JPH07120616A - Polarizing film manufacturing method - Google Patents
Polarizing film manufacturing methodInfo
- Publication number
- JPH07120616A JPH07120616A JP28760893A JP28760893A JPH07120616A JP H07120616 A JPH07120616 A JP H07120616A JP 28760893 A JP28760893 A JP 28760893A JP 28760893 A JP28760893 A JP 28760893A JP H07120616 A JPH07120616 A JP H07120616A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyvinyl alcohol
- temperature
- polarizing film
- weight
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 34
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000008961 swelling Effects 0.000 claims abstract description 29
- 238000004090 dissolution Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 4
- 230000010287 polarization Effects 0.000 abstract description 15
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 150000001639 boron compounds Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000004043 dyeing Methods 0.000 description 10
- 238000012937 correction Methods 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 238000005562 fading Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229940077844 iodine / potassium iodide Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
Landscapes
- Polarising Elements (AREA)
Abstract
(57)【要約】
【目的】 本発明は、偏光性能及び耐久性能に優れ、か
つ製造時の安定性に優れた偏光フィルムの製造法を提供
する。
【構成】 ポリビニルアルコール系原反フィルムを一軸
延伸して偏光フィルムを製造するに当たり、原反フィル
ムとして厚みが３０〜１００μｍであり、かつ、熱水中
での完溶温度（Ｘ）と平衡膨潤度（Ｙ）との関係が下式
で示される範囲であるポリビニルアルコール系フィルム
を用いることを特徴とする偏光フィルムの製造法。
Ｙ＞−０．０６６７Ｘ＋６．７３ ・・・・（I）
Ｘ≧６５ ・・・・（II）
但し、Ｘ：２ｃｍ×２ｃｍのフィルム片の熱水中での完
溶温度（℃）
Ｙ：２０℃の恒温水槽中に、１０ｃｍ×１０ｃｍのフィ
ルム片を１５分間浸漬し膨潤させた後、１０５℃で２時
間乾燥を行った時に下式浸漬後のフィルムの重量／乾燥後のフィルムの重量
より算出される平衡膨潤度（重量分率）(57) [Summary] [Object] The present invention provides a method for producing a polarizing film which is excellent in polarization performance and durability and stability in production. [Structure] In producing a polarizing film by uniaxially stretching a polyvinyl alcohol-based raw film, the raw film has a thickness of 30 to 100 μm, and has a complete dissolution temperature (X) in hot water and an equilibrium swelling degree. A method for producing a polarizing film, which comprises using a polyvinyl alcohol-based film having a relationship with (Y) in a range represented by the following formula. Y> -0.0667X + 6.73 ···· (I) X ≧ 65 ··· (II) However, X: 2 cm × 2 cm complete dissolution temperature in hot water (° C.) Y: 20 A film piece of 10 cm × 10 cm was dipped in a constant temperature water bath at ℃ for 15 minutes for swelling, and then dried at 105 ° C. for 2 hours. Calculated from the weight of the film after dipping / the weight of the film after drying. Equilibrium swelling degree (weight fraction)
Description
【０００１】[0001]
【産業上の利用分野】本発明は耐久性及び偏光性能に優
れ、かつ製造時の安定性に優れた偏光フィルムの製造法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polarizing film which is excellent in durability and polarization performance and is stable during production.
【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。特
に、計器類や台所まわりの家庭電化製品においては苛酷
な条件下で使用される場合が多く、高耐久性及び高偏光
度のフィルムが要請されている。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. In particular, it is often used under severe conditions in instruments and household appliances around the kitchen, and a film having high durability and high polarization degree is required.
【０００３】現在、知られている代表的な偏光フィルム
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化処理を行うことに
よって製造されている。At present, as a typical polarizing film known, there are a polyvinyl alcohol-based film dyed with iodine and a dichroic dye, which are formed by forming an aqueous solution of polyvinyl alcohol. It is produced by uniaxially stretching it for dyeing, or after dyeing it and then uniaxially stretching it, preferably by subjecting it to a durability treatment with a boron compound.
【０００４】しかし、上記のポリビニルアルコール系偏
光フィルムの場合、ヨウ素染色品は偏光性能は良好であ
るが耐湿性や耐熱性が劣り、高湿度雰囲気下や高熱雰囲
気下にさらされると偏光度の低下いわゆる耐久性が劣る
難点があり、一方染料染色品は逆に偏光性能は劣るが耐
久性は優れているという利点を持っている。このよう
に、ポリビニルアルコール系偏光フィルムは一長一短が
あるので、その最終用途の必要性能に応じて適宜使い分
けることが余儀なくされるのが実情である。従って、偏
光性能と耐久性のいずれもが優れたポリビニルアルコー
ル系偏光フィルムが開発できれば、その用途の拡大を含
めて非常に有用であるといえる。However, in the case of the above-mentioned polyvinyl alcohol type polarizing film, the iodine dyed product has a good polarization performance but is inferior in moisture resistance and heat resistance, and its polarization degree is lowered when exposed to a high humidity atmosphere or a high heat atmosphere. So-called durability is inferior. On the other hand, dye-dyed products have the advantage that polarization performance is inferior but durability is excellent. As described above, since the polyvinyl alcohol-based polarizing film has advantages and disadvantages, it is unavoidable that the polyvinyl alcohol-based polarizing film is properly used according to the required performance of the final application. Therefore, it can be said that if a polyvinyl alcohol-based polarizing film excellent in both polarization performance and durability can be developed, it will be very useful including expansion of its application.
【０００５】そこで、本出願人は、上記課題を解決する
ために、ポリビニルアルコール系原反フィルムを染色工
程及びホウ素化合物処理工程の少なくとも一方の工程に
おいて、一軸延伸して偏光フィルムを製造する際に、原
反フィルムとして厚みが３０〜１００μｍで、かつ熱水
中での完溶温度が６５〜９０℃のＰＶＡ系フィルムを用
いることを提案した（特開平４−１７３１２５号公
報）。該方法により、高温、高湿状態での耐久性が改善
され、長期間放置してもその偏光度が変化しない偏光フ
ィルムが得られた。Therefore, in order to solve the above-mentioned problems, the present applicant has uniaxially stretched a polyvinyl alcohol raw film in at least one of the dyeing process and the boron compound treatment process to produce a polarizing film. It has been proposed to use a PVA-based film having a thickness of 30 to 100 μm and a complete dissolution temperature in hot water of 65 to 90 ° C. as a raw film (JP-A-4-173125). By this method, the durability at high temperature and high humidity was improved, and a polarizing film whose polarization degree did not change even when left for a long time was obtained.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、本発明
者等が更に検討を重ねた結果、特開平４−１７３１２５
号公報では、確かに高温、高湿での耐久性に優れた偏光
フィルムが得られてはいるものの、ポリビニルアルコー
ル系原反フィルムの厚み、熱水中における完溶温度の規
定だけでは偏光性能や耐久性能等が安定しない、即ち、
製造条件のわずかな変動において製品の偏光度にバラツ
キが生じたりすることがあり、細心の工程管理が必要と
されるということが判明した。However, as a result of further investigations by the present inventors, JP-A-4-173125
In the official gazette, although a polarizing film excellent in durability at high temperature and high humidity is certainly obtained, the polarizing performance and the thickness of the polyvinyl alcohol-based raw film and the regulation of the complete dissolution temperature in hot water are sufficient. Durability is not stable, that is,
It was found that even a slight variation in the manufacturing conditions may cause variations in the degree of polarization of the product, requiring careful process control.
【０００７】又、該公報における製造法については、一
軸延伸が最終的に７．２倍までの偏光フィルムを作製し
実験を行っているが、生産工程において精度良く延伸倍
率を制御することは容易ではなく、該工程中に延伸が
７．２倍を越えてしまうと、フィルムが切断したり、亀
裂が生じたりする等の問題が発生したりして、この点で
もその生産管理には充分な注意を払わなければならな
い。即ち、偏光フィルム製造時に、特にフィルムの延伸
時において工程中避けることの難しい延伸過剰にも耐え
得るだけの原反フィルムが要求されるようになってき
た。そのため、高度の偏光性能や耐久性能をもち、しか
も上記のような延伸過剰となった時にもフィルム切れの
ない、つまり高延伸倍率に耐え得る優れた偏光フィルム
の製造法の開発が望まれているのである。Regarding the manufacturing method in this publication, a polarizing film whose final uniaxial stretching is up to 7.2 times is prepared and an experiment is conducted, but it is easy to control the stretching ratio with high precision in the production process. However, if the stretching exceeds 7.2 times during the process, problems such as film cutting and cracking occur, which is also sufficient for production control. You must pay attention. That is, there has been a demand for a raw film that can withstand overstretching, which is difficult to avoid during the process of manufacturing a polarizing film, especially during stretching of the film. Therefore, it is desired to develop a method for producing an excellent polarizing film which has a high degree of polarization performance and durability and does not break even when it is overstretched as described above, that is, can withstand a high draw ratio. Of.
【０００８】[0008]
【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、ポリビ
ニルアルコール系原反フィルムを一軸延伸して偏光フィ
ルムを製造するに当たり、原反フィルムとして厚みが３
０〜１００μｍであり、かつ熱水中での完溶温度（Ｘ）
と平衡膨潤度（Ｙ）との関係が下式で示される範囲であ
るポリビニルアルコール系フィルム、特に平均重合度が
２６００以上のポリビニルアルコール系フィルムを用い
る場合、上記の目的が達成できることを見出し、本発明
を完成した。 Ｙ＞−０．０６６７Ｘ＋６．７３ ・・・・（I） Ｘ≧６５ ・・・・（II） 但し、Ｘ：２ｃｍ×２ｃｍのフィルム片の熱水中での完
溶温度（℃） Ｙ：２０℃の恒温水槽中に、１０ｃｍ×１０ｃｍのフィ
ルム片を１５分間浸漬し膨潤させた後、１０５℃で２時
間乾燥を行った時に下式 （浸漬後のフィルムの重量−乾燥後のフィルムの重量）
／乾燥後のフィルムの重量 より算出される平衡膨潤度（重量分率）SUMMARY OF THE INVENTION However, as a result of the inventors of the present invention earnestly conducting research to solve such a problem, in producing a polarizing film by uniaxially stretching a polyvinyl alcohol-based raw fabric film, a raw fabric film is produced. Has a thickness of 3
0 to 100 μm and the complete solution temperature (X) in hot water
And the equilibrium swelling degree (Y) are in the range represented by the following formula, particularly when a polyvinyl alcohol-based film having an average degree of polymerization of 2600 or more is used, it is found that the above object can be achieved, Completed the invention. Y> -0.0667X + 6.73 ··· (I) X ≧ 65 ··· (II) However, X: complete dissolution temperature (° C) Y: 20 of a 2 cm x 2 cm film piece in hot water. After dipping a 10 cm × 10 cm film piece for 15 minutes in a constant temperature water bath at ℃ to swell it, and drying at 105 ° C. for 2 hours, the following formula was obtained (weight of film after immersion−weight of film after drying).
/ Equilibrium swelling degree (weight fraction) calculated from the weight of the dried film
【０００９】本発明のかかる効果は上記したようにポリ
ビニルアルコール系フィルムとして特定の厚み及び特定
の完溶温度（Ｘ）と平衡膨潤度（Ｙ）との関係を有し、
好ましくは高重合度品を用いることによって得られるも
のである。尚、本発明でいう完溶温度（Ｘ）は、２ｌビ
ーカーに２０００ｍｌの水を入れ、３０℃に昇温した
後、２ｃｍ×２ｃｍのフィルム片を投入し撹拌しながら
３℃／分の速度で水温を上昇させ、フィルムが完全に溶
解する温度で定義される。又、平衡膨潤度（Ｙ）は、２
０℃の恒温水槽中に１０ｃｍ×１０ｃｍのフィルム片を
１５分間浸漬し膨潤させた後、１０５℃で２時間乾燥を
行った時、次式により算出される。 平衡膨潤度（重量分率）＝（浸漬後のフィルムの重量−
乾燥後のフィルムの重量）／乾燥後のフィルムの重量 以下、本発明について具体的に説明する。As described above, the effect of the present invention has a relationship between a specific thickness and a specific complete solution temperature (X) and an equilibrium swelling degree (Y) as a polyvinyl alcohol film.
It is preferably obtained by using a high degree of polymerization product. The complete dissolution temperature (X) in the present invention is 2000 ml of water in a 2 l beaker, the temperature is raised to 30 ° C., a film piece of 2 cm × 2 cm is charged, and the temperature is 3 ° C./min while stirring. It is defined as the temperature at which the water temperature rises and the film completely dissolves. The equilibrium swelling degree (Y) is 2
When a film piece of 10 cm × 10 cm is dipped in a constant temperature water bath of 0 ° C. for 15 minutes to be swollen and then dried at 105 ° C. for 2 hours, it is calculated by the following formula. Equilibrium swelling degree (weight fraction) = (weight of film after immersion-
The weight of the film after drying) / the weight of the film after drying The present invention will be specifically described below.
【００１０】本発明の偏光フィルムは、ポリビニルアル
コール系樹脂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
〜１００モル％、好ましくは９８〜１００モル％が実用
的である。本発明の効果を得るためには、平均重合度が
２６００以上、好ましくは３５００〜５０００が有利で
ある。２６００未満では顕著な効果は得難い。The polarizing film of the present invention is a uniaxially stretched film of a polyvinyl alcohol resin 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
Is practically 100 to 100 mol%, preferably 98 to 100 mol%. In order to obtain the effects of the present invention, it is advantageous that the average degree of polymerization is 2600 or more, preferably 3500 to 5000. If it is less than 2600, it is difficult to obtain a remarkable effect.
【００１１】該ポリビニルアルコールは公知の方法に従
って製膜される。ポリビニルアルコールを水、有機溶
剤、水／有機溶剤混合溶剤等に溶解し流延する方法が一
般的である。溶液の濃度は５〜２０重量％程度が実用的
である。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。原反フィルムとしてその膜厚は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。The polyvinyl alcohol is formed into a film by a known method. A general method is to dissolve polyvinyl alcohol in water, an organic solvent, a water / organic solvent mixed solvent, or the like and cast the solution. It is practical that the concentration of the solution is about 5 to 20% by weight. In addition, a so-called gel film forming method in which a solution of polyvinyl alcohol is introduced into a coagulation bath to form a film can be carried out. As a raw film, its thickness is 30-1
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.
【００１２】かつ、該フィルムは熱水中での完溶温度
（Ｘ）と平衡膨潤度（Ｙ）との関係が前述した通り下式
で示される範囲でなければならない。 Ｙ＞−０．０６６７Ｘ＋６．７３ ・・・・（I） Ｘ≧６５ ・・・・（II） かかる特定のフィルムはポリビニルアルコール系フィル
ムの製膜時の乾燥条件、あるいは製膜後の熱処理条件等
を調製することにより作製できるが、いずれにしてもか
かる性質をもつフィルムを用いることによってのみ、一
軸延伸が実施可能となり、製造時の安定性や生産性等が
向上するといった本発明の効果を顕著に示す偏光フィル
ムが得られるのである。熱水中での完溶温度としては
（II）式に示すように６５℃以上、好ましくは６５〜９
０℃、更に好ましくは７１〜８０℃である。Further, the film must have a relationship between the complete solution temperature (X) in hot water and the equilibrium swelling degree (Y) within the range represented by the following formula as described above. Y> −0.0667X + 6.73 (...) (I) X ≧ 65 (...) (II) The specific film is a drying condition during the film formation of the polyvinyl alcohol film, or a heat treatment condition after the film formation. Can be prepared by preparing the above, but in any case, uniaxial stretching can be carried out only by using a film having such properties, and the effects of the present invention such as the stability during production and the improvement of productivity are remarkable. Thus, the polarizing film shown in can be obtained. The temperature of complete dissolution in hot water is 65 ° C or higher, preferably 65 to 9 as shown in the formula (II).
The temperature is 0 ° C, more preferably 71 to 80 ° C.
【００１３】完溶温度が６５℃以下のフィルムでは延伸
時にフィルムが一部溶解したり劣化が起こったりして実
用にならず、一方９０℃以上のフィルムでは充分な延伸
が行われなかったり、延伸時のトラブルが発生し易くな
ったりする。又、完溶温度が上記範囲であっても、
（I）式で示す平衡膨潤度が上式範囲外のフィルムで
は、偏光フィルムの偏光性能、耐久性能、更には製造時
の製造安定性等が低下する等の問題が発生し、目的とす
る偏光フィルムが得難くなるのである。A film having a complete melting temperature of 65 ° C. or less cannot be put to practical use because the film partially melts or deteriorates during stretching, while a film having a temperature of 90 ° C. or more cannot be sufficiently stretched or is stretched. Trouble with time easily occurs. Further, even if the complete dissolution temperature is in the above range,
When the equilibrium swelling degree represented by the formula (I) is outside the range of the above formula, problems such as deterioration of polarization performance, durability performance of the polarizing film, and manufacturing stability at the time of production occur, and the desired polarization It's hard to get a film.
【００１４】上記の原反フィルムを延伸及び染色、ホウ
素化合物処理して偏光フィルムを製造するのであるが、
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、好ましくは両工程中に一軸延伸を実施す
ることが望ましいが、これに限定されることなく、一旦
延伸したフィルムを染色あるいはホウ素化合物処理した
り、染色あるいはホウ素化合物処理が終了した後一軸延
伸を行っても差し支えない。The above original film is stretched, dyed and treated with a boron compound to produce a polarizing film.
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, preferably both steps, but the invention is not limited thereto, and the once stretched film is dyed or treated with a boron compound. Alternatively, uniaxial stretching may be performed after the dyeing or the boron compound treatment is completed.
【００１５】フィルムへのヨウ素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３
０〜５００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
ては浸漬が好ましいが、塗布、噴霧等の任意の手段も適
用できる。The iodine dyeing on 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. Dyeing time is 3
Practical use is about 0 to 500 seconds. The temperature of the treatment bath is 30
-80 degreeC is preferable. A small amount of an organic solvent compatible with water may be contained in addition to the water solvent. The contact means is preferably dipping, but any means such as coating and spraying can be applied.
【００１６】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.
【００１７】本発明では、前述した如く一軸延伸におい
ては特に制限されないが、染色処理工程又はホウ素化合
物処理工程の少なくとも一方の工程中に一軸延伸するこ
とが好ましく、延伸倍率は最終的には２〜８倍、好まし
くは３〜６倍にすることが実用的で、この延伸は両工程
にわたって実施するのが好ましい。両工程において延伸
する場合、染色処理工程で１．２〜２倍、好ましくは
１．２〜１．５倍、ホウ素化合物処理工程で２〜６倍、
好ましくは２〜４倍が望ましい。かかる範囲に延伸する
にはロール延伸、テンター延伸等が任意に実施される
が、通常前者が行われる。ロール延伸は一段式、多段式
のいずれも実施可能である。In the present invention, the uniaxial stretching is not particularly limited as described above, but it is preferable that the uniaxial stretching is performed during at least one of the dyeing treatment step and the boron compound treatment step, and the stretching ratio is finally 2 to. It is practically 8 times, preferably 3 to 6 times, and it is preferable to carry out this stretching over both steps. In the case of stretching in both steps, 1.2 to 2 times, preferably 1.2 to 1.5 times in the dyeing treatment step, 2 to 6 times in the boron compound treatment step,
It is preferably 2 to 4 times. Roll stretching, tenter stretching and the like are optionally carried out for stretching in such a range, but the former is usually carried out. Roll stretching can be performed in either a single-stage type or a multi-stage type.
【００１８】このようにして得られた偏光フィルムは、
その両面あるいは片面に光学的透明度と機械的強度に優
れた保護フィルムを貼合、乾燥して偏光板として使用さ
れる。保護フィルムとしては従来から知られているセル
ロースアセテート系フィルム、アクリル系フィルム、ポ
リエステル系樹脂フィルム、ポリオレフィン系樹脂フィ
ルム、ポリカーボネート系フィルム、ポリエーテルエー
テルケトン系フィルム、ポリスルホン系フィルムが挙げ
られる。The polarizing film thus obtained is
A protective film having excellent optical transparency and mechanical strength is laminated on both sides or one side and dried to be used as a polarizing plate. Examples of the protective film include conventionally known cellulose acetate film, acrylic film, polyester resin film, polyolefin resin film, polycarbonate film, polyether ether ketone film, and polysulfone film.
【００１９】[0019]
【作用】本発明は、偏光フィルムの耐久性及び偏光性能
の安定性に優れ、かつ偏光フィルムの製造時における製
造安定性に非常に優れた製造法であり、該方法により得
られる偏光フィルムは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 present invention is a manufacturing method which is excellent in the durability of the polarizing film and in the stability of the polarizing performance and in the manufacturing stability when manufacturing the polarizing film, and the polarizing film obtained by the method is It is used for liquid crystal displays due to its characteristics, and is particularly useful for vehicles, various industrial instruments, and displays of household electric appliances.
【００２０】[0020]
【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。更に本発明では偏光性及び耐久性に関す
る性能をまとめて耐湿熱性ということで評価を行った。[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. Further, in the present invention, the performances relating to the polarization property and the durability are collectively evaluated as the wet heat resistance.
【００２１】実施例１ 平均重合度３８００、ケン化度９９．５モル％のポリビ
ニルアルコールを水に溶解し、濃度８．０％の水溶液を
得た。該液をポリエチレンテレフタレート上に流延後、
３０℃で２４時間風乾して膜厚８０μｍ、完溶温度
（Ｘ）７１．６℃、平衡膨潤度（Ｙ）２．４（該平衡膨
潤度は本願規定の（I）より算出されるＹ＞１．９５を
満足するものである）のフィルムとした。該フィルムを
１０ｃｍ幅に切断してチャックに装着した。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３０℃にて２４０秒浸漬し、同時に１．２倍に
一軸延伸し、次いでホウ酸６０ｇ／ｌ、ヨウ化カリ３０
ｇ／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。
最後に室温で２４時間乾燥した。Example 1 Polyvinyl alcohol having an average degree of polymerization of 3800 and a saponification degree of 99.5 mol% was dissolved in water to obtain an aqueous solution having a concentration of 8.0%. After casting the liquid on polyethylene terephthalate,
Air-dried at 30 ° C. for 24 hours, film thickness 80 μm, complete dissolution temperature (X) 71.6 ° C., equilibrium swelling degree (Y) 2.4 (the equilibrium swelling degree is calculated from (I) of the present specification> Film satisfying 1.95). The film was cut into a width of 10 cm and mounted on a chuck. The film was immersed in an aqueous solution containing 0.2 g / l of iodine and 60 g / l of potassium iodide at 30 ° C. for 240 seconds and simultaneously uniaxially stretched 1.2 times, and then 60 g / l of boric acid and 30 parts of potassium iodide.
It was immersed in an aqueous solution having a composition of g / l, and simultaneously treated with boric acid for 5 minutes while being uniaxially stretched 6 times.
Finally, it was dried at room temperature for 24 hours.
【００２２】これより得られた偏光フィルムについて、
水中退色温度、即ち偏光フィルムを水中に浸漬し、水温
を２〜３℃／分の割合で昇温した時に、偏光フィルムが
完全に退色する温度を測定することにより、耐湿熱性を
評価した。水中退色温度が６０℃以上の偏光フィルムは
耐湿熱性に優れており、高耐久の偏光フィルムであると
いえる。又、上記工程において、フィルムの染色後、該
フィルムをホウ酸処理中６．４倍に一軸延伸しても、フ
ィルムの切断や亀裂は見られなかった。Regarding the polarizing film thus obtained,
Wet heat resistance was evaluated by measuring the fading temperature in water, that is, the temperature at which the polarizing film completely fades when the polarizing film was immersed in water and the water temperature was raised at a rate of 2 to 3 ° C./min. A polarizing film having a fading temperature in water of 60 ° C. or higher has excellent wet heat resistance and can be said to be a highly durable polarizing film. Further, in the above process, after dyeing the film, even if the film was uniaxially stretched 6.4 times in the boric acid treatment, neither cutting nor cracking of the film was observed.
【００２３】実施例２ 平均重合度２６００、ケン化度９９．５モル％のポリビ
ニルアルコールを用いて得られる原反フィルムを４０℃
で２４時間風乾した後、９０℃で３分間熱処理して完溶
温度（Ｘ）７２℃、平衡膨潤度（Ｙ）２．２（該平衡膨
潤度は本願規定の（I）より算出されるＹ＞１．９３を
満足するものである）のフィルムとした以外は実施例１
と同様に偏光フィルムを製造した。これより得られた偏
光フィルムについて、実施例１と同様に耐湿熱性を評価
し、又、実施例１と同様にホウ酸処理中６．４倍に一軸
延伸しても、フィルムの切断や亀裂は見られなかった。Example 2 A raw film obtained by using polyvinyl alcohol having an average degree of polymerization of 2600 and a degree of saponification of 99.5 mol% was prepared at 40 ° C.
After air-drying for 24 hours at 90 ° C., heat treatment is performed for 3 minutes at 90 ° C., complete dissolution temperature (X) 72 ° C., equilibrium swelling degree (Y) 2.2 (the equilibrium swelling degree is calculated from (I) of the present application). > 1.93) except that the film is a film of Example 1
A polarizing film was manufactured in the same manner as in. With respect to the polarizing film thus obtained, the moist heat resistance was evaluated in the same manner as in Example 1, and even if the film was uniaxially stretched 6.4 times during the boric acid treatment in the same manner as in Example 1, the film was not cut or cracked. I couldn't see it.
【００２４】比較例１ 実施例１において、ポリビニルアルコールの原反フィル
ムを６０℃で２４時間乾燥して、完溶温度（Ｘ）７４．
５℃、平衡膨潤度（Ｙ）１．６（該平衡膨潤度は本願規
定の（I）より算出されるＹ＞１．７６の範囲外であ
る）のフィルムとした以外は同様に偏光フィルムを製造
した。これより得られた偏光フィルムについて、実施例
１と同様に耐湿熱性を評価し、又、実施例１と同様にホ
ウ酸処理中に一軸延伸したところ延伸倍率が６倍を越え
たところで、フィルムの切断が見られた。Comparative Example 1 In Example 1, the raw film of polyvinyl alcohol was dried at 60 ° C. for 24 hours to give a complete dissolution temperature (X) of 74.
A polarizing film was prepared in the same manner except that a film having an equilibrium swelling degree (Y) of 1.6 (the equilibrium swelling degree is outside the range of Y> 1.76 calculated from (I) of the present application) at 5 ° C. was used. Manufactured. With respect to the polarizing film thus obtained, the moist heat resistance was evaluated in the same manner as in Example 1, and when the film was uniaxially stretched during the treatment with boric acid in the same manner as in Example 1, the stretching ratio exceeded 6 times. A break was seen.
【００２５】比較例２ 実施例２において、ポリビニルアルコールの原反フィル
ムを７０℃で２４時間乾燥した後、１００℃で３分間熱
処理して完溶温度（Ｘ）７５．３℃、平衡膨潤度（Ｙ）
１．６（該平衡膨潤度は本願規定の（I）より算出され
るＹ＞１．７１の範囲外である）のフィルムとした以外
は同様に偏光フィルムを製造した。これより得られた偏
光フィルムについて、実施例１と同様に耐湿熱性を評価
し、又、実施例１と同様にホウ酸処理中に一軸延伸した
ところ延伸倍率が６倍を越えたところで、フィルムの切
断が見られた。実施例、比較例の結果をまとめて表１に
示す。Comparative Example 2 In Example 2, the polyvinyl alcohol raw film was dried at 70 ° C. for 24 hours and then heat-treated at 100 ° C. for 3 minutes to obtain a complete dissolution temperature (X) of 75.3 ° C. and an equilibrium swelling degree ( Y)
A polarizing film was produced in the same manner except that the film was 1.6 (the degree of equilibrium swelling is outside the range of Y> 1.71 calculated from (I) of the present application). With respect to the polarizing film thus obtained, the moist heat resistance was evaluated in the same manner as in Example 1, and when the film was uniaxially stretched during the treatment with boric acid in the same manner as in Example 1, the stretching ratio exceeded 6 times. A break was seen. The results of Examples and Comparative Examples are summarized in Table 1.
【００２６】[0026]
【表１】 実施例１ 実施例２ 比較例１ 比較例２ 完溶温度(Ｘ) (℃) ７１．６ ７２．０ ７４．５ ７５．３ 平衡膨潤度(Ｙ) ２.４ ２．２ １．６ １．６ (Ｙ)の範囲＜計算値＞ Ｙ＞1.95 Ｙ＞1.93 Ｙ＞1.76 Ｙ＞1.71 水中退色温度（℃） ６３ ６２ ５２ ５４ Table 1 Example 1 Example 2 Comparative Example 1 Comparative Example 2 Complete solution temperature (X) (° C) 71.6 72.0 74.5 75.3 Equilibrium swelling degree (Y) 2.4 2.2 1 6.6 Range of 1.6 (Y) <Calculated value>Y> 1.95 Y> 1.93 Y> 1.76 Y> 1.71 Water fading temperature (° C) 63 62 52 54
【００２７】[0027]
【発明の効果】本発明では、原反フィルムとして特定の
完溶温度及び平衡膨潤度を有するポリビニルアルコール
系フィルムを使用することによって、偏光フィルムの偏
光性能及び耐久性能に優れ、かつ偏光フィルム製造時の
安定性に非常に優れた効果を示す。EFFECTS OF THE INVENTION In the present invention, by using a polyvinyl alcohol film having a specific complete solution temperature and a specific equilibrium swelling degree as a raw film, the polarizing film is excellent in polarization performance and durability, and at the time of manufacturing the polarizing film. Shows a very good effect on the stability of.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年４月２５日[Submission date] April 25, 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】請求項１[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００８】[0008]
【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、ポリビ
ニルアルコール系原反フィルムを一軸延伸して偏光フィ
ルムを製造するに当たり、原反フィルムとして厚みが３
０〜１００μｍであり、かつ熱水中での完溶温度（Ｘ）
と平衡膨潤度（Ｙ）との関係が下式で示される範囲であ
るポリビニルアルコール系フィルム、特に平均重合度が
２６００以上のポリビニルアルコール系フィルムを用い
る場合、上記の目的が達成できることを見出し、本発明
を完成した。 Ｙ＞−０．０６６７Ｘ＋６．７３ ・・・・（I） Ｘ≧６５ ・・・・（II） 但し、Ｘ：２ｃｍ×２ｃｍのフィルム片の熱水中での完
溶温度（℃） Ｙ：２０℃の恒温水槽中に、１０ｃｍ×１０ｃｍのフィ
ルム片を１５分間浸漬し膨潤させた後、１０５℃で２時
間乾燥を行った時に下式浸漬後のフィルムの重量／乾燥後のフィルムの重量 より算出される平衡膨潤度（重量分率）However, the inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, when manufacturing a polarizing film by uniaxially stretching a polyvinyl alcohol-based raw film, the original film is used. Has a thickness of 3
0 to 100 μm and the complete solution temperature (X) in hot water
It was found that the above object can be achieved by using a polyvinyl alcohol-based film having a relationship between the equilibrium swelling degree (Y) and the degree of equilibrium swelling (Y) in the range represented by the following formula, particularly when a polyvinyl alcohol-based film having an average polymerization degree of 2600 or more is used, Completed the invention. Y> -0.0667X + 6.73 ···· (I) X ≧ 65 ··· (II) However, X: 2 cm × 2 cm complete dissolution temperature in hot water (° C.) Y: 20 A film piece of 10 cm × 10 cm was dipped in a constant temperature water bath at ℃ for 15 minutes for swelling, and then dried at 105 ° C. for 2 hours. Calculated from the weight of the film after dipping / the weight of the film after drying. Equilibrium swelling degree (weight fraction)
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】本発明のかかる効果は上記したようにポリ
ビニルアルコール系フィルムとして特定の厚み及び特定
の完溶温度（Ｘ）と平衡膨潤度（Ｙ）との関係を有し、
好ましくは高重合度品を用いることによって得られるも
のである。尚、本発明でいう完溶温度（Ｘ）は、２ｌビ
ーカーに２０００ｍｌの水を入れ、３０℃に昇温した
後、２ｃｍ×２ｃｍのフィルム片を投入し撹拌しながら
３℃／分の速度で水温を上昇させ、フィルムが完全に溶
解する温度で定義される。又、平衡膨潤度（Ｙ）は、２
０℃の恒温水槽中に１０ｃｍ×１０ｃｍのフィルム片を
１５分間浸漬し膨潤させた後、１０５℃で２時間乾燥を
行った時、次式により算出される。平衡膨潤度（重量分率）＝浸漬後のフィルムの重量／乾
燥後のフィルムの重量 以下、本発明について具体的に説明する。As described above, the effect of the present invention has a relationship between a specific thickness and a specific complete solution temperature (X) and an equilibrium swelling degree (Y) as a polyvinyl alcohol film.
It is preferably obtained by using a high degree of polymerization product. The complete dissolution temperature (X) in the present invention is 2000 ml of water in a 2 l beaker, the temperature is raised to 30 ° C., a film piece of 2 cm × 2 cm is charged, and the temperature is 3 ° C./min while stirring. It is defined as the temperature at which the water temperature rises and the film completely dissolves. The equilibrium swelling degree (Y) is 2
When a film piece of 10 cm × 10 cm is dipped in a constant temperature water bath of 0 ° C. for 15 minutes to be swollen and then dried at 105 ° C. for 2 hours, it is calculated by the following formula. Equilibrium swelling degree (weight fraction) = weight of film after immersion / dry
The weight of the film after drying Hereinafter, the present invention will be specifically described.
Claims (3)
一軸延伸して偏光フィルムを製造するに当たり、原反フ
ィルムとして厚みが３０〜１００μｍであり、かつ、熱
水中での完溶温度（Ｘ）と平衡膨潤度（Ｙ）との関係が
下式で示される範囲であるポリビニルアルコール系フィ
ルムを用いることを特徴とする偏光フィルムの製造法。 Ｙ＞−０．０６６７Ｘ＋６．７３ ・・・・（I） Ｘ≧６５ ・・・・（II） 但し、Ｘ：２ｃｍ×２ｃｍのフィルム片の熱水中での完
溶温度（℃） Ｙ：２０℃の恒温水槽中に、１０ｃｍ×１０ｃｍのフィ
ルム片を１５分間浸漬し膨潤させた後、１０５℃で２時
間乾燥を行った時に下式 （浸漬後のフィルムの重量−乾燥後のフィルムの重量）
／乾燥後のフィルムの重量 より算出される平衡膨潤度（重量分率）1. When producing a polarizing film by uniaxially stretching a polyvinyl alcohol raw fabric film, the raw fabric film has a thickness of 30 to 100 μm and is in equilibrium with a complete solution temperature (X) in hot water. A method for producing a polarizing film, which comprises using a polyvinyl alcohol-based film having a swelling degree (Y) in a range represented by the following formula. Y> -0.0667X + 6.73 ···· (I) X ≧ 65 ··· (II) However, X: 2 cm × 2 cm complete dissolution temperature in hot water (° C.) Y: 20 After dipping a 10 cm × 10 cm film piece in a constant temperature water bath at 15 ° C. for 15 minutes to allow it to swell, it was dried at 105 ° C. for 2 hours using the following formula (weight of film after immersion−weight of film after drying).
/ Equilibrium swelling degree (weight fraction) calculated from the weight of the dried film
ルアルコール系原反フィルムを用いることを特徴とする
請求項１記載の製造法。2. The method according to claim 1, wherein a polyvinyl alcohol raw film having a complete dissolution temperature of 65 to 90 ° C. is used.
アルコール系原反フィルムを用いることを特徴とする請
求項１記載の製造法。3. The method according to claim 1, wherein a polyvinyl alcohol-based raw film having an average degree of polymerization of 2600 or more is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28760893A JP3327423B2 (en) | 1993-10-21 | 1993-10-21 | Manufacturing method of polarizing film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28760893A JP3327423B2 (en) | 1993-10-21 | 1993-10-21 | Manufacturing method of polarizing film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07120616A true JPH07120616A (en) | 1995-05-12 |
| JP3327423B2 JP3327423B2 (en) | 2002-09-24 |
Family
ID=17719478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28760893A Ceased JP3327423B2 (en) | 1993-10-21 | 1993-10-21 | Manufacturing method of polarizing film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3327423B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1090517A (en) * | 1996-09-17 | 1998-04-10 | Sumitomo Chem Co Ltd | Iodine-based polarizing plate |
| KR20110102902A (en) | 2008-12-18 | 2011-09-19 | 가부시키가이샤 구라레 | Preparation of Polarizing Film |
| JP2016048382A (en) * | 2015-10-28 | 2016-04-07 | 株式会社クラレ | Polyvinyl alcohol film |
| KR20160120356A (en) | 2008-12-18 | 2016-10-17 | 주식회사 쿠라레 | Polyvinyl alcohol film |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3118841B1 (en) | 2006-07-14 | 2021-01-06 | Dexerials Corporation | Resin composition and display apparatus |
| KR101498309B1 (en) | 2007-04-09 | 2015-03-03 | 데쿠세리아루즈 가부시키가이샤 | image display device |
| JP5401824B2 (en) | 2007-04-09 | 2014-01-29 | デクセリアルズ株式会社 | Image display device |
| JP2009186957A (en) | 2007-04-09 | 2009-08-20 | Sony Chemical & Information Device Corp | Resin composition and display device |
| JP5470735B2 (en) | 2007-04-10 | 2014-04-16 | デクセリアルズ株式会社 | Manufacturing method of image display device |
-
1993
- 1993-10-21 JP JP28760893A patent/JP3327423B2/en not_active Ceased
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1090517A (en) * | 1996-09-17 | 1998-04-10 | Sumitomo Chem Co Ltd | Iodine-based polarizing plate |
| KR20110102902A (en) | 2008-12-18 | 2011-09-19 | 가부시키가이샤 구라레 | Preparation of Polarizing Film |
| KR20160120356A (en) | 2008-12-18 | 2016-10-17 | 주식회사 쿠라레 | Polyvinyl alcohol film |
| JP2016048382A (en) * | 2015-10-28 | 2016-04-07 | 株式会社クラレ | Polyvinyl alcohol film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3327423B2 (en) | 2002-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4789925B2 (en) | Iodine polarizing film, method for producing the same, and polarizing plate using the same | |
| JP2543748B2 (en) | Polarizing film and manufacturing method thereof | |
| JP2631403B2 (en) | Manufacturing method of polarized film with excellent durability | |
| WO2018021274A1 (en) | Polarizing film and production method therefor | |
| JP3021494B2 (en) | Polarizing film and manufacturing method thereof | |
| JP5079184B2 (en) | Polarized film | |
| JPH07120616A (en) | Polarizing film manufacturing method | |
| JP2512408B2 (en) | Method for producing polarizing film with excellent polarization | |
| JPH06172554A (en) | Polarizing film and its production | |
| JPH0520723B2 (en) | ||
| JPH06254958A (en) | Polyvinyl alcohol resin stretched film | |
| JP3392196B2 (en) | Manufacturing method of polarizing film | |
| JP3283564B2 (en) | Method for producing polyvinyl alcohol-based film | |
| JPH06235815A (en) | Polarizing film and manufacturing method thereof | |
| JPH07306316A (en) | Polarizing plate manufacturing method | |
| JP2895435B2 (en) | Manufacturing method of polarizing film with excellent durability | |
| JP4060321B2 (en) | Polarized film | |
| JPH07198939A (en) | Polarizing film manufacturing method | |
| JP2018180022A (en) | Method of manufacturing polarizer | |
| JPH06265727A (en) | Method for manufacturing polarizing film | |
| JPH04223404A (en) | polarizing film | |
| JPH06289224A (en) | Polarizing film manufacturing method | |
| JP3273627B2 (en) | Polarizing film | |
| JPH1152130A (en) | Manufacturing method of polarizing film | |
| JP3730397B2 (en) | Manufacturing method of polarizing film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 19940425 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 19981111 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20000717 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20001106 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20001221 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20011210 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20020117 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20020320 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20020626 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20020627 |
|
| RVOP | Cancellation by post-grant opposition |