JP3405607B2 - Coating liquid for forming alignment film and liquid crystal display cell - Google Patents
Coating liquid for forming alignment film and liquid crystal display cellInfo
- Publication number
- JP3405607B2 JP3405607B2 JP24819094A JP24819094A JP3405607B2 JP 3405607 B2 JP3405607 B2 JP 3405607B2 JP 24819094 A JP24819094 A JP 24819094A JP 24819094 A JP24819094 A JP 24819094A JP 3405607 B2 JP3405607 B2 JP 3405607B2
- Authority
- JP
- Japan
- Prior art keywords
- alignment film
- liquid crystal
- crystal display
- transparent electrode
- display cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Description
【0001】[0001]
【発明の技術分野】本発明は、液晶表示セルに用いられ
る透明電極付基板の透明電極上に配向膜を形成するため
の塗布液、および基板上に透明電極および配向膜がこの
順序で形成された透明電極付基板を備えた液晶表示セル
に関する。TECHNICAL FIELD The present invention relates to a coating solution for forming an alignment film on a transparent electrode of a substrate with a transparent electrode used in a liquid crystal display cell, and a transparent electrode and an alignment film formed on the substrate in this order. And a liquid crystal display cell having a substrate with a transparent electrode.
【0002】[0002]
【発明の技術的背景】従来より、ガラス基板上に透明電
極および配向膜がこの順序で形成された一対の透明電極
付基板を備えた液晶表示セルが知られている。この液晶
表示セルでは透明電極としてITO(Indium Tin Oxid
e) などの透明導電性膜が形成されている。また、配向
膜としてはポリイミドなどの重合体が用いられている。2. Description of the Related Art Conventionally, there has been known a liquid crystal display cell provided with a pair of substrates with transparent electrodes in which a transparent electrode and an alignment film are formed in this order on a glass substrate. In this liquid crystal display cell, ITO (Indium Tin Oxid) is used as a transparent electrode.
A transparent conductive film such as e) is formed. A polymer such as polyimide is used as the alignment film.
【0003】さらに、上述した透明電極部位に、透明電
極とともに薄膜トランジスタ(TFT)が形成された液
晶表示セルも知られている。これらの液晶表示セルで
は、前記一対の透明電極付基板の配向膜間にスペーサを
介在させることにより透明電極間距離が一定となるよう
に調整されている。また、これらの液晶表示セルは、こ
のようにして所定の間隔に調整された透明電極間に液晶
を封入することによって製造されている。Further, a liquid crystal display cell in which a thin film transistor (TFT) is formed together with the transparent electrode in the transparent electrode portion described above is also known. In these liquid crystal display cells, a spacer is interposed between the alignment films of the pair of transparent electrode-attached substrates so that the distance between the transparent electrodes is adjusted to be constant. Further, these liquid crystal display cells are manufactured by enclosing a liquid crystal between the transparent electrodes adjusted to have a predetermined interval in this way.
【0004】ところで、これらの液晶表示セルを製造す
る際には、前記一対の透明電極付基板のそれぞれの配向
膜に、配向膜と接する液晶が所定の方向に配向するよう
にラビング処理が行われている。When manufacturing these liquid crystal display cells, a rubbing process is performed on each of the alignment films of the pair of substrates with transparent electrodes so that the liquid crystal in contact with the alignment films is aligned in a predetermined direction. ing.
【0005】この際、従来の液晶表示セルでは、配向膜
上に静電気が発生し、この静電気が透明電極を通して瞬
時に大量に放電され、この放電過程で配向膜が発熱して
破壊されたり、TFTを備えた液晶表示セルでTFT素
子に性能低下が生じたり、あるいは配向膜の帯電に起因
する表示むらが液晶表示セルに生じたりする場合があ
る。At this time, in the conventional liquid crystal display cell, static electricity is generated on the alignment film, and a large amount of static electricity is instantaneously discharged through the transparent electrode. In some cases, the liquid crystal display cell provided with the above may cause deterioration in performance of the TFT element, or display unevenness due to charging of the alignment film may occur in the liquid crystal display cell.
【0006】これに対し、本出願人は、前記一対の透明
電極付基板の透明電極と配向膜との間に導電性透明保護
膜を形成すると前記静電気に起因する配向膜の破壊が防
止されることを見出し、このような導電性透明保護膜を
有する一対の透明電極付基板を備えた液晶表示セルを提
案している(特開平5−232459号公報)。On the other hand, the applicant of the present invention can prevent the alignment film from being destroyed by the static electricity by forming a conductive transparent protective film between the transparent electrodes and the alignment film of the pair of substrates with transparent electrodes. In view of this, a liquid crystal display cell provided with a pair of substrates with transparent electrodes having such a conductive transparent protective film has been proposed (JP-A-5-232459).
【0007】また、この導電性透明保護膜は、液晶表示
セルで静止画像を長時間表示した後に生じる画像の焼き
付き、すなわち、液晶表示セルを駆動して画像を変化さ
せようとしても画像が変化しないという現象を防止する
上でも効果的であることが本発明者らによって確認され
ている。なお、この画像の焼き付きは、液晶表示セルの
透明電極間に電圧を印加すると液晶中に含まれているイ
オン性の不純物が配向膜に吸着するために生じると推定
される。Further, the conductive transparent protective film causes image sticking which occurs after a still image is displayed on the liquid crystal display cell for a long time, that is, the image does not change even when the liquid crystal display cell is driven to change the image. It has been confirmed by the present inventors that it is effective in preventing such a phenomenon. It is presumed that this image sticking occurs because the ionic impurities contained in the liquid crystal are adsorbed to the alignment film when a voltage is applied between the transparent electrodes of the liquid crystal display cell.
【0008】この導電性透明保護膜を形成する際には、
通常、300〜500℃の温度で透明電極が形成された
基板が加熱される。この加熱により、透明電極の抵抗値
が上昇して液晶表示セルを駆動する際に必要とされる消
費電力が増加したり、あるいはTFTやカラーフィルタ
ーを備えた液晶表示セルではTFTの性能やカラーフィ
ルターの性能が低下するおそれがある。When forming this conductive transparent protective film,
Usually, the substrate on which the transparent electrode is formed is heated at a temperature of 300 to 500 ° C. Due to this heating, the resistance value of the transparent electrode rises to increase the power consumption required for driving the liquid crystal display cell, or in the case of a liquid crystal display cell equipped with a TFT or a color filter, the performance of the TFT or the color filter Performance may decrease.
【0009】このような点から、導電性透明保護膜を透
明電極付基板の透明電極と配向膜との間に形成しなくて
も、静電気に起因する配向膜の破壊や液晶表示セルで生
じる画像の焼き付きが防止できるような液晶表示セルの
出現が望まれている。From this point of view, even if the conductive transparent protective film is not formed between the transparent electrode of the substrate with the transparent electrode and the alignment film, the alignment film is broken due to static electricity or an image generated in the liquid crystal display cell. It has been desired to develop a liquid crystal display cell capable of preventing image sticking.
【0010】ところで、特開平3−92824号公報に
は、強誘電性液晶表示素子の双安定性を改良する目的
で、導電性微粒子が分散含有された配向膜を備えた液晶
表示素子が開示され、また、導電性微粒子としては、S
bがドープされた酸化錫などのような電子伝導性無機酸
化物微粒子、あるいは微粒子状の導電性有機高分子(カ
チオン性またはアニオン性のポリマー・ビーズ)が開示
されている。By the way, Japanese Patent Laid-Open No. 3-92824 discloses a liquid crystal display device having an alignment film containing conductive fine particles dispersed therein for the purpose of improving the bistability of the ferroelectric liquid crystal display device. Further, as the conductive fine particles, S
Electron-conductive inorganic oxide fine particles such as tin oxide doped with b, or fine-particle conductive organic polymers (cationic or anionic polymer beads) are disclosed.
【0011】しかしながら、液晶表示セルの透明電極上
に、電子伝導性無機酸化物微粒子を分散させた配向膜が
形成されている場合、液晶表示セルの液晶内に混入して
いる異物のほとんどが電子伝導性であるために、この異
物と電子伝導性無機酸化物微粒子とが接触すると、この
接触部位で導通が生じ易く、この導通によって液晶表示
セルに表示不良が生じるおそれがある。However, when the alignment film in which the electron conductive inorganic oxide fine particles are dispersed is formed on the transparent electrode of the liquid crystal display cell, most of the foreign substances mixed in the liquid crystal of the liquid crystal display cell are electrons. Because of the conductivity, when the foreign matter and the electron conductive inorganic oxide fine particles come into contact with each other, conduction is likely to occur at the contact portion, and this conduction may cause a display defect in the liquid crystal display cell.
【0012】また、液晶表示セルの透明電極上に、上述
した微粒子状の導電性有機高分子を分散させた配向膜が
形成されている場合、この導電性有機高分子は湿度によ
り導電性が大きく変化し、このため、配向膜を形成する
際の条件に応じて、得られた液晶表示セルの性能に差異
が生じたり、配向膜の表面に露出している導電性有機高
分子と液晶との相互作用により、液晶表示セルに色むら
が生じたり、あるいは液晶表示セル中の液晶に配向むら
が生じるおそれがあり、特に液晶表示セルの性能につき
長期信頼性に問題がある。Further, when an alignment film in which the above-mentioned fine particulate conductive organic polymer is dispersed is formed on the transparent electrode of the liquid crystal display cell, the conductive organic polymer has a high conductivity due to humidity. Therefore, depending on the conditions when forming the alignment film, there is a difference in the performance of the obtained liquid crystal display cell, or the conductive organic polymer exposed on the surface of the alignment film and the liquid crystal The interaction may cause unevenness in color in the liquid crystal display cell or uneven alignment in the liquid crystal in the liquid crystal display cell, and in particular, there is a problem in long-term reliability regarding the performance of the liquid crystal display cell.
【0013】[0013]
【発明の目的】本発明は、上記のような従来技術に伴う
問題点を解決しようとするものであって、配向膜に電子
伝導性無機酸化物微粒子や上述した微粒子状の導電性有
機高分子を含有させたことに起因する問題点が回避で
き、しかも帯電防止能に優れ、液晶表示セルで生じる画
像の焼き付きが防止できるような配向膜を形成すること
ができる配向膜形成用塗布液、およびこのような優れた
配向膜を有する液晶表示セルを提供することを目的とし
ている。It is an object of the present invention to solve the problems associated with the prior art as described above, in which the alignment film has an electron conductive inorganic oxide fine particle or the above-mentioned fine particle-shaped conductive organic polymer. A coating solution for forming an alignment film capable of avoiding the problems caused by containing, and excellent in antistatic ability, and capable of forming an alignment film capable of preventing image sticking that occurs in a liquid crystal display cell, and It is an object of the present invention to provide a liquid crystal display cell having such an excellent alignment film.
【0014】[0014]
【発明の概要】本発明に係る配向膜形成用塗布液は、導
電性微粒子と配向膜形成用材料と有機溶媒とからなり、
前記導電性微粒子がイオン伝導性無機化合物微粒子であ
ることを特徴としている。SUMMARY OF THE INVENTION The coating solution for forming an alignment film according to the present invention comprises conductive fine particles, an alignment film forming material and an organic solvent.
It is characterized in that the conductive fine particles are ion conductive inorganic compound fine particles.
【0015】本発明に係る液晶表示セルは、基板上に透
明電極および配向膜がこの順序で形成された透明電極付
基板を備え、前記配向膜がイオン伝導性無機化合物微粒
子を含有していることを特徴としている。The liquid crystal display cell according to the present invention comprises a substrate with a transparent electrode in which a transparent electrode and an alignment film are formed in this order on a substrate, and the alignment film contains ion-conductive inorganic compound fine particles. Is characterized by.
【0016】[0016]
【発明の具体的説明】配向膜形成用塗布液
まず、本発明に係る配向膜形成用塗布液について具体的
に説明する。DETAILED DESCRIPTION OF THE INVENTION Alignment Film Forming Coating Liquid First, the alignment film forming coating liquid according to the present invention will be specifically described.
【0017】本発明に係る配向膜形成用塗布液は、導電
性微粒子と配向膜形成用材料と有機溶媒とからなってい
る。有機溶媒としては、従来の配向膜形成用塗布液で用
いられている有機溶媒が採用され、具体的にはN−メチ
ルピロリドン、γ−ブチルラクトン、ブチルセルソル
ブ、高級アルコール、グリコール類などが挙げられる。The coating liquid for forming an alignment film according to the present invention comprises conductive fine particles, a material for forming an alignment film and an organic solvent. As the organic solvent, an organic solvent used in a conventional coating liquid for forming an alignment film is adopted, and specific examples thereof include N-methylpyrrolidone, γ-butyl lactone, butyl cellosolve, higher alcohols and glycols. To be
【0018】配向膜形成用材料としては、従来の配向膜
形成用塗布液で用いられている配向膜形成用材料が採用
され、具体的にはポリアミック酸、可溶性ポリイミド、
ポリビニルアルコールなどが挙げられる。As the material for forming the alignment film, the material for forming the alignment film which is used in the conventional coating liquid for forming the alignment film is adopted, and specifically, polyamic acid, soluble polyimide,
Examples thereof include polyvinyl alcohol.
【0019】本発明に係る配向膜形成用塗布液では導電
性微粒子としてイオン伝導性無機化合物微粒子が採用さ
れる。イオン伝導性無機化合物としては、たとえばパイ
ロクロア型結晶構造を有する金属酸化物が挙げられる。
また、このようなパイロクロア型結晶構造を有する金属
酸化物としては、アンチモン、鉛、ビスマス、ルテニウ
ム、カドミウム、イットリウム、タリウム、インジウ
ム、銅、ガドリニウムなどの金属酸化物、または2種以
上のこれらの金属酸化物が複合化した複合金属酸化物が
挙げられる。これらの金属酸化物中には、P、B、Si
およびTiから選ばれる少なくとも1種の元素がドープ
されていてもよい。さらにモリブドリン酸、タングスト
リン酸などのヘテロポリ酸もイオン伝導性を示すので本
発明でイオン伝導性無機化合物として用いられる。In the coating liquid for forming an alignment film according to the present invention, ion conductive inorganic compound fine particles are used as the conductive fine particles. Examples of the ion conductive inorganic compound include metal oxides having a pyrochlore type crystal structure.
Examples of the metal oxide having such a pyrochlore type crystal structure include metal oxides such as antimony, lead, bismuth, ruthenium, cadmium, yttrium, thallium, indium, copper and gadolinium, or two or more of these metals. Examples thereof include composite metal oxides in which oxides are composited. Among these metal oxides, P, B, Si
And at least one element selected from Ti may be doped. Further, heteropolyacids such as molybdophosphoric acid and tungstophosphoric acid also show ionic conductivity, and are therefore used as the ion conductive inorganic compound in the present invention.
【0020】イオン伝導性無機化合物微粒子の平均粒径
は、約100nm以下、特に10〜80nmであること
が好ましい。平均粒径がこのような範囲にあるイオン伝
導性無機化合物微粒子を含む配向膜形成用塗布液を用い
ることにより、イオン伝導性無機化合物微粒子が単分散
された配向膜を透明電極付基材の透明電極上に形成する
ことができる。The average particle size of the ion-conductive inorganic compound fine particles is preferably about 100 nm or less, and particularly preferably 10 to 80 nm. By using a coating liquid for forming an alignment film containing ion-conductive inorganic compound fine particles having an average particle size in such a range, an alignment film in which the ion-conductive inorganic compound fine particles are monodispersed can be used as a transparent substrate for transparent electrodes. It can be formed on the electrode.
【0021】イオン伝導性無機化合物微粒子が単分散さ
れた配向膜を透明電極付基材の透明電極上に形成する点
から、本発明に係る配向膜形成用塗布液中にイオン伝導
性無機化合物微粒子が単分散されていることが好まし
い。From the viewpoint of forming an alignment film in which fine particles of ion-conductive inorganic compound are monodispersed on a transparent electrode of a substrate with a transparent electrode, the coating liquid for forming an alignment film according to the present invention contains fine particles of ion-conductive inorganic compound. Are preferably monodispersed.
【0022】イオン伝導性無機化合物微粒子が単分散さ
れている配向膜形成用塗布液を得る方法としては、配向
膜形成用材料を有機溶媒中に溶解して含む配向膜形成用
材料の溶液中にイオン伝導性無機化合物微粒子を直接分
散させる方法、配向膜形成用材料の溶液に用いられてい
る有機溶媒、あるいはこの有機溶媒と相溶する有機溶媒
中にイオン伝導性無機化合物微粒子が分散されているゾ
ルと、配向膜形成用材料の溶液とを混合する方法などが
挙げられる。As a method of obtaining a coating liquid for forming an alignment film in which fine particles of an ion-conductive inorganic compound are monodispersed, a liquid of the alignment film forming material containing the alignment film forming material dissolved in an organic solvent is used. A method of directly dispersing the ion-conductive inorganic compound fine particles, the organic solvent used in the solution of the material for forming an alignment film, or the ion-conductive inorganic compound fine particles dispersed in an organic solvent compatible with the organic solvent. Examples thereof include a method of mixing the sol and a solution of the alignment film forming material.
【0023】本発明に係る配向膜形成用塗布液中の配向
膜形成用材料とイオン伝導性無機化合物微粒子との配合
量は、配向膜形成用塗布液を用いて形成される配向膜の
樹脂成分1重量部当り0.01重量部以上、0.8重量
部以下、好ましくは0.05〜0.4重量部のイオン伝
導性無機化合物微粒子が配向膜形成用塗布液中に含まれ
るように調整することが望ましい。The amount of the alignment film forming material and the ion conductive inorganic compound fine particles in the alignment film forming coating liquid according to the present invention is determined by the resin component of the alignment film formed by using the alignment film forming coating liquid. It is adjusted so that 0.01 parts by weight or more and 0.8 parts by weight or less, preferably 0.05 to 0.4 parts by weight of the ion conductive inorganic compound fine particles are contained in the coating liquid for forming an alignment film per 1 part by weight. It is desirable to do.
【0024】上記配合量が0.01重量部未満の場合に
は本発明の目的を達成するのに充分な帯電防止能を発揮
する配向膜が得られないことがあり、逆に、0.8重量
部を越える場合には充分な硬度および機械的強度を有す
る配向膜が得られないことがある。If the amount is less than 0.01 parts by weight, an alignment film exhibiting sufficient antistatic ability to achieve the object of the present invention may not be obtained, and conversely 0.8 If it exceeds the weight part, an alignment film having sufficient hardness and mechanical strength may not be obtained.
【0025】本発明に係る配向膜形成用塗布液の固形分
濃度は、塗布液の流動性、後述するような厚さの配向膜
を形成するなどの点から、1〜50重量%、好ましくは
5〜30重量%であることが望ましい。The solid content concentration of the coating liquid for forming an alignment film according to the present invention is 1 to 50% by weight, preferably from the viewpoint of fluidity of the coating liquid and formation of an alignment film having a thickness as described later. It is preferably 5 to 30% by weight.
【0026】本発明に係る配向膜形成用塗布液から、た
とえば次のようにして透明電極付基板の透明電極上に配
向膜が形成される。まず、スピナー法、フレキソ印刷法
などの方法で透明電極付基板の透明電極上に本発明に係
る配向膜形成用塗布液を塗布する。From the coating liquid for forming an alignment film according to the present invention, an alignment film is formed on a transparent electrode of a substrate with a transparent electrode as follows, for example. First, the coating liquid for forming an alignment film according to the present invention is applied onto the transparent electrode of the substrate with a transparent electrode by a method such as a spinner method or a flexographic printing method.
【0027】このようにして透明電極上に塗膜が形成さ
れた透明電極付基板を120〜250℃の温度で加熱し
て透明電極付基板の透明電極上に配向膜を形成する。次
いで、このようにして得られた配向膜の表面に、配向膜
と接する液晶が所定の方向に配向するようにラビング処
理を施す。The substrate with a transparent electrode having a coating film formed on the transparent electrode in this manner is heated at a temperature of 120 to 250 ° C. to form an alignment film on the transparent electrode of the substrate with a transparent electrode. Then, the surface of the alignment film thus obtained is subjected to rubbing treatment so that the liquid crystal in contact with the alignment film is aligned in a predetermined direction.
【0028】液晶表示セル
次いで、本発明に係る液晶表示セルについて説明する。
本発明に係る液晶表示セルは、基板上に少なくとも透明
電極および配向膜がこの順序で形成された透明電極付基
板を備えている。 Liquid Crystal Display Cell Next, the liquid crystal display cell according to the present invention will be described.
The liquid crystal display cell according to the present invention includes a substrate with a transparent electrode in which at least a transparent electrode and an alignment film are formed in this order on the substrate.
【0029】基板としては、公知の液晶表示セルで用い
られている基板が採用でき、通常、ガラス、プラスチッ
クなどの透明基板が用いられている。この基板上には、
ITO薄膜などの公知の透明電極が形成されている。ま
た、この透明電極部位には、透明電極とともに薄膜トラ
ンジスタ(TFT)、カラーフィルターなどが形成され
ていてもよい。さらには、透明電極と配向膜との間に透
明保護膜が形成されていてもよい。As the substrate, a substrate used in a known liquid crystal display cell can be adopted, and a transparent substrate such as glass or plastic is usually used. On this board,
A known transparent electrode such as an ITO thin film is formed. In addition, a thin film transistor (TFT), a color filter or the like may be formed together with the transparent electrode at this transparent electrode portion. Furthermore, a transparent protective film may be formed between the transparent electrode and the alignment film.
【0030】本発明では、この透明電極上に上述したよ
うなイオン伝導性無機化合物微粒子を含む配向膜が形成
されている。この配向膜の厚さは、通常、10〜100
nm、好ましくは30〜70nmである。In the present invention, an alignment film containing the above-mentioned ion conductive inorganic compound fine particles is formed on this transparent electrode. The thickness of this alignment film is usually 10 to 100.
nm, preferably 30 to 70 nm.
【0031】本発明に係る液晶表示セルで配向膜中に含
まれているイオン伝導性無機化合物微粒子は、電子が粒
子内を移動することによって導電性を示す電子伝導性粒
子とは異なり、カチオンまたはアニオンが粒子内を移動
することによって導電性を示す。このため、イオン伝導
性無機化合物微粒子は、液晶表示セル中で液晶に混入し
ている電子伝導性の異物と接触してもこの接触部位で導
通が生じ難く、電子伝導性粒子と液晶に混入している異
物との接触部位で生じる導通に起因する液晶表示セルの
表示不良が生じるおそれはない。In the liquid crystal display cell according to the present invention, the ion conductive inorganic compound fine particles contained in the alignment film are different from the electron conductive particles which show conductivity due to the movement of electrons in the particles, and are different from cations or The anion moves inside the particles to show conductivity. Therefore, even if the ion-conductive inorganic compound fine particles come into contact with an electron-conductive foreign substance mixed in the liquid crystal in the liquid crystal display cell, conduction is unlikely to occur at this contact portion, and the ion-conductive inorganic compound fine particles are mixed in the liquid crystal display cell. There is no possibility that a display defect of the liquid crystal display cell will occur due to conduction occurring at a contact portion with a foreign substance.
【0032】電子伝導性物質の代表例としては、Sbが
ドープされた酸化錫が挙げられる。このSbがドープさ
れた酸化錫では、4価の錫酸化物の結晶格子中に5価の
Sbがドープされており、このSb部位で生じた自由電
子が電気伝導に関与する。A typical example of the electron conductive material is tin oxide doped with Sb. In this tin oxide doped with Sb, pentavalent Sb is doped in the crystal lattice of tetravalent tin oxide, and free electrons generated at this Sb site participate in electric conduction.
【0033】これに対し、イオン伝導性無機化合物の代
表例としては、酸化アンチモンが挙げられる。この酸化
アンチモンは、Sb2 O5 ・nH2 Oで示される含水酸
化物であり、図1に示すようにH+ (プロトン)を内包
する結晶構造をとるといわれている。酸化アンチモンで
は、このH+ が電気伝導に関与する。On the other hand, a typical example of the ion conductive inorganic compound is antimony oxide. This antimony oxide is a hydrous oxide represented by Sb 2 O 5 .nH 2 O, and is said to have a crystal structure containing H + (proton) as shown in FIG. In antimony oxide, this H + participates in electric conduction.
【0034】また、イオン伝導性無機化合物微粒子は、
上述した微粒子状の導電性有機高分子のように湿度によ
り導電性が大きく変化することはなく、また、液晶と相
互作用して液晶表示セルに色むらを生じさせたり、ある
いは液晶表示セル中の液晶に配向むらを生じさせたりす
るおそれもない。The ion conductive inorganic compound fine particles are
Unlike the above-mentioned fine particle-shaped conductive organic polymer, the conductivity does not greatly change due to humidity, and it interacts with the liquid crystal to cause color unevenness in the liquid crystal display cell, or in the liquid crystal display cell. There is no possibility of causing uneven alignment in the liquid crystal.
【0035】本発明に係る液晶表示セルは、上述したよ
うな配向膜を有する一対の透明電極付基板を備えてい
る。この一対の透明電極付基板を備えた液晶表示セル
は、たとえば、それぞれの配向膜に所定のラビング処理
を施した後、この一対の透明電極付基板の配向膜間にス
ペーサを介設し、次いでこのようにして一定間隔に調整
された透明電極間に液晶を封入するなど、公知の方法で
製造される。The liquid crystal display cell according to the present invention comprises a pair of substrates with transparent electrodes having the above-mentioned alignment film. A liquid crystal display cell provided with this pair of substrates with transparent electrodes, for example, after subjecting each alignment film to a predetermined rubbing treatment, a spacer is provided between the alignment films of the pair of substrates with transparent electrodes, and then It is manufactured by a known method such as enclosing a liquid crystal between the transparent electrodes adjusted to have a constant interval in this way.
【0036】[0036]
【発明の効果】本発明に係る配向膜形成用塗布液によれ
ば、イオン伝導性無機化合物微粒子を含む帯電防止性に
優れた配向膜を透明電極付基材の透明電極上に形成する
ことができる。EFFECTS OF THE INVENTION According to the coating liquid for forming an alignment film of the present invention, an alignment film containing ion conductive inorganic compound fine particles and having excellent antistatic properties can be formed on a transparent electrode of a substrate with a transparent electrode. it can.
【0037】このため、このようなイオン伝導性無機化
合物微粒子を含む配向膜が透明電極上に形成された本発
明に係る液晶表示セルでは、配向膜をラビング処理した
際に配向膜に発生した静電気の放電に起因する配向膜の
破壊およびTFT素子の性能低下、あるいは配向膜の帯
電に起因する液晶表示セルの表示むらが防止され、ま
た、液晶表示セルに連続的に長時間静止画像を表示して
も表示画像の焼き付きが起こることがなく、したがって
表示画像の焼き付きに起因する液晶表示セルの表示むら
が生じることもない。Therefore, in the liquid crystal display cell according to the present invention in which the alignment film containing such ion-conductive inorganic compound fine particles is formed on the transparent electrode, the static electricity generated in the alignment film when the alignment film is rubbed is rubbed. Of the alignment film and the deterioration of the performance of the TFT element due to the discharge of the liquid crystal, or the display unevenness of the liquid crystal display cell due to the charging of the alignment film is prevented, and the still image is continuously displayed on the liquid crystal display cell for a long time. However, the image sticking of the display image does not occur, and thus the display unevenness of the liquid crystal display cell due to the image sticking of the display image does not occur.
【0038】さらに本発明に係る液晶表示セルは、電子
伝導性無機化合物微粒子を含む配向膜が透明電極上に形
成された液晶表示セルとは異なり、液晶表示セル中で液
晶に混入している電子伝導性の異物と接触してもこの接
触部位で導通が生じ難く、この接触部位での導通に起因
する液晶表示セルの表示不良が生じるおそれはない。ま
た、本発明に係る液晶表示セルでは、導電性有機高分子
材料に起因する問題点、たとえば導電性の湿度による変
化、液晶表示セルの色むら、液晶の配向むらなどが生じ
ることもない。Further, the liquid crystal display cell according to the present invention is different from the liquid crystal display cell in which the alignment film containing the electron conductive inorganic compound fine particles is formed on the transparent electrode, and the electrons mixed in the liquid crystal in the liquid crystal display cell. Even if a conductive foreign substance is contacted, conduction is unlikely to occur at this contact portion, and there is no risk of display failure in the liquid crystal display cell due to conduction at this contact portion. Further, in the liquid crystal display cell according to the present invention, problems caused by the conductive organic polymer material, for example, changes in conductivity due to humidity, uneven color of the liquid crystal display cell, uneven alignment of liquid crystal, etc. do not occur.
【0039】また、本発明によれば、イオン伝導性無機
化合物微粒子の配合量などに応じてハードコート膜とし
ての機能を有している配向膜を透明電極付基材の透明電
極上に形成することができ、したがって、液晶表示セル
で異物やスペーサーなどにより配向膜が損傷して生じる
液晶表示セルの表示不良が防止できる上、ラビングに起
因する配向膜の傷の発生も防止できる。Further, according to the present invention, an alignment film having a function as a hard coat film is formed on a transparent electrode of a substrate with a transparent electrode according to the compounding amount of the ion conductive inorganic compound fine particles and the like. Therefore, it is possible to prevent defective display of the liquid crystal display cell caused by damage to the alignment film due to foreign matters or spacers in the liquid crystal display cell, and also to prevent damage to the alignment film due to rubbing.
【0040】また、上記のような高温加熱処理を行わな
くてもよいので、本発明によれば、耐熱温度が約150
〜200℃のカラーフィルターを備えたカラーフィルタ
ー付液晶表示セルを提供することができる。Further, according to the present invention, the heat resistant temperature is about 150, since the high temperature heat treatment as described above does not have to be performed.
It is possible to provide a liquid crystal display cell with a color filter having a color filter of up to 200 ° C.
【0041】[0041]
【実施例】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。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【0042】[0042]
【実施例1】配向膜形成用材料(日産化学工業(株)
製、サンエバー SE−4110、固形分濃度:8重量
%)100gに、表1に示す平均粒径の酸化アンチモン
微粒子を表1に示す分散媒中に分散させた酸化アンチモ
ンゾル(固形分濃度10重量%)16gを混合すること
により実施例1の配向膜形成用塗布液を調製した。Example 1 Material for forming an alignment film (Nissan Chemical Co., Ltd.)
Manufactured by San-Ever SE-4110, solid content concentration: 8% by weight), and antimony oxide sol (solid content concentration: 10% by weight) obtained by dispersing antimony oxide fine particles having an average particle size shown in Table 1 in a dispersion medium shown in Table 1. %) 16 g to prepare a coating liquid for forming an alignment film of Example 1.
【0043】ガラス基板上にITO透明電極がパターン
状に形成された透明電極付基板(旭硝子(株)製、30
Ωタイプ)の透明電極上に、実施例1の配向膜形成用塗
布液ををフレキソ印刷法で塗布し、90℃で5分間乾燥
した後、200℃で30分間焼成して、ガラス基板上に
透明電極および配向膜がこの順序で形成されている透明
電極付基板を作成した。A substrate with a transparent electrode in which ITO transparent electrodes are formed in a pattern on a glass substrate (manufactured by Asahi Glass Co., Ltd., 30
The coating liquid for forming an alignment film of Example 1 was applied onto a transparent electrode of (Ω type) by a flexographic printing method, dried at 90 ° C. for 5 minutes, and then baked at 200 ° C. for 30 minutes to form a glass substrate. A substrate with a transparent electrode in which a transparent electrode and an alignment film were formed in this order was prepared.
【0044】この透明電極付基板の配向膜に対して次の
ような評価を行った。
(1)膜厚
配向膜の膜厚を接触式膜厚計(テイラーホブソン社製)
で測定した。
(2)表面抵抗
配向膜の表面抵抗をアナログ絶縁抵抗計(横河インスツ
ルメンツ社製 2406A24)で測定した。
(3)鉛筆硬度
所定の硬さの鉛筆に荷重1Kgを負荷しながら鉛筆で配
向膜上に線引きした後、配向膜上に形成された傷の有無
を観察し、配向膜上に傷を形成させる最低の鉛筆硬度で
配向膜の硬度を評価した。
(4)耐擦傷性
配向膜上でベンコットンを荷重500gで50回摺動さ
せ、透明電極付基板の透明電極面まで傷が達していない
場合を良(○)と評価し、透明電極付基板の透明電極面
まで傷が達している場合を不良(×)と評価した。
(5)外観
配向膜の濁りおよび白化の有無を観察し、濁りおよび白
化がいずれもない場合を良(○)と評価し、濁りおよび
白化のうち、すくなくともどちらか一方がある場合を不
良(×)と評価した。
(6)帯電減衰時間
配向膜に帯電させた後の帯電減衰時間をオネストメータ
ー(春日電気(株)製)で測定し、帯電減衰時間が短い
程、配向膜の帯電防止性能がよいと評価した。The following evaluation was performed on the alignment film of the substrate with the transparent electrode. (1) Film thickness The film thickness of the alignment film is measured by a contact-type film thickness meter (Taylor Hobson).
It was measured at. (2) Surface resistance The surface resistance of the alignment film was measured with an analog insulation resistance tester (2406A24 manufactured by Yokogawa Instruments). (3) Pencil hardness A pencil having a predetermined hardness is drawn on the alignment film with a load of 1 kg while observing the presence or absence of scratches formed on the alignment film to form scratches on the alignment film. The hardness of the alignment film was evaluated with the lowest pencil hardness. (4) Bencotton was slid 50 times under a load of 500 g on the scratch-resistant alignment film, and when the scratches did not reach the transparent electrode surface of the substrate with transparent electrodes, it was evaluated as good (○), and the substrate with transparent electrodes was evaluated. The case where the scratch reached the transparent electrode surface was evaluated as defective (x). (5) Appearance The presence or absence of turbidity and whitening of the alignment film was observed, and when neither turbidity nor whitening was evaluated as good (○), when at least one of turbidity and whitening was poor (×) ) Was evaluated. (6) Charge decay time The charge decay time after charging the alignment film was measured with a Honest meter (produced by Kasuga Electric Co., Ltd.), and the shorter the charge decay time was, the better the antistatic performance of the alignment film was evaluated. .
【0045】上記(1)〜(6)の評価結果を表2に示
す。Table 2 shows the evaluation results of the above (1) to (6).
【0046】[0046]
【実施例2、参考例1】酸化アンチモンゾルに代えて表
1に示すイオン伝導性無機化合物微粒子および分散媒か
らなるイオン伝導性無機化合物ゾルを用いた以外は実施
例1と同様にして実施例2および参考例1の配向膜形成
用塗布液を調製した。Example 2, Reference Example 1 An example was carried out in the same manner as in Example 1 except that the ion conductive inorganic compound sol consisting of the ion conductive inorganic compound fine particles and the dispersion medium shown in Table 1 was used in place of the antimony oxide sol. 2 and the coating liquid for forming an alignment film of Reference Example 1 were prepared.
【0047】このようにして得られた実施例2および参
考例1の配向膜形成用塗布液を用いて、それぞれ実施例
1と同様にしてガラス基板上に透明電極および配向膜が
この順序で形成されている透明電極付基板を作成し、そ
れぞれの透明電極付基板の配向膜に対して実施例1と同
様の評価を行った。Thus obtained Example 2 and Reference
Using the coating liquid for forming an alignment film of Consideration 1, a substrate with a transparent electrode in which a transparent electrode and an alignment film were formed in this order on a glass substrate was prepared in the same manner as in Example 1, and the respective transparent substrates were formed. The same evaluation as in Example 1 was performed on the alignment film of the electrode-attached substrate.
【0048】結果を表2に示す。The results are shown in Table 2.
【0049】[0049]
【実施例4】配向膜形成用材料(日本合成ゴム(株)
製、オプトマー AL−1524、固形分濃度:24重
量%)100gに、表1に示す平均粒径の酸化アンチモ
ン微粒子を表1に示す分散媒中に分散させた酸化アンチ
モンゾル(固形分濃度10重量%)48gを混合するこ
とにより実施例4の配向膜形成用塗布液を調製した。Example 4 Material for forming an alignment film (Nippon Synthetic Rubber Co., Ltd.)
Manufactured by Optomer AL-1524, solid content concentration: 24% by weight), antimony oxide sol having an average particle size shown in Table 1 dispersed in a dispersion medium shown in Table 1 (solid content concentration 10% by weight). %) 48 g to prepare a coating liquid for forming an alignment film of Example 4.
【0050】このようにして得られた実施例4の配向膜
形成用塗布液を用いて、実施例1と同様にしてガラス基
板上に透明電極および配向膜がこの順序で形成されてい
る透明電極付基板を作成し、この透明電極付基板の配向
膜に対して実施例1と同様の評価を行った。Using the coating liquid for forming an alignment film of Example 4 thus obtained, a transparent electrode and an alignment film are formed in this order on a glass substrate in the same manner as in Example 1. An attached substrate was prepared, and the same evaluation as in Example 1 was performed on the alignment film of the substrate with the transparent electrode.
【0051】結果を表2に示す。The results are shown in Table 2.
【0052】[0052]
【実施例5、参考例2】酸化アンチモンゾルに代えて表
1に示すイオン伝導性無機化合物微粒子および分散媒か
らなるイオン伝導性無機化合物ゾルを用いた以外は実施
例4と同様にして実施例5および参考例2の配向膜形成
用塗布液を調製した。Example 5, Reference Example 2 An example was carried out in the same manner as in Example 4 except that the ion conductive inorganic compound sol comprising the ion conductive inorganic compound fine particles and the dispersion medium shown in Table 1 was used in place of the antimony oxide sol. 5 and the coating liquid for forming an alignment film of Reference Example 2 were prepared.
【0053】このようにして得られた実施例5および参
考例2の配向膜形成用塗布液を用いて、それぞれ実施例
1と同様にしてガラス基板上に透明電極および配向膜が
この順序で形成されている透明電極付基板を作成し、そ
れぞれの透明電極付基板の配向膜に対して実施例1と同
様の評価を行った。Thus obtained Example 5 and Reference
Using the coating liquid for forming an alignment film of Consideration 2 , a transparent electrode-attached substrate in which a transparent electrode and an alignment film were formed in this order on a glass substrate was prepared in the same manner as in Example 1, and the respective transparent substrates were formed. The same evaluation as in Example 1 was performed on the alignment film of the electrode-attached substrate.
【0054】結果を表2に示す。The results are shown in Table 2.
【0055】[0055]
【比較例1】実施例1の配向膜形成用塗布液に代えて配
向膜形成用材料(日産化学工業(株)製、サンエバー
SE−4110、固形分濃度:8重量%)のみを用いた
以外は実施例1と同様にしてガラス基板上に透明電極お
よび配向膜がこの順序で形成されている透明電極付基板
を作成し、それぞれの透明電極付基板の配向膜に対して
実施例1と同様の評価を行った。Comparative Example 1 Instead of the coating liquid for forming an alignment film of Example 1, a material for forming an alignment film (manufactured by Nissan Chemical Industries, Ltd., Sun Ever)
SE-4110, solid content concentration: 8% by weight) was used to prepare a substrate with a transparent electrode in which a transparent electrode and an alignment film were formed in this order on a glass substrate in the same manner as in Example 1, The same evaluation as in Example 1 was performed on the alignment films of the respective substrates with transparent electrodes.
【0056】結果を表2に示す。The results are shown in Table 2.
【0057】[0057]
【表1】 [Table 1]
【0058】[0058]
【表2】 [Table 2]
【0059】[0059]
【実施例7、参考例2】実施例1ないし2、参考例1で
それぞれ得られたガラス基板上に透明電極および配向膜
がこの順序で形成されている2枚の透明電極付基板の配
向膜表面に所定のラビング処理を施した後、この2枚の
透明電極付基板を用いて、セルギャップ6.5μmのS
TN液晶表示セルを10組ずつ作成した。それぞれの液
晶表示セルを用いて液晶表示装置を組み立て、その作動
状態を観察したところ、液晶表示装置の液晶表示セルに
はいずれも表示むらが生じなかった。また、DC3Vで
100時間通電した後の液晶表示セルにはいずれも焼き
付けが生じていなかった。Example 7, Reference Example 2 Alignment films of two substrates with transparent electrodes, in which transparent electrodes and alignment films are formed in this order on the glass substrates obtained in Examples 1 and 2 and Reference Example 1 , respectively. After subjecting the surface to a predetermined rubbing treatment, using these two substrates with transparent electrodes, S with a cell gap of 6.5 μm was obtained.
Ten sets of TN liquid crystal display cells were prepared. When a liquid crystal display device was assembled using the respective liquid crystal display cells and the operating state thereof was observed, no display unevenness occurred in the liquid crystal display cells of the liquid crystal display device. In addition, the liquid crystal display cell after being energized at DC 3V for 100 hours was not burned.
【0060】[0060]
【比較例2】比較例1で得られたガラス基板上に透明電
極および配向膜がこの順序で形成されている透明電極付
基板を用いた以外は実施例7と同様にしてSTN液晶表
示セルを備えた液晶表示装置を10組組み立て、実施例
7と同様の評価を行った。Comparative Example 2 An STN liquid crystal display cell was prepared in the same manner as in Example 7 except that the transparent electrode-provided substrate in which the transparent electrode and the alignment film were formed in this order on the glass substrate obtained in Comparative Example 1 was used. Ten sets of the provided liquid crystal display devices were assembled and the same evaluation as in Example 7 was performed.
【0061】この結果、10組中4組の液晶表示セルに
表示むらが生じ、6組の液晶表示セルに焼き付けが生じ
ていた。As a result, display unevenness occurred in 4 of the 10 liquid crystal display cells, and burn-in occurred in the 6 liquid crystal display cells.
【0062】[0062]
【実施例8】ガラス基板上に透明電極、TFTおよび実
施例4の配向膜形成用塗布液を用いて形成された配向膜
がこの順序で積層されている透明電極付基板と、ガラス
基板上にカラーフィルター、透明電極および実施例4の
配向膜形成用塗布液を用いて形成された配向膜がこの順
序で積層されている透明電極付基板とを用いてセルギャ
ップ5.0μmのTFT型液晶カラー表示セルを10組
作成した。[Embodiment 8] A transparent electrode substrate on which a transparent electrode, a TFT and an alignment film formed by using the coating liquid for forming an alignment film of Example 4 are laminated in this order on a glass substrate, and on a glass substrate A TFT type liquid crystal color having a cell gap of 5.0 μm using a color filter, a transparent electrode and a substrate with a transparent electrode in which an alignment film formed using the alignment film forming coating liquid of Example 4 is laminated in this order. Ten sets of display cells were created.
【0063】この液晶表示セルを用いて液晶表示装置を
組み立て、その作動状態を観察したところ、液晶表示装
置の表示セルにはいずれも表示むらが生じなかった。ま
た、DC3Vで100時間通電した後の表示セルにはい
ずれも焼き付けが生じていなかった。When a liquid crystal display device was assembled using this liquid crystal display cell and the operating state thereof was observed, no display unevenness occurred in the display cell of the liquid crystal display device. No burn-in occurred in any of the display cells after energization at DC 3V for 100 hours.
【0064】[0064]
【比較例3】実施例4の配向膜形成用塗布液に代えて配
向膜形成用材料(日産化学工業(株)製、サンエバー
SE−4110、固形分濃度:8重量%)のみを用いて
配向膜が形成されている以外は実施例8と同様にしてT
FT型液晶カラー表示セルを備えた液晶表示装置を組み
立て、その作動状態を観察したところ、10組中2組の
液晶表示セルに表示むらが生じ、4組の液晶表示セルに
焼き付けが生じた。Comparative Example 3 An alignment film forming material (manufactured by Nissan Kagaku Kogyo Co., Ltd., Sun Ever) was used in place of the alignment film forming coating liquid of Example 4.
SE-4110, solid content concentration: 8% by weight) T was prepared in the same manner as in Example 8 except that the alignment film was formed.
When a liquid crystal display device equipped with an FT type liquid crystal color display cell was assembled and the operating state thereof was observed, display unevenness occurred in two of the ten liquid crystal display cells, and burning occurred in four of the liquid crystal display cells.
【図1】 図1は、イオン伝導性無機化合物微粒子の電
気伝導機構を説明するための図面である。FIG. 1 is a drawing for explaining an electric conduction mechanism of ion-conductive inorganic compound fine particles.
フロントページの続き (72)発明者 戸 梶 秀 章 福岡県北九州市若松区北湊町13番2号 触媒化成工業株式会社若松工場内 (56)参考文献 特開 平6−25529(JP,A) 特開 平8−54629(JP,A) 特開 平8−54631(JP,A) (58)調査した分野(Int.Cl.7,DB名) G02F 1/1337 Front Page Continuation (72) Inventor Hideaki Tokaji 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu, Fukuoka Prefecture Inside the Wakamatsu Plant of Catalysts & Chemicals Industries Co., Ltd. (56) Kaihei 8-54629 (JP, A) JP-A-8-54631 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) G02F 1/1337
Claims (2)
媒とからなり、前記導電性微粒子がイオン伝導性無機化
合物微粒子であり、 前記イオン伝導性無機化合物が、P、B、SiおよびT
iから選ばれる少なくとも1種の元素がドープされてい
てもよいSb2O5・nH2Oであることを特徴とする配向
膜形成用塗布液。 1. A conductive fine particle, an alignment film forming material, and an organic solvent, wherein the conductive fine particle is an ion conductive inorganic compound fine particle, and the ion conductive inorganic compound is P, B, Si and T.
A coating liquid for forming an alignment film, which is Sb 2 O 5 .nH 2 O which may be doped with at least one element selected from i.
で形成された透明電極付基板を備え、前記配向膜がイオ
ン伝導性無機化合物微粒子を含有してなり、かつ前記イ
オン伝導性無機化合物が、P、B、SiおよびTiから
選ばれる少なくとも1種の元素がドープされていてもよ
いSb 2 O 5 ・nH 2 Oであることを特徴とする液晶表示セ
ル。2. A substrate with a transparent electrode having a transparent electrode and an alignment film formed in this order on a substrate, wherein the alignment film contains fine particles of an ion-conductive inorganic compound, and the ion-conductive inorganic compound. Is Sb 2 O 5 .nH 2 O which may be doped with at least one element selected from P, B, Si and Ti.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24819094A JP3405607B2 (en) | 1994-10-13 | 1994-10-13 | Coating liquid for forming alignment film and liquid crystal display cell |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24819094A JP3405607B2 (en) | 1994-10-13 | 1994-10-13 | Coating liquid for forming alignment film and liquid crystal display cell |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH08114803A JPH08114803A (en) | 1996-05-07 |
JP3405607B2 true JP3405607B2 (en) | 2003-05-12 |
Family
ID=17174549
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP24819094A Expired - Lifetime JP3405607B2 (en) | 1994-10-13 | 1994-10-13 | Coating liquid for forming alignment film and liquid crystal display cell |
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Country | Link |
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JP (1) | JP3405607B2 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10133205A (en) * | 1996-11-05 | 1998-05-22 | Mitsubishi Electric Corp | Liquid crystal display device |
JP2002080828A (en) * | 2000-09-11 | 2002-03-22 | Toshiba Corp | Antistatic dispersion and antistatic film and image display |
US7253861B2 (en) | 2000-12-28 | 2007-08-07 | Asahi Glass Company | Liquid crystal optical element comprising a resin layer having a surface hardness of b or less |
US6674494B2 (en) | 2000-12-28 | 2004-01-06 | Optrex Corporation | Liquid crystal optical element and test method for its boundary layer |
JP6683955B2 (en) * | 2014-11-13 | 2020-04-22 | 日産化学株式会社 | Liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element |
JP6575770B2 (en) * | 2014-11-13 | 2019-09-18 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
JP6864251B2 (en) * | 2015-10-29 | 2021-04-28 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
-
1994
- 1994-10-13 JP JP24819094A patent/JP3405607B2/en not_active Expired - Lifetime
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JPH08114803A (en) | 1996-05-07 |
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