JPS62178908A - Production of polyimide polarizer - Google Patents
Production of polyimide polarizerInfo
- Publication number
- JPS62178908A JPS62178908A JP2178586A JP2178586A JPS62178908A JP S62178908 A JPS62178908 A JP S62178908A JP 2178586 A JP2178586 A JP 2178586A JP 2178586 A JP2178586 A JP 2178586A JP S62178908 A JPS62178908 A JP S62178908A
- Authority
- JP
- Japan
- Prior art keywords
- imparting agent
- polymer
- polyamic acid
- film
- imide ring
- 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
- 229920001721 polyimide Polymers 0.000 title claims abstract description 14
- 239000004642 Polyimide Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000004952 Polyamide Substances 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 3
- 229920002647 polyamide Polymers 0.000 claims abstract description 3
- 230000010287 polarization Effects 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 125000005462 imide group Chemical group 0.000 claims 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 239000002120 nanofilm Substances 0.000 claims 1
- 150000003949 imides Chemical group 0.000 abstract description 18
- 229920006254 polymer film Polymers 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 8
- 238000003892 spreading Methods 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 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 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- NZKTVPCPQIEVQT-UHFFFAOYSA-N 2-[4-[(4-aminophenyl)diazenyl]-n-(2-hydroxyethyl)anilino]ethanol Chemical compound C1=CC(N)=CC=C1N=NC1=CC=C(N(CCO)CCO)C=C1 NZKTVPCPQIEVQT-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- UNBOSJFEZZJZLR-UHFFFAOYSA-N 4-(4-nitrophenylazo)aniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 UNBOSJFEZZJZLR-UHFFFAOYSA-N 0.000 description 1
- QDPSGELUBXFKSB-UHFFFAOYSA-N 4-[(4-aminophenyl)diazenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1N=NC1=CC=C(N)C2=CC=CC=C12 QDPSGELUBXFKSB-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- NLMHXPDMNXMQBY-UHFFFAOYSA-L chembl260999 Chemical compound [Na+].[Na+].C1=CC(NC(=O)C)=CC=C1N=NC(C(=CC1=C2)S([O-])(=O)=O)=C(O)C1=CC=C2NC(=O)NC1=CC=C(C(O)=C(N=NC=2C=CC=CC=2)C(=C2)S([O-])(=O)=O)C2=C1 NLMHXPDMNXMQBY-UHFFFAOYSA-L 0.000 description 1
- PBOIUUROGJVVNC-UHFFFAOYSA-L disodium 2-hydroxy-5-[[4-[[2-methoxy-4-[(3-sulfonatophenyl)diazenyl]phenyl]carbamoylamino]phenyl]diazenyl]benzoate Chemical compound [Na+].[Na+].COc1cc(ccc1NC(=O)Nc1ccc(cc1)N=Nc1ccc(O)c(c1)C([O-])=O)N=Nc1cccc(c1)S([O-])(=O)=O PBOIUUROGJVVNC-UHFFFAOYSA-L 0.000 description 1
- DSARWKALPGYFTA-UHFFFAOYSA-L disodium 4-hydroxy-7-[(5-hydroxy-6-phenyldiazenyl-7-sulfonatonaphthalen-2-yl)carbamoylamino]-3-phenyldiazenylnaphthalene-2-sulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(NC(=O)NC=3C=C4C=C(C(N=NC=5C=CC=CC=5)=C(O)C4=CC=3)S([O-])(=O)=O)=CC=C2C(O)=C1N=NC1=CC=CC=C1 DSARWKALPGYFTA-UHFFFAOYSA-L 0.000 description 1
- DSCVOQXQGTYXMV-UHFFFAOYSA-L disodium 6-amino-3-[[4-[(3-carboxy-4-hydroxyphenyl)diazenyl]naphthalen-1-yl]diazenyl]-4-oxidonaphthalene-2-sulfonate Chemical compound NC1=CC=C2C=C(C(N=NC3=C4C=CC=CC4=C(C=C3)N=NC3=CC=C(O)C(=C3)C(=O)O[Na])=C(O)C2=C1)S(=O)(=O)O[Na] DSCVOQXQGTYXMV-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- BQHRKYUXVHKLLZ-UHFFFAOYSA-M sodium 7-amino-2-[[4-[(4-aminophenyl)diazenyl]-2-methoxy-5-methylphenyl]diazenyl]-3-sulfonaphthalen-1-olate Chemical compound [Na+].COc1cc(N=Nc2ccc(N)cc2)c(C)cc1N=Nc1c(O)c2cc(N)ccc2cc1S([O-])(=O)=O BQHRKYUXVHKLLZ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 1
- FKVXIGHJGBQFIH-UHFFFAOYSA-K trisodium 5-amino-3-[[4-[4-[(7-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C=C4C=CC(=CC4=C3[O-])N)S(=O)(=O)O)N=NC5=C(C6=C(C=C(C=C6C=C5S(=O)(=O)O)S(=O)(=O)[O-])N)[O-].[Na+].[Na+].[Na+] FKVXIGHJGBQFIH-UHFFFAOYSA-K 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、偏光能付与剤を配向状態で含むイミド環含有
高分子フィルムからなる耐湿性、耐熱性、耐薬品性等の
耐久性に優れるポリイミド系偏光子の製造方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a polyimide-based polyimide film having excellent durability such as moisture resistance, heat resistance, and chemical resistance, which is composed of an imide ring-containing polymer film containing a polarization ability imparting agent in an oriented state. The present invention relates to a method for manufacturing a polarizer.
従来の技術及び問題点
液晶表示素子の車載用部品や計測器等の屋外使用装置へ
の普及に伴う耐熱性の要求、あるいはＯＡ機器等の大型
ないし細密表示装置への普及に伴う視認性向上の点より
の薄型化の要求、更には偏光板の電極基板化を実現する
ための耐液晶性等の耐薬品性の要求に応えうる偏光子の
提供が課題となっている。Conventional technologies and problems There is a need for heat resistance as liquid crystal display elements become more widespread in automotive parts and outdoor devices such as measuring instruments, and a need to improve visibility as liquid crystal display elements become more widespread in large or minute display devices such as office automation equipment. The challenge is to provide a polarizer that can meet the demands for thinner polarizers as well as the demands for chemical resistance such as liquid crystal resistance in order to realize the use of polarizing plates as electrode substrates.
従来、ポリビニルアルコール（ＰＶＡ）やポリエチレン
テレフタレート（ＰＥＴ）で代表される低融点高分子か
らなるフィルムを基材とするフィルム状偏光子が知られ
ている。BACKGROUND ART Film-like polarizers have been known that use a film made of a low melting point polymer such as polyvinyl alcohol (PVA) or polyethylene terephthalate (PET) as a base material.
しかしながら、従来のフィルム状偏光子では、上記の要
求に応えることができない。すなわち、ＰＶＡ系の偏光
子は耐湿性、耐熱性に劣り、これを偏光板として実用に
供するためには透明フィルムを貼着してその表面を保護
する必要があり、そのため偏光板の薄型化に逆行すると
いう問題点があった。他方、ＰＥＴ系の偏光子にはその
基材のガラス転移点が低く、高温使用下における寸法安
定性、光学特性の維持性に劣り、総じて耐熱性等の耐久
性に劣るという問題点があった。However, conventional film polarizers cannot meet the above requirements. In other words, PVA-based polarizers have poor moisture resistance and heat resistance, and in order to use them as polarizing plates, it is necessary to attach a transparent film to protect the surface. There was a problem with going backwards. On the other hand, PET-based polarizers have the problem that the base material has a low glass transition point, poor dimensional stability and maintenance of optical properties under high-temperature use, and overall poor durability such as heat resistance. .
問題点を解決するための手段
本発明者らは上記の問題点を克服し、耐湿性、耐熱性、
耐薬品性等としての耐久性に優れるフィルム状偏光子を
得るために鋭意研究を重ねた結果、ポリイミド系のフィ
ルムを基材とする新規な偏光子の製造方法の開発に成功
し、本発明をなすに至った。Means for Solving the Problems The present inventors have overcome the above problems, and have improved moisture resistance, heat resistance,
As a result of extensive research in order to obtain a film-like polarizer with excellent durability in terms of chemical resistance, etc., we succeeded in developing a new method for producing a polarizer using a polyimide film as a base material. I arrived at the eggplant.
すなわち、本発明は、（Ａ）ポリアミド酸系高分子と偏
光能付与剤との混合溶液を台上に展開し、その展開層を
加熱処理して偏光能付与剤を含むイミド環含有高分子フ
ィルムを得る工程、（Ｂ）前記Ａ工程における加熱処理
の一貫として又はＡ工程終了後にポリアミド酸系高分子
ないしイミド環含有高分子のフィルムを延伸処理する工
程からなることを特徴とするポリイミド系偏光子の製造
方法を提供するものである。That is, in the present invention, (A) a mixed solution of a polyamic acid-based polymer and a polarization ability imparting agent is developed on a table, and the developed layer is heat-treated to produce an imide ring-containing polymer film containing the polarization ability imparting agent. (B) as part of the heat treatment in step A or after the completion of step A, stretching a polyamic acid polymer or imide ring-containing polymer film. The present invention provides a method for manufacturing.
本発明の製造方法においては先ず、ポリアミド酸系高分
子（ポリアミド酸そのものも含む）と偏光能付与剤との
混合溶液を台上に展開し、その展開層を加熱処理して偏
光能付与剤を含むイミド環含有高分子フィルムを得る（
Ａ工程）。In the production method of the present invention, first, a mixed solution of a polyamic acid-based polymer (including polyamic acid itself) and a polarizing ability imparting agent is spread on a table, and the developed layer is heated to add the polarizing ability imparting agent. Obtain an imide ring-containing polymer film containing (
A process).
ポリアミド酸系高分子と偏光能付与剤との混合溶液の調
製方式については特に限定はない。不活性溶媒中で所定
量の酸無水物とジアミンを重合処理してポリアミド酸系
高分子とした反応液又はその希釈液に偏光能付与剤を混
合溶解せしめる方式、あるいは粉末状等のポリアミド酸
系高分子、望ましくは未反応モノマないし低分子量重合
体を除去したポリアミド酸系高分子と偏光能付与剤を適
宜な溶媒に溶解させる方式などを代表的な調製方式とし
てあげることができる。前者の反応液を利用する方式は
、ポリアミド酸系高分子の製造段階を含めた全体評価の
点より工程数が少ない利点を有する。There are no particular limitations on the method for preparing the mixed solution of the polyamic acid polymer and the polarization ability imparting agent. A method in which a polarizing agent is mixed and dissolved in a reaction solution or a diluted solution of a polyamic acid polymer obtained by polymerizing a predetermined amount of acid anhydride and diamine in an inert solvent, or a polyamic acid polymer in powder form, etc. Typical preparation methods include a method in which a polymer, preferably a polyamic acid polymer from which unreacted monomers or low molecular weight polymers have been removed, and a polarizing ability imparting agent are dissolved in an appropriate solvent. The former method using a reaction solution has the advantage of requiring fewer steps than the overall evaluation including the manufacturing steps of the polyamic acid polymer.
なお、ポリアミド酸系高分子に対する偏光能付与剤の混
合割合は、目的とするポリイミド系偏光子の透過率等に
より適宜に決定することができる。The mixing ratio of the polarizing ability imparting agent to the polyamic acid polymer can be appropriately determined depending on the transmittance of the intended polyimide polarizer.
一般にはポリアミド酸系高分子１００重量部に対し偏光
能付与剤５０重量部以下の割合である。Generally, the proportion of the polarizing ability imparting agent is 50 parts by weight or less per 100 parts by weight of the polyamic acid polymer.
本発明において用いられるポリアミド酸系高分子として
は、例えば３．３′，４．４’−ビフェニルテトラカル
ボン酸二無水物、３，４．４’−ビフェニルトリカルボ
ン酸無水物、ピロメリット酸二無水物、３．３′，４．
４’−ベンゾフェノンテトラカルポン酸二無水物、３，
４．４’−ベンゾフェノントリカルボン酸無水物、１．
２．３．４−ブタンテトラカルボン酸二無水物、１．２
．３−ブタントリカルボン酸無水物等で代表される酸無
水物の１種又は２種以上と、例えば３．３°−ジアミノ
ジフェニルスルホン、３，３″−ジアミノジフェニルエ
ーテル、３．３’−ジアミノジフェニルメタン、ビス（
４−（３−アミノフェノキシ）フェニル〕スルホン、ヘ
キサメチレンジアミン等で代表されるシア、ミンの１種
又は２種以上を構成成分とするものなどを例示すること
ができる。就中、３．３′，４゜４゛−ビフェニルテト
ラカルボン酸二無水物と、３．３゛−ジアミノジフェニ
ルスルホン又はビス〔４−（３−アミノフェノキシ）フ
ェニル〕スルホンを少なくとも主構成成分とするポリア
ミド酸系高分子が光学特性等の点で好ましく用いられる
。Examples of the polyamic acid polymer used in the present invention include 3.3',4.4'-biphenyltetracarboxylic dianhydride, 3,4.4'-biphenyltricarboxylic anhydride, and pyromellitic dianhydride. Things, 3.3', 4.
4'-benzophenonetetracarboxylic dianhydride, 3,
4.4'-benzophenonetricarboxylic anhydride, 1.
2.3.4-Butanetetracarboxylic dianhydride, 1.2
．． One or more acid anhydrides represented by 3-butanetricarboxylic anhydride and the like, for example, 3.3°-diaminodiphenylsulfone, 3,3″-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, Screw(
Examples include those containing one or more of cya and mine as constituent components, typified by 4-(3-aminophenoxy)phenyl]sulfone, hexamethylene diamine, and the like. Among them, at least 3.3',4'4'-biphenyltetracarboxylic dianhydride and 3,3'-diaminodiphenylsulfone or bis[4-(3-aminophenoxy)phenyl]sulfone are the main constituents. Polyamic acid-based polymers are preferably used in terms of optical properties and the like.
なお、本発明において用いるポリアミド酸系高分子とし
ては限定するものではないが、酸無水物１モルあたりジ
アミン０．８〜１．２モルの配合割合で重合処理したも
のが適当であり、その際、Ｎ、Ｎ−ジメヂルホルムアミ
ド又はＮ、Ｎ−ジメチルアセトアミドを少な（とも主成
分とする溶媒中で重合処理したものが、得られるポリイ
ミド系偏光子の光学特性の点で好ましい。Although the polyamic acid-based polymer used in the present invention is not limited, it is appropriate to use a polymer that has been polymerized at a blending ratio of 0.8 to 1.2 moles of diamine per 1 mole of acid anhydride. , N,N-dimedylformamide or N,N-dimethylacetamide in a solvent containing a small amount (both of which are main components) is preferable from the viewpoint of the optical properties of the resulting polyimide polarizer.
一方、ポリアミド酸系高分子の溶液に混合溶解せしめら
れる偏光能付与剤としては例えば二色性染料などをあげ
ることができる。その二色性染料の代表的具体例として
は、Ｃ，１，ディスパース（旧５ｐｅｒｓｅ ）ブラッ
ク１ （Ｃ，１，１１３６５） 、Ｃ，１デイスパース
ブラツク ２ （Ｃ，１，１１２５５） 、Ｃ。On the other hand, examples of the polarizing ability imparting agent that can be mixed and dissolved in the polyamic acid polymer solution include dichroic dyes. Representative examples of the dichroic dye include C,1, Disperse Black 1 (C,1,11365), C,1 Disperse Black 2 (C,1,11255), and C.
■、ダイレクト（口１ｒｅｃｔ ）ブラック２２（Ｃ，
１，３５４３５） 、Ｃ，Ｉ 、ダイレクトブラック１
９（Ｃ，１，３５２５５） 、Ｃ，！ 、ダイレクトブ
ラック１７（Ｃ，１，２７７００） 、Ｃ，Ｉ 、ダイ
レクトブルー ２（Ｃ、１，２２５９０）、Ｃ，１，ダ
イレクトバイオレット（Ｃ，１，２２５５０）、Ｃ，１
，ダイレクトレッド ７５ （Ｃ，１，２５３８０）、
Ｃ，１，ディスパースオレンジ３（Ｃ，１，１１００５
） 、Ｃ，Ｉ 、ダイレクトブラック５１ （Ｃ，１，
２７７２０） 、Ｃ，Ｉ 、ダイレクトブラウン ２（
Ｃ，１，２２３１１）、Ｃ，１，ダイレクトブルーフ１
（Ｃ、Ｉ 、３４１４０）、Ｃ，１，ダイレクトレッ
ド３３ （Ｃ，１，２２３０６）、Ｃ，１，ダイレクト
オレンジ３９ （Ｃ、Ｉ 、４０２１５ ）、ｃ、ｒ、
ダイレクトレッド ８１ （Ｃ，１，２８１６０） 、
Ｃ。■, Direct (mouth 1 rect) Black 22 (C,
1,35435), C,I, Direct Black 1
9(C,1,35255),C,! , Direct Black 17 (C, 1, 27700), C, I, Direct Blue 2 (C, 1, 22590), C, 1, Direct Violet (C, 1, 22550), C, 1
, Direct Red 75 (C, 1, 25380),
C,1, Disperse Orange 3 (C,1,11005
), C,I, Direct Black 51 (C,1,
27720), C,I, Direct Brown 2(
C, 1, 22311), C, 1, Direct Bruf 1
(C, I, 34140), C, 1, Direct Red 33 (C, 1, 22306), C, 1, Direct Orange 39 (C, I, 40215), c, r,
Direct Red 81 (C, 1, 28160),
C.
１、ダイレクトイエロ ４４ （Ｃ，１，２９０００）
、Ｃ，Ｉ 。1. Direct Yellow 44 (C, 1,29000)
,C,I.
ダイレクトオレンジ２６ （Ｃ，１，２９１５０） 、
Ｃ，Ｉ 。Direct Orange 26 (C, 1, 29150),
C,I.
ダイレクトオレンジ２９ （Ｃ，Ｉ 、２９１５５）
、Ｃ，Ｉ 。Direct Orange 29 (C, I, 29155)
,C,I.
ダイレクトレッド２３ （Ｃ，Ｉ 、２９１６０） 、
Ｃ，Ｉ 、ダイレクトブルー２５ （Ｃ、１，２３７９
０）などをあげることができる。Direct Red 23 (C, I, 29160),
C, I, Direct Blue 25 (C, 1,2379
0) etc.
一方、混合溶液を適宜な台上に流延させるなどして展開
形成した展開層を加熱処理することにより、該展開層が
乾燥処理されてフィルム状物が形成されると共に、ポリ
アミド酸系高分子における酸アミド結合部とカルボキシ
ル基との反応によるイミド環が形成されて、偏光能付与
剤を含むイミド環含有高分子フィルムが得られるのであ
るが、その際、展開層の厚さは一般に約１ｆｆＩＩ１１
以下とすることが適当である。また、加熱処理は乾燥の
ための低温処理と、イミド環形成のための高温処理の少
な（とも２段の温度条件で行うことが一般に望ましい。On the other hand, by heat-treating the spread layer formed by spreading the mixed solution on an appropriate table, the spread layer is dried to form a film-like material, and the polyamic acid-based polymer An imide ring is formed by the reaction between the acid amide bond and the carboxyl group, and an imide ring-containing polymer film containing a polarization ability imparting agent is obtained.
The following is appropriate. In addition, it is generally desirable that the heat treatment be performed under two-stage temperature conditions: a low-temperature treatment for drying and a high-temperature treatment for imide ring formation.
乾燥処理温度としては常温ないし１５０℃が、イミド環
形成のための処理温度としては１２０〜３００℃が一般
に適当である。なお、イミド環形成のための処理時間は
処理温度、展開層の厚さによっても異なるが、１〜１２
時間が一般である。Generally, a suitable drying temperature is room temperature to 150°C, and a suitable temperature for forming an imide ring is 120 to 300°C. Note that the processing time for imide ring formation varies depending on the processing temperature and the thickness of the spread layer, but is 1 to 12
time is common.
本発明において展開層を乾燥させて得たフィルム状物は
これを延伸処理して、その偏光能付与剤を一定方向に配
向せしめることにより偏光能を有するイミド環含有高分
子フィルムとされる（Ｂ工程〉。その延伸処理は前記Ａ
工程における加熱処理の一貫として該フィルム状物に対
し行ってもよいし、その加熱処理を終えて得たイミド環
含有高分子フィルムに対し行ってもよい。延伸処理は通
常、加熱下に行われその加熱温度しては２００〜３５０
℃が一般である。また、延伸倍率としては１２０〜１０
００％が適当である。In the present invention, the film-like material obtained by drying the spreading layer is stretched to orient the polarization ability imparting agent in a certain direction, thereby forming an imide ring-containing polymer film having polarization ability (B Step> The stretching process is as described in A above.
The heat treatment may be performed on the film as part of the heat treatment in the process, or it may be performed on the imide ring-containing polymer film obtained after the heat treatment. Stretching treatment is usually performed under heating, and the heating temperature is 200 to 350.
℃ is common. In addition, the stretching ratio is 120 to 10
00% is appropriate.
このようにして、ポリイミドなどで代表されるイミド環
含有高分子からなるフィルムを基材とし、このフィルム
基材中に偏光能付与剤を一定方向の配向状態で含むポリ
イミド系偏光子が得られる。In this way, a polyimide polarizer is obtained, which uses a film made of an imide ring-containing polymer typified by polyimide as a base material and contains a polarizing ability imparting agent in a fixed direction orientation state in the film base material.
なお、該ポリイミド系偏光子の厚さとしては、通例の偏
光子と同様のｌＯ〜５００即が一般であるがこれに限定
されない。The thickness of the polyimide polarizer is generally 10 to 500 mm, which is the same as that of a typical polarizer, but is not limited thereto.
発明の効果
本発明によれば、イミド環含有高分子フィルムを基材と
し、耐湿性、耐熱性、耐薬品性等としての耐久性及び高
温下における寸法安定性、光学特性の維持性に優゛れる
と共に、耐液晶性等に優れることに基づいて偏光子自体
の電極基板化が可能であり、従って偏光板ひいては液晶
表示素子の一層の薄型化を可能にするポリイミド系偏光
子を簡単な操作で容易に、かつ効率的に得ることができ
る。Effects of the Invention According to the present invention, an imide ring-containing polymer film is used as a base material and has excellent durability in terms of moisture resistance, heat resistance, chemical resistance, etc., dimensional stability under high temperatures, and maintenance of optical properties. In addition, due to its excellent liquid crystal resistance, the polarizer itself can be used as an electrode substrate. Therefore, it is possible to use a polyimide polarizer with simple operations, which allows for further thinning of polarizing plates and, by extension, liquid crystal display elements. can be obtained easily and efficiently.
実施例 以下、部は重量部を意味する。Example Hereinafter, parts mean parts by weight.
実施例 １
３．３°、４．４’−ビフェニルテトラカルボン酸二無
水物 １００部
ビス（４−（３−アミノフェノキシ）
フェニル〕スルホン １４７部
上記の量のモノマをジメチルアセトアミド７８２部中に
加えて窒素気流下、かきまぜながら２５℃に１２時間保
って反応させて得たポリアミド酸の溶液に、ｃ、ｒ、ダ
イレクトレッド８１ （Ｃ、ｒ 、２８１６０ ）を１
部混合せしめて溶解液を得た。Example 1 100 parts of 3.3°, 4.4'-biphenyltetracarboxylic dianhydride 147 parts of bis(4-(3-aminophenoxy)phenyl]sulfone The above amount of monomer was added to 782 parts of dimethylacetamide. 1 of C, R, Direct Red 81 (C, R, 28160) was added to a polyamic acid solution obtained by reacting the polyamic acid by keeping it at 25°C for 12 hours while stirring under a nitrogen stream.
A solution was obtained by partially mixing.
次に、得られた溶解液をガラス板上に流延させて厚さ約
０．３箇の展開層を形成し、これを１００℃で３時間加
熱して乾燥させ、厚さ約５０μｍのポリアミド酸フィル
ムを得た。ついで、このフィルムを１５０℃で１時間、
２００℃で２時間、２５０℃で１時間加熱したのち、２
８０℃に加熱しながら２．５倍に一軸延伸し、得られた
延伸フィルムを更に、その長さが変わらないように保持
して２５０℃で１時間加熱し、イミド環が形成された厚
さ２５νｍのポリイミド系偏光子を得た。Next, the obtained solution was cast onto a glass plate to form a spread layer with a thickness of about 0.3, and this was dried by heating at 100°C for 3 hours to form a polyamide layer with a thickness of about 50 μm. An acid film was obtained. Next, this film was heated at 150°C for 1 hour.
After heating at 200℃ for 2 hours and 250℃ for 1 hour,
Uniaxially stretched 2.5 times while heating to 80°C, the resulting stretched film was further heated at 250°C for 1 hour while keeping its length unchanged, and the thickness at which imide rings were formed was A 25 νm polyimide polarizer was obtained.
比較例 １
厚さ７５μｍのポリビニルアルコールフィルムを１重量
％Ｃ，１，ダイレクトレッド８１（Ｃ，１，２８１６０
）水溶液（３０℃）中に浸漬して４倍の長さに一軸延伸
し、厚さ２５塀のポリビニルアルコール系偏光子を得た
。Comparative Example 1 A polyvinyl alcohol film with a thickness of 75 μm was coated with 1% by weight C,1, Direct Red 81 (C,1,28160
) It was immersed in an aqueous solution (30° C.) and uniaxially stretched to four times the length to obtain a polyvinyl alcohol polarizer with a thickness of 25 mm.
比較例２
比較例１で得たポリビニルアルコール系偏光子の両面に
保護部材として厚さ８０μｍ日のトリアセチルセルロー
スフィルムを接着剤を介して貼り合わせることにより偏
光板を得た。Comparative Example 2 A polarizing plate was obtained by bonding triacetyl cellulose films with a thickness of 80 μm as a protective member to both sides of the polyvinyl alcohol polarizer obtained in Comparative Example 1 via an adhesive.
評価試験
［耐熱性１
実施例、比較例で得た偏光子又は偏光板を１８０℃で２
４時間加熱したものについて、波長５２５ｎｔｎの光線
における偏光度の変化を調べた。Evaluation test [Heat resistance 1 The polarizers or polarizing plates obtained in Examples and Comparative Examples were heated at 180°C for 2
After heating for 4 hours, changes in the degree of polarization of light with a wavelength of 525 ntn were investigated.
［耐薬品性］
種々の薬品（２５℃）中に１時間浸漬したのち取り出し
その外観上の変化を調べた。[Chemical Resistance] After being immersed in various chemicals (25° C.) for 1 hour, the samples were taken out and changes in appearance were examined.
結果を表に示した。The results are shown in the table.
なお、いずれの比較例においても加熱により収縮してそ
の偏光度を測定できなかった。In addition, in any of the comparative examples, the degree of polarization could not be measured due to shrinkage due to heating.
表より、本発明によるポリイミド系偏光子は耐熱性、耐
薬品性ないし寸法安定性、光学特性の維持性などに優れ
ていることが分かる。From the table, it can be seen that the polyimide polarizer according to the present invention is excellent in heat resistance, chemical resistance or dimensional stability, maintainability of optical properties, etc.
Claims (1)
合溶液を台上に展開し、その展開層を加熱処理して偏光
能付与剤を含むイミド環含有高分子フィルムを得る工程
、 （Ｂ）前記Ａ工程における加熱処理の一貫として又はＡ
工程終了後にポリアミド酸系高分子ないしイミド環含有
高分子のフィルムを延伸処理する工程からなることを特
徴とするポリイミド系偏光子の製造方法。 ２、混合溶液が不活性溶媒中で酸無水物とジアミンを重
合処理してポリアミド酸系高分子とした反応液、又はそ
の希釈液に偏光能付与剤を混合溶解せしめて得たもので
ある特許請求の範囲第１項記載の方法。 ３、ポリアミド酸系高分子が３，３′，４，４′−ビフ
ェニルテトラカルボン酸二無水物と、３，３′−ジアミ
ノジフェニルスルホン又はビス〔４−（３−アミノフェ
ノキシ）フェニル〕スルホンを構成成分とするものであ
る特許請求の範囲第１項記載の方法。 ４、偏光能付与剤が二色性染料である特許請求の範囲第
１項記載の方法。 ５、溶媒がＮ，Ｎ−ジメチルホルムアミド又はＮ，Ｎ−
ジメチルアセトアミドを少なくとも主成分とするもので
ある特許請求の範囲第１項又は第２項記載の方法。 ６、延伸倍率が１２０〜１０００％である特許請求の範
囲第１項記載の方法。[Claims] 1. (A) A mixed solution of a polyamic acid polymer and a polarization ability imparting agent is developed on a table, and the developed layer is heat-treated to form an imide ring-containing polymer containing a polarization ability imparting agent. A step of obtaining a molecular film, (B) as part of the heat treatment in step A or A
A method for producing a polyimide polarizer, which comprises the step of stretching a film of a polyamic acid polymer or an imide ring-containing polymer after the completion of the process. 2. A patent in which the mixed solution is obtained by mixing and dissolving a polarizing ability imparting agent in a reaction solution obtained by polymerizing an acid anhydride and a diamine in an inert solvent to form a polyamide acid polymer, or a diluted solution thereof. The method according to claim 1. 3. The polyamic acid polymer contains 3,3',4,4'-biphenyltetracarboxylic dianhydride and 3,3'-diaminodiphenylsulfone or bis[4-(3-aminophenoxy)phenyl]sulfone. The method according to claim 1, wherein the method is a constituent ingredient. 4. The method according to claim 1, wherein the polarization ability imparting agent is a dichroic dye. 5. The solvent is N,N-dimethylformamide or N,N-
The method according to claim 1 or 2, which contains dimethylacetamide as at least a main component. 6. The method according to claim 1, wherein the stretching ratio is 120 to 1000%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2178586A JPS62178908A (en) | 1986-02-03 | 1986-02-03 | Production of polyimide polarizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2178586A JPS62178908A (en) | 1986-02-03 | 1986-02-03 | Production of polyimide polarizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62178908A true JPS62178908A (en) | 1987-08-06 |
Family
ID=12064717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2178586A Pending JPS62178908A (en) | 1986-02-03 | 1986-02-03 | Production of polyimide polarizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62178908A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567219A (en) * | 1994-07-20 | 1996-10-22 | Galileo Electro-Optics Corporation | Polyimide coated heavy metal fluoride glass fiber and method of manufacture |
| US5714196A (en) * | 1994-07-20 | 1998-02-03 | Galileo Corporation | Method of forming a strippable polyimide coating for an optical fiber |
| JP2002267841A (en) * | 2001-03-09 | 2002-09-18 | Mitsui Chemicals Inc | Polarizing film for polarizing lens |
-
1986
- 1986-02-03 JP JP2178586A patent/JPS62178908A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567219A (en) * | 1994-07-20 | 1996-10-22 | Galileo Electro-Optics Corporation | Polyimide coated heavy metal fluoride glass fiber and method of manufacture |
| US5714196A (en) * | 1994-07-20 | 1998-02-03 | Galileo Corporation | Method of forming a strippable polyimide coating for an optical fiber |
| JP2002267841A (en) * | 2001-03-09 | 2002-09-18 | Mitsui Chemicals Inc | Polarizing film for polarizing lens |
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