JP3838366B2 - Liquid crystal element - Google Patents

Description

  The present invention relates to a liquid crystal device comprising a liquid crystal composition comprising a polymer polymerized between electrodes and a liquid crystal. In particular, the present invention relates to a liquid crystal element using a terphenyl methacrylate derivative as the polymer.

In recent years, a display element in which liquid crystal and a polymer are dispersed is attracting attention as a bright display element that does not use a polarizing plate. The operating principle of this display element utilizes the difference in refractive index between the liquid crystal and the polymer. When the refractive index of the liquid crystal and the polymer matches with the application of an electric field, it shows a transmission state, and the refractive index is different due to electric field removal In this case, the scattering state is indicated (Japanese Patent Publication No. 58-501631, called NCAP). A reverse mode display element that transmits when no electric field is applied and scatters when an electric field is applied has also been developed (Mol. Cryst. Liq. Cryst., 198, 357, (1991), referred to as a reverse type). For these modes, a method for improving the visibility by mixing pigments has also been proposed. Polymers used in these display elements are already biphenyl derivatives, phenylbenzoate derivatives as mesogen groups, benzene rings and benzene rings bonded with a Schiff base, compounds having a tolan derivative, etc. 5-224187, WO 93/08497) is known.

  However, liquid crystal display elements using these polymers have the disadvantages of low specific resistance, high drive voltage, and insufficient reflectivity during scattering. In addition, there are several types of compounds in which the polymer precursor is difficult to dissolve in the liquid crystal composition.

  The present invention responds to such a request in the actual situation, and the purpose thereof is that the specific resistance value does not decrease even when irradiated with ultraviolet rays, and the precursor of the polymer is one kind or two or more kinds. It is an object to provide a novel compound which is compatible with liquid crystal, can be driven at a low voltage, and is bright and excellent in reflectivity.

  The liquid crystal device of the present invention is a liquid crystal device comprising a liquid crystal composition comprising a polymer polymerized between electrodes and a liquid crystal, wherein the polymer is

（上式中、Ｘ₁，Ｘ₂，Ｘ₃，Ｘ₄，Ｘ₅，Ｘ₆，Ｘ₇，Ｘ₈，Ｘ₉，Ｘ₁₀，Ｘ₁₁，Ｘ₁₂はそれぞれ水素原子、またはフッ素原子、または塩素原子、またはメチル基、またはニトリル基を表し、Ｙは水素原子、またはフッ素原子、または塩素原子、または炭素数が１〜１０の直鎖アルキル基、またはニトリル基を示す）で表される構成要素かまたは

(In the above formula, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ are each a hydrogen atom, a fluorine atom, or A chlorine atom, a methyl group, or a nitrile group, and Y represents a hydrogen atom, a fluorine atom, a chlorine atom, a straight-chain alkyl group having 1 to 10 carbon atoms, or a nitrile group) Element or

（上式中、Ｘ₁，Ｘ₂，Ｘ₃，Ｘ₄，Ｘ₅，Ｘ₆，Ｘ₇，Ｘ₈，Ｘ₉，Ｘ₁₀，Ｘ₁₁，Ｘ₁₂はそれぞれ水素原子、またはフッ素原子、または塩素原子、またはメチル基、またはニトリル基を表す）で表される構成要素を含むことを特徴とする。
相分離させた液晶と高分子をシアリングにより配向させてもよい。また液晶及び高分子を互いに配向分散させた表示素子において、液晶と高分子がゲルネットワーク状に相分離していてもよい。また液晶及び高分子を互いに配向分散させた液晶素子を作成するには、高分子を形成する前駆体としてターフェニルメタクリレート誘導体を0.1〜20％含有させ、そのターフェニルメタクリレート誘導体を重合させる。また液晶及び高分子を互いに配向分散させた表示素子において、２色性色素を含有することを特徴とする。また液晶及び高分子を互いに配向分散させた表示素子において、表示素子表面側での配向方向が、主たる光の入射方向と素子表面の法線を含む平面に対して垂直であることを特徴とする。あるいは表示素子表面側での高分子の配向方向が裏面側での高分子の配向方向と異なることを特徴とする。また液晶及び高分子を互いに配向分散させた表示素子において、液晶及び高分子分散層を挟持する２枚の電極の１方が光反射性の電極であることを特徴とする。
次に、本発明で用いるターフェニルメタクリレート誘導体（１）と（２）の一般的製造方法について述べる。

(In the above formula, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ are each a hydrogen atom, a fluorine atom, or A component represented by a chlorine atom, a methyl group, or a nitrile group).
The phase separated liquid crystal and polymer may be aligned by shearing. In the display element in which the liquid crystal and the polymer are aligned and dispersed with each other, the liquid crystal and the polymer may be phase-separated in a gel network form. In order to prepare a liquid crystal element in which liquid crystal and polymer are aligned and dispersed, 0.1 to 20% of terphenyl methacrylate derivative is contained as a precursor for forming the polymer, and the terphenyl methacrylate derivative is polymerized. A display element in which liquid crystal and polymer are aligned and dispersed with each other contains a dichroic dye. Further, in a display element in which liquid crystal and polymer are aligned and dispersed with each other, the alignment direction on the display element surface side is perpendicular to a plane including a main light incident direction and a normal line of the element surface. . Alternatively, the polymer orientation direction on the display element surface side is different from the polymer orientation direction on the back surface side. In addition, in a display element in which liquid crystal and polymer are aligned and dispersed, one of the two electrodes sandwiching the liquid crystal and polymer dispersion layer is a light reflective electrode.
Next, a general method for producing the terphenyl methacrylate derivatives (1) and (2) used in the present invention will be described.

工程１）化合物(I)と化合物(II)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(III)を得る。
工程２）化合物(IV)と化合物(III)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(V)を得る。
工程３）化合物(V)を酢酸中で臭化水素酸と反応させ化合物(VI)を得る。ただし(V)の化合物中にニトリル基が存在するときはジクロロメタン中で三臭化ほう素と反応させ化合物(VI)を得る。
工程４）化合物(VI)とメタクリロイルクロライドをクロロホルム中でトリエチルアミンの存在下反応させ化合物（１）を得る。

Step 1) Compound (III) is obtained by reacting compound (I) and compound (II) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step 2) Compound (V) is obtained by reacting compound (IV) and compound (III) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step 3) Compound (VI) is obtained by reacting compound (V) with hydrobromic acid in acetic acid. However, when a nitrile group is present in the compound (V), it is reacted with boron tribromide in dichloromethane to obtain compound (VI).
Step 4) Compound (VI) and methacryloyl chloride are reacted in chloroform in the presence of triethylamine to obtain compound (1).

工程１'）化合物(I)と化合物(II')をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(III')を得る。
工程２'）化合物(IV)と化合物(III')をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(V')を得る。
工程３'）化合物(V')を酢酸中で臭化水素酸と反応させ化合物(VI')を得る。ただし(V')の化合物中にニトリル基が存在するときはジクロロメタン中で三臭化ほう素と反応させ化合物(VI')を得る。
工程４'）化合物(VI')とメタクリロイルクロライドをクロロホルム中でトリエチルアミンの存在下反応させ化合物（２）を得る。
以上が一般的合成方法であるが、各々の化合物の合成方法は存在する置換基により少しづつ変わってくる。それは置換基の種類あるいは結合している位置により、入手可能（市販されている）な原料が限られてくることと、反応性に違いが生ずるためである。次に具体的な合成方法として化合物１−ａ〜ｈと２−ａ〜ｅの化合物の合成方法を述べる。

Step 1 ′) Compound (III ′) is obtained by reacting compound (I) and compound (II ′) in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate.
Step 2 ′) Compound (V) is obtained by reacting compound (IV) and compound (III ′) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step 3 ′) Compound (VI ′) is obtained by reacting compound (V ′) with hydrobromic acid in acetic acid. However, when a nitrile group is present in the compound (V ′), the compound (VI ′) is obtained by reacting with boron tribromide in dichloromethane.
Step 4 ′) Compound (2 ′) is obtained by reacting compound (VI ′) with methacryloyl chloride in chloroform in the presence of triethylamine.
The above is a general synthesis method, but the synthesis method of each compound changes little by little depending on the substituents present. This is because available materials (commercially available) are limited depending on the type of the substituent or the bonding position, and the reactivity is different. Next, a method for synthesizing the compounds 1-a to h and 2-a to e will be described as a specific synthesis method.

工程Ａ−１）化合物(1)をテトラヒドロフラン中でマグネシウムと反応させグリニヤール試薬とした後、ほう酸トリイソプロピルと反応させ化合物(2)を得る。
工程Ａ−２）化合物(2)と化合物(3)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(4)を得る。
工程Ａ−３）化合物(4)を酢酸中で臭化水素酸と反応させ化合物(5)を得る。
工程Ａ−４）化合物(5)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(1-a)を得る。

Step A-1) Compound (1) is reacted with magnesium in tetrahydrofuran to give a Grignard reagent, and then reacted with triisopropyl borate to obtain compound (2).
Step A-2) Compound (4) is obtained by reacting compound (2) and compound (3) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step A-3) Compound (4) is reacted with hydrobromic acid in acetic acid to give compound (5).
Step A-4) Compound (1-a) is obtained by reacting compound (5) and compound (6) in chloroform in the presence of triethylamine.

工程Ｂ−１）化合物(7)を二硫化炭素中で塩化アルミニウムの存在下でアルキルカルボニルクロライドと反応させ化合物(8)を得る。
工程Ｂ−２）化合物(8)をトリエチレングリコール中で水酸化カリウムの存在下でヒドラジン一水和物と反応させ化合物(9)を得る。
工程Ｂ−３）化合物(9)ををテトラヒドロフラン中でマグネシウムと反応させグリニヤール試薬とした後、ほう酸トリメチルと反応させ化合物(10)を得る。
工程Ｂ−４）化合物(10)をテトラヒドロフラン中で過酸化水素水と水と反応させ化合物(11)を得る。
工程Ｂ−５）化合物(11)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(1-b)を得る。

Step B-1) Compound (8) is obtained by reacting compound (7) with alkylcarbonyl chloride in the presence of aluminum chloride in carbon disulfide.
Step B-2) Compound (8) is reacted with hydrazine monohydrate in the presence of potassium hydroxide in triethylene glycol to obtain compound (9).
Step B-3) Compound (9) is reacted with magnesium in tetrahydrofuran to form a Grignard reagent, and then reacted with trimethyl borate to obtain compound (10).
Step B-4) Compound (11) is obtained by reacting compound (10) with hydrogen peroxide and water in tetrahydrofuran.
Step B-5) Compound (1-b) is obtained by reacting compound (11) and compound (6) in chloroform in the presence of triethylamine.

工程Ｃ−１）化合物(12)と化合物(13)を二硫化炭素中で塩化アルミニウムの存在下で反応させ化合物(14)を得る。
工程Ｃ−２）化合物(14)をリン酸とポリリン酸の混合中で塩化ヒドロキシルアンモニウムと反応させた後、水酸化ナトリウムで処理して化合物(15)を得る。
工程Ｃ−３）化合物(15)を酢酸中で亜硝酸ナトリウムと硫酸と反応させジアゾニウム塩にした後、塩化銅と塩酸と反応させ化合物せ化合物(16)を得る。
工程Ｃ−４）化合物(2)と化合物(16)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(17)を得る。
工程Ｃ−５）化合物(17)を酢酸中で臭化水素酸と反応させ化合物(18)を得る。
工程Ｃ−６）化合物(18)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(1-c)を得る。

Step C-1) Compound (12) and compound (13) are reacted in carbon disulfide in the presence of aluminum chloride to obtain compound (14).
Step C-2) Compound (14) is reacted with hydroxylammonium chloride in a mixture of phosphoric acid and polyphosphoric acid, and then treated with sodium hydroxide to obtain compound (15).
Step C-3) Compound (15) is reacted with sodium nitrite and sulfuric acid in acetic acid to form a diazonium salt, and then reacted with copper chloride and hydrochloric acid to obtain compound (16).
Step C-4) Compound (17) is obtained by reacting compound (2) and compound (16) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step C-5) Compound (17) is reacted with hydrobromic acid in acetic acid to obtain compound (18).
Step C-6) Compound (1-c) is obtained by reacting compound (18) and compound (6) in chloroform in the presence of triethylamine.

工程Ｄ−１）化合物(14)をジオキサン中で臭素と水酸化ナトリウムと反応させ化合物(19)を得る。
工程Ｄ−２）化合物(19)を塩化チオニルと反応させ化合物(20)を得る。
工程Ｄ−３）化合物(20)をジオキサン中でアンモニアと反応させ化合物(21)を得る。
工程Ｄ−４）化合物(21)を塩化チオニルと反応させ化合物(22)を得る。
工程Ｄ−５）化合物(2)と化合物(22)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(23)を得る。
工程Ｄ−６）化合物(23)をジクロロメタン中で三臭化ほう素と反応させ化合物(24)を得る。
工程Ｄ−７）化合物(24)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(1-d)を得る。

Step D-1) Compound (14) is reacted with bromine and sodium hydroxide in dioxane to obtain compound (19).
Step D-2) The compound (19) is reacted with thionyl chloride to obtain the compound (20).
Step D-3) Compound (21) is obtained by reacting compound (20) with ammonia in dioxane.
Step D-4) Compound (21) is reacted with thionyl chloride to obtain compound (22).
Step D-5) Compound (23) is obtained by reacting compound (2) and compound (22) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step D-6) Compound (23) is reacted with boron tribromide in dichloromethane to obtain compound (24).
Step D-7) Compound (1-d) is obtained by reacting compound (24) and compound (6) in chloroform in the presence of triethylamine.

工程Ｅ−１）化合物(2)と化合物(25)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(26)を得る。
工程Ｅ−２）化合物(26)を酢酸中で臭化水素酸と反応させ化合物(27)を得る。
工程Ｅ−３）化合物(27)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(1-e)を得る。

Step E-1) Compound (26) is obtained by reacting compound (2) and compound (25) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step E-2) Compound (26) is reacted with hydrobromic acid in acetic acid to give compound (27).
Step E-3) Compound (1-e) is obtained by reacting compound (27) and compound (6) in chloroform in the presence of triethylamine.

工程Ｆ−１）化合物(28)を酢酸中で亜硝酸ナトリウムと硫酸と反応させジアゾニウム塩とした後、ベンゼンと反応させ化合物(29)を得る。
工程Ｆ−２）化合物(2)と化合物(29)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(30)を得る。
工程Ｆ−３）化合物(30)を酢酸中で臭化水素酸と反応させ化合物(31)を得る。
工程Ｆ−４）化合物(31)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(1-f)を得る。

Step F-1) Compound (28) is reacted with sodium nitrite and sulfuric acid in acetic acid to form a diazonium salt, and then reacted with benzene to obtain compound (29).
Step F-2) Compound (30) is obtained by reacting compound (2) and compound (29) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step F-3) The compound (30) is reacted with hydrobromic acid in acetic acid to obtain the compound (31).
Step F-4) Compound (1-f) is obtained by reacting compound (31) and compound (6) in chloroform in the presence of triethylamine.

工程Ｇ−１）化合物(25)を二硫化炭素中で塩化アルミニウムの存在下でアルキルカルボニルクロライドと反応させ化合物(32)を得る。
工程Ｇ−２）化合物(32)をトリフルオロ酢酸中でトリエチルシランと反応させ化合物(33)を得る。
工程Ｇ−３）化合物(2)と化合物(33)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(34)を得る。
工程Ｇ−４）化合物(34)を酢酸中で臭化水素酸と反応させ化合物(35)を得る。
工程Ｇ−５）化合物(35)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(1-g)を得る。

Step G-1) Compound (32) is obtained by reacting compound (25) with alkylcarbonyl chloride in the presence of aluminum chloride in carbon disulfide.
Step G-2) The compound (32) is reacted with triethylsilane in trifluoroacetic acid to obtain the compound (33).
Step G-3) Compound (34) is obtained by reacting compound (2) and compound (33) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step G-4) Compound (35) is reacted with hydrobromic acid in acetic acid to give compound (35).
Step G-5) Compound (35) and compound (6) are reacted in chloroform in the presence of triethylamine to obtain compound (1-g).

工程Ｈ−１）化合物(25)を二硫化炭素中で塩化アルミニウムの存在下アセチルクロライドと反応させ化合物(36)を得る。
工程Ｈ−２）化合物(36)をジオキサン中で臭素と水酸化ナトリウムと反応させ化合物(37)を得る。
工程Ｈ−３）化合物(37)を塩化チオニルと反応させ化合物(38)を得る。
工程Ｈ−４）化合物(38)をジオキサン中でアンモニアと反応させ化合物(39)を得る。
工程Ｈ−５）化合物(39)を塩化チオニルと反応させ化合物(40)を得る。
工程Ｈ−６）化合物(2)と化合物(40)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(41)を得る。
工程Ｈ−７）化合物(41)をジクロロメタン中で三臭化ほう素と反応させ化合物(42)を得る。
工程Ｈ−８）化合物(42)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(1-h)を得る。

Step H-1) The compound (25) is reacted with acetyl chloride in the presence of aluminum chloride in carbon disulfide to obtain the compound (36).
Step H-2) The compound (36) is reacted with bromine and sodium hydroxide in dioxane to obtain the compound (37).
Step H-3) Compound (38) is obtained by reacting compound (37) with thionyl chloride.
Step H-4) Compound (38) is reacted with ammonia in dioxane to obtain compound (39).
Step H-5) The compound (39) is reacted with thionyl chloride to obtain the compound (40).
Step H-6) Compound (41) is obtained by reacting compound (2) and compound (40) in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate.
Step H-7) The compound (41) is reacted with boron tribromide in dichloromethane to obtain the compound (42).
Step H-8) Compound (1-h) is obtained by reacting Compound (42) and Compound (6) in chloroform in the presence of triethylamine.

工程Ｉ−１）化合物(2)と化合物(43)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(44)を得る。
工程Ｉ−２）化合物(44)を酢酸中で臭化水素酸と反応させ化合物(45)を得る。
工程Ｉ−３）化合物(45)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(2-a)を得る。

Step I-1) Compound (44) is obtained by reacting compound (2) and compound (43) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step I-2) Compound (44) is reacted with hydrobromic acid in acetic acid to give compound (45).
Step I-3) Compound (45) and compound (6) are reacted in chloroform in the presence of triethylamine to obtain compound (2-a).

工程Ｊ−１）化合物(2)と化合物(46)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(47)を得る。
工程Ｊ−２）化合物(47)を酢酸中で臭化水素酸と反応させ化合物(48)を得る。
工程Ｊ−３）化合物(48)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(2-b)を得る。

Step J-1) Compound (47) is obtained by reacting compound (2) and compound (46) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step J-2) The compound (47) is reacted with hydrobromic acid in acetic acid to obtain the compound (48).
Step J-3) Compound (48) and compound (6) are reacted in chloroform in the presence of triethylamine to obtain compound (2-b).

工程Ｋ−１）化合物(2)と化合物(49)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(50)を得る。
工程Ｋ−２）化合物(50)を酢酸中で臭化水素酸と反応させ化合物(51)を得る。
工程Ｋ−３）化合物(51)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(2-c)を得る。

Step K-1) Compound (50) is obtained by reacting compound (2) and compound (49) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step K-2) The compound (50) is reacted with hydrobromic acid in acetic acid to obtain the compound (51).
Step K-3) Compound (2-c) is obtained by reacting compound (51) and compound (6) in chloroform in the presence of triethylamine.

工程Ｌ−１）化合物(2)と化合物(52)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(53)を得る。
工程Ｌ−２）化合物(53)を酢酸中で臭化水素酸と反応させ化合物(54)を得る。
工程Ｌ−３）化合物(54)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(2-d)を得る。

Step L-1) Compound (53) is obtained by reacting compound (2) and compound (52) in the presence of tetrakistriphenylphosphine palladium and sodium carbonate in a mixed solvent of benzene and ethanol.
Step L-2) The compound (53) is reacted with hydrobromic acid in acetic acid to obtain the compound (54).
Step L-3) Compound (54) and compound (6) are reacted in chloroform in the presence of triethylamine to obtain compound (2-d).

工程Ｍ−１）化合物(2)と化合物(55)をベンゼンとエタノールの混合溶媒中でテトラキストリフェニルフォスフィンパラジウムと炭酸ナトリウムの存在下で反応させ化合物(56)を得る。
工程Ｍ−２）化合物(56)を酢酸中で臭化水素酸と反応させ化合物(57)を得る。
工程Ｍ−３）化合物(57)と化合物(6)をクロロホルム中でトリエチルアミンの存在下反応させ化合物(2-e)を得る。

Step M-1) Compound (56) is obtained by reacting compound (2) and compound (55) in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate.
Step M-2) The compound (56) is reacted with hydrobromic acid in acetic acid to obtain the compound (57).
Step M-3) The compound (57) and the compound (6) are reacted in chloroform in the presence of triethylamine to obtain the compound (2-e).

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 Synthesis of Compound (1-a)
Production of p-terphenyl-4-yl methacrylate.
Step A-1) 2.0 g of magnesium was placed in a flask purged with nitrogen, and a solution prepared by dissolving 12.5 g of 4-bromoanisole in 100 ml of tetrahydrofuran was slowly added dropwise while stirring with a magnetic stirrer. After confirming that the reaction progressed due to exotherm, stirring was continued for 15 hours to prepare a Grignard reagent. The newly prepared flask was purged with nitrogen, and a solution of 25 g of triisopropyl borate dissolved in 10 ml of tetrahydrofuran was added thereto, and then the Grignard reagent was added dropwise and stirred for 20 hours. The reaction solution was extracted with chloroform and washed 3 times with water, and then chloroform was distilled off. The residue was recrystallized from a mixed solvent of methanol and water to obtain 5.8 g of 4-methoxyphenylboric acid.
Step A-2) 50 ml of 2M aqueous sodium carbonate solution and 70 ml of benzene were placed in a flask purged with nitrogen, and further 8.9 g of 4-bromobiphenyl and 1.1 g of tetrakistriphenylphosphine palladium were placed. The solution which melt | dissolved 4-methoxyphenyl boric acid 5.8g in ethanol 50ml was dripped there, and it recirculate | refluxed for 5 hours. The reaction solution was extracted with chloroform and washed with water, and then chloroform was distilled off. The residue was recrystallized from a mixed solvent of chloroform and methanol to obtain 3.5 g of 4-methoxy-p-terphenyl.
Step A-3) An eggplant-shaped flask was charged with 3.5 g of 4-methoxy-p-terphenyl, 30 ml of hydrobromic acid, and 150 ml of acetic acid and refluxed for 20 hours. The reaction solution was cooled to room temperature, filtered and washed with water. Recrystallization from a mixed solvent of acetone and methanol gave 2.4 g of 4-hydroxy-p-terphenyl.
Step A-4) Put 100 ml of chloroform, 2.4 g of 4-hydroxy-p-terphenyl and 2 ml of triethylamine in a flask purged with nitrogen, and dissolve completely in a hot water bath at 40 ° C. To this, 1.3 ml of distilled and purified methacryloyl chloride was slowly added dropwise, and stirring was continued for 5 hours. The reaction solution is washed with dil.HClaq., Saturated NaHCO ₃ aq., Water, methanol is added to prevent polymerization, and chloroform and methanol are distilled off. When crystals appeared during distillation, the crystals were taken out and further recrystallized with methanol to obtain 2.4 g of the compound p-terphenyl-4-yl methacrylate of the present invention. The melting point of this compound was 211 ° C.
When the nuclear magnetic resonance spectrum (NMR) of this compound was measured, the following results were obtained.

ＮＭＲ（δ，ＣＤＣｌ₃）
２．０９（ｓ，３Ｈ，ＣＨ₃）， ５．７８（ｓ，１Ｈ，Ｈ_h）６．３８（ｓ，１Ｈ，Ｈ_i） ， ７．２３（ｄ，２Ｈ，Ｈ_a）７．３６（ｔ，１Ｈ，Ｈ_g） ， ７．４６（ｄ，２Ｈ，Ｈ_f）７．６４（ｄ，８Ｈ，Ｈ_b，Ｈ_c，Ｈ_dおよびＨ_e）またこの化合物の赤外吸収スペクトルを図１に示す。

NMR (δ, CDCl ₃ )
2.09 (s, 3 H, CH ₃ ), 5.78 (s, 1 H, H _h ) 6.38 (s, 1 H, H _i ), 7.23 (d, 2 H, H _a ) 7.36 ( _{t, 1H, H g),} 7.46 (d, 2H, H f) 7.64 (d, 8H, H b, FIG infrared absorption spectrum of the H _c, H _d and H _e) and this compound 1 Shown in

Example 2 Synthesis of Compound (1-b)
Preparation of 4 "-pentyl-p-terphenyl-4-yl methacrylate.
Step B-1) A flask is charged with 12.0 g of aluminum chloride and 200 ml of carbon disulfide, and 9.4 g of pentanoyl chloride is added dropwise with stirring. While this mixture was cooled in an ice-water bath, a solution of 20 g of 4-bromo-p-terphenyl in 800 ml of a dilute carbon was added dropwise over 1 hour. After dropwise addition, the mixture was stirred for 3 hours under cooling, removed from the ice-water bath and left overnight. The reaction mixture was then poured into 50 ml of hydrochloric acid and 200 g of ice while stirring. The aqueous layer of the mixed solution was extracted with chloroform, combined with the oil layer, washed twice with 10% aqueous sodium hydroxide and twice with water, and then the solvent was distilled off. The residue was recrystallized from chloroform to obtain 17.2 g of 4-bromo-4 "-pentanoyl-p-terphenyl.
Step B-2) A flask is charged with 17.2 g of 4-bromo-4 ″ -pentanoyl-p-terphenyl, 6.6 g of hydrazine monohydrate, and 700 ml of triethylene glycol, and heated to 180 ° C. with vigorous stirring. After cooling to 90 ° C. or lower, 5.8 g of potassium hydroxide is added, heated to 190 ° C. with stirring, and stirred for 5 hours at 190 to 195 ° C. After cooling the reaction solution to room temperature, 500 ml of water is added and stirred. The crystals were filtered from and washed with water, and the crystals were recrystallized with a mixed solvent of chloroform and acetone to obtain 15.0 g of 4-bromo-4 "-pentyl-p-terphenyl.
Step B-3) Put 1.2 g of magnesium and 50 ml of tetrahydrofuran in a flask purged with nitrogen, and add a little ethanol while stirring with a magnetic stirrer to activate magnesium. Set the flask in a 70 ° C. warm bath and add 15.0 g of 4-bromo-4 ″ -pentyl-p-terphenyl in a dropping funnel while warming the solution so that it does not precipitate. After the dropwise addition, reflux for 3 hours to Grignard. A solution prepared by dissolving 4.5 g of trimethyl borate in 250 ml of tetrahydrofuran was placed in a newly prepared nitrogen-substituted flask and cooled to -10 ° C or lower, and then the Grignard reagent was slowly added dropwise thereto and stirring was continued for 2 hours. And a 4 "-pentyl-p-terphenyl-4-yl boric acid solution is obtained. This is used for the next reaction in a solution state.
Step B-4) Add 3.3 ml of acetic acid to the 4 ″ -pentyl-p-terphenyl-4-yl boric acid solution obtained in the reaction of Step B-3, stir, and add 4.4 ml of hydrogen peroxide and 3.9 ml of water. Add dropwise and continue stirring for 30 minutes.After returning the reaction solution to room temperature, add 500 ml of 10% aqueous solution of ammonium iron sulfate (12 hydrate), stir for 10 minutes and add 500 ml of water to make the crystals float. The crystals were separated by filtration, dried and recrystallized from chloroform to obtain 3.4 g of 4-hydroxy-4 "-pentyl-p-terphenyl.
Step B-5) Into a flask purged with nitrogen, 30 ml of chloroform, 3.4 g of 4-hydroxy-4 "-pentyl-p-terphenyl and 1.3 ml of triethylamine are placed and dissolved completely in a hot water bath at 40 ° C. 0.86 ml of distilled and purified methacryloyl chloride was slowly added dropwise, and the stirring reaction was continued for ₃ hours.After the reaction solution was washed with dil.HClaq., Saturated NaHCO ₃ aq., Water, methanol was added to prevent polymerization and chloroform was added. When the crystals appear during distillation, the crystals are taken out and recrystallized with methanol. The product is further purified by a silica gel column using chloroform as a developing solvent to give the compound 4 ″ -pentyl of the present invention. 1.9 g of -p-terphenyl-4-yl methacrylate was obtained. The melting point of this compound was 223.8 ° C.
The infrared absorption spectrum of this compound is shown in FIG.

Similarly, the following compounds can be synthesized.
4 "-methyl-p-terphenyl-4-yl methacrylate 4" -ethyl-p-terphenyl-4-yl methacrylate 4 "-propyl-p-terphenyl-4-yl methacrylate 4" -butyl-p-ter Phenyl-4-yl methacrylate 4 "-hexyl-p-terphenyl-4-yl methacrylate 4" -heptyl-p-terphenyl-4-yl methacrylate 4 "-octyl-p-terphenyl-4-yl methacrylate 4" -Nonyl-p-terphenyl-4-yl methacrylate 4 "-decyl-p-terphenyl-4-yl methacrylate (Example 3) [Synthesis of Compound (1-c)]
Preparation of 4 "-chloro-p-terphenyl-4-yl methacrylate.
Step C-1) A flask was charged with 12.3 g of 4-bromobiphenyl, 9.2 g of aluminum chloride and 100 ml of carbon disulfide, and a solution of 5 g of acetyl chloride dissolved in 20 ml of carbon disulfide was stirred for 30 minutes in a salt-ice water bath. Was added dropwise and stirred for 2 hours. The reaction product is poured into 40 ml of concentrated hydrochloric acid containing 80 g of ice while stirring, and the oil layer is separated. Wash the oil layer with 10% aqueous hydrochloric acid and water. Carbon disulfide in the oily substance was distilled off under reduced pressure of an aspirator, and the residue was distilled under reduced pressure to obtain 8.7 g of 4-acetyl-4′-bromobiphenyl.
Step C-2) 8.7 g of 4-acetyl-4′-bromobiphenyl, 6.7 g of hydroxylammonium chloride, 88 ml of phosphoric acid and 36 ml of polyphosphoric acid were placed in a flask and heated to 160 ° C. with stirring for 3 to 4 hours. Thereafter, the mixture was stirred at 160 to 170 ° C. for 10 minutes. The reaction solution was poured into 200 g of ice and stirred. The precipitated crystals were filtered and washed thoroughly. The obtained crystal was put in an aqueous solution obtained by dissolving 20 g of sodium hydroxide in 100 ml of water, and stirred at room temperature for 3 hours. The crystals were filtered, sufficiently washed with water, dried and distilled under reduced pressure to obtain 6.7 g of 4- (4′-bromophenyl) aniline.
Step C-3) 15 ml of concentrated sulfuric acid was placed in a flask, cooled in an ice-water bath, and 2 g of sodium nitrite was added at a rate that kept the liquid temperature at 20 ° C. or lower with stirring. Thereafter, the mixture was heated to 50 ° C. to dissolve the crystals. Next, 26 ml of acetic acid was added dropwise at such a rate that the liquid temperature was kept at 15 to 25 ° C. under cooling and stirring in an ice-water bath. Under cooling and stirring in an ice-water bath, 6.7 g of 4- (4′-bromophenyl) aniline was added at a rate that kept the liquid temperature at 20-25 ° C. Further, the mixture was stirred at a liquid temperature of 20 to 25 ° C. for 1 hour to dissolve the crystals to prepare a diazonium salt. In a separate flask, 4 g of copper (I) chloride and 16 ml of concentrated hydrochloric acid were taken, and the diazonium salt solution prepared earlier was added dropwise at 20 ° C. or lower with cooling and stirring in an ice-water bath. Thereafter, the mixture was cooled and stirred in an ice-water bath until foaming ceased, and then allowed to stand at 80 ° C. until foaming ceased. 100 ml of water was added to the reaction solution, extracted with chloroform, washed with water, and chloroform was distilled off. The residue was distilled under reduced pressure to obtain 4.5 g of 4-bromo-4′-chlorobiphenyl.
Step C-4) Into a flask purged with nitrogen, 23 ml of a 2M aqueous sodium carbonate solution and 30 ml of benzene are placed, and 4.5 g of 4-bromo-4′-chlorobiphenyl and 0.17 g of tetrakistriphenylphosphine palladium are placed. A solution prepared by dissolving 2.6 g of 4-methoxyphenylboric acid in 20 ml of ethanol is added dropwise thereto and refluxed for 5 hours. The reaction solution is extracted with chloroform and washed with water, and then chloroform is distilled off. The residue was purified with a silica gel column using chloroform as a developing solvent, and then recrystallized from acetone to obtain 2.7 g of 4-chloro-4 "-methoxy-p-terphenyl.
Step C-5) 2.7 g of 4-chloro-4 "-methoxy-p-terphenyl, 4.6 ml of hydrobromic acid and 46 ml of acetic acid are placed in an eggplant-shaped flask and refluxed for 12 hours. The residue was recrystallized from acetone to give 2.1 g of 4-chloro-4 "-hydroxy-p-terphenyl.
Step C-6) Into a flask purged with nitrogen, 9 ml of chloroform, 2.1 g of 4-chloro-4 ″ -hydroxy-p-terphenyl and 1.5 ml of triethylamine are placed and dissolved in a hot water bath at 40 ° C. completely. To this, 0.9 g of distilled methacryloyl chloride was slowly added dropwise and the reaction was continued for ₃ hours.After washing the reaction solution with dil.HClaq., Saturated NaHCO ₃ aq., Water, methanol was added to prevent polymerization and chloroform was added. When the crystals appear during the distillation, the crystals are taken out and recrystallized with methanol. The product is further purified by a silica gel column using chloroform as a developing solvent to give the compound 4 ″ -chloro of the present invention. 1.1 g of p-terphenyl-4-yl methacrylate was obtained. The melting point was 251 ° C.

Example 4 Synthesis of Compound (1-d)
Preparation of 4 "-cyano-p-terphenyl-4-yl methacrylate.
Step D-1) 19 g of sodium hydroxide was placed in a flask and dissolved in 100 ml of water and stirred.
Into this, 29 g of bromine was added dropwise. The flask was cooled in an ice-water bath, and a solution obtained by dissolving 14.3 g of 4-acetyl-4′-bromobiphenyl in 40 ml of 1,4-dioxane was added dropwise. The flask was then slowly heated to 40 ° C. and stirred for 1 hour. The reaction solution was poured into a mixture of 100 ml of concentrated hydrochloric acid and 150 g of ice, and the precipitated crystals were filtered and then washed with water. The obtained crystals were recrystallized from ethanol to obtain 13 g of 4- (4′-bromophenyl) benzoic acid.
Step D-2) A flask was charged with 13 g of 4- (4′-bromophenyl) benzoic acid and 17 g of thionyl chloride and refluxed for 5 hours. Thereafter, thionyl chloride was distilled off under reduced pressure, and the obtained crystals were washed with hexane to obtain 12.1 g of 4- (4′-bromophenyl) benzoyl chloride.
Step D-3) 75 ml of 1,4-dioxane was taken in a flask, and the flask was cooled in an ice-water bath to saturate ammonia gas. A solution prepared by dissolving 12.1 g of 4- (4′-bromophenyl) benzoyl chloride in 40 ml of 1,4-dioxane was added dropwise thereto. Thereafter, the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into water, and the precipitated crystals were filtered, washed with water, and then dried to obtain 9.7 g of 4- (4′-bromophenyl) benzamide.
Step D-4) A flask was charged with 9.7 g of 4- (4′-bromophenyl) benzamide and 20 g of thionyl chloride and refluxed for 7 hours. Thereafter, thionyl chloride was distilled off under reduced pressure, and the residue was extracted with chloroform, washed twice with water, twice with 5% aqueous potassium hydroxide solution and twice with water, and then chloroform was distilled off. The residue was recrystallized from a mixed solvent of acetone and methanol to obtain 6.2 g of 4- (4′-bromophenyl) bezonitrile.
Step D-5) Into a nitrogen-substituted flask, 30 ml of a 2M aqueous sodium carbonate solution and 43 ml of benzene are placed, and 6.2 g of 4- (4′-bromophenyl) bezonitrile and 0.24 g of tetrakistriphenylphosphine palladium are placed. The solution which melt | dissolved 4-methoxyphenyl boric acid 3.6g in ethanol 29ml is dripped there, and it recirculate | refluxs for 5 hours.
After cooling the reaction solution, the mixture is extracted with chloroform and washed with water, and then chloroform is distilled off.
The residue was recrystallized from a mixed solvent of acetone and methanol to obtain 2.8 g of 4 ″ -cyano-4-methoxy-p-terfeni.
Step D-6) A solution obtained by dissolving 5.7 g of boron tribromide in 40 ml of methylene chloride was placed in a flask, and 2.8 g of 4 "-cyano-4-methoxy-p-terphenyl was dissolved in 120 ml of methylene chloride. The solution was added dropwise at room temperature. After stirring overnight, the reaction solution was poured into water and the precipitated crystals were filtered and washed with water. The obtained crystals were recrystallized from a mixed solvent of acetone and water, and 4 ". 1.7 g of -cyano-4-hydroxy-p-terphenyl was obtained.
Step D-7) Put 8.7 ml of chloroform, 1.7 g of 4 ″ -cyano-4-hydroxy-p-terphenyl and 1.4 ml of triethylamine in a flask purged with nitrogen, and dissolve completely in a hot water bath at 40 ° C. Then, 1.4 g of distilled and purified methacryloyl chloride was slowly added dropwise, and the stirring reaction was continued for ₃ hours.After washing the reaction solution with dil.HClaq., Saturated NaHCO ₃ aq., Water, methanol was added to prevent polymerization. Chloroform and methanol are distilled off. When crystals appear during distillation, the crystals are taken out and recrystallized with methanol. The product is purified by a silica gel column using chloroform as a developing solvent to give compound 4 ″-of the present invention. 1.2 g of cyano-p-terphenyl-4-yl methacrylate was obtained. The melting point of this compound was 227.2 ° C.

Example 5 [Synthesis of Compound (1-e)]
Production of 3'-fluoro-p-terphenyl-4-yl methacrylate.
Step E-1) In a flask purged with nitrogen, 37 ml of a 2M sodium carbonate aqueous solution and 47 ml of benzene are placed, and further 6.6 g of 4-bromo-2-fluorobiphenyl and 0.3 g of tetrakistriphenylphosphine palladium are placed. Thereto is added dropwise a solution of 4 g of 4-methoxyphenylboric acid in 30 ml of ethanol, and the mixture is refluxed for 5 hours. The reaction solution is extracted with chloroform and washed with water, and then chloroform is distilled off. The residue was purified by a silica gel column using chloroform as a developing solvent and then recrystallized from acetone to obtain 5 g of 3′-fluoro-4-methoxy-p-terphenyl. The melting point of this compound was 130.5 ° C.
Step E-2) Into an eggplant-shaped flask, 5 g of 3′-fluoro-4-methoxy-p-terphenyl, 9 ml of hydrobromic acid and 90 ml of acetic acid are added and refluxed for 12 hours. The reaction solution is cooled to room temperature, filtered and washed with water. The residue was recrystallized from acetone to give 2.9 g of 3′-fluoro-4-hydroxy-p-terphenyl.
Step E-3) Into a flask purged with nitrogen, 17 ml of chloroform, 2.9 g of 3′-fluoro-4-hydroxy-p-terphenyl and 2.3 ml of triethylamine are added and dissolved completely in a hot water bath at 40 ° C. Then, 1.4 ml of distilled and purified methacryloyl chloride is slowly added dropwise, and the stirring reaction is continued for 3 hours. The reaction solution is washed with dil.HClaq., Saturated NaHCO ₃ aq., Water, methanol is added to prevent polymerization, and chloroform and methanol are distilled off. When crystals appear during distillation, remove them, add methanol and recrystallize. Further, the product was purified by a silica gel column using chloroform as a developing solvent to obtain 2.5 g of the compound 3′-fluoro-p-terphenyl-4-yl methacrylate of the present invention. The melting point of this compound was 141.7 ° C. The infrared absorption spectrum of this compound is shown in FIG.

Example 6 [Synthesis of Compound (1-f)]
Production of 3'-chloro-p-terphenyl-4-yl methacrylate.
Step F-1) 45 g of 4-bromo-2-chloroaniline was dissolved by heating in 18 ml of water, cooled to room temperature, 43 ml of concentrated hydrochloric acid was added, and the mixture was stirred at 90 ° C. for 30 minutes and then cooled to room temperature. Thereafter, the mixture was cooled to 0 to 5 ° C., and a solution obtained by dissolving 15.3 g of sodium nitrite in 32 ml of water was added dropwise. Thereafter, 270 ml of benzene was added while maintaining the reaction solution at 0 to 5 ° C. After stirring at room temperature for 2 hours, 50 ml of 5N aqueous sodium hydroxide solution was added, and the mixture was extracted with chloroform. The chloroform layer was washed 3 times with water, and then chloroform was distilled off. The residue was steamed and purified by hexane-silica gel chromatography to obtain 9.1 g of 4-bromo-2-chlorobiphenyl.
Step F-2) Into a flask purged with nitrogen, 47 ml of a 2M aqueous sodium carbonate solution and 60 ml of benzene are placed, and further 9.1 g of 4-bromo-2-chlorobiphenyl and 0.34 g of tetrakistriphenylphosphine palladium are placed. The solution which melt | dissolved 4-methoxyphenyl boric acid 5.2g in ethanol 40ml is dripped there, and it recirculate | refluxs for 5 hours. The reaction solution is extracted with chloroform and washed with water, and then chloroform is distilled off. The residue was purified by a silica gel column using chloroform as a developing solvent, and then recrystallized from a mixed solvent of acetone and methanol to obtain 6.1 g of 3′-chloro-4-methoxy-p-terphenyl. The melting point of this compound was 96.0 ° C.
Step F-3) Put 3'-chloro-4-methoxy-p-terphenyl 6.1g, hydrobromic acid 10ml, acetic acid 100ml in an eggplant type flask and reflux for 12 hours. The reaction solution is cooled to room temperature, filtered and washed with water. The residue was recrystallized from acetone to obtain 3.7 g of 3′-chloro-4-hydroxy-p-terphenyl.
Step F-4) 23 ml of chloroform, 3.7 g of 3′-chloro-4-hydroxy-p-terphenyl and 3.1 ml of triethylamine are placed in a flask purged with nitrogen, and dissolved completely in a hot water bath at 40 ° C. 1.9 g of distilled and purified methacryloyl chloride is slowly added dropwise thereto, and the stirring reaction is continued for 3 hours. The reaction solution is washed with dil.HClaq., Saturated NaHCO ₃ aq., Water, methanol is added to prevent polymerization, and chloroform and methanol are distilled off. When crystals appear during distillation, remove them, add methanol and recrystallize. Further, the product was purified by a silica gel column using chloroform as a developing solvent to obtain 1.8 g of the compound 3′-chloro-p-terphenyl-4-yl methacrylate of the present invention. The melting point of this compound was 104.2 ° C.

Example 7 Synthesis of Compound (1-g)
Preparation of 4 "-ethyl-3'-fluoro-p-terphenyl-4-yl methacrylate.
Step G-1) A flask is charged with 5.0 g of 4-bromo-2-fluorobiphenyl, 6.7 g of aluminum chloride, and 20 ml of 1,1,2,2-tetrachloroethane, and 1.9 g of acetyl chloride with stirring in a salt-ice water bath. Was added dropwise over 30 minutes, and the mixture was stirred for 2 hours. The reaction product is poured into 20 ml of concentrated hydrochloric acid containing 50 g of ice while stirring, and the oil layer is separated. Wash the oil layer with 10% aqueous hydrochloric acid and water. 1,1,2,2-Tetrachloroethane in the oil was distilled off under reduced pressure of an aspirator, and the residue was distilled under reduced pressure (186 ° C./2 mmHg) to give 4′-acetyl-4-bromo-2-fluorobiphenyl 5.3. g was obtained.
Step G-2) While stirring a solution obtained by dissolving 5.3 g of 4′-acetyl-4-bromo-2-fluorobiphenyl in 15 ml of trifluoroacetic acid at room temperature, 4.7 g of triethylsilane was slowly added dropwise and stirring was continued for 5 hours. . The reaction mixture is poured into 40 ml of 20% NaOH aqueous solution and 30 g of ice while stirring, the oil layer is separated, and the aqueous layer is extracted with chloroform. The oil layer and the chloroform layer were combined and washed with 20% NaOH aqueous solution and water. Chloroform was distilled off and the residue was distilled under reduced pressure (155 ° C./3 mmHg) to obtain 4.7 g of 4-bromo-4′-ethyl-2-fluorobiphenyl.
Step G-3) Into a flask purged with nitrogen, 40 ml of a 2M aqueous sodium carbonate solution and 60 ml of benzene are added, and 4.7 g of 4-bromo-4′-ethyl-2-fluorobiphenyl and 0.17 g of tetrakistriphenylphosphine palladium are added. The solution which melt | dissolved 4-methoxyphenyl boric acid 2.6g in ethanol 40ml is dripped there, and it recirculate | refluxs for 5 hours. After cooling the reaction solution, the mixture is extracted with chloroform and washed with water, and then chloroform is distilled off. The residue was recrystallized from a mixed solvent of acetone and methanol to obtain 4.1 g of 4 ″ -ethyl-3′-fluoro-4-methoxy-p-terphenyl. This compound showed a liquid crystal phase and a crystalline phase. -Nematic liquid crystal phase transition point (hereinafter referred to as C-N point) is 100.8 ℃
The nematic liquid crystal phase-isotropic liquid transition point (hereinafter referred to as NI point) was 179.7 ° C.
Step G-4) 4.1 g of 4 ″ -ethyl-3′-fluoro-4-methoxy-p-terphenyl, 7 ml of hydrobromic acid, and 30 ml of acetic acid are placed in an eggplant-shaped flask and refluxed for 20 hours. After cooling, the mixture is filtered and washed with water, and the residue is recrystallized from a mixed solvent of acetone and methanol to obtain 2.9 g of 4 ″ -ethyl-3′-fluoro-4-hydroxy-p-terphenyl.
Step G-5) Into a flask purged with nitrogen, 40 ml of chloroform, 2.9 g of 4 ″ -ethyl-3′-fluoro-4-hydroxy-p-terphenyl and 2.1 ml of triethylamine were placed, and heated in a 40 ° C. hot water bath. To this solution, 1.3 ml of distilled and purified methacryloyl chloride was slowly added dropwise, and the reaction was continued for ₃ hours.The reaction solution was washed with dil.HClaq., Saturated NaHCO ₃ aq. Methanol is added to distill off chloroform and methanol.When crystals appear during distillation, take out and recrystallize with methanol.The product is further purified with a silica gel column using chloroform as a developing solvent. 2.1 g of compound 4 ″ -ethyl-3′-fluoro-p-terphenyl-4-yl methacrylate was obtained. The melting point was 123.5 ° C. The infrared absorption spectrum of this compound is shown in FIG.

Similarly, the following compounds were obtained.
4 "-methyl-3'-fluoro-p-terphenyl-4-yl methacrylate.
4 "-propyl-3'-fluoro-p-terphenyl-4-yl methacrylate. 4"-butyl-3'-fluoro-p-terphenyl-4-yl methacrylate. 4 "-pentyl-3'-fluoro-p-terphenyl-4-yl methacrylate.

Melting point 106.5 ° C
4 "-hexyl-3'-fluoro-p-terphenyl-4-yl methacrylate. 4"-heptyl-3'-fluoro-p-terphenyl-4-yl methacrylate. 4 "-octyl-3'-fluoro-p-terphenyl-4-yl methacrylate. 4"-nonyl-3'-fluoro-p-terphenyl-4-yl methacrylate. 4 "-decyl-3'-fluoro-p-terphenyl-4-yl methacrylate.

Example 8 Synthesis of Compound (1-h)
Preparation of 4 "-cyano-3'-fluoro-p-terphenyl-4-yl methacrylate.
Step H-1) 44 g of 4′-acetyl-4-bromo-2-fluorobiphenyl was obtained in the same manner as in Step G-1.
Step H-2) 55 g of sodium hydroxide was placed in a flask and dissolved in 300 ml of water and stirred.
The bromine 84g was dripped in it. The flask was cooled in an ice-water bath, and a solution of 44 g of 4′-acetyl-4-bromo-2-fluorobiphenyl in 114 ml of 1,4-dioxane was added dropwise. The flask was then slowly heated to 40 ° C. and stirred for 1 hour. The reaction solution was poured into a mixture of 230 ml of concentrated hydrochloric acid and 450 g of ice, and the precipitated crystals were filtered and then washed with water. The obtained crystals were recrystallized from ethanol to obtain 40 g of 4- (4′-bromo-2′-fluorophenyl) benzoic acid.
Step H-3) A flask was charged with 40 g of 4- (4′-bromo-2′-fluorophenyl) benzoic acid and 50 g of thionyl chloride and refluxed for 5 hours. Thereafter, thionyl chloride was distilled off under reduced pressure, and the obtained crystals were washed with hexane to obtain 37 g of 4- (4′-bromo-2′-fluorophenyl) benzoyl chloride.
Step H-4) 200 ml of 1,4-dioxane was taken in a flask, and the flask was cooled in an ice-water bath to saturate ammonia gas. A solution prepared by dissolving 32 g of 4- (4′-bromo-2′-fluorophenyl) benzoyl chloride in 120 ml of 1,4-dioxane was added dropwise thereto. Thereafter, the mixture was stirred for 1 hour at room temperature. The reaction solution was poured into water, and the precipitated crystals were filtered, washed with water, and then dried to obtain 28 g of 4- (4′-bromo-2′-fluorophenyl) benzamide.
Step H-5) A flask was charged with 28 g of 4- (4′-bromo-2′-fluorophenyl) benzamide and 64 g of thionyl chloride and refluxed for 7 hours. Thereafter, thionyl chloride was distilled off under reduced pressure, and the residue was extracted with chloroform, washed twice with water, twice with 5% aqueous potassium hydroxide solution and twice with water, and then chloroform was distilled off. The residue was recrystallized from a mixed solvent of acetone and methanol to obtain 20 g of 4- (4′-bromo-2′-fluorophenyl) bezonitrile.
Step H-6) Into a flask purged with nitrogen, 70 ml of 2M aqueous sodium carbonate solution and 90 ml of benzene are placed, and 13 g of 4- (4′-bromo-2′-fluorophenyl) benzonitrile and 0.5 g of tetrakistriphenylphosphine palladium are placed. A solution prepared by dissolving 7.6 g of 4-methoxyphenylboric acid in 60 ml of ethanol is added dropwise thereto and refluxed for 5 hours. After cooling the reaction solution, the mixture is extracted with chloroform and washed with water, and then chloroform is distilled off. The residue was recrystallized from a mixed solvent of acetone and methanol to obtain 6.6 g of 4 ″ -cyano-3′-fluoro-4-methoxy-p-terfeny. This compound exhibited a liquid crystal phase, and C—N The point was 126.3 ° C and the NI point was 247.3 ° C.
Step H-7) A solution obtained by dissolving 5.7 g of boron tribromide in 40 ml of methylene chloride was placed in a flask, and 3 g of 4 ″ -cyano-3′-fluoro-4-methoxy-p-terphenyl was added to the methylene chloride. A solution dissolved in 120 ml was added dropwise at room temperature, and after stirring overnight, the reaction solution was poured into water, the precipitated crystals were filtered and washed with water, and the obtained crystals were recrystallized from a mixed solvent of acetone and water. As a result, 2 g of 4 ″ -cyano-3′-fluoro-4-hydroxy-p-terphenyl was obtained.
Step H-8) Put 10 ml of chloroform, 2 g of 4 ″ -cyano-3′-fluoro-4-hydroxy-p-terphenyl and 1.4 ml of triethylamine in a flask purged with nitrogen and completely warm in a 40 ° C. water bath. To this, 0.9 g of distilled methacryloyl chloride was slowly added dropwise, and the stirring reaction was continued for ₃ hours.After washing the reaction solution with dil.HClaq., Saturated NaHCO ₃ aq., Water, methanol was added to prevent polymerization. Chloroform and methanol are distilled off, and if crystals appear during distillation, take out and recrystallize with methanol.The product is further purified by silica gel column using chloroform as a developing solvent to obtain the compound of the present invention. 1.6 g of 4 ″ -cyano-3′-fluoro-p-terphenyl-4-yl methacrylate was obtained. This compound showed a liquid crystal phase, and its CN point was 146.2 ° C.

Example 9 Synthesis of Compound (2-a)
Preparation of p-terphenyl-4,4 "-diyl dimethacrylate.
Step I-1) Into a flask purged with nitrogen, 40 ml of a 2M aqueous sodium carbonate solution and 60 ml of benzene are placed, and further 3.8 g of p-dibromobenzene and 0.9 g of tetrakistriphenylphosphine palladium are placed. A solution prepared by dissolving 5 g of 4-methoxyphenylboric acid in 40 ml of ethanol is added dropwise thereto and refluxed for 5 hours. After cooling the reaction solution, the precipitate was filtered out and washed with acetone and water to obtain 3.8 g of 4,4 ″ -dimethoxy-p-terphenyl.
Step I-2) Place 3.8 g of 4,4 "-dimethoxy-p-terphenyl, 20 ml of hydrobromic acid, and 150 ml of acetic acid in an eggplant-shaped flask and reflux for 30 hours. The residue is dissolved in acetone to remove non-dissolved material (raw material). Acetone is distilled off and recrystallized in a mixed solvent of acetone and methanol to obtain 4,4 ″ -dihydroxy-p-terphenyl. 2.0 g was obtained.
Step I-3) 50 ml of chloroform, 2.0 g of 4,4 ″ -dihydroxy-p-terphenyl and 3.2 ml of triethylamine are placed in a flask purged with nitrogen, and dissolved completely in a hot water bath at 40 ° C. Distilled and purified 2.0 ml of methacryloyl chloride was slowly added dropwise, and the reaction was continued for ₃ hours.After washing the reaction solution with dil.HClaq., Saturated NaHCO ₃ aq., Water, methanol was added to prevent polymerization and chloroform and methanol. When crystals appear during distillation, the crystals are taken out, recrystallized from methanol, and purified by a silica gel column using chloroform as a developing solvent to give the compound p-terphenyl-4 of the present invention. , 4 "-diyldimethacrylate 0.4g was obtained. Since this compound thermally polymerizes at around 220 ° C., the melting point could not be measured. The infrared absorption spectrum of this compound is shown in FIG.

Example 10 Synthesis of Compound (2-b)
Preparation of 2'-methyl-p-terphenyl-4,4 "-diyl dimethacrylate.
Step J-1) Into a flask purged with nitrogen, 60 ml of 2M aqueous sodium carbonate solution and 70 ml of benzene are placed, and 5 g of 2,5-dibromotoluene and 0.44 g of tetrakistriphenylphosphine palladium are placed. A solution prepared by dissolving 6.7 g of 4-methoxyphenylboric acid in 45 ml of ethanol is added dropwise thereto and refluxed for 5 hours. After cooling the reaction solution, the precipitate was filtered out, washed with water and then recrystallized from a mixed solvent of acetone and methanol to obtain 2.3 g of 2'-methyl-4,4 "-dimethoxy-p-terphenyl. This compound exhibited a liquid crystal phase, and the CN point was 128.6 ° C. and the NI point was 158.7 ° C.
Step J-2) An eggplant-shaped flask was charged with 2.3 g of 2′-methyl-4,4 ″ -dimethoxy-p-terphenyl, 150 ml of hydrobromic acid and 100 ml of acetic acid, and refluxed for 30 hours. The reaction solution was cooled to room temperature. The residue was recrystallized from a mixed solvent of acetone and water to obtain 1.9 g of 2'-methyl-4,4 "-dihydroxy-p-terphenyl.
Step J-3) Put 18 ml of chloroform, 1.9 g of 2′-methyl-4,4 ″ -dihydroxy-p-terphenyl and 2.9 ml of triethylamine in a flask purged with nitrogen, and completely warm in a 40 ° C. water bath. Then, 1.7 g of distilled and purified methacryloyl chloride was slowly added dropwise thereto, and the stirring reaction was continued for ₃ hours.After washing the reaction solution with dil.HClaq., Saturated NaHCO ₃ aq., Water, methanol was added to prevent polymerization. Put chloroform and methanol into it, remove it when crystals appear during distillation, add methanol to recrystallize it, and purify the product with a silica gel column using chloroform as a developing solvent to obtain compound 2 of the present invention. 1.2 g of '-methyl-p-terphenyl-4,4 "-diyl dimethacrylate was obtained. The melting point of this compound was 131.7 ° C.

Example 11 Synthesis of Compound (2-c)
Preparation of 2'-fluoro-p-terphenyl-4,4 "-diyl dimethacrylate.
Step K-1) Into a flask purged with nitrogen, 100 ml of 2M aqueous sodium carbonate solution and 130 ml of benzene are placed, and further 5.8 g of 1,4-dibromo-2-fluorobenzene and 0.9 g of tetrakistriphenylphosphine palladium are placed. A solution prepared by dissolving 8.4 g of 4-methoxyphenylboric acid in 90 ml of ethanol is added dropwise thereto and refluxed for 11 hours.
After cooling the reaction solution, the mixture is extracted with chloroform and washed with water, and then chloroform is distilled off. The residue was recrystallized from acetone and methanol to obtain 2.3 g of 2′-fluoro-4,4 ″ -dimethoxy-p-terphenyl. This compound showed a liquid crystal phase, and the CN point was 182.7 ° C. Yes, the N-I point was 241.9 ° C.
Step K-2) Place 2'-fluoro-4,4 "-dimethoxy-p-terphenyl 2.3 g, 7.5 ml of hydrobromic acid and 38 ml of acetic acid in an eggplant flask and reflux for 20 hours. Cool the reaction solution to room temperature. The residue was recrystallized in a mixed solvent of acetone and methanol to obtain 2.1 g of 2′-difluoro-4,4 ″ -dihydroxy-p-terphenyl.
Step K-3) Put 23 ml of chloroform, 2.1 g of 2′-fluoro-4,4 ″ -dihydroxy-P-terphenyl and 3.2 ml of triethylamine in a flask purged with nitrogen, and completely warm in a 40 ° C. water bath. is dissolved. was slowly added dropwise of methacryloyl chloride 1.9ml distilling purified thereto, continued stirring for 3 hours the reaction. the reaction solution Dil.HClaq., saturated NaHCO ₃ aq., washed with water, methanol for polymerization inhibition Put chloroform and methanol into it, remove it when crystals appear during distillation, add methanol to recrystallize it, and purify the product with a silica gel column using chloroform as a developing solvent to obtain compound 2 of the present invention. 1.9 g of '-fluoro-p-terphenyl-4,4 "-diyl dimethacrylate was obtained. The melting point of this compound was 186.2 ° C. The infrared absorption spectrum of this compound is shown in FIG.

Example 12 Synthesis of Compound (2-d)
Preparation of 2'-chloro-p-terphenyl-4,4 "-diyl dimethacrylate.
Step L-1) In a flask purged with nitrogen, 52 ml of a 2M sodium carbonate aqueous solution and 70 ml of benzene are placed, and further 5 g of 1,4-dibromo-2-chlorobenzene and 0.44 g of tetrakistriphenylphosphine palladium are placed. A solution prepared by dissolving 6.7 g of 4-methoxyphenylboric acid in 45 ml of ethanol is added dropwise thereto and refluxed for 11 hours. After cooling the reaction solution, the mixture is extracted with chloroform and washed with water, and then chloroform is distilled off. The residue was recrystallized from a mixed solvent of acetone and chloroform to obtain 3 g of 2′-chloro-4,4 ″ -dimethoxy-p-terphenyl. This compound showed a liquid crystal phase, and the CN point was The temperature was 110.2 ° C and the NI point was 163.5 ° C.
Step L-2) An eggplant-shaped flask was charged with 3 g of 2′-chloro-4,4 ″ -dimethoxy-p-terphenyl, 9.2 ml of hydrobromic acid and 47 ml of acetic acid and refluxed for 20 hours. The reaction solution was cooled to room temperature. Thereafter, the mixture was filtered and washed with water, and the residue was recrystallized from a mixed solvent of acetone and chloroform to obtain 2.9 g of 2′-chloro-4,4 ″ -dihydroxy-p-terphenyl.
Step L-3) Put 28 ml of chloroform, 2.9 g of 2′-chloro-4,4 ″ -dihydroxy-P-terphenyl and 3.9 ml of triethylamine in a flask purged with nitrogen, and completely warm in a 40 ° C. water bath. To this solution, 2.3 g of distilled and purified methacryloyl chloride was slowly added dropwise, and the stirring reaction was continued for ₃ hours.After washing the reaction solution with dil.HClaq., Saturated NaHCO ₃ aq., Water, methanol was added to prevent polymerization. Put chloroform and methanol into it, remove it when crystals appear during distillation, add methanol to recrystallize it, and purify the product with a silica gel column using chloroform as a developing solvent to obtain compound 2 of the present invention. 2.0 g of '-chloro-p-terphenyl-4,4 "-diyl dimethacrylate was obtained. The melting point of this compound was 132.6 ° C.

Example 13 Synthesis of Compound (2-e)
Preparation of 2 ', 5'-difluoro-p-terphenyl-4,4 "-diyl dimethacrylate.
Step M-1) Into a flask purged with nitrogen, 84 ml of 2M aqueous sodium carbonate solution and 110 ml of benzene are placed, and further 8.2 g of 1,4-dibromo-2,5-difluorobenzene and 0.8 g of tetrakistriphenylphosphine palladium are placed. A solution prepared by dissolving 11 g of 4-methoxyphenylboric acid in 70 ml of ethanol is added dropwise thereto and refluxed for 11 hours. After cooling the reaction solution, the mixture is extracted with chloroform and washed with water, and then chloroform is distilled off. The residue was recrystallized from a mixed solvent of acetone and chloroform to obtain 1.3 g of 2 ′, 5′-difluoro-4,4 ″ -dimethoxy-p-terphenyl. This compound exhibited a liquid crystal phase, and C The -N point was 194.3 ° C and the NI point was 195.1 ° C.
Step M-2) Place 2 ', 5'-difluoro-4,4 "-dimethoxy-p-terphenyl 1.3 g, 3.9 ml hydrobromic acid, 20 ml acetic acid in an eggplant flask and reflux for 20 hours.
The reaction solution is cooled to room temperature, filtered and washed with water. The residue was recrystallized from a mixed solvent of acetone and chloroform to obtain 1.1 g of 2 ′, 5′-difluoro-4,4 ″ -dihydroxy-p-terphenyl.
Step M-3) Since 12 ml of chloroform, 1.1 g of 2 ′, 5′-difluoro-4,4 ″ -dihydroxy-P-terphenyl and 1.7 ml of triethylamine were placed in a flask purged with nitrogen, and heated in a 40 ° C. water bath. Then, 1.0 g of distilled and purified methacryloyl chloride is slowly added dropwise thereto, and the stirring reaction is continued for ₃ hours.The reaction solution is washed with dil.HClaq., Saturated NaHCO ₃ aq. For this purpose, methanol is added to distill off chloroform and methanol, and if crystals appear during distillation, they are taken out and recrystallized from methanol, and the product is purified on a silica gel column using chloroform as a developing solvent to obtain the present invention. Of the compound 2 ′, 5′-difluoro-p-terphenyl-4,4 ″ -diyl dimethacrylate was obtained. The melting point of this compound was 190.0 ° C. The infrared absorption spectrum of this compound is shown in FIG.

(Examples 19 to 28)
(Display element)
As shown in FIG. 8, an electrode 3 made of a transparent electrode film (for example, ITO film) is formed on glass substrates 1 and 2, and an alignment film made of polyimide or the like is applied thereon. Next, the alignment control layer 4 is formed by rubbing, and the glass substrates 1 and 2 are arranged to face each other with a sealant 5 interposed therebetween, and the compositions shown below are respectively injected between the glass substrates to form a TN type liquid crystal cell. Created.

  In this example, TL202 and MJ91261 (both manufactured by Merck) as the liquid crystal, S-1011 (manufactured by Merck) as the chiral component, S-344 (manufactured by Mitsui Toatsu Dye) as the dichroic dye, polymer precursor The compounds of the present invention and the existing compounds biphenyl-4-yl methacrylate and biphenyl-4,4′-diyl dimethacrylate were used.

  The measured composition was 90.9% of an 8: 2 mixture of TL202 and MJ91261, 0.5% of S-1011 and 3.6% of S-344 as the base liquid crystal, and the polymer precursor to the base liquid crystal Two types were used and mixed 5%. Thus, the kind of polymer | macromolecule used was changed as shown in Table 16, and the composition of Examples 19-28 was prepared.

  This liquid crystal composition was sealed in the above-described empty panel, and the polymer precursor was photopolymerized by ultraviolet irradiation to separate the liquid crystal and the polymer into phases. The measurement was performed at a cell temperature of 20 ° C. and a cell gap of 5 μm.

  The liquid crystal device thus fabricated is placed in an optical system as shown in FIG. 9, a signal whose peak value is changed with a 1 KHz short wave is applied, the reflectance is measured while changing the voltage, and the minimum reflection is obtained. Rate, maximum reflectivity, threshold voltage (voltage value when 5% change from minimum reflectivity to maximum reflectivity, hereinafter referred to as Vth), saturation voltage (when 95% change from minimum reflectivity to maximum reflectivity) Voltage value, hereinafter referred to as Vsat). Also, the time required for the reflectance to increase by 95% when the voltage is turned on as the response speed (the applied voltage is Vth at this time) (rising speed), and the time when the reflectance is reduced by 95% after the voltage is turned off (the rise speed) (Falling speed) was measured. The reflectance was 100% when white fine paper was placed instead of the element. By the way, it has already been investigated that the reflectivity of the element has a viewing angle dependency due to the rotation of the element in which the value of the reflectivity changes depending on the incident direction of light even if the incident angle to the panel is constant. Therefore, in order to match the measurement conditions, the reflectivity shown here is a value obtained when the panel is fixed at an incident angle at which the reflectivity is maximized. Thus, the measurement result of the liquid crystal element was obtained as shown in the following table.

  Examples 19 to 28 are cases in which two types of compounds of a monofunctional group and a bifunctional group were used as the polymer precursor. By using the bifunctional group, Vth and Vsat increase, but there is an effect of preventing the display element from being burned. In Examples 19 to 22, the existing compound biphenyl-4-yl methacrylate was used as a monofunctional group, and the compound of the present invention was used as a bifunctional group. In Example 19, Vth is reduced by 2.3 V and the maximum reflectance is increased by nearly 20% compared to the case where biphenyl-4-yl methacrylate and biphenyl-4,4′-diyl dimethacrylate are used as the polymer precursor. I was able to. In Examples 23 to 27, the compound of the present invention was used for one functional group, and the existing compound biphenyl-4,4'-diyl dimethacrylate was used for the bifunctional group. In this case, Vth is reduced by 2.0 to 2.6 V and the maximum reflectance is increased by 10 to 20% compared to the case where biphenyl-4-yl methacrylate and biphenyl-4,4′-diyl dimethacrylate are used as polymer precursors. I was able to. Example 28 is an example in which the compound of the present invention was used for both monofunctional and bifunctional groups. Compared with the case where biphenyl-4-yl methacrylate and biphenyl-4,4'-diyl dimethacrylate were used as the polymer precursor, Vth was reduced by 2.3 V and the maximum reflectance could be increased by 30%.

As described above, by using the liquid crystal composition of the present invention, it was possible to obtain a liquid crystal display element having a driving voltage lower than that of a conventional liquid crystal element, a large maximum reflectance, and a bright and easy-to-view display. Moreover, although it is compatible with the liquid crystal of the compound of the present invention, there is no problem in preparing the compositions of Examples 19 to 28, and there is sufficient solubility in practical polymer precursor content. I understood it. Furthermore, the specific resistance of the liquid crystal composition contained as a polymer precursor as a display element was 1.5 to 2.0 × 10 ¹¹ Ωcm, and the voltage holding ratio was 98% or more, which was a value with no problem in operation.

  In the above embodiment, a TN liquid crystal display cell is used, but the same effect can be obtained when an MIM element, a TFT element or the like is used.

  Here, the mixing ratio of the liquid crystal is not limited to the above example, but if MJ91261 is increased too much, the specific resistance decreases, which is not preferable. On the other hand, too much TL202 is not preferable because the driving voltage increases and the scattering degree also decreases. Even if another liquid crystal is mixed in this liquid crystal composition at an arbitrary ratio, it functions as a display element.

  The chiral component can be used without being limited to those shown here. As the chiral component, a polymer precursor having a chiral center can also be used. Also, the mixing ratio is not limited to the amount shown here, but if it is added too much, the hysteresis tends to increase.

  The dichroic dye can be used without being limited to those shown here, but if possible, a substance having little absorption in the ultraviolet region is preferable. Of course, it is more preferable if the two-color ratio is high. About the color of a pigment | dye, it can select arbitrarily according to a use. The content of the pigment is not limited to the amount shown here, but if it is too large, the pigment crystallizes or the display becomes dark.

  Although the polymerization initiator was not used here, a photosensitizer can also be used. However, it is used with care because the specific resistance tends to decrease.

  The polymer precursor to be used can be used by mixing other photopolymerizable polymer precursors. The content of the polymer precursor may not be the amount shown here, but if the amount is too small, the scattering degree becomes weak, and if the amount is too large, the driving voltage becomes high.

In this case, ultraviolet rays having a length of 300 nm or longer were used as the polymerization conditions, but polymerization can be performed using light shorter than this. However, since the specific resistance tends to decrease, care must be taken in the polymerization. The light intensity is 3 mW / cm ² , but is not limited to this. When the light intensity is weak, the polymerization time is lengthened, and when the light intensity is strong, the polymerization time is shortened. However, if the light intensity is too strong, the specific resistance tends to decrease. Polymerization is easy when slightly heated (about 20-50 ° C) during photopolymerization.

  As the reflective electrode, any electrode that reflects light, such as aluminum, silver, nickel, and chromium, can be used. The electrode may be transparent, and a reflective background plate may be used on the back side of the element.

  The alignment process may be any method as long as the liquid crystal is aligned.

  As described above, the use of the compound of the present invention makes it possible to produce a liquid crystal element having a lower driving voltage and a higher reflectance than liquid crystal elements using conventional compounds and compositions. Further, the compound of the present invention had good compatibility when mixed with any conventional liquid crystal composition. By using the compound of the present invention, a bright power-saving man-machine interface such as a large-capacity display can be easily and inexpensively manufactured.

The infrared absorption spectrum figure of p-terphenyl-4-yl methacrylate obtained in Example 1 of this invention. Infrared absorption spectrum of 4 煤 | pentyl-p-terphenyl-4-yl methacrylate obtained in Example 2 of the present invention. The infrared absorption spectrum figure of 3'-fluoro-p-terphenyl-4-yl methacrylate obtained in Example 5 of this invention. Infrared absorption spectrum of 4 煤 | ethyl-3'-fluoro-p-terphenyl-4-yl methacrylate obtained in Example 7 of the present invention. The infrared absorption spectrum figure of p-terphenyl-4,4 煤 | diyl dimethacrylate obtained in Example 9 of the present invention. Infrared absorption spectrum of 2'-fluoro-p-terphenyl-4,4 煤 | diyl dimethacrylate obtained in Example 11 of the present invention. Infrared absorption spectrum of 2 ', 5'-difluoro-p-terphenyl-4,4 煤 | diyl dimethacrylate obtained in Example 13 of the present invention. The figure which shows the cross section of the display element in Examples 19-28 of this invention. The figure which shows the optical system at the time of measuring the electro-optical characteristic of the display element in Examples 19-28 of this invention.

Explanation of symbols

1, 2 Glass substrate 3 Electrode 4 Orientation control layer 5 Sealant 6 Dye 7 Liquid crystal 8 Polymer (9 Reflective background plate when no reflective electrode is used)
DESCRIPTION OF SYMBOLS 10 Display element 11 Light source 12 Imaging lens 13 Photomultiplier tube

Claims (4)

In a liquid crystal device comprising a liquid crystal composition comprising a liquid crystal and a polymerized polymer between electrodes, the polymer is

(In the above formula, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ are each a hydrogen atom, a fluorine atom, or A chlorine atom, a methyl group, or a nitrile group, and Y represents a hydrogen atom, a fluorine atom, a chlorine atom, a straight-chain alkyl group having 1 to 10 carbon atoms, or a nitrile group) A liquid crystal element comprising an element. The liquid crystal element according to claim 1, wherein the polymer is

(Wherein R represents a linear alkyl group having 1 to 10 carbon atoms),

(Wherein R represents a linear alkyl group having 1 to 10 carbon atoms), and

A liquid crystal element comprising a component selected from the group consisting of: In a liquid crystal device comprising a liquid crystal composition comprising a liquid crystal and a polymerized polymer between electrodes, the polymer is

(In the above formula, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ are each a hydrogen atom, a fluorine atom, or A liquid crystal element comprising a component represented by a chlorine atom, a methyl group, or a nitrile group. 4. The liquid crystal element according to claim 3, wherein the polymer is

,as well as

The liquid crystal element characterized by including the component represented by these.

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