JPH0374705B2 - - Google Patents
Info
- Publication number
- JPH0374705B2 JPH0374705B2 JP61179838A JP17983886A JPH0374705B2 JP H0374705 B2 JPH0374705 B2 JP H0374705B2 JP 61179838 A JP61179838 A JP 61179838A JP 17983886 A JP17983886 A JP 17983886A JP H0374705 B2 JPH0374705 B2 JP H0374705B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- formula
- dye
- compound
- guest
- 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
- -1 azo compound Chemical class 0.000 claims description 9
- RBRCCWBAMGPRSN-UHFFFAOYSA-N thieno[2,3-d][1,3]thiazole Chemical compound S1C=NC2=C1C=CS2 RBRCCWBAMGPRSN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 24
- 239000000975 dye Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 7
- 238000004040 coloring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-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
- 238000010521 absorption reaction Methods 0.000 description 1
- AVMNFQHJOOYCAP-UHFFFAOYSA-N acetic acid;propanoic acid Chemical compound CC(O)=O.CCC(O)=O AVMNFQHJOOYCAP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 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
- 239000000987 azo dye Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002904 solvent Substances 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
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- JRUMOFMQOHIADD-UHFFFAOYSA-N thieno[2,3-d][1,3]thiazol-2-amine Chemical compound S1C=CC2=C1N=C(N)S2 JRUMOFMQOHIADD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Coloring (AREA)
- Liquid Crystal (AREA)
Description
〔産業上の利用分野〕
この発明はチエノチアゾール系アゾ化合物に関
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おこなえ、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、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に、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
するとこがあり（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
じ表示品質の劣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
とはいえなかつたものであつた。
したがつて、この発明の目的は、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染料として有
用な新規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〕
この発明は下記の一般色で表わされているチエ
ノ〔２，３−ｄ〕−チアゾール系アゾ化合物を提
供する。
〔一般式〕
ここで、ｉ及びｊは、夫々０または１；ｉ及び
ｊの中、何れか一方が１のときＸ及びＹは、
[Industrial Application Field] This invention relates to thienothiazole-based azo compounds. [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. Because it becomes thinner,
Even if the dichroic ratio of the dye is high, sufficient display contrast cannot be obtained. Therefore, 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 will 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 dichroic dye is not sufficiently compatible with the liquid crystal, the dye in the liquid crystal may precipitate (this dye precipitation is noticeable at low temperatures); This may cause color unevenness on the display section and 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 that was missing. Therefore, an object of the present invention is to provide a novel compound useful as a dichroic dye for liquid crystals, which has a high dichroic ratio, high coloring ability, and excellent compatibility with liquid crystals. be. [Means for Solving the Problems] The present invention provides thieno[2,3-d]-thiazole-based azo compounds represented by the following general colors. [General formula] Here, i and j are each 0 or 1; when either one of i and j is 1, X and Y are
【式】又は、[Formula] or
【式】 ｉ及びｊが両方が１のときＸは、 Ｙは、[Formula] When both i and j are 1, X is Y is
【式】 Ｚは、【formula】 Z is
【式】 R1は、−CoH2o+1又は−oH2o [Formula] R 1 is −C o H 2o+1 or − o H 2o
【式】 R2は、Ｈ； R4は、[Formula] R 2 is H; R 4 is
前記一般式で表わされるチエノチアゾール系ア
ゾ化合物は例えば次のようにして合成することが
できる。
上記一般式（）で表わされる２−アミノチエ
ノチアゾール類を公知の方法（例えば硫酸、リン
酸等の鉱酸中でニトロシル硫酸、亜硝酸ソーダに
よるジアゾ化を行なう方法）によりジア化し、こ
のジアゾ成分をニアリン類あるいはα−ナフチル
アミン類と酢酸または酢酸−プロピオン酸溶媒中
でカツプリングさせて、アミノアゾ誘導体類を得
る。次にこのモノアゾ体を前記と同様に無機また
は有機溶媒中でジアゾ化し、この第二のジアゾ化
を行なつた成分を種々のカツプラーとカツプリン
グさせてジスアゾ化合物を得る。この後は、この
ジスアゾ化合物を前記と同様にジアゾ化し、この
第三のジアゾ化を行なつた成分をカツプラーとカ
ツプリングさせればよく、これによつてこの発明
の化合物の一つであるトリスアゾ化合物の粗製物
を得ることができる。この粗製物は通常の精製法
例えばシリカゲルクロマトグラフ法または再結晶
法等によつて所望の純度に精製することができ
る。
下記の表１は、この発明のチエノチアゾール系
アゾ化合物の構造式と、液晶中における各化合物
の特性（極大吸収波長と色相及び二色性比）を示
したものである。なお、表１における各化合物の
特性は、液晶としてBDHケミカル社のビフエニ
ル系液晶Ｅ７を使用し、かつ液晶分子をホモジニ
アス配向させたネガ表示タイプのゲスト・ホスト
型液晶表示装置に各化合物を用いた場合の測定結
果を示したもので、形式の異なるゲスト・ホスト
型液晶表示装置においては各化合物の特性は表１
とは若干異なる値を示すことがある。
The thienothiazole azo compound represented by the above general formula can be synthesized, for example, as follows. The 2-aminothienothiazole represented by the above general formula () is diazotized by a known method (for example, diazotization with nitrosylsulfuric acid or sodium nitrite in a mineral acid such as sulfuric acid or phosphoric acid), and the diazo component is is coupled with nearins or α-naphthylamines in acetic acid or acetic acid-propionic acid solvent to obtain aminoazo derivatives. Next, this monoazo compound is diazotized in an inorganic or organic solvent in the same manner as described above, and this second diazotized component is coupled with various couplers to obtain a disazo compound. After this, this disazo compound is diazotized in the same manner as described above, and this third diazotized component is coupled with a coupler, whereby the trisazo compound, which is one of the compounds of this invention, is A crude product can be obtained. This crude product can be purified to a desired purity by conventional purification methods such as silica gel chromatography or recrystallization. Table 1 below shows the structural formula of the thienothiazole azo compound of the present invention and the characteristics (maximum absorption wavelength, hue, and dichroic ratio) of each compound in the liquid crystal. The characteristics of each compound in Table 1 are as follows: Each compound was used in a negative display type guest-host liquid crystal display device that used BDH Chemical's biphenyl liquid crystal E7 as the liquid crystal and homogeneously aligned the liquid crystal molecules. The characteristics of each compound in guest-host liquid crystal display devices of different formats are shown in Table 1.
It may show a slightly different value.
【表】【table】
【表】【table】
この発明によれば、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
ぐれた二色性染料として有用なチエノチアゾール
系アゾ化合物を提供することができる。
According to the present invention, it is possible to provide a thienothiazole-based azo compound useful as a dichroic dye that has a high dichroic ratio, high coloring ability, and excellent compatibility with liquid crystals.
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……
チエノチアゾール系アゾ化合物、１６，２６，３
６……外部電源、１７……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...
Thienothiazole azo compound, 16,26,3
6...External power supply, 17...Polarizing plate.
Claims (1)
ｊの中、何れか一方が１のときＸ及びＹは、 【式】又は、【式】 ｉ及びｊが両方が１のときＸは、 Ｙは、 【式】 Ｚは、【式】 R1は、−CoH2o+1又は【式】 R2は、Ｈ； R4は、【式】【式】又は− 0CoH2o+1； R6及びR7は、夫々CoH2o+1； ｎは、１乃至４の正の整数） で示されるチエノチアゾール系アゾ化合物。[Claims] 1. General formula Here, i and j are each 0 or 1; when either one of i and j is 1, X and Y are [Formula] or [Formula] When both i and j are 1, X is , Y is [Formula] Z is [Formula] R 1 is −C o H 2o+1 or [Formula] R 2 is H; R 4 is [Formula] [Formula] or −0C o H 2o+ 1 ; R 6 and R 7 are each C o H 2o+1 ; n is a positive integer of 1 to 4) A thienothiazole-based azo compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17983886A JPS6243464A (en) | 1986-08-01 | 1986-08-01 | Thienothiazole-type azo compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17983886A JPS6243464A (en) | 1986-08-01 | 1986-08-01 | Thienothiazole-type azo compound |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58078566A Division JPS59204659A (en) | 1983-05-04 | 1983-05-04 | Dichroic dye for liquid crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6243464A JPS6243464A (en) | 1987-02-25 |
| JPH0374705B2 true JPH0374705B2 (en) | 1991-11-27 |
Family
ID=16072781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17983886A Granted JPS6243464A (en) | 1986-08-01 | 1986-08-01 | Thienothiazole-type azo compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6243464A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5322463B2 (en) * | 2008-03-11 | 2013-10-23 | 公立大学法人大阪府立大学 | Azo dichroic dye |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57123258A (en) * | 1980-12-12 | 1982-07-31 | Minnesota Mining & Mfg | Bichromophoric coloring matter |
| JPS582351A (en) * | 1981-06-29 | 1983-01-07 | Mitsubishi Chem Ind Ltd | Monoazo dye for polyester fiber |
| JPS5821451A (en) * | 1981-07-31 | 1983-02-08 | Casio Comput Co Ltd | Dichroic dye for liquid crystal |
-
1986
- 1986-08-01 JP JP17983886A patent/JPS6243464A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57123258A (en) * | 1980-12-12 | 1982-07-31 | Minnesota Mining & Mfg | Bichromophoric coloring matter |
| JPS582351A (en) * | 1981-06-29 | 1983-01-07 | Mitsubishi Chem Ind Ltd | Monoazo dye for polyester fiber |
| JPS5821451A (en) * | 1981-07-31 | 1983-02-08 | Casio Comput Co Ltd | Dichroic dye for liquid crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6243464A (en) | 1987-02-25 |
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