JPS621986B2 - - Google Patents
Info
- Publication number
- JPS621986B2 JPS621986B2 JP52052027A JP5202777A JPS621986B2 JP S621986 B2 JPS621986 B2 JP S621986B2 JP 52052027 A JP52052027 A JP 52052027A JP 5202777 A JP5202777 A JP 5202777A JP S621986 B2 JPS621986 B2 JP S621986B2
- Authority
- JP
- Japan
- Prior art keywords
- coating
- less
- weight
- film
- coating liquid
- 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
Links
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 19
- 239000000758 substrate Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Surface Treatment Of Glass (AREA)
Description
本発明はシリカの薄膜を浸漬法にて形成する際
に用いる塗布液に関するものである。
たとえば、液晶表示素子は少なくとも一方が透
明よりなる２枚の基板間に液晶を封入してなり、
表示すべきパターンに応じて液晶に選択的に電界
を形成することにより入射光の旋光や散乱を制御
し、所望のパターンを表示するものである。
ここで、液晶に選択的に電界を形成する手段と
しては、前記２枚の基板のそれぞれ対向する面上
に透明導電膜をパターンに形成し、これを電極部
として電圧を印加している。しかし一般には、透
明導電膜をパターンに形成した基板（以下ガラス
基板という）上には、前記透明導電膜を含んで透
明絶縁膜を形成し、これにより透明導電膜による
液晶の配向性の変動、電極反応による液晶の変質
を防いでいる。
この透明絶縁膜を形成する手段としては、真空
蒸着法と湿式法とがある。また湿式法には回転塗
布法と浸漬法があり、本発明は後者の浸漬法を対
象とするものである。
回転塗布法はスピンナーで回転させたガラス基
板上に塗布液を滴下して、回転の遠心力によつて
透明絶縁膜を形成させる方法で、塗布液として水
酸化シリコンを主溶質とし、エタノールを主溶剤
とする溶液が用いられている。かかる塗布液の溶
剤組成の一例を第１表に示す。
浸漬法は前記回転塗布法と異なるメカニズムで
あり、塗布液中にガラス基板を浸漬することによ
The present invention relates to a coating liquid used when forming a thin silica film by a dipping method. For example, a liquid crystal display element is made by sealing liquid crystal between two substrates, at least one of which is transparent.
A desired pattern is displayed by controlling the optical rotation and scattering of incident light by selectively forming an electric field in the liquid crystal according to the pattern to be displayed. Here, as means for selectively forming an electric field in the liquid crystal, a transparent conductive film is formed in a pattern on the opposing surfaces of the two substrates, and a voltage is applied using this as an electrode. However, in general, a transparent insulating film including the transparent conductive film is formed on a substrate (hereinafter referred to as a glass substrate) on which a transparent conductive film is formed in a pattern, and this causes variations in the orientation of liquid crystal due to the transparent conductive film. This prevents the liquid crystal from deteriorating due to electrode reactions. As means for forming this transparent insulating film, there are a vacuum evaporation method and a wet method. Wet methods include a spin coating method and a dipping method, and the present invention is directed to the latter dipping method. The spin coating method is a method in which a coating solution is dropped onto a glass substrate rotated by a spinner, and a transparent insulating film is formed by the centrifugal force of the rotation.The coating solution contains silicon hydroxide as the main solute and ethanol as the main solute. A solution is used as a solvent. An example of the solvent composition of such a coating liquid is shown in Table 1. The dipping method has a different mechanism from the above-mentioned spin coating method, and involves dipping the glass substrate in the coating solution.
【表】
つて透明絶縁膜を形成する方法で、均一な塗布膜
を得るためには塗布液の物性、塗布の雰囲気条件
などが重要なフアクターとなる。
この浸漬法の一例を第１図によつて説明する。
所定の厚さ0.5〜5.0mmのガラスにSnO2、In2O3な
どの透明導電性物質を真空蒸着し、印刷またはフ
オトエツチングにて所定のパターン１を持つたガ
ラス基板２を作る。このパターン１は一般に日の
字型で、各セグメントには配線が施されたもので
あるが、必ずしもこれに限るものではない。そし
て、容器３内の塗布液４に前記ガラス基板２を複
数枚配列させた状態で全域に至るまで浸し、上方
に一定の速度で引上げる。このようにして塗布さ
れた層状の透明絶縁膜を焼成により固化し、シリ
カの透明絶縁薄膜を形成する。かかる浸漬法は基
本製作条件として、基板の引上げ速度100〜700
mm／minが実用的で、所要膜厚としては500〜
2000A゜程度で誤差±200A゜の範囲に製作する
ことが必要である。
しかるに、従来公知のたとえば第１表に示すエ
タノールを主溶剤とした液は、25℃で1.05cp程度
の粘度を有し、蒸発速度も比較的遅い。従つて、
如何なる引上げ速度をとつても常温塗布では均一
膜厚を得ることは困難であり、液温度、基板温度
を上げることにより達成することができるが、溶
剤の拡散損失が著しく実用性が低い欠点があつ
た。
本発明は上記従来の欠点に鑑み、実用的な基板
引上げ速度によつて均一な膜厚を形成することの
できる塗布液をを提供することを目的とする。
以下本発明を詳細に説明する。
実験の結果、液粘度（25℃）と塗布膜厚のむら
については次のような傾向が判明した。
粘度0.75cpではむらが認められなく良好、
0.95cpでは基板下端にむらが認められるが実用的
には差支えない。1.05cpでは基板下端にむらが発
生し、1.15cpではむらが顕著に発生する。この事
より粘度は1.0cp以下であることが好ましい。
そこで、かかる1.0cp以下の粘度を得るため
に、主溶剤として、1.05cp（25℃）のエタノール
のかわりに0.55cp（25℃）のメタノールを使用
し、主溶剤以外の溶剤として0.3〜0.50op（20
℃）の酢酸メチル、酢酸エチル、アセトンなどを
用いた。このような溶剤よりなる塗布液の組成割
合を第２表に示すように設定し、溶質濃度6.0〜
10.0重量％（150℃３時間乾燥後重量法）とし
て、溶質濃度6.2％、7.1％、8.0％、9.8％につい
て実験したところ、第２図に示すような結果が得
られた。
第２図より明らかなように、溶質濃度6.0〜
10.0重量％で実用的な引上げ速度100〜700mm／
minにより所望のSiO2膜厚500〜2000A゜を得る
ことができ、そのバラツキも±200A゜程度の誤
差で均一に塗布することができた。[Table] In this method of forming a transparent insulating film, the physical properties of the coating liquid and the atmospheric conditions for coating are important factors in order to obtain a uniform coating film. An example of this dipping method will be explained with reference to FIG.
A transparent conductive substance such as SnO 2 or In 2 O 3 is vacuum-deposited on glass having a predetermined thickness of 0.5 to 5.0 mm, and a glass substrate 2 having a predetermined pattern 1 is produced by printing or photoetching. This pattern 1 generally has a Japanese character shape, and each segment is provided with wiring, but the pattern is not necessarily limited to this. Then, a plurality of the glass substrates 2 arranged in an array are immersed in the coating liquid 4 in the container 3 up to the entire area, and then pulled upward at a constant speed. The layered transparent insulating film thus applied is solidified by firing to form a transparent insulating thin film of silica. The basic manufacturing conditions for this dipping method are a substrate pulling rate of 100 to 700.
mm/min is practical, and the required film thickness is 500~
It is necessary to manufacture it at around 2000A° with an error of ±200A°. However, the conventionally known liquids shown in Table 1, for example, in which ethanol is the main solvent, have a viscosity of about 1.05 cp at 25° C., and the evaporation rate is also relatively slow. Therefore,
Regardless of the pulling rate, it is difficult to obtain a uniform film thickness by coating at room temperature.This can be achieved by increasing the liquid temperature and substrate temperature, but this has the disadvantage of significantly reducing solvent diffusion loss and making it impractical. Ta. SUMMARY OF THE INVENTION In view of the above-mentioned conventional drawbacks, it is an object of the present invention to provide a coating liquid that can form a uniform film thickness at a practical substrate pulling rate. The present invention will be explained in detail below. As a result of the experiment, the following trends were found regarding liquid viscosity (25°C) and coating film thickness unevenness. With a viscosity of 0.75cp, no unevenness was observed and the result was good.
At 0.95cp, unevenness is observed at the bottom edge of the board, but this does not pose a problem for practical use. At 1.05cp, unevenness occurs at the bottom edge of the board, and at 1.15cp, unevenness occurs noticeably. For this reason, the viscosity is preferably 1.0 cp or less. Therefore, in order to obtain such a viscosity of 1.0 cp or less, 0.55 cp (25 °C) methanol was used as the main solvent instead of 1.05 cp (25 °C) ethanol, and 0.3 to 0.50 op as a solvent other than the main solvent. (20
℃) methyl acetate, ethyl acetate, acetone, etc. were used. The composition ratio of the coating liquid made of such a solvent is set as shown in Table 2, and the solute concentration is 6.0 to 6.0.
Experiments were conducted with solute concentrations of 6.2%, 7.1%, 8.0%, and 9.8%, assuming that the solute concentration was 10.0% by weight (gravimetric method after drying at 150°C for 3 hours), and the results shown in FIG. 2 were obtained. As is clear from Figure 2, the solute concentration is 6.0~
Practical pulling speed of 100 to 700 mm/at 10.0% by weight
min, it was possible to obtain a desired SiO 2 film thickness of 500 to 2000 A°, and it was possible to uniformly coat the SiO 2 film with an error of about ±200 A°.
【表】
なお塗布液の組成として、第２表は一例を示し
たもので、メタノールを主溶剤とし、エタノール
25％以下、アセトン15％以下、酢酸メチル30％以
下、酢酸エチル10％以下の範囲でもよい。
以上の説明から明らかな如く、本発明の塗布液
を用いれば、実用的な基板引上げ速度によつて均
一な膜厚を形成することができる。[Table] Table 2 shows an example of the composition of the coating solution, with methanol as the main solvent and ethanol as the main solvent.
25% or less, acetone 15% or less, methyl acetate 30% or less, ethyl acetate 10% or less. As is clear from the above description, by using the coating liquid of the present invention, a uniform film thickness can be formed at a practical substrate lifting speed.
第１図は一般的な浸漬法による薄膜形成法を示
す説明図、第２図は本発明になる塗布液を用いた
場合における引上げ速度と膜厚の関係を示す図で
ある。
２……ガラス基板、４……塗布液。
FIG. 1 is an explanatory diagram showing a thin film forming method by a general dipping method, and FIG. 2 is a diagram showing the relationship between pulling speed and film thickness when the coating liquid of the present invention is used. 2...Glass substrate, 4...Coating liquid.
Claims (1)
重量％を含まず）のエタノール、30重量％以下
（０重量％を含まず）の酢酸メチル、10重量％以
下（０重量％を含まず）の酢酸エチル、15重量％
以下（０重量％を含まず）のアセトンからなる溶
剤を用い、溶質濃度6.0〜10.0重量％、常温粘度
1.0cp以下である水酸化けい素有機溶液よりなる
ことを特徴とする薄膜形成用塗布液。1 Methanol as the main component, 25% by weight or less (0
(wt%) ethanol, up to 30 wt% (excluding 0 wt%) methyl acetate, up to 10 wt% (excluding 0 wt%) ethyl acetate, 15 wt%
Using a solvent consisting of acetone below (not including 0% by weight), solute concentration 6.0 to 10.0% by weight, normal temperature viscosity.
A coating liquid for forming a thin film, characterized by comprising an organic silicon hydroxide solution having a concentration of 1.0 cp or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5202777A JPS53137885A (en) | 1977-05-09 | 1977-05-09 | Coating liquid for forming thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5202777A JPS53137885A (en) | 1977-05-09 | 1977-05-09 | Coating liquid for forming thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53137885A JPS53137885A (en) | 1978-12-01 |
| JPS621986B2 true JPS621986B2 (en) | 1987-01-17 |
Family
ID=12903321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5202777A Granted JPS53137885A (en) | 1977-05-09 | 1977-05-09 | Coating liquid for forming thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS53137885A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0423030Y2 (en) * | 1985-08-03 | 1992-05-27 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5369057A (en) * | 1976-11-30 | 1978-06-20 | Seiko Epson Corp | Coating agent for display electrodes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4941502Y1 (en) * | 1968-04-17 | 1974-11-14 | ||
| JPS5034103Y1 (en) * | 1970-12-26 | 1975-10-04 |
-
1977
- 1977-05-09 JP JP5202777A patent/JPS53137885A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5369057A (en) * | 1976-11-30 | 1978-06-20 | Seiko Epson Corp | Coating agent for display electrodes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0423030Y2 (en) * | 1985-08-03 | 1992-05-27 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53137885A (en) | 1978-12-01 |
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