WO2020158038A1 - Liquid crystal composite and liquid crystal dimmer element - Google Patents

Abstract

Provided are: a liquid crystal composite suitable for dimming which comprises a liquid crystal composition, said liquid crystal composition satisfying at least one characteristic selected from among a high upper limit temperature, a low lower limit temperature, a low viscosity, a high optical anisotropy and a high negative dielectric anisotropy or showing an appropriate balance between at least two of the aforesaid characteristics; and a liquid crystal dimmer element which comprises the liquid crystal composite.　The liquid crystal composite, which comprises a polymer and a liquid crystal composition containing a dichroic dye and a specific compound having a high negative dielectric anisotropy, may further comprise a specific compound having a high upper limit temperature or a low lower limit temperature.

Description

Liquid crystal composite and liquid crystal light control device

The present invention mainly relates to a liquid crystal light control device. More specifically, it relates to a liquid crystal light control device having a liquid crystal composite in which a polymer and a liquid crystal composition are combined.

There are methods such as using light scattering for the liquid crystal light control device. Such elements are used in building materials such as window panes and room dividers, in-vehicle parts, etc. For these elements, in addition to a hard substrate such as a glass substrate, a soft substrate such as a plastic film is used. In the liquid crystal composition sandwiched between these substrates, the alignment of liquid crystal molecules is changed by adjusting the applied voltage. Since light transmitted through the liquid crystal composition can be controlled by this method, the liquid crystal light control device is widely used in displays, optical shutters, light control windows (Patent Document 1), smart windows (Patent Document 2), and the like. Has been done.

An example of a liquid crystal light control device is a polymer dispersion type device in a light scattering mode. The liquid crystal composition is dispersed in the polymer. This element has the following features. The device is easy to manufacture. Since it is easy to control the film thickness over a wide area, it is possible to manufacture a device having a large screen. Since no polarizing plate is required, bright display is possible. Wide viewing angle because light scattering is used. Since this element has such excellent properties, it is expected to be used as a light control glass, a projection type display, a large area display and the like.

Another example is a polymer network type liquid crystal light control device. In this type of device, the liquid crystal composition is present in a three-dimensional network of polymers. This composition differs from the polymer dispersion type in that it is continuous. This type of device also has the same characteristics as the polymer-dispersed device. There is also a liquid crystal light control device in which a polymer network type and a polymer dispersion type are mixed.

A liquid crystal composition having appropriate characteristics is used for the liquid crystal light control device. By improving the characteristics of this composition, a device having good characteristics can be obtained. The relationship between the two properties is summarized in Table 1 below. The characteristics of the composition will be further described based on the device. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred maximum temperature of the nematic phase is about 70° C. or higher, and the preferred minimum temperature of the nematic phase is about −20° C. or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferable to control the light transmittance. A response time of 1 millisecond is shorter than that of other devices. Therefore, a low viscosity in the composition is preferred. Small viscosities at low temperatures are even more preferred. The elastic constant of the composition is related to the response time of the device. A large elastic constant in the composition is preferred to achieve a short response time in the device.

The optical anisotropy of the composition is related to the haze ratio of the liquid crystal light control device. The haze ratio is the ratio of diffused light to the total transmitted light. A large haze ratio is preferred when blocking light. A large optical anisotropy is preferable for a large haze ratio. A large dielectric anisotropy in the composition contributes to a low threshold voltage and a small power consumption in the device. Therefore, large dielectric anisotropy is preferable. A large specific resistance in the composition contributes to a large voltage holding ratio in the device. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance after being used for a long time is preferable. The stability and weather resistance of a composition against light and heat are related to the life of the device. When the stability and weather resistance are good, the life is long. Display defects such as afterimages and drop marks are also related to the life of the device. There is a demand for an element that has high weather resistance and is resistant to display defects.

The liquid crystal light control device has a normal mode and a reverse mode. In the normal mode, the element is opaque when no voltage is applied and becomes transparent when a voltage is applied. In the reverse mode, the element is transparent when no voltage is applied and becomes opaque when a voltage is applied. Reverse mode devices that become transparent when a device fails are expected for applications such as automobile windows.

To improve the liquid crystal light control device, the patent documents are helpful (Patent documents 3 to 6). In Patent Document 7, a device having a black liquid crystal composition prepared by adding at least three dichroic dyes was produced. In Patent Document 8, a liquid crystal material containing a dichroic dye is used for a switch layer. In Patent Document 9, a dichroic dye is used in a guest-host type liquid crystal display device. We tried to use such a dichroic dye in a liquid crystal light control device.

JP, 06-273725, A International Publication No. 2011-096386 JP 63-278035 A Japanese Patent Laid-Open No. 01-198725 Japanese Patent Laid-Open No. 07-104262 Japanese Patent Laid-Open No. 07-175045 International publication 2017-038616 JP, 2008-028655, A JP 2006-193742 A

The object of the present invention is to have a high maximum temperature of a nematic phase, a low minimum temperature of a nematic phase, a small viscosity, a large optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, a high stability to light, and a high heat resistance. It is intended to provide a liquid crystal composite which contains a liquid crystal composition satisfying at least one of properties such as high stability and a large elastic constant and is suitable for light control. Another object is to provide a liquid crystal composite that contains a liquid crystal composition having an appropriate balance between at least two of these properties and is suitable for dimming. Another object is to provide a liquid crystal light control device having such a liquid crystal composite. Another object is to provide a liquid crystal light control device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large haze ratio, high weather resistance and long life.

式（１）において、Ｒ^１およびＲ^２は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；環Ａおよび環Ｃは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、テトラヒドロピラン－２，５－ジイル、１，４－フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４－フェニレン、ナフタレン－２，６－ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン－２，６－ジイル、クロマン－２，６－ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン－２，６－ジイルであり；環Ｂは、２，３－ジフルオロ－１，４－フェニレン、２－クロロ－３－フルオロ－１，４－フェニレン、２，３－ジフルオロ－５－メチル－１，４－フェニレン、３，４，５－トリフルオロナフタレン－２，６－ジイル、７，８－ジフルオロクロマン－２，６－ジイル、３，４，５，６－テトラフルオロフルオレン－２，７－ジイル、４，６－ジフルオロジベンゾフラン－３，７－ジイル、４，６－ジフルオロジベンゾチオフェン－３，７－ジイル、または１，１，６，７－テトラフルオロインダン－２，５－ジイルであり；Ｚ^１およびＺ^２は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ａは、０、１、２、または３であり、ｂは０または１であり；そしてａとｂとの和は３以下である。 The present invention contains a liquid crystal composition and a polymer, and the liquid crystal composition has at least one compound selected from the compounds represented by the formula (1) as a first component and a dichroic compound as a first additive. The present invention relates to a liquid crystal composite containing a dye, a liquid crystal light control device containing the liquid crystal composite, and the like.

In the formula (1), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least Alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine; ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen has been replaced by fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene , 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8 -Difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3 , 7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ¹ and Z ² are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy; Is 0, 1, 2, or 3; b is 0 or 1; and the sum of a and b is 3 or less.

Advantages of the present invention include high upper temperature of nematic phase, low lower temperature of nematic phase, small viscosity, large optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to light, and high heat resistance It is intended to provide a liquid crystal composite which contains a liquid crystal composition satisfying at least one of properties such as high stability and a large elastic constant and is suitable for light control. Another advantage is to provide a liquid crystal composite that contains a liquid crystal composition having a suitable balance between at least two of these properties and is suitable for dimming. Another advantage is to provide a liquid crystal light control device having such a liquid crystal composite. Another advantage is to provide a liquid crystal light control device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large haze ratio, high weather resistance, and long life.

In this specification, terms such as “liquid crystal compound”, “polymerizable compound”, “liquid crystal composition”, “polymerizable composition”, “liquid crystal composite”, and “liquid crystal light control device” are used. The “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a liquid crystal phase, but it is a composition for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a general term for compounds added to things. This compound has a 6-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. The “polymerizable compound” is a compound added for the purpose of forming a polymer in the liquid crystal composition. Liquid crystal compounds having alkenyl are not classified as polymerizable compounds in that sense.

“The liquid crystal composition” is prepared by mixing a plurality of liquid crystal compounds. Additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a quencher, a dye, a defoaming agent, and a polar compound are added to the liquid crystal composition as needed. The proportion of the liquid crystal compound is represented by a mass percentage (mass %) based on the liquid crystal composition containing no additive even when the additive is added. The ratio of the additive is expressed as a mass percentage based on the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total amount of the liquid crystal compound. The "mass" of "mass%" may be omitted.

“The polymerizable composition” is prepared by mixing a polymerizable compound with the liquid crystal composition. That is, the polymerizable composition is a mixture of at least one polymerizable compound and the liquid crystal composition. If necessary, additives such as a polymerization initiator and a polymerization inhibitor are added to the polymerizable compound. The ratio of the polymerization initiator and the polymerization inhibitor is represented by the mass percentage based on the polymerizable compound. The proportion of the polymerizable compound or the liquid crystal composition contained in the polymerizable composition is expressed by the mass percentage based on the polymerizable composition containing no additive even when the additive is added. The “liquid crystal composite” is produced by the polymerization treatment of the polymerizable composition. “Liquid crystal light control device” is a device having a liquid crystal composite and is a general term for liquid crystal panels and liquid crystal modules used for light control.

“The maximum temperature of the nematic phase” may be abbreviated as “maximum temperature”. The "minimum temperature of the nematic phase" may be abbreviated as "minimum temperature". The expression “increasing the dielectric anisotropy” means that, in the case of a composition having a positive dielectric anisotropy, that value increases positively, and a composition having a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively. “High voltage retention” means that the device has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after a long time use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. Means to have a retention rate. The properties of the compositions and devices may be examined by aging tests.

　上記の化合物（１ｚ）を例にして説明する。式（１ｚ）において、六角形で囲んだαおよびβの記号はそれぞれ環αおよび環βに対応し、六員環、縮合環のような環を表す。添え字‘ｘ’が２のとき、２つの環αが存在する。２つの環αが表す２つの基は、同一であってもよく、または異なってもよい。このルールは、添え字‘ｘ’が２より大きいとき、任意の２つの環αに適用される。このルールは、結合基Ｚのような、他の記号にも適用される。環βの一辺を横切る斜線は、環β上の任意の水素が置換基（－Ｓｐ－Ｐ）で置き換えられてもよいことを表す。添え字‘ｙ’は置き換えられた置換基の数を示す。添え字‘ｙ’が０のとき、そのような置き換えはない。添え字‘ｙ’が２以上のとき、環β上には複数の置換基（－Ｓｐ－Ｐ）が存在する。この場合にも、「同一であってもよく、または異なってもよい」のルールが適用される。なお、このルールは、Ｒａの記号を複数の化合物に用いた場合にも適用される。

The above compound (1z) will be described as an example. In the formula (1z), symbols of α and β surrounded by a hexagon correspond to the ring α and the ring β, respectively, and represent rings such as a 6-membered ring and a condensed ring. When the subscript'x' is 2, there are two rings α. The two groups represented by the two rings α may be the same or different. This rule applies to any two rings α when the subscript'x' is greater than 2. This rule also applies to other symbols, such as the linking group Z. A diagonal line crossing one side of the ring β represents that any hydrogen on the ring β may be replaced with a substituent (—Sp—P). The subscript'y' indicates the number of substituents replaced. When the subscript'y' is 0, there is no such replacement. When the subscript'y' is 2 or more, there are plural substituents (-Sp-P) on the ring β. In this case as well, the rule of "may be the same or different" applies. Note that this rule is also applied when the Ra symbol is used for a plurality of compounds.

In formula (1z), for example, the expression "Ra and Rb are alkyl, alkoxy, or alkenyl" means that Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl. To do. That is, the group represented by Ra and the group represented by Rb may be the same or different.

At least one compound selected from the compounds represented by formula (1z) may be abbreviated as “compound (1z)”. “Compound (1z)” means one compound represented by formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. The expression "at least one compound selected from the compounds represented by formula (1z) and formula (2z)" means at least one compound selected from the group consisting of compound (1z) and compound (2z). ..

The expression "at least one'A'" means that the number of'A's is arbitrary. The expression "at least one'A' may be replaced by'B'" means that when the number of'A' is one, the position of'A' is arbitrary and the number of'A' is two. If there are more than one, those positions can be selected without limitation. The phrase “at least one —CH ₂ — may be replaced with —O—” is sometimes used. In this case, —CH ₂ —CH ₂ —CH ₂ — may be converted to —O—CH ₂ —O— by replacing non-adjacent —CH ₂ — with —O—. However, adjacent --CH ₂ --is not replaced with --O--. This is because this replacement produces —O—O—CH ₂ — (peroxide).

テトラヒドロピラン－２，５－ジイルのような二価基においても同様である。カルボニルオキシのような結合基（－ＣＯＯ－または－ＯＣＯ－）も同様である。 The alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Straight-chain alkyls are preferred over branched alkyls. The same applies to terminal groups such as alkoxy and alkenyl. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature. Since 2-fluoro-1,4-phenylene is asymmetrical to the left and right, there are leftward (L) and rightward (R) directions.

The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same applies to a linking group such as carbonyloxy (-COO- or -OCO-).

The present invention includes the following items.

式（１）において、Ｒ^１およびＲ^２は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；環Ａおよび環Ｃは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、テトラヒドロピラン－２，５－ジイル、１，４－フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４－フェニレン、ナフタレン－２，６－ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン－２，６－ジイル、クロマン－２，６－ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン－２，６－ジイルであり；環Ｂは、２，３－ジフルオロ－１，４－フェニレン、２－クロロ－３－フルオロ－１，４－フェニレン、２，３－ジフルオロ－５－メチル－１，４－フェニレン、３，４，５－トリフルオロナフタレン－２，６－ジイル、７，８－ジフルオロクロマン－２，６－ジイル、３，４，５，６－テトラフルオロフルオレン－２，７－ジイル、４，６－ジフルオロジベンゾフラン－３，７－ジイル、４，６－ジフルオロジベンゾチオフェン－３，７－ジイル、または１，１，６，７－テトラフルオロインダン－２，５－ジイルであり；Ｚ^１およびＺ^２は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ａは、０、１、２、または３であり、ｂは０または１であり；そしてａとｂとの和は３以下である。 Item 1. A liquid crystal composition and a polymer are contained, and the liquid crystal composition contains at least one compound selected from the compounds represented by the formula (1) as a first component and a dichroic dye as a first additive. , Liquid crystal composites.

In the formula (1), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least Alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine; ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen has been replaced by fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene , 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8 -Difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3 , 7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ¹ and Z ² are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy; Is 0, 1, 2, or 3; b is 0 or 1; and the sum of a and b is 3 or less.

Item 2. Item 2. The liquid crystal composite according to item 1, wherein the liquid crystal composition contains, as a first component, at least one compound selected from compounds represented by formulas (1-1) to (1-35).

式（１－１）から式（１－３５）において、Ｒ^１およびＲ^２は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルである。

In formulas (1-1) to (1-35), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and carbon 2 to 12 alkenyloxy, or 1 to 12 carbon alkyl in which at least one hydrogen is replaced by fluorine or chlorine.

Item 3. Item 3. The liquid crystal composite according to item 1 or 2, wherein the ratio of the first component is in the range of 20% to 90% based on the liquid crystal composition.

式（２）において、Ｒ^３およびＲ^４は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；環Ｄおよび環Ｅは、１，４－シクロヘキシレン、１，４－フェニレン、２－フルオロ－１，４－フェニレン、または２，５－ジフルオロ－１，４－フェニレンであり；Ｚ^３は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｃは、１、２、または３である。 Item 4. Item 4. The liquid crystal composite according to any one of items 1 to 3, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (2) as the second component.

In the formula (2), R ³ and R ⁴ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and carbon in which at least one hydrogen is replaced with fluorine or chlorine. Alkyl having 1 to 12 or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 1, 2 or 3.

式（２－１）から式（２－１３）において、Ｒ^３およびＲ^４は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルである。 Item 5. Item 5. The liquid crystal composition according to any one of items 1 to 4, wherein the second component contains at least one compound selected from compounds represented by formulas (2-1) to (2-13). Liquid crystal composite.

In formulas (2-1) to (2-13), R ³ and R ⁴ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen. Is alkyl having 1 to 12 carbons substituted with fluorine or chlorine, or alkenyl having 2 to 12 carbons having at least one hydrogen replaced with fluorine or chlorine.

Item 6. Item 6. The liquid crystal composite according to item 4 or 5, wherein the ratio of the second component is in the range of 10% to 80% based on the liquid crystal composition.

式（３）において、Ｐ^１およびＰ^２は重合性基であり；Ｚ^４は炭素数１から２０のアルキレンであり、このアルキレンにおいて、少なくとも１つの水素は、炭素数１から５のアルキル、フッ素、塩素、またはＰ^３で置き換えられてもよく、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、または－Ｎ（Ｒ^５）－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－は、炭素環式の飽和脂肪族化合物、複素環式の飽和脂肪族化合物、炭素環式の不飽和脂肪族化合物、複素環式の不飽和脂肪族化合物、炭素環式の芳香族化合物、または複素環式の芳香族化合物から２つの水素を除くことによって生成した二価基で置き換えられてもよく、これらの二価基において、炭素数は５から３５であり、少なくとも１つの水素は、Ｒ^５またはＰ^３で置き換えられてもよく、ここでＲ^５は、炭素数１から１２のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、Ｐ^３は、重合性基である。 Item 7. Item 7. The liquid crystal composite according to any one of items 1 to 6, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains the compound represented by the formula (3) as a main component.

In formula (3), P ¹ and P ² are polymerizable groups; Z ⁴ is alkylene having 1 to 20 carbons, and in this alkylene, at least one hydrogen is alkyl having 1 to 5 carbons, fluorine , Chlorine, or P ³ , and at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, —NH—, or —N(R ⁵ )—. And at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C—, and at least one —CH ₂ — is a carbocyclic group. Saturated aliphatic compound, heterocyclic saturated aliphatic compound, carbocyclic unsaturated aliphatic compound, heterocyclic unsaturated aliphatic compound, carbocyclic aromatic compound, or heterocyclic aromatic compound May be replaced by a divalent group formed by removing two hydrogens from, wherein the number of carbons is 5 to 35, and at least one hydrogen is replaced by R ⁵ or P ^3. And R ⁵ is alkyl having 1 to 12 carbons, and in this alkyl, at least one —CH ₂ — is —O—, —CO—, —COO—, or —OCO—. It may be replaced and P ³ is a polymerizable group.

式（Ｐ－１）から式（Ｐ－６）において、Ｍ^１、Ｍ^２、およびＭ^３は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。 Item 8. Item 8. The liquid crystal composite according to item 7, wherein P ¹ , P ² , and P ³ are groups selected from the polymerizable groups represented by formulas (P-1) to (P-6).

In formulas (P-1) to (P-6), M ¹ , M ² and M ³ are each hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced with fluorine or chlorine. And alkyl having 1 to 5 carbon atoms.

Item 9. Item 8. The liquid crystal composite according to item 7, wherein at least one of P ¹ , P ² , and P ³ is acryloyloxy or methacryloyloxy.

式（４）において、Ｍ^４およびＭ^５は、水素またはメチルであり；Ｚ^５は炭素数２１から８０のアルキレンであり、このアルキレンにおいて、少なくとも１つの水素は、炭素数１から２０のアルキル、フッ素、または塩素で置き換えられてもよく、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、または－Ｎ（Ｒ^５）－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、ここでＲ^５は、炭素数１から１２のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよい。 Item 10. Item 7. The liquid crystal composite according to any one of items 1 to 6, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains the compound represented by the formula (4) as a main component.

In formula (4), M ⁴ and M ⁵ are hydrogen or methyl; Z ⁵ is alkylene having 21 to 80 carbons, and in this alkylene, at least one hydrogen is alkyl having 1 to 20 carbons, It may be replaced by fluorine or chlorine, and at least one —CH ₂ — is replaced by —O—, —CO—, —COO—, —OCO—, —NH—, or —N(R ⁵ )—. At least one —CH ₂ —CH ₂ — may be replaced by —CH═CH— or —C≡C—, wherein R ⁵ is alkyl having 1 to 12 carbons. , In this alkyl, at least one —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—.

式（５）において、Ｍ^６は水素またはメチルであり；Ｚ^６は単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく；Ｒ^６は炭素数１から４０のアルキルであり、このアルキルにおいて、少なくとも１つの水素は、フッ素、または塩素で置き換えられてもよく、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－は、炭素環式の飽和脂肪族化合物、複素環式の飽和脂肪族化合物、炭素環式の不飽和脂肪族化合物、複素環式の不飽和脂肪族化合物、炭素環式の芳香族化合物、または複素環式の芳香族化合物から２つの水素を除くことによって生成した二価基で置き換えられてもよく、これらの二価基において、炭素数は５から３５であり、少なくとも１つの水素は、炭素数１から１２のアルキルで置き換えられてもよく、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよい。 Item 11. Item 7. The liquid crystal composite according to any one of items 1 to 6, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains the compound represented by the formula (5) as a main component.

In formula (5), M ⁶ is hydrogen or methyl; Z ⁶ is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one hydrogen may be replaced by fluorine or chlorine. , At least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—; R ⁶ is alkyl having 1 to 40 carbons, wherein At least one hydrogen may be replaced by fluorine, or chlorine, and at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—, at least One —CH ₂ — is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, a carbocyclic It may be replaced by a divalent group formed by removing two hydrogens from an aromatic compound or a heterocyclic aromatic compound, and in these divalent groups, the number of carbon atoms is 5 to 35 and at least 1 One hydrogen may be replaced by an alkyl having 1 to 12 carbons, in which at least one —CH ₂ — is replaced by —O—, —CO—, —COO—, or —OCO—. May be.

Item 12. In formula (5), M ⁶ is hydrogen or methyl; Z ⁶ is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one hydrogen may be replaced by fluorine or chlorine. , At least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—; R ⁶ is alkyl of 1 to 40 carbons, wherein The at least one hydrogen may be replaced by fluorine or chlorine, and the at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—. 11. The liquid crystal composite according to item 11.

式（６）、式（７）、および式（８）において、環Ｆ、環Ｇ、環Ｉ、環Ｊ、環Ｋ、および環Ｌは、１，４－シクロヘキシレン、１，４－フェニレン、１，４－シクロヘキセニレン、ピリジン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ナフタレン－２，６－ジイル、またはフルオレン－２，７－ジイルであり、ここで、少なくとも１つの水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１から５のアルキル、炭素数１から５のアルコキシ、炭素数２から５のアルコキシカルボニル、または炭素数１から５のアルカノイルで置き換えられてもよく；Ｚ^７、Ｚ^９、Ｚ^１１、Ｚ^１２、およびＺ^１６は、単結合、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－であり；Ｚ^８、Ｚ^１０、Ｚ^１３、およびＺ^１５は、単結合、－ＯＣＨ_２－、－ＣＨ_２Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＳ－、－ＳＣＯ－、－ＯＣＯＯ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－ＣＦ_２Ｏ－、－ＯＣＦ_２－、－ＣＨ_２ＣＨ_２－、－ＣＦ_２ＣＦ_２－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ_２ＣＨ_２ＣＯＯ－、－ＯＣＯＣＨ_２ＣＨ_２－、－ＣＨ＝ＣＨ－、－Ｎ＝ＣＨ－、－ＣＨ＝Ｎ－、－Ｎ＝Ｃ（ＣＨ_３）－、－Ｃ（ＣＨ_３）＝Ｎ－、－Ｎ＝Ｎ－、または－Ｃ≡Ｃ－であり；Ｚ^１４は単結合、－Ｏ－または－ＣＯＯ－であり；Ｘは、水素、フッ素、塩素、トリフルオロメチル、トリフルオロメトキシ、シアノ、炭素数１から２０のアルキル、炭素数２から２０のアルケニル、炭素数１から２０のアルコキシ、または炭素数２から２０のアルコキシカルボニルであり；ｅおよびｇは１から４の整数であり；ｊおよびｌは、０から３の整数であり；ｊおよびｌの和は１から４であり；ｄ、ｆ、ｈ、ｉ、ｋ、およびｍは、０から２０の整数であり；Ｍ^７からＭ^１２は、水素またはメチルである。 Item 13. From the paragraph 1 wherein the polymer is derived from a mixture of polymerizable compounds, the mixture containing as a main component a compound selected from the compounds represented by formula (6), formula (7) and formula (8) 7. The liquid crystal composite according to any one of item 6.

In formula (6), formula (7), and formula (8), ring F, ring G, ring I, ring J, ring K, and ring L are 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, where: At least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 2 to 5 carbons Or may be replaced with an alkanoyl having 1 to 5 carbon atoms; Z ⁷ , Z ⁹ , Z ¹¹ , Z ¹² and Z ¹⁶ are single bonds, —O—, —COO—, —OCO—, or — OCO—; Z ⁸ , Z ¹⁰ , Z ¹³ , and Z ¹⁵ are single bonds, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —COS—, —SCO—, — OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N- , -N=N-, or -C≡C-; Z ¹⁴ is a single bond, -O- or -COO-; X is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano. Is alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, or alkoxycarbonyl having 2 to 20 carbons; e and g are integers from 1 to 4; j And l are integers from 0 to 3; the sum of j and l is 1 to 4; d, f, h, i, k, and m are integers from 0 to 20; M ⁷ to M ¹² is hydrogen or methyl.

Item 14. Item 14. The liquid crystal composite according to any one of items 1 to 13, wherein the first additive is at least one dichroic dye selected from benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and anthraquinones. body.

Item 15. Item 15. The liquid crystal composite according to any one of items 1 to 14, wherein the ratio of the first additive is in the range of 0.03% to 25% based on the liquid crystal composition.

Item 16. Item 16. The method according to any one of Items 1 to 15, wherein the ratio of the liquid crystal composition is in the range of 50% to 95% and the ratio of the polymer is in the range of 5% to 50% based on the liquid crystal composite. Liquid crystal composite.

Item 17. Item 17. The liquid crystal composite is obtained by using as a precursor a polymerizable composition containing a liquid crystal composition and a polymerizable compound, and the polymerizable composition contains a photopolymerization initiator as an additive. Liquid crystal composite.

Item 18. A liquid crystal light control device in which the light control layer is the liquid crystal composite according to any one of items 1 to 17, the light control layer is sandwiched between a pair of transparent substrates, and the transparent substrate has a transparent electrode.

Item 19. The liquid crystal light control device according to item 18, wherein the transparent substrate is a glass plate or an acrylic plate.

Item 20. The liquid crystal light control device according to item 18, wherein the transparent substrate is a plastic film.

Item 21. A light control window using the liquid crystal light control device according to any one of items 18 to 20.

Item 22. A smart window using the liquid crystal light control device according to any one of items 18 to 20.

Item 23. Use of the liquid crystal composite according to any one of items 1 to 17 for a liquid crystal light control device.

Item 24. Use of the liquid crystal composite according to any one of items 1 to 17 for a liquid crystal light control device in which the transparent substrate is a plastic film.

Item 25. Use of the liquid crystal composite according to any one of items 1 to 17 for a light control window.

Item 26. Use of the liquid crystal composite according to any one of items 1 to 17 for a smart window.

The present invention also includes the following items. (A) As the first component, the compound (1-1), the compound (1-3), the compound (1-6), the compound (1-8), the compound (1-10), the compound ( Item 13. The liquid crystal composite according to item 2, which contains a polymer and a liquid crystal composition containing at least one compound selected from the compound (1-34).

(B) As the second component, the compound (2-1), the compound (2-3), the compound (2-5), the compound (2-6), the compound (2-7), and the compound according to Item 5. Item 6. The liquid crystal composite according to item 5, which contains a liquid crystal composition containing at least one compound selected from (2-8) and a polymer.

The present invention also includes the following items. (C) A liquid crystal composite as described above, wherein the proportion of the liquid crystal composition is in the range of 50% to 90% and the proportion of the polymer is in the range of 10% to 50% based on the liquid crystal composite. (D) A liquid crystal composite as described above, wherein the ratio of the liquid crystal composition is in the range of 50% to 85% and the ratio of the polymer is in the range of 15% to 50% based on the liquid crystal composite. (E) A liquid crystal composite as described above, wherein the ratio of the liquid crystal composition is in the range of 60% to 80% and the ratio of the polymer is in the range of 20% to 40% based on the liquid crystal composite.

The present invention also includes the following items. (F) A liquid crystal composite as described above, wherein the proportion of the liquid crystal composition is in the range of 75% to 97% and the proportion of the polymer is in the range of 3% to 25% based on the liquid crystal composite. (G) The above liquid crystal composite, wherein the ratio of the liquid crystal composition is in the range of 80% to 96% and the ratio of the polymer is in the range of 4% to 20% based on the liquid crystal composite. (H) Based on the liquid crystal composite, the liquid crystal composition has a ratio of 85% to 95% and a polymer ratio of 5% to 15%.

The present invention also includes the following items. (I) The above liquid crystal composite containing, as the second additive, at least one of an optically active compound, an antioxidant, an ultraviolet absorber, a quencher, a defoaming agent, a polar compound, a polymerization initiator, and a polymerization inhibitor. body.

The liquid crystal light control device of the present invention will be described in the following order. First, the structure of the liquid crystal composite will be described. Secondly, the constitution of the liquid crystal composition will be explained. Thirdly, the main characteristics of the liquid crystal compound and the main effects of the compound on the liquid crystal composition and the device will be described. Fourth, the combination of components in the liquid crystal composition, the preferable ratio of the components and the basis thereof will be described. Fifth, a preferable form of the liquid crystal compound will be described. Sixth, preferable liquid crystal compounds are shown. Seventh, preferred forms of the polymerizable compound and one example thereof will be described. Eighth, a preferable form of the dichroic dye and an example thereof will be described. Ninth, the method of synthesizing the component compounds will be described. Tenth, an additive that may be added to the polymerizable composition will be described. Finally, the liquid crystal composite and the light control element will be described.

First, the structure of the liquid crystal composite will be explained. The liquid crystal composite is obtained by polymerizing the polymerizable composition. The polymerizable composition is a mixture of the liquid crystal composition and the polymerizable compound. The dielectric anisotropy of this liquid crystal composition is negative. The polymerizable composition gives a liquid crystal composite because the polymer produced by polymerization undergoes phase separation. That is, a liquid crystal composite in which a polymer and a liquid crystal composition are combined is produced. This liquid crystal composite is suitable for a reverse mode element that is transparent when no voltage is applied and becomes opaque when a voltage is applied. The optical anisotropy of the liquid crystal composition and the refractive index of the polymer are related to the transparency of the liquid crystal light control device. Generally, the optical anisotropy (Δn) of the liquid crystal composition is preferably large. The optical anisotropy is preferably 0.15 or more, more preferably 0.18 or more.

In a polymer-dispersed device, the liquid crystal composition is dispersed like droplets in the polymer. Each of the droplets is separate and not continuous. On the other hand, in the polymer network type device, the polymer has a three-dimensional network structure, and the liquid crystal composition is surrounded by the networks but is continuous. In these devices, the proportion of the liquid crystal composition based on the liquid crystal composite is preferably large in order to efficiently scatter light. The proportion of the polymer is preferably large because the driving voltage is lowered by making the droplets and the mesh smaller.

A preferable ratio of the liquid crystal composition is in the range of about 50% to about 95% based on the liquid crystal composite. This preferred percentage is also in the range of about 50% to about 90%. A more desirable ratio is in the range of approximately 50% to approximately 85%. A particularly desirable ratio is in the range of approximately 60% to approximately 80%. A particularly desirable ratio is in the range of approximately 70% to approximately 80%. Since the total amount of the liquid crystal composite and the polymer is 100%, the ratio of the polymer can be easily calculated. The ratio of the polymer based on the liquid crystal composite is the same as the ratio of the polymerizable compound based on the polymerizable composition.

A preferred ratio of the liquid crystal composition is in the range of about 75% to about 97% based on the liquid crystal composite in order to efficiently scatter light or block sunlight. A more desirable ratio is in the range of approximately 80% to approximately 96%. A particularly desirable ratio is in the range of approximately 85% to approximately 95%.

When the ratio of the liquid crystal composition and the polymer is within these ranges, a polymer network type device is produced. When the proportion of polymer is high, it seems that polymer dispersed structures are mixed. On the other hand, when the proportion of the polymer is smaller, a polymer-supported orientation type device is produced. This is abbreviated as PSA (polymer sustained alignment) element. In Example 1 of WO 2012/050178, it is described that "the monomer was added so as to be 0.5 wt% with respect to the liquid crystal material" (paragraph 0105). As can be seen from this description, in the PSA element, a small amount of the polymerizable compound is added to the liquid crystal material (liquid crystal composition).

In the PSA element, the polymer adjusts the pretilt angle of liquid crystal molecules. The liquid crystal molecules are stabilized by optimizing the pretilt angle, and the response time of the device is shortened. On the other hand, in the polymer network type device of the reverse mode, the liquid crystal molecules are vertically aligned by the action of the alignment film, so that the device is transparent. When a voltage is applied to this element, the liquid crystal molecules are aligned in parallel with the substrate. Since there is a difference between the refractive index of the polymer and the refractive index of the liquid crystal molecules, light scattering occurs and the device becomes opaque. Therefore, unlike the PSA element, the polymer network type element does not require a polarizing plate.

Second, the composition of the liquid crystal composition will be explained. This composition contains a plurality of liquid crystal compounds. The composition may contain additives. Additives are optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, defoamers, polymerization initiators, polymerization inhibitors, polar compounds and the like. This composition is classified into composition A and composition B from the viewpoint of the liquid crystal compound. The composition A may further contain other liquid crystal compounds, additives, etc. in addition to the liquid crystal compounds selected from the compound (1) and the compound (2). The "other liquid crystal compound" is a liquid crystal compound different from the compound (1) and the compound (2). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

Composition B consists essentially of liquid crystal compounds selected from compound (1) and compound (2). “Substantially” means that the composition B may contain an additive, but does not contain any other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of cost reduction, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing with other liquid crystal compounds.

Third, the main characteristics of liquid crystal compounds and the main effects of these compounds on liquid crystal compositions and devices will be explained. The main characteristics of the component compounds are summarized in Table 2. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. The symbols L, M, and S are classifications based on qualitative comparison among component compounds, and 0 (zero) means extremely small.

The main effects of the component compounds on the properties of the composition are as follows. The compound (1) increases the dielectric anisotropy. The compound (2) increases the maximum temperature or decreases the minimum temperature.

Fourth, the combination of components in the liquid crystal composition, the preferable ratio of the components and the basis thereof will be explained. A preferred combination of components in the composition is the first component+second component.

The preferable ratio of the first component is about 20% or more for increasing the dielectric anisotropy, and about 90% or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 25% to approximately 85%. A particularly desirable ratio is in the range of approximately 30% to approximately 80%.

The preferable ratio of the second component is about 10% or more for increasing the maximum temperature or decreasing the minimum temperature, and about 80% or less for increasing the dielectric anisotropy. A more desirable ratio is in the range of approximately 15% to approximately 75%. A particularly desirable ratio is in the range of approximately 20% to approximately 70%.

Fifth, a preferable form of the liquid crystal compound will be described. In formulas (1) and (2), R ¹ and R ² are each hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or having 2 to 12 carbons. Alkenyloxy or C1-C12 alkyl in which at least one hydrogen has been replaced by fluorine or chlorine. Desirable R ¹ or R ² is alkyl having 1 to 12 carbons for increasing the stability against light or heat, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy.

R ³ and R ⁴ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and alkyl having 1 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine. Or alkenyl having 2 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine. Desirable R ³ or R ⁴ is alkenyl having 2 to 12 carbons for increasing the maximum temperature or decreasing the minimum temperature, and alkyl for having 1 to 12 carbons for increasing stability to light or heat. is there.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is methyl, ethyl, propyl, butyl, or pentyl for decreasing the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, It is 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity. The preferred configuration of -CH=CH- in these alkenyls depends on the position of the double bond. Trans is preferable in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferable in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More desirable alkenyloxy is allyloxy or 3-butenyloxy for decreasing the viscosity.

Preferred examples of alkyl in which at least one hydrogen is replaced by fluorine or chlorine include fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. , Or 8-fluorooctyl. A more preferable example is 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl for increasing the dielectric anisotropy.

Preferred examples of alkenyl in which at least one hydrogen has been replaced by fluorine or chlorine include 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro. -4-pentenyl, or 6,6-difluoro-5-hexenyl. A more preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.

または

であり、好ましくは

である。 Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1 in which at least one hydrogen is replaced by fluorine or chlorine. , 4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or chlorine Is chroman-2,6-diyl replaced by. Preferred ring A or ring C is 1,4-cyclohexylene for decreasing the minimum temperature or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature. Tetrahydropyran-2,5-diyl is

Or

And preferably

Is.

好ましい環Ｂは、粘度を下げるために２，３－ジフルオロ－１，４－フェニレンであり、誘電率異方性を上げるために４，６－ジフルオロジベンゾチオフェン－３，７－ジイルである。 Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4. 5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4,6- Difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4) Is.

Preferred ring B is 2,3-difluoro-1,4-phenylene for decreasing the viscosity and 4,6-difluorodibenzothiophene-3,7-diyl for increasing the dielectric anisotropy.

Ring D and Ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring D or ring E is 1,4-cyclohexylene for increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.

Z ¹ and Z ² are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ¹ or Z ² is a single bond or ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy. Particularly preferred Z ¹ or Z ² is a single bond. Z ³ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferable Z ³ is a single bond in order to improve stability to light and heat.

A is 1, 2, or 3; b is 0 or 1; the sum of a and b is 3 or less. Preferred a is 1 for decreasing the minimum temperature, and 2 or 3 for increasing the maximum temperature. Preferred b is 0 for increasing the dielectric anisotropy, and 1 for decreasing the minimum temperature. c is 1, 2, or 3. Preferred c is 1 for decreasing the minimum temperature and 2 or 3 for increasing the maximum temperature.

Sixth, preferable liquid crystal compounds are shown. Preferred compound (1) includes compounds (1-1) to (1-35) described in item 2. In these compounds, at least one of the first components is compound (1-1), compound (1-3), compound (1-6), compound (1-8), compound (1-10), compound ( 1-14) or the compound (1-34) is preferable. At least two of the first components are compound (1-1) and compound (1-8), compound (1-1) and compound (1-14), compound (1-3) and compound (1-8), Compound (1-3) and compound (1-14), compound (1-3) and compound (1-34), compound (1-6) and compound (1-8), compound (1-6) and compound It is preferably (1-10), or a combination of compound (1-6) and compound (1-14).

Preferred compounds (2) are the compounds (2-1) to (2-13) described in item 5. In these compounds, at least one of the second components is compound (2-1), compound (2-3), compound (2-5), compound (2-6), compound (2-7), or compound It is preferably (2-8). At least two of the second components are compound (2-1) and compound (2-5), compound (2-1) and compound (2-6), compound (2-1) and compound (2-7), compound (2-1) and compound (2-8) compound (2-3) and compound (2-5), compound (2-3) and compound (2-6), compound (2-3) and compound (2 -7) or a combination of the compound (2-3) and the compound (2-8) is preferable.

Seventh, a preferable form of the polymerizable compound and an example thereof will be described. A polymer is derived from the polymerizable compound. The polymerizable compound may be a single compound or a mixture of a plurality of compounds. A preferable polymerizable compound is the compound (3), the compound (4), or the compound (5). Preferred polymerizable compound is compound (6), compound (7), or compound (8). The polymerizable compound may be a mixture of compounds selected from the compound (3) to the compound (8). This mixture may contain a polymerizable compound different from compounds (3) to (8). Such a mixture contains a compound selected from the compound (3) to the compound (8) as a main component. Here, the main component means a component that occupies the largest proportion in the mixture. For example, in a mixture of 40% compound (3), 30% compound (4), and 30% compound (5), the main component is compound (3). Even when the polymerizable compound used is only the compound (3), the compound (3) is called the main component.

7-1. Compound (3)
In formula (3), Z ⁴ is alkylene having 1 to 20 carbons, and in this alkylene, at least one hydrogen may be replaced with alkyl having 1 to 5 carbons, fluorine, chlorine, or P ^3. , At least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —NH—, or —N(R ⁵ )—, and at least one —CH ₂ —CH ₂ — may be replaced by —CH═CH— or —C≡C—, and at least one —CH ₂ — is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic Divalent compounds formed by removing two hydrogens from a compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, a carbocyclic aromatic compound, or a heterocyclic aromatic compound A group may be substituted, and in these divalent groups, the number of carbon atoms is 5 to 35, and at least one hydrogen may be substituted with R ⁵ or P ³ . Here, R ⁵ is alkyl having 1 to 12 carbons, and in this alkyl, at least one —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—. Good.

Examples of divalent groups formed by removing two hydrogens from a carbocyclic or heterocyclic saturated aliphatic compound are 1,4-cyclohexylene, decahydronaphthalene-2,6-diyl and tetrahydropyran-2. ,5-diyl, 1,3-dioxane-2,5-diyl and the like. Examples of divalent groups formed by removing two hydrogens from a carbocyclic or heterocyclic unsaturated aliphatic compound are 1,4-cyclohexenylene, dihydropyran-2,5-diyl and the like. Examples of divalent groups formed by removing two hydrogens from a carbocyclic or heterocyclic aromatic compound are 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, naphthalene-1,2-diyl, pyrimidine-2,5-diyl and the like.

Preferred Z ⁴ is alkylene having 1 to 20 carbons, in which at least one hydrogen may be replaced by alkyl having 1 to 5 carbons, and at least one —CH ₂ — is —O. At least one —CH ₂ — is replaced by a divalent group formed by removing two hydrogens from a carbocyclic saturated aliphatic compound or a carbocyclic aromatic compound. Also, in these divalent groups, the number of carbon atoms is 5 to 35. More desirable Z ⁴ is alkylene having 1 to 20 carbons, in which at least one hydrogen may be replaced by alkyl having 1 to 5 carbons, and at least one —CH ₂ — is — It may be replaced with O-.

Preferred Z ⁴ contains a ring structure such as 1,4-cyclohexylene or 1,4-phenylene in order to improve the compatibility with the liquid crystal composition. Preferred Z ⁴ includes a chain structure such as alkylene for easily forming a network structure.

P ¹ , P ² , and P ³ are polymerizable groups. Preferred polymerizable groups are formulas (P-1) to (P-6). In these formulas, the wavy line indicates the binding site. More preferred polymerizable groups are formulas (P-1) to (P-3). P ¹ , P ² , and P ³ may be acryloyloxy or methacryloyloxy.

In formulas (P-1) to (P-6), M ¹ , M ² and M ³ are each hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced with fluorine or chlorine. And alkyl having 1 to 5 carbon atoms. Preferred M ¹ , M ² or M ³ is hydrogen or methyl for increasing the reactivity. More preferred M ¹ is hydrogen or methyl, and more preferred M ² or M ³ is hydrogen.

式（３－１）において、ｐは１から６の整数であり、式（３－２）において、ｑは５から２０の整数である。 Examples of the compound (3) are the compounds (3-1) to (3-3).

In the formula (3-1), p is an integer of 1 to 6, and in the formula (3-2), q is an integer of 5 to 20.

In the compound (3), when the number of polymerizable groups is large, the polymer surrounding the droplet becomes hard or the network becomes dense due to crosslinking. Preferred polymerizable compounds having at least one acryloyloxy (-OCO-CH = CH ₂₎ or methacryloyloxy _{(-OCO- (CH 3) C =} CH 2). Compound (3) gives the corresponding polymer by polymerization. When the compound (3) is volatile, its oligomer may be used. The preferred polymer is colorless and transparent and is insoluble in the liquid crystal composition. The preferred polymer has excellent adhesion to the substrate of the device and reduces the driving voltage. In order to improve this effect, a polymerizable compound different from the compound (3) may be used in combination.

7-2. Compound (4)
In formula (4), M ⁴ and M ⁵ are hydrogen or methyl. Preferred M ⁴ or M ⁵ is hydrogen for increasing the reactivity.

Z ⁵ is alkylene having 21 to 80 carbons, in which at least one hydrogen may be replaced by alkyl having 1 to 20 carbons, fluorine, or chlorine, and at least one —CH ₂ — ^May be replaced by —O—, —CO—, —COO—, —OCO—, —NH—, or —N(R ⁵ )—, and at least one —CH ₂ —CH ₂ — is — CH═CH— or —C≡C—, wherein R ⁵ is alkyl having 1 to 12 carbons, and in this alkyl, at least one —CH ₂ — is —O—, It may be replaced with —CO—, —COO—, or —OCO—. Preferred Z ⁵ is alkylene having 21 to 60 carbon atoms for low voltage driving, in which at least one hydrogen may be replaced by alkyl having 1 to 20 carbons, and at least one- CH ₂ — may be replaced with —O—, —COO—, or —OCO—.

More preferred Z ⁵ is alkylene in which at least one hydrogen has been replaced with alkyl for low voltage driving. It is preferred to prevent steric hindrance when the two hydrogens of the alkylene have been replaced by alkyl. For example, two alkyls are sufficiently separated, or one of the alkyls is an alkyl having 1 to 5 carbons. The same applies when at least three hydrogens are replaced by alkyl.

式（４－１）において、Ｒ^７およびＲ^９は、炭素数１から５のアルキルであり、Ｒ^８およびＲ^１０は、炭素数５から２０のアルキルであり、これらのアルキルにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、Ｚ^７は炭素数１３から３０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよい。 An example of the compound (4) is the compound (4-1).

In formula (4-1), R ⁷ and R ⁹ are alkyl having 1 to 5 carbons, and R ⁸ and R ¹⁰ are alkyl having 5 to 20 carbons, and in these alkyls, at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—, and Z ⁷ is an alkylene having 13 to 30 carbon atoms, and in this alkylene, at least one — CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—.

式（４－１－１）および式（４－１－２）において、例えば、Ｒ^７およびＲ^９は、エチルであり、Ｒ^８およびＲ^１０は、－ＣＨ_２ＯＣＯＣ_９Ｈ_１９、－ＣＨ_２ＯＣＯＣ_１０Ｈ_２１、－ＣＨ_２ＯＣ_８Ｈ_１７、または－ＣＨ_２ＯＣ_１１Ｈ_２３である。 Examples of the compound (4-1) are the compound (4-1-1) and the compound (4-1-2).

In formulas (4-1-1) and (4-1-2), for example, R ⁷ and R ⁹ are ethyl, and R ⁸ and R ¹⁰ are —CH ₂ OCOC ₉ H ₁₉ , —CH _2. OCOC ₁₀ H ₂₁ , —CH ₂ OC ₈ H ₁₇ , or —CH ₂ OC ₁₁ H ₂₃ .

The compound (4) is diacrylate or dimethacrylate. Since Z ^{5 in the} formula (4) is alkylene or the like, the polymer easily forms a network structure. When the molecular chain of Z ⁵ is short, the cross-linking sites of the polymer are close to each other, resulting in a small mesh. When the molecular chain of Z ⁵ is long, the cross-linking site of the polymer is separated and the degree of freedom of molecular movement is improved, so that the driving voltage is lowered. When Z ⁵ is branched, the degree of freedom is further improved, and thus the driving voltage is further reduced. In order to improve this effect, a polymerizable compound different from the compound (4) may be used in combination.

7-3. Compound (5)
In formula (5), M ⁶ is hydrogen or methyl. Preferred M ⁶ is hydrogen for increasing the reactivity.

Z ⁶ is a single bond or alkylene having 1 to 5 carbons, and in this alkylene, at least one hydrogen may be replaced with fluorine or chlorine, and at least one —CH ₂ — is —O—, — It may be replaced with CO-, -COO-, or -OCO-. Preferred Z ⁶ is a single bond or alkylene having 1 to 5 carbons, in which at least one —CH ₂ — is replaced with —O—, —CO—, —COO—, or —OCO—. May be.

R ⁶ is alkyl having 1 to 40 carbons, and in this alkyl, at least one hydrogen may be replaced by fluorine or chlorine, and at least one —CH ₂ — is —O—, —CO—. , —COO—, or —OCO—, and at least one —CH ₂ — is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated fat. Group compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds, or divalent groups formed by removing two hydrogens from a heterocyclic aromatic compound, In the divalent group of 5 to 35 carbon atoms, at least one hydrogen may be replaced by an alkyl having 1 to 12 carbon atoms, and in this alkyl, at least one —CH ₂ — is —O. It may be replaced with -, -CO-, -COO-, or -OCO-. Preferred R ⁶ is alkyl having 5 to 30 carbons. More desirable R ⁶ is branched alkyl having 5 to 30 carbons.

式（５－１）から式（５－５）において、Ｒ^１１は、炭素数５から２０のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、Ｒ^１２およびＲ^１３は、炭素数３から１０のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよい。 Examples of compound (5) are compound (5-1) to compound (5-6).

In formulas (5-1) to (5-5), R ¹¹ is alkyl having 5 to 20 carbon atoms, and in this alkyl, at least one —CH ₂ — is —O—, —CO—, It may be replaced with —COO— or —OCO—, and R ¹² and R ¹³ are alkyl having 3 to 10 carbons, and in this alkyl, at least one —CH ₂ — is —O—, — It may be replaced with CO-, -COO-, or -OCO-.

The compound (5) is acrylate or methacrylate. When R ^{6 in} formula (5) has a cyclic structure, the affinity with the liquid crystal composition is improved. When R ⁶ is alkylene, the polymer tends to form a network structure. In this polymer, alkylene improves the degree of freedom of molecular motion, so that the driving voltage is lowered. In order to further improve this effect, a polymerizable compound different from the compound (5) may be used in combination.

7-4. Compounds (6) to (8)
In formula (6), formula (7), and formula (8), ring F, ring G, ring I, ring J, ring K, and ring L are 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, where: At least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 2 to 5 carbons Or may be replaced with an alkanoyl having 1 to 5 carbon atoms. In formulas (6), (7), and (8), preferred rings are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methyl-1, It is 4-phenylene, 2-methoxy-1,4-phenylene, or 2-trifluoromethyl-1,4-phenylene. A more preferred ring is 1,4-cyclohexylene or 1,4-phenylene.

Z ⁷ , Z ⁹ , Z ¹¹ , Z ¹² , and Z ¹⁶ are single bonds, —O—, —COO—, —OCO—, or —OCOO—. Z ⁸ , Z ¹⁰ , Z ¹³ and Z ¹⁵ are a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —COS—, —SCO—, —OCOO—, —CONH. -, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO- , -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N -, or -C≡C-. Z ¹⁴ is a single bond, —O—, or —COO—. In formula (6) and formula (7), preferred Z ⁸ , Z ¹⁰ , Z ¹³ or Z ¹⁵ is a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH. ₂ CH ₂ —, —CH ₂ CH ₂ COO—, or —OCOCH ₂ CH ₂ —.

X is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, or alkoxy having 2 to 20 carbons. It is carbonyl.

e and g are integers from 1 to 4; j and l are integers from 0 to 3; the sum of j and l is 1 to 4; d, f, h, i, k, and m are , An integer from 0 to 20.

M ⁷ to M ¹² are hydrogen or methyl.

Examples of the compound (6) are the compounds (6-1) to (6-24).

式（６－１）から式（６－２４）において、Ｍ^７は水素またはメチルであり、ｄは１から２０の整数である。

In formulas (6-1) to (6-24), M ⁷ is hydrogen or methyl, and d is an integer of 1 to 20.

Examples of compound (7) are compound (7-1) to compound (7-31).

式（７－１）から式（７－３１）において、Ｍ^８およびＭ^９は、水素またはメチルであり、ｆおよびｈは、１から２０の整数である。

In formulas (7-1) to (7-31), M ⁸ and M ⁹ are hydrogen or methyl, and f and h are integers from 1 to 20.

Examples of compound (8) are compound (8-1) to compound (8-10).

式（８－１）から式（８－１０）において、Ｍ^１０、Ｍ^１１、およびＭ^１２は、水素またはメチルであり、ｉ、ｋ、およびｍは、１から２０の整数である。

In formulas (8-1) to (8-10), M ¹⁰ , M ¹¹ , and M ¹² are hydrogen or methyl, and i, k, and m are integers from 1 to 20.

The compound (6), the compound (7), and the compound (8) have at least one acryloyloxy (—OCO—CH═CH ₂ ) or methacryloyloxy (—OCO—(CH ₃ )C═CH ₂ ). Liquid crystal compounds have mesogens (rigid sites that induce liquid crystallinity), but these compounds also have mesogens. Therefore, these compounds are aligned with the liquid crystal compound in the same direction by the action of the alignment film. This orientation is maintained after polymerization. Such a liquid crystal composite has high transparency. In order to improve other properties, a polymerizable compound different from the compound (6), the compound (7), and the compound (8) may be used in combination.

Eighth, the preferred form of the dichroic dye and an example thereof will be described. The liquid crystal light control device is sometimes used for partitioning a room. In such a case, one dichroic dye may be added to the liquid crystal composition. A mixture of dyes may be added. The liquid crystal light control device is sometimes used to block sunlight. In such a case, a black (or blackish) dichroic dye is added to the liquid crystal composition. Black is prepared by mixing cyan, magenta and yellow dichroic dyes. At least two dyes are mixed. Preferably two, three, four, five or six dyes are mixed. Particularly preferably, 3 or 4 dyes are mixed.

Such dichroic dyes have at least some of the characteristics described below. a) The dye molecule is linear. b) A skeleton peculiar to dichroic dyes such as a benzothiadiazole ring and a diketopyrrolopyrrole ring exists in the center of the molecule. c) The benzene ring and the thiophene ring which constitute the molecule together with the unique skeleton are located on the same plane. d) The side chain is alkyl or alkoxy. e) Having a conjugated double bond in the central part.

Examples of the skeleton peculiar to the dichroic dye are as follows. From the left, the compound names are benzothiadiazole, diketopyrrolopyrrole, azo compound, and perylene.

Examples of dichroic dyes are benzothiadiazoles, diketopyrrolopyrroles, azo compounds (azo compounds), azomethine compounds (methine compounds), methine compounds (anthraquinones). , Merocyanines, naphthoquinones, tetrazines, pyrromethenes, and rylenes such as perylenes and terrylenes. Preferred dichroic dyes are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, anthraquinones, and rylenes. Particularly preferred dichroic dyes are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and rylenes. For example, benzothiadiazoles means a dichroic dye having a benzothiadiazole ring.

A preferable ratio of the dichroic dye is in the range of 0.03% to 25% based on the liquid crystal composition. A more desirable ratio is in the range of 0.03% to 20%. A particularly desirable ratio is in the range of 0.03% to 15%.

Examples of the dichroic dye include compounds (9-1) to (9-110).

式（９－１）から（９－１１０）において、Ｅｔはエチルであり、ｎ－ＢｕおよびｎＢｕはブチルであり、ｎ－Ｐｅｎｔはペンチルであり、ｎ－Ｈｅｘはヘキシルである。

In formulas (9-1) to (9-110), Et is ethyl, n-Bu and nBu are butyl, n-Pent is pentyl and n-Hex is hexyl.

Examples of commercially available dichroic dyes are G-207, G-241, G-305, G-470, G-471, G-472, LSB-278, LSB-335, NKX- manufactured by Nagase & Co. 1366, NKX-3538, NKX-3540, NKX-3622, NKX-3739, NKX-3742, NKX-3773, NKX-4010, and NKX-4033; S-428, SI-426, SI- manufactured by Mitsui Chemicals Fine. 486, M-412, and M-483.

Ninth, explain the synthesis method of the component compounds. These compounds can be synthesized by known methods. A synthetic method is illustrated. The compound (1-1) is synthesized by the method described in JP-A-2-503441. The compound (2-1) is synthesized by the method described in JP-A-59-176221. Antioxidants are commercially available. The compound (11-1) described below can be obtained from Sigma-Aldrich Corporation. Compound (11-2) and the like are synthesized by the method described in US Pat. No. 3,660,505. The polymerizable compound is commercially available or can be synthesized by a known method.

Compounds for which no synthetic method has been described are organic synthesis (Organic Synthesis, John Wiley&& Sons, Inc.), organic reactions (Organic Reactions, John Wiley& Sons, Inc.), Comprehensive Organic Synthesis (Organic Synthesis) Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. The composition is prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and heated to dissolve each other.

Tenth, an additive that may be added to the polymerizable composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, defoamers, polymerization initiators, polymerization inhibitors, polar compounds and the like. The additive may be added to the liquid crystal composition or the polymerizable compound instead of the polymerizable composition.

An optically active compound is added to a liquid crystal composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such a compound are the compound (10-1) to the compound (10-5). A desirable ratio of the optically active compound is about 5% or less. A more desirable ratio is in the range of approximately 0.01% to approximately 2%.

In order to prevent a decrease in specific resistance due to heating in the atmosphere or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time, the compound (11-1 From (4) to (11-3), an antioxidant may be added to the composition.

Compounds with low volatility are effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the maximum temperature after using the device for a long time. A preferable ratio of the antioxidant is about 50 ppm or more to obtain the effect, and about 600 ppm or less so as not to lower the upper limit temperature or to raise the lower limit temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.

Preferred examples of the ultraviolet absorber are benzophenone derivative, benzoate derivative, triazole derivative and the like. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer include compounds (12-1) to (12-16). A desirable ratio of these absorbers and stabilizers is about 50 ppm or more for obtaining the effect, and about 10,000 ppm or less for not lowering the upper limit temperature or for not raising the lower limit temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

The quencher is a compound that receives the light energy absorbed by the liquid crystal compound and converts it into heat energy to prevent the liquid crystal compound from decomposing. Preferred examples of the quencher include compounds (13-1) to (13-7). A desirable ratio of these quenchers is about 50 ppm or more for obtaining the effect, and about 20,000 ppm or less for not raising the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

Defoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are added to the composition to prevent foaming. The preferable ratio of the defoaming agent is about 1 ppm or more to obtain the effect, and about 1000 ppm or less to prevent display defects. A more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.

UV irradiation is preferred for the polymerization of the polymerizable compound. Examples of the ultraviolet irradiation lamp are a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp and the like. When a photopolymerization initiator is used, the wavelength of ultraviolet rays is preferably in the absorption wavelength region of the photopolymerization initiator. Avoid the absorption wavelength range of the liquid crystal composition. A preferred wavelength is 330 nm or more. A more preferable wavelength is 350 nm or more, for example 365 nm. The reaction may be performed near room temperature or may be performed by heating.

It may be polymerized in the presence of a polymerization initiator such as a photopolymerization initiator. Appropriate conditions for the polymerization and suitable types and amounts of initiators are known to the person skilled in the art and are described in the literature. For example, the photoinitiators Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF) are suitable for radical polymerization.

When storing a polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually mixed with the liquid crystal composition without removing the polymerization inhibitor. Examples of the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

A polar compound is a polar organic compound. Here, a compound having an ionic bond is not included. Atoms such as oxygen, sulfur, and nitrogen are more electronegative and tend to have a partial negative charge. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity arises from the uneven distribution of partial charges among different atoms in the compound. For example, the polar compound has at least one of the partial structures such as —OH, —COOH, —SH, —NH ₂ , >NH, >N—.

The polar group has non-covalent interactions with the surface of the glass substrate, metal oxide film, etc. This compound is adsorbed on the substrate surface by the action of the polar group and controls the alignment of liquid crystal molecules. The polar compound may control not only the liquid crystal molecule but also the polymerizable compound. Such effects are expected for polar compounds.

Finally, I will explain the liquid crystal composite and the light control element. The method for preparing the liquid crystal composite from the polymerizable composition is as follows. First, the polymerizable composition is sandwiched between a pair of substrates. The sandwiching is performed by a vacuum injection method or a liquid crystal dropping method at a temperature higher than the upper limit temperature of the polymerizable composition. In the devices manufactured by these methods, display defects such as flow marks and drop marks may occur. The trace is a trace of the polymerizable composition flowing through the device. The drop mark is a mark on which the polymerizable composition is dropped. It is preferable to suppress such display defects. Next, the polymerizable compound is polymerized by heat or light. Ultraviolet irradiation is preferred for the polymerization. Polymerization causes phase separation of the polymer from the polymerizable composition. As a result, a light control layer (liquid crystal layer) is formed between the substrates. This light control layer is classified into a polymer dispersion type, a polymer network type, and a mixed type of both.

Aging may cause a change over time. The haze rate may change compared to the initial stage. The smaller the change in haze ratio, the better. When the haze change rate is small, good transparency and opacity are maintained. The haze change rate is preferably 20% or less. A more preferable haze change rate is 10% or less or 5% or less.

-If the element is used for a long time, flicker may occur on the display screen. It is presumed that this flicker is associated with image burn-in and is caused by a difference between the potential of the positive frame and the potential of the negative frame when driven by an alternating current. The flicker rate (%) can be represented by (|luminance when positive voltage is applied−luminance when negative voltage is applied)/(average luminance)×100. The flicker rate of the element is preferably in the range of 0% to 1%. The occurrence of flicker can be suppressed by appropriately selecting the component compounds of the polymerizable composition contained in the device.

If the element is used for a long time, the brightness may partly decrease. An example of such a display defect is a line afterimage. This is a phenomenon in which different voltages are repeatedly applied to two adjacent electrodes, so that the luminance between the electrodes decreases in a stripe shape. This phenomenon is presumed to be due to the accumulation of ionic impurities contained in the liquid crystal composition on the alignment film near the electrodes.

Such a light control element has a light control layer (liquid crystal layer) sandwiched by a pair of transparent substrates having transparent electrodes. An example of the substrate is a material that does not easily deform, such as a glass plate, a quartz plate, or an acrylic plate. Another example is a flexible transparent plastic film such as an acrylic film or a polycarbonate film. Depending on the application, one of the substrates may be an opaque material such as silicone resin. This substrate has a transparent electrode thereon. Examples of transparent electrodes are indium tin oxide (ITO) and conductive polymers. The substrate may have an alignment film on the transparent electrode.

　For the alignment film, a thin film such as polyimide or polyvinyl alcohol is suitable. For example, the polyimide alignment film can be obtained by applying a polyimide resin composition on a transparent substrate, thermally curing at a temperature of 180° C. or higher, and rubbing with a cotton cloth or rayon cloth as necessary.

　The pair of substrates should face each other with the transparent electrode layer inside. A spacer may be added to make the thickness between the substrates uniform. Examples of spacers are glass particles, plastic particles, alumina particles, photo spacers and the like. The preferred thickness of the light control layer is about 2 μm to about 50 μm, more preferably about 5 μm to about 20 μm. A general-purpose sealant can be used to bond the pair of substrates. An example of the sealant is an epoxy thermosetting composition.

In such an element, a light absorption layer, a diffuse reflection plate, etc. can be arranged on the back surface of the element, if necessary. It is also possible to add functions such as specular reflection, diffuse reflection, retroreflection, and hologram reflection.

Such an element has a function as a light control film or light control glass. When the element is in the form of a film, it can be attached to an existing window or sandwiched between a pair of glass plates to form a laminated glass. Such elements are used for windows installed on the outer wall or as a partition between the conference room and the corridor. That is, there are applications such as electronic blinds, dimming windows, and smart windows. Furthermore, the function as an optical switch can be used for a liquid crystal shutter or the like.

The present invention will be described in more detail by way of examples. The invention is not limited to these examples. In the examples, the composition (M1), the composition (M2) and the like are described. In the examples, the mixture of composition (M1) and composition (M2) is not mentioned. However, we shall consider this mixture also disclosed. A mixture of at least two compositions selected from the examples shall also be considered disclosed. The synthesized compound was identified by a method such as NMR analysis. The characteristics of the compounds, compositions and devices were measured by the following methods.

NMR analysis: For measurement, DRX-500 manufactured by Bruker BioSpin Co. was used. ^{In the 1} H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl ₃ and the measurement was performed at room temperature under the conditions of 500 MHz and 16 times of integration. Tetramethylsilane was used as an internal standard. ^{In 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and the number of times of integration was 24. In the explanation of the nuclear magnetic resonance spectrum, s means a singlet, d a doublet, t a triplet, q a quartet, quin a quintet, sex a sextet, m a multiplet, and br a broad.

Gas chromatographic analysis: A Shimadzu GC-14B gas chromatograph was used for the measurement. The carrier gas is helium (2 mL/min). The sample vaporization chamber was set at 280°C and the detector (FID) was set at 300°C. A capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; fixed liquid phase dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used to separate the component compounds. The column was held at 200° C. for 2 minutes and then heated to 280° C. at a rate of 5° C./minute. The sample was prepared in an acetone solution (0.1%), and 1 μL thereof was injected into the sample vaporization chamber. The recorder is a C-R5A type Chromatopac manufactured by Shimadzu, or its equivalent. The obtained gas chromatogram showed the retention time of peaks and the area of peaks corresponding to the component compounds.

As the solvent for diluting the sample, chloroform, hexane, etc. may be used. The following capillary column may be used to separate the component compounds. HP-1 made by Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), Rtx-1 made by Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), BP-1 made by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). A capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation may be used for the purpose of preventing compound peaks from overlapping.

The ratio of the liquid crystal compound contained in the composition may be calculated by the following method. The mixture of liquid crystal compounds is analyzed by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio of the liquid crystal compound. When the above-described capillary column is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio of the liquid crystal compound can be calculated from the peak area ratio.

Measurement sample: When measuring the characteristics of the composition and the device containing this composition, the composition was directly used as a sample. When measuring the characteristics of a compound, a sample for measurement was prepared by mixing this compound (15%) with a mother liquid crystal (85%). The characteristic value of the compound was calculated by extrapolation from the value obtained by the measurement. (Extrapolated value)={(measured value of sample)−0.85×(measured value of mother liquid crystal)}/0.15. When the smectic phase (or crystal) was precipitated at 25° C. in this ratio, the ratios of the compound and the mother liquid crystal were changed in the order of 10%:90%, 5%:95%, 1%:99%. Values of maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy of the compound were obtained by this extrapolation method.

The following mother liquid crystals were used.

Measurement method: The characteristics were measured by the following methods. Most of these are the methods described in the JEITA standard (JEITA/ED-2521B), which is deliberated and established by the Japan Electronics and Information Technology Industries Association (JEITA), or a method modified from this. Met. No thin film transistor (TFT) was attached to the TN (twisted nematic) element used for the measurement.

(1) Maximum temperature of the nematic phase (NI; °C): The sample was placed on a hot plate of a melting point measuring device equipped with a polarization microscope and heated at a rate of 1 °C/min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. The maximum temperature of the nematic phase may be abbreviated as “maximum temperature”.

(2) Minimum temperature of nematic phase (T _C ; °C): A sample having a nematic phase was placed in a glass bottle and placed in a 0°C, -10°C, -20°C, -30°C, and -40°C freezer for 10 days. After storage, the liquid crystal phase was observed. For example, T _C was described as <−20° C. when the sample remained in the nematic phase at −20° C. and changed to a crystalline or smectic phase at −30° C. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

(3) Viscosity (bulk viscosity; η; measured at 20°C; mPa·s): An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for measurement.

(4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s): For measurement, a rotational viscosity measurement system LCM-2 type manufactured by Toyo Technica Co., Ltd. was used. The sample was put in a VA (vertical alignment) device in which the distance (cell gap) between two glass substrates was 10 μm. A rectangular wave (55 V, 1 ms) was applied to this device. The peak current and the peak time of the transient current generated by this application were measured. The rotational viscosity value was obtained using these measured values and the dielectric anisotropy. The dielectric anisotropy was measured by the method described in Measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25° C.): The measurement was carried out using an Abbe refractometer with a polarizing plate attached to the eyepiece, using light having a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. The refractive index n∥ was measured when the polarization direction was parallel to the rubbing direction. The refractive index n⊥ was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated from the formula of Δn=n∥−n⊥.

(6) Dielectric anisotropy (Δε; measured at 25° C.): The value of dielectric anisotropy was calculated from the equation Δε=ε∥−ε⊥. Dielectric constants (ε∥ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε∥): A well-washed glass substrate was coated with a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL). The glass substrate was rotated with a spinner and then heated at 150° C. for 1 hour. The sample was put in a VA element having a distance (cell gap) between the two glass substrates of 4 μm, and the element was sealed with an adhesive that was cured by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecule was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well washed glass substrate. After firing this glass substrate, the obtained alignment film was rubbed. The sample was put in a TN device in which the distance (cell gap) between the two glass substrates was 9 μm and the twist angle was 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecule was measured.

(7) Threshold voltage (Vth; measured at 25° C.; V): LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. Put the sample in a VA element of normally black mode where the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures this element with UV light is applied. Used to seal. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased from 0 V to 20 V by 0.02 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve in which the transmittance is 100% when the light amount is maximum and the transmittance is 0% when the light amount is minimum was created. The threshold voltage is represented by the voltage when the transmittance becomes 10%.

(8) Voltage holding ratio (VHR; measured at 25° C.; %): The TN device used for measurement had a polyimide alignment film, and the distance (cell gap) between two glass substrates was 3.5 μm. .. A sample was put in this TN device, and the TN device was sealed with an adhesive curable by ultraviolet rays. This TN device was placed in a constant temperature bath at 60° C. and charged by applying a pulse voltage (1 V, 60 microseconds, 3 Hz). The decaying voltage was measured with a high-speed voltmeter for 166.6 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of the area A with respect to the area B.

(9) Voltage holding ratio (UV-VHR; measured at 25° C.; %): A TN device containing a sample was irradiated with 5 mmW of ultraviolet rays for 166.6 minutes using a black light as a light source. The voltage holding ratio was measured and the stability to ultraviolet rays was evaluated. The configuration of the TN device and the method of measuring the voltage holding ratio are described in Measurement (8). A composition having a large UV-VHR has great stability to ultraviolet rays. UV-VHR is preferably 90% or more, more preferably 95% or more.

(10) Voltage holding ratio (heating VHR; measured at 25° C.; %): The TN device containing the sample was heated in a constant temperature bath at 120° C. for 20 hours, and then the voltage holding ratio was measured to determine stability against heat. evaluated. The configuration of the TN device and the method of measuring the voltage holding ratio are described in Measurement (8). A composition having a large heated VHR has great stability to heat. The heating VHR is preferably 90% or more, more preferably 95% or more.

(11) Response time (τ; measured at 25° C.; ms): LCD-5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was put in a VA device in a normally black mode in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was antiparallel. The device was sealed with an adhesive that was cured with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The response time was expressed as the time required to change the transmittance from 90% to 10% (fall time; fall time; millisecond).

(12) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25° C.; pN): EC-1 type elastic constant measuring instrument manufactured by Toyo Technica Co., Ltd. for measurement Using. The sample was put in a VA device in which the distance (cell gap) between two glass substrates was 20 μm. A charge of 20 V to 0 V was applied to this device, and the electrostatic capacity and the applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) values using the formula (2.98) and formula (2.101) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun). Then, the value of the elastic constant was obtained from the formula (2.100).

(13) Specific resistance (ρ; measured at 25° C.; Ωcm): 1.0 mL of a sample was placed in a container equipped with an electrode. A direct current voltage (10 V) was applied to this container, and the direct current after 10 seconds was measured. The specific resistance was calculated from the following formula. (Specific resistance)={(voltage)×(electric capacity of container)}/{(direct current)×(dielectric constant of vacuum)}

(14) Pretilt angle (degree): A spectroscopic ellipsometer M-2000U (manufactured by J. A. Woollam Co., Inc.) was used to measure the pretilt angle.

(15) Alignment stability (stability of liquid crystal alignment axis): Changes in the liquid crystal alignment axis on the electrode side of an FFS (fringe field switching) element were evaluated. The liquid crystal orientation angle φ (before) on the electrode side before stress application was measured. After applying a rectangular wave of 4.5 V and 60 Hz to the device for 20 minutes, the device was short-circuited for 1 second, and after 1 second and 5 minutes, the liquid crystal orientation angle φ (after) on the electrode side was measured again. From these values, changes in liquid crystal alignment angle (Δφ; deg.) after 1 second and 5 minutes were calculated using the following formula. Δφ (deg.) = φ (after)-φ (before)
These measurements were performed with reference to J. Hilfiker, B. Johs, C. Herzinger, JF Elman, E. Montbach, D. Bryant, and PJ Bos, Thin Solid Films, 455-456, (2004) 596-600. .. It can be said that the smaller the change (Δφ), the smaller the change rate of the liquid crystal alignment axis, and the more stable the liquid crystal molecules.

(16) Flicker rate (measured at 25° C.; %): For measurement, a multimedia display tester 3298F manufactured by Yokogawa Electric Co., Ltd. was used. The light source was an LED. The sample was put into a normally black mode device in which the distance (cell gap) between the two glass substrates was 3.5 μm and the rubbing direction was antiparallel. The device was sealed with an adhesive that was cured with ultraviolet light. A voltage was applied to this element, and the voltage at which the amount of light transmitted through the element was maximized was measured. While applying this voltage to the element, the sensor part was brought close to the element and the displayed flicker rate was read. The smaller the flicker rate, the better.

(17) Line afterimage (Line Image Sticking Parameter; LISP;%): A line afterimage was generated by applying electrical stress to the element. The luminance of the area having the line afterimage and the luminance of the remaining area (reference area) were measured. The ratio of the decrease in luminance due to the line afterimage was calculated, and the size of the line afterimage was expressed by this ratio.

17a) Luminance measurement: An image of the device was photographed using an imaging color luminance meter (Radiant Zemax, PM-1433F-0). The brightness of each region of the device was calculated by analyzing the image using software (Prometric 9.1, manufactured by Radiant Imaging). An LED backlight having an average luminance of 3500 cd/m ² was used as a light source.

17b) Setting of stress voltage: A sample is put into an FFS device (16 cells of 4 cells in length×4 cells in width) having a cell gap of 3.5 μm and having a matrix structure, and an adhesive that cures this element with ultraviolet rays is used. And sealed. Polarizing plates were arranged on the upper surface and the lower surface of the device so that the polarization axes were orthogonal to each other. This device was irradiated with light and a voltage (rectangular wave, 60 Hz) was applied. The voltage was stepwise increased in the range of 0 V to 7.5 V in steps of 0.1 V, and the brightness of the transmitted light at each voltage was measured. The voltage when the brightness becomes maximum is abbreviated as V255. The voltage when the luminance becomes 21.6% of V255 (that is, 127 gradations) is abbreviated as V127.

17c) Stress condition: V255 (rectangular wave, 30 Hz) was applied to the stress region and 0.5 V (rectangular wave, 30 Hz) was applied to the stress region under conditions of 60° C. and 23 hours to display a checker pattern. Next, V127 (rectangular wave, 0.25 Hz) was applied, and the luminance was measured under the condition that the exposure time was 4000 milliseconds.

17d) Calculation of line afterimage: Of 16 cells, 4 cells in the central portion (2 cells in the vertical direction×2 cells in the horizontal direction) were used for the calculation. The 4 cells were divided into 25 regions (5 cells in the vertical direction×5 cells in the horizontal direction). The average brightness of the four areas (two vertical cells×two horizontal cells) at the four corners is abbreviated as the brightness A. The area excluding the four corner areas from the 25 area was a cross shape. The minimum value of the luminance is abbreviated as the luminance B in the four regions excluding the central intersection region from the cross-shaped region. The line afterimage was calculated from the following formula. (Line afterimage)=(luminance A−luminance B)/luminance A×100. The line afterimage is preferably small.

(18) Surface afterimage (Face Image Sticking Parameter; FISP;%): A surface afterimage was generated by applying electrical stress to the element. The luminance of the area having the surface afterimage and the luminance of the remaining area were measured at 25°C. The ratio of the change in luminance due to the surface afterimage was calculated, and the size of the surface afterimage was expressed by this ratio.

18a) "Measurement of luminance", "setting of stress voltage", and "stress condition" were in accordance with the procedure described in the section "Line afterimage".

18b) The surface afterimage was calculated from the following formula. (Surface afterimage)=(luminance C−luminance D)/luminance D×100. Here, the brightness C was the average brightness of 8 cells to which V255 was applied, and the brightness D was the average brightness of 8 cells to which 0.5V was applied. The surface afterimage is preferably small. When the dielectric anisotropy of the liquid crystal composition was positive, the surface afterimage was shown by P-FISP. When negative, the surface afterimage was indicated by N-FISP.

(19) Haze ratio (%): A haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the haze ratio.

(20) Haze change rate (%): A weather resistance test of the device was performed. The haze was measured before and after the test, and the haze change rate was calculated. This test was conducted according to Japanese Industrial Standard (JIS) K5600-7-7, accelerated weather resistance and accelerated light resistance (xenon lamp method). The measurement conditions were illuminance (UVA; 180 W/m ² ), irradiation time (100 hours), black panel temperature (63±2° C.), bath temperature (35° C.), bath relative humidity (40% RH). It was

(21) Helical pitch (P; measured at room temperature; μm): The helical pitch was measured by the wedge method. See "Liquid Crystal Handbook", page 196 (published in 2000, Maruzen). The sample was placed in a wedge-shaped cell and allowed to stand at room temperature for 2 hours, and then the spacing (d2-d1) of the disclination line was observed with a polarizing microscope (Nikon Corporation, trade name MM40/60 series). The spiral pitch (P) was calculated from the following equation in which the angle of the wedge cell was represented by θ. P=2×(d2-d1)×tan θ.

(22) Characteristics of light control element When measuring the characteristics of a liquid crystal display element, an element of a glass substrate is usually used. On the other hand, in a liquid crystal light control device, a plastic film may be used as a substrate. Therefore, an element having a substrate of polycarbonate was prepared and characteristics such as threshold voltage and response time were measured. This measured value was compared with the case of the element of the glass substrate. As a result, the two types of measured values were almost the same. Therefore, the characteristics of the device on the glass substrate were measured, and the results were described.

Example of composition is shown below. The liquid crystal compounds are represented by symbols based on the definition in Table 3 below. In Table 3, the configuration of 1,4-cyclohexylene is trans. The number in parentheses after the symbolized compound represents the chemical formula to which the compound belongs. The symbol (−) means other liquid crystal compound. Finally, the characteristic values of the composition are summarized.

In the examples, the following compositions are selected and used.
[Composition (M1)]
3-HB(2F,3F)-O2 (1-1) 10%
5-HB(2F,3F)-O2 (1-1) 10%
2-HHB(2F,3F)-O2 (1-8) 4%
3-HHB(2F,3F)-O2 (1-8) 10%
5-HHB(2F,3F)-O2 (1-8) 9%
2-HBB(2F,3F)-O2 (1-14) 4%
3-HBB(2F,3F)-O2 (1-14) 8%
5-HBB(2F,3F)-O2 (1-14) 6%
3-HH-4 (2-1) 14%
3-HB-O2 (2-2) 10%
3-HHB-O1 (2-5) 4%
3-HHB-1 (2-5) 5%
3-HBB-2 (2-6) 6%
NI=103.4° C.; Tc<−20° C.; η=26.9 mPa·s; Δn=0.107; Δε=−3.6; Vth=2.45V; γ1=181.8 mPa·s.

[Composition (M2)]
2-BB(2F,3F)-O2 (1-6) 8%
3-BB(2F,3F)-O2 (1-6) 13%
5-BB(2F,3F)-O2 (1-6) 13%
2-HHB(2F,3F)-O2 (1-8) 4%
3-HHB(2F,3F)-O2 (1-8) 10%
5-HHB(2F,3F)-O2 (1-8) 9%
3-HBB(2F,3F)-O2 (1-14) 10%
5-HBB(2F,3F)-O2 (1-14) 6%
3-HHB-1 (2-5) 9%
3-HHB-3 (2-5) 9%
5-B(F)BB-2 (2-7) 9%
NI=100.7° C.; Tc<−20° C.; η=34.3 mPa·s; Δn=0.153; Δε=−4.6; Vth=2.23 V; γ1=248.2 mPa·s.

[Composition (M3)]
2-BB(2F,3F)-O2 (1-6) 6%
3-BB(2F,3F)-O2 (1-6) 13%
5-BB(2F,3F)-O2 (1-6) 10%
2-HBB(2F,3F)-O2 (1-14) 3%
3-HBB(2F,3F)-O2 (1-14) 10%
4-HBB(2F,3F)-O2 (1-14) 5%
5-HBB(2F,3F)-O2 (1-14) 10%
1-BB-3 (2-3) 5%
3-HBB-2 (2-6) 10%
5-B(F)BB-2 (2-7) 12%
5-B(F)BB-3 (2-7) 10%
3-BB (2F, 5F) B-3 (2) 6%
NI=92.2° C.; Tc<−20° C.; η=41.8 mPa·s; Δn=0.195; Δε=−3.2; Vth=2.61 V; γ1=194.0 mPa·s.

[Composition (M4)]
3-HB(2F,3F)-O2 (1-1) 12%
5-HB(2F,3F)-O2 (1-1) 10%
2-HHB(2F,3F)-O2 (1-8) 5%
3-HHB(2F,3F)-O2 (1-8) 10%
5-HHB(2F,3F)-O2 (1-8) 9%
3-HBB(2F,3F)-O2 (1-14) 8%
5-HBB(2F,3F)-O2 (1-14) 7%
3-HH-4 (2-1) 14%
3-HB-O2 (2-2) 10%
3-HHB-O1 (2-5) 4%
3-HHB-1 (2-5) 8%
3-HBB-2 (2-6) 3%
NI=101.7° C.; Tc<−20° C.; η=26.1 mPa·s; Δn=0.102; Δε=−3.5; Vth=2.46 V; γ1=174.0 mPa·s.

[Composition (M5)]
2-BB(2F,3F)-O2 (1-6) 8%
3-BB(2F,3F)-O2 (1-6) 12%
5-BB(2F,3F)-O2 (1-6) 12%
2-HHB(2F,3F)-O2 (1-8) 4%
3-HHB(2F,3F)-O2 (1-8) 10%
5-HHB(2F,3F)-O2 (1-8) 9%
3-HBB(2F,3F)-O2 (1-14) 10%
5-HBB(2F,3F)-O2 (1-14) 6%
3-HB-O2 (2-2) 3%
3-HHB-1 (2-5) 9%
3-HHB-3 (2-5) 9%
5-B(F)BB-2 (2-7) 8%
NI=100.8° C.; Tc<−20° C.; η=32.9 mPa·s; Δn=0.150; Δε=−4.5; Vth=2.29 V; γ1=240.3 mPa·s.

[Composition (M6)]
2-BB(2F,3F)-O2 (1-6) 6%
3-BB(2F,3F)-O2 (1-6) 10%
5-BB(2F,3F)-O2 (1-6) 10%
2-HBB(2F,3F)-O2 (1-14) 3%
3-HBB(2F,3F)-O2 (1-14) 10%
4-HBB(2F,3F)-O2 (1-14) 5%
5-HBB(2F,3F)-O2 (1-14) 10%
1-BB-3 (2-3) 6%
3-HBB-2 (2-6) 12%
5-B(F)BB-2 (2-7) 12%
5-B(F)BB-3 (2-7) 10%
3-BB (2F, 5F) B-3 (2) 6%
NI=95.6° C.; Tc<−20° C.; η=41.2 mPa·s; Δn=0.200; Δε=−3.0; Vth=2.73 V; γ1=192.4 mPa·s.

[Composition (M7)]
3-BB(2F,3F)-O2 (1-6) 12%
5-BB(2F,3F)-O2 (1-6) 12%
3-HHB(2F,3F)-O2 (1-8) 10%
5-HHB(2F,3F)-O2 (1-8) 8%
2-HBB(2F,3F)-O2 (1-14) 4%
3-HBB(2F,3F)-O2 (1-14) 10%
5-HBB(2F,3F)-O2 (1-14) 6%
3-HB-O2 (2-2) 12%
3-HHB-1 (2-5) 8%
3-HHB-3 (2-5) 6%
3-HBB-2 (2-6) 12%
NI=105.9° C.; Tc<−20° C.; η=29.9 mPa·s; Δn=0.143; Δε=−3.6; Vth=2.58V; γ1=226.9 mPa·s.

[Composition (M8)]
2-BB(2F,3F)-O2 (1-6) 4%
3-BB(2F,3F)-O2 (1-6) 10%
5-BB(2F,3F)-O2 (1-6) 10%
3-HHB(2F,3F)-O2 (1-8) 3%
2-HBB(2F,3F)-O2 (1-14) 3%
3-HBB(2F,3F)-O2 (1-14) 10%
4-HBB(2F,3F)-O2 (1-14) 6%
5-HBB(2F,3F)-O2 (1-14) 10%
1-BB-3 (2-3) 5%
3-HBB-2 (2-6) 10%
5-B(F)BB-2 (2-7) 12%
5-B(F)BB-3 (2-7) 10%
3-BB (2F, 5F) B-3 (2) 7%
NI=100.7° C.; Tc<−20° C.; η=42.4 mPa·s; Δn=0.200; Δε=−3.1; Vth=2.75 V; γ1=281.2 mPa·s.

[Composition (M9)]
3-BB(2F,3F)-O2 (1-6) 14%
5-BB(2F,3F)-O2 (1-6) 14%
3-HHB(2F,3F)-O2 (1-8) 8%
5-HHB(2F,3F)-O2 (1-8) 8%
2-HBB(2F,3F)-O2 (1-14) 3%
3-HBB(2F,3F)-O2 (1-14) 10%
5-HBB(2F,3F)-O2 (1-14) 6%
3-HB-O2 (2-2) 12%
3-HHB-1 (2-5) 5%
3-HHB-3 (2-5) 5%
3-HBB-2 (2-6) 12%
5-B(F)BB-2 (2-7) 3%
NI=97.8° C.; Tc<−20° C.; η=29.2 mPa·s; Δn=0.150; Δε=−3.8; Vth=2.46V; γ1=217.0 mPa·s.

[Composition (M10)]
3-HB(2F,3F)-O2 (1-1) 7%
3-H1OB(2F,3F)-O2 (1-3) 5%
3-DhB(2F,3F)-O2 (1-4) 3%
3-BB(2F,3F)-O2 (1-6) 12%
3-HHB(2F,3F)-O1 (1-8) 3%
3-HHB(2F,3F)-O2 (1-8) 5%
V-HHB(2F,3F)-O2 (1-8) 3%
V2-HHB(2F,3F)-O2 (1-8) 3%
3-HH1OB(2F,3F)-O2 (1-10) 3%
3-HBB(2F,3F)-O2 (1-14) 3%
V-HBB(2F,3F)-O2 (1-14) 3%
3-HBB(2F,3Cl)-O2 (1-15) 3%
2-BB (2F, 3F) B-3 (1-19) 5%
1-B2BB(2F,3F)-O2 (1-22) 3%
V-HH2BB(2F,3F)-O2 (1-24) 3%
2O-DBTF2-O4 (1-34) 3%
3-HH-V (2-1) 21%
3-HH-4 (2-1) 3%
3-HHEH-3 (2-4) 3%
V-HBB-2 (2-6) 3%
3-HB(F)HH-2 (2-10) 3%
NI=82.5° C.; Tc<−20° C.; η=21.3 mPa·s; Δn=0.117; Δε=−4.1; Vth=2.08V; γ1=130.1 mPa·s.

[Composition (M11)]
3-HB(2F,3F)-O4 (1-1) 6%
3-H2B(2F,3F)-O2 (1-2) 8%
3-H1OB(2F,3F)-O2 (1-3) 5%
3-BB(2F,3F)-O2 (1-6) 10%
2-HHB(2F,3F)-O2 (1-8) 7%
3-HHB(2F,3F)-O2 (1-8) 7%
5-HHB(2F,3F)-O2 (1-8) 7%
2-HBB(2F,3F)-O2 (1-14) 4%
3-HBB(2F,3F)-O2 (1-14) 7%
5-HBB(2F,3F)-O2 (1-14) 6%
3-HH-V (2-1) 11%
1-BB-3 (2-3) 6%
3-HHB-1 (2-5) 4%
3-HHB-O1 (2-5) 4%
3-HBB-2 (2-6) 4%
3-B(F)BB-2 (2-7) 4%
NI=87.6° C.; Tc<−20° C.; Δn=0.126; Δε=−4.5; η=25.3 mPa·s.

[Composition (M12)]
3-HB(2F,3F)-O2 (1-1) 5%
5-HB(2F,3F)-O2 (1-1) 7%
3-BB(2F,3F)-O2 (1-6) 8%
3-HHB(2F,3F)-O2 (1-8) 5%
5-HHB(2F,3F)-O2 (1-8) 4%
3-HH1OB(2F,3F)-O2 (1-10) 5%
2-HBB(2F,3F)-O2 (1-14) 3%
3-HBB(2F,3F)-O2 (1-14) 9%
4-HBB(2F,3F)-O2 (1-14) 4%
5-HBB(2F,3F)-O2 (1-14) 8%
2-BB (2F, 3F) B-3 (1-19) 4%
3-HH-V (2-1) 27%
3-HH-V1 (2-1) 6%
V-HHB-1 (2-5) 5%
NI=81.2° C.; Tc<−20° C.; Δn=0.107; Δε=−3.2; η=15.5 mPa·s.

[Composition (M13)]
3-H2B(2F,3F)-O2 (1-2) 7%
3-HHB(2F,3F)-O2 (1-8) 8%
3-HH1OB(2F,3F)-O2 (1-10) 8%
2-HchB(2F,3F)-O2 (1-12) 8%
3-HDhB(2F,3F)-O2 (1-13) 3%
5-HDhB(2F,3F)-O2 (1-13) 4%
2-BB (2F, 3F) B-3 (1-19) 7%
2-BB (2F, 3F) B-4 (1-19) 7%
4-HH-V (2-1) 15%
3-HH-V1 (2-1) 6%
1-HH-2V1 (2-1) 6%
3-HH-2V1 (2-1) 4%
V2-BB-1 (2-3) 5%
1V2-BB-1 (2-3) 5%
3-HHB-1 (2-5) 3%
3-HB(F)BH-3 (2-12) 4%
NI=88.2° C.; Tc<−20° C.; Δn=0.115; Δε=−2.1; η=18.3 mPa·s.

[Composition (M14)]
V2-H2B(2F,3F)-O2 (1-2) 8%
V2-H1OB(2F,3F)-O4 (1-3) 4%
3-BB(2F,3F)-O2 (1-6) 7%
2-HHB(2F,3F)-O2 (1-8) 7%
3-HHB(2F,3F)-O2 (1-8) 7%
3-HH2B(2F,3F)-O2 (1-9) 7%
5-HH2B(2F,3F)-O2 (1-9) 4%
V-HH2B(2F,3F)-O2 (1-9) 6%
V2-HBB(2F,3F)-O2 (1-14) 5%
V-HBB(2F,3F)-O2 (1-14) 5%
V-HBB(2F,3F)-O4 (1-14) 6%
2-HH-3 (2-1) 12%
1-BB-5 (2-3) 12%
3-HHB-1 (2-5) 4%
3-HHB-O1 (2-5) 3%
3-HBB-2 (2-6) 3%
NI=89.9° C.; Tc<−20° C.; Δn=0.122; Δε=−4.2; η=23.4 mPa·s.

[Composition (M15)]
3-HB(2F,3F)-O2 (1-1) 3%
V-HB(2F,3F)-O2 (1-1) 3%
V2-HB(2F,3F)-O2 (1-1) 5%
5-H2B(2F,3F)-O2 (1-2) 5%
V2-BB(2F,3F)-O2 (1-6) 3%
1V2-BB(2F,3F)-O2 (1-6) 3%
3-HHB(2F,3F)-O2 (1-8) 6%
V-HHB(2F,3F)-O2 (1-8) 6%
V-HHB(2F,3F)-O4 (1-8) 5%
V2-HHB(2F,3F)-O2 (1-8) 4%
V-HHB(2F,3Cl)-O2 (1-11) 3%
V2-HBB(2F,3F)-O2 (1-14) 5%
V-HBB(2F,3F)-O2 (1-14) 4%
V-HBB(2F,3F)-O4 (1-14) 5%
V2-BB (2F, 3F) B-1 (1-19) 4%
3-HH-V (2-1) 27%
3-HH-V1 (2-1) 6%
V-HHB-1 (2-5) 3%
NI=77.1° C.; Tc<−20° C.; Δn=0.101; Δε=−3.0; η=13.9 mPa·s.

[Composition (M16)]
3-HB(2F,3F)-O4 (1-1) 6%
3-H2B(2F,3F)-O2 (1-2) 8%
3-H1OB(2F,3F)-O2 (1-3) 4%
3-BB(2F,3F)-O2 (1-6) 7%
2-HHB(2F,3F)-O2 (1-8) 6%
3-HHB(2F,3F)-O2 (1-8) 10%
5-HHB(2F,3F)-O2 (1-8) 8%
2-HBB(2F,3F)-O2 (1-14) 5%
3-HBB(2F,3F)-O2 (1-14) 7%
5-HBB(2F,3F)-O2 (1-14) 5%
2-HH-3 (2-1) 12%
1-BB-3 (2-3) 6%
3-HHB-1 (2-5) 3%
3-HHB-O1 (2-5) 4%
3-HBB-2 (2-6) 6%
3-B(F)BB-2 (2-7) 3%
NI=93.0° C.; Tc<−20° C.; Δn=0.124; Δε=−4.5; η=25.0 mPa·s.

[Composition (M17)]
V-HB(2F,3F)-O2 (1-1) 7%
V2-BB(2F,3F)-O2 (1-6) 10%
V-HHB(2F,3F)-O1 (1-8) 7%
V-HHB(2F,3F)-O2 (1-8) 9%
V2-HHB(2F,3F)-O2 (1-8) 8%
3-HH2B(2F,3F)-O2 (1-9) 9%
V-HBB(2F,3F)-O2 (1-14) 8%
V-HBB(2F,3F)-O4 (1-14) 6%
3-HH-V (2-1) 15%
3-HH-V1 (2-1) 6%
2-HH-3 (2-1) 9%
3-HH-5 (2-1) 3%
1V2-HH-3 (2-1) 3%
NI=87.5° C.; Tc<−20° C.; Δn=0.100; Δε=−3.4; η=18.9 mPa·s.

[Composition (M18)]
3-HB(2F,3F)-O2 (1-1) 7%
5-HB(2F,3F)-O2 (1-1) 7%
3-BB(2F,3F)-O2 (1-6) 8%
3-HHB(2F,3F)-O2 (1-8) 4%
5-HHB(2F,3F)-O2 (1-8) 5%
3-HH1OB(2F,3F)-O2 (1-10) 5%
2-HBB(2F,3F)-O2 (1-14) 3%
3-HBB(2F,3F)-O2 (1-14) 8%
4-HBB(2F,3F)-O2 (1-14) 5%
5-HBB(2F,3F)-O2 (1-14) 8%
2-BB (2F, 3F) B-3 (1-19) 4%
3-HH-V (2-1) 33%
V-HHB-1 (2-5) 3%
NI=76.4° C.; Tc<−20° C.; Δn=0.104; Δε=−3.2; η=15.6 mPa·s.

[Composition (M19)]
2-H1OB(2F,3F)-O2 (1-3) 6%
3-H1OB(2F,3F)-O2 (1-3) 4%
3-BB(2F,3F)-O2 (1-6) 3%
2-HH1OB(2F,3F)-O2 (1-10) 14%
2-HBB(2F,3F)-O2 (1-14) 7%
3-HBB(2F,3F)-O2 (1-14) 11%
5-HBB(2F,3F)-O2 (1-14) 9%
2-HH-3 (2-1) 5%
3-HH-VFF (2-1) 30%
1-BB-3 (2-3) 5%
3-HHB-1 (2-5) 3%
3-HBB-2 (2-6) 3%
NI=78.3° C.; Tc<−20° C.; Δn=0.103; Δε=−3.2; η=17.7 mPa·s.

[Composition (M20)]
V-HB(2F,3F)-O2 (1-1) 10%
V2-HB(2F,3F)-O2 (1-1) 10%
2-H1OB(2F,3F)-O2 (1-3) 3%
3-H1OB(2F,3F)-O2 (1-3) 3%
2O-BB(2F,3F)-O2 (1-6) 3%
V2-BB(2F,3F)-O2 (1-6) 8%
V2-HHB(2F,3F)-O2 (1-8) 5%
V-HHB(2F,3Cl)-O2 (1-11) 7%
2-HBB(2F,3F)-O2 (1-14) 3%
3-HBB(2F,3F)-O2 (1-14) 3%
V-HBB(2F,3F)-O2 (1-14) 6%
V-HBB(2F,3F)-O4 (1-14) 8%
3-HH-4 (2-1) 14%
V-HHB-1 (2-5) 10%
3-HBB-2 (2-6) 7%
NI=75.9° C.; Tc<−20° C.; Δn=0.114; Δε=−3.9; η=24.7 mPa·s.

[Composition (M21)]
3-HB(2F,3F)-O2 (1-1) 3%
2O-B(2F)B(2F,3F)-O2 (1-7) 5%
2O-B(2F)B(2F,3F)-O4 (1-7) 12%
2-HHB(2F,3F)-O2 (1-8) 4%
3-HHB(2F,3F)-O2 (1-8) 8%
5-HBB(2F,3F)-O2 (1-14) 4%
3-dhBB(2F,3F)-O2 (1-16) 8%
3-HB (2F, 3F) B-2 (1-17) 4%
3-HH-V (2-1) 33%
3-HH-V1 (2-1) 5%
3-HB-O2 (2-2) 3%
1-BB-3 (2-3) 3%
3-HHB-1 (2-5) 6%
2-BB(F)B-3 (2-8) 2%
NI=72.6° C.; Tc<−20° C.; Δn=0.105; Δε=−2.5; η=15.7 mPa·s.

[Composition (M22)]
3-HB(2F,3F)-O4 (1-1) 6%
3-H2B(2F,3F)-O2 (1-2) 8%
3-H1OB(2F,3F)-O2 (1-3) 4%
3-BB(2F,3F)-O2 (1-6) 7%
2-HHB(2F,3F)-O2 (1-8) 7%
3-HHB(2F,3F)-O2 (1-8) 7%
3-HH2B(2F,3F)-O2 (1-9) 7%
5-HH2B(2F,3F)-O2 (1-9) 4%
2-HBB(2F,3F)-O2 (1-14) 5%
3-HBB(2F,3F)-O2 (1-14) 5%
4-HBB(2F,3F)-O2 (1-14) 6%
2-HH-3 (2-1) 12%
1-BB-5 (2-3) 12%
3-HHB-1 (2-5) 4%
3-HHB-O1 (2-5) 3%
3-HBB-2 (2-6) 3%
NI=82.8° C.; Tc<−20° C.; Δn=0.118; Δε=−4.4; η=22.5 mPa·s.

[Composition (M23)]
3-HB(2F,3F)-O2 (1-1) 7%
5-HB(2F,3F)-O2 (1-1) 7%
3-BB(2F,3F)-O2 (1-6) 8%
3-HHB(2F,3F)-O2 (1-8) 5%
5-HHB(2F,3F)-O2 (1-8) 4%
3-HH1OB(2F,3F)-O2 (1-10) 4%
2-HBB(2F,3F)-O2 (1-14) 3%
3-HBB(2F,3F)-O2 (1-14) 8%
4-HBB(2F,3F)-O2 (1-14) 5%
5-HBB(2F,3F)-O2 (1-14) 8%
2-BB (2F, 3F) B-3 (1-19) 5%
3-HH-V (2-1) 27%
3-HH-V1 (2-1) 6%
V-HHB-1 (2-5) 3%
NI=78.1° C.; Tc<−20° C.; Δn=0.107; Δε=−3.2; η=15.9 mPa·s.

[Composition (M24)]
3-HB(2F,3F)-O2 (1-1) 10%
5-HB(2F,3F)-O2 (1-1) 10%
3-H2B(2F,3F)-O2 (1-2) 8%
5-H2B(2F,3F)-O2 (1-2) 8%
3-HDhB(2F,3F)-O2 (1-13) 5%
2-HBB(2F,3F)-O2 (1-14) 6%
3-HBB(2F,3F)-O2 (1-14) 8%
4-HBB(2F,3F)-O2 (1-14) 7%
5-HBB(2F,3F)-O2 (1-14) 7%
3-HH-4 (2-1) 14%
V-HHB-1 (2-5) 10%
3-HBB-2 (2-6) 7%
NI=88.5° C.; Tc<−20° C.; Δn=0.108; Δε=−3.8; η=24.6 mPa·s.

[Composition (M25)]
2O-B(2F)B(2F,3F)-O2 (1-7) 6%
2O-B(2F)B(2F,3F)-O4 (1-7) 13%
2-HHB(2F,3F)-O2 (1-8) 4%
3-HHB(2F,3F)-O2 (1-8) 4%
3-HHB(2F,3F)-1 (1-8) 4%
3-dhBB(2F,3F)-O2 (1-16) 5%
3-HB(2F)B(2F,3F)-O2 (1-18) 7%
V-H2BBB(2F,3F)-O2 (1-25) 5%
3-HH-V (2-1) 42%
3-HH-V1 (2-1) 5%
1-BB-3 (2-3) 3%
V-HHB-1 (2-5) 2%
NI=71.8° C.; Tc<−20° C.; Δn=0.103; Δε=−2.5; η=14.2 mPa·s.

[Composition (M26)]
3-HB(2F,3F)-O4 (1-1) 15%
3-chB(2F,3F)-O2 (1-5) 7%
2-HchB(2F,3F)-O2 (1-12) 8%
3-HBB(2F,3F)-O2 (1-14) 8%
4-HBB(2F,3F)-O2 (1-14) 5%
5-HBB(2F,3F)-O2 (1-14) 7%
3-dhBB(2F,3F)-O2 (1-16) 5%
5-HH-V (2-1) 18%
7-HB-1 (2-2) 5%
V-HHB-1 (2-5) 7%
V2-HHB-1 (2-5) 7%
3-HBB(F)B-3 (2-13) 8%
NI=98.8° C.; Tc<−20° C.; Δn=0.111; Δε=−3.2; η=23.9 mPa·s.

[Composition (M27)]
3-H2B(2F,3F)-O2 (1-2) 18%
5-H2B(2F,3F)-O2 (1-2) 17%
3-HHB(2F,3Cl)-O2 (1-11) 5%
3-HDhB(2F,3F)-O2 (1-13) 5%
3-HBB(2F,3Cl)-O2 (1-15) 8%
5-HBB(2F,3Cl)-O2 (1-15) 7%
3-HH-V (2-1) 11%
3-HH-VFF (2-1) 7%
F3-HH-V (2-1) 10%
3-HHEH-3 (2-4) 4%
3-HB(F)HH-2 (2-10) 4%
3-HHEBH-3 (2-11) 4%
NI=77.5° C.; Tc<−20° C.; Δn=0.084; Δε=−2.6; η=22.8 mPa·s.

[Composition (M28)]
3-HB(2F,3F)-O2 (1-1) 8%
3-H2B(2F,3F)-O2 (1-2) 10%
3-BB(2F,3F)-O2 (1-6) 10%
2O-BB(2F,3F)-O2 (1-6) 3%
2-HHB(2F,3F)-O2 (1-8) 4%
3-HHB(2F,3F)-O2 (1-8) 7%
2-HHB(2F,3F)-1 (1-8) 5%
3-HDhB(2F,3F)-O2 (1-13) 6%
2-HBB(2F,3F)-O2 (1-14) 4%
3-HBB(2F,3F)-O2 (1-14) 7%
3-dhBB(2F,3F)-O2 (1-16) 4%
2-BB (2F, 3F) B-3 (1-19) 6%
2-BB (2F, 3F) B-4 (1-19) 6%
3-HH1OCro(7F,8F)-5 (1-27) 4%
3-HH-V (2-1) 11%
1-BB-5 (2-3) 5%
NI=70.6° C.; Tc<−20° C.; Δn=0.129; Δε=−4.3; η=27.0 mPa·s.

[Composition (M29)]
3-HB(2F,3F)-O2 (1-1) 5%
V2-BB(2F,3F)-O2 (1-6) 8%
3-HHB(2F,3F)-O2 (1-8) 6%
V-HHB(2F,3F)-O2 (1-8) 7%
V-HHB(2F,3F)-O4 (1-8) 4%
2-HBB(2F,3F)-O2 (1-14) 2%
3-HBB(2F,3F)-O2 (1-14) 6%
V-HBB(2F,3F)-O2 (1-14) 7%
V-HBB(2F,3F)-O4 (1-14) 6%
2-BB (2F, 3F) B-3 (1-19) 5%
V-HH-V (2-1) 24%
V-HH-V1 (2-1) 20%
NI=73.5° C.; Tc<−20° C.; Δn=0.106; Δε=−2.7; η=17.0 mPa·s.

[Composition (M30)]
3-DhB(2F,3F)-O2 (1-4) 5%
2-BB(2F,3F)-O2 (1-6) 9%
3-BB(2F,3F)-O2 (1-6) 9%
3-HH2B(2F,3F)-O2 (1-9) 6%
3-HDhB(2F,3F)-O2 (1-13) 14%
2-HBB(2F,3F)-O2 (1-14) 2%
3-HBB(2F,3F)-O2 (1-14) 6%
V-HBB(2F,3F)-O2 (1-14) 7%
2-HH-3 (2-1) 19%
3-HHB-1 (2-5) 3%
V-HHB-1 (2-5) 10%
V2-HHB-1 (2-5) 10%
NI=86.0° C.; Tc<−20° C.; Δn=0.110; Δε=−3.8; η=22.9 mPa·s.

In the examples, the following polymerizable compounds are selected and used.

The black dichroic dye (A) is prepared according to Example 42 of Patent Document 9 by mixing the following four dyes. The proportion and color of the dye are 56.3% (yellow), 12.6% (orange), 9.6% (red), and 21.5% (blue) in order from the top.

[Example 1]
Fabrication of liquid crystal light control device-1
The composition (M1) had a negative dielectric anisotropy. 95% of the composition (M1) and 5% of the polymerizable compound (RM-1) are mixed to prepare a polymerizable composition. The above black dye (A) is added to this composition at a rate of 5% based on the composition (M1). Irgacure 651 (photopolymerization initiator; BASF) is added at a rate of 0.3% based on the polymerizable compound. This polymerizable composition is injected into a device in which the distance (cell gap) between two glass substrates is 3.5 μm. The temperature at the time of injection is 140°C. This device is irradiated with 18 mW/cm ² ultraviolet rays for 56 seconds with a high-pressure mercury lamp to produce a device having a liquid crystal composite. This element is transparent. When a voltage of 45 V is applied to this element and it is irradiated with light, it becomes black. This indicates that the device is in reverse mode.

[Comparative Example 1]
In the above experimental procedure, the polymerizable composition is prepared without adding the black dye (A) to the composition. According to the above operation, a device having a liquid crystal composite is manufactured. This element is transparent. When a voltage of 45 V is applied to this element and it is irradiated with light, the element becomes opaque. However, the surface of the device is bright.

[Example 2]
Fabrication of liquid crystal light control device-2
Next, the two kinds of polymerizable compounds are combined. 90% of the composition (M1), 5% of the polymerizable compound (RM-8) and 5% of the polymerizable compound (RM-11) are mixed to prepare a polymerizable composition. The black dye (A) is added to this composition at a rate of 5% based on the composition (M1). Irgacure 651 (photopolymerization initiator; BASF) is added at a rate of 0.3% based on the polymerizable compound. This polymerizable composition is injected into a device in which the distance (cell gap) between two glass substrates is 3.5 μm. The temperature at the time of injection is 140°C. This device is irradiated with 18 mW/cm ² ultraviolet rays for 56 seconds with a high-pressure mercury lamp to produce a device having a liquid crystal composite. This element is transparent. When a voltage of 45 V is applied to this element and it is irradiated with light, it becomes black. This indicates that the device is in reverse mode. ..

[Example 3]
Measurement of Haze Change Rate The elements manufactured in Examples 1 and 2 are placed in a haze meter so that the elements are perpendicular to incident light. A voltage in the range of 0V to 60V is applied to this element, and the haze ratio is measured. Next, the haze ratio after the weather resistance test performed under the condition described in Measurement (20) is measured, and the haze change ratio is calculated. The haze change rate is small. This indicates that the liquid crystal light control device has a small change with time.

The liquid crystal light control device containing the liquid crystal composite of the present invention can be used for light control windows, smart windows, and the like.

Claims (26)

A liquid crystal composition and a polymer are contained, and the liquid crystal composition contains at least one compound selected from the compounds represented by the formula (1) as a first component and a dichroic dye as a first additive. , Liquid crystal composites.

In the formula (1), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least Alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine; ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen has been replaced by fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene , 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8 -Difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3 , 7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ¹ and Z ² are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy; Is 0, 1, 2, or 3; b is 0 or 1; and the sum of a and b is 3 or less. The liquid crystal composite according to claim 1, wherein the liquid crystal composition contains at least one compound selected from compounds represented by formulas (1-1) to (1-35) as a first component.

In formulas (1-1) to (1-35), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and carbon 2 to 12 alkenyloxy, or 1 to 12 carbon alkyl in which at least one hydrogen is replaced by fluorine or chlorine. The liquid crystal composite according to claim 1 or 2, wherein the ratio of the first component is in the range of 20% to 90% based on the liquid crystal composition. The liquid crystal composite according to claim 1, wherein the liquid crystal composition contains, as the second component, at least one compound selected from the compounds represented by formula (2).

In the formula (2), R ³ and R ⁴ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and carbon in which at least one hydrogen is replaced with fluorine or chlorine. Alkyl having 1 to 12 or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 1, 2 or 3. The liquid crystal composition contains as a second component at least one compound selected from compounds represented by formulas (2-1) to (2-13). Liquid crystal composite.

In formulas (2-1) to (2-13), R ³ and R ⁴ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen. Is alkyl having 1 to 12 carbons substituted with fluorine or chlorine, or alkenyl having 2 to 12 carbons having at least one hydrogen replaced with fluorine or chlorine. The liquid crystal composite according to claim 4 or 5, wherein the ratio of the second component is in the range of 10% to 80% based on the liquid crystal composition. The liquid crystal composite according to any one of claims 1 to 6, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains a compound represented by the formula (3) as a main component.

In formula (3), P ¹ and P ² are polymerizable groups; Z ⁴ is alkylene having 1 to 20 carbons, and in this alkylene, at least one hydrogen is alkyl having 1 to 5 carbons, fluorine , Chlorine, or P ³ , and at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, —NH—, or —N(R ⁵ )—. And at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C—, and at least one —CH ₂ — is a carbocyclic group. Saturated aliphatic compound, heterocyclic saturated aliphatic compound, carbocyclic unsaturated aliphatic compound, heterocyclic unsaturated aliphatic compound, carbocyclic aromatic compound, or heterocyclic aromatic compound May be replaced by a divalent group formed by removing two hydrogens from, wherein the number of carbons is 5 to 35, and at least one hydrogen is replaced by R ⁵ or P ^3. And R ⁵ is alkyl having 1 to 12 carbons, and in this alkyl, at least one —CH ₂ — is —O—, —CO—, —COO—, or —OCO—. It may be replaced and P ³ is a polymerizable group. 8. The liquid crystal composite according to claim 7, wherein P ¹ , P ² , and P ³ are groups selected from the polymerizable groups represented by formula (P-1) to formula (P-6).

In formulas (P-1) to (P-6), M ¹ , M ² and M ³ are each hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced with fluorine or chlorine. And alkyl having 1 to 5 carbon atoms. The liquid crystal composite according to claim 7, wherein at least one of P ¹ , P ² , and P ³ is acryloyloxy or methacryloyloxy. The liquid crystal composite according to any one of claims 1 to 6, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains the compound represented by the formula (4) as a main component.

In formula (4), M ⁴ and M ⁵ are hydrogen or methyl; Z ⁵ is alkylene having 21 to 80 carbons, and in this alkylene, at least one hydrogen is alkyl having 1 to 20 carbons, It may be replaced by fluorine or chlorine, and at least one —CH ₂ — is replaced by —O—, —CO—, —COO—, —OCO—, —NH—, or —N(R ⁵ )—. At least one —CH ₂ —CH ₂ — may be replaced by —CH═CH— or —C≡C—, wherein R ⁵ is alkyl having 1 to 12 carbons. , In this alkyl, at least one —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—. The liquid crystal composite according to any one of claims 1 to 6, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains a compound represented by the formula (5) as a main component.

In formula (5), M ⁶ is hydrogen or methyl; Z ⁶ is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one hydrogen may be replaced by fluorine or chlorine. , At least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—; R ⁶ is alkyl having 1 to 40 carbons, wherein At least one hydrogen may be replaced by fluorine, or chlorine, and at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—, at least One —CH ₂ — is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, a carbocyclic It may be replaced by a divalent group formed by removing two hydrogens from an aromatic compound or a heterocyclic aromatic compound, and in these divalent groups, the number of carbon atoms is 5 to 35 and at least 1 One hydrogen may be replaced by an alkyl having 1 to 12 carbons, in which at least one —CH ₂ — is replaced by —O—, —CO—, —COO—, or —OCO—. May be. In formula (5), M ⁶ is hydrogen or methyl; Z ⁶ is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one hydrogen may be replaced by fluorine or chlorine. , At least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—; R ⁶ is alkyl of 1 to 40 carbons, wherein At least one hydrogen may be replaced by fluorine or chlorine, and at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—. Item 12. The liquid crystal composite according to item 11. The polymer is derived from a mixture of polymerizable compounds, the mixture containing as a main component a compound selected from compounds represented by formula (6), formula (7) and formula (8). 7. The liquid crystal composite according to any one of items 1 to 6.

In formula (6), formula (7), and formula (8), ring F, ring G, ring I, ring J, ring K, and ring L are 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, where: At least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 2 to 5 carbons Or may be replaced with an alkanoyl having 1 to 5 carbon atoms; Z ⁷ , Z ⁹ , Z ¹¹ , Z ¹² and Z ¹⁶ are single bonds, —O—, —COO—, —OCO—, or — OCO—; Z ⁸ , Z ¹⁰ , Z ¹³ , and Z ¹⁵ are single bonds, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —COS—, —SCO—, — OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N- , -N=N-, or -C≡C-; Z ¹⁴ is a single bond, -O- or -COO-; X is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano. Is alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, or alkoxycarbonyl having 2 to 20 carbons; e and g are integers from 1 to 4; j And l are integers from 0 to 3; the sum of j and l is 1 to 4; d, f, h, i, k, and m are integers from 0 to 20; M ⁷ to M ¹² is hydrogen or methyl. The liquid crystal according to any one of claims 1 to 13, wherein the first additive is at least one dichroic dye selected from benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and anthraquinones. Complex. The liquid crystal composite according to any one of claims 1 to 14, wherein the ratio of the first additive is in the range of 0.03% to 25% based on the liquid crystal composition. 16. The liquid crystal composition according to claim 1, wherein the proportion of the liquid crystal composition is in the range of 50% to 95%, and the proportion of the polymer is in the range of 5% to 50%. The liquid crystal composite described. The liquid crystal composite is obtained by using a polymerizable composition containing a liquid crystal composition and a polymerizable compound as a precursor, and the polymerizable composition contains a photopolymerization initiator as an additive. The liquid crystal composite described. A liquid crystal light control device in which the light control layer is the liquid crystal composite according to any one of claims 1 to 17, the light control layer is sandwiched between a pair of transparent substrates, and the transparent substrates have transparent electrodes. The liquid crystal light control device according to claim 18, wherein the transparent substrate is a glass plate or an acrylic plate. The liquid crystal light control device according to claim 18, wherein the transparent substrate is a plastic film. A dimming window using the liquid crystal dimming device according to any one of claims 18 to 20. A smart window using the liquid crystal light control device according to any one of claims 18 to 20. Use of the liquid crystal composite according to any one of claims 1 to 17 for a liquid crystal light control device. Use of the liquid crystal composite according to any one of claims 1 to 17 for a liquid crystal light control device in which the transparent substrate is a plastic film. Use of the liquid crystal composite according to any one of claims 1 to 17 for a light control window. Use of the liquid crystal composite according to any one of claims 1 to 17 for a smart window.