JP2622748B2 - Water-soluble azo dye and polarizing film containing the same - Google Patents
Water-soluble azo dye and polarizing film containing the sameInfo
- Publication number
- JP2622748B2 JP2622748B2 JP1146634A JP14663489A JP2622748B2 JP 2622748 B2 JP2622748 B2 JP 2622748B2 JP 1146634 A JP1146634 A JP 1146634A JP 14663489 A JP14663489 A JP 14663489A JP 2622748 B2 JP2622748 B2 JP 2622748B2
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- Japan
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- parts
- acid
- polarizing film
- dye
- water
- Prior art date
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- Polarising Elements (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 各種の織物や紙などの染色のほか、特にポリビニルア
ルコール系偏光膜用の二色性色素として有用なアゾ染料
及びそれを含有する偏光膜に関する。Description: TECHNICAL FIELD The present invention relates to an azo dye useful as a dichroic dye for a polyvinyl alcohol-based polarizing film, and a polarizing film containing the same, in addition to dyeing various fabrics and papers.
従来の技術 ポリビニルアルコール系偏光膜用の二色性色素として
は従来ヨードが用いられており高い偏光率を示すという
特徴がある反面ヨードの揮発性がたかい為、偏光膜の耐
久性が劣るという問題がある。この為合成染料を使用し
た偏光膜が製造されているがその偏光率、堅牢度等にま
だ問題が多い。2. Description of the Related Art Conventionally, iodine has been used as a dichroic dye for a polyvinyl alcohol-based polarizing film, and has a characteristic of exhibiting a high polarization rate. On the other hand, the durability of the polarizing film is poor due to high volatility of iodine. There is. For this reason, polarizing films using synthetic dyes have been manufactured, but there are still many problems in the polarization ratio, fastness and the like.
発明が解決しようとする課題 ポリビニルアルコール系偏光膜に使用される合成染料
は既存の繊維用のものの転用が多い為偏光率がモード系
のものに比べてかなり低く用途が限定されている。従っ
てヨード並の偏光率を示す染料の開発が望まれている。Problems to be Solved by the Invention Synthetic dyes used for a polyvinyl alcohol-based polarizing film are often diverted from existing ones for fibers, so that their polarizability is considerably lower than that of mode-based ones, and their applications are limited. Therefore, development of a dye exhibiting a polarization index comparable to iodine is desired.
課題を解決するための手段 本発明者らは前記した課題を解決すべき鋭意検討を行
った結果遊離酸として式（１） 〔式（１）においてＡはメチル基を持つこともあるベン
ゼン環又はナフタリン環を、Ｒはアミノ基、メチルアミ
ノ基、エチルアミノ基又はフエニルアミノ基をそれぞれ
表す。〕 で表される水溶性染料またはこの銅錯塩染料が耐熱性、
耐光性等の堅牢度が優れる上に特に偏光率に優れている
ことを見出し本発明を完成させた。即ち本発明は遊離酸
として前記式（１）で表される水溶性染料またはこの銅
錯塩染料及びこれを含有する偏光膜を提供する。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the free acid of formula (1) [In the formula (1), A represents a benzene ring or a naphthalene ring which may have a methyl group, and R represents an amino group, a methylamino group, an ethylamino group or a phenylamino group. The water-soluble dye represented by this or the copper complex salt dye is heat-resistant,
The present inventors have found that they have excellent fastness such as light fastness and also have particularly excellent polarization ratio, and have completed the present invention. That is, the present invention provides a water-soluble dye represented by the above formula (1) or a copper complex salt dye thereof as a free acid and a polarizing film containing the same.
本発明を詳細に説明する。 The present invention will be described in detail.
式（１）の使用性染料は通常のアゾ染料の製法に従い
公知のジアゾ化、カップリング法で容易に製造出来る。The usable dye of the formula (1) can be easily produced by a known diazotization / coupling method in accordance with a usual azo dye production method.
即ちスルファニル酸、メタニル酸、２−メチルアニリ
ン−４−スルホン酸、アニリン−2,4−ジスルホン酸、
アニリン−2,5−ジスルホン酸、ナフチオン酸、２−ナ
フチルアミン−６−スルホン酸、２−ナフチルアミン−
4,8−ジスルホン酸、２−ナフチルアミン−3,6−ジスル
ホン酸、２−ナフチルアミン−5,7−ジスルホン酸、２
−ナフチルアミン−6,8−ジスルホン酸などをジアゾ化
し、ｐ−クレシジンと常法によりカップリングさせてモ
ノアゾ化合物を製造し、これを再びジアゾ化してｐ−ク
レシジンにカップリングさせてアミノ基を持ったジスア
ゾ中間体を製造する。これらの中間体の製造法において
ジアゾ化法はジアゾ成分の塩酸、硫酸などの鉱酸水溶液
またはけん濁液に亜硝酸ナトリウムなどの亜硝酸塩を混
合するという順法によるか、あるいはジアゾ成分の中乃
至弱アルカリ性の水溶液に亜硝酸塩を加えておき、これ
と鉱酸を混合するという逆法によってもよい。ジアゾ化
の温度は−10〜40℃が適当である。That is, sulfanilic acid, metanilic acid, 2-methylaniline-4-sulfonic acid, aniline-2,4-disulfonic acid,
Aniline-2,5-disulfonic acid, naphthionic acid, 2-naphthylamine-6-sulfonic acid, 2-naphthylamine-
4,8-disulfonic acid, 2-naphthylamine-3,6-disulfonic acid, 2-naphthylamine-5,7-disulfonic acid, 2
Diazotization of -naphthylamine-6,8-disulfonic acid or the like and coupling with p-cresidine by a conventional method to produce a monoazo compound, which was again diazotized and coupled to p-cresidine to have an amino group Produce a disazo intermediate. In the production method of these intermediates, the diazotization method is a conventional method of mixing a nitric acid salt such as sodium nitrite with an aqueous solution or suspension of a mineral acid such as hydrochloric acid and sulfuric acid of the diazo component, or a method of mixing the diazo component within or The reverse method of adding a nitrite to a weakly alkaline aqueous solution and mixing it with a mineral acid may be used. An appropriate temperature for the diazotization is -10 to 40 ° C.
カップリングはアミン類の塩酸、酢酸などの酸性水溶
液と上記ジアゾ液を混合し中和してpH3〜７にすればよ
い。カップリングの温度は−10〜40℃が適当である。The coupling may be performed by mixing an acidic aqueous solution of amines such as hydrochloric acid and acetic acid with the above diazo solution and neutralizing the mixture to pH 3 to 7. An appropriate coupling temperature is -10 to 40 ° C.
生成したアミノアゾ化合物はそのまゝ或は酸析や塩析
により析出させ過して取り出すか、所望なら溶液又は
けん濁液のまゝ次のジアゾ化工程へ進むこともできる。The produced aminoazo compound may be precipitated as it is or by acid precipitation or salting out, and may be taken out, or, if desired, the solution or suspension may be subjected to the next diazotization step.
ジアゾニウム塩が難溶性でけん濁液となっている場合
は過してプレスケーキとして次のジアゾ化工程で使う
こともできる。When the diazonium salt is hardly soluble and becomes a suspension, it can be used as a press cake in the next diazotization step.
この様にして得た中間体のジスアゾ化合物をジアゾ化
し、Ｊ−酸、Ｎ−メチルＪ酸、Ｎ−エチルＪ酸又はＮ−
フエニルＪ酸にアルカリ性でカップリングさせて式
（１）の水溶性染料が得られる。The thus obtained intermediate disazo compound is diazotized to give a J-acid, N-methyl J acid, N-ethyl J acid or N-acid.
Alkaline coupling with phenyl J acid gives the water-soluble dye of formula (1).
上記においてジアゾ化法は前記の順法によっても良い
がアミノアゾ化合物が酸性では溶解性が著しく小さい場
合には逆法による方が好ましい。ジアゾ化の温度は０〜
40℃が適当である。ジアゾ液はけん濁液となっている
が、これをそのまゝ使うことも、過してジアゾニウム
塩のプレスケーキを取り出すこともできる。In the above, the diazotization method may be performed according to the above-mentioned normal method, but when the solubility of the aminoazo compound is extremely small when the aminoazo compound is acidic, the reverse method is more preferable. The diazotization temperature is between 0 and
40 ° C is appropriate. The diazo liquid is a suspension, which can be used as it is or can be used to remove the diazonium salt press cake.
カップリングはカップリング成分のアルカリ水溶液に
前記ジアゾニウム塩のけん濁液またはジアゾニウム塩を
小量づつ添加する。この際液がpH8〜11を保つ様必要に
応じアルカリを添加する。アルカリとしてはナトリウ
ム、カリウム、リチウムなどの炭酸塩、アンモニヤ、モ
ノ、ジ、トリエタノールアミンなどのアミンの使用が好
ましく、これ以外にナトリウム、カリウムなどの水酸化
物や重炭酸塩を併用してもよい。また必要に応じピリジ
ンや尿素などの通常のカップリング促進剤を添加しても
よい。For coupling, a small amount of the suspension or diazonium salt of the diazonium salt is added to the aqueous alkali solution of the coupling component. At this time, an alkali is added as necessary so that the solution maintains pH 8 to 11. As the alkali, sodium, potassium, carbonates such as lithium, ammonia, mono, di, amines such as triethanolamine are preferably used, and in addition to these, hydroxides such as sodium and potassium or bicarbonates may be used in combination. Good. If necessary, a usual coupling accelerator such as pyridine or urea may be added.
カップリングの温度は−10〜40℃が適当である。カッ
プリング終了後必要に応じ塩化ナトリウムまたは／およ
び塩化カリウムを加えて塩析して取り出す。An appropriate coupling temperature is -10 to 40 ° C. After completion of the coupling, if necessary, sodium chloride and / or potassium chloride are added, and salted out and taken out.
又式（１）の水溶性染料の銅錯塩を得るには通常の方
法に依ればよい。即ち式（１）の水溶性染料を水溶液
中、硫酸銅、塩化銅、酢酸銅などの銅塩と通常70〜110
℃に加熱する。この際必要に応じアンモニア、モノエタ
ノールアミン、ジエタノールアミン、モノプロパノール
アミン、ピリジンなどの有機アミンを添加することも出
来る。In order to obtain the copper complex salt of the water-soluble dye of the formula (1), a conventional method may be used. That is, the water-soluble dye of the formula (1) is mixed with a copper salt such as copper sulfate, copper chloride, copper acetate or the like in an aqueous solution usually at 70 to 110.
Heat to ° C. At this time, if necessary, an organic amine such as ammonia, monoethanolamine, diethanolamine, monopropanolamine, or pyridine can be added.
本発明の偏光膜を調製する為の基材としては繊維素系
樹脂（セロファン）、PVA、変性PVA、PVAと他の樹脂の
共重合物等が用いられる。これらのうち好ましいもの
は、PVA、変性PVA、PVAと他の樹脂の共重合物等であ
り、以下これらをPVA系基材という。PVA系基材として
は、通常の純PVAの他、不飽和カルボン酸又はその誘導
体、不飽和スルホン酸又はその誘導体、炭素数２〜30の
α−オレフィン等で約15モル％未満共重合変性された変
性ポリビニルアルコール、ポリビニルホルマール、ポリ
ビニルアセトアセタール、ポリビニルブチラール等のポ
リビニルアセタール、エチレン含量15〜55モル％のエチ
レン−酢酸ビニル共重合体ケン化物等が挙げられる。こ
れらの基材から偏光膜を製造する方法としては、成型さ
れたPVA系フィルムそのものを染色する方法、PVA系樹脂
の溶液に染料を添加し、原液染色後製膜する方法等を挙
げる事が出来る。まずPVA系フィルムの一般的な染色方
法及び延伸法について説明する。As a substrate for preparing the polarizing film of the present invention, a fibrous resin (cellophane), PVA, modified PVA, a copolymer of PVA and another resin, or the like is used. Among these, preferred are PVA, modified PVA, copolymers of PVA and other resins, and these are hereinafter referred to as PVA-based substrates. As a PVA-based substrate, in addition to ordinary pure PVA, an unsaturated carboxylic acid or a derivative thereof, an unsaturated sulfonic acid or a derivative thereof, an α-olefin having 2 to 30 carbon atoms, and the like are copolymerized and modified with less than about 15 mol%. And polyvinyl acetal such as modified polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal and polyvinyl butyral, and saponified ethylene-vinyl acetate copolymer having an ethylene content of 15 to 55 mol%. Examples of a method for producing a polarizing film from these base materials include a method of dyeing a molded PVA-based film itself, a method of adding a dye to a PVA-based resin solution, and a method of forming a film after dyeing an undiluted solution. . First, a general dyeing method and a stretching method for a PVA-based film will be described.
式（１）の水溶性染料又はその銅錯体及び必要に応じ
て無機塩、界面活性剤等の染色助剤を含有する染浴中に
０℃ないし70℃、好ましくは30〜45℃でPVA系フィルム
を浸漬して染色し、次いで必要に応じてホウ酸処理し、
乾燥する。該染色フィルムに偏光機能を付与させる為に
染色前、染色後または染色中に一軸方向に２倍以上特に
好ましくは2.5〜４倍延伸する。染色前又は染色後に延
伸する場合には湿式延伸の他に乾式条件（通常常温ない
し180℃の範囲）で行ってもよく、また染色と同時に延
伸する場合には染浴中で０〜70℃好ましくは30〜45℃で
延伸する。In a dye bath containing a water-soluble dye of the formula (1) or a copper complex thereof and, if necessary, a dyeing aid such as an inorganic salt or a surfactant, a PVA system is used at 0 to 70 ° C, preferably 30 to 45 ° C. Dipping and dyeing the film, then optionally boric acid treatment,
dry. In order to impart a polarizing function to the dyed film, the film is stretched in a uniaxial direction at least twice or more, preferably 2.5 to 4 times before, after or during dyeing. In the case of stretching before or after dyeing, in addition to wet stretching, it may be performed under dry conditions (usually in the range of room temperature to 180 ° C.). Is stretched at 30 to 45 ° C.
次に原液染色後製膜する方法は、まずPVA系基材（樹
脂）を水、有機溶媒、水−アルコール混合溶媒等の溶媒
に溶解し、式（１）の水溶性染料又はその銅錯塩染料を
添加し、原液染色を行う。この染色原液を流延法、溶液
塗布法、押出法等によって製膜し、染色フィルムを製造
する。このよう経してえられた染色フィルムに偏光機能
を付与させる為に該染色フィルムを前記同様の湿式また
は乾式条件で一軸方向に延伸する。ここで一軸延伸とは
完全に一軸方向にのみフィルムを延伸する（自由幅一軸
延伸）他、延伸方向に直角の方向にも幅方向の収縮を防
止する為若干の延伸を行う事（一定幅一軸延伸）をも意
味する。Next, in the method of forming a film after dyeing the undiluted solution, first, a PVA-based substrate (resin) is dissolved in a solvent such as water, an organic solvent, or a water-alcohol mixed solvent, and a water-soluble dye of the formula (1) or a copper complex salt dye thereof Is added and stock solution staining is performed. The dyeing stock solution is formed into a film by a casting method, a solution coating method, an extrusion method, or the like, to produce a dyed film. In order to impart a polarizing function to the dyed film thus obtained, the dyed film is uniaxially stretched under the same wet or dry condition as described above. Here, the uniaxial stretching means that the film is completely stretched only in the uniaxial direction (free-width uniaxial stretching), and that the film is slightly stretched in a direction perpendicular to the stretching direction to prevent shrinkage in the width direction (uniaxial stretching with a constant width). Stretching).
またフィルムの染色法としては前記したような浸漬に
よる染色又は原液染色による染色法が一般的であるが印
捺糊を調製しこれをフィルムに捺染し、加熱して内部拡
散により染着させる方法を採用する事も出来る。As a method for dyeing a film, dyeing by immersion or dyeing by undiluted solution as described above is common.However, a method of preparing a printing paste, printing this on a film, heating and dyeing by internal diffusion is used. Can also be adopted.
式（１）で表される水溶性染料又はその銅錯塩染料は
単独で又はそれら同志で混合して使用することが出来る
他、更にはこれらの染料と他の染料と配合することによ
り種々の色相に染色された高偏光率の偏光膜を製造する
事ができる。特に多用されるグレーヌはブラック用の配
合成分として式（１）で表される水溶性染料又はその銅
錯塩染料を使用した場合すぐれた偏光能及び好ましい吸
収特性を示す偏光膜がえられる。又その熱に対する安定
性がすぐれている。The water-soluble dye represented by the formula (1) or the copper complex salt dye thereof can be used alone or as a mixture thereof, and further, various hue can be obtained by blending these dyes with other dyes. It is possible to produce a polarizing film having a high polarization rate and dyed in a low color. In particular, when using a water-soluble dye represented by the formula (1) or a copper complex dye thereof as a black component, a polarizing film exhibiting excellent polarization ability and preferable absorption characteristics can be obtained. Also, its heat stability is excellent.
この様にして製造された偏光膜はそのまま使用される
他、特に高い耐久性を要求される分野においてはポリエ
ステル、塩化ビニール、セルローズトリアセテート、ア
クリル樹脂、ポリエーテルスルホン等の支持フィルムを
接着したり特殊アクリル樹脂等でコーティングして高偏
光率でしかも高耐久性の偏光板として使用に供すること
も出来る。The polarizing film produced in this way is used as it is, and especially in the field where high durability is required, a supporting film such as polyester, vinyl chloride, cellulose triacetate, acrylic resin, polyether sulfone, etc. It can be used as a polarizing plate having a high polarization rate and high durability by coating with an acrylic resin or the like.
本発明の式（１）の染料の中で次記式（２）及び
（４）の染料が好ましい例としてあげられる。Among the dyes of the formula (1) of the present invention, the dyes of the following formulas (2) and (4) are preferred examples.
即ちこれらの染料は深い青色の好ましい色相でPVAに
対する良好な染着性と高いカラーバリューを持ち、特に
偏光率の高い偏光フィルムが得られる特長がある。しか
も水溶性も良好で取り扱いが容易である。 That is, these dyes have a favorable deep blue hue, have good dyeing properties with respect to PVA, and have high color value, and are characterized in that a polarizing film having a particularly high polarization ratio can be obtained. Moreover, it has good water solubility and is easy to handle.
実施例 以下に本発明を具体例によって説明する。Examples Hereinafter, the present invention will be described with reference to specific examples.
実施例中、構造式はすべて遊離酸の形で示し部は重量
部を示す。In the examples, all structural formulas are shown in the form of free acid, and parts are parts by weight.
実施例1. ２−メチル−５−メトキシ−４−アミノアゾベンゼン
−４′−スルホン酸ナトリウム34.3部（1/10モル）を水
300部にとかし濃塩酸25部と亜硝酸ナトリウム6.9部を加
えてジアゾ化し、この中へｐ−クレシジン13.7部を塩酸
水溶液にとかして加えたのち、酢酸ナトリウムを加えて
pH4まで中和してカップリングさせた。反応終了後ろ過
して次式で表されるジスアゾ化合物47.5部を含むプレス
ケーキを得た。Example 1. 34.3 parts (1/10 mol) of sodium 2-methyl-5-methoxy-4-aminoazobenzene-4'-sulfonate was added to water
25 parts of concentrated hydrochloric acid and 6.9 parts of sodium nitrite were added to 300 parts of diazotization, and 13.7 parts of p-cresidine was dissolved in an aqueous hydrochloric acid solution, and then sodium acetate was added.
Neutralized to pH 4 and coupled. After completion of the reaction, the mixture was filtered to obtain a press cake containing 47.5 parts of a disazo compound represented by the following formula.
このプレスケーキを温水2000部中に水酸化ナトリウム
で中和して溶解し、その中に亜硝酸ナトリウム８部を加
えた溶液を、５％塩酸溶液400部中に約20℃で滴下して
ジアゾ化した。ジアゾ化終了後過剰の亜硝酸をスルファ
ミン酸を加えて分解したのちこのジアゾニウム塩の懸濁
液をＮ−フエニルＪ酸31.5部を10％炭酸ナトリウム水溶
液600部に溶解した液中に約20℃で滴下してカップリン
グさせた。２時間かきまぜたのち塩化ナトリウム90部を
加えて塩析し一夜かきまぜてからろ過し、３％塩化ナト
リウム水溶液で洗い、乾燥して次式（２）で表されるト
リスアゾ染料72部を得た。 This press cake is neutralized and dissolved in 2,000 parts of warm water with sodium hydroxide, and a solution obtained by adding 8 parts of sodium nitrite thereto is added dropwise to 400 parts of a 5% hydrochloric acid solution at about 20 ° C. to obtain a diazo compound. It has become. After completion of diazotization, excess nitrous acid is decomposed by adding sulfamic acid, and then a suspension of this diazonium salt is dissolved in a solution prepared by dissolving 31.5 parts of N-phenyl J acid in 600 parts of a 10% aqueous sodium carbonate solution at about 20 ° C. It was dropped and coupled. After stirring for 2 hours, 90 parts of sodium chloride was added, salted out, stirred overnight, filtered, washed with a 3% aqueous solution of sodium chloride, and dried to obtain 72 parts of a trisazo dye represented by the following formula (2).
このトリスアゾ染料の0.3g/の染浴を調製し40℃に
保持し、厚さ75μのポリビニルアルコールフィルムを浸
漬し２分間染色した。濡れたまゝの染色フィルムを５％
ホウ酸水溶液中で40℃で４倍に延伸しこの状態のまゝ水
洗、乾燥して青紫色の偏光フィルムを製造した。その偏
光フィルムの吸収極大λmaxでの偏光率ρ（max）を測定
した結果単板透過率43％、λmaxは600nmでρ（max）は9
7.5％であった。 A 0.3 g / dye bath of this trisazo dye was prepared and maintained at 40 ° C., and a 75 μm thick polyvinyl alcohol film was immersed and dyed for 2 minutes. 5% wet dyed dyed film
The film was stretched 4 times at 40 ° C. in a boric acid aqueous solution, washed with water in this state, and dried to produce a blue-violet polarizing film. As a result of measuring the polarization ratio ρ (max) at the absorption maximum λmax of the polarizing film, the single plate transmittance was 43%, λmax was 600 nm, and ρ (max) was 9%.
7.5%.
こゝで吸収極大波長λmaxでの偏光率ρ（max）はその
波長での平行位透過率Ｔ 直交位透過率⊥（max）を用いて次式によって表され
る。Here, the polarization ratio ρ (max) at the maximum absorption wavelength λmax is the parallel transmittance T at that wavelength. It is expressed by the following equation using the orthogonal position transmittance ⊥ (max).
比較のため偏光膜用の青紫色染料として知られている
C.T.Direct Violet9（下記構造式）を使用して 前記同様に偏光膜を調製した所λmaxは575nmで単板透過
率43％の時のρ（max）は92.5％で本発明の染料の方が
すぐれていた。 Known as a blue-violet dye for polarizing films for comparison
Using CTDirect Violet9 (the following structural formula) When the polarizing film was prepared in the same manner as described above, λmax was 575 nm, and ρ (max) was 92.5% when the transmittance of the single plate was 43%, and the dye of the present invention was superior.
実施例2. 実施例１に於いてＮ−フエニルＪ酸の代わりにＮ−メ
チルＪ酸25.3部を使用して式（３）で、表されるトリス
アゾ染料を得た。Example 2 A trisazo dye represented by the formula (3) was obtained by using 25.3 parts of N-methyl J acid in Example 1 in place of N-phenyl J acid.
このトリスアゾ染料の水溶液で実施例１と同様にポリ
ビニルアルコールフィルムを処理し赤味青の偏光フィル
ムを製造した。その偏光フィルムの吸収極大λmaxでの
偏光率ρ（max）を測定した結果単板透過率43％、λmax
は585nmでρ（max）は95.5％であった。 A polyvinyl alcohol film was treated with this aqueous solution of the trisazo dye in the same manner as in Example 1 to produce a reddish blue polarizing film. As a result of measuring the polarization ratio ρ (max) at the absorption maximum λmax of the polarizing film, the single plate transmittance was 43% and λmax
Was 585 nm and ρ (max) was 95.5%.
実施例3. ２−アミノ−4,8−ナフタレンジスルホン酸30.3部（1
/10モル）を水600部に溶かし濃塩酸26部と亜硝酸ナトリ
ウム７部を加えてジアゾ化した。終了後過剰の亜硝酸を
スルファミン酸を加えて分解したのちこの中へｐ−クレ
シジン13.7部を塩酸水溶液に溶かして加え15〜20℃にて
酢酸ナトリウムを加え、pH4まで中和しカップリングさ
せた。反応終了後、析出した結晶を過して次式のモノ
アゾ化合物43.7部を得た。Example 3. 30.3 parts of 2-amino-4,8-naphthalenedisulfonic acid (1
/ 10 mol) in 600 parts of water and diazotized by adding 26 parts of concentrated hydrochloric acid and 7 parts of sodium nitrite. After completion, excess nitrous acid was decomposed by adding sulfamic acid, and then 13.7 parts of p-cresidine was dissolved in an aqueous hydrochloric acid solution, and sodium acetate was added at 15 to 20 ° C., neutralized to pH 4, and coupled. . After the completion of the reaction, the precipitated crystals were filtered to obtain 43.7 parts of a monoazo compound represented by the following formula.
このモノアゾ化合物を水500部中で水酸化ナトリウム
で中和して溶解し、亜硝酸ナトリウム８部を加えた溶液
を10％塩酸水溶液300部中に15〜20℃にて滴下しジアゾ
化した。 The monoazo compound was neutralized and dissolved in 500 parts of water with sodium hydroxide, and a solution to which 8 parts of sodium nitrite was added was dropped into 300 parts of a 10% aqueous hydrochloric acid solution at 15 to 20 ° C. to perform diazotization.
終了後、過剰の亜硝酸をスルファミン酸にて分解した
のちこの中へｐ−クレシジン13.7部を塩酸水溶液に溶か
して加え15〜20℃にて酢酸ナトリウムを加え、pH4まで
中和しカップリングさせた。反応終了後、析出した結晶
を過して次式のジスアゾ化合物52.2部を得た。After completion, excess nitrous acid was decomposed with sulfamic acid, and then 13.7 parts of p-cresidine was dissolved in an aqueous hydrochloric acid solution, sodium acetate was added at 15 to 20 ° C, and the mixture was neutralized to pH 4 and coupled. . After completion of the reaction, the precipitated crystals were filtered to obtain 52.2 parts of a disazo compound represented by the following formula.
次にこのジシアゾ化合物を水1000部に水酸化ナトリウ
ムで中和して溶解し、亜硝酸ナトリウム７部を加えた溶
液を10％塩酸水溶液250部中に15〜20℃にて滴下しジア
ゾ化した。 Next, the dithiazo compound was neutralized and dissolved in 1000 parts of water with sodium hydroxide, and a solution to which 7 parts of sodium nitrite was added was dropped into 250 parts of a 10% aqueous hydrochloric acid solution at 15 to 20 ° C. to perform diazotization. .
ジアゾ化終了後、過剰の亜硝酸をスルファミン酸にて
分解後このジアゾニウム塩液をＮ−フエニルＪ酸30.5部
を10％炭酸ナトリウム水溶液500部に溶解した液中に15
〜20℃にて滴下しカップリングさせた。After completion of the diazotization, excess nitrous acid is decomposed with sulfamic acid, and the diazonium salt solution is added to a solution prepared by dissolving 30.5 parts of N-phenyl J acid in 500 parts of a 10% aqueous sodium carbonate solution.
The mixture was added dropwise at 2020 ° C. for coupling.
反応終了後、塩化ナトリウム100部を加えて塩析後、
過し乾燥して次式のトリスアゾ染料79部を得た。After completion of the reaction, after adding 100 parts of sodium chloride and salting out,
After drying, 79 parts of a trisazo dye represented by the following formula was obtained.
このトリスアゾ染料の0.3g/染浴を調製し、実施例
１と同様にポリビニルアルコールフィルムを処理し、青
色の偏光フィルムを製造した。その偏光フィルムの吸収
極大λmaxでの偏光率ρ（max）を測定した結果、単板透
過率43％、λmaxは600nmでρ（max）は97.5％であっ
た。 A 0.3 g / dye bath of this trisazo dye was prepared, and a polyvinyl alcohol film was treated in the same manner as in Example 1 to produce a blue polarizing film. As a result of measuring the polarization ratio ρ (max) at the absorption maximum λmax of the polarizing film, the single plate transmittance was 43%, λmax was 600 nm, and ρ (max) was 97.5%.
実施例4. 実施例１〜３と同様な方法により次表に示される一般
式（１）の染料を製造した。Example 4. Dyes of the general formula (1) shown in the following table were produced in the same manner as in Examples 1 to 3.
表中色相、λmaxは共にPVAフィルムを染色した時のも
のを示す。Both the hue and λmax in the table are those obtained when the PVA film was dyed.
実施例5. 前記実施例１記載の式（２）の染料７部を水100部に
とかし、モノエタノールアミン7.0部を加えたのち結晶
硫酸銅2.4部の水溶液を加えて90℃で３時間加熱した。
塩化ナトリウム6.0部を加え冷却塩析し一夜かきまぜて
からろ過し、５％塩化ナトリウム水溶液で洗い、乾燥し
て次式（16）で表されるトリスアゾ染料6.1部を得た。 Example 5 7 parts of the dye of the formula (2) described in Example 1 was dissolved in 100 parts of water, 7.0 parts of monoethanolamine was added, and an aqueous solution of 2.4 parts of crystalline copper sulfate was added, followed by heating at 90 ° C. for 3 hours. did.
6.0 parts of sodium chloride was added, and the mixture was cooled and salted out, stirred overnight, filtered, washed with a 5% aqueous solution of sodium chloride, and dried to obtain 6.1 parts of a trisazo dye represented by the following formula (16).
このトリスアゾ染料の水溶液で実施例１と同様にポリ
ビニルアルコールフィルムを処理し青色の偏光フィルム
を製造した。その偏光フィルムの吸収極大λmaxでの偏
光率ρ（max）を測定した結果、単板透過率43％、λmax
は635nmでρ（max）は96.0％であった。 A polyvinyl alcohol film was treated with the aqueous solution of the trisazo dye in the same manner as in Example 1 to produce a blue polarizing film. As a result of measuring the polarization ratio ρ (max) at the absorption maximum λmax of the polarizing film, the single plate transmittance was 43%,
Was 635 nm and ρ (max) was 96.0%.
実施例6. 実施例３記載の式（４）のトリスアゾ染料46.3部（1/
20モル）を水1000部に溶かしこの中にモノエタノールア
ミン18.3部、次に硫酸銅（Cu SO4・5H2O）13部に加え
加熱し90〜95℃にて銅化反応させた。反応終了後、塩化
ナトリウム80部を加えて塩析後、過し乾燥して次式の
トリスアゾ銅錯塩染料46.8部を得た。Example 6. 46.3 parts of a trisazo dye of the formula (4) described in Example 3 (1 /
20 mol) 18.3 parts of monoethanolamine in this dissolved in 1000 parts of water, then was whether the reaction with sulfuric acid copper (Cu SO 4 · 5H 2 O ) was added to 13 parts of heated 90-95 ° C.. After completion of the reaction, 80 parts of sodium chloride was added, salted out, filtered and dried to obtain 46.8 parts of a trisazo copper complex salt dye represented by the following formula.
このトリスアゾ銅錯塩染料0.3g/染浴を調製し、実
施例１と同様にポリビニルアルコールフィルムを処理し
帯緑青色の偏光フィルムを製造した。その偏光フィルム
の吸収極大λmaxでの偏光率ρ（max）を測定した結果、
単板透過率43％、λmaxは630nmでρ（max）は95.9％で
あった。 0.3 g of this trisazo copper complex dye / dye bath was prepared, and a polyvinyl alcohol film was treated in the same manner as in Example 1 to produce a greenish blue polarizing film. As a result of measuring the polarization ratio ρ (max) at the absorption maximum λmax of the polarizing film,
The single-plate transmittance was 43%, λmax was 630 nm, and ρ (max) was 95.9%.
実施例7. 実施例5,6と同様な方法により前記の各式の染料を原
料として次表に示す銅錯塩染料を製造した。Example 7. Copper complex salt dyes shown in the following table were produced in the same manner as in Examples 5 and 6, using the dyes of the above formulas as raw materials.
色相、λmaxは共にPVAフィルムに染色したものについ
てである。Both the hue and λmax are those obtained by dyeing a PVA film.
発明の効果 殊にポバール系フィルムの染色に供して高い偏光率並
びに高い熱安定性を有する偏光膜を与える水溶性トリス
アゾ染料が得られた。そしてこの偏光膜は青色系偏光膜
としてすぐれた光学特性を有する。 Effect of the Invention In particular, a water-soluble trisazo dye which is used for dyeing a poval film to give a polarizing film having a high polarization rate and a high thermal stability was obtained. This polarizing film has excellent optical characteristics as a blue polarizing film.
Claims (2)
ゼン環又はナフタリン環を、Ｒはアミノ基、メチルアミ
ノ基、エチルアミノ基又はフエニルアミノ基をそれぞれ
表す。〕 で表される水溶性染料またはこの銅錯塩染料1. The free acid of the formula (1) [In the formula (1), A represents a benzene ring or a naphthalene ring which may have a methyl group, and R represents an amino group, a methylamino group, an ethylamino group or a phenylamino group. ] Or a copper complex salt dye represented by
溶性染料またはこの銅錯塩染料を含有する偏光膜2. A polarizing film containing the water-soluble dye of the formula (1) or the copper complex salt dye according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1146634A JP2622748B2 (en) | 1989-06-12 | 1989-06-12 | Water-soluble azo dye and polarizing film containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1146634A JP2622748B2 (en) | 1989-06-12 | 1989-06-12 | Water-soluble azo dye and polarizing film containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0312606A JPH0312606A (en) | 1991-01-21 |
| JP2622748B2 true JP2622748B2 (en) | 1997-06-18 |
Family
ID=15412168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1146634A Expired - Fee Related JP2622748B2 (en) | 1989-06-12 | 1989-06-12 | Water-soluble azo dye and polarizing film containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2622748B2 (en) |
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| WO2014162633A1 (en) | 2013-04-03 | 2014-10-09 | 日本化薬株式会社 | Achromatic polarization element, and polarization plate |
| WO2014162634A1 (en) | 2013-04-03 | 2014-10-09 | 日本化薬株式会社 | Achromatic dye-based polarization element, and polarization plate |
| US10209417B2 (en) | 2013-04-03 | 2019-02-19 | Nippon Kayaku Kabushiki Kaisha | Achromatic dye-based highly-transmissive polarization element, and polarization plate |
| US10209418B2 (en) | 2013-04-03 | 2019-02-19 | Nippon Kayaku Kabushiki Kaisha | Achromatic polarization element, and polarization plate |
| US10215902B2 (en) | 2013-04-03 | 2019-02-26 | Nippon Kayaku Kabushiki Kaisha | Achromatic dye-based polarization element, and polarization plate |
| KR20160138070A (en) | 2014-03-31 | 2016-12-02 | 닛뽄 가야쿠 가부시키가이샤 | Azo compound, dye-based polarizing film containing same, and polarizing plate |
| US10150871B2 (en) | 2014-03-31 | 2018-12-11 | Nippon Kayaku Kabushiki Kaisha | Azo compound, dye-based polarizing film containing same, and polarizing plate |
| US10007142B2 (en) | 2015-05-20 | 2018-06-26 | Nippon Kayaku Kabushiki Kaisha | Dye-based polarizer as well as polarizing plate and liquid crystal display device using the polarizer |
| WO2017146212A1 (en) | 2016-02-26 | 2017-08-31 | 日本化薬株式会社 | Azo compound or salt thereof, and polarizing film containing same |
| WO2017199916A1 (en) | 2016-05-16 | 2017-11-23 | 株式会社ポラテクノ | Polarizing member and head-up display device comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0312606A (en) | 1991-01-21 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |