JP3948799B2 - Trifunctional compounds and polymer liquid crystals - Google Patents
Trifunctional compounds and polymer liquid crystals Download PDFInfo
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- JP3948799B2 JP3948799B2 JP29448197A JP29448197A JP3948799B2 JP 3948799 B2 JP3948799 B2 JP 3948799B2 JP 29448197 A JP29448197 A JP 29448197A JP 29448197 A JP29448197 A JP 29448197A JP 3948799 B2 JP3948799 B2 JP 3948799B2
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- C—CHEMISTRY; METALLURGY
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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Description
【0001】
【発明の属する技術分野】
本発明は、重合性の3官能化合物に関し、詳細には、光学、表示、記録材料等として利用されるトリ(メタ)アクリル構造を有する重合性化合物およびその重合物からなる高分子液晶に関する。
【0002】
【従来の技術及び発明が解決しようとする課題】
近年、液晶物質はTN型やSTN型に代表されるディスプレイ素子等の液晶分子の可逆的運動を利用した表示媒体への応用以外にも、その配向性と屈折率、誘電率、磁化率等の物理的性質の異方性を利用して、位相差板、偏光板、光偏光プリズム、各種光フィルター等の光学異方体への応用が検討されている。
【0003】
このように液晶物質を構成材料をする光学異方体には、安定で均一な光学特性を得るために、液晶状態における液晶分子の均一な配向状態を半永久的に固定化して、機械的にも熱的にも安定なガラス転移温度(以下、「Tg」ともいう)の高い、配向性に優れた重合物(高分子液晶)とすることが必須である。
【0004】
液晶状態における液晶分子の均一な配向状態構造を半永久的に固定化する手段としては、例えば、重合性官能基を有する液晶性化合物又はこのような化合物を含有する重合性液晶組成物を、液晶状態で均一に配向させた後、液晶状態を保持したまま紫外線等のエネルギー線を照射することによって光重合させて、均一な配向状態を半永久的に固定化する方法が既に知られている。
【0005】
このような高分子液晶のための単量体としては、特開昭62−70406号公報等にモノ官能の単量体が多数提案され、特開平2−91047号公報、特開平6−16616号公報、特開平6−240260号公報および特開平7−101900号公報には2官能の単量体が提案され、特開平8−104870号公報には3官能の単量体が提案されている。
【0006】
2官能、3官能の単量体は、重合後の耐熱性、耐溶剤性を改善するうえで有効な手段であることが知られている。
【0007】
しかしながら、公知の3官能単量体は、各々異なる芳香環に(メタ)アクリロイルオキシ基が結合した構造を有しており、化合物自身の液晶性が乏しく、他の直鎖上の液晶性化合物との配向性に劣るため、満足のいくものではなかった。
【0008】
従って、本発明の目的は、配向性に優れ、耐熱性、耐溶剤性に優れた高分子液晶を提供し得る液晶性化合物及び該化合物の重合物からなる高分子液晶を提供することにある。
【0009】
【課題を解決するための手段】
本発明者は、鋭意検討を重ねた結果、1つの芳香環に2個の(メタ)アクリロイルオキシ基を導入することにより、上記目的を達成し得ることを知見した。
【0010】
本発明は、上記知見に基づきなされたもので、下記〔化2〕(前記〔化1〕と同じ)の一般式(I)で表される3官能化合物を提供するものである。
【0011】
【化2】
【0012】
また、本発明は、上記3官能化合物と他の重合性化合物との混合物からなる重合性組成物を提供するものである。
また、本発明は、上記3官能化合物の単独重合物若しくは2種以上の共重合物からなる高分子液晶を提供するものである。
また、本発明は、上記3官能化合物と他の重合性化合物との共重合物からなる高分子液晶を提供するものである。
【0013】
【発明の実施の形態】
以下に本発明の3官能化合物および高分子液晶について詳細に説明する。
【0014】
本発明の3官能化合物において、上記一般式(I)中の環A、BおよびCで表される6員環としては、例えば、1,4−位に結合手を有する2価の、ベンゼン、シクロヘキサン、シクロヘキセン、ジオキサン、ピリジン、ピリミジンなどが挙げられる。
【0015】
また、lは0〜14を表し、lが14より大きいと本発明の3官能化合物を重合して得られる高分子液晶のガラス転移温度が低下して配向状態の安定性が低下する。
【0016】
また、nおよびpは各々0または1を示し、0≦n+p≦2であり、n+pが2より大きいと、得られる重合物が剛直になり配向性に乏しくなる。
【0017】
本発明の3官能化合物はそれ自身液晶性を示しても示さなくても良く、後述のように、その単独重合物若しくは2種以上の共重合物、または本発明の3官能化合物と他の重合性化合物との混合物からなる重合性組成物を得、該組成物を重合することにより得られる共重合物、即ち本発明の3官能化合物と他の重合性化合物との共重合物において液晶性を示し、得られるポリマーのTgが高く、有機溶媒への耐溶解性に優れ、塗布性、配向性にも優れる高分子液晶(液晶性ポリマー)を与えるものであれば良い。
【0018】
本発明の3官能化合物のより具体的な例としては、下記〔化3〕〜〔化7〕に示す化合物No.1〜5などが挙げられる。ただし、本発明は以下の化合物により制限を受けるものではない。
【0019】
【化3】
【0020】
【化4】
【0021】
【化5】
【0022】
【化6】
【0023】
【化7】
【0024】
本発明の3官能化合物の合成方法としては、特に限定されるものではなく、例えば、3,4−ジヒドロキシ安息香酸とアクリル酸クロライドを反応して3,4−ビスアクリロイルオキシ安息香酸を得、これと、4−(ω−アクリロイルオキシアルキレンオキシ)安息香酸およびハイドロキノンのモノエステルとをエステル化することで合成される。
【0025】
本発明の3官能化合物は、単独でまたは他の重合性化合物(共重合成分)との混合物からなる重合性組成物として(必要に応じ光重合開始剤等を用いて)、熱または光により重合されて高分子液晶として種々の用途に用いられる。
【0026】
ここで、共重合する際に用いられる上記の他の重合性化合物としては、特に限定されるものではなく、例えば、4-(2- メタクリロイルオキシエチルオキシ) 安息香酸-4'-メトキシフェニル、4-(6- メタクリロイルオキシヘキシルオキシ) 安息香酸ビフェニル、4-(2- メタクリロリルオキシエチルオキシ) 安息香酸-4'-シアノビフェニル、4-(2- メタクリロリルオキシエチルオキシ) 安息香酸-3',4'- ジフルオロフェニル、4-(2- メタクリロイルオキシエチルオキシ) 安息香酸ナフチル、4-アクリロイルオキシ-4'-デシルビフェニル、4-アクリロイルオキシ-4'-シアノビフェニル、4-(2- メタクリロイルオキシエチルオキシ)-4'- メトキシビフェニル、4-(2- メタクリロイルオキシエチルオキシ)-4'-(4"- フルオロベンジルオキシ)-ビフェニル、4-アクリロイルオキシ-4'-プロピルシクロヘキシルフェニル、4-メタクリロイル-4'-ブチルビシクロヘキシル、4-アクリロイル-4'-アミルトラン、4-アクリロイル-4'-(3,4- ジフルオロフェニル) ビシクロヘキシル、4-(2- アクリロイルオキシエチル) 安息香酸(4- アミルフェニル) 、4-(2- アクリロイルオキシエチル) 安息香酸(4-(4'- プロピルシクロヘキシル) フェニル) などのモノアクリレート化合物、1,4−ビス(4−(6−アクリロイルオキシヘキシルオキシ)ベンゾイルオキシ)ベンゼン、1,4−ビス(4−(2−アクリロイルオキシエチルオキシ)ベンゾイルオキシ)ベンゼン、ビス(4−(2−アクリロイルオキシエチルオキシ)フェニル)テレフタレート、4−(4−アクリロイルオキシフェニル)カルボニルオキシ−(6−アクリロイルオキシヘキシルオキシフェニル)カルボニルオキシベンゼン、4−(4−アクリロイルオキシフェニル)カルボニルオキシ−(3−アクリロイルオキシプロピルオキシフェニル)カルボニルオキシベンゼン、4−アクリロイルオキシ安息香酸−4−(2−アクリロイルオキシエチル)フェニルエステル、4−アクリロイルオキシ安息香酸−4−(3−アクリロイルオキシプロピル)フェニルエステル等のジアクリレート化合物が挙げられる。
【0027】
本発明の3官能化合物と他の重合性化合物との共重合物を得る際における各単量体(本発明の3官能化合物と他の重合性化合物との混合物からなる重合性組成物における該3官能化合物および該他の重合性化合物)の重量比は特に限定されるものではないが、本発明の3官能化合物の含有量は全単量体中に3重量%以上が好ましく、5重量%以上が特に好ましい。3重量%未満では得られる液晶性ポリマーのTgが低く、また、耐溶剤性が低下して実用的でなくなる。
【0028】
上述したように、本発明の3官能化合物を用いて重合物とすることにより、Tgが高く、有機溶媒への耐溶解性に優れ、塗布性、配向性にも優れる本発明の高分子液晶を得ることができる。
【0029】
【実施例】
以下に本発明の3官能化合物の具体的な合成例(実施例)を示す。ただし、本発明はこれらの合成例によりなんら制限されるものではない。
【0030】
化合物No.4の合成
3,4−ジヒドロキシ安息香酸10.0g(65ミリモル)および2,6−ルチジン16.7g(156ミリモル)をテトラヒドロフラン70mlに溶解し、撹拌下、アクリル酸クロリド11.8g(130ミリモル)を室温でゆっくり滴下した。室温で1時間反応し、有機溶媒を留去して、トルエン150mlおよび水150mlを加え、油水分離した。有機層を2回水洗して、硫酸ナトリウムで脱水後、脱溶媒して3,4−ビス(アクリロイルオキシ)安息香酸8.2g(収率48.2%)を得た。
【0031】
3,4−ビス(アクリロイルオキシ)安息香酸1.31g(5ミリモル)、4−アクリロイルオキシフェノール0.821g(5ミリモル)および4−ジメチルアミノピリジン0.056g(0.5ミリモル)を10mlの塩化メチレンに溶解し、N,N'- ジシクロヘキシルカルボジイミド(以下、「DCC」という)1.08g(5.25ミリモル)を滴下し、室温で1時間撹拌した。析出物をろ別し、ろ液より脱溶媒後、残渣をシリカゲルカラム処理し、得られた固体をメタノールより再結晶して融点106.8℃の白色固体0.6g(収率30.0%)を得た。
【0032】
得られた固体の、赤外吸収スペクトルは、
3125cm-1、3075cm-1、1740cm-1、1640cm-1、1610cm-1、1505cm-1、1400cm-1、
1295cm-1、1240cm-1、1190cm-1、1150cm-1、1030cm-1のピークを示した。
【0033】
化合物No.3の合成
3,4−ビス(アクリロイルオキシ)安息香酸1.97g(7.5ミリモル)、4−(6−アクリロイルオキシヘキシルオキシ)安息香酸−4−ヒドロキシフェニルエステル2.88g(7.5ミリモル)および4−ジメチルアミノピリジン0.084g(0.75ミリモル)を20mlの塩化メチレンに溶解し、DCC1.62g(7.88ミリモル)を滴下し、室温で1時間撹拌した。析出物をろ別し、ろ液より脱溶媒後、残渣をシリカゲルカラム処理し、得られた固体を酢酸エチル/メタノール(=1/1)より再結晶して融点111.8℃の白色固体1.45g(収率30.9%)を得た。
【0034】
得られた固体の、赤外吸収スペクトルは、次のピークを示した。
3100cm-1、3075cm-1、2975cm-1、2875cm-1、1750cm-1、1710cm-1、1635cm-1、
1600cm-1、1500cm-1、1400cm-1、1280cm-1、1270cm-1、1170cm-1、1140cm-1、
1070cm-1、1020cm-1
相転移温度は、次の通りである(C:結晶相、I:等方相、N:ネマティック相)。
【0035】
共重合物の合成
下記〔表1〕記載の配合物1g(重量比を〔表1〕に示している)をジクロロメタン5gに溶解して撹拌後、脱溶媒して液晶組成物を得た。得られた液晶組成物の昇温時および降温時の相転移温度を測定した。その結果を下記〔表1〕に示す。
【0036】
また、液晶組成物1gに光重合開始剤(PZ−408:旭電化工業株式会社製)0.05gを加え、シクロヘキサノン2gに溶解した。調整した溶液を、ラビング処理を施したポリイミド配向膜を有するガラス板にスピンコーターで塗布し、30℃減圧下で溶媒を除去した。得られたキャスト膜に30℃でブラックライト蛍光ランプで5分間照射し、水銀ランプで550mJに相当する紫外線を照射して硬化膜を得た。得られた硬化膜の耐溶剤性を、硬化膜上にクロロホルムおよびシクロヘキサノンを1滴滴下して評価した。結果はいずれも膨潤や剥がれがなく、優れた耐溶剤性を示した。
【0037】
なお、共重合物に用いた本発明の3官能化合物以外の単量体を以下に示す。
【0038】
【化8】
【0039】
【化9】
【0040】
【化10】
【0041】
【化11】
【0042】
【表1】
【0043】
特定の構造を有する重合性の本発明の3官能化合物により、耐溶剤性に優れた硬化物が得られることが判る。
【0044】
【発明の効果】
本発明の3官能化合物は、配向性に優れ、耐熱性、耐溶剤性に優れた高分子液晶を提供し得るものである。
また、本発明の高分子液晶は、配向性に優れ、耐熱性、耐溶剤性に優れたものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymerizable trifunctional compound, and in particular, to a polymerizable compound having a tri (meth) acrylic structure used as an optical, display, recording material or the like and a polymer liquid crystal composed of the polymer.
[0002]
[Prior art and problems to be solved by the invention]
In recent years, liquid crystal materials have a high degree of orientation, refractive index, dielectric constant, magnetic susceptibility, etc., in addition to application to display media using the reversible motion of liquid crystal molecules such as TN type and STN type display elements. Applications to optical anisotropic bodies such as retardation plates, polarizing plates, light polarizing prisms, and various optical filters have been studied using the anisotropy of physical properties.
[0003]
In order to obtain stable and uniform optical characteristics, the optically anisotropic body that constitutes the liquid crystal substance as described above has a uniform alignment state of liquid crystal molecules in the liquid crystal state and is fixed mechanically. It is essential to obtain a polymer (polymer liquid crystal) having a high glass transition temperature (hereinafter also referred to as “Tg”) which is thermally stable and excellent in orientation.
[0004]
As a means for semi-permanently fixing the uniform alignment state structure of the liquid crystal molecules in the liquid crystal state, for example, a liquid crystal compound having a polymerizable functional group or a polymerizable liquid crystal composition containing such a compound is used in the liquid crystal state. There is already known a method of semi-permanently fixing a uniform alignment state by performing photopolymerization by irradiating energy rays such as ultraviolet rays while maintaining the liquid crystal state after the alignment is uniformly performed.
[0005]
As such monomers for polymer liquid crystals, many monofunctional monomers have been proposed in JP-A-62-70406, etc., and JP-A-2-91047 and JP-A-6-16616. Japanese Patent Laid-Open No. 6-240260 and Japanese Patent Laid-Open No. 7-101900 propose bifunctional monomers, and Japanese Patent Laid-Open No. 8-104870 proposes trifunctional monomers.
[0006]
Bifunctional and trifunctional monomers are known to be effective means for improving heat resistance and solvent resistance after polymerization.
[0007]
However, the known trifunctional monomer has a structure in which a (meth) acryloyloxy group is bonded to different aromatic rings, and the compound itself has poor liquid crystallinity. The orientation was inferior, so it was not satisfactory.
[0008]
Accordingly, an object of the present invention is to provide a liquid crystal compound that can provide a polymer liquid crystal that is excellent in orientation, heat resistance, and solvent resistance, and a polymer liquid crystal composed of a polymer of the compound.
[0009]
[Means for Solving the Problems]
As a result of extensive studies, the present inventor has found that the above object can be achieved by introducing two (meth) acryloyloxy groups into one aromatic ring.
[0010]
The present invention has been made on the basis of the above findings, and provides a trifunctional compound represented by the following general formula (I) represented by the following [Chemical Formula 2] (same as the above [Chemical Formula 1]).
[0011]
[Chemical 2]
[0012]
The present invention also provides a polymerizable composition comprising a mixture of the above trifunctional compound and another polymerizable compound.
The present invention also provides a polymer liquid crystal comprising a homopolymer or a copolymer of two or more of the above trifunctional compounds.
The present invention also provides a polymer liquid crystal comprising a copolymer of the above trifunctional compound and another polymerizable compound.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The trifunctional compound and polymer liquid crystal of the present invention are described in detail below.
[0014]
In the trifunctional compound of the present invention, examples of the 6-membered ring represented by the rings A, B and C in the general formula (I) include divalent benzene having a bond at the 1,4-position, Examples include cyclohexane, cyclohexene, dioxane, pyridine, and pyrimidine.
[0015]
Moreover, l represents 0-14, and when l is larger than 14, the glass transition temperature of the polymer liquid crystal obtained by polymerizing the trifunctional compound of the present invention is lowered and the stability of the alignment state is lowered.
[0016]
N and p each represent 0 or 1, and 0 ≦ n + p ≦ 2, and if n + p is larger than 2, the resulting polymer becomes rigid and poor in orientation.
[0017]
The trifunctional compound of the present invention itself may or may not exhibit liquid crystallinity, and as described later, the homopolymer or two or more types of copolymers, or the trifunctional compound of the present invention and other polymerizations. In a copolymer obtained by polymerizing the composition obtained from a mixture with a polymerizable compound, that is, a copolymer of the trifunctional compound of the present invention and another polymerizable compound, liquid crystallinity is obtained. As long as the obtained polymer has a high Tg, has excellent resistance to dissolution in an organic solvent, and provides a polymer liquid crystal (liquid crystalline polymer) excellent in coating property and orientation.
[0018]
More specific examples of the trifunctional compound of the present invention include compound Nos. Shown in the following [Chemical Formula 3] to [Chemical Formula 7]. 1-5 etc. are mentioned. However, the present invention is not limited by the following compounds.
[0019]
[Chemical 3]
[0020]
[Formula 4]
[0021]
[Chemical formula 5]
[0022]
[Chemical 6]
[0023]
[Chemical 7]
[0024]
The method for synthesizing the trifunctional compound of the present invention is not particularly limited. For example, 3,4-dihydroxybenzoic acid and acrylic acid chloride are reacted to obtain 3,4-bisacryloyloxybenzoic acid. And 4- (ω-acryloyloxyalkyleneoxy) benzoic acid and hydroquinone monoester.
[0025]
The trifunctional compound of the present invention is polymerized by heat or light, either alone or as a polymerizable composition comprising a mixture with another polymerizable compound (copolymerization component) (using a photopolymerization initiator as required). As a polymer liquid crystal, it is used for various applications.
[0026]
Here, the other polymerizable compound used in the copolymerization is not particularly limited, and examples thereof include 4- (2-methacryloyloxyethyloxy) benzoic acid-4′-methoxyphenyl, 4 -(6-Methacryloyloxyhexyloxy) biphenyl benzoate, 4- (2-methacrylolyloxyethyloxy) benzoate-4'-cyanobiphenyl, 4- (2-methacryloyloxyethyloxy) benzoate-3 ', 4'-Difluorophenyl, 4- (2-methacryloyloxyethyloxy) naphthyl benzoate, 4-acryloyloxy-4'-decylbiphenyl, 4-acryloyloxy-4'-cyanobiphenyl, 4- (2-methacryloyl) Oxyethyloxy) -4'-methoxybiphenyl, 4- (2-methacryloyloxyethyloxy) -4 '-(4 "-fluorobenzyloxy) -biphenyl, 4-acryloyloxy-4'-propyl Chlohexylphenyl, 4-methacryloyl-4'-butylbicyclohexyl, 4-acryloyl-4'-amyltran, 4-acryloyl-4 '-(3,4-difluorophenyl) bicyclohexyl, 4- (2-acryloyloxyethyl ) Monoacrylate compounds such as benzoic acid (4-amylphenyl), 4- (2-acryloyloxyethyl) benzoic acid (4- (4'-propylcyclohexyl) phenyl), 1,4-bis (4- (6- Acryloyloxyhexyloxy) benzoyloxy) benzene, 1,4-bis (4- (2-acryloyloxyethyloxy) benzoyloxy) benzene, bis (4- (2-acryloyloxyethyloxy) phenyl) terephthalate, 4- ( 4-acryloyloxyphenyl) carbonyloxy- (6-acryloyloxyhexyloxyphenyl) cal Bonyloxybenzene, 4- (4-acryloyloxyphenyl) carbonyloxy- (3-acryloyloxypropyloxyphenyl) carbonyloxybenzene, 4-acryloyloxybenzoic acid-4- (2-acryloyloxyethyl) phenyl ester, 4- And diacrylate compounds such as acryloyloxybenzoic acid-4- (3-acryloyloxypropyl) phenyl ester.
[0027]
Each monomer in the case of obtaining a copolymer of the trifunctional compound of the present invention and another polymerizable compound (the 3 in the polymerizable composition comprising a mixture of the trifunctional compound of the present invention and another polymerizable compound) The weight ratio of the functional compound and the other polymerizable compound) is not particularly limited, but the content of the trifunctional compound of the present invention is preferably 3% by weight or more in all monomers, and is 5% by weight or more. Is particularly preferred. If it is less than 3% by weight, the Tg of the obtained liquid crystalline polymer is low, and the solvent resistance is lowered, making it impractical.
[0028]
As described above, by using the trifunctional compound of the present invention as a polymer, the polymer liquid crystal of the present invention having a high Tg, excellent resistance to dissolution in an organic solvent, and excellent coating properties and orientation. Obtainable.
[0029]
【Example】
Specific synthesis examples (Examples) of the trifunctional compound of the present invention are shown below. However, the present invention is not limited by these synthesis examples.
[0030]
Synthesis of Compound No. 4 10.0 g (65 mmol) of 3,4-dihydroxybenzoic acid and 16.7 g (156 mmol) of 2,6-lutidine were dissolved in 70 ml of tetrahydrofuran, and 11.8 g of acrylic acid chloride (11.8 g) with stirring. 130 mmol) was slowly added dropwise at room temperature. The mixture was reacted at room temperature for 1 hour, the organic solvent was distilled off, 150 ml of toluene and 150 ml of water were added, and oil-water separation was performed. The organic layer was washed twice with water, dehydrated with sodium sulfate, and then desolvated to obtain 8.2 g (yield 48.2%) of 3,4-bis (acryloyloxy) benzoic acid.
[0031]
1.31 g (5 mmol) of 3,4-bis (acryloyloxy) benzoic acid, 0.821 g (5 mmol) of 4-acryloyloxyphenol and 0.056 g (0.5 mmol) of 4-dimethylaminopyridine were dissolved in 10 ml of chloride. After dissolving in methylene, 1.08 g (5.25 mmol) of N, N′-dicyclohexylcarbodiimide (hereinafter referred to as “DCC”) was added dropwise, and the mixture was stirred at room temperature for 1 hour. The precipitate was filtered off, and after removing the solvent from the filtrate, the residue was subjected to silica gel column treatment. The resulting solid was recrystallized from methanol to give 0.6 g of white solid having a melting point of 106.8 ° C. (yield: 30.0%). )
[0032]
The infrared absorption spectrum of the obtained solid is
3125cm -1, 3075cm -1, 1740cm -1 , 1640cm -1, 1610cm -1, 1505cm -1, 1400cm -1,
The peaks at 1295 cm −1 , 1240 cm −1 , 1190 cm −1 , 1150 cm −1 and 1030 cm −1 were shown.
[0033]
Synthesis of Compound No. 3 1.97 g (7.5 mmol) of 3,4-bis (acryloyloxy) benzoic acid, 2.88 g of 4- (6-acryloyloxyhexyloxy) benzoic acid-4-hydroxyphenyl ester (7 0.5 mmol) and 0.084 g (0.75 mmol) of 4-dimethylaminopyridine were dissolved in 20 ml of methylene chloride, 1.62 g (7.88 mmol) of DCC was added dropwise, and the mixture was stirred at room temperature for 1 hour. The precipitate was filtered off, the solvent was removed from the filtrate, the residue was subjected to silica gel column treatment, and the obtained solid was recrystallized from ethyl acetate / methanol (= 1/1) to give a white solid 1 having a melting point of 111.8 ° C. Obtained .45 g (yield 30.9%).
[0034]
The infrared absorption spectrum of the obtained solid showed the following peak.
3100cm -1, 3075cm -1, 2975cm -1 , 2875cm -1, 1750cm -1, 1710cm -1, 1635cm -1,
1600cm -1, 1500cm -1, 1400cm -1 , 1280cm -1, 1270cm -1, 1170cm -1, 1140cm -1,
1070cm -1, 1020cm -1
The phase transition temperatures are as follows (C: crystal phase, I: isotropic phase, N: nematic phase).
[0035]
Synthesis of copolymer 1 g of the formulation described in [Table 1] below (weight ratio shown in [Table 1]) was dissolved in 5 g of dichloromethane, stirred and then desolvated to obtain a liquid crystal composition. The phase transition temperature at the time of temperature rise and temperature fall of the obtained liquid crystal composition was measured. The results are shown in [Table 1] below.
[0036]
Further, 0.05 g of a photopolymerization initiator (PZ-408: manufactured by Asahi Denka Kogyo Co., Ltd.) was added to 1 g of the liquid crystal composition, and dissolved in 2 g of cyclohexanone. The adjusted solution was applied to a glass plate having a rubbed polyimide alignment film with a spin coater, and the solvent was removed at 30 ° C. under reduced pressure. The obtained cast film was irradiated with a black light fluorescent lamp for 5 minutes at 30 ° C. and irradiated with ultraviolet rays corresponding to 550 mJ with a mercury lamp to obtain a cured film. The solvent resistance of the obtained cured film was evaluated by dropping one drop of chloroform and cyclohexanone on the cured film. As a result, there was no swelling or peeling, and the solvent resistance was excellent.
[0037]
In addition, monomers other than the trifunctional compound of the present invention used for the copolymer are shown below.
[0038]
[Chemical 8]
[0039]
[Chemical 9]
[0040]
[Chemical Formula 10]
[0041]
Embedded image
[0042]
[Table 1]
[0043]
It can be seen that a cured product having excellent solvent resistance can be obtained by the polymerizable trifunctional compound of the present invention having a specific structure.
[0044]
【The invention's effect】
The trifunctional compound of the present invention can provide a polymer liquid crystal that is excellent in orientation, heat resistance, and solvent resistance.
Moreover, the polymer liquid crystal of the present invention is excellent in orientation, heat resistance and solvent resistance.
Claims (4)
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