JPH0633000A - Coating solution for forming insulation film with high refractive index for liquid crystal display device - Google Patents
Coating solution for forming insulation film with high refractive index for liquid crystal display deviceInfo
- Publication number
- JPH0633000A JPH0633000A JP19077392A JP19077392A JPH0633000A JP H0633000 A JPH0633000 A JP H0633000A JP 19077392 A JP19077392 A JP 19077392A JP 19077392 A JP19077392 A JP 19077392A JP H0633000 A JPH0633000 A JP H0633000A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- liquid crystal
- crystal display
- hydrolyzate
- film
- 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
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、液晶表示素子の透明導
電膜の絶縁保護膜に関し、更に詳しくは、液晶表示素子
の透明導電膜に塗布し、加熱硬化する事により、絶縁
性、表面硬度に優れた被膜を形成し、液晶表示素子の信
頼性、生産歩留りを向上させる塗布液に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating protective film for a transparent conductive film of a liquid crystal display device, and more specifically, it is applied to the transparent conductive film of a liquid crystal display device and cured by heating to obtain insulation and surface hardness. The present invention relates to a coating liquid that forms an excellent coating and improves the reliability and production yield of liquid crystal display devices.
【０００２】[0002]
【従来の技術】液晶表示素子の大型化に伴い、透明電極
の絶縁、保護の目的で、酸化物被膜を形成する事が行わ
れている。酸化物被膜の形成方法は、蒸着法、スパッタ
リング法等で代表される気相法と酸化物被膜形成用塗布
液を用いる塗布法が知られているが、生産性、大型基板
への被膜形成の容易さから、塗布法が多く用いられてい
る。塗布液としては、テトラアルコキシシランの加水分
解物及びその他の金属アルコキシドや金属キレート化物
との複合物が知られている。2. Description of the Related Art With the increase in size of liquid crystal display devices, oxide films have been formed for the purpose of insulating and protecting transparent electrodes. As a method for forming an oxide film, a vapor phase method represented by a vapor deposition method, a sputtering method or the like and a coating method using a coating solution for forming an oxide film are known. The coating method is often used because of its ease. As a coating liquid, a hydrolyzate of tetraalkoxysilane and a complex with other metal alkoxide or metal chelate are known.
【０００３】[0003]
【発明が解決しようとする課題】塗布法による絶縁被膜
形成は、透明導電膜の抵抗変化、省エネルギー、ガラス
の変形等の問題から、３００℃以下の温度で加熱硬化す
ることが望まれている。テトラアルコキシシランの加水
分解物を塗布液として用いた場合、３００℃以下の温度
では、有機基の分解は終了するが、シラノールの縮合は
完全に行われず、珪素原子に結合した水酸基、いわゆる
シラノール基は残存することは知られている。一方、チ
タンアルコキシドの様に加水分解速度の早いものは、水
酸基の消滅は低温で行われるが、未分解のアルコキシ基
やキレート化された場合のキレート化合物が、４５０℃
以上の高温まで残存する事が知られている。In forming an insulating film by a coating method, it is desired to heat cure at a temperature of 300 ° C. or less in view of problems such as resistance change of a transparent conductive film, energy saving, and glass deformation. When a hydrolyzate of tetraalkoxysilane is used as the coating liquid, decomposition of the organic group is completed at a temperature of 300 ° C. or lower, but silanol condensation is not completely performed, and a hydroxyl group bonded to a silicon atom, a so-called silanol group. Are known to survive. On the other hand, in the case of titanium alkoxide, which has a high hydrolysis rate, the disappearance of the hydroxyl group is carried out at a low temperature, but the undecomposed alkoxy group and the chelated compound in the case of being chelated have a temperature of 450 ° C.
It is known to remain at the above high temperatures.
【０００４】上記、水酸基や未分解有機基が残存する塗
膜は、絶縁抵抗が低く、これらを、液晶表示素子用透明
導電膜の絶縁、保護膜として用いた場合、液晶表示素子
の表示ムラや、表示欠陥が発生する問題があった。塗布
液に用いられるテトラアルコキシシランの一部又は全て
を、モノアルキルトリアルコキシシランとした場合、シ
ラノールの残存量が少なくなることは、モノアルキルト
リアルコキシシランの加水分解速度や縮合速度から明ら
かであるが、モノアルキルトリアルコキシシランの加水
分解物より得られる硬化塗膜は、３００℃以下の低温で
硬化した場合、表面の撥水性が高く、絶縁、保護膜とし
て用いた場合、液晶配向膜、特にポリイミド液晶配向膜
の塗布性が、著しく劣り、塗布できないという問題があ
る。またポリイミド配向膜との密着力を改善したとして
も、SiO2系の被膜は屈折率が低い為、表示セルにした場
合、透明電極の付いている部分とガラス部分との光透過
率が変化し、透明電極部分が透けて見えてしまう、所謂
骨見え現象がおこる問題がある。The above-mentioned coating film in which hydroxyl groups and undecomposed organic groups remain has a low insulation resistance, and when these are used as an insulating or protective film for a transparent conductive film for a liquid crystal display element, display unevenness of the liquid crystal display element or There was a problem that a display defect occurred. When a part or all of the tetraalkoxysilane used in the coating liquid is a monoalkyltrialkoxysilane, it is clear from the hydrolysis rate and condensation rate of the monoalkyltrialkoxysilane that the residual amount of silanol decreases. However, a cured coating film obtained from a hydrolyzate of monoalkyltrialkoxysilane has high water repellency on the surface when cured at a low temperature of 300 ° C. or lower, and when used as an insulating or protective film, a liquid crystal alignment film, particularly There is a problem that the coating property of the polyimide liquid crystal alignment film is remarkably poor and cannot be coated. Even if the adhesion with the polyimide alignment film is improved, since the SiO 2 -based coating has a low refractive index, the light transmittance between the transparent electrode-attached portion and the glass portion changes when used as a display cell. However, there is a problem that a so-called bone appearance phenomenon occurs in which the transparent electrode portion is transparent and visible.
【０００５】本発明はテトラアルコキシシランとトリア
ルコキシシランの加水分解物と、テトラアルコキシチタ
ンと、Ｂｉ、Ｃｅ、Ｙ、Ｚｒの金属の金属塩と、析出防
止剤とからなる塗布液組成物に関し、更に、絶縁性、表
面硬度に優れ、かつポリイミド液晶配向膜の塗布性に優
れた、液晶表示素子の高屈折率絶縁被膜として有用な硬
化塗膜を与えうる、絶縁被膜形成用塗布液に関するもの
である。The present invention relates to a coating solution composition comprising a hydrolyzate of tetraalkoxysilane and trialkoxysilane, tetraalkoxytitanium, a metal salt of a metal of Bi, Ce, Y or Zr, and a precipitation inhibitor, Further, it relates to a coating liquid for forming an insulating coating, which has excellent insulating properties, surface hardness, and excellent coatability of a polyimide liquid crystal alignment film, and which can give a cured coating useful as a high refractive index insulating coating of a liquid crystal display device. is there.
【０００６】[0006]
【課題を解決するための手段】本発明の液晶表示素子絶
縁被膜形成用塗布液は、下記(a)〜(d)の各物質を含有
し、且つ析出防止剤が有機溶媒に溶解されてなる塗布液
において、(a)〜(d)の各物質がモル比で(a)が０〜０．
３、(b)が０．３〜０．６、(c)が０〜０．２、(d)が
０．２〜０．５の範囲にあり、上記各物質は下記組成よ
り成る。 (a) 下記一般式〔１〕で示されるテトラアルコキシシラ
ンの加水分解物 Si(OR)4 〔１〕 （Ｒは炭素数１〜５のアルキル基を表す。） (b) 下記一般式〔２〕で表されるトリアルコキシシラン
の加水分解物 R1Si(OR2)3 〔２〕 （Ｒ1 は置換基を有する事もあるアルキル基、アルケニ
ル基、アリール基を表し、Ｒ2 は炭素数１〜５のアルキ
ル基を表す。） (c) 下記一般式〔３〕で示されるテトラアルコキシチタ
ン Ti(OR4)4 〔３〕 （Ｒ4 は炭素数１〜５のアルキル基を表す。） (d) Ｂｉ、Ｃｅ、Ｙ、Ｚｒの金属の金属塩の少なくとも
１種以上A liquid crystal display element insulating coating forming coating solution of the present invention comprises the following substances (a) to (d), and a precipitation inhibitor dissolved in an organic solvent. In the coating liquid, the substances (a) to (d) have a molar ratio of (a) of 0 to 0.
3, (b) is 0.3 to 0.6, (c) is 0 to 0.2, and (d) is 0.2 to 0.5, and each of the above substances has the following composition. (a) Hydrolyzate of tetraalkoxysilane represented by the following general formula [1] Si (OR) 4 [1] (R represents an alkyl group having 1 to 5 carbon atoms.) (b) The following general formula [2] ] Hydrolyzed product of trialkoxysilane R 1 Si (OR 2 ) 3 [2] (R 1 represents an alkyl group, an alkenyl group or an aryl group which may have a substituent, and R 2 represents the number of carbon atoms. (C) Tetraalkoxytitanium Ti (OR 4 ) 4 [3] represented by the following general formula [3] (R 4 represents an alkyl group having 1 to 5 carbon atoms). (d) At least one metal salt of Bi, Ce, Y and Zr metals
【０００７】本発明に用いられるテトラアルコキシシラ
ンは一般式〔１〕で表され、Ｒは炭素数１〜５のアルキ
ル基を表すが、好ましくは、メチル基、エチル基であ
る。又、トリアルコキシシランは一般式〔２〕で表さ
れ、Ｒ1 としては、メチル基、エチル基、プロピル基、
ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オク
チル基、ステアリル基、ビニル基、３−クロロプロピル
基、３−ヒドロキシプロピル基、３−グリシドキシピロ
ピル基、３−メタクリルオキシプロピル基、フェニル基
等が挙げられる。またＲ2 は、炭素数１〜５のアルキル
基であるが、好ましくはメチル基及びエチル基である。The tetraalkoxysilane used in the present invention is represented by the general formula [1], and R represents an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group. Trialkoxysilane is represented by the general formula [2], and R 1 is a methyl group, an ethyl group, a propyl group,
Butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, vinyl group, 3-chloropropyl group, 3-hydroxypropyl group, 3-glycidoxypyropyr group, 3-methacryloxypropyl group, phenyl Groups and the like. R 2 is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group and an ethyl group.
【０００８】上記テトラアルコキシシランとトリアルコ
キシシランは、モル比でトリアルコキシシランに対して
テトラアルコキシシランが、０〜０．５倍モルの範囲の
組成で用いられる。The above tetraalkoxysilane and trialkoxysilane are used in a molar ratio of tetraalkoxysilane to trialkoxysilane in a range of 0 to 0.5 times.
【０００９】本発明の金属塩は、被膜を低温硬化した場
合の硬度向上の目的と、硬化被膜の高屈折率化の目的
と、硬化塗膜へのポリイミド配向膜の塗布性向上の目的
で、用いられるが、金属の酸化物の屈折率を考慮し、ビ
スマス、イットリウム、ジルコニウム、セリウムの塩酸
塩、硝酸塩、硫酸塩、蓚酸塩、酢酸塩及びそれらの塩基
性塩等が挙げられる。The metal salt of the present invention is used for the purpose of improving the hardness when the coating is cured at a low temperature, for increasing the refractive index of the cured coating, and for improving the coating property of the polyimide alignment film on the cured coating. The bismuth, yttrium, zirconium, and cerium hydrochlorides, nitrates, sulfates, oxalates, acetates, and basic salts thereof can be used in consideration of the refractive index of the metal oxide.
【００１０】本発明に用いられる析出防止剤は、上記金
属塩が、塗膜乾燥時、結晶化し塗膜表面に析出する事
を、防ぐ目的で用いられる。析出防止剤としては、エチ
レングリコール、Ｎ−メチルピロリドン、ジメチルフォ
ルムアミド、ジメチルアセトアミド及びそれらの誘導体
が、１種以上用いられ、その使用量は、金属塩をＭＯn/
2 に換算して、重量比でＭＯn/2 に対し少なくとも１以
上用いられる。The precipitation preventing agent used in the present invention is used for the purpose of preventing the above metal salt from crystallizing and precipitating on the surface of the coating film when the coating film is dried. As the precipitation inhibitor, one or more of ethylene glycol, N-methylpyrrolidone, dimethylformamide, dimethylacetamide and their derivatives are used, and the amount thereof is MO n /
2 in terms of used at least 1 or more to MO n / 2 by weight.
【００１１】本発明の塗布液に含まれるテトラアルコキ
シシランとトリアルコキシシランの加水分解物は、上記
アルコキシシランを酸触媒の存在下又は、上記金属塩の
存在下、有機溶媒中、加水分解することにより得られ
る。アルコキシシランの加水分解は、アルコキシシラン
の全アルコキシド基のモル数に対して、０．５〜２．５
倍モルの水によって行われる。金属塩が含水塩で有る場
合には、その水分も上記加水分解に用いられる水の量に
算入される。The hydrolyzate of tetraalkoxysilane and trialkoxysilane contained in the coating liquid of the present invention is obtained by hydrolyzing the above alkoxysilane in the presence of an acid catalyst or the above metal salt in an organic solvent. Is obtained by The hydrolysis of the alkoxysilane is carried out by adding 0.5 to 2.5 to the number of moles of all the alkoxide groups of the alkoxysilane.
It is done with double molar water. When the metal salt is a hydrous salt, its water content is also included in the amount of water used for the hydrolysis.
【００１２】上記金属塩とアルコキシシランの加水分解
物との混合は、上記した如く、アルコキシシランの加水
分解時に、混合されていても良いし、アルコキシシラン
の加水分解終了後、混合しても、何方でも良い。また、
アルコキシチタンとアルコキシシランは同時に加水分解
する事も出きるが、アルコキシシランの加水分解物をア
ルコキシチタンの有機溶媒溶液に混合する事が好まし
い。The above-mentioned metal salt and the hydrolyzate of the alkoxysilane may be mixed at the time of hydrolysis of the alkoxysilane, or may be mixed after the hydrolysis of the alkoxysilane, as described above. Anyone is fine. Also,
Although alkoxytitanium and alkoxysilane can be hydrolyzed at the same time, it is preferable to mix a hydrolyzate of alkoxysilane with a solution of alkoxytitanium in an organic solvent.
【００１３】アルコキシシランの加水分解及び上記アル
コキシチタンの溶解の際用いられる有機溶媒の例として
は、メタノール、エタノール、プロパノール、ブタノー
ル等のアルコール類、アセトン、メチルエチルケトン等
のケトン類、ベンゼン、トルエン、キシレン等の芳香族
炭化水素類、エチレングリコール、プロピレングリコー
ル、ヘキシレングリコール等のグリコール類、エチルセ
ロソルブ、ブチルセロソルブ、エチルカルビトール、ブ
チルカルビトール、ジエチルセロソルブ、ジエチルカル
ビトール等のグリコールエーテル類、Ｎ−メチルピロリ
ドン、ジメチルフォルムアミド等が挙げられ、それらを
１種もしくは２種以上混合して用いられるが、転写印
刷、スピンコート等の塗布法を考慮した場合、沸点１２
０℃以上の、グリコール類及びグリコールエーテル類が
好ましい。Examples of the organic solvent used in the hydrolysis of the alkoxysilane and the dissolution of the alkoxytitanium include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, benzene, toluene and xylene. Aromatic hydrocarbons such as, ethylene glycol, propylene glycol, hexylene glycol and other glycols, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol and other glycol ethers, N-methyl Pyrrolidone, dimethylformamide and the like can be mentioned, and they can be used alone or as a mixture of two or more thereof, but when considering a coating method such as transfer printing and spin coating, a boiling point of 12
Glycols and glycol ethers having a temperature of 0 ° C. or higher are preferable.
【００１４】アルコキシシランの加水分解の為の水の添
加は通常室温で行われるが、必要に応じて加熱下に行っ
ても良い。加水分解の終了後、熟成の目的で５０℃以上
１５０℃以下の温度で加熱しても差し支え無い。また、
塗布液の高沸点化、高粘度化の目的で、加水分解終了後
又はアルコキシチタンとアルコキシシランの加水分解物
の混合後、副生する低沸点のアルコール類を留去する事
もできる。Water for the hydrolysis of the alkoxysilane is usually added at room temperature, but it may be added with heating if necessary. After completion of hydrolysis, heating may be performed at a temperature of 50 ° C. or higher and 150 ° C. or lower for the purpose of aging. Also,
For the purpose of raising the boiling point and the viscosity of the coating liquid, it is also possible to distill off the low-boiling point alcohol by-produced after the completion of hydrolysis or after mixing the hydrolyzate of alkoxytitanium and alkoxysilane.
【００１５】本発明の塗布液は、アルコキシシランをSi
O2、アルコキシチタンをTiO2、金属塩をMOn/2 にそれぞ
れ換算し、SiO2＋TiO2＋MOn/2 分を固形分として１〜１
５重量％の範囲に含む事が好ましい。本発明の液晶表示
素子用絶縁膜形成用塗布液は、ディッピング、スピンコ
ート、転写印刷、刷毛塗り、ロールコート、スプレー等
通常使用される塗布法に適用される事ができ、そしてそ
の塗膜を乾燥後、１００℃以上の温度で加熱する事によ
り、ポリイミド配向膜の塗布性に優れた、液晶表示素子
の表示性能に悪影響を及ぼさない、絶縁性に優れた、高
屈折率の硬化被膜を得ることができる。The coating liquid of the present invention contains alkoxysilane as Si.
O 2 and alkoxytitanium are converted into TiO 2 and metal salts are converted into MO n / 2 , respectively, and SiO 2 + TiO 2 + MO n / 2 minutes is 1 to 1 as solid content.
It is preferably contained in the range of 5% by weight. The coating liquid for forming an insulating film for a liquid crystal display device of the present invention can be applied to commonly used coating methods such as dipping, spin coating, transfer printing, brush coating, roll coating and spraying, and the coating film After drying, by heating at a temperature of 100 ° C. or higher, a cured coating film having excellent coating properties of the polyimide alignment film, having no adverse effect on the display performance of the liquid crystal display device, having excellent insulation properties, and having a high refractive index is obtained. be able to.
【００１６】[0016]
【作用】本発明に用いられるテトラアルコキシシランと
トリアルコキシシランは、トリアルコキシシランに対し
てテトラアルコキシシランがモル比で、０〜０．５倍モ
ルの範囲で、良好な絶縁性と塗膜形成能を有し、且つ液
晶表示素子の絶縁膜として用いた場合に、表示性能に悪
影響を及ぼさない。上記モル比が０．５より大きいと、
トリアルコキシシランを用いた効果が少なく、液晶表示
素子の表示性能に悪影響を与える。The tetraalkoxysilane and the trialkoxysilane used in the present invention have good insulating properties and coating film formation when the molar ratio of the tetraalkoxysilane to the trialkoxysilane is 0 to 0.5 times. And has no adverse effect on display performance when used as an insulating film of a liquid crystal display element. When the above molar ratio is greater than 0.5,
The effect of using trialkoxysilane is small, which adversely affects the display performance of the liquid crystal display element.
【００１７】アルコキシシラン(a) 及び(b) は、モル比
でそれぞれ０〜０．３、０．３〜０．６であるが、(a)
＋(b) がモル比で０．３〜０．６の場合に良好な塗膜形
成能を示す。上記モル比が０．３より小さいと、塗膜の
機械的強度、耐薬品性が低下する。 一方０．６より大
きいと塗膜の屈折率が小さくなり、透明電極の骨見え現
象が起こる。Alkoxysilanes (a) and (b) have a molar ratio of 0 to 0.3 and 0.3 to 0.6, respectively.
When + (b) is in a molar ratio of 0.3 to 0.6, good film forming ability is exhibited. When the above molar ratio is less than 0.3, the mechanical strength and chemical resistance of the coating film deteriorate. On the other hand, when it is larger than 0.6, the refractive index of the coating film becomes small, and the bone appearance phenomenon of the transparent electrode occurs.
【００１８】アルコキシチタン(c) は、モル比で０〜
０．２の範囲で用いられる。アルコキシチタンを用いる
事により、塗膜の屈折率を高くする事が容易に行える
が、上記モル比が０．２を越えると、塗膜を３００℃以
下の低温で焼成した場合、塗膜の電気絶縁性が低下し、
やはり液晶表示素子の表示性能に悪影響を与える。金属
塩(d) は、モル比で０．２〜０．５の範囲で用いられ
る。０．２より少ないと、塗膜を３００℃以下の低温で
硬化した場合の硬化被膜の機械的強度が低い上、ポリイ
ミド配向膜の塗布性に劣り、更に塗膜の屈折率も低いも
のとなる。一方０．５より多く用いても、硬化被膜の機
械的強度、配向膜塗布性が向上しないばかりか、硬化被
膜の耐薬品性が低下する。The alkoxytitanium (c) has a molar ratio of 0 to
Used in the range of 0.2. The use of alkoxy titanium makes it easy to increase the refractive index of the coating film, but if the above molar ratio exceeds 0.2, when the coating film is baked at a low temperature of 300 ° C. or lower, the electrical conductivity of the coating film becomes high. The insulation is reduced,
After all, it adversely affects the display performance of the liquid crystal display element. The metal salt (d) is used in a molar ratio of 0.2 to 0.5. When it is less than 0.2, the cured coating has low mechanical strength when cured at a low temperature of 300 ° C. or lower, the coating property of the polyimide alignment film is poor, and the refractive index of the coating is low. . On the other hand, if it is used in an amount of more than 0.5, not only the mechanical strength of the cured film and the coating property of the alignment film are not improved, but also the chemical resistance of the cured film is lowered.
【００１９】析出防止剤は、金属塩をＭＯn/2 に換算し
て、ＭＯn/2 に対して重量比で１倍より少ないと、塗膜
乾燥時の金属塩の結晶析出防止効果が少なく、金属塩の
結晶化が起こり、塗膜が白濁し均一な硬化被膜が得られ
ない。加水分解の際に用いられる水は、アルコキシシラ
ンの全アルコキシド基に対して、モル比で０．５倍より
少ないと、加水分解が不十分となり、アルコキシシラン
のモノマーが多量に残り、塗布液の成膜性が悪くなり、
得られる硬化被膜の機械的強度も向上しない。反対に
２．５倍より多いと、塗布液の貯蔵安定性が乏しくな
り、塗布液の粘度増加、ゲル化等を引き起こす。When the weight ratio of the precipitation inhibitor in terms of MO n / 2 in terms of MO n / 2 is less than 1 time, the effect of preventing the precipitation of crystals of the metal salt when the coating film is dried is small. However, crystallization of the metal salt occurs and the coating film becomes cloudy, and a uniform cured film cannot be obtained. If the molar ratio of the water used during the hydrolysis is less than 0.5 times the total alkoxide groups of the alkoxysilane, the hydrolysis will be insufficient and a large amount of the alkoxysilane monomer will remain. The film formability deteriorates,
The mechanical strength of the obtained cured coating is not improved either. On the other hand, when the amount is more than 2.5 times, the storage stability of the coating solution becomes poor, and the viscosity of the coating solution increases and gelation occurs.
【００２０】本発明の塗布液は、アルコキシシランをSi
O2、アルコキシチタンをTiO2、金属塩をＭＯn/2 に換算
し、SiO2＋TiO2＋ＭＯn/2 分が１重量％より少ないと、
一回の塗布により得られる塗膜の厚みが薄く、所定の厚
みを得るために多数回の塗布が必要となり効率的で無
い。一方１５重量％を越えると、一回の塗布により得ら
れる塗膜の厚みが厚くなり、均一な被膜を得ることが困
難となり、塗布液の貯蔵安定性も乏しくなり、塗布液の
粘度増加、ゲル化等を引き起こす。The coating solution of the present invention contains alkoxysilane as Si.
O 2 and alkoxytitanium are converted into TiO 2 , and metal salts are converted into MO n / 2 , and when SiO 2 + TiO 2 + MO n / 2 minutes is less than 1% by weight,
The thickness of the coating film obtained by one-time application is thin, and many applications are required to obtain a predetermined thickness, which is not efficient. On the other hand, if it exceeds 15% by weight, the thickness of the coating film obtained by one-time coating becomes thick, it becomes difficult to obtain a uniform coating film, the storage stability of the coating liquid becomes poor, the viscosity of the coating liquid increases, and the gel Cause changes.
【００２１】[0021]
（塗布液の製造） （実施例１）還流管を備えつけた反応フラスコにトリア
ルコキシシランとしてメチルトリエトキシシラ４．２ｇ
と、溶媒としてブチルセロソルブ５０ｇを入れ、マグネ
チックスターラーを用いて撹拌、混合した。そこへ、金
属塩として硝酸セリウム６水和物８．０ｇを水１．２ｇ
と析出防止剤としてエチレングリコール１０ｇに溶解混
合したものを添加した。添加混合後、液温は２０℃から
２８℃へ発熱した。そのまま３０分撹拌を続けアルコキ
シシランの加水分解物とした。別の還流管を備えつけた
反応フラスコにアルコキシチタンとしてテトラプロポキ
シチタン３．５ｇと溶媒としてブチルセロソルブ２６．
６ｇを入れ撹拌、混合し、撹拌しながら先のアルコキシ
シラン加水分解物を添加、混合し、塗布液とした。 こ
のものは、SiO2／TiO2／CeO2＝５／２／３となってい
る。塗布液の粘度、固形分等を表−１に示す。(Production of Coating Liquid) (Example 1) 4.2 g of methyltriethoxysila as trialkoxysilane in a reaction flask equipped with a reflux tube.
Then, 50 g of butyl cellosolve was added as a solvent, and the mixture was stirred and mixed using a magnetic stirrer. Then, 8.0 g of cerium nitrate hexahydrate as a metal salt was added to 1.2 g of water.
Then, what was dissolved and mixed in 10 g of ethylene glycol was added as a precipitation inhibitor. After the addition and mixing, the liquid temperature exothermed from 20 ° C to 28 ° C. Stirring was continued for 30 minutes as it was to obtain a hydrolyzate of alkoxysilane. In a reaction flask equipped with another reflux tube, 3.5 g of tetrapropoxy titanium as alkoxy titanium and butyl cellosolve 26.
6 g was put and stirred and mixed, and the above alkoxysilane hydrolyzate was added and mixed while stirring to obtain a coating liquid. This product has SiO 2 / TiO 2 / CeO 2 = 5/2/3. Table 1 shows the viscosity and solid content of the coating liquid.
【００２２】（実施例２〜７）実施例１と同様の製造法
を用い、各種組成の塗布液を製造した。組成等を表−１
に示す。(Examples 2 to 7) Using the same manufacturing method as in Example 1, coating solutions of various compositions were manufactured. Table 1
Shown in.
【００２３】（比較例１）還流管を備えつけた反応フラ
スコにテトラアルコキシシランとして、テトラエトキシ
シラン８．９ｇと、溶媒としてブチルセロソルブ４０ｇ
を入れ、マグネチックスターラーを用いて撹拌、混合し
た。そこへ、触媒として硝酸０．５ｇを水４．６ｇとエ
チレングリコール１０ｇに溶解混合したものを添加し
た。添加混合後、液温は２０℃から２８℃へ発熱した。
そのまま３０分撹拌を続け、アルコキシシラン加水分解
物とした。別の還流管を備えつけた反応フラスコにアル
コキシチタンとしてテトライソプロポキシチタン１１．
９ｇと溶媒としてブチルセロソルブ２６．４ｇを入れ撹
拌、混合し、撹拌しながら先のアルコキシシラン加水分
解物を添加、混合し、塗布液とした。(Comparative Example 1) In a reaction flask equipped with a reflux tube, 8.9 g of tetraethoxysilane as tetraalkoxysilane and 40 g of butyl cellosolve as a solvent.
, And stirred and mixed using a magnetic stirrer. As a catalyst, 0.5 g of nitric acid dissolved and mixed in 4.6 g of water and 10 g of ethylene glycol was added thereto. After the addition and mixing, the liquid temperature exothermed from 20 ° C to 28 ° C.
The stirring was continued for 30 minutes as it was to obtain an alkoxysilane hydrolyzate. Tetraisopropoxy titanium as alkoxy titanium in a reaction flask equipped with another reflux tube.
9 g and 26.4 g of butyl cellosolve as a solvent were put and stirred, and the above alkoxysilane hydrolyzate was added and mixed while stirring to obtain a coating liquid.
【００２４】塗布液の組成、粘度、固形分等を表−１に
示す。Table 1 shows the composition, viscosity, solid content and the like of the coating liquid.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表中の略号はそれぞれ下記の通りである。
TEOS:テトラエトキシシラン TMOS:テトラメトキシシラ
ン MTMS:メチルトリメトキシシラン TPT:テトライソ
プロポキシチタン CN:硝酸セリウム六水和物 BN:硝酸
ビスマス五水和物 ZN:硝酸ジルコニル二水和物 YN:硝
酸イットリウム六水和物 EG:エチレングリコール NM
P:Ｎ−メチルピロリドン BS:ブチルセロソルブThe abbreviations in the table are as follows.
TEOS: Tetraethoxysilane TMOS: Tetramethoxysilane MTMS: Methyltrimethoxysilane TPT: Tetraisopropoxytitanium CN: Cerium nitrate hexahydrate BN: Bismuth nitrate pentahydrate ZN: Zirconyl nitrate dihydrate YN: Yttrium nitrate Hexahydrate EG: Ethylene glycol NM
P: N-methylpyrrolidone BS: Butyl cellosolve
【００２７】（被膜試験例）実施例で得られた塗布液
を、透明導電膜としてＩＴＯ膜を全面にスパッタリング
により成膜した厚さ１．１mmのガラス基板に、スピンコ
ーターを用い回転数４０００rpm で２０sec 回転させ、
成膜した。ホットプレート上で６０℃で３分乾燥したの
ち、クリーンオーブンで３００℃で３０分加熱し、硬化
被膜とし、被膜物性を測定した。屈折率測定用には、上
記ＩＴＯ付きガラス基板に代わり、シリコン基板に同様
の方法で成膜、焼成した。(Film coating test example) The coating solution obtained in the example was applied to a glass substrate having a thickness of 1.1 mm on which an ITO film as a transparent conductive film was formed on the entire surface by sputtering using a spin coater at a rotation speed of 4000 rpm. Rotate for 20 seconds,
A film was formed. After drying on a hot plate at 60 ° C. for 3 minutes, it was heated at 300 ° C. for 30 minutes in a clean oven to form a cured film, and the film properties were measured. For measuring the refractive index, a film was formed on the silicon substrate in the same manner as the above-mentioned glass substrate with ITO and baked.
【００２８】さらに、得られた硬化塗膜上へ、ポリイミ
ド（日産化学工業（株）商品名「サンエバーＳＥ−１５
０」）をスピンコートし、ポリイミド配向膜の塗布性を
検討した。結果を表−２に示す。Further, polyimide (manufactured by Nissan Chemical Industries, Ltd., trade name "SAN EVER SE-15") was applied onto the obtained cured coating film.
0 ") was spin-coated to examine the coating properties of the polyimide alignment film. The results are shown in Table-2.
【００２９】[0029]
【表２】 [Table 2]
【００３０】被膜について試験した、表−２記載の項目
について説明する。 硬度 ：加熱硬化後の被膜を、ＪＩＳ Ｋ５４００
鉛筆硬度試験法により表面硬度を測定した。 体積抵抗：被膜表面に電極としてアルミニウムを蒸着
し、測定した。 配向膜塗布性：硬化被膜へのポリイミド配向膜の塗布
性を目視により観察した。塗布性が良好な場合は○で、
不良な場合は×で表す。The items listed in Table 2 which were tested for the coating will be described. Hardness: The coating after heat curing is JIS K5400
The surface hardness was measured by the pencil hardness test method. Volume resistance: Aluminum was vapor-deposited on the surface of the coating film as an electrode and measured. Alignment film coatability: The coatability of the polyimide alignment film on the cured coating was visually observed. ○ when the coating property is good,
When defective, it is indicated by x.
【００３１】屈折率：自動エリプソメトリーで測定し
た。Refractive index: Measured by automatic ellipsometry.
【００３２】（液晶セル表示性能試験例）実施例で得ら
れた塗布液を、２枚のＩＴＯ透明電極付きガラス（表面
抵抗３０Ω／□、線幅２５０μ、線間２５μ）にスピン
コートし、３００℃３０分熱処理する事により０．１μ
の絶縁膜を形成した。更に絶縁膜上にポリイミド樹脂Ｓ
Ｅ−１５０をスピンコートし、２５０℃で１時間熱処理
する事により０．１μのポリイミド配向膜を形成した。
次にラビング処理を施し、スペーサーを挟んで、ラビン
グ方向を２４０°ツイストさせてセルを組み立てた。(Example of Liquid Crystal Cell Display Performance Test) Two coatings of glass with ITO transparent electrodes (surface resistance 30 Ω / □, line width 250 μ, line interval 25 μ) were spin-coated with the coating solution obtained in the example, and 300 0.1μ by heat treatment at ℃ 30 minutes
The insulating film of was formed. Furthermore, the polyimide resin S on the insulating film
E-150 was spin-coated and heat-treated at 250 ° C. for 1 hour to form a polyimide alignment film of 0.1 μm.
Next, a rubbing treatment was performed, a spacer was sandwiched, and the rubbing direction was twisted by 240 ° to assemble a cell.
【００３３】このセルに、液晶（メルク ＺＬＩ−２２
９３）を注入し、０．１Ｈｚ、±５Ｖの三角波を印加し
表示を観察した。更に、このセルに６０℃で１００Ｈ
ｚ、±５Ｖの矩形波を１５時間印加したエージング試験
を行い、その後上記条件で表示を観察した。結果を表−
２に示す。表中、表示むらが認められた場合は×で、認
められない場合は○で示した。Liquid crystal (Merck ZLI-22
93) was injected, a triangular wave of 0.1 Hz and ± 5 V was applied, and the display was observed. Furthermore, add 100H to this cell at 60 ℃.
An aging test was performed by applying a rectangular wave of z, ± 5 V for 15 hours, and then the display was observed under the above conditions. Table of results
2 shows. In the table, when the display unevenness is observed, it is indicated by x, and when it is not observed, it is indicated by o.
【００３４】[0034]
【発明の効果】本発明の塗布液は、撥水性の高いトリア
ルコキシシランをその組成に含んでいるにもかかわら
ず、ポリイミド配向膜の塗布性に優れ、機械的強度に優
れ、１．６５以上の屈折率を有する絶縁被膜を形成せし
める。また、被膜を液晶表示素子の絶縁膜として用いた
場合、絶縁性が高く液晶素子の表示性能に悪影響を及ぼ
す事が無く、またその高い屈折率により透明電極の骨見
え現象の少ない液晶表示素子用の絶縁膜として有用であ
る。INDUSTRIAL APPLICABILITY The coating liquid of the present invention is excellent in coatability of a polyimide alignment film and excellent in mechanical strength, even though it contains trialkoxysilane having high water repellency in its composition, and is 1.65 or more. An insulating film having a refractive index of is formed. Further, when the film is used as an insulating film of a liquid crystal display element, it has a high insulating property and does not adversely affect the display performance of the liquid crystal element, and due to its high refractive index, it is for a liquid crystal display element in which the bone appearance phenomenon of the transparent electrode is small. Is useful as an insulating film.
Claims (4)
出防止剤が有機溶媒に溶解されてなる塗布液において、
(a)〜(d)の各物質がモル比で(a)が０〜０．３、(b)が
０．３〜０．６、(c)が０〜０．２、(d)が０．２〜０．
５の範囲にある液晶表示素子用高屈折率絶縁被膜形成用
塗布液。 (a) 下記一般式〔１〕で示されるテトラアルコキシシラ
ンの加水分解物 Si(OR)4 〔１〕 （Ｒは炭素数１〜５のアルキル基を表す。） (b) 下記一般式〔２〕で表されるトリアルコキシシラン
と加水分解物 R1Si(OR2)3 〔２〕 （Ｒ1 は置換基を有する事もあるアルキル基、アルケニ
ル基、アリール基を表し、Ｒ2 は炭素数１〜５のアルキ
ル基を表す。） (c) 下記一般式〔３〕で示されるテトラアルコキシチタ
ン Ti(OR4)4 〔３〕 （Ｒ4 は炭素数１〜５のアルキル基を表す。） (d) Ｂｉ、Ｃｅ、Ｙ、Ｚｒの金属の金属塩の少なくとも
１種以上1. A coating solution containing each of the following substances (a) to (d), wherein the precipitation inhibitor is dissolved in an organic solvent,
Molar ratios of the substances (a) to (d) are (a) 0 to 0.3, (b) 0.3 to 0.6, (c) 0 to 0.2, and (d) is 0.2-0.
A coating liquid for forming a high-refractive-index insulating film for a liquid crystal display device in the range of 5. (a) Hydrolyzate of tetraalkoxysilane represented by the following general formula [1] Si (OR) 4 [1] (R represents an alkyl group having 1 to 5 carbon atoms.) (b) The following general formula [2] ] Trialkoxysilane and a hydrolyzate represented by R 1 Si (OR 2 ) 3 [2] (R 1 represents an alkyl group, an alkenyl group or an aryl group which may have a substituent, and R 2 represents the number of carbon atoms. (C) Tetraalkoxytitanium Ti (OR 4 ) 4 [3] represented by the following general formula [3] (R 4 represents an alkyl group having 1 to 5 carbon atoms). (d) At least one metal salt of Bi, Ce, Y and Zr metals
塩をＭＯn/2 （ＭはＢｉ、Ｃｅ、Ｙ、Ｚｒを表し、ｎは
整数で金属Ｍの原子価を表す。）に換算して、ＭＯn/2
に対して重量比で１倍以上含む事を特徴とする液晶表示
素子用高屈折率絶縁被膜形成用塗布液。2. The precipitation preventing agent according to claim 1, wherein the metal salt is converted into MO n / 2 (M represents Bi, Ce, Y and Zr, and n represents an valence of the metal M). And then MO n / 2
A coating liquid for forming a high-refractive-index insulating film for a liquid crystal display device, characterized in that it is contained in a weight ratio of 1 time or more.
ングリコール、Ｎ−メチルピロリドン、ジメチルフォル
ムアミド、ジメチルアセトアミド及びそれらの誘導体で
あることを特徴とする液晶表示素子高屈折率絶縁被膜形
成用塗布液。3. The liquid crystal display device according to claim 1, wherein the precipitation preventing agent is ethylene glycol, N-methylpyrrolidone, dimethylformamide, dimethylacetamide or a derivative thereof. liquid.
し、２００℃以上の温度で処理する事により得られる被
膜の屈折率が、１．６５以上であることを特徴とする液
晶表示素子高屈折率絶縁被膜形成用塗布液。4. The liquid crystal display according to claim 1, wherein the coating film obtained by applying the coating liquid to the substrate and treating at a temperature of 200 ° C. or higher has a refractive index of 1.65 or higher. Coating liquid for forming high-refractive-index insulating coatings for devices.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19077392A JP3825813B2 (en) | 1992-07-17 | 1992-07-17 | Coating liquid for forming high refractive index insulating coating for liquid crystal display |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19077392A JP3825813B2 (en) | 1992-07-17 | 1992-07-17 | Coating liquid for forming high refractive index insulating coating for liquid crystal display |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0633000A true JPH0633000A (en) | 1994-02-08 |
| JP3825813B2 JP3825813B2 (en) | 2006-09-27 |
Family
ID=16263490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19077392A Expired - Fee Related JP3825813B2 (en) | 1992-07-17 | 1992-07-17 | Coating liquid for forming high refractive index insulating coating for liquid crystal display |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3825813B2 (en) |
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| WO2007020781A1 (en) * | 2005-08-19 | 2007-02-22 | Nissan Chemical Industries, Ltd. | Method for producing coating liquid for film formation |
| JP2007063375A (en) * | 2005-08-30 | 2007-03-15 | Tokyo Ohka Kogyo Co Ltd | Inorganic film-forming coating liquid |
| JP2008195862A (en) * | 2007-02-14 | 2008-08-28 | Jsr Corp | Composition for forming insulation film, and silica based film and method of forming the same |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07305027A (en) * | 1994-03-17 | 1995-11-21 | Nissan Chem Ind Ltd | Silica-containing inorganic oxide film-forming coating agent capable of patterning and method for pattern formation |
| WO2007020781A1 (en) * | 2005-08-19 | 2007-02-22 | Nissan Chemical Industries, Ltd. | Method for producing coating liquid for film formation |
| JP4941302B2 (en) * | 2005-08-19 | 2012-05-30 | 日産化学工業株式会社 | Method for producing coating liquid for film formation |
| JP2007063375A (en) * | 2005-08-30 | 2007-03-15 | Tokyo Ohka Kogyo Co Ltd | Inorganic film-forming coating liquid |
| JP2008195862A (en) * | 2007-02-14 | 2008-08-28 | Jsr Corp | Composition for forming insulation film, and silica based film and method of forming the same |
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| JPWO2012099253A1 (en) * | 2011-01-20 | 2014-06-30 | 日産化学工業株式会社 | Coating composition for touch panel, coating film and touch panel |
| JP6048148B2 (en) * | 2011-01-20 | 2016-12-21 | 日産化学工業株式会社 | Coating composition for touch panel, coating film and touch panel |
| WO2012099253A1 (en) * | 2011-01-20 | 2012-07-26 | 日産化学工業株式会社 | Coating composition for touch panels, coating film, and touch panel |
| WO2013175958A1 (en) | 2012-05-21 | 2013-11-28 | 東レ株式会社 | Substrate and touch panel member using same |
| KR20150018498A (en) | 2012-05-21 | 2015-02-23 | 도레이 카부시키가이샤 | Substrate and touch panel member using same |
| WO2013187450A1 (en) * | 2012-06-14 | 2013-12-19 | 日産化学工業株式会社 | Coating fluid for metal oxide coating film and metal oxide coating film |
| JPWO2013187450A1 (en) * | 2012-06-14 | 2016-02-08 | 日産化学工業株式会社 | Metal oxide coating liquid and metal oxide coating |
| WO2014054748A1 (en) * | 2012-10-03 | 2014-04-10 | 日産化学工業株式会社 | Application liquid capable of fine application, for forming inorganic oxide coating film, and method for manufacturing fine inorganic oxide coating film |
| JPWO2014054748A1 (en) * | 2012-10-03 | 2016-08-25 | 日産化学工業株式会社 | Coating liquid for forming finely coated inorganic oxide film and method for producing finely divided inorganic oxide film |
| KR20150110474A (en) | 2013-01-29 | 2015-10-02 | 도레이 카부시키가이샤 | Substrate and touch panel member using same |
| WO2014119372A1 (en) | 2013-01-29 | 2014-08-07 | 東レ株式会社 | Substrate and touch panel member using same |
| US9788420B2 (en) | 2013-01-29 | 2017-10-10 | Toray Industries, Inc. | Substrate and touch panel member using same |
| JPWO2014119680A1 (en) * | 2013-01-31 | 2017-01-26 | 日産化学工業株式会社 | Glass substrate and device using the same |
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