JP2822550B2 - Azulene derivatives, liquid crystal compositions and liquid crystal device using the same - Google Patents

Azulene derivatives, liquid crystal compositions and liquid crystal device using the same

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JP2822550B2
JP2822550B2 JP6153390A JP6153390A JP2822550B2 JP 2822550 B2 JP2822550 B2 JP 2822550B2 JP 6153390 A JP6153390 A JP 6153390A JP 6153390 A JP6153390 A JP 6153390A JP 2822550 B2 JP2822550 B2 JP 2822550B2
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忠義 守田
雅晴 金子
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三菱化学株式会社
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【発明の詳細な説明】 [産業上の利用分野] 本発明は新規なアズレン誘導体、これを用いた液晶組成物及び液晶素子に関し、更に詳しくは液晶表示等に有用な青色系の負ないし低い正の二色性を持つアズレン誘導体、液晶組成物、およびこれを含有する液晶素子に関する。 DETAILED DESCRIPTION OF THE INVENTION The present invention [relates] The novel azulene derivatives, relates to a liquid crystal composition and liquid crystal device using the same, more particularly negative to low positive useful blue in a liquid crystal display or the like azulene derivatives having dichroic liquid crystal composition, and a liquid crystal device containing the same.

[従来の技術および発明が解決しようとする課題] 現在、液晶表示としてはツイストネマチック(TN)型表示モード、スーパーツイスト(STN)モードなどの外に各種の表示モードが提案され、また液晶に色素を溶解して用いるゲストホスト(GH)型表示方式が、広い視野角などの特徴のために、自動車などの表示パネルとして広く用いられている。 Assignments Background of the Invention is to Solve] It twisted nematic (TN) type display mode as a liquid crystal display, outside various display modes, such as supertwisted (STN) mode is proposed, also a dye to the liquid crystal guest-host (GH) type display mode used by dissolving it, for features such as wide viewing angle, it is widely used as a display panel such as an automobile.

このGHモードはTN型の併用(TN−GH)モードなど、他のモードと併用できる点にも特徴を有し、このため使用する色素はその使用目的および表示モードに応じ、種々の色相および二色性に対する要求がある。 Etc. The GH mode TN-type combination (TN-GH) mode, characterized in that can be used in combination with other modes and thus dye to be used according to its intended use and display modes, various hues and secondary there is a need for a color resistance.

このうち負の二色性を有する色素はポジのゲストホスト表示用あるいは配合色の色相補正等として、また低い正の二色性をもつ色素は配合色の色相補正用等として有用であるが、上記の特性を有する青色の色素は殆ど知られていない。 Dye Among having negative dichroism as hue correction, etc. for positive guest host display or blended color, Although dye having a low positive dichroism is useful as such a hue correction of formulation color, blue dye having the above characteristics are largely unknown.

また、色素は一般に液晶に対する溶解性が低く、特に低温での溶解安定性が低いために析出しやすいという問題点を有している。 Further, dyes are generally low solubility in liquid crystal, in particular a problem that tends to precipitate due to low solubility stability at low temperatures.

本発明は溶解安定性がすぐれた、従来殆ど知られていない青色の負ないし低い二色性を有する色素、これを含有する液晶組成物、およびこれを用いた液晶素子を提供することを目的とする。 The present invention has excellent dissolution stability, and aims to provide a negative no blue hitherto unknown almost to the dye having a low dichroic liquid crystal composition containing the same, and a liquid crystal device using the same to.

[課題を解決するための手段] 本発明の目的は、下記の一般式[I] [Means for Solving the Problems] An object of the present invention, the following general formula [I] (式中、Rはアルキル基を示す。) で表されるアズレン誘導体及びこれを少なくとも1種含有する液晶組成物並びにこの組成物を少なくとも一方が透明な電極付基板間に挟持させた液晶素子により達成される。 (Wherein, R represents an alkyl group.) The liquid crystal element in which at least one of the liquid crystal composition and the composition contains at least one azulene derivative and this was sandwiched between substrates with a transparent electrode represented by It is achieved.

本発明の一般式[I]で示されるアズレン誘導体におけるRとしては、メチル基、エチル基、分枝状または直鎖状のプロピル基、ブチル基、ヘキサル基、オクチル基などのアルキル基が挙げられる。 As R in the azulene derivative represented by the general formula [I] of the present invention, a methyl group, an ethyl group, branched or straight-chain propyl group, butyl group, Hexal group include alkyl groups such as octyl . 本発明のアズレン誘導体[I]は新規な有色の液晶化合物であり、下記の反応ルートにより2−ヒドロキシ−6−シアノアズレンを経由して合成することができる。 Azulene derivatives [I] of the present invention is a liquid crystal compound of the novel colored, it may be synthesized via 2-hydroxy-6-cyano-azulene the reaction route described below.

本発明のアズレン誘導体を含む液晶組成物は、通常のアントラキノン系、アゾ系色素が0.5ないしそれ以上のオーダーパラメータを有する正の二色性を示すのに対して、負ないしゼロ附近の低い二色性を示す点で、際立った特徴を有する。 The liquid crystal composition containing azulene derivatives of the present invention, conventional anthraquinone for azo dyes that exhibit positive dichroism having 0.5 to more order parameter, a low negative or zero neighborhood dichroism in point indicating the sex, it has a distinctive feature.

本発明の液晶組成物は前示一般式[I]で示されるアズレン誘導体を、ネマチックあるいはスメクチック相を示すビフェニル系、フェニルシクロヘキサン系、フェニルピリミジン系、シクロヘキシルシクロヘキサン系などの各種の液晶化合物または液晶組成物に公知の方法で混合することにより容易に調製することができる。 Azulene derivative liquid crystal composition represented by the front shows the general formula [I] of the present invention, biphenyl showing a nematic or smectic phase, phenylcyclohexane based, phenyl pyrimidine, various liquid crystal compounds or liquid crystal compositions, such as cyclohexyl cyclohexane system it can be readily prepared by mixing in a known manner at the object.

この場合、本発明のアズレン誘導体は広い液晶温度領域を有する液晶化合物であるため、溶解安定性のすぐれた液晶組成物を調製することができる。 In this case, azulene derivatives of the present invention is for a liquid crystal compound having a wide liquid crystal temperature range, it is possible to prepare the dissolution stability of excellent liquid crystal composition.

また本発明の液晶組成物はコレステリルノナノエートなどの、液晶相を示しても示さなくても良い光学活性化合物を含有してもよく、あるいは紫外線吸収剤、酸化防止剤などの各種の添加剤を含有しても良い。 The liquid crystal composition of the present invention, such as cholesteryl nonanoate, may contain also good optically active compound not shown also shows a liquid crystal phase, or an ultraviolet absorber, various additives such as antioxidants it may contain.

このようにして得られた液晶組成物を、少なくとも一方が透明な電極付基板間に挟持することにより、ゲストホスト効果を応用した素子[松本正一、角田市良“液晶の最新技術”工業調査会、34(1983);JLFergason,SI The thus liquid crystal compositions obtained, at least one of by sandwiched between the transparent electrode with the substrate, the element [Shoichi Matsumoto that applies guest-host effect, Tsunoda ShiRyo "LCD-art" Kogyo Chosa Kai, 34 (1983); JLFergason, SI
D85Digest,69(1985)等]などを構成することができる。 D85Digest, 69 can be configured like (1985), etc.].

[発明の効果] 本発明は負ないし低い正の二色性を有するアズレン誘導体、これを含有する液晶組成物およびこれを用いた液晶素子であり、ゲストホスト型モードの色相補正用などに使用して、より表示効果の高められた液晶素子を実現できる。 [Effect of the Invention] The present invention is azulene derivatives having a negative to low positive dichroism, a liquid crystal device using the same liquid crystal composition and containing the same, and for example, for color correction of the guest-host mode Te, it can realize a liquid crystal device which is elevated more display effect.

[実施例] 次に、本発明を実施例により、具体的に説明するが、 EXAMPLES Next, the present invention embodiment will be specifically described,
本発明はこれら実施例により何ら限定されるものではない。 The present invention is not limited by these examples.

実施例1 下記構造式 Example 1 the following structural formula で表されるアズレン誘導体1gをトリフルオロ酢酸10mlに溶解し、これに臭化水素酸20mlを加え100℃で2時間加熱反応させ、氷水300mlに反応液を加えたのちクロロホルムで抽出し、飽和食塩水でクロロホルム溶液を洗浄し無水硫酸ナトリウムで乾燥後、溶媒を留去して下記の2 Was dissolved azulene derivative 1g represented in trifluoroacetic acid 10 ml, this was heated for 2 hours reaction at 100 ° C. was added a hydrobromic acid 20 ml, and extracted with chloroform after the addition of the reaction mixture into ice water 300 ml, saturated sodium chloride after drying washed anhydrous sodium sulfate the chloroform solution with water, 2 below the solvent was distilled off
−ヒドロキシ−6−ブロムアズレンを得た。 - to obtain a hydroxy-6-bromo azulene.

上記の2−ヒドロキシ−6−ブロムアズレンを無水酢酸20ml、触媒量のピリジンを加えて一夜間反応させた後、水100mlに反応液をくわえて、室温で4時間撹拌した後、ベンゼンで抽出した。 The above 2-hydroxy-6-bromo azulene acetic anhydride 20 ml, after addition of a catalytic amount of pyridine was overnight reaction, reaction mixture was added to water 100 ml, was stirred for 4 hours at room temperature and extracted with benzene . 抽出液を飽和食塩水で洗浄し無水硫酸ナトリウムで乾燥後、溶媒を留去して得られた生成物をカラムクロマト(シリカゲル)により精製し、メタノールより再結晶させて下記構造式で示される2−アセトキシ−6−ブロムアズレンを得た(融点:112 The extract was dried washed over anhydrous sodium sulfate and saturated brine, the product obtained by distilling off the solvent was purified by column chromatography (silica gel) indicated recrystallized from methanol by the following structural formula 2 - give the acetoxy-6-bromo azulene (melting point: 112
℃)。 ℃).

上記の反応により合成した2−アセトキシ−6−ブロムアズレン0.56gを無水DMF5mlに溶解し120℃でシアン化第一銅0.33gを加え150℃で40分間加熱した後、反応液を水120ml中に加えてベンゼンで抽出した。 After heating for 40 minutes at 0.99 ° C. was added cuprous cyanide 0.33g in dissolved 120 ° C. 2-acetoxy-6-bromo azulene 0.56g synthesized by reaction of the anhydrous 5 ml of DMF, the reaction solution into water 120ml It added, and the mixture was extracted with benzene. 抽出液を飽和塩水で洗浄し無水硫酸ナトリウムで乾燥した後、カラムクロマトにより目的物を分離精製し、メタノールから再結晶させて下記の2−アセトキシ−6−シアノアズレンを得た(融点:129℃)。 The extract was dried washed anhydrous sodium sulfate saturated brine, the desired product was separated and purified by column chromatography and recrystallized from methanol to give 2-acetoxy-6-cyano-azulene below (melting point: 129 ° C. ).

上記の反応により合成した2−アセトキシ−6−シアノアズレン0.17gを100%リン酸5mlに加え室温で90分間撹拌した。 Was stirred for 90 minutes at room temperature was added the above 2-acetoxy-6-cyano-azulene 0.17g synthesized by the reaction of 100% phosphoric acid 5 ml. 反応液を水40mlに加え、酢酸エチルで抽出した。 The reaction solution was added to water 40 ml, and extracted with ethyl acetate. 抽出液を飽和食塩水で洗浄し硫酸マグネシウムで乾燥後、溶媒を留去して下記の2−ヒドロキシ−6−シアノアズレンを得た。 After drying the extract was washed with saturated brine magnesium sulfate to give 2-hydroxy-6-cyano-azulene below the solvent was distilled off.

次に、p−n−ペンチル安息香酸0.06gに塩化チオニル1mlを加え、3時間加熱還流した。 Then, it added p-n-pentyl-benzoic acid 0.06g of thionyl chloride 1 ml, was heated under reflux for 3 hours. 反応後過剰の塩化チオニルを減圧下に留去した。 The excess thionyl chloride after the reaction was distilled off under reduced pressure. これに上記の反応により合成した2−ヒドロキシ−6−シアノアズレン0.034g、 This was synthesized by the reaction of the 2-hydroxy-6-cyano-azulene 0.034 g,
ベンゼン1ml、ピリジン3滴を加え室温で1夜撹拌した。 Benzene 1 ml, and stirred overnight at room temperature was added 3 drops of pyridine.

0.1N塩酸、飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥後、溶媒を留去した。 0.1N hydrochloric acid, washed with saturated brine, dried over anhydrous sodium sulfate, the solvent was distilled off. 残留物をカラムクロマトにより精製して下記の化合物を得た。 The residue was purified by column chromatography to give the following compounds.

本化合物は117℃〜194℃に液晶領域を示す青紫の結晶であり、これを商品名ZLI−1132(メルク社)として市販されているフェニルシクロヘキサン系液晶組成物に10 This compound is a violet showing a liquid crystal region 117 ℃ ~194 ℃ crystals, 10 to the product name ZLI-1132 phenylcyclohexane-based liquid crystal composition, commercially available as (Merck)
wt%配合して得られた液晶組成物を、透明な電極付基板にホモジニアス配向処理を施し、電極が対向するように構成した厚さ50μのセルに封入して液晶素子を作製した。 The liquid crystal composition obtained by wt% blended, subjected to homogeneous alignment treatment substrate having a transparent electrode, the electrode is to produce a liquid crystal element is sealed in a cell having a thickness of 50μ configured to face. この液晶素子の配向方向に平行な偏光に対する吸収セペクトル(A Absorption Sepekutoru (A on the polarization parallel to the orientation direction of the liquid crystal element )および配向方向に垂直な偏光に対する吸収スペクトル(A )を測定した。 ) And the absorption spectrum was measured (A ⊥) to the vertical polarization in the oriented direction. 下式により S=(A S = (A by the following formula −A )/(2 +A -A ⊥) / (2 ⊥ + A ) オーダーパラメターター(S)を求めたところ、450ないし690nmにわたる波長領域において低い正の値ないし負の値を示した。 ) Was determined the order parameters starter (S), 450 to not exhibited a low positive value to a negative value in the wavelength region spanning 690 nm.

実施例2 実施例1のp−n−ペンチル安息香酸の代わりにp− Instead of p-n-pentyl-benzoic acid Example 2 Example 1 p-
n−ヘキシル安息香酸を用い、他は実施例1と同様にして下記の化合物を合成した。 Using n- hexyl benzoate, others were synthesized the following compounds in the same manner as in Example 1.

本化合物は105℃〜181℃に液晶領域を示す青紫の液晶であり、実施例1と同様の方法により液晶素子を作製してオーダーパラメータ(S)を求めたところ、実施例1 This compound is a liquid crystal violet showing a liquid crystal region 105 ℃ ~181 ℃, was determined the order parameters to produce a liquid crystal element in the same manner as in Example 1 (S), Example 1
と同様の結果を示した。 It showed similar results.

実施例3 実施例1のp−n−ペンチル安息香酸の代わりにp− Instead of p-n-pentyl-benzoic acid Example 3 Example 1 p-
n−オクチル安息香酸を用い、他は実施例1と同様にして下記の化合物を合成した。 Using n- octyl benzoic acid, others were synthesized the following compounds in the same manner as in Example 1.

本化合物は101℃〜177℃に液晶領域を示す青紫の液晶であり、実施例1と同様の方法により液晶素子を作製してオーダーパラメータ(S)を求めたところ、実施例1 This compound is a liquid crystal violet showing a liquid crystal region 101 ° C. to 177 ° C., it was determined the order parameters to produce a liquid crystal element in the same manner as in Example 1 (S), Example 1
と同様の結果を示した。 It showed similar results.

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS

第1図は実施例1のアズレン誘導体を含む液晶組成物を、ホモジニアス配向処理を施した透明電極付きセルに封入して作製した液晶素子の吸収スペクトルを表す図面であり、A FIG. 1 is a diagram representing the absorption spectrum of the liquid crystal element of the liquid crystal composition containing azulene derivative of Example 1 was prepared by sealing with a transparent electrode cell subjected to homogeneous alignment processing, A は配向方向に平行な直線偏光に対する吸収スペクトルであり、A は配向方向に垂直な直線偏光に対する吸収スペクトルを示す。 Is the absorption spectrum for the linearly polarized light parallel to the orientation direction, A denotes the absorption spectra for linearly polarized light perpendicular to the orientation direction.

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl. 6 ,DB名) C07C 255/47 C09K 19/60 G02F 1/13 CA(STN) CAOLD(STN) REGISTRY(STN) ────────────────────────────────────────────────── ─── of the front page continued (58) investigated the field (Int.Cl. 6, DB name) C07C 255/47 C09K 19/60 G02F 1/13 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

    (57)【特許請求の範囲】 (57) [the claims]
  1. 【請求項1】下記一般式[I] 1. A following general formula [I] (式中、Rはアルキル基を示す。) で表されるアズレン誘導体。 (Wherein, R. Represents an alkyl group) azulene derivative represented by the.
  2. 【請求項2】請求項1記載のアズレン誘導体を少なくとも1種含有することを特徴とする液晶組成物。 2. A liquid crystal composition characterized by containing at least one kind of azulene derivative according to claim 1, wherein.
  3. 【請求項3】請求項2記載の液晶組成物を、少なくとも一方が透明な電極付基板間に挟持させたことを特徴とする液晶素子。 3. A liquid crystal composition according to claim 2, the liquid crystal element characterized in that at least one of which is sandwiched between a transparent substrate with electrode.
JP6153390A 1990-03-13 1990-03-13 Azulene derivatives, liquid crystal compositions and liquid crystal device using the same Expired - Fee Related JP2822550B2 (en)

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US8197837B2 (en) 2003-03-07 2012-06-12 Depuy Mitek, Inc. Method of preparation of bioabsorbable porous reinforced tissue implants and implants thereof
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