JPH095759A - Liquid crystal sealing material and liquid crystal display device - Google Patents
Liquid crystal sealing material and liquid crystal display deviceInfo
- Publication number
- JPH095759A JPH095759A JP7156200A JP15620095A JPH095759A JP H095759 A JPH095759 A JP H095759A JP 7156200 A JP7156200 A JP 7156200A JP 15620095 A JP15620095 A JP 15620095A JP H095759 A JPH095759 A JP H095759A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- sealing material
- crystal display
- meth
- display panel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Liquid Crystal (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、多くの電子機器の表示
装置として用いることのできる液晶表示装置の液晶表示
パネル用の液晶シール材、ならびにこの液晶シール材に
よりシールされた液晶表示パネルを有してなる液晶表示
装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a liquid crystal sealing material for a liquid crystal display panel of a liquid crystal display device which can be used as a display device of many electronic devices, and a liquid crystal display panel sealed by this liquid crystal sealing material. The present invention relates to a liquid crystal display device.
【０００２】[0002]
【従来の技術】２枚の配向処理を施した透明電極付き基
板の間隙に液晶を封止してなる液晶表示パネルを有する
液晶表示装置に関して、前記２枚の基板を接着し、液晶
を封止する目的で使用されている液晶シール材（以下、
単にシール材と略称する）には、熱硬化型の１液タイプ
のエポキシ樹脂（三井東圧化学工業株式会社製“ストラ
クトボンドＸＮ−２１−Ｆ”）がよく知られている。2. Description of the Related Art A liquid crystal display device having a liquid crystal display panel in which liquid crystal is sealed in a gap between two substrates with transparent electrodes which have been subjected to alignment treatment, and the two substrates are adhered to each other to seal the liquid crystal. Liquid crystal sealing material used for the purpose (hereinafter,
A thermosetting one-pack type epoxy resin (“Structbond XN-21-F” manufactured by Mitsui Toatsu Chemicals, Inc.) is well known as a sealing material.
【０００３】この熱硬化型のエポキシ樹脂を成分とする
シール材は、硬化時にシール材の粘度が低下し、予め位
置合わせして貼合わせた２枚の基板間に横方向の位置ず
れ、すなわち基板のアライメントずれが生じたり、硬化
に必要な温度が約１５０℃と高いため基板にソリが生じ
たり、硬化時間が長い等の問題があり、歩留まりの低下
や、作業効率の低下、液晶表示装置の表示品位の低下を
引き起こしていた。The sealing material containing the thermosetting epoxy resin as a component has a reduced viscosity of the sealing material at the time of curing, and a lateral displacement between the two substrates previously aligned and bonded together, that is, the substrates. Misalignment occurs, the temperature required for curing is as high as about 150 ° C., and there are problems such as warping of the substrate and long curing time, which causes a decrease in yield, a decrease in work efficiency, and a liquid crystal display device. This caused a deterioration in display quality.
【０００４】こうした問題を解決するために、紫外線硬
化型、あるいは、紫外線硬化成分と熱硬化成分との併用
型シール材を使用する方法がある。まず、紫外線硬化型
のシール材としては、硬化機構がラジカル重合である
（メタ）アクリル酸系モノマーを含むものが一般的であ
る。［ここで“（メタ）アクリル……”とは“アクリル
……”及び／または“メタアクリル……”を意味するも
のであり、本発明においても同様の意味で使用され
る。］。しかし、ラジカル重合では、紫外線硬化時の硬
化収縮が大きいため、接着性、液晶パネルの耐湿性に大
きな問題がある。こうした硬化収縮を防止するために特
開平７ー１３１７３号や特開平７ー１３１７４号公報に
は変性ウレタンアクリレートを使用することも提案され
ている。In order to solve such a problem, there is a method of using an ultraviolet curable type or a combination type sealant of an ultraviolet curable component and a thermosetting component. First, as the ultraviolet curable sealant, a sealant containing a (meth) acrylic acid-based monomer whose curing mechanism is radical polymerization is generally used. [Here, "(meth) acryl ..." means "acryl ..." and / or "methacryl ...", and is used in the same meaning in the present invention. ]. However, radical polymerization causes a large problem in adhesiveness and moisture resistance of the liquid crystal panel because the curing shrinkage during ultraviolet curing is large. In order to prevent such curing shrinkage, JP-A-7-13173 and JP-A-7-13174 propose to use a modified urethane acrylate.
【０００５】次に、紫外線硬化成分と熱硬化成分との併
用型のシール材に関しては、紫外線硬化成分に（メタ）
アクリル酸系モノマーを、また、熱硬化成分にエポキシ
樹脂を使用している市販品（例えば、協立化学産業株式
会社製“ワールドロックＸ−８７００”）あるいは特開
平７ー１３１７５号等が知られている。Next, regarding the combination type sealing material of the ultraviolet curable component and the thermosetting component, the (meth) ultraviolet curable component is used.
Commercially available products using an acrylic acid-based monomer and an epoxy resin as a thermosetting component (for example, "World Rock X-8700" manufactured by Kyoritsu Chemical Industry Co., Ltd.) or JP-A-7-13175 are known. ing.
【０００６】さらに、配向処理を施した電極付き基板に
シール材を形成する工程と、対向する基板とをスペーサ
ー手段を介して貼合わせる工程との間で液晶を滴下注入
する工程を設ける滴下工法で製造される液晶パネルにお
いては、未硬化のシール材と液晶が接するため、ラジカ
ル重合機構で重合する紫外線硬化が可能なシール材が必
要となる。ここでもしカチオン重合機構で重合するモノ
マーやオリゴマーを使用する場合には、シール材に光開
始剤としてカチオン系のものを使用するため、液晶中に
イオン成分が溶出し、液晶の配向不良、電流値の増加等
の問題が発生する。そこで、液晶と接する側にラジカル
重合機構で重合する紫外線硬化型シール材、その周囲に
エポキシ系のシール材を使用する二重シール方式が特開
昭６２ー８９０２５号により提案されている。Further, a dropping method is provided in which a step of dropping and injecting liquid crystal is provided between a step of forming a sealing material on the substrate with an electrode subjected to the alignment treatment and a step of adhering the facing substrate via a spacer means. In the manufactured liquid crystal panel, since the uncured sealing material and the liquid crystal are in contact with each other, a sealing material that can be cured by ultraviolet rays and polymerizes by a radical polymerization mechanism is required. If a monomer or oligomer that is polymerized by a cationic polymerization mechanism is used here, a cation-based photoinitiator is used as the sealant, so that the ionic component is eluted in the liquid crystal, which results in poor alignment of the liquid crystal and current. Problems such as increase in value occur. Therefore, Japanese Patent Laid-Open No. 89025/1987 proposes a double seal system in which an ultraviolet-curable sealing material that polymerizes by a radical polymerization mechanism is used on the side in contact with the liquid crystal, and an epoxy-based sealing material is used around it.
【０００７】[0007]
【発明が解決しようとする課題】上記、紫外線硬化型の
シール材に関して、ラジカル重合の硬化機構を有する
（メタ）アクリル酸系モノマーから形成される樹脂を使
用した場合、硬化時の硬化収縮が大きいために接着性、
液晶パネルの耐湿性の不良といった課題が発生する。こ
うした課題を解決するために特開平７ー１３１７３号や
特開平７ー１３１７４号で提案されているように、ウレ
タンアクリレートを含むことにより硬化収縮を防止し、
基板との密着性を改善し、接着性、耐湿性の向上を図る
方法がある。しかしウレタンアクリレートは、熱膨張が
起こり耐熱性に弱い。とくに、液晶表示装置の表示の面
内均一化をはかるために行われているアニール工程で
は、アニール温度を液晶のネマチック−アイソトロピッ
ク相転移温度（通常８０℃から１２０℃）以上で行うた
めに、ウレタンアクリレートを含むシール材の膨張が発
生し、かかる液晶パネルを備えた液晶表示装置の液晶パ
ネルシール部分周辺でギャップ高による閾値電圧むらが
発生するといった課題が生じる。With respect to the above-mentioned UV-curable sealing material, when a resin formed from a (meth) acrylic acid type monomer having a radical polymerization curing mechanism is used, curing shrinkage during curing is large. For adhesiveness,
Problems such as poor moisture resistance of the liquid crystal panel occur. In order to solve these problems, as proposed in JP-A-7-13173 and JP-A-7-13174, curing shrinkage is prevented by containing urethane acrylate,
There is a method of improving the adhesion with a substrate to improve the adhesion and the moisture resistance. However, urethane acrylate undergoes thermal expansion and is weak in heat resistance. In particular, in the annealing process performed for the purpose of uniforming the in-plane display of the liquid crystal display device, since the annealing temperature is performed at the nematic-isotropic phase transition temperature of the liquid crystal (usually 80 ° C. to 120 ° C.), There is a problem in that the sealing material containing urethane acrylate expands, and a threshold voltage unevenness occurs due to a gap height around the liquid crystal panel sealing portion of a liquid crystal display device including such a liquid crystal panel.
【０００８】また、紫外線硬化成分と熱硬化成分との併
用型シール材に関しては、その紫外線硬化成分に（メ
タ）アクリル酸系モノマーから重合される樹脂、熱硬化
成分にエポキシ樹脂を使用していることから、紫外線硬
化時にエポキシ樹脂が（メタ）アクリル酸系モノマーの
ラジカル重合を阻害し、十分な重合を得るのに、大きな
紫外線エネルギーが必要となる。また、熱硬化成分がエ
ポキシ樹脂であることから、高温で長時間の熱硬化が必
要となり、生産上ガラス基板のそり等の問題から歩留ま
りが低下する危険性がある。Further, regarding the combination type sealing material of the ultraviolet curing component and the thermosetting component, a resin polymerized from a (meth) acrylic acid type monomer is used as the ultraviolet curing component and an epoxy resin is used as the thermosetting component. Therefore, a large amount of ultraviolet energy is required for the epoxy resin to inhibit radical polymerization of the (meth) acrylic acid-based monomer during ultraviolet curing and to obtain sufficient polymerization. In addition, since the thermosetting component is an epoxy resin, it is necessary to perform thermosetting at a high temperature for a long time, and there is a risk that the yield will decrease due to problems such as warpage of the glass substrate in production.
【０００９】さらに、上記の滴下工法では、二重シール
方式を採用しているが、この二重シール方式では、シー
ル幅が通常の２倍必要となり、それだけ液晶パネルの表
示部として実質的に使用できる面積が狭くなり、液晶パ
ネルの製品設計上大きな制約を与えることとなる。ここ
で前記紫外線硬化成分と熱硬化成分との併用型シール材
を使用する場合、熱硬化成分であるエポキシ樹脂が（メ
タ）アクリル酸系モノマーの紫外線によるラジカル重合
を阻害するために、十分な重合の進行が達成されないこ
とから、その後の熱硬化時に未反応のエポキシ樹脂が液
晶中に溶出し、液晶の配向不良を引き起こすこととな
る。Further, in the above dropping method, a double seal system is adopted, but this double seal system requires a seal width twice as much as usual, and that is substantially used as a display portion of a liquid crystal panel. The area that can be formed becomes narrower, which will be a great constraint on the product design of the liquid crystal panel. Here, when using the combination type sealant of the ultraviolet curing component and the thermosetting component, the epoxy resin which is the thermosetting component inhibits radical polymerization of the (meth) acrylic acid-based monomer by ultraviolet rays, and therefore, sufficient polymerization is performed. Is not achieved, the unreacted epoxy resin is eluted into the liquid crystal during the subsequent heat curing, which causes poor alignment of the liquid crystal.
【００１０】本発明は、紫外線硬化成分と熱硬化成分と
の併用型のシール材が、その重合されるモノマーないし
オリゴマー成分としてラジカル重合機構で重合する（メ
タ）アクリル酸系モノマーないしオリゴマーだけを含有
させることにより、シール材のこれらの問題点を解決
し、接着性、液晶パネルの耐湿性に優れ、紫外線硬化時
にラジカル重合が阻害されず、高温で長時間の熱硬化が
必要でなく、液晶の配向不良を引き起こす欠点がなく、
なおかつ滴下工法にも使用できる液晶表示装置の液晶表
示パネル用の液晶シール材、ならびにこの液晶シール材
によりシールされた液晶表示パネルを有してなる表示品
位、信頼性の向上した液晶表示装置を提供することを目
的とする。According to the present invention, a sealant which is a combination of an ultraviolet curing component and a thermosetting component contains only a (meth) acrylic acid type monomer or oligomer which is polymerized by a radical polymerization mechanism as a monomer or oligomer component to be polymerized. By solving these problems of the sealing material, the adhesiveness, the moisture resistance of the liquid crystal panel are excellent, the radical polymerization is not hindered at the time of UV curing, and the heat curing at a high temperature for a long time is not required. There is no defect that causes poor orientation,
In addition, a liquid crystal sealing material for a liquid crystal display panel of a liquid crystal display device that can be used in the dropping method, and a liquid crystal display device having a liquid crystal display panel sealed by the liquid crystal sealing material and having improved display quality and reliability are provided. The purpose is to do.
【００１１】[0011]
【課題を解決するための手段】上記課題を解決するため
に、本発明の液晶表示パネル用の液晶シール材は、紫外
線硬化成分と熱硬化成分とを含有する液晶シール材であ
って、その成分がエポキシ（メタ）アクリレート、（メ
タ）アクリル酸エステル、光開始剤、熱硬化剤、シラン
カップリング剤、無機充填材を必須成分として含有し、
前記（メタ）アクリル酸エステルとして、１分子中に複
数の（メタ）アクリル酸残基を有する（メタ）アクリル
酸エステルがシール材中に５〜１０重量％ならびに１分
子中に１個の（メタ）アクリル酸残基を有する（メタ）
アクリル酸エステルがシール材中に２〜１０重量％含有
してなる構成を有する。In order to solve the above-mentioned problems, a liquid crystal sealing material for a liquid crystal display panel of the present invention is a liquid crystal sealing material containing an ultraviolet curable component and a thermosetting component. Contains epoxy (meth) acrylate, (meth) acrylic acid ester, photoinitiator, thermosetting agent, silane coupling agent, and inorganic filler as essential components,
As the (meth) acrylic acid ester, a (meth) acrylic acid ester having a plurality of (meth) acrylic acid residues in one molecule is 5 to 10% by weight in the sealing material and one (meth) acrylic acid ester in one molecule. ) Having an acrylic acid residue (meth)
Acrylic ester is contained in the sealing material in an amount of 2 to 10% by weight.
【００１２】前記本発明の液晶シール材においては、エ
ポキシ（メタ）アクリレートが、ビスフェノールＡ型、
もしくはノボラック型のエポキシ（メタ）アクリレート
であって、エポキシ（メタ）アクリレートが液晶シール
材中に４０〜７０重量％の範囲で含有されている事が好
ましい。In the liquid crystal sealing material of the present invention, the epoxy (meth) acrylate is bisphenol A type,
Alternatively, it is a novolac type epoxy (meth) acrylate, and it is preferable that the epoxy (meth) acrylate is contained in the liquid crystal sealing material in the range of 40 to 70% by weight.
【００１３】また、前記本発明の液晶シール材において
は、光開始剤が、アセトフェノン系光開始剤、ベンゾイ
ン系光開始剤、ベンゾフェノン系光開始剤からなる群か
ら選ばれた光開始剤であって、光開始剤が液晶シール材
中に３〜５重量％の範囲で含有されている事が好まし
い。In the liquid crystal sealing material of the present invention, the photoinitiator is a photoinitiator selected from the group consisting of acetophenone photoinitiators, benzoin photoinitiators and benzophenone photoinitiators. The photoinitiator is preferably contained in the liquid crystal sealing material in the range of 3 to 5% by weight.
【００１４】また、前記本発明の液晶シール材において
は、熱硬化剤が、ヒドラジド、芳香族アミン、酸無水
物、イミダゾールからなる群から選ばれた熱硬化剤であ
って、熱硬化剤が液晶シール材中に２〜５重量％の範囲
で含有されている事が好ましい。In the liquid crystal sealing material of the present invention, the thermosetting agent is a thermosetting agent selected from the group consisting of hydrazides, aromatic amines, acid anhydrides and imidazoles, and the thermosetting agent is a liquid crystal. It is preferably contained in the sealing material in the range of 2 to 5% by weight.
【００１５】また、前記本発明の液晶シール材において
は、熱硬化剤が、平均粒子径が３μｍ以下の固形粒子状
の熱硬化剤である事が好ましい。また、前記本発明の液
晶シール材においては、シランカップリング剤が、グリ
シジルエトキシシラン及びグリシジルメトキシシランか
らなる群から選ばれたシランカップリング剤であって、
シランカップリング剤が液晶シール材中に２〜７重量％
の範囲で含有されている事が好ましい。In the liquid crystal sealing material of the present invention, the thermosetting agent is preferably a solid particle type thermosetting agent having an average particle size of 3 μm or less. In the liquid crystal sealing material of the present invention, the silane coupling agent is a silane coupling agent selected from the group consisting of glycidylethoxysilane and glycidylmethoxysilane,
2-7% by weight of silane coupling agent in the liquid crystal sealing material
It is preferable that the content is within the range.
【００１６】また、前記本発明の液晶シール材において
は、無機充填材が、含水硅酸マグネシウム、炭酸カルシ
ウム、酸化アルミニウム、シリカからなる群から選ばれ
た平均粒径が１．５μｍ以下の無機充填材であって、無
機充填材が液晶シール材中に８〜２０重量％の範囲で含
有されている事が好ましい。In the liquid crystal sealing material of the present invention, the inorganic filler is an inorganic filler having an average particle size of 1.5 μm or less selected from the group consisting of hydrous magnesium silicate, calcium carbonate, aluminum oxide and silica. It is preferable that the inorganic filler is contained in the liquid crystal sealing material in the range of 8 to 20% by weight.
【００１７】また、前記本発明の液晶シール材において
は、液晶表示パネルが、液晶シール材形成工程と２枚の
電極付き基板貼合わせ工程の間に、液晶を滴下注入する
工程を含む工程により製造される液晶表示パネル用の液
晶シール材として極めて好適である。In the liquid crystal sealing material of the present invention, the liquid crystal display panel is manufactured by a step including a step of dropping and injecting liquid crystal between the step of forming the liquid crystal sealing material and the step of adhering the two substrates with electrodes. It is extremely suitable as a liquid crystal sealing material for liquid crystal display panels.
【００１８】また、本発明の液晶表示装置は、上記のい
ずれかに記載の液晶表示パネル用の液晶シール材により
液晶がシールされた液晶表示パネルを有してなる液晶表
示装置である。The liquid crystal display device of the present invention is a liquid crystal display device having a liquid crystal display panel in which liquid crystal is sealed by the liquid crystal sealing material for a liquid crystal display panel as described above.
【００１９】前記本発明の液晶表示装置に於いては、液
晶表示パネルが、シール材形成工程と２枚の電極付き基
板貼合わせ工程の間に、液晶を滴下注入する工程を含む
工程により製造される液晶表示パネルである事が好まし
い。In the liquid crystal display device of the present invention, the liquid crystal display panel is manufactured by a process including a step of dropping and injecting liquid crystal between the step of forming the sealing material and the step of adhering the two substrates with electrodes. It is preferably a liquid crystal display panel.
【００２０】[0020]
【作用】本発明による液晶シール材は、紫外線硬化成分
として紫外線でラジカル重合するエポキシ（メタ）アク
リレート、（メタ）アクリル酸エステル、光開始剤の組
み合わせを使用し、熱硬化成分として、紫外線硬化成分
の紫外線照射によるラジカル重合で生成する樹脂成分を
架橋するための熱硬化剤を使用している。このようにエ
ポキシ樹脂を含有していないので、長時間加熱してエポ
キシ樹脂を硬化させる必要がなく、加熱によってシール
材の粘度が低下する事がないので、貼合わせた基板のア
ライメントずれが生じたり、基板の反りが生じる恐れが
なく、硬化収縮も少なく抑えられ、また、紫外線硬化時
にエポキシ樹脂の存在により、エポキシ（メタ）アクリ
レート、（メタ）アクリル酸エステルのラジカル重合が
阻害される恐れがない。また、熱硬化時に未反応のエポ
キシ樹脂が液晶中に溶出し、液晶の配向不良を引き起こ
す恐れもなく、接着性、耐湿性に優れた液晶パネルが実
現可能なシール材を提供できる。従って本発明のシール
材で液晶をシールされた液晶パネルを備えた液晶表示装
置は、液晶の配向不良や電流値の増加がなく、接着性、
耐湿性に優れた液晶パネルを有する表示品位が良好で信
頼性のよい液晶表示装置を提供することができる。この
様に本発明で用いるシール材はラジカル重合の硬化機構
でありながら、接着性、耐湿性に優れた液晶パネルを作
成することができるので、表示品位、信頼性の高い液晶
表示装置を提供することができる。The liquid crystal sealing material according to the present invention uses a combination of an epoxy (meth) acrylate, a (meth) acrylic acid ester, and a photoinitiator which are radically polymerized by ultraviolet rays as an ultraviolet ray curing component. A thermosetting agent is used to crosslink the resin component produced by radical polymerization by ultraviolet irradiation. Since it does not contain epoxy resin in this way, there is no need to heat the epoxy resin for a long time to cure it, and the viscosity of the sealing material does not decrease due to heating, which may cause misalignment of the bonded substrates. There is no risk of warping of the substrate, curing shrinkage is suppressed to a minimum, and there is no risk of the radical polymerization of epoxy (meth) acrylate or (meth) acrylic acid ester being hindered by the presence of epoxy resin during UV curing. . Further, it is possible to provide a sealing material that can realize a liquid crystal panel having excellent adhesiveness and moisture resistance without the risk that unreacted epoxy resin will be eluted into the liquid crystal during thermosetting to cause liquid crystal alignment failure. Therefore, the liquid crystal display device including the liquid crystal panel in which the liquid crystal is sealed with the sealing material of the present invention does not have the liquid crystal alignment defect or the increase in the current value, and the adhesiveness,
It is possible to provide a liquid crystal display device having a liquid crystal panel excellent in moisture resistance and having good display quality and high reliability. As described above, since the sealing material used in the present invention has a curing mechanism of radical polymerization, it is possible to form a liquid crystal panel having excellent adhesiveness and moisture resistance, thus providing a liquid crystal display device having high display quality and reliability. be able to.
【００２１】さらに、本発明のシール材は、硬化機構が
ラジカル重合機構であることから、紫外線硬化時の反応
割合が高く、２枚の配向処理を施した電極付き基板の一
方にシール材を形成し、残り他方の基板とスペーサー手
段を介して前記２枚の基板を貼合わせる工程の間に液晶
を滴下注入する工程を含む滴下工法を採用した場合で
も、液晶の配向状態、及び電気特性に大きな影響を与え
る事がない。特に、紫外線硬化後に行うシール材の熱硬
化でも液晶パネルのアニール温度以下で重合する熱硬化
剤を適宜選択することにより、生産性の効率を落とすこ
とはない。従って、滴下工法においても表示品位の良好
な液晶表示装置を効率よく提供できる。Furthermore, since the curing mechanism of the sealant of the present invention is the radical polymerization mechanism, the reaction rate at the time of ultraviolet curing is high, and the sealant is formed on one of the two substrates with electrodes subjected to the alignment treatment. However, even when a dropping method including a step of dropping and injecting liquid crystal between the steps of attaching the two substrates via the spacer means to the other remaining substrate is adopted, the alignment state of the liquid crystal and the electrical characteristics are large. It has no effect. In particular, even if the sealing material is thermally cured after ultraviolet curing, the efficiency of productivity is not reduced by appropriately selecting a thermal curing agent that is polymerized at an annealing temperature of the liquid crystal panel or lower. Therefore, it is possible to efficiently provide a liquid crystal display device having good display quality even in the dropping method.
【００２２】尚、本発明のシール材の成分に於いて、エ
ポキシ（メタ）アクリレート成分は比較的熱膨張が少な
く、重合が早く進むので、配向処理を施した電極付き基
板にシール材を形成する工程と、対向する基板とをスペ
ーサー手段を介して貼合わせる工程との間で液晶を滴下
注入する工程を設けるいわゆる滴下工法に使用する場合
においてもシール材と液晶が接することにより未硬化の
シール材中の成分が液晶中に溶けだして、液晶の配向不
良や得られる液晶表示装置の電流値の増大を防止するの
に有効な成分である。尚、エポキシ（メタ）アクリレー
ト成分は通常オリゴマーの形で入手でき、オリゴマーの
形で本発明の一成分原料として使用される。Among the components of the sealing material of the present invention, the epoxy (meth) acrylate component has a relatively small thermal expansion, and the polymerization proceeds rapidly. Therefore, the sealing material is formed on the substrate with electrodes subjected to the orientation treatment. An uncured seal material due to the contact between the seal material and the liquid crystal even when used in a so-called dropping method in which a step of dropping and injecting liquid crystal is provided between the step and the step of attaching the opposing substrate via the spacer means. The components inside are dissolved in the liquid crystal, and are effective components for preventing alignment failure of the liquid crystal and increase in the current value of the resulting liquid crystal display device. The epoxy (meth) acrylate component is usually available in the form of an oligomer and is used as a component raw material of the present invention in the form of an oligomer.
【００２３】（メタ）アクリル酸エステルとして、１分
子中に複数の（メタ）アクリル酸残基を有する（メタ）
アクリル酸エステルは、硬化密度を高め、熱硬化を促進
し、高温信頼性の高いシールを実現するのに有用な役割
を果たしており、この成分がシール材中に５重量％より
少ない場合には、架橋密度が不足し、熱信頼性の高い液
晶表示装置を実現することができなくなる。また、１０
重量％を越える場合には、硬化収縮が生じやすく好まし
くない。As a (meth) acrylic acid ester, having a plurality of (meth) acrylic acid residues in one molecule (meth)
Acrylic ester plays a useful role in increasing the curing density, promoting the thermal curing, and realizing a high temperature reliable seal, and when this component is less than 5% by weight in the sealing material, Since the crosslink density is insufficient, a liquid crystal display device having high thermal reliability cannot be realized. Also, 10
When it exceeds the weight%, curing shrinkage easily occurs, which is not preferable.
【００２４】また１分子中に１個の（メタ）アクリル酸
残基を有する（メタ）アクリル酸エステルは、硬化収縮
が比較的少なく、硬化収縮を抑制する成分として有用で
あり、また、重合前のモノマーの段階でエポキシ（メ
タ）アクリレート成分などの溶剤的な役割を担い、従っ
て粘度の調整剤としてシール材を印刷などによって基板
に塗布する場合に適当な粘度に調整することができる役
割を果たすことができる。この成分がシール材中に２重
量％よりも少ない場合には、シール材の硬化収縮が生じ
やすくなり、一方、１０重量％よりも多い場合には、架
橋密度が低くなり、得られる液晶表示装置の熱信頼性が
低下すると共に、量が多すぎることにより、未硬化成分
が液晶中に溶けだし、液晶の配向不良などの問題を生じ
る。The (meth) acrylic acid ester having one (meth) acrylic acid residue in one molecule has a relatively small curing shrinkage and is useful as a component for suppressing the curing shrinkage. Plays a role of a solvent such as an epoxy (meth) acrylate component at the stage of the monomer, and thus plays a role of adjusting a suitable viscosity when a sealing material is applied as a viscosity adjusting agent to a substrate by printing or the like. be able to. When this component is less than 2% by weight in the sealing material, curing shrinkage of the sealing material is likely to occur, while when it is more than 10% by weight, the crosslink density becomes low and the obtained liquid crystal display device is obtained. In addition to the decrease in the thermal reliability, the uncured component begins to dissolve in the liquid crystal due to the excessive amount, and problems such as poor alignment of the liquid crystal occur.
【００２５】光開始剤は、前記（メタ）アクリル系の各
種モノマーないしオリゴマー成分を紫外線重合するのに
必要なラジカル発生源の役割をする。熱硬化剤は、前記
紫外線重合で生成したポリマー成分の熱架橋、熱硬化に
主として寄与し、接着性の向上、熱信頼性の向上を達成
する役割を担う。The photoinitiator plays a role of a radical generating source necessary for UV-polymerizing the various (meth) acrylic monomer or oligomer components. The thermosetting agent mainly contributes to the thermal crosslinking and thermosetting of the polymer component produced by the ultraviolet polymerization, and plays a role of improving the adhesiveness and the thermal reliability.
【００２６】また、シランカップリング剤は、更に耐湿
性を向上させるに有効な成分であり、無機充填材は、剥
離強度の向上など、接着性に寄与すると共に、シール材
の粘度の調整の役割も兼ねている成分である。Further, the silane coupling agent is an effective component for further improving the moisture resistance, and the inorganic filler contributes to the adhesiveness such as the improvement of the peel strength and also has the role of adjusting the viscosity of the sealing material. It is also a component that doubles as a component.
【００２７】本発明のシール材は以上の様な成分を用い
ているので、ラジカル重合の硬化機構でありながら、接
着性、耐湿性に優れ、表示品位、信頼性の高いものとな
る。次に、更に本発明の好ましい態様について更に説明
すると、エポキシ（メタ）アクリレートが、ビスフェノ
ールＡ型、もしくは、ノボラック型のエポキシ（メタ）
アクリレートであって、液晶シール材中に４０〜７０重
量％の範囲で含有されていることが好ましく、ビスフェ
ノールＡ型、もしくはノボラック型のエポキシ（メタ）
アクリレートは印刷でシール剤を塗布する場合に適当な
粘度範囲に調整し得る粘度を有し、変性ウレタンアクリ
レートなどに比べて熱膨張などが生じにくく、好まし
い。また、使用割合を４０〜７０重量％の範囲とするこ
とにより、他のモノマー成分の割合が多くなって生じる
硬化収縮や液晶の配向不良などの問題や、シール材を印
刷などで塗布する場合に粘度が高過ぎたり、低過ぎると
言う問題もなく好ましい。Since the sealing material of the present invention uses the components as described above, it has excellent adhesiveness and moisture resistance, and has high display quality and reliability, even though it has a radical polymerization curing mechanism. Next, the preferred embodiment of the present invention will be further described. The epoxy (meth) acrylate is a bisphenol A type or novolac type epoxy (meth) acrylate.
An acrylate, which is preferably contained in the liquid crystal sealing material in the range of 40 to 70% by weight, is a bisphenol A type or novolac type epoxy (meth).
Acrylate has a viscosity that can be adjusted to an appropriate viscosity range when a sealant is applied by printing, and thermal expansion is less likely to occur as compared with modified urethane acrylate, and is preferred. Further, by setting the use ratio to be in the range of 40 to 70% by weight, when the ratio of other monomer components is increased, there are problems such as curing shrinkage and liquid crystal alignment failure, and when applying a sealing material by printing or the like. It is preferable because there is no problem that the viscosity is too high or too low.
【００２８】また、光開始剤がアセトフェノン系光開始
剤、ベンゾイン系光開始剤、ベンゾフェノン系光開始剤
からなる群から選ばれた光開始剤の場合には、通常の紫
外線ランプの波長で重合が進行しやすく、また、これら
の光開始剤は、ポットライフが長いので、シール材調整
中に重合が進行してしまう恐れがないので好ましい。光
開始剤の配合割合は、余りに少な過ぎると、紫外線硬化
が十分進行しないので、未硬化成分が液晶中に溶けだ
し、液晶の配向不良などの問題が生じる恐れが有り、余
りに多すぎると、余分な光開始剤から発生したラジカル
などが液晶中に溶け出して、得られる液晶表示装置の電
流値などに影響を及ぼすので、光開始剤は液晶シール材
中に３〜５重量％の範囲で含有されていることが好まし
い。When the photoinitiator is a photoinitiator selected from the group consisting of an acetophenone photoinitiator, a benzoin photoinitiator, and a benzophenone photoinitiator, the polymerization is carried out at the wavelength of an ordinary ultraviolet lamp. These photoinitiators are preferable because they are easy to proceed, and since the photoinitiators have a long pot life, there is no fear that polymerization will proceed during the adjustment of the sealing material. If the blending ratio of the photoinitiator is too small, the ultraviolet curing does not proceed sufficiently, so that the uncured component may start to dissolve in the liquid crystal and cause problems such as alignment failure of the liquid crystal. Radicals generated from the photoinitiator are dissolved in the liquid crystal and affect the current value of the obtained liquid crystal display device. Therefore, the photoinitiator is contained in the liquid crystal sealing material in the range of 3 to 5% by weight. Preferably.
【００２９】また、熱硬化剤をヒドラジド、芳香族アミ
ン、酸無水物、イミダゾールからなる群から選ばれた熱
硬化剤とすることにより、これらの熱硬化剤は、硬化温
度が通常液晶の分解点よりも低く、液晶を熱劣化させる
恐れが少なく好ましい。また、これらの熱硬化剤は、ポ
ットライフが長く、通常８時間以上のポットライフを有
するので、シール材調整中に熱硬化剤が分解してしまう
恐れがなく好ましい。When the thermosetting agent is a thermosetting agent selected from the group consisting of hydrazides, aromatic amines, acid anhydrides and imidazoles, these thermosetting agents usually have a curing temperature of a decomposition point of liquid crystal. It is lower than that, and there is little fear of heat deterioration of the liquid crystal, which is preferable. Further, since these thermosetting agents have a long pot life and usually have a pot life of 8 hours or more, there is no fear that the thermosetting agent will decompose during the adjustment of the sealing material, which is preferable.
【００３０】また、熱硬化剤を、平均粒子径が３μｍ以
下の固形粒子状の熱硬化剤とすることにより、固形粒子
状のものはポットライフが長く、好ましい。また、平均
粒子径が３μｍ以下とすることにより、スペーサーなど
で調整する液晶パネルの２枚の基板のギャップよりも平
均粒子径が小さいので、液晶パネルの２枚の基板のギャ
ップに、悪影響を及ぼす恐れが無く、好ましい。熱硬化
剤の平均粒子径の下限は特に制限はないが通常１μｍ程
度である。Further, by using a thermosetting agent in the form of solid particles having an average particle size of 3 μm or less, solid particles are preferable because they have a long pot life. Further, by setting the average particle diameter to 3 μm or less, the average particle diameter is smaller than the gap between the two substrates of the liquid crystal panel adjusted by a spacer or the like, which adversely affects the gap between the two substrates of the liquid crystal panel. There is no fear and it is preferable. The lower limit of the average particle diameter of the thermosetting agent is not particularly limited, but is usually about 1 μm.
【００３１】また、シランカップリング剤を、グリシジ
ルエトキシシラン及びグリシジルメトキシシランからな
る群から選ばれたシランカップリング剤とすることによ
り、これらは耐湿性の改良効果が大きく好ましい。ま
た、これらのシランカップリング剤の配合割合が余りに
少なすぎると、液晶パネルの更なる耐湿性の向上にほと
んど寄与せず、余りに多すぎると液晶中に混入して配向
不良などを生ずる恐れが有り、液晶シール材中に２〜７
重量％の範囲で含有されている場合には、この様な問題
は全く考慮しなくてよいので好ましい。By using a silane coupling agent selected from the group consisting of glycidylethoxysilane and glycidylmethoxysilane as the silane coupling agent, these are preferable because they have a large effect of improving the moisture resistance. Further, if the blending ratio of these silane coupling agents is too small, it hardly contributes to further improvement of the moisture resistance of the liquid crystal panel, and if it is too large, it may be mixed in the liquid crystal to cause alignment failure or the like. , 2 to 7 in the liquid crystal sealing material
When the content is in the range of weight%, such a problem need not be taken into consideration at all, which is preferable.
【００３２】また、無機充填材が、含水硅酸マグネシウ
ム、炭酸カルシウム、酸化アルミニウム、シリカからな
る群から選ばれた無機充填材とすることにより、これら
は平均粒径が１．５μｍ以下のものが比較的容易に入手
しやすいこと、接着性の向上効果がより大きいことと、
シール材を印刷により塗布する場合に、シール材の粘度
が調整しやすいことなどの理由から好ましい。また、平
均粒径が１．５μｍ以下の無機充填材とすることにより
シール材中への分散性が良好であり、また、スペーサー
などで調整する液晶パネルの２枚の基板のギャップより
も平均粒子径が小さいので、液晶パネルの２枚の基板の
ギャップに悪影響を及ぼす恐れが無く、好ましい。無機
充填材の平均粒子径の下限は特に制限はないが通常１５
ｎｍ程度の小さいものも好適に使用できる。無機充填材
の配合割合は、余りに少な過ぎると、更なる接着性の改
良効果が十分でなく、余りに多すぎる場合には、印刷な
どでシール材を基板に塗布形成する場合に、不適当にな
り、２枚の基板のギャップも所定の間隔に保ちにくくな
るので、液晶シール材中に８〜２０重量％の範囲で含有
されている場合には、この様な問題は全く考慮しなくて
よく、好ましい。When the inorganic filler is an inorganic filler selected from the group consisting of hydrous magnesium silicate, calcium carbonate, aluminum oxide and silica, those having an average particle size of 1.5 μm or less are preferable. Being relatively easy to obtain, having a greater effect of improving adhesiveness,
This is preferable because the viscosity of the sealing material can be easily adjusted when the sealing material is applied by printing. Further, by using an inorganic filler having an average particle size of 1.5 μm or less, the dispersibility in the sealing material is good, and the average particle size is larger than the gap between the two substrates of the liquid crystal panel adjusted by a spacer or the like. Since the diameter is small, there is no fear of adversely affecting the gap between the two substrates of the liquid crystal panel, which is preferable. The lower limit of the average particle size of the inorganic filler is not particularly limited, but usually 15
Those having a small size of about nm can be preferably used. If the blending ratio of the inorganic filler is too small, the effect of further improving the adhesiveness is not sufficient, and if it is too large, it becomes unsuitable when the sealing material is applied to the substrate by printing or the like. Since it is difficult to keep the gap between the two substrates at a predetermined interval, when the liquid crystal sealing material contains 8 to 20% by weight, such a problem need not be considered at all. preferable.
【００３３】また、１分子中に１個以上の（メタ）アク
リル酸残基を含む（メタ）アクリル酸エステルの配合量
と、無機充填剤の配合量を上記配合量マージンの中で調
節することにより、印刷性、及び貼合わせ後のアライメ
ント調整に適したシール材の粘性が得られ、効率よく液
晶表示装置の生産が行える。Further, the blending amount of the (meth) acrylic acid ester containing one or more (meth) acrylic acid residues in one molecule and the blending amount of the inorganic filler should be adjusted within the above blending amount margin. Thereby, the printability and the viscosity of the sealing material suitable for the alignment adjustment after bonding can be obtained, and the liquid crystal display device can be efficiently produced.
【００３４】しかも、無機充填剤の粒径を１．５μｍ以
下とすることにより、シール材のチキソトロピー性の向
上が図れることから、滴下工法においては、シール材の
たれによる配向の劣化、基板貼合わせ後のシール材の破
れ等の問題もなく表示品位の良好な液晶表示装置を提供
できる。Moreover, since the thixotropy of the sealing material can be improved by setting the particle size of the inorganic filler to be 1.5 μm or less, in the dropping method, the orientation is deteriorated due to the sagging of the sealing material, and the substrate is bonded. It is possible to provide a liquid crystal display device having a good display quality without problems such as breakage of the sealing material later.
【００３５】[0035]
【実施例】本発明の液晶表示装置は、使用するシール材
がラジカル重合機構である、紫外線硬化成分と熱硬化成
分との併用型であることから、信頼性と表示品位の高い
ものがえられる。本発明の液晶表示装置自体は前記シー
ル材の組成の点を除いては、従来公知の構成のものが採
用できるので、詳細な説明は省略する。EXAMPLES Since the liquid crystal display device of the present invention is a combination type of an ultraviolet curing component and a thermosetting component, which has a radical polymerization mechanism as a sealing material, it is possible to obtain high reliability and high display quality. . The liquid crystal display device of the present invention itself may have a conventionally known configuration except for the composition of the sealing material, and thus detailed description thereof will be omitted.
【００３６】シール材の各成分に関して具体例を説明す
る。エポキシ（メタ）アクリレートとしては、ビスフェ
ノールＡ型もしくはノボラック型のエポキシ（メタ）ア
クリレートが好ましく、ビスフェノールＡ型エポキシ
（メタ）アクリレートの具体例としては、例えばビスフ
ェノールＡ型グリシジルエーテル変性ジアクリレートな
どが挙げられ、ノボラック型エポキシ（メタ）アクリレ
ートの具体例としては、例えばノボラック型グリシジル
エーテル変性ジアクリレートなどが挙げられる。実施例
においては、昭和高分子株式会社製のビスフェノールＡ
型エポキシアクリレートオリゴマーである“ＳＰ−１５
６３”を使用した。Specific examples of each component of the sealing material will be described. The epoxy (meth) acrylate is preferably a bisphenol A type or novolac type epoxy (meth) acrylate, and specific examples of the bisphenol A type epoxy (meth) acrylate include bisphenol A type glycidyl ether modified diacrylate. Specific examples of the novolac type epoxy (meth) acrylate include novolac type glycidyl ether-modified diacrylate. In the examples, Showa High Polymer Co., Ltd. bisphenol A
Type epoxy acrylate oligomer "SP-15"
63 "was used.
【００３７】（メタ）アクリル酸エステルのうち、１分
子中に複数の（メタ）アクリル酸残基を有する（メタ）
アクリル酸エステルの具体例としては、例えばペンタエ
リスリトールトリアクリレート、ペンタエリスリトール
テトラアクリレートなどが挙げられ、実施例において
は、大阪有機化学工業株式会社製のペンタエリスリトー
ルトリアクリレート“ビスコート＃３００”を用いた。Among the (meth) acrylic acid esters, having a plurality of (meth) acrylic acid residues in one molecule (meth)
Specific examples of the acrylate ester include pentaerythritol triacrylate and pentaerythritol tetraacrylate. In the examples, pentaerythritol triacrylate "biscoat # 300" manufactured by Osaka Organic Chemical Industry Co., Ltd. was used.
【００３８】（メタ）アクリル酸エステルのうち、１分
子中に１個の（メタ）アクリル酸残基を有する（メタ）
アクリル酸エステルの具体例としては、例えばテトラヒ
ドロフルフリルアクリレート、２−ヒドロキシプロピル
アクリレート、エトキシジエチレングリコールアクリレ
ートなどが挙げられ、実施例においては、共栄社化学株
式会社製のエトキシジエチレングリコールアクリレート
“ＥＣ−Ａ”を使用した。Among (meth) acrylic acid esters, one (meth) acrylic acid residue is present in one molecule (meth)
Specific examples of the acrylate ester include tetrahydrofurfuryl acrylate, 2-hydroxypropyl acrylate, and ethoxydiethylene glycol acrylate. In the examples, Kyoeisha Chemical Co., Ltd. ethoxydiethylene glycol acrylate "EC-A" is used. did.
【００３９】光開始剤としてはアセトフェノン系光開始
剤、ベンゾイン系光開始剤、ベンゾフェノン系光開始剤
などが好ましく、アセトフェノン系光開始剤の具体例と
しては、例えばジエトキシアセトフェノン、４−ｔ−ブ
チル−ジシクロアセトフェノン、２，２ージメトキシー
２ーフェニルアセトンなどが挙げられ、ベンゾイン系光
開始剤の具体例としては、例えばベンゾイン、ベンゾイ
ンエチルエーテル、ベンジルメチルケタールなどが挙げ
られ、ベンゾフェノン系光開始剤の具体例としては、例
えばベンゾフェノン、４−フェニルベンゾフェノン、ヒ
ドロキシベンゾフェノンなどが挙げられ、実施例におい
ては、日本チバガイギー株式会社製の２，２ージメトキ
シー２ーフェニルアセトン“イルガキュアー６５１”を
使用した。The photoinitiator is preferably an acetophenone photoinitiator, a benzoin photoinitiator, a benzophenone photoinitiator, and specific examples of the acetophenone photoinitiator include diethoxyacetophenone and 4-t-butyl. -Dicycloacetophenone, 2,2-dimethoxy-2-phenylacetone, and the like, and specific examples of the benzoin-based photoinitiator include, for example, benzoin, benzoin ethyl ether, benzyl methyl ketal, and the like. Specific examples include, for example, benzophenone, 4-phenylbenzophenone, hydroxybenzophenone and the like. In the examples, 2,2-dimethoxy-2-phenylacetone "Irgacure 651" manufactured by Nippon Ciba-Geigy Co., Ltd. was used.
【００４０】熱硬化剤としてはヒドラジド系、芳香族ア
ミン系、酸無水物系、イミダゾール系が好ましく、ヒド
ラジド系熱硬化剤の具体例としては、例えば７，１１−
オクタデカジエンジヒドラジド、アジピン酸ジヒドラジ
ドなどが挙げられ、芳香族アミン系熱硬化剤の具体例と
しては、例えば、ジアミノジフェニルメタン、メタフェ
ニレンジアミンなどが挙げられ、酸無水物系熱硬化剤の
具体例としては、例えば、ヘキサハイドロ無水フタール
酸、テトラハイドロ無水フタール酸などが挙げられ、イ
ミダゾール系熱硬化剤の具体例としては、例えば２−エ
チルメチルイミダゾール、２−メチルイミダゾール、１
−ベンジル−２−メチルイミダゾールなどが挙げられ、
実施例においては、ヒドラジド系の固形粒子熱硬化剤で
味の素株式会社製の“ＵＤＨ”（三本ロールで平均粒子
径３μｍに調整したもの）、もしくは変性芳香族アミン
で鱗片状の油化シェルエポキシ株式会社製の“エピキュ
アＺ”を使用した。The thermosetting agent is preferably a hydrazide type, an aromatic amine type, an acid anhydride type, or an imidazole type, and specific examples of the hydrazide type thermosetting agent include, for example, 7,11-
Examples include octadecadiene dihydrazide and adipic acid dihydrazide.Specific examples of aromatic amine-based thermosetting agents include, for example, diaminodiphenylmethane and metaphenylenediamine, and specific examples of acid anhydride-based thermosetting agents. Examples include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and the like, and specific examples of the imidazole-based thermosetting agent include 2-ethylmethylimidazole, 2-methylimidazole, and 1-methylimidazole.
-Benzyl-2-methylimidazole and the like,
In the examples, "UDH" (produced by Ajinomoto Co., Inc., which is a hydrazide-based solid particle thermosetting agent) (average particle size is adjusted to 3 μm with a triple roll), or a scale oily shell epoxy with modified aromatic amine is used. "Epicure Z" manufactured by Co., Ltd. was used.
【００４１】シランカップリング剤としては、グリシジ
ルエトキシシラン及びグリシジルメトキシシランが好ま
しく用いられ、実施例においては、信越化学工業株式会
社製のγーグリシドキシプロピルトリメトキシシラン
“ＫＢＭ４０３”を使用した。As the silane coupling agent, glycidylethoxysilane and glycidylmethoxysilane are preferably used, and in the examples, γ-glycidoxypropyltrimethoxysilane "KBM403" manufactured by Shin-Etsu Chemical Co., Ltd. was used.
【００４２】無機充填剤としては、含水硅酸マグネシウ
ム、炭酸カルシウム、酸化アルミニウム、シリカなどが
好ましく用いられ、実施例においては、日本タルク株式
会社製の含水硅酸マグネシウム“スーパータルクＳＧ−
９５”（平均粒子径１．４μｍ）と、日本アエロジル株
式会社製の二酸化珪素“アエロジルＲ２０２”（平均一
次粒子径１５ｎｍ）を採用した。As the inorganic filler, hydrous magnesium silicate, calcium carbonate, aluminum oxide, silica and the like are preferably used. In the examples, hydrous magnesium silicate "Super Talc SG-" manufactured by Nippon Talc Co., Ltd. is used.
95 "(average particle diameter 1.4 μm) and silicon dioxide" Aerosil R202 "(average primary particle diameter 15 nm) manufactured by Nippon Aerosil Co., Ltd. were used.
【００４３】硬化条件としては、紫外線硬化には通常高
圧水銀ランプが用いられ、照射条件は用いるランプの種
類やシール材の組成や量、ランプからの距離などによっ
て異なり、これらの条件に応じて適宜調整すればよく、
特に限定するものではないが、例えばエネルギー量で６
００ｍＪ〜５０００ｍＪ程度の照射条件が採用される。
実施例においては高圧水銀ランプとして日本電池株式会
社製の“ＨＧＱ−２０００”を使用し、シール材への波
長４２０ｎｍ以下の紫外線の照度が２０ｍｗ／ｃｍ2
で、２分間照射し、照射エネルギーが４８００ｍＪとな
るようにした。熱硬化に関しても、用いた熱硬化剤の種
類やその他の素材の種類、配合割合などによって異な
り、特に限定するものではないが、例えば１００〜１５
０℃で１時間以上程度の条件が通常採用され、実施例に
おいては液晶パネルのアニール条件と同等の１２０℃で
１２時間行った。As the curing conditions, a high-pressure mercury lamp is usually used for ultraviolet curing, and the irradiation conditions vary depending on the type of lamp used, the composition and amount of the sealing material, the distance from the lamp, etc., and are appropriately selected according to these conditions. Just adjust it,
Although not particularly limited, for example, the amount of energy is 6
Irradiation conditions of about 00 mJ to 5000 mJ are adopted.
In the examples, "HGQ-2000" manufactured by Nippon Battery Co., Ltd. is used as a high-pressure mercury lamp, and the illuminance of ultraviolet rays having a wavelength of 420 nm or less on the sealing material is 20 mw / cm 2.
Then, irradiation was performed for 2 minutes so that the irradiation energy became 4800 mJ. The heat curing also depends on the type of the heat curing agent used, the type of other materials, the mixing ratio, etc., and is not particularly limited, but is, for example, 100 to 15
The condition of 0 ° C. for about 1 hour or more is usually adopted, and in the example, the annealing was performed at 120 ° C. for 12 hours, which is the same as the annealing condition of the liquid crystal panel.
【００４４】以下、具体的実施例ならびに比較例を挙げ
て本発明を更に説明するが、本発明はこの実施例に記載
されたもののみに限定されるものではない。 （実施例１〜３及び比較例１〜３）本発明ならびに比較
例によるシール材を用いた液晶表示装置の一実施例、比
較例を説明する。図１は、今回評価に用いた液晶パネル
の断面模式図である。ガラス基板１ａには、その内側面
にＩＴＯ（インジウムとスズの酸化物）からなる透明電
極２ａが設けられ、更にその内側面に配向処理されたポ
リイミド配向膜３ａが設けられており、ガラス基板１ｂ
には、その内側面にＩＴＯ（インジウムとスズの酸化
物）からなる透明電極２ｂが設けられ、更にその内側面
に配向処理されたポリイミド配向膜３ｂが設けられ、か
かる配向処理を施した２枚の電極付きガラス基板１ａ、
１ｂを、散布により一定の密度で配置した樹脂ビーズス
ペーサー材４（粒子径７．４μｍ）によりセルギャップ
を制御し、シール材６により前記２枚の電極付き基板を
接着し、なおかつ液晶５を封止するものである。なお配
向を制御するためのポリイミド配向膜３ａ、３ｂの設け
られている領域の外側の領域にシール材６を設け、ポリ
イミド配向膜３ａ、３ｂの設けられているる領域とは重
複しないようにしてある。尚、この実施例１〜３と比較
例１〜３は、先に液晶パネルを組み立て、後から液晶５
を注入したものである。The present invention will be further described below with reference to specific examples and comparative examples, but the present invention is not limited to those described in these examples. (Examples 1 to 3 and Comparative Examples 1 to 3) One example and a comparative example of a liquid crystal display device using the sealing material according to the present invention and the comparative example will be described. FIG. 1 is a schematic cross-sectional view of a liquid crystal panel used for this evaluation. The glass substrate 1a is provided with a transparent electrode 2a made of ITO (oxide of indium and tin) on its inner side surface, and further provided with an oriented polyimide alignment film 3a on its inner side surface.
Is provided with a transparent electrode 2b made of ITO (an oxide of indium and tin) on its inner side surface, and further provided with an oriented polyimide alignment film 3b on its inner side surface. Glass substrate with electrode 1a,
The cell gap is controlled by a resin bead spacer material 4 (particle diameter 7.4 μm) arranged at a constant density by spraying 1b, and the two electrode-attached substrates are bonded by a sealing material 6, and the liquid crystal 5 is sealed. It will stop. In addition, the sealing material 6 is provided in a region outside the region where the polyimide alignment films 3a and 3b for controlling the alignment are provided so as not to overlap with the region where the polyimide alignment films 3a and 3b are provided. is there. In Examples 1 to 3 and Comparative Examples 1 to 3, the liquid crystal panel was assembled first, and the liquid crystal 5 was formed later.
Is injected.
【００４５】以下、表１に実施例１、２、３と比較例
１、２、３のシール材の各成分とその配合量、及び、初
期と１２０℃、１２０％、２気圧のプレッシャークッカ
ーテスト（以後ＰＣＴと略称する。）８時間後の接着
性、１２０℃の高温試験での１０００時間後の液晶表示
装置の液晶の配向状態と電流値変化、６０℃９５％の耐
湿試験１０００時間後の液晶表示装置の液晶の配向状態
と電流値変化を示した。Table 1 below shows the components of the sealing materials of Examples 1, 2 and 3 and Comparative Examples 1, 2 and 3 and their amounts, and the pressure cooker test at the initial temperature of 120 ° C., 120% and 2 atm. (Hereinafter abbreviated as PCT.) Adhesion after 8 hours, alignment state and current value change of liquid crystal of liquid crystal display device after 1000 hours in high temperature test at 120 ° C., humidity resistance test at 60 ° C. 95% after 1000 hours The liquid crystal alignment state and current value change of the liquid crystal display device are shown.
【００４６】[0046]
【表１】 [Table 1]
【００４７】尚、評価基準は、通常のパソコンやワープ
ロなどのＯＡ機器が使用される環境で使用可能かどうか
の評価であるが、△印の“将来の使用に際し問題あり”
とは、よりシビアーな環境、すなわち自動車などの車載
用とか屋外での使用など近い将来開発される用途を想定
した環境条件下での使用に際し問題ありと言う意味であ
る。The evaluation standard is an evaluation as to whether or not it can be used in an environment where ordinary office automation equipment such as personal computers and word processors are used, but there is a problem in future use marked with △.
Means that there is a problem when used in a more severe environment, that is, in an environmental condition that is intended for an in-vehicle use such as an automobile or an application developed in the near future such as an outdoor use.
【００４８】実施例１と２は、１分子中に複数の（メ
タ）アクリル酸残基を有する（メタ）アクリル酸エステ
ルの一種である“ビスコート＃３００”の配合量がそれ
ぞれ５重量％と１０重量％と違い、実施例１と３は、熱
硬化剤がそれぞれ変性芳香族アミン系の“エピキュア
Ｚ”とヒドラジド系の“ＵＤＨ”と違い、その他成分
と、各成分の配合量は同じでものある。比較例１は、１
分子中に１個の（メタ）アクリル酸残基を有する（メ
タ）アクリル酸エステルの一種である“ＥＣ−Ａ”の配
合量が２０重量％と過剰に配合したもの、比較例２は
“ＥＣ−Ａ”を除いたもの、比較例３は熱硬化剤を除い
たものである。In Examples 1 and 2, the compounding amount of "biscoat # 300", which is a kind of (meth) acrylic acid ester having a plurality of (meth) acrylic acid residues in one molecule, was 5% by weight and 10%, respectively. Unlike wt%, in Examples 1 and 3, the thermosetting agent was different from the modified aromatic amine-based "Epicure Z" and the hydrazide-based "UDH", respectively. is there. Comparative Example 1 is 1
The compounding amount of "EC-A", which is one kind of (meth) acrylic acid ester having one (meth) acrylic acid residue in the molecule, was 20% by weight, which was excessively compounded, and Comparative Example 2 was "EC". -A "was removed, and Comparative Example 3 was obtained without the thermosetting agent.
【００４９】ここで、比較例１は、高温放置後の液晶の
配向状態が劣化し、しかも電流値に関しては、耐湿試
験、高温試験ともに上昇しており液晶表示装置の表示品
位が劣化している。In Comparative Example 1, the alignment state of the liquid crystal after being left at a high temperature was deteriorated, and the current value was increased in both the humidity resistance test and the high temperature test, and the display quality of the liquid crystal display device was deteriorated. .
【００５０】次に比較例２と３は、高温試験や耐湿試験
後のパネル特性には問題ないが、比較例２に関しては初
期の接着性が、比較例３に関してはＰＣＴ後の接着性が
他に比べ弱い。Next, in Comparative Examples 2 and 3, there is no problem in the panel characteristics after the high temperature test and the humidity resistance test, but the initial adhesiveness of Comparative Example 2 and the adhesiveness after PCT of Comparative Example 3 are different. Weaker than
【００５１】これらのことから、実施例１、２と３は、
接着性、高温、耐湿中での信頼性に問題なく、表示品位
が良好で信頼性のよい液晶表示装置を提供でき、良好な
シール材である事が認められる。From these facts, Examples 1, 2 and 3 are
It is recognized that there is no problem in adhesiveness, reliability in high temperature and humidity resistance, a liquid crystal display device having good display quality and high reliability can be provided, and that it is a good sealing material.
【００５２】（実施例４〜６と比較例４〜６）次に、２
枚の配向処理を施した電極付き基板の一方にシール材を
形成し、残りの他方の基板とスペーサー手段を介して前
記２枚の基板を貼合わせる工程の間に液晶を滴下注入す
る工程を含む、いわゆる滴下工法で液晶表示装置を作製
した場合の本発明による液晶表示装置の一実施例を説明
する。(Examples 4 to 6 and Comparative Examples 4 to 6) Next, 2
A step of forming a sealing material on one of the two substrates with electrodes subjected to the alignment treatment, and dropping and injecting liquid crystal between the step of bonding the other two substrates through the spacer means to the other two substrates. An embodiment of the liquid crystal display device according to the present invention when the liquid crystal display device is manufactured by a so-called dropping method will be described.
【００５３】まず滴下工法に関して図２と図３を用いて
説明する。図２は本実施例で採用する滴下工法で液晶表
示装置用の液晶パネルを製造する場合の、液晶を滴下す
る工程の概略斜視図であり、図３は滴下工法で液晶表示
装置用の液晶パネルを製造する場合の、液晶を滴下した
基板とスペーサー材を配置した対向する基板とを貼合わ
せる工程の概略断面の端面図である。First, the dropping method will be described with reference to FIGS. FIG. 2 is a schematic perspective view of a step of dropping a liquid crystal when a liquid crystal panel for a liquid crystal display device is manufactured by the dropping method adopted in this embodiment, and FIG. 3 is a liquid crystal panel for a liquid crystal display device by the dropping method. FIG. 9 is an end view of a schematic cross section of a step of laminating a substrate onto which liquid crystal has been dropped and a facing substrate on which a spacer material is arranged, in the case of manufacturing.
【００５４】図２から配向処理を施した電極付き基板１
０ｂ（図１で説明した基板１ｂと同様）の内側面の一部
にスクリーン印刷等を用いてシール材１１を任意のパタ
ーン状に形成し、そのシール材で囲まれた範囲に液晶１
２をディスペンサー等の液体吐出装置１３を用いて滴下
配置する。次に図３に示す様に、前記液晶を配置した基
板１０ｂと対向する配向処理を施した電極付き基板１０
ａ（図１で説明した基板１ａと同様）の内側面に樹脂ビ
ーズスペーサー材１４（粒子径７．４μｍ）を散布によ
り面内均一な密度で配置し固着する。そして前記基板１
０ａと１０ｂとを０．４〜１Ｔｏｒｒの減圧にした真空
槽１５内で減圧下で貼合わせ、その後大気圧により基板
を押圧することによりギャップ制御を行う。From FIG. 2, the electrode-attached substrate 1 subjected to the orientation treatment
0b (similar to the substrate 1b described in FIG. 1), a sealing material 11 is formed in an arbitrary pattern by using screen printing or the like on a part of the inner surface, and the liquid crystal 1 is surrounded by the sealing material.
2 is placed by dropping using a liquid discharge device 13 such as a dispenser. Next, as shown in FIG. 3, a substrate 10 with electrodes, which has been subjected to an alignment treatment, faces the substrate 10b on which the liquid crystal is arranged.
A resin bead spacer material 14 (particle diameter: 7.4 μm) is dispersed on the inner surface of a (similar to the substrate 1a described in FIG. 1) by spraying and fixed. And the substrate 1
Gap control is performed by bonding 0a and 10b under reduced pressure in a vacuum chamber 15 in which the pressure is reduced to 0.4 to 1 Torr, and then pressing the substrate by atmospheric pressure.
【００５５】以下、表２に実施例４〜６と比較例４〜６
の各成分とその配合量、および、シール際の配向状態、
１２０℃、１０００時間の高温試験後の電流値変化と液
晶の配向状態、６０℃９５％、１０００時間の耐湿試験
後の電流値変化と液晶の配向状態とを示す。Table 2 below shows Examples 4 to 6 and Comparative Examples 4 to 6.
Each component and its blending amount, and the orientation state at the time of sealing,
A change in current value after a high temperature test at 120 ° C. for 1000 hours and an alignment state of the liquid crystal, and a change in current value after a humidity resistance test at 60 ° C. 95% for 1000 hours and an alignment state of the liquid crystal are shown.
【００５６】[0056]
【表２】 [Table 2]
【００５７】ここで、実施例４と５は１分子中に１個の
（メタ）アクリル酸残基を有する（メタ）アクリル酸エ
ステルの一種である“ＥＣ−Ａ”の配合量が２重量％と
１０重量％と違い、実施例４と６は熱硬化剤がそれぞれ
変性芳香族アミン系の熱硬化剤“エピキュアＺ”とヒド
ラジド系の熱硬化剤“ＵＤＨ”と違い，各成分の配合量
は同じものである。比較例４は、熱硬化剤である“エピ
キュアＺ”が配合されていないもので、比較例５は、１
分子中に複数の（メタ）アクリル酸残基を有する（メ
タ）アクリル酸エステルの一種である“ビスコート＃３
００”が１５重量％と過剰に配合されたもので、比較例
６は、エポキシ樹脂として油化シェルエポキシ株式会社
製の“エピコート８０２”を配合し、熱硬化剤をそのエ
ポキシ当量だけ配合してものである。Here, in Examples 4 and 5, the compounding amount of "EC-A" which is one kind of (meth) acrylic acid ester having one (meth) acrylic acid residue in one molecule was 2% by weight. And 10% by weight, the thermosetting agents of Examples 4 and 6 are different from the modified aromatic amine type thermosetting agent "Epicure Z" and the hydrazide type thermosetting agent "UDH". Are the same. Comparative Example 4 does not contain "Epicure Z" which is a thermosetting agent, and Comparative Example 5 has 1
"Biscoat # 3" which is a kind of (meth) acrylic acid ester having a plurality of (meth) acrylic acid residues in the molecule
In the comparative example 6, "Epicoat 802" manufactured by Yuka Shell Epoxy Co., Ltd. was blended as an epoxy resin, and a thermosetting agent was blended in an epoxy equivalent amount. It is a thing.
【００５８】この結果から、比較例５と６では未硬化成
分が液晶中にとけ出しやすく、シール際での液晶の配向
不良の領域が広いため、表示エリアを侵食している。ま
た、比較例４と６では、耐湿試験後で電流値の増加が見
られ、信頼性に弱い結果となっている。これは、エポキ
シ樹脂のような紫外線硬化時に重合に関与しない成分が
多量に含まれているために、未硬化成分が水分や、高温
時の液晶により溶出した場合と、熱硬化剤が存在しない
ので、架橋密度が小さくなりその結果透湿度が大きくな
って耐湿性が低下するなどのためと考えられる。From these results, in Comparative Examples 5 and 6, the uncured component is likely to melt into the liquid crystal, and the region of poor liquid crystal alignment at the time of sealing widens the display area. Further, in Comparative Examples 4 and 6, an increase in current value was observed after the humidity resistance test, resulting in poor reliability. This is because a large amount of components such as epoxy resin that do not participate in polymerization during ultraviolet curing are contained, so when the uncured component is eluted by water or liquid crystal at high temperature, and there is no thermosetting agent. It is considered that the crosslink density is reduced, resulting in increased moisture permeability and reduced moisture resistance.
【００５９】これに対し、実施例４〜６では、シール際
の配向状態も良好で、しかも高温、耐湿中での信頼性も
問題ない。従って、本発明のシール材を使用する事によ
り、滴下工法の上でも信頼性の高い、表示品位の良好な
本発明の液晶表示装置を提供できる。On the other hand, in Examples 4 to 6, the orientation state at the time of sealing is good, and there is no problem in reliability under high temperature and humidity resistance. Therefore, by using the sealing material of the present invention, it is possible to provide the liquid crystal display device of the present invention which is highly reliable even in the dropping method and has good display quality.
【００６０】[0060]
【発明の効果】本発明のシール材は、ラジカル重合機構
を有する成分を使用したシール材であり、硬化収縮、熱
膨張が小さく、紫外線硬化時にラジカル重合が阻害され
ず、未硬化成分の液晶への溶け出しが少ない、接着性、
耐湿性に優れた液晶パネル用の液晶シール材を提供でき
る。またかかる液晶シール材によりシールされた液晶表
示パネルを有してなる表示品位が良好で信頼性の高い液
晶表示装置を提供できる。Industrial Applicability The sealing material of the present invention is a sealing material using a component having a radical polymerization mechanism, has a small curing shrinkage and thermal expansion, does not inhibit radical polymerization during ultraviolet curing, and becomes a liquid crystal of an uncured component. Little melting, adhesiveness,
A liquid crystal sealing material for a liquid crystal panel having excellent moisture resistance can be provided. Further, it is possible to provide a liquid crystal display device having a liquid crystal display panel sealed with such a liquid crystal sealing material and having a good display quality and high reliability.
【００６１】また、シール材はラジカル重合機構で重合
が進行するので、紫外線硬化を併用することにより、滴
下工法の使用や、基板のアライメントずれ、及び、シー
ル材の液だれやシール切れといった問題もなく、従って
液晶表示装置に適用した場合に生産性の向上、及び歩留
まりの向上を図ることができる。Further, since the sealing material is polymerized by a radical polymerization mechanism, by using UV curing together, there are problems such as use of a dropping method, misalignment of the substrate, dripping of the sealing material, and breakage of the sealing material. Therefore, when applied to a liquid crystal display device, it is possible to improve productivity and yield.
【図１】本発明の一実施例の液晶表示装置用の液晶パネ
ルの断面模式図。FIG. 1 is a schematic cross-sectional view of a liquid crystal panel for a liquid crystal display device according to an embodiment of the present invention.
【図２】滴下工法で液晶表示装置用の液晶パネルを製造
する場合の、液晶を滴下する工程の概略斜視図。FIG. 2 is a schematic perspective view of a step of dropping liquid crystal when a liquid crystal panel for a liquid crystal display device is manufactured by a dropping method.
【図３】滴下工法で液晶表示装置用の液晶パネルを製造
する場合の、液晶を滴下した基板とスペーサー材を配置
した対向する基板とを貼合わせる工程の概略断面の端面
図。FIG. 3 is an end view of a schematic cross-section of a step of bonding a substrate onto which liquid crystal is dropped and a facing substrate on which a spacer material is arranged, when a liquid crystal panel for a liquid crystal display device is manufactured by a dropping method.
１ａ、１ｂ 基板 ２ａ、２ｂ 透明電極 ３ａ、３ｂ ポリイミド配向膜 ４ 樹脂ビーズスペーサー材 ５ 液晶 ６ シール材 １０ａ、１０ｂ 配向処理を施した電極付き基板 １１ シール材 １２ 液晶 １３ 液体吐出装置 １４ 樹脂ビーズスペーサー材 １５ 真空槽 1a, 1b Substrate 2a, 2b Transparent electrode 3a, 3b Polyimide alignment film 4 Resin bead spacer material 5 Liquid crystal 6 Sealing material 10a, 10b Electrode-treated substrate 11 Sealing material 12 Liquid crystal 13 Liquid ejecting device 14 Resin bead spacer material 15 vacuum chamber
Claims (10)
る液晶シール材であって、その成分がエポキシ（メタ）
アクリレート、（メタ）アクリル酸エステル、光開始
剤、熱硬化剤、シランカップリング剤、無機充填材を必
須成分として含有し、前記（メタ）アクリル酸エステル
として、１分子中に複数の（メタ）アクリル酸残基を有
する（メタ）アクリル酸エステルがシール材中に５〜１
０重量％ならびに１分子中に１個の（メタ）アクリル酸
残基を有する（メタ）アクリル酸エステルがシール材中
に２〜１０重量％含有してなる液晶表示パネル用の液晶
シール材。1. A liquid crystal sealing material containing an ultraviolet curable component and a thermosetting component, the component being epoxy (meth).
Acrylate, (meth) acrylic acid ester, photoinitiator, thermosetting agent, silane coupling agent, and inorganic filler are contained as essential components, and a plurality of (meth) acrylic compounds are contained in one molecule as the (meth) acrylic acid ester. The (meth) acrylic acid ester having an acrylic acid residue is contained in the sealing material in an amount of 5 to 1
A liquid crystal sealing material for a liquid crystal display panel, which comprises 0% by weight and 2 to 10% by weight of a (meth) acrylic acid ester having one (meth) acrylic acid residue in one molecule in the sealing material.
フェノールＡ型、もしくはノボラック型のエポキシ（メ
タ）アクリレートであって、液晶シール材中に４０〜７
０重量％の範囲で含有されてなる請求項１記載の液晶表
示パネル用の液晶シール材。2. The epoxy (meth) acrylate is a bisphenol A type or a novolac type epoxy (meth) acrylate, and 40 to 7 in the liquid crystal sealing material.
The liquid crystal sealing material for a liquid crystal display panel according to claim 1, which is contained in an amount of 0% by weight.
剤、ベンゾイン系光開始剤、ベンゾフェノン系光開始剤
からなる群から選ばれた光開始剤であって、液晶シール
材中に３〜５重量％の範囲で含有されてなる請求項１ま
たは２のいずれかに記載の液晶表示パネル用の液晶シー
ル材。3. The photoinitiator is a photoinitiator selected from the group consisting of an acetophenone photoinitiator, a benzoin photoinitiator, and a benzophenone photoinitiator, and 3 to 5 parts by weight in the liquid crystal sealing material. The liquid crystal sealing material for a liquid crystal display panel according to claim 1, wherein the liquid crystal sealing material is contained in the range of%.
ン、酸無水物、イミダゾールからなる群から選ばれた熱
硬化剤であって、液晶シール材中に２〜５重量％の範囲
で含有されてなる請求項１〜３のいずれかに記載の液晶
表示パネル用の液晶シール材。4. The thermosetting agent is a thermosetting agent selected from the group consisting of hydrazides, aromatic amines, acid anhydrides and imidazoles, and is contained in the liquid crystal sealing material in an amount of 2 to 5% by weight. A liquid crystal sealing material for a liquid crystal display panel according to claim 1.
固形粒子状の熱硬化剤である請求項１〜４のいずれかに
記載の液晶表示パネル用の液晶シール材。5. The liquid crystal sealing material for a liquid crystal display panel according to claim 1, wherein the thermosetting agent is a solid particle type thermosetting agent having an average particle diameter of 3 μm or less.
トキシシラン及びグリシジルメトキシシランからなる群
から選ばれたシランカップリング剤であって、液晶シー
ル材中に２〜７重量％の範囲で含有されてなる請求項１
〜５のいずれかに記載の液晶表示パネル用の液晶シール
材。6. The silane coupling agent is a silane coupling agent selected from the group consisting of glycidylethoxysilane and glycidylmethoxysilane, and is contained in the liquid crystal sealing material in the range of 2 to 7% by weight. Claim 1
6. A liquid crystal sealing material for a liquid crystal display panel according to any one of items 5 to 5.
炭酸カルシウム、酸化アルミニウム、シリカからなる群
から選ばれた平均粒径が１．５μｍ以下の無機充填材で
あって、液晶シール材中に８〜２０重量％の範囲で含有
されてなる請求項１〜６のいずれかに記載の液晶表示パ
ネル用の液晶シール材。7. The inorganic filler is hydrous magnesium silicate,
An inorganic filler having an average particle size of 1.5 μm or less selected from the group consisting of calcium carbonate, aluminum oxide and silica, and contained in the liquid crystal sealing material in an amount of 8 to 20% by weight. 7. A liquid crystal sealing material for a liquid crystal display panel according to any one of 6 to 6.
程と２枚の電極付き基板貼合わせ工程の間に、液晶を滴
下注入する工程を含む工程により製造される液晶表示パ
ネルである請求項１〜７のいずれかに記載の液晶表示パ
ネル用の液晶シール材。8. The liquid crystal display panel is a liquid crystal display panel manufactured by a process including a process of dropping and injecting liquid crystal between a process of forming a liquid crystal sealant and a process of laminating two substrates with electrodes. A liquid crystal sealing material for a liquid crystal display panel according to any one of items 1 to 7.
示パネル用の液晶シール材により液晶がシールされた液
晶表示パネルを有してなる液晶表示装置。9. A liquid crystal display device comprising a liquid crystal display panel in which liquid crystal is sealed by the liquid crystal sealing material for a liquid crystal display panel according to claim 1.
と２枚の電極付き基板貼合わせ工程の間に、液晶を滴下
注入する工程を含む工程により製造される液晶表示パネ
ルである請求項９に記載の液晶表示装置。10. The liquid crystal display panel according to claim 9, wherein the liquid crystal display panel is manufactured by a step including a step of dropping and injecting liquid crystal between a step of forming a sealing material and a step of attaching two substrates with electrodes. The described liquid crystal display device.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15620095A JP2846842B2 (en) | 1995-06-22 | 1995-06-22 | Liquid crystal sealing material and liquid crystal display device |
| US08/608,109 US5898041A (en) | 1995-03-01 | 1996-02-28 | Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| KR1019960005203A KR100232905B1 (en) | 1995-03-01 | 1996-02-29 | The manufacturing method of lcd panel and liquid crystal seal and lcd device |
| EP96103055A EP0730188A3 (en) | 1995-03-01 | 1996-02-29 | Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| CN96106042A CN1087436C (en) | 1995-03-01 | 1996-03-01 | Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| US08/988,317 US6013339A (en) | 1995-03-01 | 1997-12-10 | Liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| US08/988,195 US6001203A (en) | 1995-03-01 | 1997-12-10 | Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| HK98101216A HK1002078A1 (en) | 1995-03-01 | 1998-02-17 | Production process of liquid crystal display panel, seal meterial for liquid crystal cell and liquid crystal display |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15620095A JP2846842B2 (en) | 1995-06-22 | 1995-06-22 | Liquid crystal sealing material and liquid crystal display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH095759A true JPH095759A (en) | 1997-01-10 |
| JP2846842B2 JP2846842B2 (en) | 1999-01-13 |
Family
ID=15622561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15620095A Expired - Fee Related JP2846842B2 (en) | 1995-03-01 | 1995-06-22 | Liquid crystal sealing material and liquid crystal display device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2846842B2 (en) |
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|---|---|
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