JPH1026760A - Liquid crystal oriented film, production of liquid crystal oriented film, liquid crystal display device, and production of liquid crystal display device - Google Patents
Liquid crystal oriented film, production of liquid crystal oriented film, liquid crystal display device, and production of liquid crystal display deviceInfo
- Publication number
- JPH1026760A JPH1026760A JP18032796A JP18032796A JPH1026760A JP H1026760 A JPH1026760 A JP H1026760A JP 18032796 A JP18032796 A JP 18032796A JP 18032796 A JP18032796 A JP 18032796A JP H1026760 A JPH1026760 A JP H1026760A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- group
- energy beam
- film
- resin 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、液晶を用いた画像
表示装置およびその製造方法に関するものであり、特
に、TV画像やコンピュータ画像等を表示する液晶を用
いた平面表示パネルに用いる液晶配向膜およびその製造
方法およびそれを用いた液晶表示装置とその製造方法に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image display device using a liquid crystal and a method of manufacturing the same, and more particularly, to a liquid crystal alignment film used for a flat display panel using a liquid crystal for displaying a TV image, a computer image, and the like. And a method of manufacturing the same, a liquid crystal display device using the same, and a method of manufacturing the same.
【0002】[0002]
【従来の技術】従来カラー液晶表示パネルは、マトリッ
クス状に配置された対向電極を形成した2つの基板の間
にポリビニルアルコールやポリイミドをスピナーで塗布
焼成して形成した被膜をフェルト布で擦って(すなわち
ラビング)作製した液晶配向膜を介して液晶を封入した
装置が一般的であった。2. Description of the Related Art Conventionally, in a color liquid crystal display panel, a film formed by applying and firing a polyvinyl alcohol or a polyimide with a spinner between two substrates having opposed electrodes arranged in a matrix is rubbed with a felt cloth. That is, a device in which liquid crystal was sealed through a liquid crystal alignment film produced by rubbing was generally used.
【0003】[0003]
【発明が解決しようとする課題】しかしながら、従来の
配向膜の作成は、上記したように、ポリビニルアルコー
ルやポリイミドを有機溶媒に溶解させ回転塗布法などを
用いて塗布形成した後、フェルト布等を用いてラビング
を行なう方法が用いられていたため、大面積パネル(例
えば14インチディスプレイ)では配向膜の均一コーテ
ィングが困難であり、また、回転塗布では塗布厚が数ミ
クロン程度にもなり、強誘電液晶のような1000オン
グストローム程度の厚みの配向膜を必要とする表示パネ
ルでは、性能が大幅に低減されるという大きな欠点があ
った。However, as described above, a conventional orientation film is formed by dissolving polyvinyl alcohol or polyimide in an organic solvent, applying the solution using a spin coating method or the like, and then applying a felt cloth or the like. The rubbing method has been used, so that it is difficult to uniformly coat the alignment film on a large-area panel (for example, a 14-inch display). Such a display panel that requires an alignment film having a thickness of about 1000 angstroms has a great disadvantage that the performance is greatly reduced.
【0004】さらに、最近では、ポリビニルシンナメイ
トやポリイミド膜を用いて偏光膜をマスクに露光してラ
ビングフリーの配向膜を提供する方法が開発されつつあ
るが、ポリビニルシンナメイトやポリイミド膜は感光感
度が数J/cm2と極めて低く露光に必要とする時間が
数分もかかってしまい実用性に乏しかった。Further, recently, a method of providing a rubbing-free alignment film by exposing a polarizing film to a mask using a polyvinyl cinnamate or polyimide film has been developed. However, the exposure time was extremely low at several J / cm 2 , and the time required for exposure took several minutes, which was not practical.
【0005】上記の問題点に鑑み、本発明の目的は、従
来のようなラビングを必要としない高信頼性の配向膜お
よびそれを短時間高能率に作成する方法を提供すること
にある。また、それを用いた表示パネルおよびその製造
方法を提供ことにある。SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a highly reliable alignment film which does not require rubbing as in the prior art, and a method for forming it with high efficiency in a short time. Another object is to provide a display panel using the same and a method for manufacturing the same.
【0006】[0006]
【課題を解決するための手段】本発明の液晶配向膜は、
上述の目的を達成するものであり、エネルギービーム感
応性基及び熱反応性基を有し、可視光域で透明な樹脂膜
が電極上に直接または任意の薄膜を介して間接的に形成
され、少なくともエネルギービーム感応性基を反応架橋
されている構成となっている。Means for Solving the Problems The liquid crystal alignment film of the present invention comprises:
It is intended to achieve the above object, having an energy beam sensitive group and a heat reactive group, a transparent resin film in the visible light region is formed directly on the electrode or indirectly through any thin film, At least an energy beam sensitive group is reactively crosslinked.
【0007】また、本発明の液晶配向膜の製造方法は、
電極の形成された所定の基板表面に直接または任意の薄
膜を介して間接的に、エネルギービーム感応性基及び熱
反応性基を有する可視光域で透明な樹脂膜を塗布形成す
る工程と、少なくとも任意のマスクを介してエネルギー
ビームを樹脂膜に照射してエネルギービーム感応性基を
反応架橋する工程とを有する構成となっている。Further, the method for producing a liquid crystal alignment film according to the present invention comprises:
A step of coating and forming a transparent resin film in a visible light region having an energy beam-sensitive group and a heat-reactive group directly or indirectly through an arbitrary thin film on a predetermined substrate surface on which electrodes are formed, at least, Irradiating the resin film with an energy beam via an arbitrary mask to react and crosslink the energy beam-sensitive group.
【0008】そして上記の構成により、従来不良の発生
率が極めて高かったラビング工程を不要とし、それを用
いた表示パネルを極めて低コストに製造できる。With the above structure, a rubbing step, which has conventionally had a very high rate of occurrence of defects, becomes unnecessary, and a display panel using the rubbing step can be manufactured at extremely low cost.
【0009】また本発明の液晶表示装置は、エネルギー
ビーム感応性基及び熱反応性基を有し、可視光域で透明
な樹脂膜が電極上に直接または任意の薄膜を介して間接
的に形成され、少なくともエネルギービーム感応性基を
反応架橋されている液晶配向膜が2つの対向する電極の
少なくとも一方の電極上に形成されており、液晶が2つ
の対向する電極に樹脂膜を介して挟まれている構成とな
っている。The liquid crystal display device of the present invention has an energy beam sensitive group and a heat reactive group, and a resin film transparent in the visible light region is formed directly on the electrode or indirectly via an arbitrary thin film. A liquid crystal alignment film having at least one energy beam-sensitive group cross-linked by reaction is formed on at least one of the two opposing electrodes, and the liquid crystal is sandwiched between the two opposing electrodes via a resin film. Configuration.
【0010】さらに本発明の液晶表示装置の製造方法
は、マトリックス状に載置された第1の電極群を有する
第1の基板上に直接または任意の薄膜を介して間接的に
エネルギービーム感応性基及び熱反応性基を有し可視光
域で透明な樹脂膜を塗布形成する工程と、少なくとも任
意のマスクを介してエネルギービームを照射してエネル
ギービーム感応性基を反応架橋させる工程と、第1の電
極群と対向するように載置した第2の電極叉は電極群を
有する第2の基板をそれぞれの電極側が対向するように
位置合わせして接着固定する工程と、第1と第2の基板
に所定の液晶を注入する工程とを有する構成となってい
る。Further, according to the method of manufacturing a liquid crystal display device of the present invention, the energy beam sensitivity can be directly or indirectly applied via a thin film on a first substrate having a first electrode group mounted in a matrix. A step of coating and forming a transparent resin film in a visible light region having a group and a heat-reactive group, and a step of irradiating an energy beam through at least an arbitrary mask to react and crosslink the energy beam-sensitive group; A step of aligning and bonding and fixing a second electrode or a second substrate having an electrode group placed so as to face the first electrode group so that the respective electrode sides face each other; And a step of injecting a predetermined liquid crystal into the substrate.
【0011】[0011]
【発明の実施の形態】以下では本発明の実施の形態にお
ける配向膜について説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS An alignment film according to an embodiment of the present invention will be described below.
【0012】そこでまず本実施の形態における配向膜の
概要について説明する。まずあらかじめ、電極の形成さ
れた所定の基板表面に直接または任意の薄膜を介して間
接的にエネルギービーム感応性基と熱反応性基を持つ可
視光域で透明な樹脂膜を塗布形成する。次に、任意のマ
スクを介してエネルギービームを照射して前記エネルギ
ービーム感応性基を反応架橋させる。Therefore, first, the outline of the alignment film in the present embodiment will be described. First, a transparent resin film in the visible light region having an energy beam sensitive group and a thermally reactive group is applied and formed directly or indirectly through an arbitrary thin film on a predetermined substrate surface on which electrodes are formed. Next, an energy beam is irradiated through an arbitrary mask to react-crosslink the energy beam-sensitive group.
【0013】このとき、エネルギービーム感応性基が感
光性基であり、マスクを介して光を照射して前記被膜内
の感光性基を反応させ、主鎖間を架橋するとともに側鎖
基を配向固定する工程をもちいれば、従来のようなラビ
ングを必要とせず通常の露光機が使用可能となり液晶配
向膜の製造工程を簡略化できる。At this time, the energy beam-sensitive group is a photosensitive group, and is irradiated with light through a mask to react the photosensitive group in the coating, cross-link between main chains and orient side groups. If the fixing step is used, a conventional exposure machine can be used without the need for rubbing as in the conventional case, and the manufacturing process of the liquid crystal alignment film can be simplified.
【0014】また、マスクとして偏光膜または回折格子
を介して露光すると、表面に筋状の凸凹を有する液晶配
向膜を高能率に製造できた。Further, when exposure was performed through a polarizing film or a diffraction grating as a mask, a liquid crystal alignment film having streaky irregularities on the surface could be manufactured with high efficiency.
【0015】このとき、偏光膜および回折格子を介して
斜めより露光するか、あるいは偏光膜を介して露光した
後回折格子を介して斜め露光するか、回折格子を介して
露光した後を偏光膜介して斜め露光することで挟み込ん
だ液晶のプレチルト角まで制御できる液晶配向膜を製造
できた。なお、回折格子を介して露光する工程において
は、感光性の被膜の表面が凸凹になるまで露光すること
が配向性を安定化する上で重要であった。At this time, exposure is performed obliquely through a polarizing film and a diffraction grating, or exposure is performed obliquely through a diffraction grating after exposure through a polarizing film, or exposure is performed through a diffraction grating. A liquid crystal alignment film that can control the pretilt angle of the interposed liquid crystal by obliquely exposing through the film was manufactured. In the step of exposing through a diffraction grating, it was important to perform exposure until the surface of the photosensitive film became uneven to stabilize the orientation.
【0016】また、エネルギービームを照射して前記エ
ネルギービーム感応性基を反応架橋する工程の前あるい
は後に加熱して熱反応性基を反応させておくと、液晶の
配向耐熱性が向上した。エネルギービームとして電子
線、X線、または紫外線が利用可能であるが、紫外線の
方が実用性が高かった。Further, when the heat-reactive group is reacted by heating before or after the step of irradiating the energy beam with the energy beam to react and crosslink the energy beam-sensitive group, the alignment heat resistance of the liquid crystal is improved. Electron beams, X-rays, or ultraviolet rays can be used as energy beams, but ultraviolet rays have been more practical.
【0017】エネルギービーム感応性基と熱反応性基を
持つ可視光域で透明な樹脂として、下記に示す化学式で
表される物質を用いれば、紫外線感光性が高く熱架橋反
応も利用できるので液晶配向膜の製造には極めて好都合
であった。When a substance represented by the following chemical formula is used as a transparent resin in the visible light region having an energy beam-sensitive group and a heat-reactive group, the liquid crystal has a high ultraviolet sensitivity and can utilize a thermal crosslinking reaction. It was very convenient for producing an alignment film.
【0018】[0018]
【化2】 Embedded image
【0019】なお、(化2)では、エネルギービーム感
応性のベンザルアセトフェノン基と熱反応性のグリシジ
ル基が側鎖基として導入されており、さらに炭化水素基
(ーCH3)が側鎖基として導入されているので、側鎖
基として炭化水素基を含んでいないものに比べさらに配
向安定性が向上した。また、この場合、透明な樹脂膜の
表面が筋状の1〜100nmの凸凹にななるまで露光す
ることが液晶の配向安定性を向上する上で重要であっ
た。In the chemical formula (2), an energy beam-sensitive benzalacetophenone group and a thermally reactive glycidyl group are introduced as a side chain group, and a hydrocarbon group (--CH 3 ) is further added to the side chain group. As a result, the alignment stability was further improved as compared with those not containing a hydrocarbon group as a side chain group. Further, in this case, it is important to improve the alignment stability of the liquid crystal by exposing the transparent resin film until the surface of the transparent resin film becomes streaky unevenness of 1 to 100 nm.
【0020】以上のような方法で、エネルギービーム感
応性基と熱反応性基を持つ可視光域で透明な樹脂膜が電
極上に直接または任意の薄膜を介して間接的に形成さ
れ、少なくとも前記エネルギービーム感応性基を反応さ
せた被膜よりなるラビングフリーの液晶配向膜を極めて
簡便な方法で製造できた。According to the method described above, a transparent resin film in the visible light region having an energy beam sensitive group and a thermally reactive group is formed directly on the electrode or indirectly through an arbitrary thin film. A rubbing-free liquid crystal alignment film composed of a film reacted with an energy beam-sensitive group could be manufactured by an extremely simple method.
【0021】そこで、実際の表示素子の製造では、あら
かじめマトリックス状に載置された第1の電極群を有す
る第1の基板上に直接または任意の薄膜を介して間接的
にエネルギービーム感応性基と熱反応性基を持つ可視光
域で透明な樹脂膜を塗布形成する工程と、および少なく
とも任意のマスクを介してエネルギービームを照射して
前記エネルギービーム感応性基を反応架橋する工程と、
前記第1の電極群と対向するように載置した第2の電極
叉は電極群を有する第2の基板を、それぞれの電極側が
対向するように位置合わせして接着固定する工程と、前
記第1と第2の基板に所定の液晶を注入する工程を用い
て、エネルギービーム感応性基と熱反応性基を持つ可視
光域で透明な樹脂膜が塗布形成され、少なくとも任意の
マスクを介してエネルギービームを照射して前記エネル
ギービーム感応性基を反応架橋させた被膜が、液晶用の
配向膜として2つの対向する電極の少なくとも一方の電
極上に形成されており、液晶が前記2つの対向する電極
に前記被膜を介して挟まれている構造の液晶表示装置を
極めて高効率で製造できた。Therefore, in the actual manufacture of a display element, the energy beam sensitive substrate is directly or indirectly connected via a thin film on a first substrate having a first electrode group previously mounted in a matrix. A step of applying and forming a transparent resin film in a visible light region having a heat-reactive group, and a step of irradiating an energy beam through at least an arbitrary mask to react and cross-link the energy beam-sensitive group,
Positioning a second substrate having a second electrode or an electrode group placed so as to face the first electrode group so that the respective electrode sides face each other; Using a step of injecting a predetermined liquid crystal into the first and second substrates, a transparent resin film in the visible light region having an energy beam sensitive group and a thermally reactive group is applied and formed, and at least through an arbitrary mask A film formed by irradiating an energy beam to react and crosslink the energy beam-sensitive group is formed on at least one of two opposing electrodes as an alignment film for liquid crystal, and the liquid crystal is exposed to the two opposing electrodes. A liquid crystal display device having a structure sandwiched between the electrodes with the film interposed therebetween could be manufactured with extremely high efficiency.
【0022】次に以下では、本発明の実施の形態におけ
る液晶配向膜について図面を参照しながら詳細に説明す
る。Next, a liquid crystal alignment film according to an embodiment of the present invention will be described in detail with reference to the drawings.
【0023】図1は、本発明の実施の形態における液晶
配向膜の製造工程断面図を示したものであり、以下では
図1(a)〜(d)に沿って本実施の形態を説明するこ
ととする。FIG. 1 is a sectional view showing a manufacturing process of a liquid crystal alignment film according to an embodiment of the present invention. Hereinafter, the present embodiment will be described with reference to FIGS. 1 (a) to 1 (d). It shall be.
【0024】まず、あらかじめ、4’メタクリロイロキ
シカルコン(4’MC)とグリシジルメタアクリレート
(GMA)を1:4のモル比で共重合して、(化2)で
示されるような感光性のベンザルアセトフェノン基と熱
架橋性のグリシジル基およびメチル基が側鎖基として導
入された可視光域で透明な樹脂(すなわち、エネルギー
ビーム感応性基と熱反応性基を持つ樹脂)を作製し、シ
クロヘキサノンで0.5%に希釈して感光液を調製し
た。First, 4 ′ methacryloyloxy chalcone (4 ′ MC) and glycidyl methacrylate (GMA) were previously copolymerized in a molar ratio of 1: 4 to obtain a photosensitive compound represented by the following chemical formula (2). A transparent resin (that is, a resin having an energy beam-sensitive group and a heat-reactive group) in the visible light region in which a glycidyl group and a methyl group capable of being thermally cross-linked with a benzalacetophenone group are introduced as a side group, The solution was diluted to 0.5% with cyclohexanone to prepare a photosensitive solution.
【0025】次に、図1(a)に示すような、あらかじ
め、ITOよりなる透明電極1の形成された所定のガラ
ス基板2の表面に、直接(またはSiO2等の絶縁性の
薄膜を介して間接的にでもよい)ディッピング法(また
はロールコーター、フレキソ印刷法が使用でも可)を用
いて上記の感光液を塗布し図1(b)に示すように感光
性でかつ熱硬化性の被膜3を形成した。Next, as shown in FIG. 1A, a predetermined glass substrate 2 on which a transparent electrode 1 made of ITO is previously formed is directly (or through an insulating thin film such as SiO 2). Or indirectly) using a dipping method (or a roll coater or a flexographic printing method may be used) to apply the above-mentioned photosensitive solution to form a photosensitive and thermosetting film as shown in FIG. 1 (b). 3 was formed.
【0026】その後、100℃で10分間加熱して大部
分の溶媒を蒸発除去した(このときの膜厚はおよそ30
0nmであった)。次に、図1(c)に示すように、1
000本/mmの回折格子4(偏光板を用いても良い
が、その場合には光透過率が悪いので露光時間を長くす
る必要がある)をマスクとして用い、電極パターンと格
子が平行になるようセットして、垂直方向よりエネルギ
ービームとして500Wの超高圧水銀灯の365nm
(i線)の波長の紫外線5(マスク通過後28mJ/c
m2)を5秒間照射して、前記感光性のベンザルアセト
フェノン基を反応架橋させると、回折格子パターン沿っ
て被膜表面にピッチ1000本/mmでおよそ30〜4
0nmの凸凹が形成された。Thereafter, the mixture was heated at 100 ° C. for 10 minutes to evaporate and remove most of the solvent (at this time, the film thickness was about 30 minutes).
0 nm). Next, as shown in FIG.
The electrode pattern and the grating are parallel to each other using a diffraction grating 4 of 000 lines / mm (a polarizing plate may be used, but in that case, the exposure time needs to be increased because the light transmittance is low). With a 500 W ultra-high pressure mercury lamp as an energy beam from the vertical direction at 365 nm
Ultraviolet light 5 of wavelength (i-line) (28 mJ / c after passing through mask)
m 2 ) for 5 seconds to react and crosslink the photosensitive benzal acetophenone group, and the coating surface has a pitch of 1000 / mm along the diffraction grating pattern at a pitch of about 1000 / mm.
The unevenness of 0 nm was formed.
【0027】なお、この時の感光膜の分光感度特性を図
2に示す。この状態で、液晶表示セルを20ミクロンギ
ヤップで組み立て、ネマチック液晶(ZLI4792;
メルク社製)を注入して配向状態を確認すると、回折格
子パターンと交差する方向に液晶が配向していることが
確認できた。また、露光量に応じて注入した液晶のプレ
チルト角を制御できることが確認できた。FIG. 2 shows the spectral sensitivity characteristics of the photosensitive film at this time. In this state, a liquid crystal display cell is assembled with a 20 micron gap, and a nematic liquid crystal (ZLI4792;
(Merck Co., Ltd.) was injected to confirm the orientation state, and it was confirmed that the liquid crystal was oriented in a direction crossing the diffraction grating pattern. It was also confirmed that the pretilt angle of the injected liquid crystal could be controlled according to the exposure amount.
【0028】一方、前述の露光工程において、回折格子
を用いて3秒間露光した後、さらに、市販のUV用偏光
板6(HNP’B;ポラロイド社製)をマスクとして用
い、回折格子パターンと偏光方向が垂直且つ基板に対し
て入射角度が45度の方向になるようセットして、エネ
ルギービームとして500Wの超高圧水銀灯を用いて3
65nm(i線)の波長の紫外線(マスク通過後3mJ
/cm2)を40秒間照射し(図1(d))、前記エネ
ルギービーム感応性基の未反応の残りをさらに反応架橋
させた。On the other hand, in the above-mentioned exposure step, after exposing for 3 seconds using a diffraction grating, a commercially available UV polarizing plate 6 (HNP'B; manufactured by Polaroid) is used as a mask, and the diffraction grating pattern and polarization Using a 500 W ultra-high pressure mercury lamp as an energy beam, the direction was set so that the direction was perpendicular and the incident angle was 45 degrees with respect to the substrate.
UV light with a wavelength of 65 nm (i-line) (3 mJ after passing through the mask)
/ Cm 2 ) for 40 seconds (FIG. 1 (d)), and the unreacted residue of the energy beam-sensitive group was further reacted and cross-linked.
【0029】この状態で、液晶表示セルを組み立て、ネ
マチック液晶を注入して配向状態を確認すると、格子パ
ターンの方向に液晶が配向して、プレチルト角はおよそ
20度になっていることが確認できた。また、この2回
目の照射において照射角度を変えることで注入した液晶
のプレチルト角を制御できることも確認できた。なお、
上記2つのプロセスで作製された配向膜はそのままでも
それぞれ配向膜として利用可能であったが、150℃程
度で熱処理すると配向膜の配向性が劣化した。In this state, the liquid crystal display cell was assembled, nematic liquid crystal was injected, and the alignment state was confirmed. It was confirmed that the liquid crystal was oriented in the direction of the lattice pattern and the pretilt angle was about 20 degrees. Was. It was also confirmed that the pretilt angle of the injected liquid crystal could be controlled by changing the irradiation angle in the second irradiation. In addition,
Although the alignment films produced by the above two processes could be used as alignment films as they were, heat treatment at about 150 ° C. deteriorated the alignment properties of the alignment films.
【0030】そこで、さらに配向膜の熱安定製を向上さ
せるため180℃で10分加熱して熱反応性のグリシジ
ル基(すなわち熱硬化性基)を開環架橋させた。この状
態で、液晶表示セルを組み立て、ネマチック液晶を注入
して配向状態を確認すると、格子パターンと垂直の方向
に液晶が配向して、プレチルト角はおよそ7度になって
いた。また、配向膜の熱安定性も170℃まで向上して
た。Then, in order to further improve the thermal stability of the alignment film, the alignment layer was heated at 180 ° C. for 10 minutes to ring-open and crosslink the thermally reactive glycidyl group (ie, thermosetting group). In this state, the liquid crystal display cell was assembled, nematic liquid crystal was injected, and the alignment state was confirmed. The liquid crystal was aligned in a direction perpendicular to the lattice pattern, and the pretilt angle was about 7 degrees. Further, the thermal stability of the alignment film was improved to 170 ° C.
【0031】なお、このときの感光性で且つ熱硬化性の
被膜の露光による反応および加熱による反応は、下記の
反応式に示したように、いずれも架橋反応である。The reaction by exposure of the photosensitive and thermosetting coating and the reaction by heating at this time are both crosslinking reactions as shown in the following reaction formula.
【0032】[0032]
【化3】 Embedded image
【0033】さらに炭化水素基(−CH3)を含まない
ものも合成して同様の実験を試みたが、液晶の配向制御
性特にプレチルト角制御安定性は−CH3を含むものに
比べて悪かった。Further, the same experiment was attempted by synthesizing a compound containing no hydrocarbon group (-CH 3 ), but the alignment controllability of the liquid crystal, especially the pretilt angle control stability, was worse than that containing -CH 3. Was.
【0034】以上のように、本実施の形態の被膜では、
エネルギービーム感応性基が感光性基であり、マスクを
介して光を照射して前記被膜内の感光性基を反応させ、
主鎖間を架橋するとともに側鎖基を配向固定できた。ま
た、i線に感度があるため(図2参照)通常の露光機が
使用可能となり液晶配向膜の製造工程が簡略化できた。As described above, in the coating of the present embodiment,
The energy beam-sensitive group is a photosensitive group, and reacts with the photosensitive group in the coating by irradiating light through a mask,
Cross-linking between the main chains and the orientation of the side chain groups could be fixed. In addition, since there is sensitivity to i-line (see FIG. 2), a normal exposure machine can be used, and the manufacturing process of the liquid crystal alignment film can be simplified.
【0035】また、マスクとして偏光膜または回折格子
を介して露光することで被膜表面に筋状の凸凹を有する
液晶配向膜を容易に製造できた。Further, by exposing through a polarizing film or a diffraction grating as a mask, a liquid crystal alignment film having streaky irregularities on the film surface could be easily produced.
【0036】さらに、このとき露光量、あるいは偏光膜
および回折格子を介して斜めより露光するか、あるいは
偏光膜を介して斜めに露光した後回折格子を介して露光
するか、回折格子を介して露光した後を偏光膜介して斜
め露光することで挟み込んだ液晶のプレチルト角まで制
御でき、また、そのようにして配向性の安定した液晶配
向膜を製造できた。なお、1回露光でプレチルト角を安
定に制御するためには、感光性の被膜の表面が所定の凸
凹になるまで露光することが重要であった。Further, at this time, the amount of exposure, or the oblique exposure through the polarizing film and the diffraction grating, the oblique exposure through the polarizing film and then the exposure through the diffraction grating, or the exposure through the diffraction grating By performing the oblique exposure after the exposure through the polarizing film, the pretilt angle of the sandwiched liquid crystal could be controlled, and a liquid crystal alignment film having stable alignment could be manufactured. In order to stably control the pretilt angle in a single exposure, it was important to perform exposure until the surface of the photosensitive film became a predetermined unevenness.
【0037】また、エネルギービームを照射して前記エ
ネルギービーム感応性基を反応架橋する工程の前あるい
は後に加熱して熱反応性基を反応させておくと、配向膜
の配向耐熱性が向上した。また、エネルギービームとし
て電子線、X線、または紫外線が利用可能であるが、実
際の製造工程では紫外線の方が実用性が高かった。Further, when the heat-reactive group is reacted by heating before or after the step of irradiating the energy beam with the energy beam-sensitive group to react and crosslink the energy beam-sensitive group, the alignment film has improved alignment heat resistance. In addition, electron beams, X-rays, or ultraviolet rays can be used as energy beams, but ultraviolet rays were more practical in actual manufacturing processes.
【0038】以上のように、エネルギービーム感応性基
と熱反応性基を持つ可視光域で透明な樹脂膜が電極上に
直接または任意の薄膜を介して間接的に形成され、少な
くとも前記エネルギービーム感応性基を反応させた被膜
よりなるラビングフリーの液晶配向膜を極めて簡便な方
法で製造できた。As described above, a transparent resin film in the visible light region having an energy beam sensitive group and a thermally reactive group is formed directly on the electrode or indirectly through an arbitrary thin film. A rubbing-free liquid crystal alignment film composed of a film having a sensitive group reacted was produced by an extremely simple method.
【0039】次に、以下では上記した液晶配向膜を用い
た液晶表示デバイス及びその製造方法について図3を参
照しながら詳細に説明する。Next, a liquid crystal display device using the above liquid crystal alignment film and a method for manufacturing the same will be described in detail with reference to FIG.
【0040】まず、あらかじめ(化2)で示されるエネ
ルギービーム感応性基と熱反応性基を持つ可視光域で透
明な樹脂をシクロヘキサノンで0.5%に希釈して調製
した感光液を作製し、図3に示すように、マトリックス
状に載置された第1の電極群11とこの電極を駆動する
トランジスター群12を有する第1の基板13上、およ
び第1の電極群と対向するように載置したカラーフィル
ター群14と第2の電極15を有する第2の基板16上
の両方の電極上に、それぞれディッピング法を用いて塗
布し感光性で且つ熱硬化性の樹脂被膜を形成した。First, a photosensitive liquid was prepared by previously diluting a transparent resin in the visible light region having an energy beam-sensitive group and a heat-reactive group represented by (Chemical Formula 2) to 0.5% with cyclohexanone. As shown in FIG. 3, on a first substrate 13 having a first electrode group 11 mounted in a matrix and a transistor group 12 for driving the electrodes, and facing the first electrode group. A photosensitive and thermosetting resin film was formed on both electrodes on the second substrate 16 having the mounted color filter group 14 and the second electrode 15 by dipping.
【0041】その後、100℃で10分間加熱してある
程度溶媒を除去し後、1000本/mmの回折格子をマ
スクとして用い、電極パターンと格子が平行になるよう
セットして、垂直方向よりエネルギービームとして50
0Wの超高圧水銀灯を用いて365nm(i線)の波長
の紫外線(マスク通過後28mJ/cm2)を5秒照射
して前記エネルギービーム感応性のベンザルアセトフェ
ノン基を反応架橋すると、電極パターンに沿っておよそ
30〜40nmの凸凹が形成された液晶配向膜17が作
製できた。After heating at 100 ° C. for 10 minutes to remove a certain amount of the solvent, the electrode pattern and the grating were set in parallel using a 1000 / mm diffraction grating as a mask. As 50
Ultraviolet light of a wavelength of 365 nm (i-line) (28 mJ / cm 2 after passing through a mask) was irradiated for 5 seconds using an ultrahigh pressure mercury lamp of 0 W for 5 seconds to react and crosslink the energy beam-sensitive benzalacetophenone group. Thus, a liquid crystal alignment film 17 having irregularities of about 30 to 40 nm was formed.
【0042】次に、前記第1と第2の基板13、16を
対抗するように位置合わせしてスペーサー18と接着剤
19でおよそ5ミクロンのギャップで固定した。その
後、前記第1と第2の基板に前記液晶20を注入した
後、偏光板21、22を組み合わせて表示素子を完成し
た。Next, the first and second substrates 13 and 16 were aligned so as to oppose each other, and were fixed with a spacer 18 and an adhesive 19 with a gap of about 5 μm. Then, after injecting the liquid crystal 20 into the first and second substrates, the display device was completed by combining the polarizing plates 21 and 22.
【0043】この様なデバイスは、バックライト23を
全面に照射しながら、ビデオ信号を用いて各々のトラン
ジスタを駆動することで矢印Aの方向に映像を表示でき
た。In such a device, an image can be displayed in the direction of arrow A by driving each transistor using a video signal while irradiating the backlight 23 over the entire surface.
【0044】[0044]
【発明の効果】以上述べてきたように、本発明の液晶配
向膜は、電極の形成された所定の基板表面に直接または
任意の薄膜を介して間接的にエネルギービーム感応性基
と熱反応性基を持つ可視光域で透明な樹脂膜を塗布形成
する工程、および少なくとも任意のマスクを介してエネ
ルギービームを照射して前記エネルギービーム感応性基
を反応架橋する工程を用いているため、高能率で均一且
つ極めて薄い配向膜を作製できる。As described above, the liquid crystal alignment film of the present invention can be directly or indirectly indirectly through an arbitrary thin film on the surface of a predetermined substrate on which an electrode is formed. A step of applying and forming a transparent resin film in a visible light region having a group, and a step of irradiating an energy beam through at least an arbitrary mask to react and crosslink the energy beam-sensitive group; Thus, a uniform and extremely thin alignment film can be produced.
【0045】また、このような液晶配向膜を用いること
で、従来のようなラビング工程を必要とせず、歩留まり
が高く極めて低コスト高信頼性の液晶表示装置を提供で
きる。Further, by using such a liquid crystal alignment film, it is possible to provide a liquid crystal display device having a high yield, extremely low cost and high reliability without requiring a rubbing step as in the conventional case.
【図1】本発明の実施の形態における液晶配向膜の製造
工程断面図FIG. 1 is a cross-sectional view illustrating a manufacturing process of a liquid crystal alignment film according to an embodiment of the present invention.
【図2】本発明の実施の形態における液晶配向膜中の感
光性且つ熱硬化性樹脂の分光感度特性を示す図FIG. 2 is a diagram showing spectral sensitivity characteristics of a photosensitive and thermosetting resin in a liquid crystal alignment film according to an embodiment of the present invention.
【図3】本発明の実施の形態における液晶表示デバイス
の断面図FIG. 3 is a cross-sectional view of the liquid crystal display device according to the embodiment of the present invention.
1 電極 2 ガラス板 3 感光性且つ熱硬化性の樹脂膜 4 回折格子マスク 5 紫外光 6 偏光板マスク 11 第1の電極群 12 トランジスタ群 13 第1の基板 14 カラーフィルター群 15 第2の電極 16 第2の基板 17 ラビングフリー液晶配向膜 18 スぺーサー 19 接着剤 20 液晶 21,22 偏光板 23 バックライト Reference Signs List 1 electrode 2 glass plate 3 photosensitive and thermosetting resin film 4 diffraction grating mask 5 ultraviolet light 6 polarizing plate mask 11 first electrode group 12 transistor group 13 first substrate 14 color filter group 15 second electrode 16 Second substrate 17 Rubbing-free liquid crystal alignment film 18 Spacer 19 Adhesive 20 Liquid crystal 21, 22 Polarizing plate 23 Backlight
Claims (13)
を有し、可視光域で透明な樹脂膜が電極上に直接または
任意の薄膜を介して間接的に形成され、少なくとも前記
エネルギービーム感応性基を反応架橋されていることを
特徴とする液晶配向膜。1. A resin film having an energy beam-sensitive group and a heat-reactive group and transparent in a visible light region is formed directly or indirectly through an arbitrary thin film on an electrode, A liquid crystal alignment film characterized in that a reactive group is reactively crosslinked.
基及び熱反応性基が側鎖基として導入されていることを
特徴とする請求項1記載の液晶配向膜。2. The liquid crystal alignment film according to claim 1, wherein an energy beam sensitive group and a heat reactive group are introduced as a side chain group in the resin film.
基、熱反応性基及び炭化水素基が側鎖基として導入され
ていることを特徴とする請求項1記載の液晶配向膜。3. The liquid crystal alignment film according to claim 1, wherein an energy beam sensitive group, a heat reactive group, and a hydrocarbon group are introduced as a side chain group in the resin film.
ることを特徴とする請求項1記載の液晶配向膜。4. The liquid crystal alignment film according to claim 1, wherein the surface of the resin film is formed with streaks.
徴とする請求項1〜4いずれかに記載の液晶配向膜。5. The liquid crystal alignment film according to claim 1, wherein the thermoreactive group is reactively crosslinked.
を用いることを特徴とする請求項1記載の液晶配向膜。 【化1】 6. The liquid crystal alignment film according to claim 1, wherein a substance represented by the following chemical formula is used as the resin film. Embedded image
たは任意の薄膜を介して間接的に、エネルギービーム感
応性基及び熱反応性基を有する可視光域で透明な樹脂膜
を塗布形成する工程と、少なくとも任意のマスクを介し
てエネルギービームを前記樹脂膜に照射して前記エネル
ギービーム感応性基を反応架橋する工程とを有する液晶
配向膜の製造方法。7. A transparent resin film in the visible light region having an energy beam-sensitive group and a heat-reactive group is applied and formed directly or indirectly through an arbitrary thin film on a predetermined substrate surface on which electrodes are formed. And irradiating the resin film with an energy beam through at least an arbitrary mask to react and crosslink the energy beam-sensitive group.
工程の前あるいは後に加熱により熱反応性基を反応架橋
させる工程を付加したことを特徴とする請求項7記載の
液晶配向膜の製造方法。8. The method for producing a liquid crystal alignment film according to claim 7, wherein a step of reacting and crosslinking the heat reactive group by heating is added before or after the step of reacting and crosslinking the energy beam sensitive group.
り、マスクを介して紫外線を照射して樹脂膜内の感光性
基を反応させ、主鎖間を架橋するとともに側鎖基を配向
固定することを特徴とする請求項7記載の液晶配向膜の
製造方法。9. The energy beam-sensitive group is a photosensitive group, and is irradiated with ultraviolet rays through a mask to react the photosensitive group in the resin film, thereby to crosslink between main chains and to fix side chain groups. The method for producing a liquid crystal alignment film according to claim 7, wherein:
いて露光することを特徴とする請求項7記載の液晶配向
膜の製造方法。10. The method according to claim 7, wherein the exposure is performed using a polarizing film or a diffraction grating as a mask.
まで露光を行うことを特徴とする請求項7記載の液晶配
向膜の製造方法。11. The method according to claim 7, wherein the exposure is performed until the surface of the resin film becomes uneven.
基を有し、可視光域で透明な樹脂膜が電極上に直接また
は任意の薄膜を介して間接的に形成され、少なくとも前
記エネルギービーム感応性基を反応架橋されている液晶
配向膜が2つの対向する電極の少なくとも一方の電極上
に形成されており、液晶が前記2つの対向する電極に前
記樹脂膜を介して挟まれていることを特徴とする液晶表
示装置。12. A resin film having an energy beam-sensitive group and a heat-reactive group and transparent in a visible light region is formed directly or indirectly through an arbitrary thin film on an electrode. A liquid crystal alignment film having a reactive group cross-linked by reaction is formed on at least one of the two opposing electrodes, and the liquid crystal is sandwiched between the two opposing electrodes via the resin film. Characteristic liquid crystal display device.
群を有する第1の基板上に直接または任意の薄膜を介し
て間接的にエネルギービーム感応性基及び熱反応性基を
有し可視光域で透明な樹脂膜を塗布形成する工程と、少
なくとも任意のマスクを介してエネルギービームを照射
して前記エネルギービーム感応性基を反応架橋させる工
程と、前記第1の電極群と対向するように載置した第2
の電極叉は電極群を有する第2の基板をそれぞれの電極
側が対向するように位置合わせして接着固定する工程
と、前記第1と第2の基板に所定の液晶を注入する工程
とを有する液晶表示装置の製造方法。13. A first substrate having a first electrode group placed in a matrix and having an energy beam sensitive group and a thermally reactive group directly or indirectly through an arbitrary thin film on a first substrate. A step of applying a transparent resin film in an optical region, a step of irradiating an energy beam through at least an arbitrary mask to react and crosslink the energy beam-sensitive group, and a step of facing the first electrode group. The second placed on
A step of positioning and bonding and fixing a second substrate having an electrode or an electrode group such that the respective electrode sides face each other, and a step of injecting a predetermined liquid crystal into the first and second substrates. A method for manufacturing a liquid crystal display device.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18032796A JP3264477B2 (en) | 1996-07-10 | 1996-07-10 | Liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display device, and method for manufacturing liquid crystal display device |
TW086109496A TW515926B (en) | 1996-07-10 | 1997-07-05 | Liquid crystal alignment film and method for producing the same, and liquid crystal display apparatus using the same and method for producing the same |
CNB971912211A CN1149437C (en) | 1996-07-10 | 1997-07-07 | Liquid crystal alignment film, method for mfg. same, liquid crystal display using the film and method, and method for mfg. for display |
KR1019980701804A KR100258847B1 (en) | 1996-07-10 | 1997-07-07 | Liquid crystal alignment film, method manufacturing the film, liquid crystal display using the film and method, and method of manufacturing the liquid crystal |
US09/029,870 US6368681B1 (en) | 1996-07-10 | 1997-07-07 | Liquid crystal alignment film, method of manufacturing the film, liquid crystal display using the film and method, and method of manufacturing the liquid crystal display |
PCT/JP1997/002354 WO1998001789A1 (en) | 1996-07-10 | 1997-07-07 | Liquid crystal alignment film, method of manufacturing the film, liquid crystal display using the film and method, and method of manufacturing the liquid crystal display |
JP36720499A JP3468507B2 (en) | 1996-07-10 | 1999-12-24 | Liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display device, and method for manufacturing liquid crystal display device |
US10/010,537 US20020054965A1 (en) | 1996-07-10 | 2001-12-05 | Liquid crystal alignment film and method for producing the same, and liquid crystal display apparatus using the same and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18032796A JP3264477B2 (en) | 1996-07-10 | 1996-07-10 | Liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display device, and method for manufacturing liquid crystal display device |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP36720499A Division JP3468507B2 (en) | 1996-07-10 | 1999-12-24 | Liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display device, and method for manufacturing liquid crystal display device |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH1026760A true JPH1026760A (en) | 1998-01-27 |
JP3264477B2 JP3264477B2 (en) | 2002-03-11 |
Family
ID=16081282
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18032796A Expired - Lifetime JP3264477B2 (en) | 1996-07-10 | 1996-07-10 | Liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display device, and method for manufacturing liquid crystal display device |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3264477B2 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001172342A (en) * | 1999-12-17 | 2001-06-26 | Nitto Denko Corp | Cholesteric liquid crystal composition, oriented film and pleochroism reflector plate |
GB2366874A (en) * | 2000-06-26 | 2002-03-20 | Ibm | Liquid Crystal Display |
JP2002098969A (en) * | 2000-09-26 | 2002-04-05 | Konica Corp | Method for manufacturing optical alignment layer |
KR100447780B1 (en) * | 2000-11-14 | 2004-09-08 | 마쯔시다덴기산교 가부시키가이샤 | Chemical adsorption solution and method of producing chemically adsorbed film using the chemical adsorption solution |
CN1308755C (en) * | 2003-09-04 | 2007-04-04 | 精工爱普生株式会社 | Orientation film forming method,orientation film,substrate for electronic device,liquid crystal panel |
JP2009512903A (en) * | 2005-11-07 | 2009-03-26 | エルジー・ケム・リミテッド | Liquid crystal alignment copolymer, liquid crystal alignment film including the same, and liquid crystal display including the same |
KR101184064B1 (en) * | 2005-06-23 | 2012-09-21 | 엘지디스플레이 주식회사 | Apparatus For Fabricating Alignment Film and Method For Fabricating Liquid Crystal Display Panel Using the same |
-
1996
- 1996-07-10 JP JP18032796A patent/JP3264477B2/en not_active Expired - Lifetime
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001172342A (en) * | 1999-12-17 | 2001-06-26 | Nitto Denko Corp | Cholesteric liquid crystal composition, oriented film and pleochroism reflector plate |
GB2366874A (en) * | 2000-06-26 | 2002-03-20 | Ibm | Liquid Crystal Display |
GB2366874B (en) * | 2000-06-26 | 2004-04-28 | Ibm | Liquid crystal display |
JP2002098969A (en) * | 2000-09-26 | 2002-04-05 | Konica Corp | Method for manufacturing optical alignment layer |
JP4626039B2 (en) * | 2000-09-26 | 2011-02-02 | コニカミノルタホールディングス株式会社 | Method for producing photo-alignment layer |
KR100447780B1 (en) * | 2000-11-14 | 2004-09-08 | 마쯔시다덴기산교 가부시키가이샤 | Chemical adsorption solution and method of producing chemically adsorbed film using the chemical adsorption solution |
CN1308755C (en) * | 2003-09-04 | 2007-04-04 | 精工爱普生株式会社 | Orientation film forming method,orientation film,substrate for electronic device,liquid crystal panel |
KR101184064B1 (en) * | 2005-06-23 | 2012-09-21 | 엘지디스플레이 주식회사 | Apparatus For Fabricating Alignment Film and Method For Fabricating Liquid Crystal Display Panel Using the same |
JP2009512903A (en) * | 2005-11-07 | 2009-03-26 | エルジー・ケム・リミテッド | Liquid crystal alignment copolymer, liquid crystal alignment film including the same, and liquid crystal display including the same |
JP4647694B2 (en) * | 2005-11-07 | 2011-03-09 | エルジー・ケム・リミテッド | Liquid crystal alignment copolymer, liquid crystal alignment film including the same, and liquid crystal display including the same |
US8123977B2 (en) | 2005-11-07 | 2012-02-28 | Lg Chem, Ltd. | Copolymer for liquid crystal alignment, liquid crystal aligning layer including copolymer for liquid crystal alignment, and liquid crystal display including liquid crystal aligning layer |
Also Published As
Publication number | Publication date |
---|---|
JP3264477B2 (en) | 2002-03-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100258847B1 (en) | Liquid crystal alignment film, method manufacturing the film, liquid crystal display using the film and method, and method of manufacturing the liquid crystal | |
US6184959B1 (en) | Liquid crystal display device having alignment film that provides alignment upon irradiation and manufacturing method the same | |
US9405152B2 (en) | Liquid crystal display and method for manufacturing same | |
US8696950B2 (en) | Liquid crystal display device and method for manufacturing the same | |
US7442494B2 (en) | Method for forming alignment layer and method for manufacturing liquid crystal display device using the same | |
JP3178773B2 (en) | Liquid crystal display device and method of manufacturing the same | |
JPH08254705A (en) | Uv ray curing compound, oriented film for liquid crystal display element and liquid crystal display element | |
JPH0743689A (en) | Information display device and its production | |
US8491973B2 (en) | Photo-alignment material and liquid crystal display device and its manufacturing method using the same | |
JP2002023164A (en) | Method for liquid crystal displaying, liquid crystal display device and device for manufacturing the same | |
JP3264477B2 (en) | Liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display device, and method for manufacturing liquid crystal display device | |
KR20090112089A (en) | Method of manufacturing liquid crystal display | |
JPH11305256A (en) | Active matrix type liquid crystal display device | |
US7067224B2 (en) | Method for fabricating a liquid crystal display device | |
JP4342168B2 (en) | Liquid crystal display device and manufacturing method thereof | |
JP3468507B2 (en) | Liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display device, and method for manufacturing liquid crystal display device | |
JP3107534B2 (en) | Liquid crystal display device and method of manufacturing the same | |
JP2000162615A (en) | Production of liquid crystal device, exposure mask and aligner | |
JP3414189B2 (en) | Reflection type color filter and method of manufacturing the same | |
KR101097537B1 (en) | fabrication method for in-plane switching mode LCD | |
US7060420B2 (en) | Fabrication method for liquid crystal display | |
JP2000227595A (en) | Production of liquid crystal display device | |
US7327425B2 (en) | Method of forming an alignment layer and an overcoat layer in a stack structure on a substrate of a liquid crystal display by separating a mixture of an alignment layer material from an overcoat layer material in a thermal curing treatment | |
JP2002309103A (en) | Liquid crystalline composition, color filter, and liquid crystal display device | |
JP3303856B2 (en) | Liquid crystal display panel and manufacturing method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071228 Year of fee payment: 6 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081228 Year of fee payment: 7 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091228 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091228 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101228 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101228 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111228 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111228 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121228 Year of fee payment: 11 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121228 Year of fee payment: 11 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131228 Year of fee payment: 12 |
|
EXPY | Cancellation because of completion of term |