JPH07134210A - Polarizing film manufacturing method - Google Patents
Polarizing film manufacturing methodInfo
- Publication number
- JPH07134210A JPH07134210A JP28309193A JP28309193A JPH07134210A JP H07134210 A JPH07134210 A JP H07134210A JP 28309193 A JP28309193 A JP 28309193A JP 28309193 A JP28309193 A JP 28309193A JP H07134210 A JPH07134210 A JP H07134210A
- Authority
- JP
- Japan
- Prior art keywords
- film
- hydrophilic polymer
- dye
- treatment
- iodine
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 31
- 230000008961 swelling Effects 0.000 claims abstract description 28
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011630 iodine Substances 0.000 claims abstract description 27
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 27
- 230000032683 aging Effects 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000011282 treatment Methods 0.000 claims description 47
- 206010042674 Swelling Diseases 0.000 claims description 24
- 230000005070 ripening Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 239000000049 pigment Substances 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract 2
- 239000000975 dye Substances 0.000 description 48
- 238000000576 coating method Methods 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000004043 dyeing Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000982 direct dye Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000003349 gelling agent Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000980 acid dye Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 2
- UFUQRRYHIHJMPB-DUCFOALUSA-L Sirius red 4B Chemical compound [Na+].[Na+].OS(=O)(=O)c1cc2cc(NC(=O)c3ccccc3)ccc2c([O-])c1\N=N\c1ccc(cc1)\N=N\c1ccc(cc1)S([O-])(=O)=O UFUQRRYHIHJMPB-DUCFOALUSA-L 0.000 description 2
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 2
- 239000001000 anthraquinone dye Substances 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- -1 etc. Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- 239000001739 pinus spp. Substances 0.000 description 2
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- 229940036248 turpentine Drugs 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000019646 color tone Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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の製法に関
する。FIELD OF THE INVENTION The present invention relates to a method for producing a polarizing film.
【０００２】[0002]
【従来技術】従来、偏光フィルムは親水性高分子フィル
ムに偏光素子として沃素や二色性色素を含む水溶液中に
浸漬し、沃素や二色性色素を吸着配向させて製造してい
る。しかしながらこの方法では水溶液中の沃素や二色性
色素の濃度が経時的に変動するため、煩雑な濃度管理が
必要であり、また浸漬法であるため、任意のパターンに
偏光性能を付与したり、複数の色調を有する多色性偏光
フィルムが得られない。2. Description of the Related Art Conventionally, a polarizing film is manufactured by immersing a hydrophilic polymer film as a polarizing element in an aqueous solution containing iodine or a dichroic dye, and adsorbing and orienting the iodine or the dichroic dye. However, in this method, since the concentration of iodine or dichroic dye in the aqueous solution changes with time, complicated concentration control is required, and since it is an immersion method, polarization performance is imparted to any pattern, A polychromatic polarizing film having a plurality of color tones cannot be obtained.
【０００３】そこでこれらを解決する製造方法として、
一軸延伸親水性高分子フィルムに沃素や二色性色素を含
有する溶液を塗布した後、加湿処理を行い吸着配向させ
る方法が提案されている(特開昭５８−８５４０５号公
報)。しかしながら、溶液塗布法は、親水性高分子フィ
ルムへの沃素や二色性色素の吸着が悪く、十分な吸着量
が得られにくい問題がある。Therefore, as a manufacturing method for solving these problems,
A method has been proposed in which a solution containing iodine or a dichroic dye is applied to a uniaxially stretched hydrophilic polymer film and then subjected to a humidification treatment for adsorption orientation (JP-A-58-85405). However, the solution coating method has a problem that iodine or dichroic dye is poorly adsorbed to the hydrophilic polymer film, and it is difficult to obtain a sufficient adsorption amount.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記塗布法に
おいて短時間に十分な量の沃素や二色性色素を親水性高
分子フィルムに吸着させるための手段を提供することを
目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide means for adsorbing a sufficient amount of iodine or dichroic dye on a hydrophilic polymer film in a short time in the above coating method.
【０００５】[0005]
【課題を解決するための手段】本発明の特徴は上記フィ
ルムに沃素および／または二色性色素の溶液を塗布して
フィルムを染色する方法において染色前にフィルムを予
め膨潤処理することにより、塗布染色法の欠点である染
色性を向上させることにある。A feature of the present invention is that in a method of dyeing a film by applying a solution of iodine and / or dichroic dye to the above film, the film is pre-swelled before dyeing. It is to improve the dyeability, which is a drawback of the dyeing method.
【０００６】即ち、本発明は配向処理した親水性高分子
フィルムを水性膨潤剤で膨潤処理し、これに沃素および
／または二色性色素を含有する溶液を塗布し、次いで熟
成処理することを特徴とする偏光フィルムの製法、また
は親水性高分子フィルムを水性膨潤剤で膨潤処理し、こ
れに沃素および／または二色性色素を含有する溶液を塗
布し、次いで熟成処理し、それらの工程中、または熟成
処理後に、配向処理することを特徴とする偏光フィルム
の製法に関する。That is, the present invention is characterized in that an oriented hydrophilic polymer film is swelled with an aqueous swelling agent, a solution containing iodine and / or a dichroic dye is applied thereto, and then an aging treatment is carried out. A method for producing a polarizing film, or a swelling treatment of a hydrophilic polymer film with an aqueous swelling agent, applying a solution containing iodine and / or a dichroic dye thereto, and then aging treatment, during those steps, Alternatively, the invention relates to a method for producing a polarizing film, which comprises performing an orientation treatment after the aging treatment.
【０００７】本発明において、偏光フィルムの原料とな
る親水性高分子フィルムは予め配向処理した親水性高分
子フィルムを用いてもよく、あるいは後の処理工程中の
いずれか、または熟成処理後にフィルムを配向処理して
もよい。In the present invention, the hydrophilic polymer film used as the raw material of the polarizing film may be a hydrophilic polymer film which has been preliminarily oriented, or the hydrophilic polymer film may be used either during the subsequent treatment step or after the aging treatment. You may perform an orientation process.
【０００８】親水性高分子フィルムとしては従来偏光フ
ィルム製造用に用いられてきた高分子フィルムであれば
いずれでもよいが、典型的にはポリビニルアルコール系
フィルム、部分ホルマール化ポリビニルアルコール系フ
ィルム、エチレン−酢酸ビニル共重合体鹸化物(ＥＶＯ
Ｈ)フィルムなどがある。The hydrophilic polymer film may be any polymer film conventionally used for producing a polarizing film, but is typically a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, ethylene- Saponified vinyl acetate copolymer (EVO
H) Film etc.
【０００９】配向処理は典型的には一軸延伸処理により
行う。延伸は加熱空気、水、あるいは硼酸などのゲル化
剤を含む水溶液中で行う。延伸倍率は２−８倍、好まし
くは２−５倍が適当である。The orientation treatment is typically performed by a uniaxial stretching treatment. Stretching is performed in heated air, water, or an aqueous solution containing a gelling agent such as boric acid. The stretching ratio is 2-8 times, preferably 2-5 times.
【００１０】配向処理は予め配向処理した親水性高分子
フィルムを使用してもよく、あるいは未配向親水性高分
子フィルムを膨潤処理する前、膨潤処理工程中、染色工
程その前後、熟成処理工程中、または熟成処理後に行っ
てもよい。通常、工程の便利さから予め配向処理した親
水性高分子フィルムを用いるか、熟成処理後に延伸す
る。配向した親水性高分子フィルムは配向を維持するた
め、配向親水性高分子フィルムをゲル化剤、例えば硼酸
の水溶液に浸漬してゲル化させてもよい。配向処理した
親水性高分子フィルムは、その後の膨潤処理、染色処
理、熟成処理、あるいは乾燥などの工程を緊張下で行な
ってもよい。The orientation treatment may use a hydrophilic polymer film that has been oriented in advance, or before the swelling treatment of the non-oriented hydrophilic polymer film, during the swelling treatment step, before and after the dyeing treatment, and during the aging treatment treatment. Alternatively, it may be performed after the aging treatment. Usually, for the convenience of the process, a hydrophilic polymer film which has been preliminarily oriented is used, or it is stretched after aging treatment. In order to maintain the orientation of the oriented hydrophilic polymer film, the oriented hydrophilic polymer film may be gelled by immersing it in a gelling agent, for example, an aqueous solution of boric acid. The hydrophilic polymer film subjected to the orientation treatment may be subjected to subsequent swelling treatment, dyeing treatment, aging treatment, drying or the like under tension.
【００１１】配向処理は必ずしも一工程である必要はな
く、必要に応じて複数回行なってもよい。膨潤処理は本
発明の最も特徴的な工程であり、これによって染色時間
を短縮でき、染料濃度を向上させることができ、従って
染色性を改良できる。The orientation treatment does not necessarily have to be one step, and may be performed a plurality of times as necessary. The swelling treatment is the most characteristic step of the present invention, whereby the dyeing time can be shortened, the dye concentration can be improved, and therefore the dyeability can be improved.
【００１２】膨潤処理は水、膨潤剤、例えばメタノー
ル、エタノール、アセトン等有機溶媒との混合水溶液、
あるいはゲル化剤、例えば硼酸などの水溶液(水性膨潤
剤)中に親水性高分子フィルムを浸漬することにより行
う。膨潤処理温度は通常１０−６０℃、より好ましくは
２０−４０℃である。１０℃より低いと親水性高分子フ
ィルム中への沃素および／または二色性色素の吸着速度
が低下する。また６０℃より高いと親水性高分子フィル
ムの強度が弱くなり、処理中に破断などの作業性低下の
原因になる。処理時間は温度など他の条件によって異な
るが、５秒以上、特に１−１０分が好ましい。５秒より
短いと膨潤が不十分となる。膨潤時間は膨潤による体積
膨張が安定になるに必要な時間であればよく、通常、フ
ィルム長さで約１０−４０％、特に２０％前後、含水量
でもとのフィルムの３０−１５０重量％増、より好まし
くは４０−１００重量％増程度に膨潤させるのが好まし
い。配向した親水性高分子フィルムを使用したときは配
向フィルムの収縮を防止するために緊張下で行う。ゲル
化剤水溶液を用いて配向を固定化してもよいが染色性が
低下するため、ゲル化剤の使用は染色処理の後で行うほ
うが好ましい。The swelling treatment is carried out by mixing water, a swelling agent such as a mixed aqueous solution with an organic solvent such as methanol, ethanol or acetone,
Alternatively, the hydrophilic polymer film is immersed in a gelling agent, for example, an aqueous solution of boric acid (aqueous swelling agent). The swelling treatment temperature is usually 10-60 ° C, more preferably 20-40 ° C. If the temperature is lower than 10 ° C, the adsorption rate of iodine and / or dichroic dye in the hydrophilic polymer film decreases. On the other hand, if the temperature is higher than 60 ° C., the strength of the hydrophilic polymer film becomes weak, which may cause a decrease in workability such as breakage during processing. The treatment time varies depending on other conditions such as temperature, but is preferably 5 seconds or longer, and particularly preferably 1-10 minutes. If it is shorter than 5 seconds, the swelling will be insufficient. The swelling time may be any time required for stabilizing the volume expansion due to swelling, and is usually about 10-40%, especially around 20% in the film length, and 30-150% by weight increase of the original film by the water content. More preferably, it is swelled to about 40 to 100% by weight. When an oriented hydrophilic polymer film is used, it is performed under tension to prevent the oriented film from shrinking. The orientation may be fixed by using a gelling agent aqueous solution, but the dyeing property is deteriorated, and therefore it is preferable to use the gelling agent after the dyeing treatment.
【００１３】膨潤処理した親水性高分子フィルム表面に
沃素および／または二色性色素を含有する塗布液を塗布
する。A coating solution containing iodine and / or a dichroic dye is applied to the surface of the swelled hydrophilic polymer film.
【００１４】二色性色素の例は偏光フィルム製造用に使
用できる色素であればいずれでもよい。一般的には直接
染料、酸性染料のごとき二色性染料が用いられる。特に
直接染料は二色性が高いため有用である。直接染料とし
ては、アゾ系染料、アントラキノン系染料、キノフタロ
ン系染料、ベリレン系染料、ナフトキノン系染料、テト
ラジン系染料、ベンジジン系染料などを用いることがで
きる。親水性高分子フィルム表面に吸着させる沃素や色
素の量は色素の種類にもよるが、沃素では０.０００１
−１g／m2(フィルム表面)、より好ましくは０.０１−
０.１ｇ／ｍ2、色素では０.００１−５ｇ／ｍ2(フィル
ム表面)、より好ましくは０.０５−０.５ｇ／ｍ2になる
ようにする。そのための好適な塗布液は沃素含量約０.
０００１−１重量％、より好ましくは０.０１−０.１重
量％、色素含量約０.００１−５重量％、より好ましく
は０.０５−０.５重量％である。また塗布液粘度は塗布
温度２０℃で１０−１００,０００cps、より好ましくは
５００−５,０００cpsである。塗布方法はバーコーター
・コーテイング、ロール・コーテイング、グラビア・コ
ーテイング、ナイフコーター・コーテイング、ダイコー
ター・コーテイング、アプリケーター・コーティングな
どが例示される。塗布液の粘度を調整するため適当なチ
クソトロピー剤、増粘剤、サギング剤などの他、安定
剤、湿潤剤、拡展剤などを配合してもよく、ミネラル・
ターペンなどを水に乳化剤で乳化した捺染用エマルジョ
ンをベースに用いてもよい。沃素を用いるときはハイド
ロトロープ剤として沃化カリウムなどを配合してもよ
い。またグリセリン、エチレングリコール、エタノール
などの有機溶剤を配合してもよい。（直接染料や酸性染
料を使用するときの説明があれば、後処理を含めて挿入
してください）The dichroic dye may be any dye that can be used for producing a polarizing film. Generally, dichroic dyes such as direct dyes and acid dyes are used. Direct dyes are particularly useful because they have high dichroism. As the direct dye, an azo dye, anthraquinone dye, quinophthalone dye, berylene dye, naphthoquinone dye, tetrazine dye, benzidine dye and the like can be used. The amount of iodine or dye adsorbed on the surface of the hydrophilic polymer film depends on the type of dye, but with iodine, 0.0001
-1 g / m 2 (film surface), more preferably 0.01-
0.1 g / m 2, the dye 0.001-5g / m 2 (film surface), and more preferably set to be in 0.05-0.5g / m 2. A suitable coating liquid for that purpose has an iodine content of about 0.
0001-1% by weight, more preferably 0.01-0.1% by weight, pigment content about 0.001-5% by weight, more preferably 0.05-0.5% by weight. The viscosity of the coating solution is 10-100,000 cps, more preferably 500-5,000 cps at a coating temperature of 20 ° C. Examples of the coating method include bar coater coating, roll coating, gravure coating, knife coater coating, die coater coating, and applicator coating. In order to adjust the viscosity of the coating liquid, in addition to suitable thixotropic agents, thickeners, sagging agents, etc., stabilizers, wetting agents, spreading agents, etc. may be added.
A printing emulsion obtained by emulsifying a turpentine or the like in water with an emulsifier may be used as a base. When iodine is used, potassium iodide or the like may be added as a hydrotrope agent. Further, an organic solvent such as glycerin, ethylene glycol or ethanol may be added. (If there is an explanation when using a direct dye or acid dye, insert it including post-treatment)
【００１５】熟成処理は恒温恒湿条件下で行うのが好ま
しい。好適な条件は３０−８０℃、１−９９％ＲＨで１
−３０分、好ましくは４０−５０℃、５０−９９％ＲＨ
である。３０℃以下、１％ＲＨ以下では染色性が悪く、
８０℃以上では親水性高分子フィルムの破断や溶解を生
じる。なお、熟成処理は高湿度条件で行なう方が好まし
い。熟成処理においても十分な染色性は得られるが、熟
成処理の方がより高い染色性が得られるため望ましい。The aging treatment is preferably carried out under constant temperature and humidity conditions. The preferred conditions are 30-80 ° C, 1-99% RH and 1
-30 minutes, preferably 40-50 ° C, 50-99% RH
Is. If the temperature is 30 ° C or lower and 1% RH or lower, the dyeability is poor,
At 80 ° C or higher, the hydrophilic polymer film is broken or dissolved. The aging treatment is preferably performed under high humidity conditions. Sufficient dyeability can be obtained even in the aging treatment, but the aging treatment is preferable because higher dyeability can be obtained.
【００１６】フィルムを洗浄して残留物を除去し、得ら
れたフィルムがまだ配向処理されていないときは配向処
理し、必要によりゲル化処理する。 得られた偏光フィ
ルムはそのままでは強度的に弱いため、その両面または
片面に表面保護層として光学的に透明なフィルム、例え
ばトリアセチルセルロースフィルム、ポリカーボネート
フィルム、ポリメチルメタクリレートフィルムなどを接
着して偏光板とする。接着はアクリル系接着剤、ウレタ
ン系接着剤、エポキシ系接着剤などを用いて行えばよ
い。The film is washed to remove the residue, and if the obtained film is not already oriented, it is oriented and, if necessary, gelled. Since the resulting polarizing film is weak in strength as it is, an optically transparent film such as a triacetyl cellulose film, a polycarbonate film, or a polymethylmethacrylate film is adhered to both or one surface of the polarizing plate as a polarizing plate. And The adhesion may be performed using an acrylic adhesive, a urethane adhesive, an epoxy adhesive, or the like.
【００１７】以下、実施例をあげて説明する。なお、実
施例中の各染料名は、カラーインデックスジェネリック
ネームで表わす。 実施例１ 厚さ７５μｍのポリビニルアルコールフィルムを、予め
３０℃の水中に１０分間浸漬し、膨潤フィルムを得た。
この膨潤フィルムの重量は約７０％増加していた。この
フィルムに直ちにＣ．Ｉ．ダイレクト・ブラック１１８
を０.３重量％含むエマルジョン（１５００−２０００
ｃｐｓ； ミネラル・タ−ペン４０重量％、糊料１０重
量％、乳化剤１０重量％、水３９.７重量％）を１６０
ｇ／ｍ２の坪量で均一にアプリケーターを用いて塗布し
た。これを４０℃、９８％ＲＨにて３分間熟成処理し
た。糊剤を水洗除去した後、水中(２０℃)で４倍に一軸
延伸し、５０℃で１０分間乾燥し、二色性色素偏光フィ
ルムを得た。Examples will be described below. Each dye name in the examples is represented by a color index generic name. Example 1 A polyvinyl alcohol film having a thickness of 75 μm was previously immersed in water at 30 ° C. for 10 minutes to obtain a swollen film.
The weight of this swollen film increased by about 70%. The film immediately showed C.I. I. Direct Black 118
Emulsion containing 0.3% by weight (1500-2000
cps; mineral tape 40% by weight, paste 10% by weight, emulsifier 10% by weight, water 39.7% by weight) 160
A basis weight of g / m 2 was applied uniformly using an applicator. This was aged at 40 ° C. and 98% RH for 3 minutes. After the sizing agent was washed off with water, it was uniaxially stretched 4 times in water (20 ° C.) and dried at 50 ° C. for 10 minutes to obtain a dichroic dye polarizing film.
【００１８】実施例２ 厚さ７５μｍのポリビニルアルコールフィルムを３０℃
の水中で２．５倍に一軸延伸した。緊張下に保持しなが
ら以下の膨潤、塗布および熟成処理を行った。膨潤処理
は一軸延伸後のフィルムを乾燥することなく３０℃の水
中に１０分間浸漬することにより行い、乾燥時に比べフ
ィルム重量は約８０重量％増加した。この膨潤フィルム
に、Ｃ．Ｉ．ダイレクト・ブラック １１８ ０．３重
量％を含む実施例１で用いたのと同じエマルジョンを塗
布し、４０℃、９８％ＲＨにて３分間熟成処理を行っ
た。水洗後、水中で初期フィルムの長さに対して４倍に
一軸延伸を行い、５０℃で１０分間乾燥し、二色性色素
偏光フィルムを得た。Example 2 A polyvinyl alcohol film having a thickness of 75 μm was placed at 30 ° C.
Was uniaxially stretched 2.5 times in water. The following swelling, coating and aging treatments were carried out while keeping under tension. The swelling treatment was performed by immersing the uniaxially stretched film in water at 30 ° C. for 10 minutes without drying, and the film weight increased by about 80% by weight as compared with the time of drying. This swelling film was coated with C.I. I. The same emulsion as used in Example 1 containing 0.3% by weight of Direct Black 118 was applied and aged at 40 ° C. and 98% RH for 3 minutes. After washing with water, the film was uniaxially stretched to 4 times the length of the initial film and dried at 50 ° C. for 10 minutes to obtain a dichroic dye polarizing film.
【００１９】実施例３ 染料をＣ．Ｉ．ダイレクト・レッド ８１を用いた以
外、実施例１と同様にして二色性色素偏光フィルムを得
た。Example 3 The dye is a C.I. I. A dichroic dye polarizing film was obtained in the same manner as in Example 1 except that Direct Red 81 was used.
【００２０】実施例４ 染料の代わりに沃素０.０３重量％を用いた以外、実施
例１と同様にして沃素系偏光フィルムを得た。Example 4 An iodine type polarizing film was obtained in the same manner as in Example 1 except that 0.03% by weight of iodine was used instead of the dye.
【００２１】実施例５ 塗布後の熟成処理を４０℃、５０％ＲＨ、３分間に変え
た以外は、実施例１と同様にして二色性色素偏光フィル
ムを得た。Example 5 A dichroic dye polarizing film was obtained in the same manner as in Example 1 except that the aging treatment after coating was changed to 40 ° C., 50% RH, and 3 minutes.
【００２２】実施例６ 塗布後の熟成処理を４０℃、３０％ＲＨ、３分間の熟成
処理に変えた以外は、実施例１と同様にして二色性色素
偏光フィルムを得た。Example 6 A dichroic dye polarizing film was obtained in the same manner as in Example 1 except that the aging treatment after coating was changed to aging treatment at 40 ° C., 30% RH for 3 minutes.
【００２３】比較例１ 膨潤処理を行わない以外、実施例１と同様の処理を行
い、二色性色素偏光フィルムを得た。Comparative Example 1 The same process as in Example 1 was carried out except that the swelling process was not carried out to obtain a dichroic dye polarizing film.
【００２４】比較例２ 厚さ７５μｍのポリビニルアルコールフィルムを水中に
て２．５倍に一軸延伸し、緊張下に保持しながら、５０
℃で１０分間乾燥後、膨潤処理することなく、以下実施
例２と同様にして二色性色素偏光フィルムを得た。Comparative Example 2 A polyvinyl alcohol film having a thickness of 75 μm was uniaxially stretched 2.5 times in water and kept under tension while maintaining a tension of 50.
After drying at 0 ° C. for 10 minutes, a dichroic dye polarizing film was obtained in the same manner as in Example 2 below without swelling treatment.
【００２５】比較例３ 膨潤処理を行わない以外、実施例３と同様にして二色性
色素偏光フィルムを得た。Comparative Example 3 A dichroic dye polarizing film was obtained in the same manner as in Example 3 except that the swelling treatment was not performed.
【００２６】比較例４ 膨潤処理を行わない以外、実施例４と同様にして沃素系
偏光フィルムを作製した。Comparative Example 4 An iodine type polarizing film was produced in the same manner as in Example 4 except that the swelling treatment was not performed.
【００２７】実施例７ 実施例１−６および比較例１−４で得られた偏光フィル
ムの単体透過率および偏光度を以下に示す方法では測定
し、その結果を表１に示す。最大吸収波長は、Ｃ．Ｉ．
ダイレクト・ブラック １１８を用いた実施例１、２、
５、６比較例１、２および４では６８０ｎｍ、Ｃ．Ｉ．
ダイレクト・レッド８１を用いた実施例３および比較例
３では５２０ｎｍである。Example 7 The single transmittance and the degree of polarization of the polarizing films obtained in Examples 1-6 and Comparative Examples 1-4 were measured by the methods described below, and the results are shown in Table 1. The maximum absorption wavelength is C.I. I.
Examples 1 and 2 using Direct Black 118,
In Comparative Examples 1, 2 and 4, 680 nm, C.I. I.
It is 520 nm in Example 3 and Comparative Example 3 using Direct Red 81.
【００２８】単体透過率：分光光度計にて１枚の偏光フ
ィルムの可視領域における最大吸収波長での透過率を求
めた。沃素系偏光フィルムでは、４００−７００ｎｍの
平均透過率を求めた。 Single Transmittance : The transmittance at the maximum absorption wavelength in the visible region of one polarizing film was determined with a spectrophotometer. For the iodine type polarizing film, the average transmittance of 400 to 700 nm was determined.
【００２９】偏光度：分光光度計にて２枚の偏光フィル
ムを、その主配向軸方向に重ね合わせたとき、並びに主
配向軸方向が直交するように重ね合わせたときの分光曲
線を求め、用いた二色性色素の最大吸収波長における透
過率をそれぞれＴ１、Ｔ２とし、次式より偏光度Ｖを求
めた。沃素系偏光フィルムでは、４００−７００ｎｍの
平均透過率をそれぞれＴ1、Ｔ2とした。 Ｖ＝{(Ｔ1−Ｔ2)／(Ｔ1＋Ｔ2)}0.5×１００Degree of polarization : A spectrophotometer is used to obtain a spectral curve when two polarizing films are superposed in the main alignment axis direction and when they are superposed so that the main alignment axis directions are orthogonal to each other. The transmittance of the dichroic dye at the maximum absorption wavelength was set to T 1 and T 2 , respectively, and the polarization degree V was calculated from the following equation. In the iodine type polarizing film, the average transmittances at 400 to 700 nm are T 1 and T 2 , respectively. V = {(T 1 −T 2 ) / (T 1 + T 2 )} 0.5 × 100
【００３０】[0030]
【表１】 単体透過率（％） 偏光度（％） 実施例 １ ３５．１ ８６．６ ２ ３１．７ ９２．５ ３ ４５．８ ７７．９ ４ ４４．３ ９５．４ ５ ４２．７ ７４．２ ６ ４４．７ ６８．４ 比較例 １ ５４．８ ４５．７ ２ ６７．３ ２４．３ ３ ６３．２ ３８．９ ４ 染まらず(偏光フィルムが得られず)Table 1 Single transmittance (%) Polarization degree (%) Example 1 35.1 86.6 2 31.7 92.5 3 45.8 77.9 4 44.3 95.4 5 42.7 74 .2 6 44.7 68.4 Comparative Example 1 54.8 45.7 2 67.3 24.3 3 63.2 38.9 4 No dyeing (polarizing film not obtained)
【００３１】[0031]
【発明の効果】本発明方法により従来の塗布法における
ごとき十分な色素吸着が得られないと言った欠点が解消
され、短時間で十分満足しうる色素吸着が達成できる。
従って効率的に偏光フィルムの製造ができる。The method of the present invention eliminates the drawback that the conventional coating method does not provide sufficient dye adsorption, and can achieve sufficiently satisfactory dye adsorption in a short time.
Therefore, the polarizing film can be efficiently manufactured.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成７年２月１０日[Submission date] February 10, 1995
【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】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】二色性色素の例は偏光フィルム製造用に使
用できる色素であればいずれでもよい。一般的には直接
染料、酸性染料のごとき二色性染料が用いられる。特に
直接染料は二色性が高いため有用である。直接染料とし
ては、アゾ系染料、アントラキノン系染料、キノフタロ
ン系染料、ベリレン系染料、ナフトキノン系染料、テト
ラジン系染料、ベンジジン系染料などを用いることがで
きる。親水性高分子フィルム表面に吸着させる沃素や色
素の量は色素の種類にもよるが、沃素では０.０００１
−１g／m2(フィルム表面)、より好ましくは０.０１−
０.１ｇ／ｍ2、色素では０.００１−５ｇ／ｍ2(フィル
ム表面)、より好ましくは０.０５−０.５ｇ／ｍ2になる
ようにする。そのための好適な塗布液は沃素含量約０.
０００１−１重量％、より好ましくは０.０１−０.１重
量％、色素含量約０.００１−５重量％、より好ましく
は０.０５−０.５重量％である。また塗布液粘度は塗布
温度２０℃で１０−１００,０００cps、より好ましくは
５００−５,０００cpsである。塗布方法はバーコーター
・コーテイング、ロール・コーテイング、グラビア・コ
ーテイング、ナイフコーター・コーテイング、ダイコー
ター・コーテイング、アプリケーター・コーティングな
どが例示される。塗布液の粘度を調整するため適当なチ
クソトロピー剤、増粘剤、サギング剤などの他、安定
剤、湿潤剤、拡展剤などを配合してもよく、ミネラル・
ターペンなどを水に乳化剤で乳化した捺染用エマルジョ
ンをベースに用いてもよい。沃素を用いるときはハイド
ロトロープ剤として沃化カリウムなどを配合してもよ
い。またグリセリン、エチレングリコール、エタノール
などの有機溶剤を配合してもよい。The dichroic dye may be any dye that can be used for producing a polarizing film. Generally, dichroic dyes such as direct dyes and acid dyes are used. Direct dyes are particularly useful because they have high dichroism. As the direct dye, an azo dye, anthraquinone dye, quinophthalone dye, berylene dye, naphthoquinone dye, tetrazine dye, benzidine dye and the like can be used. The amount of iodine or dye adsorbed on the surface of the hydrophilic polymer film depends on the type of dye, but with iodine, 0.0001
-1 g / m 2 (film surface), more preferably 0.01-
0.1 g / m 2, the dye 0.001-5g / m 2 (film surface), and more preferably set to be in 0.05-0.5g / m 2. A suitable coating liquid for that purpose has an iodine content of about 0.
0001-1% by weight, more preferably 0.01-0.1% by weight, pigment content about 0.001-5% by weight, more preferably 0.05-0.5% by weight. The viscosity of the coating solution is 10-100,000 cps, more preferably 500-5,000 cps at a coating temperature of 20 ° C. Examples of the coating method include bar coater coating, roll coating, gravure coating, knife coater coating, die coater coating, and applicator coating. In order to adjust the viscosity of the coating liquid, in addition to suitable thixotropic agents, thickeners, sagging agents, etc., stabilizers, wetting agents, spreading agents, etc. may be added.
A printing emulsion obtained by emulsifying a turpentine or the like in water with an emulsifier may be used as a base. When iodine is used, potassium iodide or the like may be added as a hydrotrope agent. Further, an organic solvent such as glycerin, ethylene glycol or ethanol may be added.
【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】００１５[Name of item to be corrected] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１５】熟成処理は恒温恒湿条件下で行うのが好ま
しい。好適な条件は３０−８０℃、１−９９％ＲＨで１
−３０分、好ましくは４０−５０℃、５０−９９％ＲＨ
である。３０℃以下、１％ＲＨ以下では染色性が悪く、
８０℃以上では親水性高分子フィルムの破断や溶解を生
じる。なお、熟成処理は高湿度条件で行なう方が好まし
い。低湿度条件においても十分な染色性は得られるが、
高湿度条件の方がより高い染色性が得られるため望まし
い。The aging treatment is preferably carried out under constant temperature and humidity conditions. The preferred conditions are 30-80 ° C, 1-99% RH and 1
-30 minutes, preferably 40-50 ° C, 50-99% RH
Is. If the temperature is 30 ° C or lower and 1% RH or lower, the dyeability is poor,
At 80 ° C or higher, the hydrophilic polymer film is broken or dissolved. The aging treatment is preferably performed under high humidity conditions. Sufficient dyeability can be obtained even in low humidity conditions,
High humidity conditions are desirable because higher dyeing properties can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 前川 惠一 大阪府寝屋川市下木田町14番５号 倉敷紡 績株式会社技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Keiichi Maekawa 14-5 Shimokitada-cho, Neyagawa-shi, Osaka Kurashiki Spinning Co., Ltd.
Claims (2)
性膨潤剤で膨潤処理し、これに沃素および／または二色
性色素を含有する溶液を塗布し、次いで熟成処理するこ
とを特徴とする偏光フィルムの製法。1. A polarized light characterized by comprising subjecting an oriented hydrophilic polymer film to a swelling treatment with an aqueous swelling agent, applying a solution containing iodine and / or a dichroic dye thereto, and then aging treatment. How to make a film.
潤処理し、これに沃素および／または二色性色素を含有
する溶液を塗布し、次いで熟成処理し、それらの工程
中、または熟成処理後に、配向処理することを特徴とす
る偏光フィルムの製法。2. A hydrophilic polymer film is swelled with an aqueous swelling agent, a solution containing iodine and / or a dichroic dye is applied thereto, and then a ripening treatment is carried out during or after those steps. A method for producing a polarizing film, which is characterized by performing an orientation treatment later.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28309193A JPH07134210A (en) | 1993-11-12 | 1993-11-12 | Polarizing film manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28309193A JPH07134210A (en) | 1993-11-12 | 1993-11-12 | Polarizing film manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07134210A true JPH07134210A (en) | 1995-05-23 |
Family
ID=17661105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28309193A Pending JPH07134210A (en) | 1993-11-12 | 1993-11-12 | Polarizing film manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07134210A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004020629A (en) * | 2002-06-12 | 2004-01-22 | Kuraray Co Ltd | Manufacturing method of polarizing film |
| WO2006011436A1 (en) * | 2004-07-28 | 2006-02-02 | Nitto Denko Corporation | Process for producing polarizing film, polarizing film, polarizing plate, optical film, and image display |
| KR100846036B1 (en) * | 2004-07-28 | 2008-07-11 | 닛토덴코 가부시키가이샤 | Manufacturing Method of Polarizing Film, Polarizing Film, Polarizing Plate, Optical Film and Image Display Device |
| WO2009011219A1 (en) * | 2007-07-19 | 2009-01-22 | Nitto Denko Corporation | Process for production of laminates |
| WO2016093278A1 (en) * | 2014-12-12 | 2016-06-16 | 住友化学株式会社 | Method for manufacturing polarizing film, and polarizing film |
| WO2016171127A1 (en) * | 2015-04-20 | 2016-10-27 | 日本化薬株式会社 | Polarizing element formed by stacking film having high retardation and layer containing dichroic dye, and display device provided with same |
-
1993
- 1993-11-12 JP JP28309193A patent/JPH07134210A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004020629A (en) * | 2002-06-12 | 2004-01-22 | Kuraray Co Ltd | Manufacturing method of polarizing film |
| WO2006011436A1 (en) * | 2004-07-28 | 2006-02-02 | Nitto Denko Corporation | Process for producing polarizing film, polarizing film, polarizing plate, optical film, and image display |
| KR100846036B1 (en) * | 2004-07-28 | 2008-07-11 | 닛토덴코 가부시키가이샤 | Manufacturing Method of Polarizing Film, Polarizing Film, Polarizing Plate, Optical Film and Image Display Device |
| CN100426020C (en) * | 2004-07-28 | 2008-10-15 | 日东电工株式会社 | Polarizing film and method for producing the same, polarizing film, polarizing plate, optical film and image display device |
| US7871665B2 (en) | 2004-07-28 | 2011-01-18 | Nitto Denko Corporation | Process for producing polarizing film, polarizing film, polarizing plate, optical film, and image display |
| WO2009011219A1 (en) * | 2007-07-19 | 2009-01-22 | Nitto Denko Corporation | Process for production of laminates |
| WO2016093278A1 (en) * | 2014-12-12 | 2016-06-16 | 住友化学株式会社 | Method for manufacturing polarizing film, and polarizing film |
| JPWO2016093278A1 (en) * | 2014-12-12 | 2017-09-21 | 住友化学株式会社 | Manufacturing method of polarizing film and polarizing film |
| JP2017219861A (en) * | 2014-12-12 | 2017-12-14 | 住友化学株式会社 | Polarizing film and polarizing plate |
| WO2016171127A1 (en) * | 2015-04-20 | 2016-10-27 | 日本化薬株式会社 | Polarizing element formed by stacking film having high retardation and layer containing dichroic dye, and display device provided with same |
| JPWO2016171127A1 (en) * | 2015-04-20 | 2018-02-08 | 日本化薬株式会社 | A polarizing element in which a film having high retardation and a layer containing a dichroic dye are laminated, and a display device provided with the polarizing element |
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