JP5010489B2 - Liquid crystal element - Google Patents

Description

  The present invention relates to a liquid crystal alignment film composition for forming an alignment film for vertically aligning liquid crystals used for a liquid crystal element, and a liquid crystal element.

  As one of the liquid crystal elements, a twisted nematic mode liquid crystal display element is widely used. In recent years, liquid crystal molecules having negative dielectric anisotropy, which are excellent in terms of viewing angle dependency and contrast ratio, are aligned vertically with respect to the substrate, and the liquid crystal molecules are operated in parallel with the substrate by applying a voltage. An alignment mode liquid crystal display element has been actively developed.

  As a method for aligning liquid crystal molecules perpendicularly to a substrate, a method of providing a liquid crystal alignment film made of polyimide on an ITO surface on a glass substrate is disclosed (Patent Document 1: Japanese Patent Application Laid-Open No. 2001-305549, Patent Document). 2: JP 2001-311080 A, Patent Document 3: JP 2002-323701 A, Patent Document 4: JP 2003-295194 A). In these methods, the vertical alignment film is formed by applying a solution obtained by dissolving polyamic acid or the like in an organic solvent with a spinner or the like, then imidizing by a heat treatment at 120 to 250 ° C., and further imparting a vertical alignment ability. It is formed by performing a rubbing process using a felt cloth or the like.

  Also disclosed is a method using a non-rubbing vertical alignment material polyimide resin for aligning liquid crystal molecules perpendicularly to a substrate by a non-rubbing method (Patent Document 5: JP-T-2006-516757). In this method, after a polyamic acid is applied by a spin method, the substrate is pre-baked at 100 ° C. for 30 minutes and imidized by baking at 250 ° C. for 1 hour to form a vertical alignment film.

  Furthermore, a method of providing a vertical alignment film using a liquid crystal aligning agent made of polyamic acid or the like having a conjugated enone structure is disclosed (Patent Document 6: Japanese Patent Application Laid-Open No. 2003-114437). In this method, a solution in which an aligning agent is dissolved in an organic solvent is applied by a spinner or the like, then imidized by a heat treatment at 150 to 250 ° C., and further irradiated with ultraviolet rays at 320 to 450 nm to give vertical alignment ability. ing.

JP 2001-305549 A JP 2001-311080 A JP 2002-323701 A JP 2003-295194 A JP-T-2006-516757 JP 2003-114437 A

  However, in the liquid crystal alignment film formed by the above method, when TFTs or wirings are formed on the substrate surface, the substrate surface has irregularities, and uneven coating due to the irregularities occurs, resulting in uniform liquid crystal There was a problem that an alignment film could not be obtained.

  Moreover, since it heat-processed at 120-250 degreeC after apply | coating with a spinner etc., there existed a problem that it cannot apply to a flexible general purpose plastic film other than a glass substrate as a board | substrate.

  Further, when the alignment ability is expressed by the rubbing method, there is a problem that uneven rubbing occurs due to the presence of irregularities on the substrate surface, the alignment becomes non-uniform, and the liquid crystal alignment is disturbed.

  Furthermore, the rubbing method in which the alignment film is rubbed with a rubbing cloth is liable to generate static electricity and fine dust, and the TFT is also easily damaged, so that display defects are likely to occur.

  Therefore, in order to solve the above-mentioned conventional problems, the present invention does not require a high-temperature heat treatment and a rubbing treatment, and an alignment film composition that can form a uniform alignment film excellent in vertical alignment ability, Another object of the present invention is to provide a liquid crystal element using the liquid crystal alignment film composition and a memory liquid crystal element having bistability.

The above problems are solved by the present invention described below.
(1) providing a "following general formula (1) consisting of triphenylene compound (I) of the liquid crystal alignment film composition you containing at least one kind represented by the liquid crystal alignment film, represented by the general formula (2) A liquid crystal device comprising a liquid crystal composition containing at least one triphenylene compound (II) and a chiral agent ;

（式中、Lは−Ｏ−か−Ｓ−、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、及びＲ₅は同じか異なった炭素数４以上の炭化水素基、Ｒ₆は炭素数４以上の２価の炭化水素基、Ｒ₇は−ＳｉＲ₈Ｒ₉Ｒ₁₀、又は−Ｐ(＝Ｏ)(ＯＨ)₂、Ｒ₈、Ｒ₉、及びＲ₁₀は同じか異なった−Ｃｌ、−ＯＨ、−ＯＣＨ₃、又は−ＯＣ₂Ｈ₅である。）

(In the formula, L is —O— or —S—, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are the same or different hydrocarbon groups having 4 or more carbon atoms, and R ₆ is 4 or more carbon atoms. Divalent hydrocarbon group, R ₇ is —SiR ₈ R ₉ R ₁₀ , or —P (═O) (OH) ₂ , R ₈ , R ₉ , and R ₁₀ are the same or different —Cl, —OH , -OCH _3, or -OC ₂ H _5.)

（式中、Ｒ _1２ 、Ｒ _１３ 、Ｒ _１４ 、Ｒ _１５ 、及びＲ _１６ は同じか異なった炭素数４以上の炭化水素基、Ｒ _１７ は炭素数３以上のアルキル基、アルコキシ基、又はアルコキシカルボニル基、Ｘ _１ 、Ｘ _２ 、Ｘ _３ 、Ｘ _４ 、Ｘ _５ 、Ｘ _６ 、Ｘ _７ 、Ｘ _８ 、Ｘ _９ 、Ｘ _１０ 、Ｘ _４ｎ＋７ 、Ｘ _４ｎ＋８ 、Ｘ _４ｎ＋９ 、及びＸ _{４ｎ＋１０} は水素原子、フッ素原子又は塩素原子、ｎは１以上の整数、Ｑは両末端あるいは片末端に−Ｃ(＝Ｏ)、−Ｏ、−Ｃ（＝Ｏ）−Ｏ又は−Ｏ−Ｃ（＝Ｏ）を有する炭素数４以上の２価の基、Ｑ _ｎ は−Ｃ（＝Ｏ）−Ｏ−、又は−Ｏ−Ｃ（＝Ｏ）−である。）」、
（２）「前記第（１）項に記載の液晶素子を用いることを特徴とする表示装置」。

(Wherein R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ are the same or different hydrocarbon groups having 4 or more carbon atoms, R ₁₇ is an alkyl group, alkoxy group, or alkoxycarbonyl having 3 or more carbon atoms) Group, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X _{4n + 7} , X _{4n + 8} , X _{4n + 9} , and X _{4n + 10} are hydrogen atoms and fluorine atoms Or chlorine atom, n is an integer of 1 or more, Q is the number of carbon atoms having —C (═O), —O, —C (═O) —O or —O—C (═O) at both ends or one end. A divalent group of 4 or more, Q _n is —C (═O) —O—, or —O—C (═O) —.
( 2 ) “a display device using the liquid crystal element according to item ( 1 )”.

  According to the present invention, a liquid crystal alignment film composition that does not require high-temperature heat treatment and rubbing treatment, can form a uniform alignment film excellent in vertical alignment ability, and liquid crystal alignment disorder and display defects In addition, it is possible to provide a liquid crystal element having no bistability and a memory liquid crystal element having bistability.

  The liquid crystal alignment film composition of the present invention is characterized by containing at least one triphenylene compound (I) represented by the following general formula (1).

（式中、Lは−Ｏ−か−Ｓ−、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、及びＲ₅は同じか異なった炭素数４以上の炭化水素基、Ｒ₆は炭素数４以上の２価の炭化水素基、Ｒ₇は−ＳｉＲ₈Ｒ₉Ｒ₁₀、又は−Ｐ(＝Ｏ)(ＯＨ)₂、Ｒ₈、Ｒ₉、及びＲ₁₀は同じか異なった−Ｃｌ、−ＯＨ、−ＯＣＨ₃、又は−ＯＣ₂Ｈ₅である。）

(In the formula, L is —O— or —S—, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are the same or different hydrocarbon groups having 4 or more carbon atoms, and R ₆ is 4 or more carbon atoms. Divalent hydrocarbon group, R ₇ is —SiR ₈ R ₉ R ₁₀ , or —P (═O) (OH) ₂ , R ₈ , R ₉ , and R ₁₀ are the same or different —Cl, —OH , -OCH _3, or -OC ₂ H _5.)

In the triphenylene compound (I) represented by the general formula (1), the compound is an adsorbing moiety that is chemically or physically adsorbed on a transparent electrode such as ITO provided on a glass substrate or a plastic film substrate, that is, a substituent. Π-π stacking with a portion represented by R ₇ in a direction parallel to the substrate surface (that is, a triphenylene group is aligned in a direction perpendicular to the substrate) to form a stable structure, thereby forming a liquid crystal molecule Having an orientation control moiety for controlling the orientation of the compound, ie, substituents R ₁ -L-, R ₂ -L-, R ₃ -L-, R ₄ -L-, R ₅ -L- and -R ₆ -L- The triphenylene moiety.

That is, the substituent R ₇ of the adsorption moiety is —SiR ₈ R ₉ R ₁₀ , or —P (═O) (OH) ₂ , and the substituents R ₈ , R ₉ , and R ₁₀ are the same or different— Cl, —OH, —OCH ₃ , or —OC ₂ H ₅ , which can be chemically or physically adsorbed on a transparent electrode such as ITO provided on a glass substrate or a plastic film substrate.

In addition, the substituents R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ in the orientation control part are the same or different hydrocarbon groups having 4 or more carbon atoms, and are good for hydrocarbons having 3 or less carbon atoms. Vertical alignment ability is not expressed. Specifically, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Examples include nonadecyl group, eicosyl group (icosyl group), heneicosyl group (henicosyl group), docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, and triacontyl group. Preferably, it is a C4-C12 hydrocarbon group.

The substituent R ₆ is a hydrocarbon divalent group having 4 or more carbon atoms that is the same as or different from R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ , and specifically includes a butylene group, a pentylene group, Hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, eicosylene group (icosylene group), hen Examples include an eicosylene group (henicosylene group), a docosylene group, a tricosylene group, a tetracosylene group, a pentacosylene group, a hexacosylene group, a heptacosylene group, an octacosylene group, a nonacosylene group, and a triacontylene group. A hydrocarbon group having 8 to 18 carbon atoms is preferred, and a hydrocarbon group having more carbon atoms than the adjacent substituent R _{5 in} order to effectively adsorb the substituent R ₇ to the substrate.

In addition, the liquid crystal alignment film composition of the present invention can use a plurality of triphenylene compounds (I) represented by the general formula (1), but in order to develop good vertical alignment ability, In order to keep the distance from the substrate constant, it is preferable to use a compound having a hydrocarbon group having the same carbon number as the substituent R ₆ .

The triphenylene compound (I) represented by the general formula (1) can be produced by, for example, the method shown in the following formula without being limited by the linking group L and the substituents R _{1 to} R ₆ . (J. Mater. Chem. 2001, 11, 1612-1617, J. Am. Chem. Soc. 2004, 126, 3856-3867, J. Mater. Chem. 1997, 7, 601-605, Liquid Crystals 2003, 30 571-578, Org. Synth., Coll. Vol VI, 1988, 700, J. Mater. Chem. 1997, 7, 601-605, J. Org. Chem. 1963, 28, 2975-2979, Langmuir 2000, 16 , 7449-7456.)

As the triphenylene compound (I) represented by the general formula (1), for example, the following compounds can be used.
No. 1-8; [18- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -phosphonic acid,
No. 1; 8- (3,6,7,10,11-pentakisbutyloxytriphenylene-2-yloxy) -octadecyl] -phosphonic acid,
No. 2; 8- (3,6,7,10,11-pentakisbutyloxytriphenylene-2-ylthio) -octadecyl] -phosphonic acid,
No. 3; 8- (3,6,7,10,11-pentakisbutylthiotriphenylene-2-yloxy) -octadecyl] -phosphonic acid,
No. 4; 8- (3,6,7,10,11-pentakisbutylthiotriphenylene-2-ylthio) -octadecyl] -phosphonic acid,
No. 5; [18- (3,6,7,10,11-pentakispentyloxytriphenylene-2-yloxy) -octadecyl] -phosphonic acid,
No. 6; [18- (3,6,7,10,11-pentakispentyloxytriphenylene-2-ylthio) -octadecyl] -phosphonic acid,
No. 7; [18- (3,6,7,10,11-pentakispentylthiotriphenylene-2-yloxy) -octadecyl] -phosphonic acid,
No. 8; [18- (3,6,7,10,11-pentakispentylthiotriphenylene-2-ylthio) -octadecyl] -phosphonic acid.

  No. 9-12; 2; [18- (3,6,7,10,11-pentakishexyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -phosphonic acid.

  No. 13-16; [18- (3,6,7,10,11-pentakisheptyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -phosphonic acid.

  No. 17-20; [18- (3,6,7,10,11-pentakisoctyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -phosphonic acid.

  No. 21-24; [18- (3,6,7,10,11-pentakisnonyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -phosphonic acid.

  No. 25-28; [18- (3,6,7,10,11-pentakisdecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -phosphonic acid.

  No. 29-32; [18- (3,6,7,10,11-pentakisundecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -phosphonic acid.

  No. 33-36; [18- (3,6,7,10,11-pentakisdodecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -phosphonic acid.

  No. 37-40; [18- (3,6,7,10,11-pentakistridecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -phosphonic acid.

  No. 41-44; [18- (3,6,7,10,11-pentakistetradecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -phosphonic acid.

  No. 45-48; [16- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -phosphonic acid.

  No. 49-52; [16- (3,6,7,10,11-pentakispentyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -phosphonic acid.

  No. 53-56; [16- (3,6,7,10,11-pentakishexyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -phosphonic acid.

  No. 57-60; [16- (3,6,7,10,11-pentakisheptyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -phosphonic acid.

  No. 61-64; [16- (3,6,7,10,11-pentakisoctyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -phosphonic acid.

  No. 65-68; [16- (3,6,7,10,11-pentakisnonyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -phosphonic acid.

  No. 69-72; [16- (3,6,7,10,11-pentakisdecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -phosphonic acid.

  No. 73-76; [16- (3,6,7,10,11-pentakisundecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -phosphonic acid.

  No. 77-80; [16- (3,6,7,10,11-pentakisdodecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -phosphonic acid.

  No. 81-84; [14- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -phosphonic acid.

  No. 85-88; [14- (3,6,7,10,11-pentakispentyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -phosphonic acid.

  No. 89-92; [14- (3,6,7,10,11-pentakishexyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -phosphonic acid.

  No. 93-96; [14- (3,6,7,10,11-pentakisheptyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -phosphonic acid.

  No. 97-100; [14- (3,6,7,10,11-pentakisoctyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -phosphonic acid.

  No. 101-104; [14- (3,6,7,10,11-pentakisnonyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -phosphonic acid.

  No. 105-108; [14- (3,6,7,10,11-pentakisdecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -phosphonic acid.

  No. 109-112; [12- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -phosphonic acid.

  No. 113-116; [12- (3,6,7,10,11-pentakispentyl (oxy or thio) triphenylene-2-yl (oxy or thio))-dodecyl] -phosphonic acid.

  No. 117-120; [12- (3,6,7,10,11-pentakishexyl (oxy or thio) triphenylene-2-yl (oxy or thio))-dodecyl] -phosphonic acid.

  No. 121-124; [12- (3,6,7,10,11-pentakisheptyl (oxy or thio) triphenylene-2-yl (oxy or thio))-dodecyl] -phosphonic acid.

  No. 125-128; [12- (3,6,7,10,11-pentakisoctyl (oxy or thio) triphenylene-2-yl (oxy or thio))-dodecyl] -phosphonic acid.

  No. 129-132; [11- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-undecyl] -phosphonic acid.

  No. 133-136; [11- (3,6,7,10,11-pentakispentyl (oxy or thio) triphenylene-2-yl (oxy or thio))-undecyl] -phosphonic acid.

  No. 137-140; [11- (3,6,7,10,11-pentakishexyl (oxy or thio) triphenylene-2-yl (oxy or thio))-undecyl] -phosphonic acid.

  No. 141-144; [11- (3,6,7,10,11-pentakisheptyl (oxy or thio) triphenylene-2-yl (oxy or thio))-undecyl] -phosphonic acid.

  No. 145-148; [8- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octyl] -phosphonic acid.

  No. 149-152; [8- (3,6,7,10,11-pentakispentyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octyl] -phosphonic acid.

No. 153-176; [18- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -tri (chloro, methoxy or ethoxy) silane That is,
No. 153; [18- (3,6,7,10,11-pentakisbutyloxytriphenylene-2-yloxy) -octadecyl] -trichlorosilane,
No. 154; [18- (3,6,7,10,11-pentakisbutyloxytriphenylene-2-yloxy) -octadecyl] -trimethoxysilane,
No. 155; [18- (3,6,7,10,11-pentakisbutyloxytriphenylene-2-yloxy) -octadecyl] -triethoxysilane,
No. 156; [18- (3,6,7,10,11-pentakisbutyloxytriphenylene-2-ylthio) -octadecyl] -trichlorosilane,
No. 157; [18- (3,6,7,10,11-pentakisbutyloxytriphenylene-2-ylthio) -octadecyl] -trimethoxysilane,
No. 158; [18- (3,6,7,10,11-pentakisbutyloxytriphenylene-2-ylthio) -octadecyl] -triethoxysilane,
No. 159; [18- (3,6,7,10,11-pentakisbutylthiotriphenylene-2-yloxy) -octadecyl] -trichlorosilane,
No. 160; [18- (3,6,7,10,11-pentakisbutylthiotriphenylene-2-yloxy) -octadecyl] -trimethoxysilane,
No. 161; [18- (3,6,7,10,11-pentakisbutylthiotriphenylene-2-yloxy) -octadecyl] -triethoxysilane,
No. 162; [18- (3,6,7,10,11-pentakisbutylthiotriphenylene-2-ylthio) -octadecyl] -trichlorosilane,
No. 163; [18- (3,6,7,10,11-pentakisbutylthiotriphenylene-2-ylthio) -octadecyl] -trimethoxysilane,
No. 164; [18- (3,6,7,10,11-pentakisbutylthiotriphenylene-2-ylthio) -octadecyl] -triethoxysilane,
No. 165; [18- (3,6,7,10,11-pentakispentyloxytriphenylene-2-yloxy) -octadecyl] -trichlorosilane,
No. 166; [18- (3,6,7,10,11-pentakispentyloxytriphenylene-2-yloxy) -octadecyl] -trimethoxysilane,
No. 167; [18- (3,6,7,10,11-pentakispentyloxytriphenylene-2-yloxy) -octadecyl] -triethoxysilane,
No. 168; [18- (3,6,7,10,11-pentakispentyloxytriphenylene-2-ylthio) -octadecyl] -trichlorosilane,
No. 169; [18- (3,6,7,10,11-pentakispentyloxytriphenylene-2-ylthio) -octadecyl] -trimethoxysilane,
No. 170; [18- (3,6,7,10,11-pentakispentyloxytriphenylene-2-ylthio) -octadecyl] -triethoxysilane,
No. 171; [18- (3,6,7,10,11-pentakispentylthiotriphenylene-2-yloxy) -octadecyl] -trichlorosilane,
No. 172; [18- (3,6,7,10,11-pentakispentylthiotriphenylene-2-yloxy) -octadecyl] -trimethoxysilane,
No. 173; [18- (3,6,7,10,11-pentakispentylthiotriphenylene-2-yloxy) -octadecyl] -triethoxysilane,
No. 174; [18- (3,6,7,10,11-pentakispentylthiotriphenylene-2-ylthio) -octadecyl] -trichlorosilane,
No. 175; [18- (3,6,7,10,11-pentakispentylthiotriphenylene-2-ylthio) -octadecyl] -trimethoxysilane,
No. 176; [18- (3,6,7,10,11-pentakispentylthiotriphenylene-2-ylthio) -octadecyl] -triethoxysilane.

  No. 177-188; [18- (3,6,7,10,11-pentakishexyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 189-200; [18- (3,6,7,10,11-pentakisheptyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 201-212; [18- (3,6,7,10,11-pentakisoctyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 213-224; [18- (3,6,7,10,11-pentakisnonyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 225-236; [18- (3,6,7,10,11-pentakisdecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 237-248; [18- (3,6,7,10,11-pentakisundecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -tri (chloro, methoxy or ethoxy) Silane.

  No. [18- (3,6,7,10,11-pentakisdodecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 261-272; [18- (3,6,7,10,11-pentakistridecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -tri (chloro, methoxy or ethoxy) Silane.

  No. 273-284; [18- (3,6,7,10,11-pentakistetradecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octadecyl] -tri (chloro, methoxy or ethoxy) Silane.

  No. 285-296; [16- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 297-308; [16- (3,6,7,10,11-pentakispentyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 309-320; [16- (3,6,7,10,11-pentakishexyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. [16- (3,6,7,10,11-pentakisheptyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 333-344; [16- (3,6,7,10,11-pentakisoctyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 345-356; [16- (3,6,7,10,11-pentakisnonyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 357-368; [16- (3,6,7,10,11-pentakisdecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 369-380; [16- (3,6,7,10,11-pentakisundecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -tri (chloro, methoxy or ethoxy) Silane.

  No. 381-392; [16- (3,6,7,10,11-pentakisdodecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-hexadecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 393-414; [14- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 415-426; [14- (3,6,7,10,11-pentakispentyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 427-438; [14- (3,6,7,10,11-pentakishexyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 439-450; [14- (3,6,7,10,11-pentakisheptyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 451-462; [14- (3,6,7,10,11-pentakisoctyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 463-474; [14- (3,6,7,10,11-pentakisnonyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 475-486; [14- (3,6,7,10,11-pentakisdecyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 487-498; [12- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-tetradecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 499-510; [12- (3,6,7,10,11-pentakispentyl (oxy or thio) triphenylene-2-yl (oxy or thio))-dodecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 511-522; [12- (3,6,7,10,11-pentakishexyl (oxy or thio) triphenylene-2-yl (oxy or thio))-dodecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 523-534; [12- (3,6,7,10,11-pentakisheptyl (oxy or thio) triphenylene-2-yl (oxy or thio))-dodecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 535-546; [12- (3,6,7,10,11-pentakisoctyl (oxy or thio) triphenylene-2-yl (oxy or thio))-dodecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 547-558; [11- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-undecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 559-570; [11- (3,6,7,10,11-pentakispentyl (oxy or thio) triphenylene-2-yl (oxy or thio))-undecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 571-582; [11- (3,6,7,10,11-pentakishexyl (oxy or thio) triphenylene-2-yl (oxy or thio))-undecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. [11- (3,6,7,10,11-pentakisheptyl (oxy or thio) triphenylene-2-yl (oxy or thio))-undecyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 595-606; [8- (3,6,7,10,11-pentakisbutyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octyl] -tri (chloro, methoxy or ethoxy) silane .

  No. 607-618; [8- (3,6,7,10,11-pentakispentyl (oxy or thio) triphenylene-2-yl (oxy or thio))-octyl] -tri (chloro, methoxy or ethoxy) silane Etc.

Furthermore, as the liquid crystal alignment film composition of the present invention, in addition to the triphenylene compound (I) represented by the general formula (1), a compound having a linear hydrocarbon group having a substituent R ₇ at the terminal ( A) can also be mixed and used. Examples of the linear hydrocarbon group having a substituent R ₇ at the terminal include those represented by the general formula R ₁₁ -R ₇ (wherein R ₁₁ is a linear hydrocarbon group having 4 or more carbon atoms, and R ₇ is the same as described above. And a compound having a linear hydrocarbon group represented by

In the compound (A) represented by the general formula R ₁₁ -R ₇ , the compound is applied to a transparent electrode such as ITO provided on a glass substrate or a plastic film substrate in the same manner as the compound represented by the general formula (1). It consists of a chemically or physically adsorbing part, that is, a part represented by the substituent R ₇ and a part aggregated by van der Waals force or the like, that is, a part represented by the substituent R ₁₁ . The substituent R ₁₁ aggregates with the portion represented by the substituent R ₆ of the triphenylene compound (I) represented by self and the general formula (1), and thus has a function of making the structure of the liquid crystal alignment film more stable.

Specific examples of the substituent R ₁₁ include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group , Octadecyl group, nonadecyl group, eicosyl group (icosyl group), heneicosyl group (henicosyl group), docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, and triacontyl group Can be mentioned. Preferably, in order to develop good vertical alignment ability, an alkyl group having the same or less carbon number as the substituent R ₆ defining the distance between the triphenylene moiety and the substrate in the general formula (1) Is preferred.

A preferable mixing ratio of the triphenylene compound (I) represented by the general formula (1) and the compound (A) represented by R ₁₁ -R ₇ is 1: 0.1 to 1:40 in terms of molar ratio, More preferably, the molar ratio is 1: 0.5 to 1:10.

Moreover, in order to obtain a uniform alignment film, the liquid crystal alignment film composition of the present invention comprises a triphenylene compound (I) represented by general formula (1) or a triphenylene compound represented by general formula (1) ( I) and the compound (A) represented by the general formula R ₁₁ -R ₇ are preferably used as a solution dissolved in an organic solvent that dissolves the alignment film. It is formed by washing and drying at room temperature. Even if heat treatment or rubbing treatment is not performed, a uniform liquid crystal alignment film having excellent vertical alignment is obtained.

  As an organic solvent, the triphenylene compound (I) represented by the general formula (1) is dissolved, and an organic solvent having a low boiling point is preferable in terms of drying.

  In addition, a liquid crystal element using the liquid crystal alignment film composition of the present invention is immersed in a glass substrate or a plastic substrate provided with electrodes such as ITO in the liquid crystal alignment composition as described above, and then washed and dried. It can be produced by forming an alignment film on ITO, arranging the electrode surfaces facing each other, producing a display cell having a certain distance between the electrode surfaces by a spacer, and injecting a liquid crystal composition. A known composition can be used as the liquid crystal composition. Any liquid crystal composition having a different dielectric anisotropy can be used.

  A cross section of a typical liquid crystal element of the present invention is shown in FIG. The liquid crystal element includes a substrate 1, an electrode 2, a liquid crystal alignment film 3, a sealing material 4, a liquid crystal composition 5, a spacer 6, and a drive circuit 7. Depending on the display method, an optical film such as a polarizing plate or a reflecting plate can be used.

  Furthermore, the liquid crystal element of the present invention is provided with an alignment film made of a liquid crystal alignment film composition containing at least one triphenylene compound (I) represented by the above general formula (1), and the following general formula (2): A liquid crystal composition containing at least one triphenylene compound (II) represented and a chiral agent is used.

（ここで、Ｒ_1２、Ｒ_１３、Ｒ_１４、Ｒ_１５、及びＲ_１６は同じか異なった炭素数４以上の炭化水素基、Ｒ_１７は炭素数３以上のアルキル基、アルコキシ基、又はアルコキシカルボニル基、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４、Ｘ_５、Ｘ_６、Ｘ_７、Ｘ_８、Ｘ_９、Ｘ_１０、Ｘ_４ｎ＋７、Ｘ_４ｎ＋８、Ｘ_４ｎ＋９、及びＸ_{４ｎ＋１０}は水素原子、フッ素原子又は塩素原子、ｎは１以上の整数、Ｑは両末端あるいは片末端に−Ｃ(＝Ｏ)、−Ｏ、−Ｃ（＝Ｏ）−Ｏ又は−Ｏ−Ｃ（＝Ｏ）を有する炭素数４以上の２価の基、Ｑ_ｎは−Ｃ（＝Ｏ）−Ｏ−、又は−Ｏ−Ｃ（＝Ｏ）−である。）

(Wherein R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ are the same or different hydrocarbon groups having 4 or more carbon atoms, R ₁₇ is an alkyl group, alkoxy group, or alkoxycarbonyl having 3 or more carbon atoms) Group, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X _{4n + 7} , X _{4n + 8} , X _{4n + 9} , and X _{4n + 10} are hydrogen atoms and fluorine atoms Or chlorine atom, n is an integer of 1 or more, Q is the number of carbon atoms having —C (═O), —O, —C (═O) —O or —O—C (═O) at both ends or one end. 4 or more divalent groups, Q _n is —C (═O) —O— or —O—C (═O) —.

  The triphenylene compound (II) represented by the general formula (2) contained in the liquid crystal composition of the liquid crystal element of the present invention comprises a disc-like discotic liquid crystalline triphenylene portion and a rod-like calamitic liquid crystalline aromatic ester portion. .

  The discotic discotic liquid crystalline triphenylene portion has a disk surface due to interaction with the alignment film surface triphenylene group existing on the outermost surface of the liquid crystal alignment film made of the triphenylene compound (I) represented by the general formula (1). Alignment is performed in a direction parallel to the normal direction of the alignment film plane. Therefore, the rod-shaped calamitic liquid crystalline aromatic ester portion can be aligned from a direction parallel to the normal direction of the alignment film plane to a direction close to vertical. As a result, the cholesteric (chiral nematic) liquid crystal composition in the liquid crystal device has a homeotropic alignment when the triphenylene compound (II) is aligned in a direction parallel to the normal direction of the alignment film plane and the spiral is broken. When the nematic phase is (vertically aligned) and the triphenylene compound (II) is aligned in a direction perpendicular to the normal direction of the alignment film plane, the cholesteric phase in which the helical axis is aligned in a direction parallel to the hard film plane Show. That is, the change in the orientation of the triphenylene compound (II) existing at the interface of the alignment film causes a phase change in the entire liquid crystal phase.

  As the chiral agent, a known chiral agent can be used, which imparts a twist to the alignment of liquid crystal molecules. By adding a chiral agent to a liquid crystal composition containing at least one type of triphenylene compound (II) represented by the general formula (2), a specific phenomenon appears. That is, bistability is exhibited.

  Therefore, a liquid crystal alignment film comprising a liquid crystal alignment film composition containing at least one triphenylene compound (I) represented by the general formula (1) of the present invention is provided, and the triphenylene represented by the general formula (2) A bistable liquid crystal element using a liquid crystal composition containing at least one kind of compound (II) and a chiral agent can maintain a display state without consuming electric power. It can be used as a display.

  In order to develop this unique bistability, 1 to 100 μmol of the triphenylene compound (II) represented by the general formula (2) and 1 g of the liquid crystal composition, and the helical pitch is 80 to the cell thickness. It is preferable to use a chiral agent in an amount of ˜135%. More preferably, 5 to 50 μmol of the triphenylene compound (II) represented by the general formula (2) and a chiral agent in such an amount that the helical pitch is 90 to 120% with respect to the cell thickness are used.

R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ of the discotic discotic liquid crystalline triphenylene portion of the compound (II) are the same or different hydrocarbon groups having 4 or more carbon atoms, and the number of carbon atoms is With hydrocarbons of 3 or less, bistability does not appear because the discotic liquid crystalline triphenylene part aggregates in the liquid crystal composition or the disk surface does not align in the direction parallel to the normal direction of the alignment film plane. . Specifically, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Examples include nonadecyl group, eicosyl group (icosyl group), heneicosyl group (henicosyl group), docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, and triacontyl group. Preferably, it is a C4-C12 hydrocarbon group.

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , and X ₆ in the discotic liquid crystalline triphenylene moiety are a hydrogen atom, a fluorine atom, or a chlorine atom.

X ₇ , X ₈ , X ₉ , X ₁₀ , X _{4n + 7} , X _{4n + 8} , X _{4n + 9} , and X _{4n + 10} of the rod-like calamitic liquid crystalline aromatic ester part are a hydrogen atom, a fluorine atom or a chlorine atom, and n is 1 or more Is an integer. By making at least one of the substituent group consisting of X ₇ , X ₈ , X ₉ , X ₁₀ , X _{4n + 7} , X _{4n + 8} , X _{4n + 9} , and X _{4n + 10} a fluorine atom or a chlorine atom, preferably a chlorine atom, The triphenylene compound (II) represented by the general formula (2) exhibits two-frequency drive characteristics. That is, the rod-shaped calamitic liquid crystalline aromatic ester portion exhibits positive dielectric anisotropy under a low frequency voltage of several kHz or less, and negative dielectric anisotropy under a high frequency voltage of several tens kHz or more. Indicates. Therefore, by changing the frequency of the applied voltage, the rod-like calamitic liquid crystalline aromatic ester portion of the triphenylene compound (II) represented by the general formula (2) is in a planar alignment (horizontal alignment) state and a homeotropic alignment ( It is possible to switch between the state of (vertical alignment).

Q, which is a linking group between the discotic liquid crystalline triphenylene moiety and the calamitic liquid crystalline aromatic ester moiety, is —C (═O), —O, —C (═O) —O or —O at both ends or one end. A divalent group having 4 or more carbon atoms having —C (═O), specifically, —C (═O) — (CH ₂ ) _S — in which the right end is bonded to a calamitic liquid crystalline aromatic ester moiety. C (= O)-(s is an integer of 2 or more),
_{-C (= O) - (CH} 2) S -C (= O) -O- (s is an integer of 2 or more),
_{-C (= O) - (CH} 2) S -O-C (= O) - (s is an integer of 2 or more),
_{-C (= O) - (CH} 2) t -O- (t is an integer of 3 or more),
_{-C (= O) - (CH} 2) t - (t is an integer of 3 or more),
_{- (CH 2) t -C (} = O) - (t is an integer of 3 or more),
_{- (CH 2) t -C (} = O) -O- (t is an integer of 3 or more),
_{- (CH 2) t -O-} C (= O) - (t is an integer of 3 or more),
_{- (CH 2) u -O- (} u is an integer of 4 or more), or _{- (CH 2) u - (} u is an integer of 4 or more)
Etc. Since electric field responsiveness will fall when a coupling group is too long, s, t, and u are preferably 2-14, 3-15, and 4-16, respectively.

Q _n of the calamitic liquid crystalline aromatic ester portion is —C (═O) —O— or —O—C (═O) —. n is an integer of 1 or more. Since the compatibility with the liquid crystal composition decreases as the molecular weight of the calamitic liquid crystalline aromatic ester portion increases, n is preferably 1 to 6, and more preferably 1 to 3.

R ₁₇ is an alkyl group having 3 or more carbon atoms, an alkoxy group, or an alkoxycarbonyl group, specifically, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group (icosyl group), heneicosyl group (henicosyl group), docosyl group, tricosyl group, tetracosyl group, Alkyl groups such as pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, and triacontyl group,
Propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyl Oxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, eicosyloxy group (icosyloxy group), heneicosyloxy group (henicosyloxy group), docosyloxy group, tricosyloxy group, Alkyloxy groups such as tetracosyloxy group, pentacosyloxy group, hexacosyloxy group, heptacosyloxy group, octacosyloxy group, nonacosyloxy group, and triacontyloxy group,
Propyloxycarbonyl group, butyloxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, undecyloxycarbonyl group, dodecyloxycarbonyl group , Tridecyloxycarbonyl group, tetradecyloxycarbonyl group, pentadecyloxycarbonyl group, hexadecyloxycarbonyl group, heptadecyloxycarbonyl group, octadecyloxycarbonyl group, nonadecyloxycarbonyl group, eicosyloxycarbonyl group (icosyl) Oxycarbonyl group), henecosyloxycarbonyl group (henicosyloxycarbonyl group), docosyloxycarbonyl group, tricosyloxy Carbonyl group, tetracosyloxycarbonyl group, pentacosyloxycarbonyl group, hexacosyloxycarbonyl group, heptacosyloxycarbonyl group, octacosyloxycarbonyl group, nonacosyloxycarbonyl group, and triacontyloxycarbonyl And alkyloxycarbonyl group such as a group. Preferably, it is a C3-C12 alkyl group, an alkoxy group, or an alkoxycarbonyl group.

The triphenylene compound (II) represented by the general formula (2) can be produced, for example, by the method shown in the following formula. (Chem. Mater. 2000, 12, 782-789, J. Mater. Chem. 1993, 3, 241-245, J. Am. Chem. Soc. 2004, 126, 1161-1167, Chem. Mater. 2000, 12 , 782-789, Synthesis 1981, 396-397, J. Am. Chem. Soc. 1998, 120, 2908-2918
Tetrahedron Lett. See 1993, 34, 1639-1642. )

As the triphenylene compound (II) represented by the general formula (2),
No. 1000-1039; (2 or 3)-(chloro or fluoro) -4- [4- (3,6,7,10,11-pentaboxy-triphenylene-2-yloxy) butoxy] -benzoic acid 4- (propyl Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenyl ester,
That is, no. 1000-1009; 2-chloro-4- [4- (3,6,7,10,11-pentaboxy-triphenylene-2-yloxy) -butoxy] -benzoic acid 4- (propyl, butyl, pentyl, hexyl, Heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenyl ester,
No. 1010-1019; 2-fluoro-4--4- [4- (3,6,7,10,11-pentaboxy-triphenylene-2-yloxy) -butoxy] -benzoic acid 4- (propyl, butyl, pentyl, hexyl) , Heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenyl ester,
No. 1020-1029; 3-chloro-4- [4- (3,6,7,10,11-pentaboxy-triphenylene-2-yloxy) -butoxy] -benzoic acid 4- (propyl, butyl, pentyl, hexyl, Heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenyl ester,
No. 1030-1039; 3-Fluoro-4- [4- (3,6,7,10,11-pentaboxy-triphenylene-2-yloxy) -butoxy] -benzoic acid 4- (propyl, butyl, pentyl, hexyl) , Heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenyl ester.

  No. 1040-1439; (2 or 3)-(chloro or fluoro) -4- [4- (3,6,7,10,11-pentaboxy-triphenylene-2-yloxy)-(pentyl, hexyl, heptyl, octyl) , Nonyl, decyl, undecyl, dodecyl, tridecyl, or tetradecyl) oxy] -benzoic acid 4- (propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenyl ester.

  No. 1440-1759; (2 or 3)-(chloro or fluoro) -4- [4-3,6,7,10,11-pentakis- (pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl or tetradecyl) oxy-triphenylene-2-yloxy) -butoxy] -benzoic acid 4- (propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) -phenyl ester.

  No. 1760-2559; (2 or 3)-(chloro or fluoro) -4- [4-3,6,7,10,11-pentakis- (pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) ) Oxy-triphenylene-2-yloxy)-(pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, or tetradecyl) oxy] -benzoate 4- (propyl, butyl, pentyl, hexyl, heptyl, Octyl, nonyl, decyl, undecyl, or dodecyl) -phenyl ester.

  No. 2560-2599; (2 or 3)-(chloro or fluoro) -4- [4-3,6,7,10,11-pentaboxy-triphenylene-2-yloxy) -butoxy] -benzoic acid 4- (4 -(Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenoxycarbonyl) -phenyl ester.

  No. 2600-2999; (2 or 3)-(chloro or fluoro) -4- [4-3,6,7,10,11-pentaboxy-triphenylene-2-yloxy)-(pentyl, hexyl, heptyl, octyl, Nonyl, decyl, undecyl, dodecyl, tridecyl, or tetradecyl) oxy] -benzoic acid 4- (4- (propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenoxycarbonyl)- Phenyl ester.

  No. 3000-3399; (2 or 3)-(chloro or fluoro) -4- [4-3,6,7,10,11-pentakis- (pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl or tetradecyl) oxy-triphenylene-2-yloxy) -butoxy] -benzoic acid 4- (4- (propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) -phenoxycarbonyl) -Phenyl ester.

  No. 3400-3799; (2 or 3)-(chloro or fluoro) -4- [4-3,6,7,10,11-pentakis- (pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl or tetradecyl) oxy-triphenylene-2-yloxy)-(pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl) oxy] -benzoic acid 4- (4- (propyl, butyl , Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenoxycarbonyl) -phenyl ester.

  No. 3800-4199; (2 or 3)-(chloro or fluoro) -4- {4- [4- (3,6,7,10,11-pentaboxy-triphenylene-2-yloxy) -butoxy] -benzoyloxy } -Benzoic acid 4- (propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenyl ester.

  No. 4200-4599; (2 or 3)-(chloro or fluoro) -4- {4- [4- (3,6,7,10,11-pentaboxy-triphenylene-2-yloxy)-(pentyl, hexyl, Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, or tetradecyl) oxy] -benzoyloxy} -benzoate 4- (propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -Phenyl ester.

  No. 4600-4999; (2 or 3)-(chloro or fluoro) -4- {4- [4- (3,6,7,10,11-pentakis- (pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, or tetradecyl) oxy-triphenylene-2-yloxy) -butoxy] -benzoyloxy} -benzoate 4- (propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl ) -Phenyl ester.

  No. 5000-5399; (2 or 3)-(chloro or fluoro) -4- {4- [4- (3,6,7,10,11-pentakis- (pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, or tetradecyl) oxy-triphenylene-2-yloxy)-(pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, or tetradecyl) oxy] -benzoyloxy} -benzoic acid 4 -(Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) -phenyl ester.

    No. 5400-5799; (2 or 3)-(chloro or fluoro) -4- [4- (3,6,7,10,11-pentaboxy-triphenylene-2-yloxy)-(butyryl, pentanoyl, hexanoyl, heptanoyl) , Octanoyl, nonanoyl, decanoyl, undecanoyl or dodecanoyl) oxy] -benzoic acid 4- (4-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenoxycarbonyl) -phenyl ester

    No. 5800-6199; (2 or 3)-(chloro or fluoro) -4- [4- (3,6,7,10,11-pentakis- (pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl) , Tridecyl, or tetradecyl) oxy-triphenylene-2-yloxy)-(butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl or dodecanoyl) oxy] -benzoate 4- (4-propyl, butyl, pentyl, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) -phenoxycarbonyl) -phenyl ester, and the like.

  A liquid crystal device using the liquid crystal alignment film composition of the present invention is obtained by immersing a glass substrate or a plastic substrate provided with electrodes such as ITO in the liquid crystal alignment composition as described above, and then cleaning and drying the substrate. Then, an alignment film is formed on the ITO, the electrode surfaces are arranged to face each other, a display cell having a certain distance between the electrode surfaces is produced by a spacer, and the triphenylene compound (II) represented by the general formula (2) It can be produced by injecting a liquid crystal composition containing a chiral agent. A known composition can be used as the liquid crystal composition. Any liquid crystal composition having a different dielectric anisotropy (having a positive, negative, or zero dielectric constant) can be used.

  Furthermore, it is also possible to use a liquid crystal composition in which a positive or negative dichroic dye is added to a liquid crystal composition containing the triphenylene compound (II) represented by the general formula (2) and a chiral agent. By using a positive or negative dichroic dye, display according to the color tone of the dichroic dye can be performed in a bistable planar alignment state and a homeotropic alignment state, respectively. As the positive or negative dichroic dye, a known dichroic dye can be used.

  The liquid crystal element of the present invention can be used in various forms as a display device in which the liquid crystal element occupies a part or all of the liquid crystal element.

  For example, the liquid crystal element of the present invention constitutes a part or all of a small card such as a business card or a credit card, thereby producing a card capable of displaying information. Can be used as a point card or membership card. By increasing the size of such a small card with excellent portability, a display device is produced as a substitute display for displays and recording paper (output paper for copying machines, printers, etc.) used in general offices. You can also When a memory-type liquid crystal element having bistability is used as the liquid crystal element of such a display device, the display can be held without consuming electric power, so that it is an excellent display device from the viewpoint of saving resources and energy. is there. In addition, by incorporating the liquid crystal element of the present invention into various articles such as home appliances, information can be provided instead of a conventional liquid crystal monitor. Furthermore, the liquid crystal element of the present invention can be used for various advertisements, signboards, and the like. In this case as well, the entire surface can be constituted by a liquid crystal element, but it is also possible to realize an effective display by being incorporated in a part of a poster or the like. In addition, the liquid crystal element of the present invention can give flexibility to a medium by a configuration including a substrate, so that the liquid crystal element can be shaped in various applications including the card, sheet, display, signboard, and advertisement. It can be used for a wide range of applications without being restricted by.

  Hereinafter, the present invention will be described specifically by way of examples.

Synthesis Example <Synthesis of 1,2-bishexyloxy-4-iodobenzene>
After adding 69.3 g (253 mmol) of iodine, 32.8 g (144 mmol) of periodic acid, 150 mL of distilled water, and 22.5 mL of concentrated sulfuric acid to 750 mL of glacial acetic acid, the mixture was stirred at room temperature for 5 minutes, and then 80. 00 g (287 mmol) of 1,2-dihexyloxybenzene was added and stirred at 40 ° C. for 24 hours. The resulting reaction mixture was cooled to room temperature, washed with aqueous KOH (1M, 1.5 L) and 3 L distilled water, and extracted with 800 mL chloroform. The organic phase was dried over MgSO ₄ and the solvent was distilled off. The residue was purified by column chromatography and then distilled to obtain 218.6 g of a light brown liquid.

<Synthesis of 3,4,3 ′, 4′-tetrakishexyloxybiphenyl>
A mixture consisting of 1200 mL distilled water / acetone (1/1), 194 g Pd / C (Pd: 10%), 194 g Zn powder, and 200 g (495 mmol) 1,2-bishexyloxy-4-iodobenzene Was stirred at 50 ° C. for 24 hours. The resulting reaction mixture was filtered through a glass filter and extracted with chloroform. The organic phase was washed with distilled water and dried over MgSO ₄ . The solvent was distilled off to obtain 123 g of a yellow solid. Recrystallization from ethanol gave 58.5 g of a white solid.

<Synthesis of 2-hexyloxyphenol>
A mixture consisting of 740 mL methyl ethyl ketone, 120 g (1.09 mol) catechol, 178 g (1.09 mmol) 1-bromohexane, and 211 g (1.53 mol, 1.4 eq.) Potassium carbonate was refluxed for 25 hours. After cooling, the mixture was filtered and the solvent was distilled off. 202 g of the residue was purified by column chromatography on silica gel and distilled to obtain 101 g of a clear liquid.

<Synthesis of 1- (16-bromohexadecyl) -2-hexyloxybenzene>
To 350 mL of dehydrated methylene chloride was added 12.8 g (66 mmol) of 2-hexyloxyphenol, 23.3 g (73 mmol) of 16-bromohexadecan-1-ol, and 20.0 g (99 mmol) of tri-n-butylphosphine. In addition, it was ice-cooled under argon. While stirring, 25.0 g (99 mmol) of 1,1 ′-(azodicarbonyl) dipiperidine was added in small portions, followed by 150 mL of methylene chloride. The mixture was stirred at room temperature for 30 minutes under argon and then refluxed for 6 hours. After cooling, the reaction solution was dropped into 100 mL of hexane and filtered. The filtrate was concentrated and purified by silica gel column chromatography to obtain 26.5 g of a clear liquid.

<Synthesis of 2- (16-bromohexadecyl) -3,6,7,10,11-pentakishexyloxytriphenylene>
In 40 mL of methylene chloride, 5.70 g (10 mmol) of 3,3 ′, 4,4′-tetrakishexyloxybiphenyl and 15.3 g (31 mmol) of 1- (16-bromohexadecyl) -2-hexyloxybenzene were added. Dissolve and add 10.0 g (62 mmol) of FeCl ₃ under argon and stir at room temperature for 3 hours. The resulting reaction mixture was dropped into 800 mL of methanol and filtered through to obtain 102 g of a solid. Purification by column chromatography on silica gel gave a yellow solid. Recrystallization from ethanol gave 8.2 g of a white solid.

<Synthesis of [16- (3,6,7,10,11-pentakishexyloxytriphenylene-2-yloxy) -hexadecyl] -phosphonic acid diethyl ester>
To 6.1 g (5.8 mmol) of 2- (16-bromohexadecyl) -3,6,7,10,11-pentakishexyloxytriphenylene was added 20 mL of triethyl phosphite under argon and at 150 ° C. Stir for 27 hours. Excess triethyl phosphite was distilled off, and the residue was purified by silica gel column chromatography to obtain 5.4 g of a white solid.

<[16- (3,6,7,10,11-pentakishexyloxytriphenylene-2-yloxy) -hexadecyl] -phosphonic acid (Compound (I) corresponding to oxy-oxy of Nos. 53 to 56) Synthesis>
Dissolve 2.0 g (1.8 mmol) of [16- (3,6,7,10,11-pentakishexyloxytriphenylene-2-yloxy) -hexadecyl] -phosphonic acid diethyl ester in 15 mL of methylene chloride; 1.2 mL of trimethylsilyl bromide was added under argon and stirred at room temperature. After 27 hours, the solvent and excess trimethylsilyl bromide were distilled off, and the residue was dissolved in 100 mL of ethanol. After stirring at room temperature for 48 hours, the solvent was distilled off to obtain 1.9 g of a white solid. Melting point Mp: 57-58 ° C. Molecular weight MS m / z by MALDI-TOF / MS method: 1048 (calculated value: C ₆₄ H ₁₀₅ O ₉ P 1048.75), FIG. 16 shows an infrared spectrum chart of this phosphonate ester.

<Synthesis of 2-chloro-4-hydroxy-benzoic acid ethyl ester>
A solution consisting of 34.5 g (200 mmol) of 2-chloro-4-hydroxy-benzoic acid, 5 mL of concentrated sulfuric acid and 400 mL of ethanol was refluxed for 18 hours. The resulting mixture was added to 1.2 L water and extracted with 1.5 L methylene chloride. The mixture was washed with an aqueous sodium hydrogen carbonate solution and water, dried over magnesium sulfate, and the solvent was distilled off. The residue was recrystallized from hexane / ethyl acetate to give 20.4 g of a light orange solid.

<Synthesis of 4-benzyloxy-2-chloro-benzoic acid ethyl ester>
After adding 16.76 g (83.5 mmol) of 2-chloro-4-hydroxy-benzoic acid ethyl ester and 23.1 g (167 mmol) of potassium carbonate to 100 mL of methyl ethyl ketone, 17.1 g (100 mmol) of bromomethylbenzene Was added with stirring. After refluxing for 28 hours, it was cooled and filtered. The filtrate was concentrated and the residue was purified by silica gel column chromatography to give 21.1 g of a pale yellow solid.

<Synthesis of 4-benzyloxy-2-chloro-benzoic acid>
17.7 g (60.9 mmol) of 4-benzyloxy-2-chloro-benzoic acid ethyl ester and 4.87 g (122 mmol) of sodium hydroxide were added to a mixed solvent consisting of 180 mL of methanol and 18 mL of water for 6 hours. Refluxed. After cooling, concentrated hydrochloric acid was added until the pH reached 5, and the precipitate was filtered off. Washed with water and dried to give 8.5 g of white solid.

<Synthesis of 4-benzyloxy-benzoic acid 4-pentyl-phenyl ester>
12.6 g (55.0 mmol) 4-benzyloxy-benzoic acid, 8.2 g (50.0 mmol) 4-pentylphenol, and 0.61 g (5.0 mmol) 4-dimethylamino in 150 mL methylene chloride. After adding pyridine, 11.4 g (55.0 mmol) of dicyclohexylcarbodiimide was added with stirring under argon. After stirring for 6 hours under argon, the mixture was filtered and the filtrate was concentrated. The residue was purified by silica gel column chromatography to obtain 18.7 g of a white solid.

<Synthesis of 4-hydroxy-benzoic acid 4-pentyl-phenyl ester>
Add 15.6 g (41.5 mmol) 4-benzyloxy-benzoic acid 4-pentyl-phenyl ester, 25 mL cyclohexene, 0.78 g palladium hydroxide / carbon to 100 mL dehydrated ethanol and reflux for 10 hours under argon. did. The resulting reaction mixture was filtered and the filtrate was concentrated. The residue was recrystallized from toluene to give 11.0 g of a white solid.

<Synthesis of 4-benzyloxy-2-chloro-benzoic acid 4- (4-pentyl-phenoxycarbonyl) -phenyl ester>
In 50 mL of methylene chloride, 1.84 g (7.0 mmol) of 4-benzyloxy-2-chloro-benzoic acid, 1.90 g (6.7 mmol) of 4-hydroxy-benzoic acid 4-pentyl-phenyl ester, and 0.082 g (0.67 mmol) of 4-dimethylaminopyridine was dissolved and 1.45 g (7.0 mmol) of dicyclohexylcarbodiimide was added with stirring under argon. After stirring for 8 hours under argon, the mixture was filtered and the filtrate was concentrated. The residue was purified by silica gel column chromatography to obtain 3.3 g of a white solid.

<Synthesis of 2-chloro-4-hydroxy-benzoic acid 4- (4-pentyl-phenoxycarbonyl) -phenyl ester>
2.5 g (4.7 mmol) 4-benzyloxy-2-chloro-benzoic acid 4- (4-pentyl-phenoxycarbonyl) -phenyl ester, 20 mL cyclohexene, 0.13 g palladium hydroxide / carbon in 25 mL In addition to dehydrated ethanol, the mixture was refluxed for 12 hours under argon. The resulting reaction mixture was filtered and the filtrate was concentrated. The residue was recrystallized from hexane / ethyl acetate to give 1.65 g of a white solid.

<2-Chloro-4- [9- (3,6,7,10,11-pentakis-hexyloxy-triphenylene-2-yloxy) -nonanoyloxy] -benzoic acid 4- (4-pentyloxy-phenoxycarbonyl)- Synthesis of Phenyl Ester (Compound (II) of No. 3125)>
0.70 g (0.78 mmol) 9- (3,6,7,10,11-pentakis-hexyloxy-triphenylene-2-yloxy) -nonanoic acid, 0.34 g (0.78 mmol) 2-chloro- 4-Hydroxy-benzoic acid 4- (4-pentyl-phenoxycarbonyl) -phenyl ester and 0.009 g (0.08 mmol) 4-dimethylaminopyridine are dissolved in 20 mL methylene chloride and 0.16 g under argon. (0.78 mmol) of dicyclohexylcarbodiimide was added with stirring. After stirring for 22 hours under argon, the mixture was filtered and the filtrate was concentrated. The residue was purified by silica gel column chromatography to give 0.44 g of a white solid. Melting point Mp: 55 ° C. Molecular weight MS m / z by APCI method: 283 (−), 1010 (+), 1028 (+) (calculated value: C ₈₁ H ₁₀₉ ClO ₁₁ 1292.77). FIG. 17 shows an infrared spectrum chart of this compound.

Example 1
Two glass substrates with ITO of 1.1 mm thickness (SuperITO-A, ITO layer: about 100 nm thick, ULVAC Film Co., Ltd.) were prepared, hydrogen peroxide solution (about 30%), aqueous ammonia solution (about 30%) and ion exchange water (each mixed at a ratio of 1: 1: 5), sonicated for about 15 minutes, and then immersed in the same solution at 60 ° C. for 60 minutes to clean the ITO surface. did.

<Preparation of liquid crystal alignment film composition>
[16- (3,6,7,10,11-pentakishexyloxytriphenylene-2-yloxy) -hexadecyl-phosphonic acid (R _{1 to} R ₅ in general formula (1): hexyl group obtained in Synthesis Example , R ₆ : hexadecylene group, R ₇ : —P (═O) (OH) ₂ ) 10.5 mg was dissolved in 10 mL of ethanol to prepare an alignment film composition. Two washed glass substrates with ITO were immersed in the obtained liquid crystal alignment film composition, subjected to ultrasonic treatment at room temperature for 15 minutes, and then allowed to stand at 20 ° C. in the same solution. After 24 hours, the substrate is taken out, thoroughly washed with ion exchange water, dried by air blow (room temperature), then thoroughly washed with methanol, dried by nitrogen blow (room temperature), and an alignment film is provided on the ITO surface. It was.

<Production of display cell and liquid crystal element>
Next, the glass substrate with ITO provided with the two alignment films as described above is disposed (opposed arrangement) so that the electrode surfaces face each other, and the internal space having a distance between the electrode surfaces of about 18 μm by the resin film spacer. A display cell was manufactured by forming the display cell.
The produced display cell is filled with a liquid crystal composition MLC-6610 (manufactured by Merck Japan), heated to a temperature at which the liquid crystal composition exhibits an isotropic phase, cooled to room temperature, and the gap is sealed with an adhesive. Thus, a liquid crystal display element was produced.

<Evaluation of orientation characteristics>
About the liquid crystal display element produced as mentioned above, the result of having observed the conoscopic image using the polarizing microscope is shown in FIG. If the intersection of the ten characters in the circle is at the center of the circle, it indicates that the liquid crystal is vertically aligned. When the crossing point of the crossed characters deviates from the center of the circle, the longer the distance is, the more the liquid crystal is tilted. As shown in FIG. 1, it can be seen that the liquid crystal composition obtained in Example 1 is vertically aligned with respect to the substrate surface. In addition, the conoscopic image was found to be uniform with no unevenness, since the same result was obtained regardless of the location, regardless of which part was observed. That is, it was found that the liquid crystal composition obtained in Example 1 was so-called homeotropic alignment that was uniformly vertically aligned with the substrate surface.

Example 2
A liquid crystal alignment film composition was prepared in the same manner as in Example 1 except that RDP-95407 (Dainippon Ink & Chemicals, Inc.) was used as the liquid crystal composition, and a display cell and a liquid crystal element were prepared. Evaluated. FIG. 2 shows the observation result of the conoscopic image. The liquid crystal composition was homeotropically aligned with respect to the substrate surface.

Example 3
As the liquid crystal alignment film composition, 10.5 mg of [16- (3,6,7,10,11-pentakishexyloxytriphenylene-2-yloxy) -hexadecyl] -phosphonic acid and 55.6 mg of tetradecylphosphonic acid A liquid crystal alignment film composition was prepared in the same manner as in Example 1 except that a solution in which 10 ml of ethanol was dissolved in 10 mL of ethanol, a display cell and a liquid crystal element were prepared, and alignment characteristics were evaluated. FIG. 3 shows the observation result of the conoscopic image. The liquid crystal composition was homeotropically aligned with respect to the substrate surface.

Example 4
A liquid crystal alignment film composition was prepared in the same manner as in Example 3 except that RDP-95407 (Dainippon Ink & Chemicals, Inc.) was used as the liquid crystal composition, and a display cell and a liquid crystal element were prepared. Evaluated. FIG. 4 shows the observation result of the conoscopic image. The liquid crystal composition was homeotropically aligned with respect to the substrate surface.

Example 5
As a liquid crystal alignment film composition, 10.5 mg of [16- (3,6,7,10,11-pentakishexyloxytriphenylene-2-yloxy) -hexadecyl] -phosphonic acid and 41.7 mg of tetradecylphosphonic acid A solution (9/1) of RDP-95407 (Dainippon Ink Chemical Co., Ltd.) and liquid crystal composition MX-001543 (Merck Japan Co., Ltd.) was used as a liquid crystal composition. A liquid crystal device was prepared in the same manner as in Example 1 except that the weight ratio was used, and the alignment characteristics were evaluated. FIG. 5 shows the observation result of the conoscopic image. It was found that the liquid crystal composition had a so-called homeotropic alignment in which the liquid crystal composition was uniformly aligned vertically to the substrate surface.

Example 6
As a liquid crystal alignment film composition, 10.5 mg of [16- (3,6,7,10,11-pentakishexyloxytriphenylene-2-yloxy) -hexadecyl] -tri (chloro, methoxy or ethoxy) silane and 55 A liquid crystal alignment film composition was prepared in the same manner as in Example 5 except that a solution of 6 mg of tetradecyltri (chloro, methoxy or ethoxy) silane dissolved in 10 mL of ethanol was used, and a display cell and a liquid crystal device were produced. The orientation characteristics were evaluated. FIG. 6 shows the observation result of the conoscopic image. The liquid crystal composition was homeotropically aligned with respect to the substrate surface.

Example 7
[16- (3,6,7,10,11-pentakishexyloxytriphenylene-2-yloxy) -hexadecyl-phosphonic acid (R _{1 to} R ₅ in the general formula (1): —C obtained in the synthesis example _{6 H 13, R 6: -C} 16 H 32 -, was obtained in the same manner as _{R 7 :-P (= O) (} OH) 2) [12- (3,6,7,10,11- penta Kishexyloxytriphenylene-2-yloxy) -dodecyl-phosphonic acid (R _{1 to} R ₅ in the general formula (1): —C ₆ H ₁₃ , R ₆ : —C ₁₂ H ₂₄ —, R _7: —P (= A liquid crystal alignment film composition was prepared in the same manner as in Example 1 except that a solution in which 5.0 mg of O) (OH) ₂ ) was dissolved in 10 mL of ethanol was used, and a display cell and a liquid crystal element were prepared. Characteristics were evaluated. FIG. 7 shows the observation result of the conoscopic image. The liquid crystal composition was homeotropically aligned with respect to the substrate surface.

Example 8
<Production of display cell and liquid crystal element>
An ITO-attached glass substrate provided with two liquid crystal alignment films prepared in the same manner as in Example 1 is placed so that the electrode surfaces face each other (opposite placement), and an electrode surface of about 16 μm is formed by a resin film spacer. A display cell was manufactured by forming an internal space having a distance.
In the produced display cell, MX-001543 (manufactured by Merck Japan) 1 g, 2-chloro-4- [9- (3,6,7,10,11-pentakis-hexyloxy-triphenylene) obtained in Synthesis Example -2-yloxy) -nonanoyloxy] -benzoic acid 4- (4-pentyloxy-phenoxycarbonyl) -phenyl ester (R _{12 to} R ₁₆ in the general formula (2): —C ₆ H ₁₃ , R ₁₇ : —C ₅ H ₁₁ , n: 2, X _{1 to} R ₁₃ and X _{15 to} X ₁₈ : —H, X ₁₄ : —Cl, Q: —C ₈ H ₁₆ COO— (the left end is bound to the triphenylene side), Q ₁ and Q ₂ is -COO- (the left end is bonded to the triphenylene side) 33 mg (25 μmol) and 9 mg of a chiral agent CN (made by Merck Japan) are dissolved to have a chiral pitch of 19 μm. A liquid crystal composition is obtained and filled, heated to a temperature at which the liquid crystal composition exhibits an isotropic phase (112 ° C.) or higher, then cooled to room temperature, and the gap is sealed with an adhesive to produce a liquid crystal element did.

<Evaluation of orientation characteristics and bistability>
For the liquid crystal element produced as described above, 5V-1 kHz and 5V-100kHz voltage application was alternately repeated three times, and then a 5V-1 kHz voltage was applied and a conoscopic image was obtained using a polarizing microscope. Observed. FIG. 8 shows the observation result of the conoscopic image. The liquid crystal composition was homeotropically aligned uniformly with respect to the substrate surface. Thereafter, the voltage application of 5V-1 kHz was stopped, and conoscopic images were observed 1 minute and 1 hour later. Each observation result is shown in FIG. 9 and FIG. It was found that the homeotropic orientation was maintained uniformly even under no-electric condition.

Next, for the same liquid crystal element as described above, voltage application of 5 V-100 kHz and 5 V-1 kHz was alternately repeated three times, and then an orthoscope image was observed using a polarizing microscope in a state where a voltage of 5 V-100 kHz was applied. . FIG. 11 shows the observation result of the orthoscope image. The liquid crystal composition was so-called planar alignment that was uniformly aligned parallel to the substrate surface. Then, the voltage application of 5V-100kHz was stopped and the orthoscope image was observed over time. The observation results after 1 minute, 1 hour, and 24 hours from the stop of voltage application are shown in FIGS. 12, 13, and 14, respectively.
Immediately after the voltage application is stopped, a fingerprint structure peculiar to the cholesteric phase is observed when the helical axis is uniformly aligned parallel to the substrate surface, and the liquid crystal composition is a nematic phase in a planar alignment state in which the helix has been dissolved. Thus, it was found that the phase transition to the recovered cholesteric phase was maintained and the orientation state was maintained even in a non-electric state.

  Therefore, it is clear that the above liquid crystal element is a bistable liquid crystal display element capable of maintaining a homeotropic alignment state and a state where the helical axis is uniformly aligned parallel to the substrate surface without electricity. It became.

Example 9
<Production of display cell and liquid crystal element>
[16- (3,6,7,10,11-pentakishexyloxytriphenylene-2-yloxy) -hexadecyl-phosphonic acid (R _{1 to} R ₅ in the general formula (1): —C obtained in the synthesis example _{6 H 13, R 6: -C} 16 H 32 -, was obtained in the same manner as R 7 :-P (= O) ( OH) 2) [8- (3,6,7,10,11- penta Kishexyloxytriphenylene-2-yloxy) -octyl-phosphonic acid (R _{1 to} R ₅ in the general formula (1): —C ₆ H ₁₃ , R ₆ : —C ₈ H ₁₆ —, R _7: —P (= A liquid crystal alignment film composition was prepared in the same manner as in Example 1 except that 5.0 mg of O) (OH) ₂ ) dissolved in 10 mL of ethanol was used, and a display cell was prepared.
To the produced display cell, 1 g of RDP-95407 (manufactured by Dainippon Ink & Chemicals, Inc.) was added to 2-chloro-4- [9- (3,6,7,10,11-) obtained in the synthesis example. Pentakis-hexyloxy-triphenylene-2-yloxy) -nonanoyloxy] -benzoic acid 4- (4-pentyl-phenoxycarbonyl) -phenyl ester (R _{12 to} R ₁₆ in the general formula (2): —C ₆ H ₁₃ , R _{17: -C 5 H 11, n} : 2, X 1 ~X 13 and _{X 15 ~X 18: -H, X} 14: -Cl, Q: -C 8 H 16 COO- ( wherein the left end is bonded to the triphenylene side) , Q ₁ and Q ₂ are 2-chloro-4- {4- [8- (3,6,7,10,11-pentakis) obtained in the same manner as —COO— (the left end is bonded to the triphenylene side). -Hexyloxy-trif [Enylene-2-yloxy) -octyloxy] -benzoyloxy} -benzoic acid 4-pentyl-phenyl ester (R _{12 to} R ₁₆ in the general formula (2): —C ₆ H ₁₃ , R ₁₇ : —C ₅ H ₁₁ , N: 2, X _{1 to} X ₁₇ : —H, X ₁₈ : —Cl, Q: —C ₈ H ₁₆ O— (the left end is bonded to the triphenylene side), Q ₁ and Q ₂ are —COO— (the left end is (Bonded to the triphenylene side)) 65 mg (50 μmol) and 9 mg chiral agent CN (manufactured by Merck Japan) are dissolved to obtain a liquid crystal composition having a 19 μm chiral pitch and filled therewith. After heating to above the temperature showing the phase (105 ° C.), it was cooled to room temperature, and the gap was sealed with an adhesive to produce a liquid crystal element.

<Evaluation of orientation characteristics and bistability>
About the liquid crystal element produced as mentioned above, after repeating the voltage application of 25V-1kHz and 10V-100kHz 3 times alternately, in the state which applied the voltage of 25V-1kHz, a conoscopic image was used. Observed. The liquid crystal composition was homeotropically aligned uniformly with respect to the substrate surface. Then, the voltage application of 25V-1kHz was stopped and the conoscopic image was observed 1 hour later. The observation results are shown in FIG. It was found that the homeotropic orientation was maintained uniformly even under no-electric condition.
Next, for the same liquid crystal element as described above, voltage application of 25V-100 kHz and 10V-1 kHz was alternately repeated three times, and then an orthoscope image was observed using a polarizing microscope in a state where a voltage of 5V-100 kHz was applied. . The liquid crystal composition was so-called planar alignment that was uniformly aligned parallel to the substrate surface. Thereafter, voltage application at 5 V-100 kHz was stopped, and an orthoscopic image was observed after 1 hour. The observation results are shown in FIG. It was found that the state (cholesteric phase) in which the helical axis was uniformly aligned parallel to the substrate surface was maintained even in a non-electric state.

Example 10
<Production of display cell and liquid crystal element>
An ITO-attached glass substrate provided with two liquid crystal alignment films prepared in the same manner as in Example 1 is disposed so that the electrode surfaces face each other (facing each other), and a distance of about 16 μm between the electrode surfaces by a resin film spacer A display cell was fabricated in such a manner that an internal space having a distance was formed.
In the produced display cell, MX-001545 (Merck Japan Co., Ltd.) 1 g, 2-chloro-4- [9- (3,6,7,10,11-pentakis-hexyloxy-triphenylene) obtained in Synthesis Example -2-yloxy) -nonanoyloxy] -benzoic acid 4- (4-pentyl-phenoxycarbonyl) -phenyl ester (R _{12 to} R ₁₆ in the general formula (2): —C ₆ H ₁₃ , R ₁₇ : —C ₅ H ₁₁ , n: 2, X _{1 to} X ₁₃ and X _{15 to} X ₁₈ : —H, X ₁₄ : —Cl, Q: —C ₈ H ₁₆ COO— (the left end is bound to the triphenylene side), Q ₁ and Q ₂ Is 2-chloro-4- [8- (3,6,7,10,11-pentakis-hexyloxy-triphenyl-2-) obtained in the same manner as -COO- (the left end is bonded to the triphenylene side)). Iruo Xyl) -octyloxy] -benzoic acid 4- (4-pentyl-phenylcarbonyl) -phenyl ester (R _{12 to} R ₁₆ in the general formula (2): —C ₆ H ₁₃ , R ₁₇ : —C ₅ H ₁₁ , n: 2, X _{1 to} X ₁₃ and X _{15 to} X ₁₈ : —H, X ₁₄ : —Cl, Q: —C ₈ H ₁₆ O— (the left end is bound to the triphenylene side), Q ₁ and Q ₂ are − COO— (the left end is bound to the triphenylene side)) 65 mg (50 μmol) and 9 mg of the chiral agent CN (manufactured by Merck Japan) are dissolved to obtain a liquid crystal composition having a 19 μm chiral pitch and filled therewith. The composition was heated to a temperature equal to or higher than the temperature at which the composition exhibited an isotropic phase (115 ° C.), then cooled to room temperature, and the gap was sealed with an adhesive to produce a liquid crystal element.

<Evaluation of orientation characteristics and bistability>
For the liquid crystal element produced as described above, the voltage application of 10V-1 kHz and 10V-100kHz was alternately repeated three times, and then a conoscopic image was obtained using a polarizing microscope in a state where a voltage of 10V-1 kHz was applied. Observed. The liquid crystal composition was homeotropically aligned uniformly with respect to the substrate surface. Thereafter, the voltage application of 10V-1 kHz was stopped, and a conoscopic image was observed after 1 hour. The observation results are shown in FIG. It was found that the homeotropic orientation was maintained uniformly even under no-electric condition.
Next, for the same liquid crystal element as described above, voltage application of 10V-100 kHz and 10V-1 kHz was alternately repeated three times, and then an orthoscope image was observed using a polarizing microscope in a state where a voltage of 10V-100 kHz was applied. . The liquid crystal composition was so-called planar alignment that was uniformly aligned parallel to the substrate surface.
Thereafter, voltage application at 10 V-100 kHz was stopped, and an orthoscopic image was observed after 1 hour. The observation results are shown in FIG. It was found that the state (cholesteric phase) in which the helical axis was uniformly aligned parallel to the substrate surface was maintained even in a non-electric state.

  Therefore, it is clear that the above liquid crystal element is a bistable liquid crystal display element capable of maintaining a homeotropic alignment state and a state where the helical axis is uniformly aligned parallel to the substrate surface without electricity. It became.

Example 11
<Production of liquid crystal element>
Except for using a liquid crystal composition prepared by dissolving 0.8 wt% of dichroic dye S-416 (manufactured by Mitsui Toatsu Co., Ltd.) in the liquid crystal composition used in Example 8, the same manner as in Example 8 was used. A liquid crystal element was produced.

<Evaluation of reflectance>
About the liquid crystal element produced above, the voltage application of 10 V-1 kHz and 10 V-100 kHz was alternately repeated three times, and then the liquid crystal composition was uniform using a polarizing microscope with the voltage of 10 V-1 kHz applied. It was confirmed that homeotropic orientation was observed. Thereafter, the voltage application of 10V-1 kHz is stopped, and the reflected light of the display medium is reflected in the wavelength region of 400 to 800 nm by 45-degree irradiation-vertical light reception using Photo MCPD-1000 manufactured by Otsuka Electronics Co., Ltd. The rate was measured as 100%. The result is shown in FIG. 22 (dotted line).
Next, the voltage application of 10 V-1 kHz and 10 V-100 kHz is alternately repeated three times, and then the liquid crystal composition is uniformly planarly aligned using a polarizing microscope in a state where a voltage of 10 V-100 kHz is applied. It was confirmed. After that, the voltage application of 10V-100kHz is stopped, and the reflected light of the display medium is reflected in the wavelength region of 400 to 800 nm by 45 degree irradiation-vertical light reception using Photo MCPD-1000 manufactured by Otsuka Electronics Co., Ltd. The rate was measured as 100%. The result is shown in FIG. 22 (solid line).

  Therefore, it was revealed that the liquid crystal element can be used as a display device.

2 is a conoscopic image of the liquid crystal element obtained in Example 1. FIG. 6 is a conoscopic image of a liquid crystal element obtained in Example 2. 6 is a conoscopic image of a liquid crystal element obtained in Example 3. FIG. 6 is a conoscopic image of a liquid crystal element obtained in Example 4. 6 is a conoscopic image of a liquid crystal element obtained in Example 5. 10 is a conoscopic image of a liquid crystal element obtained in Example 6. 10 is a conoscopic image of a liquid crystal element obtained in Example 7. 10 is a conoscopic image of a liquid crystal element obtained in Example 8. 10 is a conoscopic image of a liquid crystal element obtained in Example 8. 10 is a conoscopic image of a liquid crystal element obtained in Example 8. 10 is an orthoscopic image of a liquid crystal element obtained in Example 8. FIG. 10 is an orthoscopic image of a liquid crystal element obtained in Example 8. FIG. 10 is an orthoscopic image of a liquid crystal element obtained in Example 8. FIG. 10 is an orthoscopic image of a liquid crystal element obtained in Example 8. FIG. FIG. 3 is a cross-sectional view of a display element showing an example of a liquid crystal element of the present invention. It is an IR spectrum chart of [16- (3,6,7,10,11-pentakishexyloxytriphenylene-2-yloxy) -hexadecyl] -phosphonic acid used in Examples. <2-Chloro-4- [9- (3,6,7,10,11-pentakis-hexyloxy-triphenylene-2-yloxy) -nonanoyloxy] -benzoic acid 4- (4-pentyloxy) used in the examples -Phenoxycarbonyl) -phenyl ester IR spectrum chart. 10 is a conoscopic image of a liquid crystal element obtained in Example 9. 10 is an orthoscopic image of a liquid crystal element obtained in Example 9. FIG. 10 is a conoscopic image of a liquid crystal element obtained in Example 10. FIG. 10 is an orthoscopic image of a liquid crystal element obtained in Example 10. FIG. FIG. 10 is a graph showing the reflectance of the liquid crystal element obtained in Example 11.

Explanation of symbols

1: Substrate 2: Electrode 3: Liquid crystal alignment film 4: Sealing material 5: Liquid crystal composition 6: Spacer 7: Drive circuit

Claims (2)

Triphenylene compound represented by the following general formula (1) a liquid crystal alignment film comprising the liquid crystal alignment film composition you containing at least one or more (I) provided, triphenylene compound represented by the general formula (2) (II A liquid crystal composition containing at least one or more) and a chiral agent.

(In the formula, L is —O— or —S—, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are the same or different hydrocarbon groups having 4 or more carbon atoms, and R ₆ is 4 or more carbon atoms. Divalent hydrocarbon group, R ₇ is —SiR ₈ R ₉ R ₁₀ , or —P (═O) (OH) ₂ , R ₈ , R ₉ , and R ₁₀ are the same or different —Cl, —OH , -OCH _3, or -OC ₂ H _5.)

(Wherein R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ are the same or different hydrocarbon groups having 4 or more carbon atoms, R ₁₇ is an alkyl group, alkoxy group, or alkoxycarbonyl having 3 or more carbon atoms) Group, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X _{4n + 7} , X _{4n + 8} , X _{4n + 9} , and X _{4n + 10} are hydrogen atoms and fluorine atoms Or chlorine atom, n is an integer of 1 or more, Q is the number of carbon atoms having —C (═O), —O, —C (═O) —O or —O—C (═O) at both ends or one end. 4 or more divalent groups, Q _n is —C (═O) —O— or —O—C (═O) —. A display device comprising the liquid crystal element according to claim 1 .

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