TW202035658A - Liquid crystal composite, liquid crystal light control device, light control window and smart window - Google Patents

Abstract

The present invention provides: a liquid crystal composite body that is suitable for light control and contains a liquid crystal composition which satisfies at least one of characteristics including a high upper limit temperature, a low lower limit temperature, a low viscosity, a large optical anisotropy, a large positive dielectric anisotropy, a high resistivity, high stability with respect to light, high stability with respect to heat, a high elastic constant and a short helical pitch, or which has an adequate balance between at least two of these characteristics; and a liquid crystal light control element which comprises this liquid crystal composite body. A liquid crystal composite body which contains a polymer and a liquid crystal composition that contains an optically active compound and a specific compound having a large positive dielectric anisotropy; and this liquid crystal composite body may additionally contain a dichroic dye or a specific compound that has a high upper limit temperature or a low lower limit temperature.

Description

Liquid crystal composites, liquid crystal dimming elements, dimming windows and smart windows

The present invention mainly relates to a liquid crystal dimming element. In more detail, the present invention relates to a liquid crystal dimming element having a liquid crystal composite composed of a polymer and a liquid crystal composition having negative dielectric anisotropy.

In the liquid crystal dimming element, there are methods using light scattering and the like. Such elements are used in building materials such as window glass or room partitions, vehicle parts, etc. In these devices, not only hard substrates such as glass substrates, but also soft substrates such as plastic films are used. For the liquid crystal composition sandwiched by these substrates, the arrangement of the liquid crystal molecules is changed by adjusting the applied voltage. With this method, the light transmitted through the liquid crystal composition can be controlled, so liquid crystal dimming elements are widely used in displays, optical shutters, dimming windows (Patent Document 1), smart windows (Patent Document 2), etc. in.

An example of a liquid crystal dimming element is a light scattering mode polymer dispersion type element. The liquid crystal composition is dispersed in the polymer. This element has the following characteristics. The production of components is easy. It is easy to control the film thickness in a large area, so it is possible to produce a large-screen device. No polarizing plate is needed, so a clear display can be achieved. Due to the use of light scattering, the field of view is wide. This element can be expected to be used in dimming glass, projection type displays, large-area displays, etc. due to its excellent properties.

Another example is a polymer network type liquid crystal dimming element. In this type of device, a liquid crystal composition exists in the three-dimensional network of the polymer. The composition is continuous and differs from the polymer dispersion type in this respect. This type of device also has the same characteristics as the polymer dispersion type device. There are also liquid crystal dimming elements in which polymer network type and polymer dispersion type are mixed.

A liquid crystal composition having appropriate characteristics is used for the liquid crystal light control element. By improving the characteristics of the composition, a device with good characteristics can be obtained. The relationship between the two characteristics is summarized in Table 1 below. The characteristics of the composition will be further explained based on the element. The temperature range of the nematic phase is related to the temperature range in which the element can be used. The preferred upper limit temperature of the nematic phase is about 70°C or higher, and the preferred lower limit 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. In order to control the transmittance of light, it is preferable that the response time be short. Ideally, the response time is 1 millisecond shorter than other components. Therefore, it is preferable that the viscosity of the composition is small. It is particularly preferable that the viscosity at low temperature is small. The elastic constant of the composition is related to the response time of the device. In order to achieve a short response time in the device, it is preferable that the elastic constant of the composition be large.

[Table 1] Characteristics of liquid crystal composition and liquid crystal dimming element Numbering Characteristics of liquid crystal composition Characteristics of liquid crystal dimming components 1 Wide temperature range of nematic phase Wide range of usable temperature 2 Low viscosity Short response time 3 Large optical anisotropy High haze rate 4 Large positive or negative dielectric anisotropy Low threshold voltage, low power consumption 5 Specific resistance High voltage retention rate 6 Stable to light and heat long life 7 Large elastic constant Short response time

The optical anisotropy of the composition is correlated with the haze ratio of the liquid crystal dimming element. The haze ratio is the ratio of diffused light to total transmitted light. When blocking light, the haze rate is preferably large. For a large haze ratio, it is preferable that the optical anisotropy is large. The large dielectric anisotropy of the composition contributes to low threshold voltage or low power consumption in the device. Therefore, it is preferable that the dielectric anisotropy is large. The high specific resistance of the composition contributes to the high voltage retention rate in the device. Therefore, it is preferably a composition having a large specific resistance in the initial stage. It is preferably a composition having a large specific resistance even after long-term use. The stability or weather resistance of the composition to light or heat is related to the life of the element. When the stability or weather resistance is good, the life is long. Display defects such as afterimages or drip marks are also related to the life of the device. A device with high weather resistance and low display defects is desired.

There are normal mode and reverse mode in the liquid crystal dimming element. In the normal mode, the device is opaque when no voltage is applied, and when voltage is applied, the device becomes transparent. This mode is suitable for room partitions. In the reverse mode, the device becomes transparent when no voltage is applied, and becomes opaque when voltage is applied. In this mode, it becomes transparent when the component fails, so it is suitable for the window of a car.

We have tried to improve the liquid crystal dimming element while referring to Patent Document 3 to Patent Document 6. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 06-273725 [Patent Document 2] International Publication No. 2011-96386 [Patent Document 3] Japanese Patent Laid-Open No. 63-278035 [Patent Document 4] Japanese Patent Laid-Open No. 01-198725 [Patent Document 5] Japanese Patent Laid-open No. 07-104262 [Patent Document 6] Japanese Patent Laid-Open No. 07-175045

[The problem to be solved by the invention] The subject of the present invention is to provide a liquid crystal composite suitable for dimming by combining an optically active compound in a liquid crystal composition. Another problem is to provide a liquid crystal composite including a liquid crystal composition suitable for dimming, the liquid crystal composition satisfies a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, low viscosity, and high optical anisotropy , At least one of the characteristics of large positive dielectric anisotropy, large specific resistance, high stability to light, high stability to heat, large elastic constant, and small spiral pitch. Another problem is to provide a liquid crystal composite including a liquid crystal composition suitable for dimming, the liquid crystal composition having an appropriate balance between at least two of these characteristics. Another subject is to provide a liquid crystal dimming element having such a liquid crystal composite. Another issue is to provide a liquid crystal dimming element with short response time, high voltage holding rate, low threshold voltage, high haze rate, high weather resistance, and long life. [Means to solve the problem]

式（1）中，R¹ 為碳數1至12的烷基、碳數1至12的烷氧基或碳數2至12的烯基；環A為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、2,6-二氟-1,4-伸苯基、嘧啶-2,5-二基、1,3-二噁烷-2,5-二基或四氫吡喃-2,5-二基；Z¹ 為單鍵、伸乙基、伸乙烯基、伸乙炔基、亞甲氧基、羰氧基或二氟亞甲氧基；X¹ 及X² 為氫或氟；Y¹ 為氟、氯、氰基、至少一個氫經氟或氯取代的碳數1至12的烷基、至少一個氫經氟或氯取代的碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數2至12的烯氧基；a為1、2、3或4。 [發明的效果]The present invention relates to a liquid crystal composite and a liquid crystal dimming element having the liquid crystal composite. The liquid crystal composite includes a liquid crystal composition and a polymer, and the liquid crystal composition contains a component A selected from formula (1). At least one compound among the compounds shown and an optically active compound as additive A.

In formula (1), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons; ring A is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine- 2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ¹ is a single bond, ethylene, vinylene, acetylene Group, methyleneoxy group, carbonyloxy group or difluoromethyleneoxy group; X ¹ and X ² are hydrogen or fluorine; Y ¹ is fluorine, chlorine, cyano, at least one hydrogen is replaced by fluorine or chlorine. The carbon number is 1 An alkyl group having to 12, an alkoxy group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkenyloxy group having 2 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; a is 1, 2 , 3, or 4. [Effects of the invention]

The advantage of the present invention is to provide a liquid crystal composite suitable for dimming by combining an optically active compound in a liquid crystal composition. Another advantage is to provide a liquid crystal composite that includes a liquid crystal composition and is suitable for dimming. The liquid crystal composition satisfies a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, low viscosity, and high optical anisotropy. , At least one of the characteristics of large positive dielectric anisotropy, large specific resistance, high stability to light, high stability to heat, large elastic constant, and small spiral pitch. Another advantage is to provide a liquid crystal composite including a liquid crystal composition and suitable for dimming, the liquid crystal composition having an appropriate balance between at least two of these characteristics. Another advantage is to provide a liquid crystal dimming element with such a liquid crystal composite. Another advantage is to provide a liquid crystal dimming element with the characteristics of short response time, high voltage holding rate, low threshold voltage, high haze rate, 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 dimming element" are used. A "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and although it does not have a liquid crystal phase, it is used for the purpose of adjusting the temperature range, viscosity, and dielectric anisotropy of the nematic phase. The general term for the compounds added to the composition. This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecules (liquid crystal molecules) are rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the liquid crystal composition. The liquid crystal compound having an alkenyl group is not classified as a polymerizable compound in terms of its meaning.

The "liquid crystal composition" is prepared by mixing multiple liquid crystal compounds. To the liquid crystal composition, additives such as optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, and polar compounds are added as necessary. Even when an additive is added, the ratio of the liquid crystal compound is represented by the mass percentage (mass %) based on the liquid crystal composition that does not contain the additive. The ratio of the additives is expressed by the mass percentage based on the liquid crystal composition that does not contain the additives. That is, the ratio of liquid crystal compounds or additives is calculated based on the total amount of liquid crystal compounds. Furthermore, sometimes the "mass %" is simply referred to as "%".

The "polymerizable composition" is prepared by mixing a polymerizable compound in a liquid crystal composition. That is, the polymerizable composition is a mixture of at least one polymerizable compound and a liquid crystal composition. To the polymerizable compound, additives such as a polymerization initiator and a polymerization inhibitor are added as necessary. The ratio of the polymerization initiator and the polymerization inhibitor is expressed by the mass percentage based on the total amount of the polymerizable compound. When an additive is added, the ratio of the polymerizable compound or the liquid crystal composition contained in the polymerizable composition is also represented by the mass percentage based on the polymerizable composition not containing the additive. The "liquid crystal composite" is produced by the polymerization process of the polymerizable composition. "Liquid crystal dimming element" is an element with a liquid crystal composite, and is a general term for liquid crystal panels and liquid crystal modules used for dimming.

The "upper limit temperature of the nematic phase" is sometimes simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes referred to simply as the "lower limit temperature". The expression "increasing dielectric anisotropy" refers to a positive increase in the value of a composition with positive dielectric anisotropy, and a negative value in the case of a composition with negative dielectric anisotropy Increase to the ground. "High voltage holding rate" means that the device has a large voltage holding rate not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and after long-term use, not only at room temperature, but also at At a temperature close to the upper limit temperature, the device also has a large voltage holding rate. Sometimes the characteristics of the composition or element are studied through time-varying tests.

以所述化合物（1z）為例來進行說明。式（1z）中，由六邊形包圍的α及β的記號分別與環α及環β相對應，且表示六員環、縮合環之類的環。當下標‘x’為2時，存在兩個環α。兩個環α所表示的兩個基可相同，或亦可不同。該規則適用於下標‘x’大於2時的任意兩個環α。該規則亦適用於鍵結基Z之類的其他記號。將環β的一邊橫切的斜線表示環β上的任意氫可經取代基（-Sp-P）取代。下標‘y’表示經取代的取代基的數量。當下標‘y’為0時，不存在此種取代。當下標‘y’為2以上時，於環β上存在多個取代基（-Sp-P）。「可相同，或亦可不同」的規則亦適用於該情況。再者，該規則亦適用於將Ra的記號用於多種化合物中的情況。

Take the compound (1z) as an example for description. In the formula (1z), the symbols α and β surrounded by a hexagon correspond to the ring α and the ring β, respectively, and represent a ring such as a six-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 tokens such as the bond base Z. The oblique line crossing one side of the ring β indicates that any hydrogen on the ring β can be replaced by a substituent (-Sp-P). The subscript'y' represents the number of substituted substituents. When the subscript'y' is 0, there is no such substitution. When the subscript'y' is 2 or more, there are multiple substituents (-Sp-P) on ring β. The "may be the same or different" rule also applies to this situation. Furthermore, this rule also applies to the case where the symbol of Ra is used in a variety 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. 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 simply referred to as "compound (1z)". "Compound (1z)" means one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1z). The same is true for 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 of compound (1z) and compound (2z).

"Main component" refers to the component that occupies the largest proportion in the mixture or composition. For example, in a mixture of 40% of compound (1z), 35% of compound (2z), and 25% of compound (3z), the main component is compound (1z). When the component is only compound (1z), compound (1z) is also called the main component. When the compound (1z) is a single compound, the compound is also called the main component.

The expression "at least one'A'" means that the number of'A's is arbitrary. The expression "at least one'A' can be replaced by'B'" means that when the number of'A' is one, the position of'A' is arbitrary, and when the number of'A' is more than two, their positions Can also choose unlimitedly. The expression "at least one -CH ₂ -can be substituted by -O-" is sometimes used. In this case, -CH ₂ -CH ₂ -CH ₂ -can be converted to -O-CH ₂ -O- by replacing non-adjacent -CH ₂ -with -O-. However, the adjacent -CH ₂ -is not substituted by -O-. The reason is that -OO-CH _2- (peroxide) is generated in the substitution.

四氫吡喃-2,5-二基之類的二價基中亦相同。羰氧基之類的鍵結基（-COO-或-OCO-）亦相同。The alkyl group of the liquid crystal compound is linear or branched, and does not include a cyclic alkyl group. Straight-chain alkyl is better than branched alkyl. These conditions are the same for terminal groups such as alkoxy and alkenyl. In order to increase the maximum temperature, the three-dimensional configuration related to 1,4-cyclohexylene is the trans configuration better than the cis configuration. Since 2-fluoro-1,4-phenylene is left-right asymmetric, there are leftward (L) and rightward (R) directions.

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

The present invention includes the following items.

式（1）中，R¹ 為碳數1至12的烷基、碳數1至12的烷氧基或碳數2至12的烯基；環A為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、2,6-二氟-1,4-伸苯基、嘧啶-2,5-二基、1,3-二噁烷-2,5-二基或四氫吡喃-2,5-二基；Z¹ 為單鍵、伸乙基、伸乙烯基、伸乙炔基、亞甲氧基、羰氧基或二氟亞甲氧基；X¹ 及X² 為氫或氟；Y¹ 為氟、氯、氰基、至少一個氫經氟或氯取代的碳數1至12的烷基、至少一個氫經氟或氯取代的碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數2至12的烯氧基；a為1、2、3或4。Item 1. A liquid crystal composite comprising a liquid crystal composition and a polymer, the liquid crystal composition containing as component A at least one compound selected from compounds represented by formula (1) and an optically active compound as additive A.

In formula (1), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons; ring A is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine- 2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ¹ is a single bond, ethylene, vinylene, acetylene Group, methyleneoxy group, carbonyloxy group or difluoromethyleneoxy group; X ¹ and X ² are hydrogen or fluorine; Y ¹ is fluorine, chlorine, cyano, at least one hydrogen is replaced by fluorine or chlorine. The carbon number is 1 An alkyl group having to 12, an alkoxy group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkenyloxy group having 2 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; a is 1, 2 , 3, or 4.

Item 2. The liquid crystal composite according to Item 1, wherein the liquid crystal composition contains at least one compound selected from the group consisting of compounds represented by formula (1-1) to formula (1-47) as component A.

式（1-1）至式（1-47）中，R¹ 為碳數1至12的烷基、碳數1至12的烷氧基或碳數2至12的烯基，X¹ 及X² 為氫或氟；Y¹ 為氟、氯、氰基、至少一個氫經氟或氯取代的碳數1至12的烷基、至少一個氫經氟或氯取代的碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數2至12的烯氧基。

In formulas (1-1) to (1-47), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons, X ¹ and X ² is hydrogen or fluorine; Y ¹ is fluorine, chlorine, cyano, an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine An oxy group or an alkenyloxy group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine.

Item 3. The liquid crystal composite according to item 1 or 2, wherein the ratio of component A is in the range of 5% to 90% based on the liquid crystal composition.

式（2）中，R² 及R³ 為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、或者至少一個氫經氟或氯取代的碳數2至12的烯基；環B及環C為1,4-伸環己基、1,3-伸苯基、1,4-伸苯基、2-氟-1,4-伸苯基、2,5-二氟-1,4-伸苯基或嘧啶-2,5-二基；Z² 為單鍵、伸乙基、伸乙烯基、伸乙炔基、亞甲氧基或羰氧基；b為1、2或3。Item 4. The liquid crystal composite according to any one of items 1 to 3, wherein the liquid crystal composition contains, as the component B, at least one compound selected from compounds represented by formula (2).

In formula (2), R ² and R ³ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, or at least one hydrogen substituted by fluorine or chlorine Alkenyl with 2 to 12 carbons; ring B and ring C are 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene , 2,5-difluoro-1,4-phenylene or pyrimidine-2,5-diyl; Z ² is a single bond, ethylene, ethylene, ethynylene, methyleneoxy or carbonyloxy基; b is 1, 2 or 3.

Item 5. The liquid crystal composite according to any one of items 1 to 4, wherein the liquid crystal composition contains as component B selected from the group of compounds represented by formula (2-1) to formula (2-23) At least one compound.

式（2-1）至式（2-23）中，R² 及R³ 為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、或者至少一個氫經氟或氯取代的碳數2至12的烯基。

In formulas (2-1) to (2-23), R ² and R ³ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, or An alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.

Item 6. The liquid crystal composite according to Item 4 or Item 5, wherein the ratio of component B is in the range of 5% to 90% based on the liquid crystal composition.

式（3）中，R⁴ 及R⁵ 為氫、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基或碳數2至12的烯氧基；環D及環F為1,4-伸環己基、1,4-伸環己烯基、四氫吡喃-2,5-二基、1,4-伸苯基、至少一個氫經氟或氯取代的1,4-伸苯基、萘-2,6-二基、至少一個氫經氟或氯取代的萘-2,6-二基、色原烷-2,6-二基、或者至少一個氫經氟或氯取代的色原烷-2,6-二基；環E為2,3-二氟-1,4-伸苯基、2-氯-3-氟-1,4-伸苯基、2,3-二氟-5-甲基-1,4-伸苯基、3,4,5-三氟萘-2,6-二基、7,8-二氟色原烷-2,6-二基、3,4,5,6-四氟芴-2,7-二基、4,6-二氟二苯並呋喃-3,7-二基、4,6-二氟二苯並噻吩-3,7-二基或1,1,6,7-四氟茚滿-2,5-二基；Z³ 及Z⁴ 為單鍵、伸乙基、伸乙烯基、亞甲氧基或羰氧基；c為0、1、2或3，d為0或1，c與d的和為3以下。Item 7. The liquid crystal composite according to any one of items 1 to 6, wherein the liquid crystal composition contains as component C at least one compound selected from the group of compounds represented by formula (3).

In formula (3), R ⁴ and R ⁵ are hydrogen, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkylene oxide having 2 to 12 carbons. Ring D and ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen Fluorine or chlorine substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chroman-2,6-diyl , Or Chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; ring E 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-difluoro Orthane-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-tetrafluoroindan-2,5-diyl; Z ³ and Z ⁴ are single bond, ethylene, ethylene Group, methyleneoxy or carbonyloxy; c is 0, 1, 2 or 3, d is 0 or 1, and the sum of c and d is 3 or less.

Item 8. The liquid crystal composite according to any one of items 1 to 7, wherein the liquid crystal composition contains, as the component C, a compound selected from the group consisting of compounds represented by formula (3-1) to formula (3-35) At least one compound.

式（3-1）至式（3-35）中，R⁴ 及R⁵ 為氫、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基或碳數2至12的烯氧基。

In formulas (3-1) to (3-35), R ⁴ and R ⁵ are hydrogen, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and an alkenyl group having 2 to 12 carbons. Or an alkenyloxy group having 2 to 12 carbons.

Item 9. The liquid crystal composite according to Item 7 or Item 8, wherein the ratio of component C is in the range of 3% to 25% based on the liquid crystal composition.

式（4）中，P¹ 及P² 為聚合性基；Z⁵ 為碳數1至20的伸烷基，該伸烷基中，至少一個氫可經碳數1至5的烷基、氟、氯或P³ 取代，至少一個-CH₂ -可經-O-、-CO-、-COO-、-OCO-、-NH-或-N(R⁶ )-取代，至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，至少一個-CH₂ -可經藉由自碳環式的飽和脂肪族化合物、雜環式的飽和脂肪族化合物、碳環式的不飽和脂肪族化合物、雜環式的不飽和脂肪族化合物、碳環式的芳香族化合物或雜環式的芳香族化合物中去除兩個氫而生成的二價基取代，該些二價基中，碳數為5至35，且至少一個氫可經R⁶ 或P³ 取代，此處，R⁶ 為碳數1至12的烷基，該烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代，P³ 為聚合性基。Item 10. The liquid crystal composite according to any one of items 1 to 9, wherein the polymer is derived from a precursor, and the main component of the precursor is a compound represented by formula (4).

In formula (4), P ¹ and P ² are polymerizable groups; Z ⁵ is an alkylene group having 1 to 20 carbons. In the alkylene group, at least one hydrogen may be passed through an alkylene group having 1 to 5 carbons or fluorine. , Chlorine or P ³ substitution, at least one -CH ₂ -can be substituted by -O-, -CO-, -COO-, -OCO-, -NH- or -N(R ⁶ )-, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one -CH ₂ -can be substituted by carbocyclic saturated aliphatic compounds, heterocyclic saturated aliphatic compounds, carbocyclic Unsaturated aliphatic compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds or heterocyclic aromatic compounds are substituted by a divalent group formed by removing two hydrogens, and these divalent groups , The carbon number is 5 to 35, and at least one hydrogen may be substituted by R ⁶ or P ³ , where R ⁶ is an alkyl group having 1 to 12 carbons, in which at least one -CH ₂ -may be- O-, -CO-, -COO- or -OCO- substituted, and P ³ is a polymerizable group.

式（P-1）至式（P-6）中，M¹ 、M² 及M³ 為氫、氟、碳數1至5的烷基、或者至少一個氫經氟或氯取代的碳數1至5的烷基。Item 11. The liquid crystal composite according to Item 10, wherein P ¹ , P ² and P ³ are groups selected from 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 hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or a carbon number 1 in which at least one hydrogen is substituted by fluorine or chlorine To 5 alkyl groups.

Item 12. The liquid crystal composite according to Item 10, wherein at least one of P ¹ , P ² and P ³ is an acryloxy group or a methacryloxy group.

式（5）中，M⁴ 及M⁵ 為氫或甲基；Z⁶ 為碳數21至80的伸烷基，該伸烷基中，至少一個氫可經碳數1至20的烷基、氟或氯取代，至少一個-CH₂ -可經-O-、-CO-、-COO-、-OCO-、-NH-或-N(R⁶ )-取代，至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，此處，R⁶ 為碳數1至12的烷基，該烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代。Item 13. The liquid crystal composite according to any one of items 1 to 9, wherein the polymer is derived from a precursor, and the main component of the precursor is a compound represented by formula (5).

In formula (5), M ⁴ and M ⁵ are hydrogen or methyl; Z ⁶ is an alkylene having 21 to 80 carbons. In the alkylene, at least one hydrogen may be an alkylene having 1 to 20 carbons, Fluorine or chlorine substitution, at least one -CH ₂ -can be substituted by -O-, -CO-, -COO-, -OCO-, -NH- or -N(R ⁶ )-, at least one -CH ₂ CH _2- It may be substituted by -CH=CH- or -C≡C-, where R ⁶ is an alkyl group having 1 to 12 carbons. In the alkyl group, at least one -CH ₂ -may be substituted by -O-, -CO- , -COO- or -OCO- substitution.

式（6）中，M⁶ 為氫或甲基；Z⁷ 為單鍵或碳數1至5的伸烷基，該伸烷基中，至少一個氫可經氟或氯取代，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代；R⁷ 為碳數1至40的烷基，該烷基中，至少一個氫可經氟或氯取代，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代，至少一個-CH₂ -可經藉由自碳環式的飽和脂肪族化合物、雜環式的飽和脂肪族化合物、碳環式的不飽和脂肪族化合物、雜環式的不飽和脂肪族化合物、碳環式的芳香族化合物或雜環式的芳香族化合物中去除兩個氫而生成的二價基取代，該些二價基中，碳數為5至35，且至少一個氫可經碳數1至12的烷基取代，該烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代。Item 14. The liquid crystal composite according to any one of Items 1 to 9, wherein the polymer is derived from a precursor, and the main component of the precursor is a compound represented by formula (6).

In formula (6), M ⁶ is hydrogen or methyl; Z ⁷ is a single bond or an alkylene having 1 to 5 carbon atoms. In the alkylene, at least one hydrogen can be replaced by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO-, -COO- or -OCO-; R ⁷ is an alkyl group having 1 to 40 carbons, in which at least one hydrogen may be substituted by fluorine or chlorine, and at least one -CH ₂ -can be substituted by -O-, -CO-, -COO- or -OCO-, at least one -CH ₂ -can be substituted by carbocyclic saturated aliphatic compound, heterocyclic saturated aliphatic A compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, a carbocyclic aromatic compound or a heterocyclic aromatic compound is substituted by a divalent group generated by removing two hydrogens, In these divalent groups, the carbon number is 5 to 35, and at least one hydrogen can be substituted by an alkyl group having 1 to 12 carbons. In the alkyl group, at least one -CH ₂ -can be replaced by -O-, -CO- , -COO- or -OCO- substitution.

Item 15. The liquid crystal composite according to Item 14, wherein in formula (6), M ⁶ is hydrogen or methyl; Z ⁷ is a single bond or an alkylene having 1 to 5 carbon atoms, and in the alkylene, At least one hydrogen may be substituted by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO-, -COO- or -OCO-; R ⁷ is an alkyl group having 1 to 40 carbons, and the alkyl group Among them, at least one hydrogen can be replaced by fluorine or chlorine, and at least one -CH ₂ -can be replaced by -O-, -CO-, -COO- or -OCO-.

式（7）、式（8）及式（9）中，環G、環I、環J、環K、環L及環M為1,4-伸環己基、1,4-伸苯基、1,4-伸環己烯基、吡啶-2,5-二基、1,3-二噁烷-2,5-二基、萘-2,6-二基或芴-2,7-二基，此處，至少一個氫可經氟、氯、氰基、羥基、甲醯基、三氟乙醯基、二氟甲基、三氟甲基、碳數1至5的烷基、碳數1至5的烷氧基、碳數2至5的烷氧基羰基或碳數1至5的烷醯基取代；Z⁸ 、Z¹⁰ 、Z¹² 、Z¹³ 及Z¹⁷ 為單鍵、-O-、-COO-、-OCO-或-OCOO-；Z⁹ 、Z¹¹ 、Z¹⁴ 及Z¹⁶ 為單鍵、-OCH₂ -、-CH₂ O-、-COO-、-OCO-、-COS-、-SCO-、-OCOO-、-CONH-、-NHCO-、-CF₂ O-、-OCF₂ -、-CH₂ CH₂ -、-CF₂ CF₂ -、-CH=CHCOO-、-OCOCH=CH-、-CH₂ CH₂ COO-、-OCOCH₂ CH₂ -、-CH=CH-、-N=CH-、-CH=N-、-N=C(CH₃ )-、-C(CH₃ )=N-、-N=N-或-C≡C-；Z¹⁵ 為單鍵、-O-或-COO-；Y² 為氫、氟、氯、三氟甲基、三氟甲氧基、氰基、碳數1至20的烷基、碳數2至20的烯基、碳數1至20的烷氧基或碳數2至20的烷氧基羰基；f及h為1至4的整數；k及m為0至3的整數，k及m的和為1至4；e、g、i、j、l及n為0至20的整數；M⁷ 至M¹² 為氫或甲基。Item 16. The liquid crystal composite according to any one of items 1 to 9, wherein the polymer is derived from a precursor, and the main component of the precursor is represented by formula (7), formula (8) or formula (9) Represents the compound.

In formula (7), formula (8) and formula (9), ring G, ring I, ring J, ring K, ring L and ring M 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-di In this case, at least one hydrogen may be fluorine, chlorine, cyano, hydroxy, methanoyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl with 1 to 5 carbons, carbon number 1 to 5 alkoxy group, carbon number 2 to 5 alkoxycarbonyl group or carbon number 1 to 5 alkoxy group substitution; Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ and Z ¹⁷ are single bonds, -O -, -COO-, -OCO- or -OCOO-; Z ⁹ , Z ¹¹ , Z ¹⁴ and Z ¹⁶ 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 ¹⁵ is a single bond, -O- or -COO-; Y ² is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoro Methoxy, cyano, 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; f and h are An integer from 1 to 4; k and m are an integer from 0 to 3, and the sum of k and m is from 1 to 4; e, g, i, j, l and n are an integer from 0 to 20; M ⁷ to M ¹² are Hydrogen or methyl.

式（10-1）至式（10-7）中，R⁸ 至R¹⁶ 為氫、氟、氯、氰基、-SF₅ 或碳數1至10的烷基，該烷基中，至少一個-CH₂ -可經-O-、-COO-或-OCO-取代，至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代；環N、環P、環Q、環T、環U、環X、環Y及環Z為1,4-伸環己基、1,4-伸苯基、1,3-二噁烷-2,5-二基、四氫吡喃-2,5-二基、四氫吡喃-3,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基或雙環[2.2.2]辛烷-1,4-二基，該些環中，至少一個氫可經氟或氯取代；環R、環S、環V及環W為5,6,7,8-四氫萘-1,2-二基或萘-1,2-二基；Z¹⁸ 至Z²⁵ 為單鍵或碳數1至20的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代，至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代；X³ 至X⁸ 為氫或氟；p、q、r、s、t、u、v及w為1、2或3。Item 17. The liquid crystal composite according to any one of items 1 to 16, wherein the additive A is at least one selected from the group consisting of optically active compounds represented by formula (10-1) to formula (10-7) Compound.

In formula (10-1) to formula (10-7), R ⁸ to R ¹⁶ are hydrogen, fluorine, chlorine, cyano, -SF ₅ or an alkyl group having 1 to 10 carbons, and at least one of the alkyl groups -CH ₂ -may be substituted by -O-, -COO- or -OCO-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen Can be substituted by fluorine or chlorine; ring N, ring P, ring Q, ring T, ring U, ring X, ring Y and ring Z are 1,4-cyclohexyl, 1,4-phenylene, 1,3 -Dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, tetrahydropyran-3,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5 -Diyl or bicyclo[2.2.2]octane-1,4-diyl, in these rings, at least one hydrogen can be replaced by fluorine or chlorine; ring R, ring S, ring V and ring W are 5,6 ,7,8-Tetrahydronaphthalene-1,2-diyl or naphthalene-1,2-diyl; Z ¹⁸ to Z ²⁵ are single bonds or alkylenes having 1 to 20 carbon atoms, in which, At least one -CH ₂ -can be substituted by -O-, -CO-, -COO- or -OCO-, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, these In the group, at least one hydrogen may be replaced by fluorine or chlorine; X ³ to X ⁸ are hydrogen or fluorine; p, q, r, s, t, u, v, and w are 1, 2, or 3.

Item 18. The liquid crystal composite according to any one of Items 1 to 17, wherein the ratio of the additive A is in the range of 0.03% to 25% based on the liquid crystal composition.

Item 19. The liquid crystal composite according to any one of Items 1 to 18, wherein the spiral pitch of the liquid crystal composition is 10 μm or less.

Item 20. The liquid crystal composite according to any one of Items 1 to 19, wherein the liquid crystal composition contains a dichroic dye as additive B.

Item 21. The liquid crystal composite according to Item 20, wherein the additive B is selected from benzothiadiazoles, diketopyrrolopyrroles, azo compounds and anthraquinone At least one dichroic pigment in the class (anthraquinones).

Item 22. The liquid crystal composite according to Item 20 or Item 21, wherein the ratio of the additive B is in the range of 0.01% to 25% based on the liquid crystal composition.

Item 23. The liquid crystal composite according to any one of Items 1 to 22, wherein based on the liquid crystal composite, the ratio of the polymer is in the range of 3% to 40%, and the ratio of the liquid crystal composition is 97% to 60% Range.

Item 24. The liquid crystal composite according to any one of Items 1 to 22, wherein based on the liquid crystal composite, the ratio of the polymer is in the range of 10% to 70%, and the ratio of the liquid crystal composition is 90% to 30% Range.

Item 25. A liquid crystal dimming element, wherein the dimming layer is the liquid crystal composite according to any one of items 1 to 24, and the dimming layer is sandwiched by a pair of transparent substrates, and the transparent substrate has transparent electrodes.

Item 26. The liquid crystal dimming device according to Item 25, wherein the transparent substrate is a glass plate or an acrylic plate.

Item 27. The liquid crystal dimming device according to Item 25, wherein the transparent substrate is a plastic film.

Item 28. The liquid crystal dimming element according to any one of items 25 to 27, which has the liquid crystal composite according to any one of items 1 to 24, and has an illuminance (180 W/m ² ), The haze change rate before and after the weather resistance test performed under the conditions of irradiation time (100 hours) and tank temperature (35°C) is 20% or less.

Item 29. A dimming window using the liquid crystal dimming element according to any one of Items 25 to 28.

Item 30. A smart window using the liquid crystal dimming element according to any one of items 25 to 28.

Item 31. Use of a liquid crystal composite, which is the liquid crystal composite according to any one of items 1 to 24, which is used in a liquid crystal dimming element.

Item 32. Use of a liquid crystal composite, the liquid crystal composite being the liquid crystal composite according to any one of items 1 to 24, which is used in a liquid crystal dimming element whose transparent substrate is a plastic film.

Item 33. Use of a liquid crystal composite, which is the liquid crystal composite according to any one of Items 1 to 24, which is used in a dimming window.

Item 34. Use of a liquid crystal composite, which is the liquid crystal composite according to any one of items 1 to 24, which is used in a smart window.

The present invention also includes the following items. (A) The liquid crystal composite as described above, wherein the liquid crystal composition contains, as the component A, at least one compound in which Y ¹ in the compound (1) described in Item ¹ is fluorine. (B) The liquid crystal composite as described above, wherein the liquid crystal composition contains as Component A, at least one compound in which Y ¹ in the compound (1) described in Item ¹ is a cyano group.

The present invention also includes the following items. (C) The liquid crystal composite as described above, wherein the liquid crystal composition contains the compound (1-1), the compound (1-2), the compound (1-3), and the compound described in item 2 as the component A (1-9), compound (1-13), compound (1-16), compound (1-21), compound (1-22), compound (1-23), compound (1-24), compound ( 1-27), at least one compound of compound (1-28), compound (1-33), compound (1-36), compound (1-41), and compound (1-42).

The present invention also includes the following items. (D) The liquid crystal composite as described above, wherein the liquid crystal composition contains as component B, the compound (2-1), compound (2-2), compound (2-3), compound (2-4), compound (2-6), compound (2-9), compound (2-10), compound (2-12), compound (2-13), compound (2-14), compound ( 2-16), at least one compound of compound (2-17), compound (2-19) and compound (2-21).

The present invention also includes the following items. (E) The liquid crystal composite as described above, wherein the liquid crystal composition contains as component C, the compound (3-1), compound (3-5), compound (3-6), compound At least one compound among (3-7), compound (3-8), compound (3-12), compound (3-14), compound (3-19), and compound (3-34).

The present invention also includes the following items. (F) The liquid crystal composite as described above, wherein the ratio of the polymer is in the range of 3% to 40% based on the liquid crystal composite, and the ratio of the liquid crystal composition is in the range of 97% to 60%. (G) The liquid crystal composite as described above, wherein the ratio of the polymer is in the range of 4% to 20% based on the liquid crystal composite, and the ratio of the liquid crystal composition is in the range of 96% to 80%. (H) The liquid crystal composite as described above, wherein the ratio of the polymer is in the range of 5% to 10% based on the liquid crystal composite, and the ratio of the liquid crystal composition is in the range of 95% to 90%.

The present invention also includes the following items. (I) The liquid crystal composite as described above, wherein the ratio of the polymer is in the range of 10% to 70% based on the liquid crystal composite, and the ratio of the liquid crystal composition is in the range of 90% to 30%. (J) The liquid crystal composite as described above, wherein based on the liquid crystal composite, the ratio of the polymer is in the range of 20% to 60%, and the ratio of the liquid crystal composition is in the range of 80% to 40%. (K) The liquid crystal composite as described above, wherein based on the liquid crystal composite, the ratio of the polymer is in the range of 30% to 40%, and the ratio of the liquid crystal composition is in the range of 70% to 60%.

The present invention also includes the following items. (1) The liquid crystal composite as described above, wherein the precursor of the liquid crystal composite is a polymerizable composition, and the polymerizable composition contains a liquid crystal composition, a polymerizable compound, and a photopolymerization initiator as an additive C.

We tried to improve the LCD dimming element. In order to improve the liquid crystal dimming element, a method of using a chiral nematic composition instead of the nematic composition described in Table 1 (approach) is considered. The reason is that it is expected that a liquid crystal composite obtained by combining a polymer with a chiral nematic composition which is a mixture of a nematic composition and an optically active compound can be used in a liquid crystal light control element. We have studied the possibilities and completed the present invention.

The present invention relates to a liquid crystal composite comprising a polymer and a liquid crystal composition having a chiral nematic phase, and a liquid crystal dimming element having the composite. In order to be suitable for dimming elements, an optically active compound (chiral agent) is added to the nematic liquid crystal composition. The chiral nematic liquid crystal composition is prepared in the following manner. The liquid crystal composite includes a chiral nematic liquid crystal composition and a polymer. The type of compound suitable as a component of the liquid crystal composite is not reported in the literature. We found that a certain type of liquid crystal composite shows a focal conic state, a planar state, a homeotropic state, etc. depending on the conditions, and is suitable for dimming elements.

The present invention will be described in the following order. First, the liquid crystal composite will be described. Second, the liquid crystal composition will be described. Third, the main characteristics of the liquid crystal compound and the main effects of the compound on the liquid crystal composition or device will be described. Fourth, the combination or preferred ratio of liquid crystal compounds will be described. Fifth, the preferred embodiment of the liquid crystal compound will be described. Sixth, a preferable liquid crystal compound is shown. Seventh, the preferred form of the polymerizable compound and an example thereof will be described. Eighth, the preferred form of the optically active compound and an example thereof will be described. Ninth, the synthesis method of the component compounds will be explained. Tenth, the additives that can be added to the polymerizable composition will be described. Finally, the liquid crystal dimming element will be described.

First, the liquid crystal composite will be described. The precursor of the liquid crystal composite is a polymerizable composition. The liquid crystal composite is produced by the polymerization of a polymerizable composition. The polymerizable composition is a mixture of a polymerizable compound and a liquid crystal composition. An optically active compound as additive A is added to the liquid crystal composition. The polymerizable composition is put into the element and polymerized. The polymer produced by polymerization undergoes phase separation to provide a liquid crystal composite. Elements having a liquid crystal composite are classified into polymer stable alignment type, polymer network type, and polymer dispersion type according to polymer polymerization.

When the proportion of the polymer is small, a polymer sustained alignment type element is produced. This is abbreviated as PSA element. It is described in Example 1 of International Publication No. 2012-050178 that "the monomer is added so as to be 0.5 wt% with respect to the liquid crystal material" (paragraph 0105). As can be understood from this description, in a PSA element, a small amount of a polymerizable compound is added to a liquid crystal material (liquid crystal composition). In PSA devices, the polymer adjusts the pretilt angle of liquid crystal molecules. By optimizing the pretilt angle, the liquid crystal molecules are stabilized and the response time of the device is shortened.

When the proportion of the polymer is large, a polymer dispersion type element is produced. In this type of device, the liquid crystal composition is dispersed in the polymer like droplets. Each droplet is microencapsulated and is not continuous. The liquid crystal molecules are arranged along the inner wall of the capsule, so they are in a random state. Since the refractive index of the polymer is different from that of the liquid crystal molecules, the incident light is scattered. The component is opaque. When a voltage is applied to the element, the refractive index of the liquid crystal molecules changes. If the refractive index is the same as the refractive index of the polymer, incident light passes through the element, and the element becomes transparent.

On the other hand, when the ratio of the polymer is moderate, a polymer network type element is produced. In this type of device, the polymer has a three-dimensional grid structure, and the liquid crystal composition is surrounded by the grid and is continuous. The liquid crystal molecules are in a random state, and the device is opaque. When a voltage is applied to the element, the liquid crystal molecules are aligned in the direction of the electric field, so the element becomes transparent. In order to efficiently cause light scattering, the ratio of the liquid crystal composition based on the liquid crystal composite is preferably large. When the droplet or grid is large, the driving voltage is low. Therefore, from the viewpoint of low driving voltage, the proportion of the polymer is preferably small. When the droplet or grid is small, the response time is short. Therefore, from the viewpoint of short response time, the ratio of the polymer is preferably large.

In order to scatter incident light, the preferable ratio of the polymer is in the range of about 3% to about 40% based on the liquid crystal composite. Based on the liquid crystal composite, a particularly preferable ratio is in the range of about 4% to about 20%. Based on the liquid crystal composite, a particularly preferable ratio is in the range of about 5% to about 10%. Since the total of the polymer and the liquid crystal composition is 100%, the ratio of the liquid crystal composition can be easily calculated. In addition, 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.

In order to improve the adhesion between the dimming layer (liquid crystal composite) and the substrate, based on the liquid crystal composite, the preferable ratio of the polymer is in the range of about 10% to about 70%. Based on the liquid crystal composite, a particularly preferable ratio is in the range of about 20% to about 60%. Based on the liquid crystal composite, a particularly preferable ratio is in the range of about 30% to about 40%.

When the proportion of the polymer is in the range of about 3% to about 70%, a polymer network type element or a polymer dispersion type element is produced. The polymer network type and the polymer dispersion type are mixed according to the ratio of the polymer. Among these devices, unlike PSA devices, no polarizer is needed. In the polymer network type element, an alignment film is used as necessary.

The method of preparing a liquid crystal composite from the polymerizable composition is as follows. First, the polymerizable composition is sandwiched between a pair of substrates. The clamping 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 devices manufactured by these methods, display defects such as flow marks or drip marks may occur. Flow marks are traces of polymerizable composition flowing through the device. The drip mark is the mark after dropping the polymerizable composition. It is preferable to suppress such display defects. Then, the polymerizable compound is polymerized by heat or light. It is preferable to irradiate ultraviolet rays during polymerization. By polymerization, the polymer phase separates from the polymerizable composition. Thereby, a light-adjusting layer (liquid crystal composite) is formed between the substrates.

Second, the liquid crystal composition will be described. This composition contains a variety of liquid crystal compounds. The composition may also contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, polymerization initiators, polymerization inhibitors, polar compounds, and the like. From the viewpoint of a liquid crystal compound, the composition is classified into a composition A and a composition B. The composition A contains not only a liquid crystal compound selected from the compound (1), the compound (2), and the compound (3), but may further contain other liquid crystal compounds, additives, and the like. "Other liquid crystal compounds" are liquid crystal compounds different from compound (1), compound (2), and compound (3). Such compounds are mixed in the composition for the purpose of further adjusting the characteristics.

Composition B substantially contains only liquid crystal compounds selected from the group consisting of compound (1), compound (2), and compound (3). "Substantially" means that although composition B may contain additives, it does not contain other liquid crystal compounds. Compared with composition A, the number of components of composition B is small. From the viewpoint of cost reduction, composition B is superior to composition A. The composition A is superior to the composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.

Third, the main characteristics of the liquid crystal compound and the main effects of the compound on the liquid crystal composition or device will be described. The main characteristics of the component compounds are summarized in Table 2. 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 between component compounds, and the symbol 0 (zero) means less than S.

[Table 2] Characteristics of liquid crystal compounds Compound Compound (1) Compound (2) Compound (3) Upper temperature S～L S～L S～L Viscosity M～L S～M M～L Optical anisotropy M～L S～L M～L Dielectric anisotropy S～L 0 M～L ¹⁾ Specific resistance L L L 1) The value of dielectric anisotropy is negative, and the sign indicates the magnitude of the absolute value

The main effects of the component compounds on the characteristics of the composition are as follows. The compound (1) increases the dielectric anisotropy. Compound (2) increases the upper limit temperature or decreases the lower limit temperature. Compound (3) increases the dielectric constant in the minor axis direction of liquid crystal molecules.

Fourth, the combination or preferred ratio of liquid crystal compounds will be described. A preferred combination is component A+component B, component A+component C or component A+component B+component C. A particularly preferred combination is component A+component B or component A+component B+component C. It is also possible to combine specific one or two compounds selected from component A with component B (or component C). The same applies to component B or component C.

In order to increase the dielectric anisotropy, the preferable ratio of the component A is about 5% or more, and in order to reduce the minimum temperature, the preferable ratio of the component A is about 90% or less. A particularly preferred ratio is in the range of about 10% to about 85%. A particularly preferred ratio is in the range of about 20% to about 80%.

In order to increase the upper limit temperature or lower the lower limit temperature, the preferable ratio of component B is about 5% or more, and in order to increase the dielectric anisotropy, the preferable ratio of component B is about 90% or less. A particularly preferred ratio is in the range of about 10% to about 85%. A particularly preferred ratio is in the range of about 20% to about 80%.

In order to increase the dielectric constant in the minor axis direction of the liquid crystal molecules, the preferred ratio of component C is about 3% or more, and in order to reduce the minimum temperature, the preferred ratio of component C is about 25% or less. A particularly preferred ratio is in the range of about 5% to about 20%. A particularly preferred ratio is in the range of about 5% to about 15%.

Fifthly, a preferred embodiment of the liquid crystal compound will be described. In Formula (1), Formula (2), and Formula (3), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons. In order to improve the stability to light or heat, R ¹ is preferably an alkyl group having 1 to 12 carbons.

R ² and R ³ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, or alkenyls having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine base. In order to increase the upper limit temperature or lower the lower limit temperature, preferably R ² or R ³ is an alkenyl group having 2 to 12 carbons. In order to improve the stability to light or heat, preferably R ² or R ³ is a carbon number of 1 to 12's alkyl group.

R ⁴ and R ⁵ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. In order to improve the stability to light or heat, R ⁴ or R ⁵ is preferably an alkyl group having 1 to 12 carbons. In order to increase the dielectric constant in the short axis direction of the liquid crystal molecules, R ⁴ or R ^{5 is} preferably It is an alkoxy group having 1 to 12 carbons.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. In order to reduce the viscosity, particularly preferred alkyl groups are methyl, ethyl, propyl, butyl or pentyl.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy. In order to reduce the viscosity, particularly preferred alkoxy groups are methoxy or ethoxy.

The preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3 -Pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. In order to reduce the viscosity, particularly preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl or 3-pentenyl. The preferred configuration of -CH=CH- in these alkenyl groups depends on the position of the double bond. In order to reduce viscosity and other reasons, preferred among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl Trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. In order to reduce the viscosity, particularly preferred alkenyloxy groups are allyloxy or 3-butenyloxy.

Preferred examples of alkyl groups in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl or 8-fluorooctyl. In order to increase the dielectric anisotropy, particularly preferable examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl.

Preferred examples of alkenyl groups in which at least one hydrogen is replaced by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl , 5,5-difluoro-4-pentenyl or 6,6-difluoro-5-hexenyl. In order to reduce the viscosity, particularly preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

或

， 較佳為

。Ring A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6- Difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl. In order to increase the optical anisotropy, the preferred ring A is 1,4-phenylene or 2-fluoro-1,4-phenylene. In order to increase the maximum temperature, the three-dimensional configuration related to 1,4-cyclohexylene is the trans configuration better than the cis configuration. Tetrahydropyran-2,5-diyl is

or

, Preferably

.

Ring B and Ring C are 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1 ,4-phenylene or pyrimidine-2,5-diyl. In order to increase the upper limit temperature or lower the lower limit temperature, the ring B or ring C is preferably 1,4-cyclohexylene, and in order to reduce the lower limit temperature, the ring B or ring C is preferably 1,4-phenylene.

Ring D and ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen through fluorine or Chlorine-substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is substituted with fluorine or chlorine, chroman-2,6-diyl or at least A chroman-2,6-diyl group in which hydrogen is replaced by fluorine or chlorine. In order to reduce the lower limit temperature or to increase the upper limit temperature, ring D or ring F is preferably 1,4-cyclohexylene. In order to reduce the lower limit temperature, ring D or ring F is preferably 1,4-phenylene.

為了降低黏度，較佳的環E為2,3-二氟-1,4-伸苯基，為了提高液晶分子的短軸方向上的介電常數，較佳的環E為4,6-二氟二苯並噻吩-3,7-二基。Ring E 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-tetrafluoroindan-2,5-diyl (InF4).

In order to reduce the viscosity, the preferable ring E is 2,3-difluoro-1,4-phenylene. In order to increase the dielectric constant in the short axis direction of the liquid crystal molecules, the preferable ring E is 4,6-di Fluorodibenzothiophene-3,7-diyl.

Z ¹ is a single bond, ethylene, ethylene, ethynylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy. In order to increase the upper limit temperature, Z ¹ is preferably a single bond, and in order to increase the dielectric anisotropy, Z ¹ is preferably a difluoromethyleneoxy group. Particularly preferred Z ¹ is a single bond. Z ² is a single bond, ethylene, ethylene, ethynylene, methyleneoxy or carbonyloxy. In order to improve the stability to light or heat, Z ² is preferably a single bond. Z ³ and Z ⁴ are single bonds, ethylene groups, ethylene groups, methyleneoxy groups or carbonyloxy groups. In order to reduce the viscosity, preferably Z ³ or Z ⁴ is a single bond, in order to reduce the minimum temperature, preferably Z ³ or Z ⁴ is an ethylene group, in order to increase the dielectric constant in the short axis direction of the liquid crystal molecules, preferably Z ³ or Z ⁴ is methyleneoxy. Particularly preferred Z ³ or Z ⁴ is a single bond.

Divalent groups such as methyleneoxy are left-right asymmetric. Among the methyleneoxy groups, -CH ₂ O- is better than -OCH ₂ -. Among carbonyloxy groups, -COO- is better than -OCO-. Among the difluoromethyleneoxy groups, -CF ₂ O- is better than -OCF ₂ -.

a is 1, 2, 3, or 4. In order to reduce the lower limit temperature, a preferable value of a is 2, and in order to increase dielectric anisotropy, a preferable value of a is 3. b is 1, 2 or 3. In order to reduce the lower limit temperature, b is preferably 1, and in order to increase the upper limit temperature, b is preferably 2 or 3. c is 0, 1, 2, or 3, d is 0 or 1, and the sum of c and d is 3 or less. In order to reduce the lower limit temperature, the preferred c is 1, and in order to increase the upper limit temperature, the preferred c is 2 or 3. In order to reduce the viscosity, the preferable d is 0, and in order to reduce the lower limit temperature, the preferable d is 1.

X ¹ and X ² are hydrogen or fluorine. In order to increase the upper limit temperature, preferably X ¹ or X ² is hydrogen, and in order to increase the dielectric anisotropy, preferably X ¹ or X ² is fluorine.

Y ¹ is fluorine, chlorine, cyano, an alkyl group with 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, an alkoxy group with 1 to 12 in which at least one hydrogen is replaced by fluorine or chlorine, or at least one Alkenyloxy having 2 to 12 carbons in which hydrogen is substituted by fluorine or chlorine. In order to reduce the viscosity, the preferred Y ¹ is fluorine, and in order to increase the dielectric anisotropy, the preferred Y ¹ is cyano.

A preferable example of an alkyl group in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethyl. A preferable example of an alkoxy group in which at least one hydrogen is substituted by fluorine or chlorine is trifluoromethoxy. A preferable example of an alkenyloxy group in which at least one hydrogen is replaced by fluorine or chlorine is trifluoroethyleneoxy.

Sixth, a preferable liquid crystal compound is shown. Preferred compound (1) is the compound (1-1) to the compound (1-47) described in Item 2. Among these compounds, at least one of component A is preferably compound (1-1), compound (1-2), compound (1-7), compound (1-9), compound (1-13), compound (1-16), compound (1-17), compound (1-23), compound (1-24), compound (1-28), compound (1-29), compound (1-30), compound ( 1-33), compound (1-34), compound (1-41) or compound (1-42). Preferably, at least two of component A are compound (1-1) and compound (1-2), compound (1-1) and compound (1-9), compound (1-2) and compound (1-9) ), compound (1-1) and compound (1-16), compound (1-2) and compound (1-16), compound (1-9) and compound (1-16), compound (1-9) And compound (1-24), compound (1-16) and compound (1-24), compound (1-9) and compound (1-41), compound (1-16) and compound (1-41), Compound (1-9) and compound (1-42) or a combination of compound (1-16) and compound (1-42).

Preferred compound (2) is the compound (2-1) to the compound (2-23) described in Item 5. Among these compounds, at least one of component B is preferably compound (2-1), compound (2-2), compound (2-3), compound (2-6), compound (2-9), compound (2-10), compound (2-11), compound (2-12), compound (2-13), compound (2-16), compound (2-20), or compound (2-21). Preferably at least two of component B are compound (2-2) and compound (2-9), compound (2-2) and compound (2-10), compound (2-2) and compound (2-12) ), compound (2-9) and compound (2-10), compound (2-9) and compound (2-12) or a combination of compound (2-10) and compound (2-12).

Preferred compound (3) is the compound (3-1) to the compound (3-35) described in item 8. Among these compounds, at least one of component C is preferably compound (3-1), compound (3-3), compound (3-6), compound (3-8), compound (3-10), compound (3-14) or compound (3-34). Preferably, at least two of component C are compound (3-1) and compound (3-8), compound (3-1) and compound (3-14), compound (3-3) and compound (3-8) ), compound (3-3) and compound (3-14), compound (3-3) and compound (3-34), compound (3-6) and compound (3-8), compound (3-6) And compound (3-10) or a combination of compound (3-6) and compound (3-14).

Seventh, a preferable aspect of the polymerizable compound and an example thereof will be described. The polymerizable compound derives a polymer by polymerization. The precursor of the polymer is a polymerizable compound. The polymerizable compound may be a single compound or a mixture of multiple compounds. The preferred polymerizable compound is compound (4), compound (5) or compound (6). The preferred polymerizable compound is compound (7), compound (8) or compound (9). The polymerizable compound may be a mixture of compounds selected from compound (4) to compound (9). The mixture may contain a polymerizable compound different from the compound (4) to the compound (9). Such a mixture contains compound (4), compound (5) or compound (6) as a main component. Such a mixture contains compound (7), compound (8) or compound (9) as a main component.

7-1. Compound (4) In formula (4), Z ⁵ is an alkylene having 1 to 20 carbons. In the alkylene, at least one hydrogen can be passed through an alkylene having 1 to 5 carbons, fluorine, or chlorine. Or P ³ substitution, at least one -CH ₂ -can be substituted by -O-, -CO-, -COO-, -OCO-, -NH- or -N(R ⁶ )-, at least one -CH ₂ CH _2- Can be substituted by -CH=CH- or -C≡C-, at least one -CH ₂ -can be substituted by carbocyclic saturated aliphatic compounds, heterocyclic saturated aliphatic compounds, carbocyclic unsaturated Aliphatic compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds or heterocyclic aromatic compounds are substituted by divalent groups generated by removing two hydrogens. Among these divalent groups, carbon The number is 5 to 35, and at least one hydrogen may be substituted by R ⁶ or P ³ . Here, R ⁶ is an alkyl group having 1 to 12 carbon atoms, and in the alkyl group, at least one -CH ₂ -may be substituted with -O-, -CO-, -COO- or -OCO-.

Examples of divalent groups generated by removing two hydrogens from carbocyclic or heterocyclic saturated aliphatic compounds are 1,4-cyclohexylene, decalin-2,6-diyl, tetrahydro Pyran-2,5-diyl, 1,3-dioxane-2,5-diyl, etc. Examples of divalent groups generated by removing two hydrogens from carbocyclic or heterocyclic unsaturated aliphatic compounds are 1,4-cyclohexenylene, dihydropyran-2,5-di Base etc. Examples of divalent groups generated by removing two hydrogens from carbocyclic or heterocyclic aromatic compounds are 1,4-phenylene and 1,4-phenylene in which at least one hydrogen is substituted by fluorine , 1,2,3,4-tetrahydronaphthalene-2,6-diyl, naphthalene-1,2-diyl, pyrimidine-2,5-diyl, etc.

Preferably Z ⁵ is an alkylene having 1 to 20 carbons, in which at least one hydrogen may be substituted by an alkyl having 1 to 5 carbons, and at least one -CH ₂ -may be substituted by -O-, At least one -CH ₂ -may be substituted by a divalent group generated by removing two hydrogens from a carbocyclic saturated aliphatic compound or a carbocyclic aromatic compound. In these divalent groups, the number of carbons is 5 to 35. Particularly preferred Z ⁵ is an alkylene having 1 to 20 carbons, in which at least one hydrogen may be substituted by an alkyl having 1 to 5 carbons, and at least one -CH ₂ -may be substituted by -O-.

In order to improve the compatibility with the liquid crystal composition, Z ⁵ preferably contains a ring structure such as 1,4-cyclohexylene or 1,4-phenylene. In order to easily form a lattice structure, it is preferable that Z ⁵ contains a chain structure such as an alkylene group.

P ¹ , P ² and P ³ are polymerizable groups. Preferred polymerizable groups are formula (P-1) to formula (P-6). In these formulas, the wavy line indicates the position of the bond. Particularly preferred polymerizable groups are formula (P-1) to formula (P-3). P ¹ , P ² and P ³ may be acryloxy or methacryloxy.

In formulas (P-1) to (P-6), M ¹ , M ² and M ³ are hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or at least one hydrogen substituted by fluorine or chlorine with carbon numbers 1 to 5的alkyl. In order to improve the reactivity, preferred M ¹ , M ² or M ³ are hydrogen or methyl. More preferably, M ¹ is hydrogen or methyl, and more preferably M ² or M ³ is hydrogen.

式（4-1）中，p為1至6的整數，式（4-2）中，q為5至20的整數，式（4-4）中，r為1至15的整數。An example of the compound (4) is as follows.

In formula (4-1), p is an integer from 1 to 6, in formula (4-2), q is an integer from 5 to 20, and in formula (4-4), r is an integer from 1 to 15.

In the compound (4), when there are many polymerizable groups, the polymer surrounding the droplets due to crosslinking becomes firm, or the polymer mesh becomes dense. The preferred polymerizable compound has at least one acryloxy group (-OCO-CH=CH ₂ ) or methacryloxy group (-OCO-(CH ₃ )C=CH ₂ ). Compound (4) provides the corresponding polymer by polymerization. In the case where the compound (4) is volatile, its oligomer can be used. The preferred polymer is colorless, transparent, and 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 increase this effect, a polymerizable compound different from the compound (4) may be used in combination.

7-2. Compound (5) In formula (5), M ⁴ and M ⁵ are hydrogen or methyl. In order to increase the reactivity, preferred M ⁴ or M ⁵ is hydrogen.

Z ⁶ is an alkylene having 21 to 80 carbons. In the alkylene, at least one hydrogen can be substituted by an alkyl having 1 to 20 carbons, fluorine or chlorine, and at least one -CH ₂ -can be replaced by -O-, -CO-, -COO-, -OCO-, -NH- or -N(R ⁶ )- substituted, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, here , R ⁶ is an alkyl group having 1 to 12 carbons, and in the alkyl group, at least one -CH ₂ -may be substituted with -O-, -CO-, -COO- or -OCO-. In order to achieve low-voltage driving, Z ⁶ is preferably an alkylene having 21 to 60 carbons. In the alkylene, at least one hydrogen can be substituted by an alkyl having 1 to 20 carbons, and at least one -CH ₂ -can be Replaced by -O-, -COO- or -OCO-.

In order to achieve low voltage driving, Z ⁶ is preferably an alkylene group in which at least one hydrogen is substituted by an alkyl group. When two hydrogens of the alkylene group are substituted by an alkyl group, it is preferable to avoid steric hindrance. For example, two alkyl groups are sufficiently separated, or an alkyl group having 1 to 5 carbon atoms is used in one of the alkyl groups. The same is true when at least three hydrogens are substituted by alkyl groups.

式（5-1）中，R⁸ 及R¹⁰ 為碳數1至5的烷基，R⁹ 及R¹¹ 為碳數5至20的烷基，該烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代，Z⁸ 為碳數10至30的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代。An example of the compound (5) is as follows.

In the formula (5-1), R ⁸ and R ¹⁰ are alkyl groups having 1 to 5 carbons, R ⁹ and R ¹¹ are alkyl groups having 5 to 20 carbons, and at least one -CH ₂ -may be Substituted by -O-, -CO-, -COO- or -OCO-, Z ⁸ is an alkylene having 10 to 30 carbons, in which at least one -CH ₂ -may be -O-,- CO-, -COO- or -OCO- substitution.

式（5-1-1）及式（5-1-2）中，例如R⁸ 及R¹⁰ 為乙基，R⁹ 及R¹¹ 為-CH₂ OCOC₉ H₁₉ 、-CH₂ OCOC₁₀ H₂₁ 、-CH₂ OC₈ H₁₇ 或-CH₂ OC₁₁ H₂₃ 。An example of the compound (5-1) is as follows.

In formula (5-1-1) and formula (5-1-2), for example, R ⁸ and R ¹⁰ are ethyl, and R ⁹ and R ¹¹ 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 .

Compound (5) is diacrylate or dimethacrylate. Z ^{6 in the} formula (5) is an alkylene group or the like, so the polymer easily forms a network structure. When the molecular chain of Z ⁶ is short, the cross-linking sites of the polymer are close, so the mesh becomes smaller. When the molecular chain of Z ⁶ is long, the cross-linking site of the polymer is farther away, and the degree of freedom of molecular motion increases, so the driving voltage decreases. When Z ⁶ is branched, the degree of freedom is further increased, and therefore the driving voltage is further reduced. In order to increase this effect, a polymerizable compound different from the compound (5) may be used in combination.

7-3. Compound (6) In formula (6), M ⁶ is hydrogen or methyl. In order to improve the reactivity, preferred M ⁶ is hydrogen.

Z ⁷ is a single bond or an alkylene having 1 to 5 carbon atoms, in which at least one hydrogen can be replaced by fluorine or chlorine, and at least one -CH ₂ -can be replaced by -O-, -CO-, -COO -Or-OCO-replacement. Preferably Z ⁷ is a single bond or an alkylene group having 1 to 5 carbon atoms. In the alkylene group, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO- or -OCO-.

R ⁷ is an alkyl group having 1 to 40 carbon atoms. In the alkyl group, at least one hydrogen can be replaced by fluorine or chlorine, and at least one -CH ₂ -can be replaced by -O-, -CO-, -COO- or -OCO- Substitution, at least one -CH ₂ -can be selected from carbocyclic saturated aliphatic compounds, heterocyclic saturated aliphatic compounds, carbocyclic unsaturated aliphatic compounds, heterocyclic unsaturated aliphatic compounds , Carbocyclic aromatic compounds or heterocyclic aromatic compounds are substituted by a divalent group generated by removing two hydrogens. In these divalent groups, the carbon number is 5 to 35, and at least one hydrogen can be replaced by carbon It is substituted by an alkyl group having a number of 1 to 12. In the alkyl group, at least one -CH ₂ -may be substituted with -O-, -CO-, -COO- or -OCO-. Preferable R ⁷ is an alkyl group having 5 to 30 carbons. Particularly preferred R ⁷ is a branched alkyl group having 5 to 30 carbon atoms.

式（6-1）至式（6-5）中，R¹² 為碳數5至20的烷基，該烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代，R¹³ 及R¹⁴ 為碳數3至10的烷基，該烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代。An example of the compound (6) is as follows.

In formulas (6-1) to (6-5), R ¹² is an alkyl group having 5 to 20 carbons. In the alkyl group, at least one -CH ₂ -can be controlled by -O-, -CO-, -COO -Or -OCO- substituted, R ¹³ and R ¹⁴ are alkyl groups having 3 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted by -O-, -CO-, -COO- or -OCO- replace.

Compound (6) is acrylate or methacrylate. When R ^{7 of the} formula (6) has a cyclic structure, the affinity with the liquid crystal composition is improved. When R ⁷ is an alkylene group, the polymer easily forms a network structure. In this polymer, the degree of freedom of molecular motion is increased by the alkylation, and therefore the driving voltage is reduced. In order to further increase this effect, a polymerizable compound different from the compound (6) may be used in combination.

7-4. Compound (7) to Compound (9) In formula (7), formula (8) and formula (9), ring G, ring I, ring J, ring K, ring L and ring M 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-di In this case, at least one hydrogen may be fluorine, chlorine, cyano, hydroxy, methanoyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl with 1 to 5 carbons, carbon number The alkoxy group having 1 to 5, the alkoxycarbonyl group having 2 to 5 carbons, or the alkanoyl group having 1 to 5 carbons is substituted. In formula (7), formula (8) and formula (9), the preferred ring is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2 -Methyl-1,4-phenylene, 2-methoxy-1,4-phenylene or 2-trifluoromethyl-1,4-phenylene. Particularly preferable ring is 1,4-cyclohexylene or 1,4-phenylene.

Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ and Z ¹⁷ are single bonds, -O-, -COO-, -OCO- or -OCOO-. Z ⁹ , Z ¹¹ , Z ¹⁴ and Z ¹⁶ 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 ¹⁵ is a single bond, -O- or -COO-. Preferably Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ or Z ¹⁷ is a single bond or -O-. Preferably Z ⁹ , Z ¹¹ , Z ¹⁴ or Z ¹⁶ 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 -.

Y ² 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 an alkoxycarbonyl group having 2 to 20 carbons. Preferably Y ² is cyano, alkyl or alkoxy.

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

M ⁷ to M ¹² are hydrogen or methyl.

An example of the compound (7) is as follows.

式（7-1）至式（7-24）中，M⁷ 為氫或甲基，e為1至20的整數。

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

An example of the compound (8) is as follows.

式（8-1）至式（8-31）中，M⁸ 及M⁹ 為氫或甲基，g及i為1至20的整數。

In formula (8-1) to formula (8-31), M ⁸ and M ⁹ are hydrogen or methyl, and g and i are integers of 1-20.

An example of the compound (9) is as follows.

式（9-1）至式（9-10）中，M¹⁰ 、M¹¹ 及M¹² 為氫或甲基，j、l及n為1至20的整數。

In formula (9-1) to formula (9-10), M ¹⁰ , M ¹¹ and M ¹² are hydrogen or methyl, and j, l and n are integers from 1 to 20.

Compound (7), compound (8) and compound (9) have at least one acryloxy group (-OCO-CH=CH ₂ ) or methacryloxy group (-OCO-(CH ₃ )C=CH ₂ ) . Liquid crystal compounds have mesogens (parts that induce rigidity of liquid crystallinity), and these compounds also have mesogens. Therefore, these compounds and the liquid crystal compound are aligned in the same direction by the action of the alignment film. The alignment is also maintained after polymerization. Such a liquid crystal composite has high transparency. In order to improve other characteristics, a polymerizable compound different from the compound (7), the compound (8), and the compound (9) may be used in combination.

Eighth, the preferred form of the optically active compound and an example thereof will be described. In TN mode liquid crystal display elements, optically active compounds can also be used. In this mode, two substrates have alignment films. The rubbing direction is rotated 90 degrees to arrange the substrate. The optically active compound is added to twist the arrangement of liquid crystal molecules by 90 degrees between the substrates. The spiral pitch is quite larger than 10 μm. On the other hand, the spiral pitch of the liquid crystal dimming element is 10 μm or less. By increasing the amount of the optically active compound, the spiral pitch becomes smaller. Therefore, the optically active compound preferably has large compatibility with the composition.

Preferred optically active compounds are compound (10-1) to compound (10-7). The structures of these compounds are similar to those of compounds having liquid crystallinity. From the viewpoint of large compatibility or small spiral pitch, these compounds are preferred. Compound (10-4) and compound (10-5) have an asymmetric axis. Compound (10-6) has asymmetric carbon.

In formula (10-1) to formula (10-7), R ⁸ to R ¹⁶ are hydrogen, fluorine, chlorine, cyano, -SF ₅ or an alkyl group having 1 to 10 carbons, and at least one of the alkyl groups -CH ₂ -may be substituted by -O-, -COO-, -OCO-, -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferably, R ⁸ to R ¹⁶ are hydrogen, an alkyl group having 1 to 10 carbons, or at least one -CH ₂ -alkyl group having 1 to 10 carbons substituted with -CH=CH- or -C≡C-. Particularly preferred R ⁸ to R ¹⁶ are alkyl groups having 1 to 10 carbon atoms.

Ring N, ring P, ring Q, ring T, ring U, ring X, ring Y and ring Z are 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2, 5-diyl, tetrahydropyran-2,5-diyl, tetrahydropyran-3,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or bicyclic [2.2 .2] Octane-1,4-diyl, in these rings, at least one hydrogen may be replaced by fluorine or chlorine. Preferred ring N, ring P, ring Q, ring T, ring U, ring X, ring Y or ring Z are 1,4-cyclohexylene or 1,4-phenylene. Ring R, ring S, ring V and ring W are 5,6,7,8-tetrahydronaphthalene-1,2-diyl or naphthalene-1,2-diyl. Preferred ring R, ring S, ring V or ring W is 5,6,7,8-tetrahydronaphthalene-1,2-diyl.

Z ¹⁸ to Z ²⁵ are a single bond or an alkylene group having 1 to 20 carbon atoms. In the alkylene group, at least one -CH ₂ -can pass through -O-, -CO-, -COO-, -OCO-,- CH=CH- or -C≡C- substituted, in these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferably Z ¹⁸ to Z ²⁵ are a single bond, an alkylene having 1 to 20 carbons, or at least one -CH ₂ -substituted with -O-, -COO- or -OCO- with a carbon number of 1 to 20 alkyl. Particularly preferred Z ¹⁸ to Z ²⁵ are single bonds, -OCH ₂ -, -COO- or -OCO-.

X ³ to X ⁸ are hydrogen or fluorine. In order to increase the helical twisting power (HTP), X ³ to X ⁸ are preferably fluorine.

p, q, r, s, t, u, v, and w are 1, 2, or 3. Preferably p, q, r, s, t, u, v or w is 2 or 3.

Based on the liquid crystal composition, the preferred ratio of the optically active compound is in the range of about 0.03% to about 25%. A particularly preferable ratio is in the range of about 0.03% to about 20%. A particularly preferred ratio is in the range of about 0.03% to about 15%. The preferred spiral pitch in the liquid crystal composition is 10 μm or less. The preferred spiral pitch is 5 μm or less. The particularly preferred spiral pitch is 3 μm or less.

One example of compound (10-1) to compound (10-7) is as follows.

Ninth, the synthesis method of the component compounds will be explained. These compounds can be synthesized by known methods. Illustrate the synthesis method. The compound (1-9) and the compound (1-16) were synthesized by the method described in Japanese Patent Laid-Open No. 2-233626. Compound (2-1) was synthesized by the method described in JP S59-176221 A. The compound (3-1) was synthesized by the method described in JP 2-503441 A. Antioxidants are already commercially available. The compound (11-1) mentioned later can be obtained from Sigma-Aldrich Corporation. Compound (11-2) and the like are synthesized by the method described in the specification of US Patent No. 3660505. The polymerizable compound is commercially available or can be synthesized by a known method.

Compounds without a description of the synthesis method can be synthesized by the method described in the following book: "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Syntheses" (John Wiley & Sons, Inc.) Reactions" (John Wiley & Sons, Inc.), "Comprehensive Organic Synthesis" (Pergamon Press), "New Experimental Chemistry Lectures" ( Maruzen) and so on. The composition is prepared from the compound obtained in the manner described above using a known method. For example, the component compounds are mixed and then heated to dissolve each other.

Tenth, the additives that can be added to the polymerizable composition will be described. Such additives include antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, polymerization initiators, polymerization inhibitors, polar compounds, and the like. The additives may be added to the liquid crystal composition or polymerizable compound instead of being added to the polymerizable composition.

In order to prevent the decrease in specific resistance caused by heating in the atmosphere, or to maintain a large voltage holding rate not only at room temperature but also at a temperature close to the upper limit temperature after using the element for a long time, the compound ( 11-1) Antioxidants such as compound (11-3) are added to the composition.

In order to prevent deterioration caused by ultraviolet rays, an ultraviolet absorber may be added to the composition. A compound with low volatility is effective for maintaining a high 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. In order to obtain the effect, the preferable ratio of the antioxidant is about 50 ppm or more. In order not to reduce the upper limit temperature or to increase the lower limit temperature, the preferable ratio of the antioxidant is about 600 ppm or less. A particularly preferable ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of ultraviolet absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of light stabilizers are compound (12-1) to compound (12-16) and the like. In order to obtain the effect, the preferred ratio of these absorbents or stabilizers is about 50 ppm or more. In order not to lower the upper limit temperature or increase the lower limit temperature, the preferred ratio of these absorbents or stabilizers is about Below 10000 ppm. A particularly preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

The matting agent is a compound that prevents the decomposition of the liquid crystal compound by receiving the light energy absorbed by the liquid crystal compound and converting it into heat energy. Preferred examples of the matting agent are compound (13-1) to compound (13-7) and the like. In order to obtain the effect, the preferred ratio of these matting agents is about 50 ppm or more. In order not to increase the lower limit temperature, the preferred ratio of these matting agents is about 20,000 ppm or less. A particularly preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

In order to be suitable for elements in the guest host (GH) mode, a dichroic dye (dichroic dye) is added to the composition. Liquid crystal dimming elements are sometimes used for room partitions. In this case, a dye is added to the polymerizable composition for the purpose of absorbing specific light. A variety of pigments can be added. Liquid crystal dimming elements are sometimes used to block sunlight. In this case, a black (or blackened color) dichroic dye is added to the liquid crystal composition. Black is prepared by mixing cyan, magenta, and yellow dichroic pigments. A black dichroic dye is described in Example 42 of JP 2006-193742 A. The pigment is prepared by mixing three azo compounds with anthraquinones.

Examples of dichroic pigments are: benzothiadiazoles, diketopyrrolopyrroles, azo compounds, azomethine compounds, methine Compounds (methine compounds), anthraquinones (anthraquinones), cyanines (merocyanines), naphthoquinones (naphthoquinones), tetrazines, pyrromethenes and perylenes or Rylenes such as terrylenes.

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

The preferred dichroic pigments are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, anthraquinones and rylenes. Particularly preferred dichroic pigments are benzothiadiazoles, diketopyrrolopyrroles, azo compounds and rylenes. The skeletons of these four pigments are shown below. For example, benzothiadiazoles refer to dichroic dyes having a benzothiadiazole ring.

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

Based on the liquid crystal composition, the preferred ratio of the dichroic dye is in the range of about 0.01% to about 25%. A particularly preferred ratio is in the range of about 0.02% to about 20%. A particularly preferred ratio is in the range of about 0.03% to about 15%.

To prevent foaming, antifoaming agents such as dimethyl silicone oil and methyl phenyl silicone oil are added to the composition. In order to obtain the effect, the preferable ratio of the defoamer is about 1 ppm or more, and in order to prevent display failure, the preferable ratio of the defoamer is about 1000 ppm or less. A particularly preferred ratio is in the range of about 1 ppm to about 500 ppm.

When the polymerizable compound is polymerized, it is preferable to irradiate ultraviolet rays. Examples of ultraviolet irradiation lamps are metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, 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. The preferred wavelength is 330 nm or more. A particularly preferable wavelength is 350 nm or more, for example, 365 nm. The reaction can be carried out around room temperature or under heating.

It is also possible to perform polymerization in the presence of a polymerization initiator such as a photopolymerization initiator. Appropriate conditions for polymerization or appropriate types and amounts of initiators are known to those having ordinary knowledge in the technical field to which the present invention belongs, and are described in the literature. For example, as a photopolymerization initiator, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF) or Darocur 1173 ( Registered trademark; BASF (BASF)) is suitable for free radical polymerization.

When storing the polymerizable compound, in order to prevent polymerization, a polymerization inhibitor may be added. The polymerizable compound is usually mixed in the liquid crystal composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are: hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tertiary butylcatechol, 4-methoxyphenol, phenothiazine, etc. .

Polar compounds are organic compounds with polarity. Here, no compound having an ionic bond is included. Atoms such as oxygen, sulfur, and nitrogen are negatively charged and tend to have partial negative charges. Carbon and hydrogen are neutral or have a tendency to have a partial positive charge. Polarity is caused by the uneven distribution of partial charges among atoms of different species in the compound. For example, the polar compound has at least one partial structure such as -OH, -COOH, -SH, -NH ₂ , >NH, and >N-.

The polar group has a non-covalent bonding interaction with the surface of a glass substrate, a metal oxide film, and the like. The polar compound is adsorbed on the surface of the substrate by the action of the polar group and controls the alignment of the liquid crystal molecules. Polar compounds not only control liquid crystal molecules, but sometimes also control polymerizable compounds. Such effects are expected for polar compounds.

Finally, the liquid crystal dimming element will be described. The nematic composition is a mixture of rod-shaped liquid crystal compounds. The chiral nematic composition is prepared by adding an optically active compound (chiral agent) to the nematic composition. The liquid crystal molecules are given a right twist or a left twist by the action of the optically active compound, thereby becoming a focal conic state. In the tiny area, the liquid crystal molecules are arranged in layers, and the direction of the liquid crystal molecules in each layer is twisted in a spiral shape. The axis of twist in the spiral structure is called a spiral axis. The length corresponding to one cycle in the spiral structure is called the spiral pitch. The focal conic state is a collection of such tiny areas, and the direction of the spiral axis is random.

Figure 1 shows the dimming element in the normal mode. The dimming layer (liquid crystal composite) is sandwiched by two substrates. In the element on the left (not applied), the triangles (liquid crystal molecules) represent the tiny areas of the focal conic state, and the curves represent the polymer grid. In the element (application) on the right, the vertical bars (liquid crystal molecules) show a homeotropic state.

A polymerizable compound is mixed with a composition in a focal cone state to prepare a polymerizable composition. This composition is put into a display element. The device has an Indium Tin Oxide (ITO) electrode. The component has not been aligned. While applying a voltage to the element, ultraviolet rays were irradiated to proceed a polymerization reaction to produce an element having a liquid crystal composite. Due to the scattering of light, the element is opaque. By applying voltage to the device, the liquid crystal molecules transition from the focal conic state to the vertical state. Since light is transmitted, the device is transparent. The vertical state is restored to the focal conic state due to the removal of the voltage.

Figure 2 shows the dimming element in reverse mode. This element has a horizontal alignment film, which is different from the element of FIG. 1 in this respect. The liquid crystal molecules are in a planar state due to the action of the alignment film. The element is transparent. By applying a voltage to the device, the liquid crystal molecules transition to a focal conic state. The element becomes opaque due to light scattering. The state of the focal cone is restored to the planar state due to the removal of the voltage.

Sometimes changes over time are caused by long-term use of components. The haze rate sometimes changes from the initial stage. The change of haze rate should be small. When the haze change rate is small, a good state of transparency/opacity can be maintained. The haze change rate is preferably 20% or less. The haze change rate is particularly 10% or less. The excellent haze change rate is 5% or less.

The haze change rate is an important factor for the long life of the liquid crystal dimming element. When testing the weather resistance of the element, the haze change rate before and after it is preferably small. In order to achieve a small haze change rate, it is important to select the type of liquid crystal compound and combine it with a specific polymerizable compound to study the ratio of each component compound. In order to obtain better results, it is useful to study the type or amount of additives, polymerization conditions, and the like.

If the device is used for a long time, flicker may sometimes occur in the display screen. It is speculated that the flicker is related to the ghosting of the image, and when the element is driven by AC, the flicker is generated due to the difference between the potential of the positive frame and the potential of the negative frame. The flicker rate (%) can be represented by (|brightness when a positive voltage is applied-brightness when a negative voltage is applied|)/(average brightness)×100. The flicker rate of the element is preferably in the range of 0% to 1%.

When the device is used for a long time, the brightness may be partially reduced. An example of such poor display is line afterimage. This is a phenomenon in which different voltages are repeatedly applied to two adjacent electrodes, and the brightness between the electrodes is reduced in stripes. It is estimated that this phenomenon is caused by the accumulation of ionic impurities contained in the liquid crystal composition in the vicinity of the electrode.

Such a dimming element has a dimming layer (liquid crystal composite) sandwiched between a pair of transparent substrates having transparent electrodes. An example of the substrate is a non-deformable material such as a glass plate, a quartz plate, and an acrylic plate. Another example is a flexible transparent plastic film such as acrylic film and polycarbonate film. According to the application, one of the substrates can be an opaque material such as silicone resin. The substrate may have transparent electrodes thereon. Examples of transparent electrodes are indium tin oxide (tin-doped indium oxide (ITO)) or conductive polymers. The substrate may also have an alignment film on the transparent electrode.

For the alignment film, a film such as polyimide or polyvinyl alcohol is suitable. For example, the polyimide alignment film can be formed by coating the polyimide resin composition on a transparent substrate, and thermally curing at a temperature above about 180°C, and, if necessary, by cotton or rayon cloth. Obtained by friction treatment.

The pair of substrates face each other so that the transparent electrode layer is inside. In order to make the thickness between the substrates uniform, spacers can also be placed. Examples of spacers are glass particles, plastic particles, alumina particles, photo spacers, and the like. The preferred thickness of the light modulating layer is about 2 μm to about 50 μm, and more preferably about 5 μm to about 20 μm. When bonding a pair of substrates, a commonly used sealant can be used. An example of the sealing agent is an epoxy-based 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 as necessary. Mirror reflection, diffuse reflection, retroreflective reflection, holographic reflection and other functions can also be added.

This type of element has a function as a dimming film or dimming glass. When the element is in the form of a film, it can be attached to an existing window or sandwiched by a pair of glass plates to make laminated glass. This kind of element is used for the partition of the window set on the outer wall or 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 liquid crystal shutters and the like. [Example]

The present invention will be further described in detail through examples. The present invention is not limited by these embodiments. The composition (M1), the composition (M2), etc. are described in the examples. The mixture of the composition (M1) and the composition (M2) is not described in the examples. However, it is deemed that the mixture is also revealed. It is considered that a mixture of at least two components selected from the examples is also disclosed. It is considered that a liquid crystal composite containing these mixtures or a liquid crystal dimming element having the composite belong to the present invention, and it is reasonable to have the effects of the present invention. The synthesized compound is identified by nuclear magnetic resonance (NMR) analysis and other methods. The characteristics of the compound, composition, and device are measured by the following methods.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for measurement. ^{In the 1} H-NMR measurement, the sample is dissolved in a deuterated solvent such as CDCl ₃ and the measurement is performed under the conditions of 500 MHz and 16 cumulative times at room temperature. Use tetramethylsilane as the internal standard. ^{In the 19} F-NMR measurement, CFCl _{3 was} used as an internal standard, and the measurement was carried out at 24 times of accumulation. In the description of NMR spectrum, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet (Quintet), sex refers to sextet, m refers to multiplet, and br refers to broad.

Gas chromatographic analysis: GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL/min). The sample vaporization chamber is set to 280°C, and the detector (flame ionization detector (FID)) is set to 300°C. When the component compounds are separated, the capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. is used; the fixed liquid phase is dimethyl polysilicon Oxane; non-polar). After the column was kept at 200°C for 2 minutes, the temperature was increased to 280°C at a rate of 5°C/min. After preparing the sample into an acetone solution (0.1%), inject 1 μL into the sample vaporization chamber. The recorder is the C-R5A Chromatopac manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram shows the peak retention time and peak area corresponding to the component compounds.

The solvent used to dilute the sample can be chloroform, hexane, etc. In order to separate the component compounds, the following capillary column can also be used. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies, Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness) manufactured by Restek Corporation 0.25 μm), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by SGE International Pty. Ltd in Australia. For the purpose of preventing overlapping of compound peaks, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation can be used.

The ratio of the liquid crystal compound contained in the composition can be calculated by the method described below. Gas chromatography (FID) is used to analyze the mixture of liquid crystal compounds. The peak area ratio in the gas chromatogram corresponds to the ratio of liquid crystal compounds. When the capillary column described above is used, the correction factor of various liquid crystal compounds can 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 a composition or a device having the composition, the composition is directly used as a sample. When measuring the characteristics of the compound, a sample for measurement is prepared by mixing the compound (15%) in the mother liquid crystal (85%). Based on the value obtained by the measurement, the property value of the compound is calculated by extrapolation. (Extrapolated value)={(measured value of sample)-0.85×(measured value of mother liquid crystal)}/0.15. When the smectic phase (or crystal) is precipitated at 25°C under this ratio, the ratio of the compound to the mother liquid crystal is changed in the order of 10%: 90%, 5%: 95%, and 1%: 99%. This extrapolation method is used to obtain the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy related to the compound.

The following mother liquid crystals are used.

Measurement method: Use the following method to measure the characteristics. Most of these methods are methods described in the JEITA standard (JEITA·ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA), or modified成的方法。 Into the method. In the twisted nematic (TN) element used for the measurement, the Thin Film Transistor (TFT) is not installed.

(1) The upper limit temperature of the nematic phase (NI; °C): Place the sample on the hot plate of the melting point measuring device including the polarizing microscope, and heat it at a rate of 1 °C/min. The temperature at which a part of the sample changes from a nematic phase to an isotropic liquid is measured. The upper limit temperature of the nematic phase is sometimes referred to simply as the "upper limit temperature".

(2) Lower limit temperature of nematic phase (T _C ; ℃): Put the sample with nematic phase into a glass bottle, and set it at 0℃, -10℃, -20℃, -30℃ and -40℃ After 10 days of storage in a freezer, the liquid crystal phase was observed. For example, when a sample maintains a nematic phase at -20°C and changes to a crystalline or smectic phase at -30°C, T _{C is} described as <-20°C. The lower limit temperature of the nematic phase is sometimes referred to simply as the "lower limit temperature".

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

(4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s): According to M. Imai et al. "Molecular Crystals and Liquid Crystals" No. 259 The measurement is performed by the method described on page 37 (1995). A sample was placed in a TN device with a torsion angle of 0° and a gap between two glass substrates (cell gap) of 5 μm. The voltage was applied stepwise in units of 0.5 V in the range of 16 V to 19.5 V to this element. After no voltage was applied for 0.2 seconds, it was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage (2 seconds) applied. Measure the peak current and peak time of the transient current generated by the application. The value of rotational viscosity is obtained based on these measured values and the calculation formula (10) described on page 40 of the paper by M. Imai et al. The value of dielectric anisotropy required for this calculation is obtained by the method described below using an element for measuring the rotational viscosity.

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25°C): Use light with a wavelength of 589 nm to measure with an Abbe refractometer equipped with a polarizing plate on the eyepiece. After rubbing the surface of the main beam in one direction, drop the sample on the main beam. The refractive index n∥ is measured when the direction of polarized light is parallel to the direction of rubbing. The refractive index n⊥ is measured when the direction of polarized light is perpendicular to the direction of rubbing. The value of optical anisotropy is calculated according to the formula of Δn=n∥-n⊥.

(6) Dielectric anisotropy (Δε; measured at 25°C): A sample is placed in a TN device with a gap (cell gap) of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (10 V, 1 kHz) was applied to the device, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. A sine wave (0.5 V, 1 kHz) was applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy is calculated by the formula Δε=ε∥-ε⊥.

(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 is a halogen lamp. The sample was placed in a normally white mode (normally white mode) TN device with a distance (cell gap) of 0.45/Δn (μm) between two glass substrates and a twist angle of 80 degrees. The voltage (32 Hz, rectangular wave) applied to the device was increased from 0 V to 10 V in steps of 0.02 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light passing through the element was measured. A voltage-transmittance curve in which the transmittance is 100% when the amount of light reaches the maximum and the transmittance is 0% when the amount of light is the smallest is prepared. The threshold voltage is expressed by the voltage when the transmittance becomes 90%.

(8) Voltage retention rate (VHR; measured at 25°C; %): The TN device used in the measurement has a polyimide alignment film, and the interval (cell gap) between two glass substrates is 5 μm. A sample is placed in the TN device, and sealed with an adhesive that is cured with ultraviolet rays. The TN device was placed in a 60°C thermostat, and a pulse voltage (1 V, 60 microseconds, 3 Hz) was applied to charge. A high-speed voltmeter was used to measure the attenuated voltage during 166.6 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was obtained. Area B is the area without attenuation. The voltage retention rate is expressed by the percentage of area A to area B.

(9) Voltage retention rate (UV-VHR; measured at 25°C; %): For the TN device with the sample placed, black light was used as the light source and irradiated with 5 milliwatts of ultraviolet rays for 166.6 minutes. The voltage retention rate was measured to evaluate the stability to ultraviolet rays. The configuration of the TN element and the method of measuring the voltage holding ratio are described in Measurement (8). The composition with large UV-VHR has large stability to ultraviolet rays. The UV-VHR is preferably 90% or more, more preferably 95% or more.

(10) Voltage holding rate (heating VHR; measured at 25°C; %): After heating the TN device with the sample in a constant temperature bath at 120°C for 20 hours, measure the voltage holding rate to evaluate the heat resistance stability. The configuration of the TN element and the method of measuring the voltage holding ratio are described in Measurement (8). A composition having a large heating VHR has a large 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): LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a normally white mode (normally white mode) TN device with a distance (cell gap) of 5.0 μm between two glass substrates and a twist angle of 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to the device. At this time, the element was irradiated with light from the vertical direction, and the amount of light passing through the element was measured. When the amount of light reaches the maximum, the transmittance is regarded as 100%, and when the amount of light is minimum, the transmittance is regarded as 0%. Rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. Fall time (τf: fall time; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time is expressed by the sum of the rise time and the fall time obtained in the manner described above.

(12) Elastic constant (K; measured at 25°C; pN): The HP4284A type LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. was used for the measurement. A sample was placed in a horizontal alignment element with a distance (cell gap) of 20 μm between two glass substrates. Apply a charge of 0 V to 20 V to the device, and measure the capacitance and applied voltage. Use the equations (2.98) and (2.101) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Kogyo) to fit the measured capacitance (C) and the applied voltage (V) to the equation (2.99) Obtain the values of K11 and K33. Next, calculate K22 using the previously calculated values of K11 and K33 in the formula (3.18) on page 171 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun). The spring constant is expressed by the average value of K11, K22, and K33 obtained in the above-mentioned manner.

(13) Specific resistance (ρ; measured at 25°C; Ωcm): Put 1.0 mL of sample in a container with electrodes. A DC voltage (10 V) was applied to the container, and the DC current after 10 seconds was measured. The specific resistance is calculated by the following formula. (Specific resistance)={(voltage)×(capacitance of container)}/{(DC current)×(dielectric constant of vacuum)}

(14) Helical pitch (P; measured at room temperature; μm): Helical pitch is measured by the wedge method. Refer to "LCD Handbook" page 196 (issued in 2000, Maruzen). Put the sample into the wedge cell and let it stand for 2 hours at room temperature. Observe the disclination line interval (by a polarizing microscope (Nikon) (stock), trade name MM40/60 series). d2-d1). The helical pitch (P) is calculated by the following formula expressing the angle of the wedge-shaped unit as θ. P=2×(d2-d1)×tanθ.

(15) Dielectric constant in the short axis direction (ε⊥; measured at 25°C): Place the test in a TN device with a gap (cell gap) of 9 μm between two glass substrates and a twist angle of 80 degrees. kind. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured after 2 seconds.

(16) Pretilt angle (degrees): Spectroscopic ellipsometer M-2000U (manufactured by J. A. Woollam Co., Inc.) was used for the measurement of pretilt angle.

(17) Alignment stability (liquid crystal alignment axis stability): Evaluate the change of the liquid crystal alignment axis on the electrode side of fringe field switching (FFS) elements. Measure the alignment angle ϕ of the liquid crystal on the electrode side before stress is applied (before), then apply a rectangular wave of 4.5 V and 60 Hz to the device for 20 minutes, buffer for 1 second, and measure the electrode side again after 1 second and 5 minutes later. The liquid crystal alignment angle ϕ (after). From these values, the following equation was used to calculate the change (Δϕ; degrees) of the liquid crystal alignment angle after 1 second and 5 minutes. Δϕ(degree)=ϕ(after)-ϕ(before) These measurements are based on J. Hilfiker, B. Johs, C. Herzinger, JF Elman, E. Mumba The "Thin Solid Films" of Qi (E. Montbach), D. Bryant and PJ Bos (PJ Bos) 455-456 (2004) 596-600 are used as reference. It can be said that the smaller the Δϕ, the smaller the rate of change of the liquid crystal alignment axis, and the more stable the liquid crystal molecules.

(18) Flicker rate (measured at 25°C; %): A multimedia display tester (multimedia display tester) 3298F manufactured by Yokogawa Electric Corporation was used for the measurement. The light source is a light emitting diode (Light Emitting Diode, LED). The sample is placed in a normally black mode (normally black mode) element where the distance between two glass substrates (cell gap) is 3.5 μm and the rubbing direction is anti-parallel. The device is sealed with an adhesive that is cured by ultraviolet light. A voltage is applied to the element, and the voltage at which the amount of light passing through the element reaches the maximum is measured. While applying this voltage to the element, the sensor unit is brought close to the element, and the displayed flicker rate is read.

(19) Line Image Sticking Parameter (LISP; %): Line Image Sticking Parameter is generated by applying electrical stress to the component. Measure the brightness of the area where the line afterimage exists and the brightness of the remaining area (reference area). Calculate the ratio of the decrease in brightness due to the line afterimage, and use the ratio to express the size of the line afterimage.

19a) Measurement of brightness: An imaging color brightness meter (manufactured by Radiant Zemax, PM-1433F-0) was used to capture the image of the component. By using software (Prometric 9.1, manufactured by Radiant Zemax), the image is analyzed to calculate the brightness of each area of the device. The light source uses an LED backlight with an average brightness of 3500 cd/m ² .

19b) Setting of stress voltage: Place a sample in an FFS element with a cell gap of 3.5 μm and a matrix structure (16 cells of 4 vertical cells × 4 horizontal cells), and use an adhesive cured by ultraviolet light seal. Polarizing plates are respectively arranged on the upper surface and the lower surface of the element such that the polarization axis is orthogonal. Light was irradiated to the element and voltage (rectangular wave, 60 Hz) was applied. The voltage is in the range of 0 V to 7.5 V, and is gradually increased in units of 0.1 V, and the brightness of the transmitted light at each voltage is measured. The voltage when the brightness reaches the maximum is referred to as V255 for short. The voltage when the brightness reaches 21.6% of V255 (ie, 127 gray scale) is referred to as V127 for short.

19c) Stress conditions: V255 (rectangular wave, 30 Hz) is applied to the stress area under the conditions of 60°C for 23 hours, and 0.5 V (rectangular wave, 30 Hz) is applied to the reference area to display a checkerboard pattern. Then, V127 (rectangular wave, 0.25 Hz) was applied, and the brightness was measured under the condition of an exposure time of 4000 milliseconds.

19d) Calculation of line afterimages: 4 of the 16 units (2 units in the vertical x 2 units in the horizontal) in the central part of the 16 units are used for calculation. The 4 cells are divided into 25 areas (5 cells in vertical x 5 cells in horizontal). The average brightness of the 4 areas (2 vertical cells × 2 horizontal cells) located at the four corners is referred to as brightness A for short. The area formed by removing the four corners from the 25 areas is a cross. In the four areas obtained by removing the central intersection area from the cross-shaped area, the minimum value of the brightness is simply referred to as the brightness B. The line residual image is calculated by the following equation. (Line afterimage)=(Brightness A-Brightness B)/Brightness A×100. The afterimage of the line should be small.

(20) Face Image Sticking Parameter (FISP; %): The face image sticking parameter is generated by applying electrical stress to the component. The brightness of the area where the afterimage exists and the brightness of the remaining area were measured at 25°C. Calculate the ratio of the brightness change caused by the afterimage of the surface, and express the size of the afterimage by this ratio.

20a) "Measurement of brightness", "Setting of stress voltage", and "Conditions of stress" follow the order described in the item "Line afterimage".

20b) The facial afterimage is calculated by the following formula. (Afterimage)=(Brightness C-Brightness D)/Brightness D×100. Here, the brightness C is the average brightness of 8 cells to which V255 is applied, and the brightness D is the average brightness of 8 cells to which 0.5 V is applied. The afterimage of the face should be small. When the dielectric anisotropy of the liquid crystal composition is positive, the surface afterimage is represented by P-FISP. When the dielectric anisotropy of the liquid crystal composition is negative, the surface afterimage is represented by N-FISP.

(21) Haze rate (%): Haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used when measuring the haze rate.

(22) Haze change rate (%): Conduct the weather resistance test of the component. The haze was measured before and after the test, and the haze change rate was calculated. The test is carried out in accordance with Japanese Industrial Standards (JIS) K5600-7-7, accelerated weather resistance and accelerated light resistance (xenon lamp method). The super xenon weather meter (super xenon weather meter) SX75 model manufactured by Suga Tester (Stock) was used for the measurement. The measurement conditions are illuminance (UVA; 180 W/m ² ), irradiation time (100 hours), blackboard temperature (63°C±2°C), tank temperature (35°C), and relative humidity in tank (40%RH). UVA refers to ultraviolet A (ultraviolet A).

(23) Characteristics of dimming components When measuring the characteristics of a liquid crystal display element, an element of a glass substrate having a transparent electrode is generally used. On the other hand, in liquid crystal dimming devices, plastic films are sometimes used as substrates. Therefore, an element in which the substrate is polycarbonate was fabricated, and characteristics such as threshold voltage and response time were measured. The measured value is compared with the case of the glass substrate element. As a result, the two measured values were almost the same. Therefore, the characteristics were measured using the element of the glass substrate, and the result was described.

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

[table 3]

The following compositions were used in the examples.

[Composition (M1)] 5-HB-CL (1-1) 12% 3-BB(F)B(F,F)-F (1-24) 6% 3-BB(F,F)XB( F,F)-F (1-28) 20% 3-BB(F)B(F,F)XB(F,F)-F (1-41) 4% 4-BB(F)B(F, F)XB(F,F)-F (1-41) 4% 3-BB(F,F)XB(F)B(F,F)-F (1-42) 13% 1-BB-3 ( 2-3) 10% V-HHB-1 (2-9) 8% 1-BB(F)B-2V (2-12) 3% 2-BB(F)B-2V (2-12) 4% 3-BB(F)B-2V (2-12) 4% 5-HBB(F)B-2 (2-21) 6% 5-HBB(F)B-3 (2-21) 6% NI= 79.2℃; T _C ＜-20℃; η=39.2 mPa·s; Δn=0.179; Δε=13.2; Vth=1.46 V.

[Composition (M2)] 3-HB-C (1-1) 10% 3-HB(F)-C (1-1) 15% 3-HHB-F (1-9) 4% 2-HHB( F)-F (1-9) 11% 3-HHB(F)-F (1-9) 11% 5-HHB(F)-F (1-9) 10% 3-HHB(F)-C ( 1-9) 8% 3-BB(F,F)XB(F,F)-F (1-28) 1% 3-HB-O2 (2-2) 10% 3-HHB-1 (2-9 ) 8% 3-HHB-3 (2-9) 8% 3-HHB-O1 (2-9) 4% NI=95.5℃; T _C ＜-20℃; η=22.3 mPa·s; Δn=0.100; Δε=8.1; Vth=1.50 V.

[Composition (M3)] 2-HHB(F)-F (1-9) 12% 3-HHB(F)-F (1-9) 12% 5-HHB(F)-F (1-9) 11% 3-HHB(F,F)-F (1-9) 10% 3-HHXB(F,F)-F (1-13) 1% 2-HBB(F)-F (1-16) 4.5 % 3-HBB(F)-F (1-16) 4.5% 5-HBB(F)-F (1-16) 9% 3-HBB(F,F)-F (1-16) 18% 3- HB-O2 (2-2) 5% 3-HHB-1 (2-9) 8% 3-HHB-O1 (2-9) 5% NI=101.8℃; T _C ＜-20℃; η=24.5 mPa ·S; Δn=0.105; Δε=6.1; Vth=1.76 V.

[Composition (M4)] 3-BB(F,F)XB(F,F)-F (1-28) 15% 3-BB(F,F)XB(F)B(F,F)-F (1-42) 12% 3-HB-O2 (2-2) 15% 3-HHB-1 (2-9) 8% 3-HHB-3 (2-9) 10% 3-HHB-O1 (2 -9) 5% 3-HBB-2 (2-10) 12% 2-BB(F)B-5 (2-12) 8% 3-BB(F)B-5 (2-12) 8% 3 -BB(2F,5F)B-3 (2-13) 7% NI=100.5℃; T _C ＜-20℃; η=32.3 mPa·s; Δn=0.162; Δε=6.2; Vth=2.28 V.

[Composition (M5)] 3-HB-CL (1-1) 3% 5-HXB(F,F)-F (1-7) 3% 3-HHB-OCF3 (1-9) 3% 3- HHXB(F,F)-F (1-13) 6% 3-HGB(F,F)-F (1-14) 3% 3-HB(F)B(F,F)-F (1-17 ) 5% 3-BB(F,F)XB(F,F)-F (1-28) 6% 3-HHBB(F,F)-F (1-29) 6% 5-BB(F)B (F,F)XB(F)B(F,F)-F (1-43) 2% 3-BB(2F,3F)XB(F,F)-F (1-44) 4% 3-HHB (F,F)XB(F,F)-F (1) 4% 3-HBB(2F,3F)XB(F,F)-F (1) 5% 3-HH-V (2-1) 22 % 3-HH-V1 (2-1) 10% 5-HB-O2 (2-2) 5% 3-HHEH-3 (2-8) 3% 3-HBB-2 (2-10) 7% 5-B(F)BB-3 (2-11) 3% NI=77.2℃; T _C ＜-20℃; Δn=0.101; Δε=5.8; Vth=1.88 V; η= 13.7 mPa·s; γ1=61.3 mPa·s.

The polymerizable compound is appropriately selected from the following compounds and used.

The following optically active compounds were used in the examples.

[Example 1] (1) The production composition (M1) of a liquid crystal dimming element has positive dielectric anisotropy. Based on the composition (M1), the optically active compound (10-4-1) was added at a ratio of 1.0%. The spiral pitch is 1.1 μm. The polymerizable compound (RM-15) is mixed with this composition to prepare a polymerizable composition. The ratio is set to polymerizable compound (RM-15)/composition (M1)=6%/94%. Based on polymerizable compounds, Irgacure 651 (photopolymerization initiator; registered trademark; BASF) was added at a ratio of 5.0%. This polymerizable composition was injected into an element with a distance (cell gap) of 10 μm between two glass substrates. No alignment process is performed in the component. With respect to this element, while applying 30 V (60 Hz), a high-pressure mercury lamp was irradiated with 18 mW/cm ² of ultraviolet rays for 56 seconds to produce an element having a liquid crystal composite. The element is opaque. A voltage of 30 V was applied to this element, and it became transparent when irradiated with light. According to the result, the device is in normal mode.

(2) Haze change rate The element is installed in the haze meter so that the element is perpendicular to the incident light. A voltage in the range of 0 V to 60 V was applied to the device, and the haze ratio was measured. Next, the haze ratio after the weather resistance test performed under the conditions described in the measurement (22) was measured. It was 95.9% before the test and 88.6% after the test. The haze change rate is 7.3%.

[Example 2] (1) The production composition (M2) of a liquid crystal dimming element has positive dielectric anisotropy. Based on the composition (M2), the optically active compound (10-4-1) was added at a ratio of 0.94%. The spiral pitch is 1.0 μm. The polymerizable compound (RM-1) and the polymerizable compound (RM-5) are mixed in this composition to prepare a polymerizable composition. The ratio is set to polymerizable compound (RM-1)/polymerizable compound (RM-5)/composition (M2)=32%/8%/60%. Based on the mixture of polymerizable compounds, Irgacure 651 (photopolymerization initiator; registered trademark; BASF) is added at a ratio of 0.75%. This polymerizable composition was injected into an element with a distance (cell gap) of 10 μm between two glass substrates. No alignment process is performed in the component. With respect to this element, while applying 30 V (60 Hz), a high-pressure mercury lamp was irradiated with 18 mW/cm ² of ultraviolet rays for 56 seconds to produce an element having a liquid crystal composite. The element is opaque. A voltage of 30 V was applied to this element, and it became transparent when irradiated with light. According to the result, the device is in normal mode.

(2) Haze change rate The haze rate before and after the weather resistance test was measured by the same method as in Example 1, and the haze change rate was calculated. The haze change rate was 4.2%.

[Example 3 to Example 5] The same method as in Example 2 was used to calculate the haze change rate. The results are summarized in Table 4. In Examples 3 to 5, the optically active compound (10-4-1) was added at a ratio of 1.0% based on the composition. [Table 4] Production of liquid crystal dimming element Example Polymeric composition LCD dimming element Composition (60%) Polymeric compound No voltage applied Applied voltage Haze change rate (%) (32%) (8%) 2 M2 RM-1 RM-5 opaque Transparent 4.2 (87.4-83.2) 3 M3 RM-1 RM-8 opaque Transparent 7.1 (86.2-79.1) 4 M4 RM-2 RM-8 opaque Transparent 8.5 (93.6-85.1) 5 M5 RM-2 RM-6 opaque Transparent 8.2 (83.8-75.6)

From the above results, it can be seen that the elements of Example 1 to Example 5 have a normal mode. For these components, a weather resistance test described in Japanese Industrial Standards (JIS) was performed. The haze change rate before and after the test was 10% or less. From this result, it can be seen that the change over time of the liquid crystal dimming element is small. Therefore, we have concluded that a liquid crystal composite formed by combining a specific chiral nematic composition and a specific polymer can be suitably used in a liquid crystal dimming element. [Industrial availability]

The liquid crystal dimming element containing the liquid crystal composite of the present invention can be used for dimming windows, smart windows and the like.

no

Figure 1 shows the dimming element in the normal mode. Figure 2 shows the dimming element in reverse mode.

Claims (20)

A liquid crystal composite comprising a liquid crystal composition and a polymer, the liquid crystal composition containing as component A at least one compound selected from compounds represented by formula (1) and an optically active compound as additive A:

In formula (1), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons; ring A is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine- 2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ¹ is a single bond, ethylene, vinylene, acetylene Group, methyleneoxy group, carbonyloxy group or difluoromethyleneoxy group; X ¹ and X ² are hydrogen or fluorine; Y ¹ is fluorine, chlorine, cyano, at least one hydrogen is replaced by fluorine or chlorine. The carbon number is 1 An alkyl group having to 12, an alkoxy group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkenyloxy group having 2 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; a is 1, 2 , 3, or 4. The liquid crystal composite according to claim 1, wherein the liquid crystal composition contains at least one compound selected from the group consisting of compounds represented by formula (1-1) to formula (1-47) as component A:

In formulas (1-1) to (1-47), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons, X ¹ and X ² is hydrogen or fluorine; Y ¹ is fluorine, chlorine, cyano, an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine An oxy group or an alkenyloxy group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. The liquid crystal composite according to claim 1, wherein the ratio of the component A is in the range of 5% to 90% based on the liquid crystal composition. The liquid crystal composite according to claim 1, wherein the liquid crystal composition contains as component B at least one compound selected from compounds represented by formula (2):

In formula (2), R ² and R ³ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, or at least one hydrogen substituted by fluorine or chlorine Alkenyl with 2 to 12 carbons; ring B and ring C are 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene , 2,5-difluoro-1,4-phenylene or pyrimidine-2,5-diyl; Z ² is a single bond, ethylene, ethylene, ethynylene, methyleneoxy or carbonyloxy基; b is 1, 2 or 3. The liquid crystal composite according to claim 1, wherein the liquid crystal composition contains at least one compound selected from the group consisting of compounds represented by formula (2-1) to formula (2-23) as component B:

In formulas (2-1) to (2-23), R ² and R ³ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, or An alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. The liquid crystal composite according to claim 1, wherein the liquid crystal composition contains as component C at least one compound selected from compounds represented by formula (3):

In formula (3), R ⁴ and R ⁵ are hydrogen, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkylene oxide having 2 to 12 carbons. Ring D and ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen Fluorine or chlorine substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chroman-2,6-diyl , Or Chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; ring E 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-difluoro Orthane-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-tetrafluoroindan-2,5-diyl; Z ³ and Z ⁴ are single bond, ethylene, ethylene Group, methyleneoxy or carbonyloxy; c is 0, 1, 2 or 3, d is 0 or 1, and the sum of c and d is 3 or less. The liquid crystal composite according to claim 1, wherein the liquid crystal composition contains at least one compound selected from the group consisting of compounds represented by formula (3-1) to formula (3-35) as component C:

In formulas (3-1) to (3-35), R ⁴ and R ⁵ are hydrogen, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and an alkenyl group having 2 to 12 carbons. Or an alkenyloxy group having 2 to 12 carbons. The liquid crystal composite according to claim 1, wherein the polymer is derived from a precursor, and the main component of the precursor is a compound represented by formula (4):

In formula (4), P ¹ and P ² are polymerizable groups; Z ⁵ is an alkylene group having 1 to 20 carbons, and in the alkylene group, at least one hydrogen may pass through an alkylene group having 1 to 5 carbons, Fluorine, chlorine or P ³ substitution, at least one -CH ₂ -can be substituted by -O-, -CO-, -COO-, -OCO-, -NH- or -N(R ⁶ )-, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one -CH ₂ -can be substituted by carbocyclic saturated aliphatic compounds, heterocyclic saturated aliphatic compounds, carbocyclic The unsaturated aliphatic compound, heterocyclic unsaturated aliphatic compound, carbocyclic aromatic compound or heterocyclic aromatic compound is substituted by a divalent group generated by removing two hydrogens, these divalent groups Wherein the carbon number is 5 to 35, and at least one hydrogen may be substituted by R ⁶ or P ³ , where R ⁶ is an alkyl group having 1 to 12 carbons. In the alkyl group, at least one -CH ₂ -may be Substituting -O-, -CO-, -COO- or -OCO-, P ³ is a polymerizable group. The liquid crystal composite according to claim 8, wherein P ¹ , P ² and P ³ are groups selected from 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 hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or a carbon number 1 in which at least one hydrogen is substituted by fluorine or chlorine To 5 alkyl groups. The liquid crystal composite according to claim 1, wherein the polymer is derived from a precursor, and the main component of the precursor is a compound represented by formula (5):

In formula (5), M ⁴ and M ⁵ are hydrogen or methyl; Z ⁶ is an alkylene having 21 to 80 carbons, and in the alkylene, at least one hydrogen may pass through an alkyl having 1 to 20 carbons. , Fluorine or chlorine substitution, at least one -CH ₂ -can be substituted with -O-, -CO-, -COO-, -OCO-, -NH- or -N(R ⁶ )-, at least one -CH ₂ CH ₂ -May be substituted by -CH=CH- or -C≡C-, where R ⁶ is an alkyl group having 1 to 12 carbons, in which at least one -CH ₂ -may be -O-,- CO-, -COO- or -OCO- substitution. The liquid crystal composite according to claim 1, wherein the polymer is derived from a precursor, and the main component of the precursor is a compound represented by formula (6):

In formula (6), M ⁶ is hydrogen or methyl; Z ⁷ is a single bond or an alkylene having 1 to 5 carbon atoms. In the alkylene, at least one hydrogen can be replaced by fluorine or chlorine, and at least one- CH ₂ -may be substituted by -O-, -CO-, -COO- or -OCO-; R ⁷ is an alkyl group with 1 to 40 carbons, in which at least one hydrogen may be substituted by fluorine or chlorine, At least one -CH ₂ -can be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ -can be saturated by carbocyclic saturated aliphatic compound or heterocyclic saturated A divalent group formed by removing two hydrogens from aliphatic compounds, carbocyclic unsaturated aliphatic compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds or heterocyclic aromatic compounds Substitution, in these divalent groups, the carbon number is 5 to 35, and at least one hydrogen can be substituted by an alkyl group having 1 to 12 carbons. In the alkyl group, at least one -CH ₂ -can be replaced by -O-, -CO-, -COO- or -OCO- substitution. The liquid crystal composite according to claim 11, wherein in formula (6), M ⁶ is hydrogen or methyl; Z ⁷ is a single bond or an alkylene having 1 to 5 carbon atoms, and in the alkylene, at least One hydrogen can be replaced by fluorine or chlorine, and at least one -CH ₂ -can be replaced by -O-, -CO-, -COO- or -OCO-; R ⁷ is an alkyl group having 1 to 40 carbon atoms, the alkyl group Among them, at least one hydrogen can be replaced by fluorine or chlorine, and at least one -CH ₂ -can be replaced by -O-, -CO-, -COO- or -OCO-. The liquid crystal composite according to claim 1, wherein the polymer is derived from a precursor, and the main component of the precursor is a compound represented by formula (7), formula (8) or formula (9):

In formula (7), formula (8) and formula (9), ring G, ring I, ring J, ring K, ring L and ring M 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-di In this case, at least one hydrogen may be fluorine, chlorine, cyano, hydroxy, methanoyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl with 1 to 5 carbons, carbon number 1 to 5 alkoxy group, carbon number 2 to 5 alkoxycarbonyl group or carbon number 1 to 5 alkoxy group substitution; Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ and Z ¹⁷ are single bonds, -O -, -COO-, -OCO- or -OCOO-; Z ⁹ , Z ¹¹ , Z ¹⁴ and Z ¹⁶ 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 ¹⁵ is a single bond, -O- or -COO-; Y ² is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoro Methoxy, cyano, 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; f and h are An integer from 1 to 4; k and m are an integer from 0 to 3, and the sum of k and m is from 1 to 4; e, g, i, j, l and n are an integer from 0 to 20; M ⁷ to M ¹² are Hydrogen or methyl. The liquid crystal composite according to claim 1, wherein the additive A is at least one compound selected from the optically active compounds represented by formula (10-1) to formula (10-7):

In formulas (10-1) to (10-7), R ⁸ to R ¹⁶ are hydrogen, fluorine, chlorine, cyano, -SF ₅ or an alkyl group having 1 to 10 carbons, in which at least One -CH ₂ -may be substituted by -O-, -COO- or -OCO-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, among these groups, at least one Hydrogen can be substituted by fluorine or chlorine; ring N, ring P, ring Q, ring T, ring U, ring X, ring Y and ring Z are 1,4-cyclohexylene, 1,4-phenylene, 1, 3-Dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, tetrahydropyran-3,5-diyl, pyrimidine-2,5-diyl, pyridine-2, 5-diyl or bicyclo[2.2.2]octane-1,4-diyl, in these rings, at least one hydrogen can be replaced by fluorine or chlorine; ring R, ring S, ring V and ring W are 5, 6,7,8-tetrahydronaphthalene-1,2-diyl or naphthalene-1,2-diyl; Z ¹⁸ to Z ²⁵ are a single bond or an alkylene having 1 to 20 carbon atoms, said alkylene Among them, at least one -CH ₂ -can be substituted by -O-, -CO-, -COO- or -OCO-, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, In these groups, at least one hydrogen may be replaced by fluorine or chlorine; X ³ to X ⁸ are hydrogen or fluorine; p, q, r, s, t, u, v, and w are 1, 2, or 3. The liquid crystal composite according to claim 1, wherein the ratio of the additive A is in the range of 0.03% to 25% based on the liquid crystal composition. The liquid crystal composite according to claim 1, wherein the spiral pitch of the liquid crystal composition is 10 μm or less. The liquid crystal composite according to claim 1, wherein the liquid crystal composition contains a dichroic dye as additive B. A liquid crystal dimming element, wherein the dimming layer is the liquid crystal composite according to claim 1, and the dimming layer is sandwiched by a pair of transparent substrates, and the transparent substrates have transparent electrodes. A dimming window, which uses the liquid crystal dimming element described in claim 18. A smart window which uses the liquid crystal dimming element as described in claim 18.

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