JPH07120617A - Polarizing plate - Google Patents
Polarizing plateInfo
- Publication number
- JPH07120617A JPH07120617A JP28760993A JP28760993A JPH07120617A JP H07120617 A JPH07120617 A JP H07120617A JP 28760993 A JP28760993 A JP 28760993A JP 28760993 A JP28760993 A JP 28760993A JP H07120617 A JPH07120617 A JP H07120617A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polarizing
- polarizing plate
- polarizing film
- urethane prepolymer
- 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
- Polarising Elements (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は偏光フィルムと保護フィ
ルムとの接着性及び耐湿熱性に優れた偏光板に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polarizing plate which is excellent in adhesion between a polarizing film and a protective film and resistance to moist heat.
【0002】[0002]
【従来の技術】近年、卓上電子計算機、電子時計、ワー
プロ、自動車や機械類の計器類等に液晶表示装置が用い
られ、これらに伴い偏光板の需要も増大している。偏光
板は一般に偏光能を有する偏光フィルムの両面に、接着
剤層を介して保護フィルムを形成させたものである。現
在、知られている代表的なポリビニルアルコール系偏光
フィルムとしてはポリビニルアルコール系フィルムにヨ
ウ素を染色させたものと二色性染料を染色させたものが
あり、これらはポリビニルアルコールの水溶液を製膜
し、これを一軸延伸させて染色するか、染色した後一軸
延伸してから、好ましくはホウ素化合物で耐久性処理を
行ったものが用いられ、保護フィルムとしては、酢酸セ
ルロース系フィルムが表面保護フィルムとして光学的透
明性、無配向性等に優れているため汎用されている。2. Description of the Related Art In recent years, liquid crystal display devices have been used in desk-top electronic computers, electronic timepieces, word processors, measuring instruments such as automobiles and machines, and the demand for polarizing plates has increased accordingly. The polarizing plate is generally formed by forming a protective film on both surfaces of a polarizing film having a polarizing ability through an adhesive layer. Currently, as a typical polyvinyl alcohol-based polarizing film, there are a polyvinyl alcohol-based film dyed with iodine and a dichroic dye, which are used to form an aqueous solution of polyvinyl alcohol. , Which is uniaxially stretched to be dyed, or after dyeing and then uniaxially stretched, preferably subjected to a durability treatment with a boron compound, and as the protective film, a cellulose acetate film is used as a surface protective film. It is widely used because of its excellent optical transparency and non-orientation.
【0003】ポリビニルアルコール系フィルムも酢酸セ
ルロース系フィルムも親水性であるため、親水性の接着
剤を用いて貼合しているのが一般的である。しかし、こ
れでは得られる偏光板は長時間高湿雰囲気下においては
吸水率が大きく、吸水するにつれて接着力が低下し、偏
光物性の低下が起こって、いわゆる耐湿性や寸法安定性
に問題が生じたり、又、高温下に置かれると偏光度も低
下して耐熱性が損なわれたりする場合がある。Since both the polyvinyl alcohol film and the cellulose acetate film are hydrophilic, it is common to bond them by using a hydrophilic adhesive. However, the resulting polarizing plate has a large water absorption rate in a high-humidity atmosphere for a long time, the adhesive force decreases as it absorbs water, and the physical properties of the polarizing plate deteriorate, causing problems in so-called moisture resistance and dimensional stability. Or, if it is placed at a high temperature, the degree of polarization may be lowered and the heat resistance may be impaired.
【0004】これらの問題を解決するため、例えば、特
開昭56−50301号公報では、保護フィルムの酢酸
セルロース系フィルム表面をケン化処理して、接着剤と
酢酸セルロースとの接着力を強固にし、耐湿性、耐熱性
及び寸法安定性を改善することが提案されている。In order to solve these problems, for example, in JP-A-56-50301, the surface of the cellulose acetate film of the protective film is saponified to strengthen the adhesive force between the adhesive and the cellulose acetate. , Moisture resistance, heat resistance and dimensional stability have been proposed.
【0005】又、特開昭61−245107号公報で
は、偏光フィルムの表面をポリビニルアルコール、カル
ボキシメチルセルロース、ウレタン系、アクリル系、エ
ポキシ系等の親水性高分子の水溶液又は接着剤で一度処
理した後、再度接着剤を介して保護フィルムを接着する
ことによって、接着強度の改善された偏光板を提供する
ことが提案されている。Further, in JP-A-61-245107, after the surface of a polarizing film is once treated with an aqueous solution or adhesive of a hydrophilic polymer such as polyvinyl alcohol, carboxymethyl cellulose, urethane type, acrylic type, epoxy type, etc. It has been proposed to provide a polarizing plate with improved adhesive strength by adhering a protective film again via an adhesive.
【0006】[0006]
【発明が解決しようとする課題】しかしながら、特開昭
56−50301号公報では、保護フィルムと接着剤層
との接着力は改善されるものの、偏光フィルムと接着剤
層との接着力に関しては従来のままで何ら考慮されてお
らず、これでは高温、高湿状態において充分な耐久性が
得られたとは言えない。即ち、偏光フィルムの表面は内
部よりも吸着せしめたヨウ素等が多いことや、更に高
温、高湿状態ではヨウ素等が偏光フィルムの表面に一部
移行してしまうこと等が原因になって接着性を悪くす
る。これらを防止するためには接着剤層を厚くすること
が考えられるが、接着剤層を厚くすることは、工業的な
均一塗布に困難であり、光学特性についても不利となる
ために望ましい方法ではない。However, in JP-A-56-50301, although the adhesive force between the protective film and the adhesive layer is improved, the adhesive force between the polarizing film and the adhesive layer has been conventionally improved. As it is, no consideration is given, and it cannot be said that sufficient durability is obtained in a high temperature and high humidity state. That is, the surface of the polarizing film has more adsorbed iodine and the like than the inside, and in a high temperature and high humidity state, iodine and the like partially migrate to the surface of the polarizing film, which causes adhesiveness. Make it worse. It is possible to increase the thickness of the adhesive layer in order to prevent these, but it is difficult to increase the thickness of the adhesive layer for industrial uniform coating, and it is also disadvantageous in terms of optical properties. Absent.
【0007】特開昭61−245107号公報について
は、偏光フィルムと接着剤層、及び接着剤層と保護フィ
ルムの接着性の改善を目指しているもので、いくらか実
用性の高い製品が得られるものの、耐湿熱性等について
はまだ充分とはいえず、更に偏光フィルムを接着剤で処
理した後、再度接着剤を使用する必要があり、作業工程
が繁雑となり、又、ウレタン系接着剤を用いるに際して
は、ポリイソシアネートと多価アルコール等の活性水素
を有する化合物を併用することが必要不可欠とされ、こ
れらを混合撹拌した二液硬化型のウレタン系接着剤を塗
布するため、該接着剤の可使時間の影響を免れることは
できず工程管理は繁雑となり、まだまだ問題が残される
ところである。In Japanese Patent Laid-Open No. 61-245107, the aim is to improve the adhesiveness between the polarizing film and the adhesive layer, and between the adhesive layer and the protective film. However, it cannot be said that the resistance to moisture and heat is still insufficient, and it is necessary to use the adhesive again after treating the polarizing film with the adhesive, which complicates the work process, and when using the urethane adhesive, It is indispensable to use a compound having active hydrogen such as polyisocyanate and polyhydric alcohol, and since a two-component curing type urethane adhesive mixed and stirred with these is applied, the pot life of the adhesive However, the process management becomes complicated and problems still remain.
【0008】本出願人も特開平2−135402号公報
において、耐湿熱性及び寸法安定性を向上させるため、
ポリビニルアルコール系偏光フィルムと酢酸セルロース
系保護フィルムの接着剤にホウ素化合物の水溶液を使用
することを提案しているが、該方法では、接着性の点で
著しく改善された偏光板が得られているが、該偏光板は
中耐久程度のものでまだまだ満足するというものではな
く、従来の偏光板を上回る耐湿熱性を持った高耐久高偏
光度タイプの偏光板の出現が望まれているのが実情であ
る。The applicant of the present invention has also disclosed in Japanese Patent Laid-Open No. 2-135402 that in order to improve resistance to moist heat and dimensional stability,
It has been proposed to use an aqueous solution of a boron compound as an adhesive for the polyvinyl alcohol-based polarizing film and the cellulose acetate-based protective film, but in this method, a polarizing plate having significantly improved adhesiveness is obtained. However, the polarizing plate is not so satisfactory as a medium-durability one, and it is actually desired to develop a highly durable and highly polarized type polarizing plate having a heat and humidity resistance higher than that of conventional polarizing plates. Is.
【0009】[0009]
【課題を解決するための手段】しかるに、本発明者等は
かかる課題を解決すべく鋭意研究を重ねた結果、分子内
に2個以上のイソシアネート基を有する化合物(A)と
1分子中にイソシアネート基と反応する活性水素を有す
る化合物(B)とを反応させてなるウレタンプレポリマ
ー(C)を接着剤として用いて、含水率8重量%以上の
偏光フィルムと酢酸セルロース系保護フィルムを接着し
てなる偏光板が非常に強固に接着した偏光板となり、耐
湿熱性が向上し、高耐久高偏光度タイプの偏光板として
有用であることを見出し、本発明を完成した。However, as a result of intensive studies by the present inventors in order to solve such a problem, the compound (A) having two or more isocyanate groups in the molecule and the isocyanate in one molecule. Using a urethane prepolymer (C) obtained by reacting a compound (B) having active hydrogen that reacts with a group as an adhesive, a polarizing film having a water content of 8% by weight or more and a cellulose acetate-based protective film are adhered to each other. The present invention has been completed, and it was found that the resulting polarizing plate becomes a polarizing plate that adheres very firmly, has improved wet heat resistance, and is useful as a highly durable and highly polarized type polarizing plate.
【0010】即ち、本発明においてはウレタンプレポリ
マーをそのまま偏光フィルムの面に塗布するため、ウレ
タン樹脂の塗工におけるような可使時間を問題とするこ
とがなく、又、そのまま保護フィルムを接着することが
できる等加工適性に非常に優れた効果が発揮できるので
あるが、かかるウレタンプレポリマーの塗工に当たって
は基材の偏光フィルムの含水率を特定範囲にコントロー
ルすることによって高耐久、高偏光性が達成されるので
ある。以下、本発明について具体的に説明する。That is, in the present invention, since the urethane prepolymer is applied as it is to the surface of the polarizing film, there is no problem of pot life as in the application of urethane resin, and the protective film is adhered as it is. It is possible to exert a very excellent effect on processing suitability, but in coating such urethane prepolymer, by controlling the water content of the polarizing film of the base material within a specific range, high durability and high polarization property can be obtained. Is achieved. Hereinafter, the present invention will be specifically described.
【0011】本発明の偏光フィルムは、ポリビニルアル
コール系フィルムの一軸延伸フィルムである。ポリビニ
ルアルコールは通常、酢酸ビニルを重合したポリ酢酸ビ
ニルをケン化して製造されるが、本発明では必ずしもこ
れに限定されるものではなく、少量の不飽和カルボン酸
(塩、エステル、アミド、ニトリル等を含む)、オレフ
ィン類、ビニルエーテル類、不飽和スルホン酸塩等、酢
酸ビニルと共重合可能な成分を含有していても良い。ポ
リビニルアルコールにおける平均ケン化度は85〜10
0モル%、好ましくは98〜100モル%が実用的であ
る。又、本発明のポリビニルアルコールの平均重合度と
しては任意のものが使用可能であるが、1500以上、
好ましくは2600以上、より好ましくは3500〜5
000が有利である。The polarizing film of the present invention is a uniaxially stretched film of a polyvinyl alcohol film. Polyvinyl alcohol is generally produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate, but the present invention is not necessarily limited to this, and a small amount of unsaturated carboxylic acid (salt, ester, amide, nitrile, etc. , Etc.), olefins, vinyl ethers, unsaturated sulfonates and the like, and may contain a component copolymerizable with vinyl acetate. The average degree of saponification in polyvinyl alcohol is 85 to 10
0 mol%, preferably 98 to 100 mol% is practical. As the average degree of polymerization of the polyvinyl alcohol of the present invention, any can be used, but 1500 or more,
Preferably 2600 or more, more preferably 3500-5
000 is advantageous.
【0012】本発明の偏光フィルムの製造法としては、
ポリビニルアルコールを水又は有機溶媒に溶解した原液
を流延製膜して、該フィルムを延伸してヨウ素あるいは
二色性染料の水溶液に浸漬し染色するか、延伸と染色を
同時に行うか、ヨウ素あるいは二色性染料により染色し
て延伸するかした後、ホウ素化合物処理する方法が挙げ
られる。又、染色した後ホウ素化合物の溶液中で延伸す
る方法等もあり、適宜選択して用いることができる。原
液調製に際して使用される溶媒としては、例えば水はも
ちろん、ジメチルスルホキシド(DMSO)、N−メチ
ルピロリドン、グリセリン、エチレングリコール、プロ
ピレングリコール、ジエチレングリコール、トリエチレ
ングリコール、テトラエチレングリコール、トリメチロ
ールプロパン等の多価アルコール、エチレンジアミン、
ジエチレントリアミン等のアミン類及びこれらの混合物
が用いられる。The method for producing the polarizing film of the present invention includes:
A stock solution of polyvinyl alcohol dissolved in water or an organic solvent is cast to form a film, and the film is stretched and dipped in an aqueous solution of iodine or a dichroic dye for dyeing, or stretching and dyeing are performed simultaneously, or iodine or A method of treating with a boron compound after dyeing with a dichroic dye and stretching. There is also a method of dyeing and then stretching in a solution of a boron compound, which can be appropriately selected and used. Examples of the solvent used for preparing the undiluted solution include not only water but also dimethyl sulfoxide (DMSO), N-methylpyrrolidone, glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like. Polyhydric alcohol, ethylenediamine,
Amines such as diethylenetriamine and mixtures thereof are used.
【0013】上記有機溶媒中には少量、例えば5〜30
重量%の水を含有させても差し支えない。原液中のポリ
ビニルアルコールの濃度は5〜20重量%が実用的であ
る。該溶剤を用いて得られたポリビニルアルコール製膜
原液は、キャスト法、押出法等任意の方法で製膜され
る。製膜方法としては乾・湿式製膜法にて、即ち、該溶
液を口金スリットから一旦空気中、又は窒素、ヘリウ
ム、アルゴン等の不活性雰囲気中に吐出し次いで凝固浴
中に導いて未延伸フィルムを形成せしめる。又は口金か
ら吐出された製膜溶液は一旦ローラー、あるいはベルト
コンベアー等の上で溶剤を一部乾燥した後で凝固浴中に
導入しても差し支えない。A small amount, for example, 5 to 30 is contained in the above organic solvent.
It is permissible to include water in a weight percentage. The concentration of polyvinyl alcohol in the stock solution is practically 5 to 20% by weight. The polyvinyl alcohol film-forming stock solution obtained using the solvent is formed into a film by an arbitrary method such as a casting method or an extrusion method. The film forming method is a dry / wet film forming method, that is, the solution is once discharged from the mouth slit into the air or into an inert atmosphere such as nitrogen, helium, or argon, and then introduced into a coagulation bath for unstretching. Form a film. Alternatively, the film-forming solution discharged from the die may be introduced into the coagulation bath after the solvent is partially dried on a roller, a belt conveyor or the like.
【0014】又、凝固浴に用いる溶媒には前記ポリビニ
ルアルコールの溶剤と混和性を有するもので、例えばメ
タノール、エタノール、プロパノール、ブタノール等の
アルコール類、アセトン、ベンゼン、トルエン等が挙げ
られる。ポリビニルアルコール系フィルムを得る方法と
しては、その他ポリビニルアルコールの溶液を凝固浴中
に導入してフィルム化するいわゆるゲル製膜法等も実施
可能である。The solvent used in the coagulation bath is miscible with the solvent of polyvinyl alcohol, and examples thereof include alcohols such as methanol, ethanol, propanol and butanol, acetone, benzene and toluene. As a method for obtaining a polyvinyl alcohol-based film, a so-called gel film forming method in which a solution of polyvinyl alcohol is introduced into a coagulation bath to form a film may be used.
【0015】原反フィルムとしてはその膜厚は30〜1
00μm、好ましくは50〜90μmが必要である。3
0μm以下では延伸不能となり、100μm以上では膜
厚精度が低下し不適当である。前記の如くして得られる
ポリビニルアルコール未延伸フィルムは次に延伸及び染
色、ホウ素化合物処理が施される。延伸と染色更にホウ
素化合物処理は別々に行っても同時に行っても良いが、
本発明では染色工程、ホウ素化合物処理工程の少なくと
も一方の工程中に一軸延伸を実施することが望ましい。The thickness of the raw film is 30 to 1
00 μm, preferably 50 to 90 μm is required. Three
When the thickness is 0 μm or less, stretching becomes impossible, and when the thickness is 100 μm or more, the film thickness accuracy is lowered, which is unsuitable. The polyvinyl alcohol unstretched film obtained as described above is then stretched, dyed, and treated with a boron compound. The stretching and dyeing and the boron compound treatment may be carried out separately or simultaneously,
In the present invention, it is desirable to carry out uniaxial stretching during at least one of the dyeing step and the boron compound treatment step.
【0016】延伸は一軸方向に3.5〜10倍、好まし
くは4.5〜7倍延伸することが望ましい。この際、前
記と直角方向にも若干の延伸(幅方向の収縮を防止する
程度あるいはそれ以上の延伸)を行っても差し支えな
い。延伸時の温度条件は40〜130℃から選ぶのが望
ましい。更に、かかる延伸倍率は最終的に上記の範囲に
設定されれば良く、延伸操作は一段階のみならず、製造
工程の任意の範囲の段階に実施すれば良い。It is desirable that the film is stretched uniaxially by 3.5 to 10 times, preferably 4.5 to 7 times. At this time, some stretching (stretching to a degree that prevents shrinkage in the width direction or more) may be performed in the direction perpendicular to the above. The temperature condition during stretching is preferably selected from 40 to 130 ° C. Furthermore, the stretching ratio may be finally set within the above range, and the stretching operation may be carried out not only in one stage but also in any stage of the manufacturing process.
【0017】フィルムへの染色つまり偏光素子の吸着は
フィルムに偏光素子を含有する液体を接触させることに
よって行われる。通常はヨウ素−ヨウ化カリの水溶液が
用いられ、ヨウ素の濃度は0.1〜2g/l、ヨウ化カ
リの濃度は10〜50g/l、ヨウ素/ヨウ化カリの重
量比は20〜100が適当である。染色時間は30〜5
00秒程度が実用的である。処理浴の温度は30〜80
℃が好ましい。水溶媒以外に水と相溶性のある有機溶媒
を少量含有させても差し支えない。接触手段としては浸
漬、塗布、噴霧等の任意の手段が適用できる。The dyeing of the film, that is, the adsorption of the polarizing element is performed by bringing the liquid containing the polarizing element into contact with the film. Usually, an aqueous solution of iodine-potassium iodide is used, the concentration of iodine is 0.1 to 2 g / l, the concentration of potassium iodide is 10 to 50 g / l, and the weight ratio of iodine / potassium iodide is 20 to 100. Appropriate. Staining time is 30-5
Practical time is about 00 seconds. The temperature of the treatment bath is 30-80
C is preferred. A small amount of an organic solvent compatible with water may be contained in addition to the water solvent. As the contact means, any means such as dipping, coating and spraying can be applied.
【0018】染色処理されたフィルムは次いでホウ素化
合物によって処理される。ホウ素化合物としてはホウ
酸、ホウ砂が実用的である。ホウ素化合物は水溶液又は
水−有機溶媒混合液の形で濃度0.5〜2モル/l程度
で用いられ、液中には少量のヨウ化カリを共存させるの
が実用上望ましい。処理法は浸漬法が望ましいが勿論塗
布法、噴霧法も実施可能である。処理時の温度は50〜
70℃程度、処理時間は5〜20分程度が好ましく、又
必要に応じて処理中に延伸操作を行っても良い。The dyed film is then treated with a boron compound. Boric acid and borax are practical as the boron compound. The boron compound is used in the form of an aqueous solution or a water-organic solvent mixture at a concentration of about 0.5 to 2 mol / l, and it is practically desirable to allow a small amount of potassium iodide to coexist in the solution. The treatment method is preferably a dipping method, but of course, a coating method and a spraying method can also be carried out. The temperature during processing is 50-
The treatment time is preferably about 70 ° C. and the treatment time is about 5 to 20 minutes, and if necessary, a stretching operation may be performed during the treatment.
【0019】前述した如き方法で得られたポリビニルア
ルコールの偏光フィルムはその含水率が非常に高く、本
発明では該フィルムの含水率を特定範囲にコントロール
することが特徴であり、該含水率にするためには、上記
フィルムを30〜120℃で30〜500秒間乾燥する
ことによって得られる。つまり、該偏光フィルムの含水
率が最終的に8重量%以上、好ましくは8〜50重量
%、更に好ましくは10〜30重量%になるように調製
されるのである。又、含水率8重量%未満の偏光フィル
ムを調湿や再湿等の方法により含水率を上記範囲に調製
して、本発明の偏光フィルムに供することもできる。8
重量%未満の含水率ではウレタンプレポリマーとの反応
性が低下し、又硬化に時間を要すことになり、一方50
重量%を越えると基材の収縮が起こり易く、ウレタンプ
レポリマーとの密着性が低下することになって本発明の
効果は得難い。The polyvinyl alcohol polarizing film obtained by the method as described above has a very high water content, and the present invention is characterized in that the water content of the film is controlled within a specific range. In order to obtain the above, the film is obtained by drying at 30 to 120 ° C. for 30 to 500 seconds. That is, the water content of the polarizing film is finally adjusted to 8% by weight or more, preferably 8 to 50% by weight, more preferably 10 to 30% by weight. Further, a polarizing film having a water content of less than 8% by weight can be adjusted to have the water content in the above range by a method such as humidity control or rewetting, and then used for the polarizing film of the present invention. 8
If the water content is less than 5% by weight, the reactivity with the urethane prepolymer will decrease and it will take a long time to cure.
If the amount exceeds 5% by weight, the base material is likely to shrink, and the adhesiveness with the urethane prepolymer is lowered, so that the effect of the present invention is difficult to obtain.
【0020】本発明の酢酸セルロース系保護フィルムと
しては二酢酸セルロース、三酢酸セルロース等のフィル
ムがある。又、該保護フィルムの表面をアルカリでケン
化処理したり、プラズマ処理、グロー放電処理、コロナ
放電処理、高周波処理、電子線処理等を行うと、更に効
果的である。Examples of the cellulose acetate-based protective film of the present invention include films of cellulose diacetate, cellulose triacetate and the like. Further, it is more effective to saponify the surface of the protective film with an alkali, plasma treatment, glow discharge treatment, corona discharge treatment, high frequency treatment, electron beam treatment or the like.
【0021】本発明では、上記の如く得られた含水率8
重量%以上の偏光フィルムと酢酸セルロース系保護フィ
ルムとの接着に際して、接着剤としてウレタンプレポリ
マー(C)が用いられる。In the present invention, the water content of 8 is obtained as described above.
A urethane prepolymer (C) is used as an adhesive at the time of adhering the weight percentage of the polarizing film and the cellulose acetate-based protective film.
【0022】かかるウレタンプレポリマー(C)とは、
分子内に2個以上のイソシアネート基を有する化合物
(A)と1分子中にイソシアネート基と反応する活性水
素を有する化合物(B)とを反応させて組成したイソシ
アネート基含有化合物のことであり、分子内に2個以上
のイソシアネート基を有する化合物(A)としては、エ
チレンジイソシアネート、1,4−ブタンジイソシアネ
ート、1,6−ヘキサンジイソシアネート等の脂肪族系
ジイソシアネート;ジシクロヘキシルメタンジイソシア
ネート、シクロヘキサンジイソシアネート、メチルシク
ロヘキサンジイソシアネート等の脂環族系ジイソシアネ
ート;2,4及び2,6−トリレンジイソシアネート、
メチレンジフェニルジイソシアネート、ジフェニルメタ
ン−4,4ジイソシアネート、m−キシリレンジイソシ
アネート等の芳香族系ジイソシアネート;トリフェニル
メタントリイソシアネート等の芳香族系トリイソシアネ
ート等がある。The urethane prepolymer (C) is
An isocyanate group-containing compound formed by reacting a compound (A) having two or more isocyanate groups in the molecule with a compound (B) having active hydrogen that reacts with an isocyanate group in one molecule. Examples of the compound (A) having two or more isocyanate groups therein include aliphatic diisocyanates such as ethylene diisocyanate, 1,4-butane diisocyanate, and 1,6-hexane diisocyanate; dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, and methylcyclohexane diisocyanate. Alicyclic diisocyanates such as 2,4 and 2,6-tolylene diisocyanate,
There are aromatic diisocyanates such as methylene diphenyl diisocyanate, diphenylmethane-4,4 diisocyanate and m-xylylene diisocyanate; aromatic triisocyanates such as triphenylmethane triisocyanate.
【0023】又、1分子中にイソシアネート基と反応す
る活性水素を有する化合物(B)としては、モノ・ジ又
はトリ−エチレン−もしくは−プロピレン−グリコー
ル、1,4−ブタンジオール、2,2−ビス−(4−ヒ
ドロキシルヘキシル)プロパン等のジオール系、あるい
はグリセリン、ヘキサントリオール、トリメチロールプ
ロパン、トリメチロールエタン、トリメチロールベンゼ
ン等のトリオール系のポリオール;アジピン酸、コハク
酸、フタル酸、テレフタル酸あるいはアクリル酸、マレ
イン酸の共重合物等のポリカルボン酸と前記ポリオール
との縮合生成物であるポリエステルポリオール;ヒマシ
油又は他の水酸化脂肪酸のグリセライドエステル;ポリ
エチレングリコール、ポリプロピレングリコールの如き
ポリアルキレングリコール等がある。As the compound (B) having active hydrogen which reacts with an isocyanate group in one molecule, mono-di- or tri-ethylene- or -propylene-glycol, 1,4-butanediol, 2,2- A diol-based polyol such as bis- (4-hydroxylhexyl) propane, or a triol-based polyol such as glycerin, hexanetriol, trimethylolpropane, trimethylolethane, trimethylolbenzene; adipic acid, succinic acid, phthalic acid, terephthalic acid or Polyester polyol which is a condensation product of a polycarboxylic acid such as a copolymer of acrylic acid and maleic acid and the above polyol; castor oil or other glyceride ester of hydroxylated fatty acid; polyalkylene glycol such as polyethylene glycol and polypropylene glycol. There is Lumpur and the like.
【0024】又、上記化合物(A)と化合物(B)とを
反応させてウレタンプレポリマー(C)を製造するに際
して、イソシアネート基と水酸基の比が1.5/1以
上、好ましくは2/1以上であり、最終的に該ウレタン
プレポリマー(C)中の遊離イソシアネート基含有量は
3重量%以上、好ましくは7〜30重量%にコントロー
ルすることが必要で、この遊離のイソシアネート基が偏
光フィルム中の水分あるいは空気中の水分、更には保護
フィルムとして用いられる三酢酸セルロース等に含まれ
る水酸化基と架橋反応を起こして強固な接着性が得られ
るのである。遊離イソシアネート基の量が3重量%未満
では接着剤層と偏光フィルム及び保護フィルムとの接着
性が充分に期待できず好ましくない。更に、本発明で用
いるウレタンプレポリマー(C)の分子量は500〜2
000、好ましくは600〜1500であることが望ま
しく、本発明の効果を顕著に示す。When the urethane prepolymer (C) is produced by reacting the compound (A) with the compound (B), the ratio of isocyanate groups to hydroxyl groups is 1.5 / 1 or more, preferably 2/1. It is necessary to control the free isocyanate group content in the urethane prepolymer (C) to 3% by weight or more, preferably 7 to 30% by weight, and the free isocyanate group is the polarizing film. A strong adhesive property can be obtained by causing a crosslinking reaction with the water content in the air or the water content in the air, and further with a hydroxyl group contained in cellulose triacetate used as a protective film. If the amount of free isocyanate groups is less than 3% by weight, the adhesiveness between the adhesive layer and the polarizing film or protective film cannot be expected sufficiently, which is not preferable. Furthermore, the molecular weight of the urethane prepolymer (C) used in the present invention is 500 to 2
000, preferably 600 to 1500, is desirable, and the effect of the present invention is remarkably exhibited.
【0025】かくして上記ウレタンプレポリマー(C)
は偏光フィルムの偏光性を阻害しない溶剤、例えば酢酸
エチル、酢酸ブチル、酢酸セロソルブ、メチルグリコー
ルアセテート、エチレングリコールアセテート、メトキ
シブチルアセテート、メチルエチルケトン、メチルイソ
ブチルケトン、シクロヘキサノン、メチレンクロライ
ド、トルエン、キシレン、ミネラムスピリット、クレゾ
ール、キシレノール、フラフラール、ナフサ等にて所望
の粘度に希釈され、先にも述べたように偏光フィルムと
保護フィルムとの接着剤として塗布される。Thus, the above urethane prepolymer (C)
Is a solvent that does not impair the polarization of the polarizing film, such as ethyl acetate, butyl acetate, cellosolve acetate, methyl glycol acetate, ethylene glycol acetate, methoxybutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylene chloride, toluene, xylene, mineram. It is diluted to a desired viscosity with spirit, cresol, xylenol, furfural, naphtha, etc., and applied as an adhesive between the polarizing film and the protective film as described above.
【0026】通常、該接着剤は偏光フィルムあるいは保
護フィルム上に均一な膜を形成するように塗布されるの
が有利であり、塗布に際しては、乾燥後の厚みが1〜2
0μm、好ましくは5〜15μmとなるようにするのが
実用的である。1μm未満では接着力が不充分であり、
一方、20μmを越える場合は、使用量の割には効果は
増加せず、又外観が悪化し、実用的ではない。塗布操作
は必ずしもロール等を用いる塗布手段に限定されるもの
ではなく、噴霧法、浸漬法等の手段も含む。又、かかる
接着剤には、ポリビニルアルコール等の水溶性高分子を
併用しても差し支えない。Usually, the adhesive is advantageously applied so as to form a uniform film on the polarizing film or the protective film, and the thickness after drying is 1 to 2 when applied.
It is practical that the thickness is 0 μm, preferably 5 to 15 μm. If it is less than 1 μm, the adhesive strength is insufficient,
On the other hand, when it exceeds 20 μm, the effect is not increased for the amount used and the appearance is deteriorated, which is not practical. The coating operation is not necessarily limited to coating means using a roll or the like, and means such as spraying method and dipping method are also included. Further, a water-soluble polymer such as polyvinyl alcohol may be used in combination with such an adhesive.
【0027】上記偏光フィルムの少なくとも一方の面に
上記ウレタンプレポリマーを塗布し、30〜90℃で1
〜2分間乾燥し、その後、上記酢酸セルロース系保護フ
ィルムを貼り合わせ、更に20〜30℃、50〜80%
RHの条件下で1〜14日間かけて硬化させ、それによ
り偏光フィルム面と保護フィルム面が強固に接着した偏
光板が得られる。又、偏光フィルム(又は酢酸セルロー
ス系保護フィルム)にウレタンプレポリマーを塗布し、
酢酸セルロース系保護フィルム(又は偏光フィルム)と
貼り合わせた後、30〜90℃で1〜2分間乾燥し、更
に20〜30℃、50〜80%RHの条件下で1〜14
日間かけて硬化させてもよい。The urethane prepolymer is applied to at least one surface of the polarizing film, and the coating is applied at 30 to 90 ° C. for 1 hour.
~ 2 minutes, then, the above cellulose acetate-based protective film is laminated, further 20 ~ 30 ℃, 50 ~ 80%
It is cured under RH conditions for 1 to 14 days, whereby a polarizing plate in which the polarizing film surface and the protective film surface are firmly adhered to each other can be obtained. In addition, the urethane prepolymer is applied to the polarizing film (or cellulose acetate-based protective film),
After bonding with a cellulose acetate-based protective film (or a polarizing film), it is dried at 30 to 90 ° C for 1 to 2 minutes, and further 1 to 14 under the conditions of 20 to 30 ° C and 50 to 80% RH.
It may be cured over a period of days.
【0028】更に、上記偏光板には必要に応じて透明な
感圧性接着層を通常知られている方法で設けることがで
きる。該感圧性接着層としてはアクリル酸エステル、例
えばアクリル酸ブチル、アクリル酸エチル、アクリル酸
メチル、アクリル酸2−エチルヘキシル等とα−モノオ
レフィンカルボン酸、例えばアクリル酸、マレイン酸、
イタコン酸、メタクリル酸、クロトン酸等との共重合物
(アクリルニトリル、酢酸ビニル、スチロールの如きビ
ニル単量体を添加したものも含む。)を主体とするもの
が、偏光フィルムの偏光特性を阻害することがないので
特に好ましいが、これに限定されることなく、透明性を
有する感圧性接着剤であれば使用可能で、例えばポリビ
ニルエーテル系、ゴム系等でもよい。If necessary, a transparent pressure-sensitive adhesive layer can be provided on the above polarizing plate by a commonly known method. Examples of the pressure-sensitive adhesive layer include acrylic acid esters such as butyl acrylate, ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, and α-monoolefin carboxylic acids such as acrylic acid and maleic acid.
Those mainly composed of copolymers with itaconic acid, methacrylic acid, crotonic acid, etc. (including those added with vinyl monomers such as acrylonitrile, vinyl acetate and styrene) impair the polarization properties of the polarizing film. However, the pressure-sensitive adhesive is not limited to this, and any pressure-sensitive adhesive having transparency can be used. For example, polyvinyl ether-based or rubber-based adhesive may be used.
【0029】かくして得られた偏光板は、偏光フィルム
と酢酸セルロース系保護フィルムとの接着性に優れるた
め、耐久性が向上し、高温、高湿状態で長期間放置して
もその偏光性が低下しないという特性を持ち、かかる特
性を利用して液晶表示体の用途に用いられ、特に車両用
途、各種工業計器類、家庭用電化製品の表示等に有用で
ある。The thus obtained polarizing plate has excellent adhesiveness between the polarizing film and the cellulose acetate-based protective film, so that the durability is improved, and the polarizing property is lowered even when it is left for a long period of time at high temperature and high humidity. It has the property of not being used, and is used for liquid crystal display applications by utilizing such properties, and is particularly useful for vehicle applications, various industrial instruments, and display of household appliances.
【0030】[0030]
【作用】本発明は、偏光フィルムに、酢酸セルロース系
保護フィルムを接着する際、偏光フィルムの含水率を8
重量%以上にコントロールし、接着剤にウレタンプレポ
リマーを用いることが特徴で、該偏光フィルム中の水分
あるいは空気中の湿気、更には保護フィルム中の水酸化
基等がウレタンプレポリマーと反応し硬化して強固な接
着性が得られるものであり、延いては耐湿熱性に優れた
偏光板を得ることができる。According to the present invention, when the cellulose acetate protective film is adhered to the polarizing film, the water content of the polarizing film is set to 8%.
It is characterized by using a urethane prepolymer as an adhesive, with the content controlled to be more than weight%. The moisture in the polarizing film or the humidity in the air, and further the hydroxyl groups in the protective film react with the urethane prepolymer to cure. Thus, a strong adhesive property can be obtained, and thus a polarizing plate excellent in wet heat resistance can be obtained.
【0031】[0031]
【実施例】以下、本発明について実施例を挙げて具体的
に説明する。尚、実施例中「部」、「%」とあるのは特
に断りのない限り重量基準である。又、本発明でいう偏
光度はEXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "part" and "%" are based on weight unless otherwise specified. In addition, the degree of polarization in the present invention is
【数1】 で示され、H11は2枚の偏光フィルムサンプルの重ね合
わせ時において、偏光フィルムの配向方向が同一方向に
なるように重ね合わせた状態で分光光度計を用いて測定
した透過率(%)、H1は2枚のサンプルの重ね合わせ
時において、偏光フィルムの配向方向が互いに直交する
方向になるように重ね合わせた状態で測定した透過率
(%)である。[Equation 1] H 11 is a transmittance (%) measured by using a spectrophotometer in a state where the two polarizing film samples are superposed so that the orientation directions of the polarizing films are the same, when the two polarizing film samples are superposed. H 1 is a transmittance (%) measured in a state where the two polarizing plates are superposed so that the orientation directions of the polarizing films are orthogonal to each other.
【0032】実施例1 平均重合度3800、ケン化度99.5モル%、厚さ8
0μmのポリビニルアルコール系フィルムをヨウ素0.
2g/l、ヨウ化カリ60g/lよりなる水溶液中に3
0℃にて240秒浸漬し、次いでホウ酸70g/l、ヨ
ウ化カリ30g/lの組成の水溶液に浸漬すると共に、
同時に6倍に一軸延伸しつつ5分間にわたってホウ酸処
理を行った。そして30℃で24時間乾燥して、最終的
に含水率10%の偏光フィルムを得た。該フィルムに、
(A)成分:2,4−トリレンジイソシアネート(80
%)、2,6−トリレンジイソシアネート(20%)、
(B)成分:トリメチロールプロパンよりなるウレタン
プレポリマー(遊離イソシアネート基含有量:19.2
%)の60%酢酸エチル溶液を乾燥後の厚みが10μm
となるように塗布して、80℃で2分間乾燥し、アルカ
リで表面処理した三酢酸セルロースを貼り合わせ、更に
20℃、75%RHの条件下で7日間かけて硬化させ、
偏光板を得た。Example 1 Average degree of polymerization 3800, degree of saponification 99.5 mol%, thickness 8
A polyvinyl alcohol-based film having a thickness of 0 μm was treated with iodine.
3 in an aqueous solution consisting of 2 g / l and 60 g / l potassium iodide
Immerse at 0 ° C. for 240 seconds, then soak in an aqueous solution having a composition of boric acid 70 g / l and potassium iodide 30 g / l,
At the same time, boric acid treatment was carried out for 5 minutes while uniaxially stretching 6 times. Then, it was dried at 30 ° C. for 24 hours to finally obtain a polarizing film having a water content of 10%. On the film,
Component (A): 2,4-tolylene diisocyanate (80
%), 2,6-tolylene diisocyanate (20%),
Component (B): urethane prepolymer consisting of trimethylolpropane (free isocyanate group content: 19.2
%) 60% ethyl acetate solution has a thickness of 10 μm after drying.
And then dried at 80 ° C. for 2 minutes, bonded with cellulose triacetate surface-treated with alkali, and further cured at 20 ° C. and 75% RH for 7 days,
A polarizing plate was obtained.
【0033】これより得られた偏光板を90℃の水中に
30分間浸漬して、更に20℃、75%RHに4時間放
置した後、該偏光板の偏光度変化(%)を測定した。
又、偏光フィルムと三酢酸セルロースとの接着性につい
ては、水中剥離試験、即ち、偏光フィルムと保護フィル
ムの積層サンプルを幅25mm、長さ90mmに切断
し、一端を剥離させて、片方のフィルム端部に荷重(1
00g)を吊り下げ、フィルムの他方の端部をもって、
70℃の温水に浸漬した時点から、接着面が完全に剥離
するまでの時間(秒)を測定することにより、接着力を
評価した。当然のことながら剥離時間が長いほど良好で
ある。尚、評価基準は次の通りである。 ○ 剥離時間が900秒以上 △ 剥離時間が700〜900秒 × 剥離時間が700秒以下The polarizing plate thus obtained was dipped in water at 90 ° C. for 30 minutes, and allowed to stand at 20 ° C. and 75% RH for 4 hours, and then the change in polarization degree (%) of the polarizing plate was measured.
Regarding the adhesiveness between the polarizing film and cellulose triacetate, the underwater peeling test, that is, a laminated sample of the polarizing film and the protective film was cut into a width of 25 mm and a length of 90 mm, and one end was peeled off to remove one film end. Load on the part (1
00g) and hang the other end of the film
The adhesive strength was evaluated by measuring the time (seconds) from the time of immersion in hot water at 70 ° C. until the adhesive surface was completely peeled off. Naturally, the longer the peeling time, the better. The evaluation criteria are as follows. ○ Peeling time 900 seconds or more △ Peeling time 700 to 900 seconds × Peeling time 700 seconds or less
【0034】実施例2 平均重合度1700、ケン化度99.9モル%、厚さ8
0μm、含水率10%のポリビニルアルコール系フィル
ムを用い、ウレタンプレポリマー(C)を、(A)成
分:メチレンビス−(4−フェニルイソシアネート)、
(B)成分:トリメチロールエタンよりなるウレタンプ
レポリマー(遊離イソシアネート基含有量:14.0
%)に変えた以外は実施例1と同様に行い、偏光板を得
た。これより得られた偏光板を実施例1と同様に測定し
た。Example 2 Average degree of polymerization 1700, degree of saponification 99.9 mol%, thickness 8
Using a polyvinyl alcohol-based film having a thickness of 0 μm and a water content of 10%, the urethane prepolymer (C) was mixed with the component (A): methylenebis- (4-phenylisocyanate),
Component (B): urethane prepolymer consisting of trimethylolethane (content of free isocyanate group: 14.0
%) Was carried out in the same manner as in Example 1 to obtain a polarizing plate. The polarizing plate thus obtained was measured in the same manner as in Example 1.
【0035】実施例3 平均重合度4500、ケン化度99.3モル%、厚さ8
0μm、含水率15%のポリビニルアルコール系フィル
ムを用い、ウレタンプレポリマー(C)を、(A)成
分:2,4−トリレンジイソシアネート(80%)、
2,6−トリレンジイソシアネート(20%)、(B)
成分:ジエチレングリコールよりなるウレタンプレポリ
マー(遊離イソシアネート基含有量:20.0%)に変
えた以外は実施例1と同様に行い、偏光板を得た。これ
より得られた偏光板を実施例1と同様に測定した。Example 3 Average degree of polymerization 4500, degree of saponification 99.3 mol%, thickness 8
A urethane prepolymer (C) was used as a component (A): 2,4-tolylene diisocyanate (80%), using a polyvinyl alcohol-based film having a thickness of 0 μm and a water content of 15%.
2,6-Tolylene diisocyanate (20%), (B)
Component: A polarizing plate was obtained in the same manner as in Example 1 except that the urethane prepolymer composed of diethylene glycol (free isocyanate group content: 20.0%) was used. The polarizing plate thus obtained was measured in the same manner as in Example 1.
【0036】比較例1 実施例1において、含水率を5%に調製した後、ウレタ
ンプレポリマー(C)を、(A)成分:ヘキサメチレン
ジイソシアネート、(B)成分:トリメチロールプロパ
ンよりなるウレタンプレポリマー(遊離イソシアネート
基含有量:19.1%)に変えた以外は同様に行い、偏
光板を得た。これより得られた偏光板を実施例1と同様
に測定した。Comparative Example 1 In Example 1, after the water content was adjusted to 5%, the urethane prepolymer (C) was replaced with a urethane prepolymer consisting of (A) component: hexamethylene diisocyanate and (B) component: trimethylolpropane. A polarizing plate was obtained in the same manner except that the polymer (content of free isocyanate group: 19.1%) was used. The polarizing plate thus obtained was measured in the same manner as in Example 1.
【0037】比較例2 実施例1において、ウレタンプレポリマー(C)とし
て、実施例1と同様のウレタンプレポリマーにポリエス
テルポリオールを配合して遊離イソシアネート基含有量
を1.9%に調製した組成物を用いた以外は同様に行
い、偏光板を得た。これより得られた偏光板を実施例1
と同様に測定した。Comparative Example 2 A composition prepared by blending a urethane prepolymer similar to that of Example 1 with polyester polyol as the urethane prepolymer (C) in Example 1 to adjust the free isocyanate group content to 1.9%. A polarizing plate was obtained in the same manner except that was used. The polarizing plate thus obtained was used in Example 1.
It measured similarly to.
【0038】比較例3 実施例1において、ウレタンプレポリマー(C)の代わ
りに、4%ホウ酸水溶液を用いた以外は同様に行い、偏
光板を得た。これより得られた偏光板を実施例1と同様
に測定した。実施例、比較例の結果をまとめて表1に示
す。Comparative Example 3 A polarizing plate was obtained in the same manner as in Example 1, except that a 4% boric acid aqueous solution was used instead of the urethane prepolymer (C). The polarizing plate thus obtained was measured in the same manner as in Example 1. The results of Examples and Comparative Examples are summarized in Table 1.
【0039】[0039]
【表1】 [Table 1]
【0040】[0040]
【発明の効果】本発明の偏光板は、偏光フィルムと酢酸
セルロース系保護フィルムとの接着性に優れるため、耐
久性が向上し、高温、高湿状態で長期間放置してもその
偏光性が低下しないという効果を示す。EFFECTS OF THE INVENTION The polarizing plate of the present invention has excellent adhesiveness between the polarizing film and the cellulose acetate-based protective film, so that the durability is improved and its polarizing property is maintained even when left for a long period of time at high temperature and high humidity. It has the effect of not decreasing.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成6年2月7日[Submission date] February 7, 1994
【手続補正1】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0019[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0019】前述した如き方法で得られたポリビニルア
ルコールの偏光フィルムはその含水率が非常に高く、本
発明では該フィルムを30〜120℃で乾燥を行い、フ
ィルムの含水率を特定範囲にコントロールすることが特
徴である。つまり、該偏光フィルムの含水率が最終的に
8重量%以上、好ましくは8〜50重量%、更に好まし
くは10〜30重量%になるように調製されるのであ
る。又、含水率8重量%未満の偏光フィルムを調湿や再
湿等の方法により含水率を上記範囲に調製して、本発明
の偏光フィルムに供することもできる。8重量%未満の
含水率ではウレタンプレポリマーとの反応性が低下し、
又硬化に時間を要すことになり、一方50重量%を越え
ると基材の収縮が起こり易く、ウレタンプレポリマーと
の密着性が低下することになって本発明の効果は得難
い。The polarizing film of polyvinyl alcohol obtained in such previously described methods a water content is very high, the
In the invention, the film is dried at 30 to 120 ° C.
It is special to control the moisture content of the film within a specific range.
It is a sign. That is, the water content of the polarizing film is finally adjusted to 8% by weight or more, preferably 8 to 50% by weight, more preferably 10 to 30% by weight. Further, a polarizing film having a water content of less than 8% by weight can be adjusted to have the water content in the above range by a method such as humidity control or rewetting, and then used for the polarizing film of the present invention. If the water content is less than 8% by weight, the reactivity with the urethane prepolymer decreases,
Further, it takes a long time to cure, and when it exceeds 50% by weight, the substrate is likely to shrink, and the adhesiveness with the urethane prepolymer is lowered, so that the effect of the present invention is difficult to obtain.
Claims (3)
有する化合物(A)と1分子中にイソシアネート基と反
応する活性水素を有する化合物(B)とを反応させてな
るウレタンプレポリマー(C)を接着剤として用いて、
含水率8重量%以上の偏光フィルムと酢酸セルロース系
保護フィルムを接着してなることを特徴とする偏光板。1. A urethane prepolymer (C) obtained by reacting a compound (A) having two or more isocyanate groups in the molecule with a compound (B) having active hydrogen which reacts with an isocyanate group in one molecule. Using as an adhesive
A polarizing plate comprising a polarizing film having a water content of 8% by weight or more and a cellulose acetate-based protective film adhered to each other.
離イソシアネート基含有量が3重量%以上であることを
特徴とする請求項1記載の偏光板。2. The polarizing plate according to claim 1, wherein the content of free isocyanate groups in the urethane prepolymer (C) is 3% by weight or more.
使用することを特徴とする請求項1記載の偏光板。3. The polarizing plate according to claim 1, wherein a polarizing film having a water content of 8 to 50% by weight is used.
Priority Applications (1)
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JP28760993A JP3503830B2 (en) | 1993-10-21 | 1993-10-21 | Polarizer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28760993A JP3503830B2 (en) | 1993-10-21 | 1993-10-21 | Polarizer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07120617A true JPH07120617A (en) | 1995-05-12 |
JP3503830B2 JP3503830B2 (en) | 2004-03-08 |
Family
ID=17719491
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28760993A Expired - Fee Related JP3503830B2 (en) | 1993-10-21 | 1993-10-21 | Polarizer |
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JP (1) | JP3503830B2 (en) |
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1993
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