to 450 ° C. Further, the coating film can be cured by irradiating it with ultraviolet rays in an oxidizing atmosphere.
【００２５】本発明に係る平滑ガラス基板の製造方法で
は、塗膜を酸化雰囲気中での加熱のみによっても被膜を
得ることもできるが、塗膜に紫外線照射を施すことによ
り、被膜の形成時における加熱温度を低くすることがで
き、また加熱時間を短縮できるので好ましい。In the method for producing a smooth glass substrate according to the present invention, the coating film can be obtained by only heating the coating film in an oxidizing atmosphere. However, by irradiating the coating film with ultraviolet rays, the coating film can be formed at the time of forming the coating film. It is preferable because the heating temperature can be lowered and the heating time can be shortened.
【００２６】この塗膜を酸化雰囲気中での加熱および／
または紫外線照射によって硬化させると、ほとんどの−
ＳｉＮ−骨格は酸化されて−ＳｉＯ−骨格に変化する。
従来、アルコキシシラン系塗布液を塗布し加熱硬化さ
せてシリカ系被膜を形成した場合、加熱硬化時にアルコ
キシシランのＳｉＯＨ基同士の縮合反応等により被膜の
収縮が生じるといったことがあった。This coating is heated in an oxidizing atmosphere and / or
Or when cured by UV irradiation, most of-
The SiN-skeleton is oxidized and converted to a -SiO- skeleton.
Conventionally, when a silica-based coating film is formed by applying an alkoxysilane-based coating liquid and heating and curing the coating liquid, shrinkage of the coating may occur due to condensation reaction of SiOH groups of alkoxysilane during heating and curing.
【００２７】しかし本発明では、上記のようなポリシラ
ザン溶液からなる塗布液をガラス基板上に塗布し、次い
で酸化雰囲気中での加熱および／または紫外線照射によ
りシリカ系被膜を形成しているため、Ｓｉ−Ｎ結合がＳ
ｉ−Ｏ結合に変化するだけで結合間距離がほとんど変化
せず、このため得られる被膜の収縮が起こらないと考え
られる。However, in the present invention, since the coating solution composed of the polysilazane solution as described above is coated on the glass substrate and then the silica-based coating is formed by heating in an oxidizing atmosphere and / or UV irradiation, Si -N bond is S
It is considered that the inter-bond distance hardly changes only by changing to the i-O bond, and thus the shrinkage of the obtained coating film does not occur.
【００２８】したがって、上記のようなシリカ系被膜で
被覆されたガラス基板の製造方法では、従来のアルコキ
シシラン系塗布液からシリカ系保護膜を形成する方法に
比較して、膜形成時の収縮ストレスに基づくクラックの
発生が少なく、しかも塗布液組成物の分解による被膜の
ボイドがなく、緻密なシリカ系被膜を形成することが可
能となる。Therefore, in the method of manufacturing a glass substrate coated with a silica-based coating as described above, shrinkage stress at the time of film formation is higher than that in the conventional method of forming a silica-based protective film from an alkoxysilane-based coating liquid. Therefore, it is possible to form a dense silica-based coating film with less cracks due to the formation of the coating liquid and no voids in the coating film due to decomposition of the coating liquid composition.
【００２９】また、上述のようなポリシラザン溶液から
なる塗布液を、凹凸のあるガラス基板に、その凹凸を平
坦化する程度に厚く塗布してもクラックの発生等がな
く、その表面がシリカ系被膜により平滑化されたガラス
基板を得ることが可能となる。Further, even if the coating solution comprising the polysilazane solution as described above is applied to a glass substrate having irregularities thick enough to flatten the irregularities, no cracks occur and the surface thereof is a silica-based coating. It becomes possible to obtain a smoothed glass substrate.
【００３０】さらにこのようにしてガラス基板上に形成
されたシリカ系被膜は、その緻密性に優れているため、
ガラス基板からアルカリ成分が溶出するのを防止し、こ
の平滑ガラス基板上に形成される導電膜、電極膜などが
アルカリ成分によって悪影響を受けることが防止され
る。Further, since the silica-based coating film thus formed on the glass substrate is excellent in its denseness,
The alkaline component is prevented from eluting from the glass substrate, and the conductive film, electrode film, etc. formed on the smooth glass substrate are prevented from being adversely affected by the alkaline component.
【００３１】すなわちこのシリカ系被膜は、アルカリパ
ッシベーション膜として優れた特性を示す。本発明に係
る平滑ガラス基板は、液晶表示用ガラス基板、プラズマ
ディスプレイ用基板、光ディスク用基板あるいは磁気デ
ィスク用基板等平滑化が要求される場合に優れた効果を
発揮する。That is, this silica-based coating exhibits excellent characteristics as an alkali passivation film. The smooth glass substrate according to the present invention exhibits an excellent effect when smoothing is required such as a glass substrate for liquid crystal display, a substrate for plasma display, a substrate for optical disc or a substrate for magnetic disc.
【００３２】たとえば、本発明に係る平滑ガラス基板を
用いて、スパッタリング等常法にしたがいＩＴＯなどの
透明導電膜を平滑ガラス基板のシリカ系被膜上に形成す
ると、凹凸のほとんどない平滑な透明電極基板が得られ
る。この平滑性に優れた一対の透明電極基板を有する液
晶表示装置では、電極間距離にむらがなく、このため濃
度むらおよび色むらのない画像が得られる。For example, by using the smooth glass substrate according to the present invention and forming a transparent conductive film such as ITO according to a conventional method such as sputtering on the silica-based film of the smooth glass substrate, a smooth transparent electrode substrate having almost no unevenness is formed. Is obtained. In the liquid crystal display device having the pair of transparent electrode substrates having excellent smoothness, there is no unevenness in the distance between the electrodes, and therefore an image without unevenness in density and unevenness in color can be obtained.
【００３３】[0033]
【発明の効果】以上説明したように、本発明によれば、
特定のポリシラザンを含む塗布液をガラス基板上に塗布
したのち、得られた塗膜を酸化雰囲気中での加熱および
／または紫外線照射により硬化して、被膜を形成してい
るので、得られるシリカ系被膜には、塗布液組成物の分
解によるボイドがほとんど発生せず、また膜形成時の収
縮ストレスが少なくなり、このため膜形成時の収縮スト
レスに起因するクラック等が防止され、表面が平滑で緻
密なシリカ系被膜がガラス基板上に形成できる。このた
め上記のようなガラス基板上に形成されたシリカ系被膜
は、ガラス基板の表面を平滑化する上で効果的であり、
さらにアルカリパッシベーション膜としても優れた特性
を示す。As described above, according to the present invention,
Since a coating solution containing a specific polysilazane is applied on a glass substrate, the obtained coating film is cured by heating in an oxidizing atmosphere and / or ultraviolet irradiation to form a coating film. Voids due to the decomposition of the coating liquid composition are hardly generated in the coating film, and the contraction stress at the time of film formation is reduced. Therefore, cracks and the like due to the contraction stress at film formation are prevented, and the surface is smooth. A dense silica-based coating can be formed on a glass substrate. Therefore, the silica-based coating formed on the glass substrate as described above is effective in smoothing the surface of the glass substrate,
Further, it exhibits excellent characteristics as an alkali passivation film.
【００３４】また、この平滑ガラス基板を用いた液晶表
示装置においては、液晶の配向乱れや色むらがなく安定
な液晶画像が得られる。以下本発明を実施例により説明
するが、本発明はこれら実施例に限定されるものではな
い。In addition, in the liquid crystal display device using this smooth glass substrate, a stable liquid crystal image can be obtained without the liquid crystal alignment disorder and color unevenness. The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００３５】[0035]
【実施例１】１リットルの四ツ口フラスコ内に塩化メチ
レン３００ｍｌを入れ、−５℃に冷却した。次いでこの
フラスコ内にジクロロシラン３０．０ｇを加え、攪拌し
ながらさらにＮＨ3 ガスを２時間吹き込んでジクロロシ
ランとＮＨ3 との反応生成物を含む溶液を得た。得られ
た溶液から沈澱をろ過して除去した後、ろ液を減圧して
溶媒を除去することにより、樹脂状のポリシラザンＡ
（分子量２，７００）を得た。Example 1 300 ml of methylene chloride was placed in a 1-liter four-necked flask and cooled to -5 ° C. Next, 30.0 g of dichlorosilane was added to the flask, and NH 3 gas was further blown in for 2 hours while stirring to obtain a solution containing a reaction product of dichlorosilane and NH 3 . The precipitate was filtered out from the obtained solution, and the filtrate was depressurized to remove the solvent, thereby giving a resinous polysilazane A.
(Molecular weight 2,700) was obtained.
【００３６】得られたポリシラザンＡをキシレンに溶解
して固形分濃度２０重量％であるポリシラザンＡを含む
塗布液（Ａ）を調製した。この塗布液（Ａ）をガラス基
板上にディッピング法により塗布し、２００℃で乾燥
後、湿潤Ｎ2 （酸素濃度１％）中で４５０℃１時間焼成
して、膜厚２，０００オングストロームのシリカ系被膜
を形成し、平滑ガラス基板を作成した。The obtained polysilazane A was dissolved in xylene to prepare a coating solution (A) containing polysilazane A having a solid content concentration of 20% by weight. This coating liquid (A) was applied on a glass substrate by a dipping method, dried at 200 ° C., and baked at 450 ° C. for 1 hour in wet N 2 (oxygen concentration 1%) to obtain silica having a film thickness of 2,000 Å. A system coating was formed to prepare a smooth glass substrate.
【００３７】この平滑ガラス基板の表面平滑性、光透過
率および被膜の緻密性、表面硬度、密着性を下記のよう
にして評価した。 （１）表面平滑性 触針式表面粗さ計（東京精密社製サーフコム５７０Ａ）
により、平滑ガラス基板表面の微細なうねり（凹凸）を
測定した。The surface smoothness of the smooth glass substrate, the light transmittance, the denseness of the coating, the surface hardness and the adhesion were evaluated as follows. (1) Surface smoothness Stylus-type surface roughness meter (Surfcom 570A manufactured by Tokyo Seimitsu Co., Ltd.)
The fine waviness (irregularities) on the surface of the smooth glass substrate was measured by.
【００３８】（２）光透過率 平滑ガラス基板を透過する５５０ｎｍの光透過率を分光
光度計で測定した。 （３）アルカリ処理による膜厚変化 平滑ガラス基板を５重量％ＮａＯＨ水溶液に６０℃で２
０分間浸漬したのち、膜厚をエリプソメーターで測定
し、処理前後の膜厚変化を評価した。(2) Light Transmittance The light transmittance of 550 nm which passes through the smooth glass substrate was measured by a spectrophotometer. (3) Change in film thickness by alkali treatment A smooth glass substrate was immersed in a 5 wt% NaOH aqueous solution at 60 ° C.
After soaking for 0 minute, the film thickness was measured with an ellipsometer to evaluate the change in film thickness before and after the treatment.
【００３９】（４）フッ酸処理による膜厚変化 平滑ガラス基板を５５重量％ＨＦ水溶液と濃硫酸の混合
水溶液に２５℃で１分間浸漬したのち、膜厚をエリプソ
メーターで測定し、処理前後の膜厚変化を評価した。(4) Change in film thickness by hydrofluoric acid treatment After immersing a smooth glass substrate in a mixed solution of 55 wt% HF aqueous solution and concentrated sulfuric acid for 1 minute at 25 ° C., the film thickness was measured by an ellipsometer and measured before and after the treatment. The change in film thickness was evaluated.
【００４０】（５）表面硬度 プラスチック製消しゴムに１ｋｇの荷重をかけて、平滑
ガラス基板表面を２０回摺動したのち、その表面状態を
目視観察した。(5) Surface hardness After applying a load of 1 kg to a plastic eraser and sliding the surface of the smooth glass substrate 20 times, the surface condition was visually observed.
【００４１】（６）密着性 セロハンテープによるピーリングテストにより、被膜の
剥離の有無を目視観察した。(6) Adhesion property A peeling test using cellophane tape was performed to visually observe the presence or absence of peeling of the coating.
【００４２】結果を表１および図１に示す。The results are shown in Table 1 and FIG.
【００４３】[0043]
【実施例２】実施例１と同様にガラス基板に塗布液
（Ａ）を塗布し、１２０℃で乾燥後、高圧水銀ランプと
オゾナイザーを備えた紫外線照射装置で紫外線を５分間
照射した。Example 2 The coating solution (A) was applied onto a glass substrate in the same manner as in Example 1, dried at 120 ° C., and then irradiated with ultraviolet rays for 5 minutes by an ultraviolet irradiation device equipped with a high pressure mercury lamp and an ozonizer.
【００４４】その後、３５０℃で３０分間酸素濃度１％
のＮ2 中で加熱して、膜厚１５００オングストロームの
シリカ系被膜を形成し、平滑ガラス基板を作成した。こ
の平滑ガラス基板について実施例１と同様の評価を行っ
た。Thereafter, the oxygen concentration is 1% at 350 ° C. for 30 minutes.
Was heated in N 2 to form a silica-based film having a film thickness of 1500 Å, and a smooth glass substrate was prepared. The same evaluation as in Example 1 was performed on this smooth glass substrate.
【００４５】結果を表１および図２に示す。The results are shown in Table 1 and FIG.
【００４６】[0046]
【実施例３】ジクロロシラン３０．０ｇに代えてメチル
ジクロロシラン３４．２ｇを用いた以外は実施例１と同
様にしてポリシラザンＢ（分子量１，２００）を得た。
次いで得られたポリシラザンＢを含む塗布液（Ｂ）を、
実施例１と同様にして調製した。Example 3 Polysilazane B (molecular weight 1,200) was obtained in the same manner as in Example 1 except that 34.2 g of methyldichlorosilane was used instead of 30.0 g of dichlorosilane.
Next, the obtained coating liquid (B) containing polysilazane B is
Prepared as in Example 1.
【００４７】この塗布液を用いて実施例２と同様にして
シリカ系被膜を形成し、平滑ガラス基板を作成した。こ
の平滑ガラス基板について実施例１と同様の評価を行っ
た。Using this coating solution, a silica coating was formed in the same manner as in Example 2 to prepare a smooth glass substrate. The same evaluation as in Example 1 was performed on this smooth glass substrate.
【００４８】結果を表１および図３に示す。The results are shown in Table 1 and FIG.
【００４９】[0049]
【比較例１】テトラメトキシシラン１００ｇにエチルセ
ロソルブ２００ｇを加えて希釈し、この溶液に０．０１
重量％ＨＣｌ水溶液９６ｇを加えてテトラメトキシシラ
ンの加水分解を行った。室温で１時間反応させて、アル
コキシシラン（分子量２，５００）を含む塗布液を調製
した。Comparative Example 1 200 g of ethyl cellosolve was added to 100 g of tetramethoxysilane to dilute the solution, and 0.01% was added to this solution.
The tetramethoxysilane was hydrolyzed by adding 96 g of a wt% HCl aqueous solution. The reaction was carried out at room temperature for 1 hour to prepare a coating solution containing alkoxysilane (molecular weight 2,500).
【００５０】この塗布液を用いて実施例２と同様にして
ガラス基板に被膜を形成し、実施例１と同様の評価を行
った。結果を表１および図４に示す。Using this coating solution, a film was formed on a glass substrate in the same manner as in Example 2, and the same evaluation as in Example 1 was performed. The results are shown in Table 1 and FIG.
【００５１】[0051]
【実施例４】実施例１と同様にして２枚の平滑ガラス基
板を製造した。それぞれの平滑ガラス基板のシリカ系被
膜上に、スパッタリング法によりＩＴＯ透明導電膜を形
成した。次いでこのＩＴＯ透明導電膜にホトレジストを
施して、シリカ系被膜上に液晶表示装置用に液透明電極
が形成された一対の透明電極基板を得た。Example 4 Two smooth glass substrates were manufactured in the same manner as in Example 1. An ITO transparent conductive film was formed on the silica-based film of each smooth glass substrate by a sputtering method. Next, a photoresist was applied to the ITO transparent conductive film to obtain a pair of transparent electrode substrates in which a liquid transparent electrode for a liquid crystal display device was formed on the silica coating.
【００５２】このようにして得られた一対の透明電極基
板を用いて液晶表示装置を製造した。なお透明電極間の
距離は均一な粒径を有する絶縁性球状粒子スペーサによ
りほぼ６μｍ程度に調整し、液晶化合物としては市販の
ネマチック液晶を用いた。この液晶表示装置を駆動し
て、その表示画像を観察したところ、色むら、濃度むら
は見られなかった。A liquid crystal display device was manufactured using the pair of transparent electrode substrates thus obtained. The distance between the transparent electrodes was adjusted to about 6 μm with an insulating spherical particle spacer having a uniform particle size, and a commercially available nematic liquid crystal was used as the liquid crystal compound. When this liquid crystal display device was driven and the displayed image was observed, no color unevenness or density unevenness was observed.
【００５３】[0053]
【比較例２】ガラス基板上に直接透明電極を形成した以
外は実施例４と同様にして液晶表示装置を製造した。Comparative Example 2 A liquid crystal display device was manufactured in the same manner as in Example 4 except that the transparent electrode was directly formed on the glass substrate.
【００５４】この液晶表示装置を駆動して、その表示画
像を観察したところ、表示画像に一部色むら、濃度むら
が見られた。When this liquid crystal display device was driven and the display image was observed, partial color unevenness and density unevenness were found in the display image.
【００５５】[0055]
【表１】 [Table 1]
【００５６】上記の実施例１〜３により、本発明に係る
方法で得られたシリカ系被膜付ガラス基板は、その表面
がきわめて平滑であることがわかる。From the above Examples 1 to 3, it can be seen that the silica-coated glass substrate obtained by the method of the present invention has a very smooth surface.
【００５７】さらに、アルカリまたは酸による被膜の膜
厚変化が少ない。すなわち、本発明に係るシリカ系被膜
は緻密な膜であり、この被膜はアルカリパッシベーショ
ン膜としても優れていることがわかる。Further, there is little change in the film thickness of the coating film due to alkali or acid. That is, it is understood that the silica-based coating film according to the present invention is a dense film, and this coating film is also excellent as an alkali passivation film.
【図１】実施例１で得られた平滑ガラス基板の平滑性を
測定したチャート。FIG. 1 is a chart for measuring the smoothness of the smooth glass substrate obtained in Example 1.
【図２】実施例２で得られた平滑ガラス基板の平滑性を
測定したチャート。FIG. 2 is a chart in which the smoothness of the smooth glass substrate obtained in Example 2 is measured.
【図３】実施例３で得られた平滑ガラス基板の平滑性を
測定したチャート。FIG. 3 is a chart for measuring the smoothness of the smooth glass substrate obtained in Example 3.
【図４】比較例１で得られたガラス基板の平滑性を測定
したチャート。FIG. 4 is a chart for measuring the smoothness of the glass substrate obtained in Comparative Example 1.
───────────────────────────────────────────────────── 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 Ｇ０９Ｆ 9/35 7926−5Ｇ // Ｈ０１Ｂ 5/14 Ａ 7244−5Ｇ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location G09F 9/35 7926-5G // H01B 5/14 A 7244-5G
Claims (3)
水素原子または炭素原子数１〜８のアルキル基であ
る。）で表わされる繰り返し単位を有するポリシラザン
の１種または２種以上を含む塗布液から形成されたシリ
カ系被膜で、ガラス基板の表面が被覆されていることを
特徴とする平滑ガラス基板。1. The following general formula (1): (However, R 1 , R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) and include one or more polysilazanes having a repeating unit represented by A smooth glass substrate, characterized in that the surface of the glass substrate is covered with a silica-based coating formed from a coating liquid.
水素原子または炭素原子数１〜８のアルキル基であ
る。）で表わされる繰り返し単位を有するポリシラザン
の１種または２種以上を含む塗布液を、ガラス基板に塗
布したのち、得られた塗膜を酸化雰囲気中での加熱およ
び／または紫外線照射により硬化して、ガラス基板の表
面にシリカ系被膜を形成する工程を含むことを特徴とす
る平滑ガラス基板の製造方法。2. The following general formula (1): (However, R 1 , R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) and include one or more polysilazanes having a repeating unit represented by After the coating liquid is applied to the glass substrate, the coating film obtained is cured by heating in an oxidizing atmosphere and / or ultraviolet irradiation to form a silica-based coating film on the surface of the glass substrate. And a method for manufacturing a smooth glass substrate.
れたシリカ系被膜上に、透明導電膜が形成されてなる透
明電極基板を有することを特徴とする液晶表示装置。3. A liquid crystal display device, comprising a transparent electrode substrate having a transparent conductive film formed on the silica-based coating film formed on the smooth glass substrate according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27294491A JP3262815B2 (en) | 1991-10-21 | 1991-10-21 | Smooth glass substrate and method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27294491A JP3262815B2 (en) | 1991-10-21 | 1991-10-21 | Smooth glass substrate and method for manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05105486A true JPH05105486A (en) | 1993-04-27 |
| JP3262815B2 JP3262815B2 (en) | 2002-03-04 |
Family
ID=17520950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27294491A Expired - Lifetime JP3262815B2 (en) | 1991-10-21 | 1991-10-21 | Smooth glass substrate and method for manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3262815B2 (en) |
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| US20200231493A1 (en) * | 2015-09-09 | 2020-07-23 | Pilkington Group Limited | Deposition process |
| JP2019520289A (en) * | 2016-04-26 | 2019-07-18 | ピルキントン グループ リミテッド | Corrosion resistant coated glass substrate |
| JP2020175345A (en) * | 2019-04-19 | 2020-10-29 | 信越化学工業株式会社 | Method for patterning polysilazane cured film |
| CN114538790A (en) * | 2021-12-31 | 2022-05-27 | 安徽登云玻璃科技有限公司 | Method for treating inner surface of warm glass container and glass container |
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