JP2004157545A - Liquid crystal device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound, wherein a specific resistance value is not lowered even if irradiated with ultraviolet rays, a polymer precursor is good in compatibility with other one or more than two kinds of liquid crystals, a display device polymerized and phase-dispersed is driven at low voltage, and preferable in obtaining the display device that is bright and superior in reflectance. <P>SOLUTION: A liquid crystal device comprises a liquid crystal composition consisting of liquid crystal and polymerized polymer between electrodes. The polymer comprises a component represented by formula 1 (where in the formula, X<SB>1</SB>, X<SB>2</SB>, X<SB>3</SB>, X<SB>4</SB>, X<SB>5</SB>, X<SB>6</SB>, X<SB>7</SB>, X<SB>8</SB>, X<SB>9</SB>, X<SB>10</SB>, X<SB>11</SB>, or X<SB>12</SB>represents hydrogen atom, fluorine atom, chlorine atom, methyl group, or nitrile group, and Y is hydrogen atom, fluorine atom, chlorine atom, 1-10C normal chain alkyl group or nitrile group), or a component represented by formula 2 (where in the formula, X<SB>1</SB>, X<SB>2</SB>, X<SB>3</SB>, X<SB>4</SB>, X<SB>5</SB>, X<SB>6</SB>, X<SB>7</SB>, X<SB>8</SB>, X<SB>9</SB>, X<SB>10</SB>, X<SB>11</SB>, or X<SB>12</SB>represents hydrogen atom, fluorine atom, chlorine atom, methyl group, or nitrile group). <P>COPYRIGHT: (C)2004,JPO

Description

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

In recent years, as a bright display element that does not use a polarizing plate, a display element in which liquid crystal and a polymer are dispersed in each other has attracted attention. The operating principle of this display element utilizes the difference between the refractive indices of the liquid crystal and the polymer. When the refractive index of the liquid crystal and that of the polymer match when an electric field is applied, the display state indicates the transmission state. In this case, the state of scattering is indicated (Table 58-5831, which is called NCAP). A display element of a reverse mode in which the light is transmitted when no electric field is applied and the light is scattered when an electric field is applied has been developed (Mol. Cryst. Liq. Cryst., 198, 357, (1991), which is called a reverse type). For these modes, a method of improving visibility by mixing a dye has also been proposed. Examples of the polymer used in these display elements include a biphenyl derivative, a phenylbenzoate derivative, a compound having a benzene ring and a benzene ring bonded by a Schiff base as a mesogen group, and a compound having a tolane derivative (Japanese Patent Application Laid-Open Nos. 4-227684 and 4-227684). 5-224187, WO 93/08497) are known.

  However, liquid crystal display devices using these polymers have disadvantages such as low specific resistance, high driving voltage, and insufficient reflectivity during scattering. Furthermore, there were some compounds in which the polymer precursor was hardly soluble in the liquid crystal composition.

  The present invention has responded to the request in such a situation, and the purpose is that the specific resistance does not decrease even when irradiated with ultraviolet rays, and the polymer precursor is another one or two or more kinds. An object of the present invention is to provide a novel compound which has good compatibility with liquid crystal, can drive a display element polymerized and phase-dispersed at a low voltage, and is suitable for obtaining a display element which is bright and has excellent reflectance.

  The liquid crystal device of the present invention is a liquid crystal device comprising a liquid crystal composition having a liquid crystal composition comprising a polymer and a liquid crystal polymerized between electrodes, 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 , and X ₁₂ are each a hydrogen atom or 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, or a linear 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 , and X ₁₂ are each a hydrogen atom or a fluorine atom, or (Representing a chlorine atom, a methyl group, or a nitrile group).
The phase-separated liquid crystal and polymer may be aligned by shearing. In a display element in which a liquid crystal and a polymer are aligned and dispersed with each other, the liquid crystal and the polymer may be phase-separated in a gel network. Further, in order to prepare a liquid crystal element in which liquid crystal and a polymer are mutually aligned and dispersed, a terphenyl methacrylate derivative is contained as a precursor for forming a polymer in an amount of 0.1 to 20%, and the terphenyl methacrylate derivative is polymerized. A display element in which a liquid crystal and a polymer are aligned and dispersed with each other is characterized by containing a dichroic dye. In a display element in which liquid crystal and a polymer are aligned and dispersed with respect to 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 orientation direction of the polymer on the front surface side of the display element is different from the orientation direction of the polymer on the back surface side. In a display element in which a liquid crystal and a polymer are aligned and dispersed with respect to each other, one of the two electrodes sandwiching the liquid crystal and the 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 (I) and compound (II) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain compound (III).
Step 2) Compound (IV) and compound (III) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain compound (V).
Step 3) Compound (V) is reacted with hydrobromic acid in acetic acid to obtain compound (VI). However, when a nitrile group is present in the compound (V), the compound is reacted with boron tribromide in dichloromethane to obtain a compound (VI).
Step 4) Compound (VI) is reacted with methacryloyl chloride 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 (I ′) and compound (II ′) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain compound (III ′).
Step 2 ′) Compound (IV ′) is reacted with compound (III ′) in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain compound (V ′).
Step 3 ′) Compound (V ′) is reacted with hydrobromic acid in acetic acid to obtain compound (VI ′). However, when a nitrile group is present in the compound of (V ′), the compound is reacted with boron tribromide in dichloromethane to obtain a compound (VI ′).
Step 4 ′) Compound (VI ′) is reacted with methacryloyl chloride in chloroform in the presence of triethylamine to obtain compound (2).
The above is the general synthesis method, but the synthesis method of each compound changes little by little depending on the substituents present. This is because available (commercially available) raw materials are limited depending on the type of the substituents or the positions where the substituents are bonded, and a difference occurs in reactivity. Next, as a specific synthesis method, a method for synthesizing compounds 1-a to h and 2-a to e will be described.

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

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

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

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

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

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) The compound (2) and the compound (29) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain a compound (30).
Step F-3) Compound (30) is reacted with hydrobromic acid in acetic acid to obtain compound (31).
Step F-4) The compound (31) and the compound (6) are reacted in chloroform in the presence of triethylamine to obtain a compound (1-f).

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 (25) is reacted with alkylcarbonyl chloride in carbon disulfide in the presence of aluminum chloride to obtain compound (32).
Step G-2) Compound (32) is reacted with triethylsilane in trifluoroacetic acid to obtain compound (33).
Step G-3) The compound (2) and the compound (33) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain a compound (34).
Step G-4) Compound (34) is reacted with hydrobromic acid in acetic acid to obtain 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) Compound (25) is reacted with acetyl chloride in carbon disulfide in the presence of aluminum chloride to obtain compound (36).
Step H-2) Compound (36) is reacted with bromine and sodium hydroxide in dioxane to obtain compound (37).
Step H-3) Compound (37) is reacted with thionyl chloride to obtain compound (38).
Step H-4) Compound (38) is reacted with ammonia in dioxane to obtain compound (39).
Step H-5) Compound (39) is reacted with thionyl chloride to obtain compound (40).
Step H-6) The compound (2) and the compound (40) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain a compound (41).
Step H-7) Compound (41) is reacted with boron tribromide in dichloromethane to obtain compound (42).
Step H-8) Compound (42) and compound (6) are reacted in chloroform in the presence of triethylamine to obtain compound (1-h).

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) The compound (2) and the compound (43) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain a compound (44).
Step I-2) Compound (44) is reacted with hydrobromic acid in acetic acid to obtain 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) The compound (2) and the compound (46) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain a compound (47).
Step J-2) Compound (47) is reacted with hydrobromic acid in acetic acid to obtain compound (48).
Step J-3) Compound (48) is reacted with compound (6) 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 (2) and compound (49) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain compound (50).
Step K-2) Compound (50) is reacted with hydrobromic acid in acetic acid to obtain compound (51).
Step K-3) Compound (51) and compound (6) are reacted in chloroform in the presence of triethylamine to obtain compound (2-c).

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) The compound (2) and the compound (52) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain a compound (53).
Step L-2) Compound (53) is reacted with hydrobromic acid in acetic acid to obtain compound (54).
Step L-3) The compound (54) and the compound (6) are reacted in chloroform in the presence of triethylamine to obtain a 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) The compound (2) and the compound (55) are reacted in a mixed solvent of benzene and ethanol in the presence of tetrakistriphenylphosphine palladium and sodium carbonate to obtain a compound (56).
Step M-2) Compound (56) is reacted with hydrobromic acid in acetic acid to obtain compound (57).
Step M-3) Compound (57) and compound (6) are reacted in chloroform in the presence of triethylamine to obtain compound (2-e).

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

(Example 1) [Synthesis of compound (1-a)]
Preparation 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 of 12.5 g of 4-bromoanisole dissolved in 100 ml of tetrahydrofuran was slowly added dropwise while stirring with a magnetic stirrer. After confirming that the reaction proceeded due to heat generation, stirring was continued for 15 hours to prepare a Grignard reagent. A freshly 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 a Grignard reagent was added dropwise thereto, followed by stirring for 20 hours. After the reaction solution was extracted with chloroform and washed three times with water, 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) A flask purged with nitrogen was charged with 50 ml of a 2M aqueous sodium carbonate solution and 70 ml of benzene, and further charged with 8.9 g of 4-bromobiphenyl and 1.1 g of tetrakistriphenylphosphine palladium. A solution of 5.8 g of 4-methoxyphenylboric acid dissolved in 50 ml of ethanol was added dropwise thereto, and the mixture was refluxed for 5 hours. After the reaction solution was extracted with chloroform and washed with water, 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) 3.5 g of 4-methoxy-p-terphenyl, 30 ml of hydrobromic acid and 150 ml of acetic acid were placed in an eggplant-shaped flask and refluxed for 20 hours. After the reaction solution was cooled to room temperature, it was 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) 100 ml of chloroform, 2.4 g of 4-hydroxy-p-terphenyl, and 2 ml of triethylamine are placed in a nitrogen-purged flask and warmed in a water bath at 40 ° C. to be completely dissolved. 1.3 ml of methacryloyl chloride purified by distillation was slowly added dropwise thereto, and stirring was continued for 5 hours. After washing the reaction solution with dil.HClaq., Saturated NaHCO ₃ aq. And water, methanol is added to prevent polymerization, and chloroform and methanol are distilled off. When crystals appeared during the distillation, they were taken out and further recrystallized by adding 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, 3H, CH 3} ), 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, 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) 12.0 g of aluminum chloride and 200 ml of carbon disulfide are placed in a flask, and 9.4 g of pentanoyl chloride is added dropwise with stirring. While the mixture was cooled in an ice-water bath, a solution of 20 g of 4-bromo-p-terphenyl in 800 ml of carbon distillate was added dropwise over 1 hour. After the addition, the mixture was stirred for 3 hours under cooling, the ice water bath was removed, and the mixture was left overnight. Thereafter, the reaction solution was poured into 50 ml of hydrochloric acid and 200 g of ice while stirring. The aqueous layer of the mixture was extracted with chloroform, combined with the oil layer, washed twice with a 10% aqueous sodium hydroxide solution and twice with water, and 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 was added, and the mixture was 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 was added and stirred. The crystals were filtered and washed with water, and the crystals were recrystallized from a mixed solvent of chloroform and acetone to obtain 15.0 g of 4-bromo-4 ″ -pentyl-p-terphenyl.
Step B-3) 1.2 g of magnesium and 50 ml of tetrahydrofuran are placed in a flask purged with nitrogen, and a little ethanol is added while stirring with a magnetic stirrer to activate magnesium. The flask is set in a warm bath at 70 ° C., and a solution of 15.0 g of 4-bromo-4 ″ -pentyl-p-terphenyl in 350 ml of tetrahydrofuran is added by a dropping funnel while warming it to such an extent that precipitation does not occur. A reagent prepared by dissolving 4.5 g of trimethyl borate in 250 ml of tetrahydrofuran was placed in a newly prepared nitrogen-purged flask, cooled to -10 ° C or lower, and a Grignard reagent was slowly added dropwise thereto, followed by stirring for 2 hours. And 4 "-pentyl-p-terphenyl-4-yl boric acid solution. This is used for the next reaction in a solution state.
Step B-4) 3.3 ml of acetic acid was added to the 4 ″ -pentyl-p-terphenyl-4-ylboric acid solution obtained in the reaction of step B-3, and the mixture was stirred. 4.4 ml of aqueous hydrogen peroxide and 3.9 ml of water were added. After the temperature of the reaction solution was returned to room temperature, 500 ml of a 10% aqueous solution of ammonium ferrous sulfate (decahydrate) was added, and the mixture was stirred for 10 minutes, and 500 ml of water was added so that crystals would 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) 30 ml of chloroform, 3.4 g of 4-hydroxy-4 "-pentyl-p-terphenyl and 1.3 ml of triethylamine are placed in a flask purged with nitrogen, and completely dissolved in a hot water bath at 40 ° C. thereto distilled methacryloyl Rukuro slowly dropped ride 0.86ml purification, continued stirring for 3 hours the reaction. the reaction solution Dil.HClaq., saturated NaHCO ₃ aq., washed with water, put the methanol chloroform for polymerization inhibition When crystals appear during the distillation, the crystals are taken out, taken out and recrystallized by adding methanol, and the product is purified by a silica gel column using chloroform as a developing solvent to obtain the compound 4 "-pentyl of the present invention. 1.9 g of -p-terphenyl-4-yl methacrylate were obtained. The melting point of this compound was 223.8 ° C.
FIG. 2 shows the infrared absorption spectrum of this compound.

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 prepared by dissolving 5 g of acetyl chloride in 20 ml of carbon disulfide was stirred for 30 minutes in a salt-ice water bath. And stirred for 2 hours. The reaction is poured with stirring into 40 ml of concentrated hydrochloric acid containing 80 g of ice and the oil layer is separated. The oil layer is washed with 10% aqueous hydrochloric acid and water. Carbon disulfide in the oil 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. over 3 to 4 hours with stirring. 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 sufficiently washed. The obtained crystals were placed in an aqueous solution of 20 g of sodium hydroxide dissolved in 100 ml of water, and the mixture was stirred at room temperature for 3 hours. The crystals were filtered, washed sufficiently 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 keeping 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 a rate keeping the liquid temperature at 15 to 25 ° C. while 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 such a rate that the liquid temperature maintained 20 to 25 ° C. Further, the crystals were dissolved by stirring at a liquid temperature of 20 to 25 ° C. for 1 hour to prepare a diazonium salt. 4 g of copper (I) chloride and 16 ml of concentrated hydrochloric acid were placed in another flask, and the diazonium salt solution prepared above was added dropwise at 20 ° C. or lower while 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 left at 80 ° C. until foaming ceased. 100 ml of water was added to the reaction solution, and extracted with chloroform. After washing with water, chloroform was distilled off. The residue was distilled under reduced pressure to obtain 4.5 g of 4-bromo-4'-chlorobiphenyl.
Step C-4) A flask purged with nitrogen is charged with 23 ml of a 2M aqueous sodium carbonate solution and 30 ml of benzene, and further charged with 4.5 g of 4-bromo-4'-chlorobiphenyl and 0.17 g of tetrakistriphenylphosphine palladium. A solution of 2.6 g of 4-methoxyphenylboric acid in 20 ml of ethanol was added dropwise thereto, and the mixture was refluxed for 5 hours. After the reaction solution is extracted with chloroform and washed with water, chloroform is distilled off. The residue was purified by a silica gel column using chloroform as a developing solvent, and recrystallized from acetone to obtain 2.7 g of 4-chloro-4 ″ -methoxy-p-terphenyl.
Step C-5) 4-Chloro-4 "-methoxy-p-terphenyl (2.7 g), hydrobromic acid (4.6 ml), and acetic acid (46 ml) are placed in an eggplant-shaped flask, and the mixture is 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) 9 ml of chloroform, 2.1 g of 4-chloro-4 ″ -hydroxy-p-terphenyl and 1.5 ml of triethylamine are placed in a flask purged with nitrogen, and completely dissolved in a 40 ° C. water bath. thereto distilled methacryloyl Rukuro slowly dropped ride 0.9g purification, continued stirring for 3 hours the reaction. the reaction solution Dil.HClaq., saturated NaHCO ₃ aq., washed with water, put the methanol chloroform for polymerization inhibition When crystals appear during the distillation, the crystals are removed, taken out, re-crystallized by adding methanol, and the product is purified by a silica gel column using chloroform as a developing solvent to obtain the compound 4 "-chloroform of the present invention. 1.1 g of -p-terphenyl-4-yl methacrylate were obtained. 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, dissolved in 100 ml of water, and stirred.
29 g of bromine was dropped therein. The flask was cooled in an ice-water bath, and a solution of 14.3 g of 4-acetyl-4'-bromobiphenyl in 40 ml of 1,4-dioxane was added dropwise. Thereafter, the flask was 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 placed in a flask, the flask was cooled in an ice-water bath, and ammonia gas was saturated. A solution of 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 dried to obtain 9.7 g of 4- (4'-bromophenyl) benzamide.
Step D-4) 9.7 g of 4- (4′-bromophenyl) benzamide and 20 g of thionyl chloride were placed in a flask and refluxed for 7 hours. Thereafter, thionyl chloride was distilled off under reduced pressure, and the residue was extracted with chloroform and washed twice with water, twice with a 5% aqueous potassium hydroxide solution, and twice with water again, 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) A flask purged with nitrogen is charged with 30 ml of a 2M aqueous sodium carbonate solution and 43 ml of benzene, and further with 6.2 g of 4- (4′-bromophenyl) bezonitrile and 0.24 g of tetrakistriphenylphosphine palladium. A solution of 3.6 g of 4-methoxyphenylboric acid in 29 ml of ethanol was added dropwise thereto, and the mixture was 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 2.8 g of 4 "-cyano-4-methoxy-p-terphenyl.
Step D-6) A solution prepared 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, 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 to obtain 4 ″ 1.7 g of -cyano-4-hydroxy-p-terphenyl were obtained.
Step D-7) 8.7 ml of chloroform, 1.7 g of 4 ″ -cyano-4-hydroxy-p-terphenyl and 1.4 ml of triethylamine are placed in a flask purged with nitrogen, and completely dissolved in a hot water bath at 40 ° C. . slowly added dropwise methacryloyl chloride 1.4g was purified by distillation thereto, continued stirring for 3 hours the reaction. the reaction solution Dil.HClaq., saturated NaHCO ₃ aq., washed with water, put the methanol for polymerization inhibition Chloroform and methanol are distilled off.If crystals appear during the distillation, they are removed, methanol is added and recrystallized, and the product is purified by a silica gel column using chloroform as a developing solvent to obtain the compound 4 ″-of the present invention. 1.2 g of cyano-p-terphenyl-4-yl methacrylate were obtained. The melting point of this compound was 227.2 ° C.

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

(Example 6) [Synthesis of compound (1-f)]
Preparation 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 cooled to room temperature. Thereafter, the mixture was cooled to 0 to 5 ° C., and a solution of 15.3 g of sodium nitrite dissolved 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 a 5N aqueous sodium hydroxide solution was added, and the mixture was extracted with chloroform. After the chloroform layer was washed three times with water, chloroform was distilled off. After the residue was steamed, the residue was purified by hexane-silica gel chromatography to obtain 9.1 g of 4-bromo-2-chlorobiphenyl.
Step F-2) A flask purged with nitrogen is charged with 47 ml of a 2M aqueous sodium carbonate solution and 60 ml of benzene, and further charged with 9.1 g of 4-bromo-2-chlorobiphenyl and 0.34 g of palladium tetrakistriphenylphosphine. A solution of 5.2 g of 4-methoxyphenylboric acid dissolved in 40 ml of ethanol was added dropwise thereto, and the mixture was refluxed for 5 hours. After the reaction solution is extracted with chloroform and washed with water, 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 3'-chloro-4-methoxy-p-terphenyl 6.1 g. The melting point of this compound was 96.0 ° C.
Step F-3) 6.1 g of 3'-chloro-4-methoxy-p-terphenyl, 10 ml of hydrobromic acid and 100 ml of acetic acid are placed in an eggplant-shaped flask and refluxed for 12 hours. After cooling the reaction solution to room temperature, it is filtered and washed with water. The residue was recrystallized from acetone to give 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 nitrogen-purged flask and warmed in a water bath at 40 ° C. to be completely dissolved. Thereto 1.9 g of methacryloyl chloride purified by distillation is slowly dropped, and the stirring reaction is continued for 3 hours. After washing the reaction solution with dil.HClaq., Saturated NaHCO ₃ aq. And water, methanol is added to prevent polymerization, and chloroform and methanol are distilled off. If crystals appear during the distillation, remove them and add methanol to 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 was 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 was stirred in a salt-ice water bath. Was dissolved in 10 ml of 1,1,2,2-tetrachloroethane dropwise over 30 minutes and stirred for 2 hours. The reaction is poured with stirring into 20 ml of concentrated hydrochloric acid containing 50 g of ice and the oil layer is separated. The oil layer is washed with 10% aqueous hydrochloric acid and water. 1,1,2,2-Tetrachloroethane in the oil was distilled off under aspirator reduced pressure, and the residue was distilled under reduced pressure (186 ° C./2 mmHg) to obtain 4′-acetyl-4-bromo-2-fluorobiphenyl 5.3. g was obtained.
Step G-2) While stirring at room temperature a solution of 5.3 g of 4'-acetyl-4-bromo-2-fluorobiphenyl in 15 ml of trifluoroacetic acid, 4.7 g of triethylsilane was slowly added dropwise, and stirring was continued for 5 hours. . The reaction mixture is poured with stirring into 40 ml of a 20% aqueous NaOH solution and 30 g of ice, 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 a 20% aqueous NaOH 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) A flask purged with nitrogen is charged with 40 ml of a 2M aqueous sodium carbonate solution and 60 ml of benzene, and 4.7 g of 4-bromo-4'-ethyl-2-fluorobiphenyl and 0.17 g of tetrakistriphenylphosphine palladium are further charged. A solution obtained by dissolving 2.6 g of 4-methoxyphenylboric acid in 40 ml of ethanol was added dropwise thereto, and the mixture was refluxed for 5 hours. After cooling the reaction mixture, 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. A nematic liquid crystal phase transition point (hereinafter referred to as CN point) of 100.8 ° C.
And 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 was filtered and washed with water, and the residue was 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) A flask purged with nitrogen was charged with 40 ml of chloroform, 2.9 g of 4 ″ -ethyl-3′-fluoro-4-hydroxy-p-terphenyl and 2.1 ml of triethylamine, and warmed in a water bath at 40 ° C. 1.3 ml of distilled and purified methacryloyl chloride is slowly added dropwise, and the reaction is continued for 3 hours with stirring.The reaction solution is washed with dil.HClaq., Saturated NaHCO ₃ aq. After adding methanol, chloroform and methanol are distilled off.When crystals appear during the distillation, the crystals are taken out, re-crystallized by adding methanol, and the product is purified by 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. Melting point was 123.5 ° C. FIG. 4 shows the infrared absorption spectrum of this compound.

The following compounds were obtained in the same manner.
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) In a similar manner to Step G-1, 44 g of 4'-acetyl-4-bromo-2-fluorobiphenyl was obtained.
Step H-2) 55 g of sodium hydroxide was placed in a flask, dissolved in 300 ml of water, and stirred.
84 g of bromine was dropped therein. 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. Thereafter, the flask was slowly heated to 40 ° C. and stirred for 1 hour. This 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 placed in a flask, the flask was cooled in an ice-water bath, and ammonia gas was saturated. 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 at room temperature for 1 hour. The reaction solution was poured into water, and the precipitated crystals were filtered, washed with water, and dried to obtain 28 g of 4- (4′-bromo-2′-fluorophenyl) benzamide.
Step H-5) 28 g of 4- (4'-bromo-2'-fluorophenyl) benzamide and 64 g of thionyl chloride were placed in a flask and refluxed for 7 hours. Thereafter, thionyl chloride was distilled off under reduced pressure, and the residue was extracted with chloroform and washed twice with water, twice with a 5% aqueous potassium hydroxide solution, and twice with water again, 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) 70 ml of a 2M aqueous solution of sodium carbonate and 90 ml of benzene are placed in a nitrogen-purged flask, and 13 g of 4- (4'-bromo-2'-fluorophenyl) bezonitrile and 0.5 g of tetrakistriphenylphosphine palladium are further charged. A solution of 7.6 g of 4-methoxyphenylboric acid in 60 ml of ethanol was added dropwise thereto, and the mixture was 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-terphenyl. This compound showed 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 prepared 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 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, washed with water, and the obtained crystals were recrystallized from a mixed solvent of acetone and water. Thus, 2 g of 4 ″ -cyano-3′-fluoro-4-hydroxy-p-terphenyl was obtained.
Step H-8) 10 ml of chloroform, 2 g of 4 ″ -cyano-3′-fluoro-4-hydroxy-p-terphenyl and 1.4 ml of triethylamine were placed in a flask purged with nitrogen, and completely heated in a 40 ° C. water bath. is dissolved in. was slowly added dropwise methacryloyl chloride 0.9g was purified by distillation thereto, continued stirring for 3 hours the reaction. the reaction solution Dil.HClaq., saturated NaHCO ₃ aq., washed with water, for inhibiting polymerization methanol Is added, and chloroform and methanol are distilled off. When crystals appear during the distillation, the crystals are taken out, recrystallized by adding methanol, and the product is purified by a 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 the CN point was 146.2 ° C.

(Example 9) [Synthesis of compound (2-a)]
Preparation of p-terphenyl-4,4 "-diyldimethacrylate.
Step I-1) A flask purged with nitrogen is charged with 40 ml of a 2M aqueous sodium carbonate solution and 60 ml of benzene, and further charged with 3.8 g of p-dibromobenzene and 0.9 g of tetrakistriphenylphosphine palladium. A solution obtained by dissolving 5 g of 4-methoxyphenylboric acid in 40 ml of ethanol was added dropwise thereto, and the mixture was refluxed for 5 hours. After cooling the reaction solution, the precipitate was taken out by filtration and washed with acetone and water to obtain 3.8 g of 4,4 "-dimethoxy-p-terphenyl.
Step I-2) 3.8 g of 4,4 "-dimethoxy-p-terphenyl, 20 ml of hydrobromic acid and 150 ml of acetic acid are placed in an eggplant-shaped flask and refluxed for 30 hours. The reaction solution is cooled to room temperature and filtered. The residue is dissolved in acetone to remove undissolved substances (raw materials), the acetone is distilled off, and the residue is recrystallized in a mixed solvent of acetone and methanol to give 4,4 "-dihydroxy-p-terphenyl. 2.0 g were 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 nitrogen-purged flask and warmed in a water bath at 40 ° C. to be completely dissolved. was purified by distillation methacryloyl chloride 2.0ml slowly added dropwise, the. reaction mixture to continue stirring for 3 hours the reaction Dil.HClaq., saturated NaHCO ₃ aq., washed with water, chloroform g of methanol for inhibiting polymerization and methanol When crystals appear during the distillation, they are taken out, recrystallized by adding methanol, and the product is purified by a silica gel column using chloroform as a developing solvent to obtain the compound p-terphenyl-4 of the present invention. 0.4 g of 2,4 "-diyldimethacrylate was obtained. The melting point of this compound could not be measured because it was thermally polymerized at around 220 ° C. FIG. 5 shows the infrared absorption spectrum of this compound.

(Example 10) [Synthesis of compound (2-b)]
Preparation of 2'-methyl-p-terphenyl-4,4 "-diyldimethacrylate.
Step J-1) A flask purged with nitrogen is charged with 60 ml of a 2M aqueous sodium carbonate solution and 70 ml of benzene, and further charged with 5 g of 2,5-dibromotoluene and 0.44 g of tetrakistriphenylphosphine palladium. A solution of 6.7 g of 4-methoxyphenylboric acid in 45 ml of ethanol was added dropwise thereto, and the mixture was refluxed for 5 hours. After cooling the reaction solution, the precipitate was collected by filtration, washed with water, and 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, having a CN point of 128.6 ° C. and an NI point of 158.7 ° C.
Step J-2) 2.3 g of 2'-methyl-4,4 "-dimethoxy-p-terphenyl, 150 ml of hydrobromic acid and 100 ml of acetic acid are placed in an eggplant-shaped flask and refluxed for 30 hours. The reaction solution is 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) In a flask purged with nitrogen, 18 ml of chloroform, 1.9 g of 2'-methyl-4,4 "-dihydroxy-p-terphenyl and 2.9 ml of triethylamine were put and completely warmed in a 40 ° C. water bath. is dissolved. was slowly added dropwise of methacryloyl chloride 1.7g was purified by distillation thereto, continued stirring for 3 hours the reaction. the reaction solution Dil.HClaq., saturated NaHCO ₃ aq., washed with water, methanol for polymerization inhibition Then, chloroform and methanol are distilled off, and during the distillation, crystals appear, which are taken out, re-crystallized by adding methanol, and the product is purified by 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 "-diyldimethacrylate were 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 "-diyldimethacrylate.
Step K-1) A flask purged with nitrogen is charged with 100 ml of a 2M aqueous sodium carbonate solution and 130 ml of benzene, and further charged with 5.8 g of 1,4-dibromo-2-fluorobenzene and 0.9 g of tetrakistriphenylphosphine palladium. A solution obtained by dissolving 8.4 g of 4-methoxyphenylboric acid in 90 ml of ethanol was added dropwise thereto, and the mixture was refluxed for 11 hours.
After cooling the reaction mixture, 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 give 2.3 g of 2'-fluoro-4,4 "-dimethoxy-p-terphenyl. This compound showed a liquid crystal phase and had a CN point of 182.7 ° C. Yes, the NI point was 241.9 ° C.
Step K-2) 2.3 g of 2'-fluoro-4,4 "-dimethoxy-p-terphenyl, 7.5 ml of hydrobromic acid, and 38 ml of acetic acid are placed in an eggplant-shaped flask and refluxed for 20 hours. The reaction solution is cooled 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) In a flask purged with nitrogen, 23 ml of chloroform, 2.1 g of 2'-fluoro-4,4 "-dihydroxy-P-terphenyl and 3.2 ml of triethylamine are put and completely warmed 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 Then, chloroform and methanol are distilled off, and during the distillation, crystals appear, which are taken out, re-crystallized by adding methanol, and the product is purified by 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 "-diyldimethacrylate were obtained. The melting point of this compound was 186.2 ° C. FIG. 6 shows the infrared absorption spectrum of this compound.

(Example 12) [Synthesis of compound (2-d)]
Preparation of 2'-chloro-p-terphenyl-4,4 "-diyldimethacrylate.
Step L-1) In a flask purged with nitrogen, 52 ml of a 2M aqueous sodium carbonate solution and 70 ml of benzene are placed, and 5 g of 1,4-dibromo-2-chlorobenzene and 0.44 g of tetrakistriphenylphosphine palladium are further placed. A solution obtained by dissolving 6.7 g of 4-methoxyphenylboric acid in 45 ml of ethanol was added dropwise thereto, and the mixture was refluxed for 11 hours. After cooling the reaction mixture, 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 had a CN point. The temperature was 110.2 ° C, and the NI point was 163.5 ° C.
Step L-2) 3 g of 2'-chloro-4,4 "-dimethoxy-p-terphenyl, 9.2 ml of hydrobromic acid and 47 ml of acetic acid are placed in an eggplant-shaped flask and refluxed for 20 hours. The reaction solution is cooled to room temperature. 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) 28 ml of chloroform, 2.9 g of 2'-chloro-4,4 "-dihydroxy-P-terphenyl and 3.9 ml of triethylamine were placed in a flask purged with nitrogen, and completely heated in a water bath at 40 ° C. is dissolved. was slowly added dropwise of methacryloyl chloride 2.3g was purified by distillation thereto, continued stirring for 3 hours the reaction. the reaction solution Dil.HClaq., saturated NaHCO ₃ aq., washed with water, methanol for polymerization inhibition Then, chloroform and methanol are distilled off, and during the distillation, crystals appear, which are taken out, re-crystallized by adding methanol, and the product is purified by 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 "-diyldimethacrylate were 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 "-diyldimethacrylate.
Step M-1) A flask purged with nitrogen is charged with 84 ml of a 2M aqueous sodium carbonate solution and 110 ml of benzene, and further charged with 8.2 g of 1,4-dibromo-2,5-difluorobenzene and 0.8 g of tetrakistriphenylphosphine palladium. A solution of 11 g of 4-methoxyphenylboric acid dissolved in 70 ml of ethanol was added dropwise thereto, and the mixture was refluxed for 11 hours. After cooling the reaction mixture, 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. The -N point was 194.3 ° C and the NI point was 195.1 ° C.
Step M-2) 1.3 g of 2 ', 5'-difluoro-4,4 "-dimethoxy-p-terphenyl, 3.9 ml of hydrobromic acid and 20 ml of acetic acid are placed in an eggplant-shaped flask and refluxed for 20 hours.
After cooling the reaction solution to room temperature, it is 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) 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 nitrogen-purged flask, and the mixture was placed in a water bath at 40 ° C. Te is completely dissolved. was slowly added dropwise of methacryloyl chloride 1.0g was purified by distillation thereto, continued stirring for 3 hours the reaction. the reaction solution Dil.HClaq., saturated NaHCO ₃ aq., washed with water, the polymerization inhibition For this purpose, methanol is added and chloroform and methanol are distilled off.If crystals appear during the distillation, they are taken out, re-crystallized by adding methanol, and the product is purified by a silica gel column using chloroform as a developing solvent. 1.1 g of the compound 2 ', 5'-difluoro-p-terphenyl-4,4 "-diyldimethacrylate was obtained. The melting point of this compound was 190.0 ° C. FIG. 7 shows the infrared absorption spectrum of this compound.

(Examples 14 to 28)
(Display element)
As shown in FIG. 8, an electrode 3 made of a transparent electrode film (for example, an 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. Further, the glass substrates 1 and 2 are arranged to face each other with the sealant 5 interposed therebetween, and the following compositions are respectively injected between the glass substrates to form a TN type liquid crystal cell. Created.

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

  The measured composition was a base liquid crystal obtained by mixing 90.9% of a mixture of TL202 and MJ91261 at 90.9%, 0.5% of S-1011, and 3.6% of S-344. Was used alone or in combination of 5%. Thus, the compositions of Examples 14 to 28 were prepared by changing the type of the polymer used as shown in Tables 16 to 19.

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

  The liquid crystal device thus manufactured is arranged in an optical system as shown in FIG. 9, a signal having a peak value changed by a short wave of 1 KHz is applied, the reflectance is measured while changing the voltage, and the minimum reflection is measured. Rate, maximum reflectance, threshold voltage (voltage value when 5% changes from minimum reflectance to maximum reflectance, hereinafter referred to as Vth), saturation voltage (when 95% changes from minimum reflectance to maximum reflectance) (Hereinafter, referred to as Vsat). Also, as the response speed, the time required for the reflectance to increase by 95% when the voltage is turned on (the applied voltage at this time is Vth) (rise speed), and the time when the reflectance is reduced by 95% when the voltage is turned off ( Falling speed) was measured. The reflectance was 100% when white high-quality paper was placed in place of the element. By the way, it has already been investigated that the reflectance of the element has a viewing angle dependency due to the rotation of the element such that the value of the reflectance changes depending on the incident direction of light even when the angle of incidence on the panel is fixed. Therefore, in order to adjust the measurement conditions, the reflectance shown here is a value obtained when the panel is fixed at an incident angle at which the reflectance is maximized. Thus, the measurement results of the liquid crystal element were obtained as shown in the following table.

実施例14〜17は高分子前駆体を一種類だけ使用した場合の実施例である。このうち実施例14は既存化合物のビフェニル−４−イルメタクリレートを使用し、実施例15〜17は本発明化合物を使用している。この測定結果を見ると本発明化合物を使用することにより、既存化合物使用に比べ、Ｖth及びＶsatをほぼ同等にしながら、最大反射率を10〜40％ほど増加させることができた。最大反射率の増加は表示素子を作成する場合に重要な特性であり、これを増加できたことの意義は大きい。

Examples 14 to 17 are examples in which only one type of polymer precursor is used. Among them, Example 14 uses the existing compound biphenyl-4-yl methacrylate, and Examples 15 to 17 use the compound of the present invention. According to the measurement results, by using the compound of the present invention, it was possible to increase the maximum reflectance by about 10 to 40% while keeping Vth and Vsat almost equal to those of the existing compound. The increase in the maximum reflectivity is an important characteristic when producing a display element, and it is significant that the increase in the maximum reflectivity is significant.

  In Examples 18 to 28, two kinds of compounds having a monofunctional group and a bifunctional group were used as the polymer precursor. The use of a bifunctional group increases Vth and Vsat, but has the effect of preventing the display element from burning. Example 18 uses the existing compounds biphenyl-4-yl methacrylate and biphenyl-4,4'-diyl dimethacrylate. 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, compared with Example 18, Vth was lowered by 2.3 V, and the maximum reflectance was increased by nearly 20%. In Examples 23 to 27, the compound of the present invention was used as a monofunctional group, and the existing compound biphenyl-4,4'-diyldimethacrylate was used as a bifunctional group. In this case, Vth was reduced by 2.0 to 2.6 V and the maximum reflectance was increased by 10 to 20% as compared with Example 18. Example 28 is an example in which the compound of the present invention is used for both a monofunctional group and a bifunctional group. Compared with Example 18, Vth was reduced by 2.3 V, and the maximum reflectance was increased by 30%.

As described above, by using the liquid crystal composition of the present invention, a liquid crystal display device having a lower driving voltage, a higher maximum reflectance, a brighter display, and a higher visibility than conventional liquid crystal devices could be obtained. In addition, although the compound of the present invention is compatible with the liquid crystal, there is no problem in preparing the compositions of Examples 14 to 28, and there is sufficient solubility in the content of a practical polymer precursor. I understand. 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 having no operational problem.

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

  Here, the mixing ratio of the liquid crystal is not limited to the above example, but if the MJ91261 is increased too much, the specific resistance decreases, which is not preferable. On the other hand, if the amount of TL202 is too large, the driving voltage is increased, and the scattering degree is undesirably reduced. Even if another liquid crystal is mixed with 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, those having a chiral center in the polymer precursor can also be used. Also, the mixing ratio is not limited to the amount shown here, but if the mixing ratio is too large, the hysteresis tends to increase.

  The dichroic dyes can be used without being limited to those shown here, but if possible, those having low absorption in the ultraviolet region are preferable. Of course, a higher two-color ratio is more preferable. The color of the dye can be arbitrarily selected depending on the application. The content of the dye is not limited to the amount shown here, but if it is too large, the dye 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 used may be a mixture of other photopolymerizable polymer precursors. The content of the polymer precursor may not be the amount shown here, but if it is too small, the scattering degree becomes weak, and if it is too large, the driving voltage becomes high.

As the polymerization conditions, ultraviolet rays having a length of 300 nm or longer were used here, but polymerization can be performed using light shorter than this. However, care must be taken in the polymerization because the specific resistance tends to decrease. The light intensity was 3 mW / cm ² , but is not limited to this. If the light intensity is low, the polymerization time is lengthened, and if the light intensity is high, the polymerization time is shortened. However, if the light intensity is too strong, the specific resistance tends to decrease. If heated slightly (about 20-50 ° C) during photopolymerization, it will be easily polymerized.

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

  Regarding the alignment treatment, any method may be used as long as the liquid crystal is aligned.

  As described above, by using the compound of the present invention, a liquid crystal element having a lower driving voltage and a higher reflectance than a liquid crystal element using a conventional compound and composition can be manufactured. 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 produced.

FIG. 2 is an infrared absorption spectrum diagram of p-terphenyl-4-yl methacrylate obtained in Example 1 of the present invention. FIG. 4 is an infrared absorption spectrum diagram of 4 ″ -pentyl-p-terphenyl-4-yl methacrylate obtained in Example 2 of the present invention. FIG. 9 is an infrared absorption spectrum of 3′-fluoro-p-terphenyl-4-yl methacrylate obtained in Example 5 of the present invention. FIG. 9 is an infrared absorption spectrum diagram of 4 ″ -ethyl-3′-fluoro-p-terphenyl-4-yl methacrylate obtained in Example 7 of the present invention. FIG. 11 is an infrared absorption spectrum of p-terphenyl-4,4 ″ -diyldimethacrylate obtained in Example 9 of the present invention. FIG. 14 is an infrared absorption spectrum diagram of 2′-fluoro-p-terphenyl-4,4 ″ -diyldimethacrylate obtained in Example 11 of the present invention. FIG. 14 is an infrared absorption spectrum diagram of 2 ′, 5′-difluoro-p-terphenyl-4,4 ″ -diyldimethacrylate obtained in Example 13 of the present invention. FIG. 29 is a diagram showing a cross section of a display element in Examples 14 to 28 of the present invention. FIG. 29 is a diagram illustrating an optical system when measuring electro-optical characteristics of a display element in Examples 14 to 28 of the present invention.

Explanation of reference numerals

1, 2 glass substrate 3 electrode 4 alignment control layer 5 sealant 6 dye 7 liquid crystal 8 polymer (9 reflective background plate if no reflective electrode is used)
Reference Signs List 10 Display element 11 Light source 12 Imaging lens 13 Photomultiplier tube

Claims (4)

In a liquid crystal element including a liquid crystal composition having a liquid crystal composition including a liquid crystal and a polymerized polymer between electrodes, the polymer includes:

(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 , and X ₁₂ are each a hydrogen atom or 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, or a linear alkyl group having 1 to 10 carbon atoms, or a nitrile group) A liquid crystal element comprising an element. The liquid crystal device according to claim 1, wherein the polymer is:

(In the above formula, R represents a linear alkyl group having 1 to 10 carbon atoms),

(In the above formula, 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 element including a liquid crystal composition having a liquid crystal composition including a liquid crystal and a polymerized polymer between electrodes, the polymer includes:

(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 , and X ₁₂ are each a hydrogen atom or a fluorine atom, or A chlorine atom, a methyl group, or a nitrile group). The liquid crystal device according to claim 3, wherein the polymer is:

,as well as

A liquid crystal device comprising a component represented by the formula:

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