JPH0375580B2 - - Google Patents
Info
- Publication number
- JPH0375580B2 JPH0375580B2 JP61215244A JP21524486A JPH0375580B2 JP H0375580 B2 JPH0375580 B2 JP H0375580B2 JP 61215244 A JP61215244 A JP 61215244A JP 21524486 A JP21524486 A JP 21524486A JP H0375580 B2 JPH0375580 B2 JP H0375580B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- liquid crystal
- dye
- formula
- 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.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000004973 liquid crystal related substance Substances 0.000 description 20
- 239000000975 dye Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- -1 monoazo compound Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BZCRRKAWKQYZQX-UHFFFAOYSA-N n-methoxy-1,3-benzothiazol-2-amine Chemical compound C1=CC=C2SC(NOC)=NC2=C1 BZCRRKAWKQYZQX-UHFFFAOYSA-N 0.000 description 1
- VQTGUFBGYOIUFS-UHFFFAOYSA-N nitrosylsulfuric acid Chemical compound OS(=O)(=O)ON=O VQTGUFBGYOIUFS-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- OMSQHQIMCZHAKJ-UHFFFAOYSA-M sodium aniline methanesulfonate Chemical compound CS(=O)(=O)[O-].NC1=CC=CC=C1.[Na+] OMSQHQIMCZHAKJ-UHFFFAOYSA-M 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Description
〔産業上の利用分野〕
この発明はゲスト・ホスト型液晶表示装置に用
いられる液晶用染料として有用なトリスアゾ系化
合物に関する。
〔従来の技術および問題点〕
一般にゲスト・ホスト型液晶表示装置は、コン
トラストの良い表示が行なえ、しかも表示駆動に
対する応答性も良く、さらには表示色が長期にわ
たつて退色しないものが理想的であるとされてい
る。
一方、ゲスト・ホスト型液晶表示装置の表示コ
ントラストは、主に、液晶中に混入される二色性
染料の二色性比によつて左右されるが、前記染料
の着色能力が低い場合は表示色が薄くなるため
に、染料の二色性比が高くても十分な表示コント
ラストを得ることはできなくなる。このために、
染料の着色能力が低い場合は、液晶中への染料の
添加量を多くして表示色を濃くすることが必要と
なるが、染料の添加量を多くすると、染料が液晶
の動作に影響を及ぼすようになるため、表示駆動
に対する応答性が悪くなる。また、ゲスト・ホス
ト型液晶表示装置においては、液晶に対する二色
性染料の相溶性が十分でないと、液晶中の染料が
析出することがあり（この染料の析出は低温下に
おいて顕著である）、そのために表示部に色ムラ
を生じ表示品質の悪化を引き起すことがある。
従つて、前述したような理想的なゲスト・ホス
ト型液晶表示装置を得るためには、液晶中に混入
する二色性染料として、
１ 高い二色性比を有すること。
２ 高い着色能力を有し、少量の添加で十分な濃
さの表示色が得られること。
３ 液晶に対する相溶性が十分で、低温下でも析
出を生じないこと。
の３つの条件を全て満足するものを用いることが
必要であるが、従来使用されているベンゼン系ア
ゾ染料、スチルベン系染料、アントラキノン系染
料等は、いずれも前記３つの条件を全て満足する
とはいえないものであつた。
この発明はこのような実情にかんがみてなされ
たものであつて、その目的とするところは、二色
性比が高く、かつ高い着色能力を有すると共に、
液晶との相溶性にもすぐれている液晶用二色性染
料として有用な新規トリスアゾ系化合物を提供す
ることにある。
〔問題点を解決するための手段〕
すなわち、この発明のトリスアゾ系化合物は、
以下の一般式(1)で示されるものである。
上記式において、R1はＨ、−CoH2o+1又は−
OCkH2k+1を表わす。
R3は
[Industrial Application Field] This invention relates to a trisazo compound useful as a liquid crystal dye used in a guest-host type liquid crystal display device. [Prior art and problems] In general, guest-host type liquid crystal display devices should ideally be able to display images with good contrast, have good responsiveness to display driving, and display colors that do not fade over a long period of time. It is said that there is. On the other hand, the display contrast of a guest-host type liquid crystal display device is mainly influenced by the dichroic ratio of the dichroic dye mixed into the liquid crystal. Since the color becomes lighter, sufficient display contrast cannot be obtained even if the dichroic ratio of the dye is high. For this,
If the coloring ability of the dye is low, it is necessary to increase the amount of dye added to the liquid crystal to make the displayed color darker, but if the amount of dye added is increased, the dye may affect the operation of the liquid crystal. As a result, responsiveness to display driving deteriorates. In addition, in guest-host type liquid crystal display devices, if the compatibility of the dichroic dye with the liquid crystal is not sufficient, the dye in the liquid crystal may precipitate (this dye precipitation is noticeable at low temperatures). This may cause color unevenness in the display section, resulting in deterioration of display quality. Therefore, in order to obtain the ideal guest-host type liquid crystal display device as described above, the dichroic dye mixed into the liquid crystal must: 1. have a high dichroic ratio; 2. It has high coloring ability, and a display color of sufficient density can be obtained with a small amount of addition. 3. Must have sufficient compatibility with liquid crystals and not cause precipitation even at low temperatures. It is necessary to use a dye that satisfies all three conditions.However, although the conventionally used benzene-based azo dyes, stilbene-based dyes, anthraquinone-based dyes, etc. all satisfy all of the above three conditions, It was something I didn't have. This invention was made in view of these circumstances, and its purpose is to have a high dichroism ratio and high coloring ability, and to
The object of the present invention is to provide a novel trisazo compound that is useful as a dichroic dye for liquid crystals and has excellent compatibility with liquid crystals. [Means for solving the problem] That is, the trisazo compound of the present invention is
It is represented by the following general formula (1). In the above formula, R 1 is H, -C o H 2o+1 or -
Represents OC k H 2k+1 . R3 is
【式】または[expression] or
以下、この発明の実施例を説明する。
前記一般式（）で表わされるトリスアゾ系化
合物としては例えば次のような構造式で表わされ
るものがある。
より具体的には、トリスアゾ系化合物(1)は、例え
ば次のようにして合成することができる。
すなわち、(1) 式
で示される化合物10重量部を、85％リン酸150
重量部に溶解した後、５℃以下に冷却し、43％
ニトロシル硫酸９重量部を同温度に保ちながら
滴下した。さらに、上記温度において１時間攪
拌した後、その反応混合物をアニリンメタンス
ルホン酸ナトルウム33重量部を溶解した氷水
1000重量部へ滴下し、０〜５℃で３時間攪拌し
た。この反応液をろ過して得られる析出物を水
洗した後、３％水酸化ナトリウム水溶液400部
に加え、90〜95℃で１時間攪拌した。この反応
液を冷却後ろ過、水洗し、乾燥して式
で示される粗モノアゾ化合物15重量部を得た。
(2) 上記モノアゾ化合物4.0重量部をＮ，Ｎ−ジ
メチルホルムアミド200部に溶解し、５℃以下
に冷却した後、43％ニトロシル硫酸2.0重量部
を加え、ジアゾ化液を得た。
(3) このジアゾ化液を、α−ナフチルアミン4.8
重量部を含むメタノール75重量部中に滴下し、
０〜５℃で２時間攪拌した。これに、28％アン
モニア水溶液14重量部を含む氷水100重量部を
加えて、ろ過、水洗後乾燥して式
で示される粗ジスアゾ化合物4.5重量部を得た。
(4) 得られたジスアゾ化合物0.5重量部をＮ，Ｎ
−ジメチルホルムアミド10重量部に溶解し、５
℃以下に冷却しながら、43％ニトロシル硫酸
0.4重量部を加えてジアゾ化液を得た。
(5) このジアゾ化液を、Ｎ，Ｎ−ジエチルアニリ
ン1.5重量部を含むメタノール40重量部中へ滴
下し、０〜５℃で１時間攪拌した後、ろ過、水
洗およびメタノール洗浄をおこない、構造式(1)
の粗生成物0.35重量部を得た。これをトルエン
に溶解し、シリカゲルカラムによるクロマトグ
ラフイーで分離精製することにより精製した。
トリスアゾ系化合物(2)および(3)は、上記工程(1)
における式(a)の化合物の代りに、それぞれ、アミ
ノベンゾチアゾールおよび２−メトキシアミノベ
ンゾチアゾールを用いて同様の操作をおこなうこ
とによつて合成した。
トリスアゾ系化合物(4)および(5)は、上記工程(1)
における式(a)の化合物の代りに、それぞれ
Examples of the present invention will be described below. Examples of the trisazo compounds represented by the general formula () include those represented by the following structural formula. More specifically, the trisazo compound (1) can be synthesized, for example, as follows. In other words, equation (1) Add 10 parts by weight of the compound shown in 85% phosphoric acid to 150 parts by weight.
After dissolving in parts by weight, cooled to 5℃ or less, 43%
9 parts by weight of nitrosyl sulfuric acid was added dropwise while maintaining the same temperature. After further stirring at the above temperature for 1 hour, the reaction mixture was mixed with ice water containing 33 parts by weight of sodium aniline methanesulfonate.
It was added dropwise to 1000 parts by weight and stirred at 0 to 5°C for 3 hours. The precipitate obtained by filtering this reaction solution was washed with water, then added to 400 parts of a 3% aqueous sodium hydroxide solution, and stirred at 90 to 95°C for 1 hour. This reaction solution was cooled, filtered, washed with water, and dried to form a formula. 15 parts by weight of a crude monoazo compound represented by was obtained. (2) 4.0 parts by weight of the above monoazo compound was dissolved in 200 parts of N,N-dimethylformamide, cooled to below 5°C, and 2.0 parts by weight of 43% nitrosyl sulfuric acid was added to obtain a diazotized liquid. (3) This diazotized solution was mixed with α-naphthylamine 4.8
Dropped into 75 parts by weight of methanol containing parts by weight,
Stirred at 0-5°C for 2 hours. To this, 100 parts by weight of ice water containing 14 parts by weight of a 28% ammonia aqueous solution was added, filtered, washed with water and dried. 4.5 parts by weight of a crude disazo compound represented by was obtained. (4) 0.5 parts by weight of the obtained disazo compound was mixed with N,N
-Dissolved in 10 parts by weight of dimethylformamide, 5 parts by weight
43% nitrosyl sulfate while cooling below °C.
A diazotized solution was obtained by adding 0.4 parts by weight. (5) This diazotized solution was dropped into 40 parts by weight of methanol containing 1.5 parts by weight of N,N-diethylaniline, and after stirring at 0 to 5°C for 1 hour, filtration, washing with water, and washing with methanol were performed. Formula (1)
0.35 parts by weight of crude product was obtained. This was purified by dissolving it in toluene and separating and purifying it by chromatography using a silica gel column. Trisazo compounds (2) and (3) are prepared in step (1) above.
Synthesis was carried out in the same manner using aminobenzothiazole and 2-methoxyaminobenzothiazole in place of the compound of formula (a). Trisazo compounds (4) and (5) are prepared in step (1) above.
In place of the compound of formula (a) in, respectively
【式】および[expression] and
以上述べたように、この発明によれば、液晶用
染料として有用なトリスアゾ系化合物が提供され
る。
As described above, according to the present invention, a trisazo compound useful as a dye for liquid crystals is provided.
第１図はネガ表示タイプのゲスト・ホスト型液
晶表示装置の断面図、第２図はホワイト・テーラ
ー型のゲスト・ホスト型液晶表示装置の断面図、
第３図はポジ表示タイプのゲスト・ホスト型液晶
表示装置の断面図である。
１１，１２，２１，２２，３１，３２……電極
基板、１３，２３，３３……シール材、１４，２
４，３４……ホスト液晶、１５，２５，３５……
二色性染料、１６，２６，３６……外部電源、１
７……偏光板。
Figure 1 is a cross-sectional view of a negative display type guest-host type liquid crystal display device, Figure 2 is a cross-sectional view of a White-Taylor type guest-host type liquid crystal display device,
FIG. 3 is a sectional view of a positive display type guest-host type liquid crystal display device. 11, 12, 21, 22, 31, 32... Electrode substrate, 13, 23, 33... Sealing material, 14, 2
4, 34... host liquid crystal, 15, 25, 35...
Dichroic dye, 16, 26, 36...External power supply, 1
7...Polarizing plate.
Claims (1)
H2k+1、R3は【式】又は【式】R4及 びR5は、夫々独立にＨ又は−CkH2k+1、 ｎは１乃至７の正の整数、ｋは１乃至４の正の
整数）で示されるトリスアゾ系化合物。[Claims] 1. General formula (Here, R 1 is H, −C o H 2o+1 or −OC k
H 2k+1 and R 3 are [Formula] or [Formula] R 4 and R 5 are each independently H or -C k H 2k+1 , n is a positive integer from 1 to 7, and k is 1 to 4. A trisazo compound represented by a positive integer of .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21524486A JPS6279271A (en) | 1986-09-12 | 1986-09-12 | Trisazo based compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21524486A JPS6279271A (en) | 1986-09-12 | 1986-09-12 | Trisazo based compound |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2514582A Division JPS58142968A (en) | 1982-02-18 | 1982-02-18 | Two-color dye for liquid crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6279271A JPS6279271A (en) | 1987-04-11 |
| JPH0375580B2 true JPH0375580B2 (en) | 1991-12-02 |
Family
ID=16669106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21524486A Granted JPS6279271A (en) | 1986-09-12 | 1986-09-12 | Trisazo based compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6279271A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6039893A (en) * | 1997-01-24 | 2000-03-21 | Sony Corporation | Guest-host liquid crystal display device and guest-host liquid crystal composition |
| JP5152966B2 (en) * | 2007-09-28 | 2013-02-27 | 日本化薬株式会社 | Trisazo compound, ink composition, recording method and colored body |
| JP5456667B2 (en) * | 2008-05-07 | 2014-04-02 | 日本化薬株式会社 | Trisazo compound, ink composition, recording method and colored body |
| JP7010850B2 (en) * | 2017-01-20 | 2022-01-26 | 日本化薬株式会社 | Azo compounds or salts thereof, and dye-based polarizing films and dye-based polarizing plates containing them. |
| TWI720280B (en) * | 2017-01-20 | 2021-03-01 | 日商日本化藥股份有限公司 | Azo compound or salt thereof, dye-based polarizing film having the same, and dye-based polarizing plate |
| JP7232580B2 (en) * | 2018-06-01 | 2023-03-03 | 株式会社日本化学工業所 | Dichroic azo dye for polarizing film and polarizing film dyed with the dichroic azo dye |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4153343A (en) * | 1977-06-09 | 1979-05-08 | Rca Corporation | Liquid crystal dyestuffs and electro-optic devices incorporating same |
| JPS5657850A (en) * | 1979-10-18 | 1981-05-20 | Nippon Kanko Shikiso Kenkyusho:Kk | Azo compound and dichromatic dye for liquid crystal consisting of the same |
-
1986
- 1986-09-12 JP JP21524486A patent/JPS6279271A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4153343A (en) * | 1977-06-09 | 1979-05-08 | Rca Corporation | Liquid crystal dyestuffs and electro-optic devices incorporating same |
| JPS5657850A (en) * | 1979-10-18 | 1981-05-20 | Nippon Kanko Shikiso Kenkyusho:Kk | Azo compound and dichromatic dye for liquid crystal consisting of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6279271A (en) | 1987-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH026798B2 (en) | ||
| JPS60190467A (en) | Azo dye and liquid crystal material containing same | |
| US3947435A (en) | Disazo acid compounds containing one sulphonic acid group and one phosphonic or methyl-phosphinic acid group | |
| JPH0375580B2 (en) | ||
| JPH0549710B2 (en) | ||
| EP0202341B1 (en) | Dichroic azo dyes | |
| JPS639554B2 (en) | ||
| US4676923A (en) | Dichroic dyestuffs for liquid crystal and liquid crystal composition | |
| JPS5922964A (en) | Azo-based polychroic dyestuff and liquid crystal composition containing the same | |
| JPH0141663B2 (en) | ||
| EP0144020A2 (en) | Azodyes and liquid crystalline materials containing these dyes | |
| JPS6362553B2 (en) | ||
| JPH0558621B2 (en) | ||
| JPH044344B2 (en) | ||
| JPS58108287A (en) | Bichromophoric liquid crystal composition manufactured with asymmetric tris-azo dye | |
| JPH0579116B2 (en) | ||
| JPH0554508B2 (en) | ||
| JPS6160828B2 (en) | ||
| JPH0232301B2 (en) | JISUAZOSENRYONOSEIZOHO | |
| GB2120674A (en) | Dichroic dyestuffs for liquid crystals and liquid crystal compositions comprising the same | |
| JPS5996171A (en) | Cinnamate ester derivative as blue azo dye | |
| JPS62265355A (en) | Anthraquinone compound and liquid crystal composition containing the same | |
| KR900007769B1 (en) | Process for preparation of dichroic azo dyestubbs | |
| JPS63135457A (en) | Tris-azo dye | |
| JPH0374705B2 (en) |