TW202028431A - Liquid crystal composite and liquid crystal dimmer element - Google Patents

Abstract

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

Description

Liquid crystal 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.

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 manufacture 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 high dielectric anisotropy of the composition contributes to the low threshold voltage of the device or the low power consumption. Therefore, it is preferable that the dielectric anisotropy is large. The high specific resistance of the composition contributes to the high voltage retention of 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 normal mode, the device is opaque when no voltage is applied, and becomes transparent when voltage is applied. In the reverse mode, the device becomes transparent when no voltage is applied, and becomes opaque when voltage is applied. It is expected that the reverse mode element that becomes transparent when the element fails is used in the windows of automobiles.

In order to improve the liquid crystal dimming element, reference is made to patent documents (Patent Document 3 to Patent Document 6). In Patent Document 7, a device having a black liquid crystal composition is produced by adding at least three dichroic dyes. In Patent Document 8, a liquid crystal material containing a dichroic dye is used in the switching layer. In Patent Document 9, a dichroic dye is used in a guest host liquid crystal display element. We have tried to use this dichroic pigment in liquid crystal dimming elements. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 06-273725 [Patent Document 2] International Publication No. 2011-096386 [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 [Patent Document 7] International Publication No. 2017-038616 [Patent Document 8] Japanese Patent Application Publication No. 2018-028655 [Patent Document 9] Japanese Patent Laid-Open No. 2006-193742

[The problem to be solved by the invention] The subject of the present invention is to provide a liquid crystal composite suitable for dimming comprising a liquid crystal composition that satisfies a high maximum temperature of a nematic phase, a low minimum temperature of a nematic phase, a low viscosity, and optical properties At least one of the characteristics of large anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to light, high stability to heat, and large elastic constant. 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 及R² 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、碳數2至12的烯基氧基、或者至少一個氫經氟或氯所取代的碳數1至12的烷基；環A及環C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所取代的1,4-伸苯基、萘-2,6-二基、至少一個氫經氟或氯所取代的萘-2,6-二基、色原烷-2,6-二基、或者至少一個氫經氟或氯所取代的色原烷-2,6-二基；環B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；Z¹ 及Z² 為單鍵、伸乙基、伸乙烯基、亞甲基氧基、或羰基氧基；a為0、1、2、或3，b為0或1；而且a與b的和為3以下。 [發明的效果]The present invention relates to a liquid crystal composite and a liquid crystal dimming element containing the liquid crystal composite. The liquid crystal composite includes a liquid crystal composition and a polymer, and the liquid crystal composition contains a first component selected from the formula ( 1) At least one compound among the compounds shown and a dichroic dye as the first additive.

In formula (1), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and alkenyl having 2 to 12 carbons Oxy group, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; ring A and ring C are 1,4-cyclohexenyl, 1,4-cyclohexenyl, tetrahydropyridine Nyl-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen is replaced by fluorine or Chlorine-substituted naphthalene-2,6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; ring B is 2 ,3-Difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-Trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7- Diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoro Indan-2,5-diyl; Z ¹ and Z ² are single bonds, ethylene, ethylene, methyleneoxy, or carbonyloxy; a is 0, 1, 2, or 3, b Is 0 or 1; and the sum of a and b is 3 or less. [Effects of the invention]

The advantage of the present invention is to provide a liquid crystal composite that includes the following liquid crystal composition and is suitable for dimming. The liquid crystal composition satisfies the high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, and optical properties At least one of the characteristics of large anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to light, high stability to heat, and large elastic constant. Another advantage is to provide a liquid crystal composite including the following 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 a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the liquid crystal composition. 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. When an additive is added, the ratio of the liquid crystal compound is also 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, the "quality" in the "mass%" may be omitted.

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 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 that does not contain 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 It also has a large voltage holding rate at a temperature close to the upper limit temperature. 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 symbols 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)" refers to 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).

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 -will not be 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。羰基氧基之類的鍵結基（-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 及R² 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、碳數2至12的烯基氧基、或者至少一個氫經氟或氯所取代的碳數1至12的烷基；環A及環C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所取代的1,4-伸苯基、萘-2,6-二基、至少一個氫經氟或氯所取代的萘-2,6-二基、色原烷-2,6-二基、或者至少一個氫經氟或氯所取代的色原烷-2,6-二基；環B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；Z¹ 及Z² 為單鍵、伸乙基、伸乙烯基、亞甲基氧基、或羰基氧基；a為0、1、2、或3，b為0或1；而且a與b的和為3以下。Item 1. A liquid crystal composite comprising a liquid crystal composition and a polymer, the liquid crystal composition containing as a first component at least one compound selected from compounds represented by formula (1) and two as a first additive Color pigments.

In formula (1), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and alkenyl having 2 to 12 carbons Oxy group, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; ring A and ring C are 1,4-cyclohexenyl, 1,4-cyclohexenyl, tetrahydropyridine Nyl-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen is replaced by fluorine or Chlorine-substituted naphthalene-2,6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; ring B is 2 ,3-Difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-Trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7- Diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoro Indan-2,5-diyl; Z ¹ and Z ² are single bonds, ethylene, ethylene, methyleneoxy, or carbonyloxy; a is 0, 1, 2, or 3, b Is 0 or 1; and the sum of a and b is 3 or less.

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 (1-35) as the first component.

式（1-1）至式（1-35）中，R¹ 及R² 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、碳數2至12的烯基氧基、或者至少一個氫經氟或氯所取代的碳數1至12的烷基。

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

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

式（2）中，R³ 及R⁴ 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、至少一個氫經氟或氯所取代的碳數1至12的烷基、或者至少一個氫經氟或氯所取代的碳數2至12的烯基；環D及環E為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、或2,5-二氟-1,4-伸苯基；Z³ 為單鍵、伸乙基、伸乙烯基、亞甲基氧基、或羰基氧基；c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 second component at least one compound selected from compounds represented by formula (2).

In formula (2), R ³ and R ⁴ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, and at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; ring D and ring E are 1,4-cyclohexylene and 1,4-phenylene , 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, ethylene, methyleneoxy, or Carbonyloxy; c is 1, 2, or 3.

式（2-1）至式（2-13）中，R³ 及R⁴ 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、至少一個氫經氟或氯所取代的碳數1至12的烷基、或者至少一個氫經氟或氯所取代的碳數2至12的烯基。Item 5. The liquid crystal composite according to any one of items 1 to 4, wherein the liquid crystal composition contains a second component selected from compounds represented by formula (2-1) to formula (2-13) Of at least one compound.

In formulas (2-1) to (2-13), R ³ and R ⁴ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, at least An alkyl group having 1 to 12 carbons in which hydrogen is substituted by fluorine or chlorine, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine.

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

式（3）中，P¹ 及P² 為聚合性基；Z⁴ 為碳數1至20的伸烷基，所述伸烷基中，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(R⁵ )-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R⁵ 或P³ 取代，此處，R⁵ 為碳數1至12的烷基，所述烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、或-OCO-取代，P³ 為聚合性基。Item 7. The liquid crystal composite according to any one of items 1 to 6, wherein the polymer is derived from a mixture of polymerizable compounds, the mixture containing the compound represented by formula (3) as a main component.

In formula (3), P ¹ and P ² are polymerizable groups; Z ⁴ is an alkylene group having 1 to 20 carbons. In the alkylene group, at least one hydrogen may be an alkylene group having 1 to 5 carbon atoms, Fluorine, chlorine, or P ³ substitution, at least one -CH ₂ -can be substituted by -O-, -CO-, -COO-, -OCO-, -NH-, or -N(R ⁵ )-, 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 with a divalent group generated by removing two hydrogens, the In these divalent groups, the carbon number is 5 to 35, and at least one hydrogen may be substituted by R ⁵ or P ³ , where R ⁵ 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-, 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所取代的碳數1至5的烷基。Item 8. The liquid crystal composite according to Item 7, wherein P ¹ , P ² , and P ³ are groups selected from the group consisting of 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 carbon in which at least one hydrogen is replaced by fluorine or chlorine The number is an alkyl group of 1 to 5.

Item 9. The liquid crystal composite according to Item 7, wherein at least one of P ¹ , P ² , and P ³ is an acryloxy group or a methacryloxy group.

式（4）中，M⁴ 及M⁵ 為氫或甲基；Z⁵ 為碳數21至80的伸烷基，所述伸烷基中，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(R⁵ )-取代，至少一個-CH₂ -CH₂ -可經-CH=CH-或-C≡C-取代，此處，R⁵ 為碳數1至12的烷基，所述烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、或-OCO-取代。Item 10. The liquid crystal composite according to any one of Items 1 to 6, wherein the polymer is derived from a mixture of polymerizable compounds, the mixture containing the compound represented by formula (4) as a main component.

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

式（5）中，M⁶ 為氫或甲基；Z⁶ 為單鍵或碳數1至5的伸烷基，所述伸烷基中，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；R⁶ 為碳數1至40的烷基，所述烷基中，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，所述烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、或-OCO-取代。Item 11. The liquid crystal composite according to any one of items 1 to 6, wherein the polymer is derived from a mixture of polymerizable compounds, the mixture containing the compound represented by formula (5) as a main component.

In formula (5), M ⁶ is hydrogen or methyl; Z ⁶ 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 ⁶ 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 substituted by carbocyclic saturated aliphatic compound, heterocyclic It is generated by removing two hydrogens from saturated aliphatic compounds, carbocyclic unsaturated aliphatic compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds, or heterocyclic aromatic compounds Substitution with a divalent group. In these divalent groups, the carbon number is 5 to 35, and at least one hydrogen may be substituted by an alkyl group having 1 to 12 carbons. In the alkyl group, at least one -CH ₂ -may be- O-, -CO-, -COO-, or -OCO- substitution.

Item 12. The liquid crystal composite according to Item 11, wherein, in formula (5), M ⁶ is hydrogen or methyl; Z ⁶ is a single bond or an alkylene group having 1 to 5 carbon atoms, and the alkylene group Among them, 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 ⁶ is an alkyl group having 1 to 40 carbon atoms, In the alkyl group, 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-.

式（6）、式（7）、及式（8）中，環F、環G、環I、環J、環K、及環L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；Z⁷ 、Z⁹ 、Z¹¹ 、Z¹² 、及Z¹⁶ 為單鍵、-O-、-COO-、-OCO-、或-OCOO-；Z⁸ 、Z¹⁰ 、Z¹³ 、及Z¹⁵ 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-；Z¹⁴ 為單鍵、-O-或-COO-；X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；e及g為1至4的整數；j及l為0至3的整數；j及l的和為1至4；d、f、h、i、k、及m為0至20的整數；M⁷ 至M¹² 為氫或甲基。Item 13. The liquid crystal composite according to any one of items 1 to 6, wherein the polymer is derived from a mixture of polymerizable compounds, the mixture containing selected from formula (6), formula (7), and formula ( 8) The compound among the compounds shown is the main component.

In formula (6), formula (7), and formula (8), ring F, ring G, ring I, ring J, ring K, and ring L are 1,4-cyclohexylene, 1,4-phenylene Base, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2, 7-diyl group, where at least one hydrogen may be fluorine, chlorine, cyano, hydroxyl, methanoyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, or C1 to C5 alkyl , An alkoxy group having 1 to 5 carbons, an alkoxycarbonyl group having 2 to 5 carbons, or an alkoxycarbonyl group having 1 to 5 carbons; Z ⁷ , Z ⁹ , Z ¹¹ , Z ¹² , and Z ¹⁶ are Single bond, -O-, -COO-, -OCO-, or -OCOO-; Z ⁸ , Z ¹⁰ , Z ¹³ , and Z ¹⁵ are single bonds, -OCH ₂ -, -CH ₂ O-, -COO- , -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C( CH ₃ )-, -C(CH ₃ )=N-, -N=N-, or -C≡C-; Z ¹⁴ is a single bond, -O- or -COO-; X is hydrogen, fluorine, chlorine, Trifluoromethyl, trifluoromethoxy, cyano, alkyl with 1 to 20 carbons, alkenyl with 2 to 20 carbons, alkoxy with 1 to 20 carbons, or alkane with 2 to 20 carbons Oxycarbonyl; e and g are integers from 1 to 4; j and l are integers from 0 to 3; the sum of j and l is from 1 to 4; d, f, h, i, k, and m are from 0 to 20 M ⁷ to M ¹² are hydrogen or methyl.

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

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

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

Item 17. The liquid crystal composite according to any one of Items 1 to 16, wherein the liquid crystal composite is obtained by using a polymerizable composition including a liquid crystal composition and a polymerizable compound as a precursor, and the polymerization The sexual composition contains a photopolymerization initiator as an additive.

Item 18. A liquid crystal dimming element, wherein the dimming layer is the liquid crystal composite according to any one of items 1 to 17, and the dimming layer is sandwiched by a pair of transparent substrates, and the transparent substrate has a transparent electrode.

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

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

Item 21. A dimming window using the liquid crystal dimming element according to any one of Items 18 to 20.

Item 22. A smart window using the liquid crystal dimming element according to any one of items 18 to 20.

Item 23. Use of a liquid crystal composite, which is the liquid crystal composite according to any one of items 1 to 17, which is used in a liquid crystal dimming element.

Item 24. Use of a liquid crystal composite, which is the liquid crystal composite according to any one of items 1 to 17, which is used in a liquid crystal dimming element whose transparent substrate is a plastic film.

Item 25. Use of a liquid crystal composite, which is the liquid crystal composite according to any one of items 1 to 17, which is used in a dimming window.

Item 26. Use of a liquid crystal composite, which is the liquid crystal composite according to any one of items 1 to 17, which is used in a smart window.

The present invention also includes the following items. (A) The liquid crystal composite according to item 2, comprising a liquid crystal composition and a polymer, the liquid crystal composition containing as the first component, the compound (1-1) and the compound (1) selected from the item 2 -3), at least one compound of compound (1-6), compound (1-8), compound (1-10), compound (1-14), and compound (1-34).

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

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

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

The present invention also includes the following items. (I) The liquid crystal composite as described above, containing as a second additive at least an optically active compound, an antioxidant, an ultraviolet absorber, a matting agent, an antifoaming agent, a polar compound, a polymerization initiator, and a polymerization inhibitor One kind.

The liquid crystal dimming element of the present invention will be described in the following order. First, the structure of the liquid crystal composite will be described. Second, the structure of 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 of the components in the liquid crystal composition, the preferred ratio of the components, and the basis for it 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 dichroic dye 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 composite or the dimming element will be described.

First, the structure of the liquid crystal composite will be described. The liquid crystal composite is obtained by polymerization of a polymerizable composition. The polymerizable composition is a mixture of a liquid crystal composition and a polymerizable compound. The dielectric anisotropy of this liquid crystal composition is negative. The polymer produced by the polymerization of the polymerizable composition undergoes phase separation, thereby providing a liquid crystal composite. That is, a liquid crystal composite formed by combining a polymer and a liquid crystal composition is produced. The liquid crystal composite is suitable for a reverse mode element that is transparent when no voltage is applied and becomes opaque when voltage is applied. The optical anisotropy of the liquid crystal composition and the refractive index of the polymer are related to the transparency of the liquid crystal light control element. In general, the optical anisotropy (Δn) of the liquid crystal composition is preferably larger. The optical anisotropy is preferably 0.15 or more, more preferably 0.18 or more.

In a polymer dispersion type device, the liquid crystal composition is dispersed in the polymer like droplets. The individual droplets are separated and not continuous. On the other hand, in a polymer network type device, the polymer has a three-dimensional grid structure, and the liquid crystal composition is surrounded by the grid and is continuous. In these devices, in order to efficiently cause light scattering, the ratio of the liquid crystal composition based on the liquid crystal composite is preferably larger. The driving voltage drops by reducing the droplets or grids, so the proportion of polymer is preferably larger.

Based on the liquid crystal composite, the preferable ratio of the liquid crystal composition is in the range of about 50% to about 95%. The preferred ratio is also in the range of about 50% to about 90%. A particularly preferred ratio is in the range of about 50% to about 85%. A particularly preferred ratio is in the range of about 60% to about 80%. A particularly preferred ratio is in the range of about 70% to about 80%. Since the total of the liquid crystal composite and the polymer is 100%, the ratio of the polymer 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 efficiently cause light scattering or to block sunlight, based on the liquid crystal composite, the preferable ratio of the liquid crystal composition is in the range of about 75% to about 97%. A particularly preferable ratio is in the range of about 80% to about 96%. A particularly preferred ratio is in the range of about 85% to about 95%.

When the ratio of the liquid crystal composition to the polymer is within the above range, a polymer network type element is produced. When the proportion of polymer is large, a polymer dispersion structure will be mixed. On the other hand, when the proportion of the polymer is smaller, a polymer stabilized alignment type element will be produced. It is referred to as PSA (polymer sustained alignment) element for short. 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 polymerizable compound is added to the 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. On the other hand, in the reverse mode polymer network device, the liquid crystal molecules are vertically aligned by the action of the alignment film, so the device is transparent. When a voltage is applied to the element, the liquid crystal molecules are aligned in parallel with the substrate. There is a difference between the refractive index of the polymer and the refractive index of the liquid crystal molecules, which causes light scattering and the element becomes opaque. Therefore, in polymer network type devices, unlike PSA devices, no polarizer is needed.

Second, the structure of 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 not only contains a liquid crystal compound selected from the compound (1) and the compound (2), but may further contain other liquid crystal compounds, additives, and the like. "Other liquid crystal compounds" are liquid crystal compounds different from compound (1) and compound (2). Such compounds are mixed in the composition for the purpose of further adjusting the characteristics.

The composition B substantially contains only a liquid crystal compound selected from the compound (1) and the compound (2). "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. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, the composition A is superior to the composition B.

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 the notation 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 0 (zero) means extremely small.

To Table 2. Characteristics of liquid crystal compounds Compound Compound (1) Compound (2) Upper temperature S～L S～L Viscosity M～L S～M Optical anisotropy M～L S～L Dielectric anisotropy M～L ¹⁾ 0 Specific resistance 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.

Fourth, the combination of the components in the liquid crystal composition, the preferred ratio of the components, and the basis for it will be described. The preferred combination of the components in the composition is the first component + the second component.

In order to increase the dielectric anisotropy, the preferred proportion of the first component is about 20% or more, and in order to reduce the minimum temperature, the preferred proportion of the first component is about 90% or less. A particularly preferred ratio is in the range of about 25% to about 85%. A particularly preferred ratio is in the range of about 30% to about 80%.

In order to increase the upper limit temperature or reduce the lower limit temperature, the preferred ratio of the second component is about 10% or more, and in order to increase the dielectric anisotropy, the preferred ratio of the second component is about 80% or less. A particularly preferred ratio is in the range of about 15% to about 75%. A particularly preferred ratio is in the range of about 20% to about 70%.

Fifth, the preferred embodiment of the liquid crystal compound will be described. In formula (1) and formula (2), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and 2 Alkenyloxy group to 12 or an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. In order to improve the stability to light or heat, preferably R ¹ or R ² is an alkyl group having 1 to 12 carbons. In order to increase the dielectric anisotropy, preferably R ¹ or R ² is 1 to 12 carbons.的alkoxy。

R ³ and R ⁴ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, and carbon numbers 1 to 12 in which at least one hydrogen is replaced by fluorine or chlorine An alkyl group or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. In order to increase the upper limit temperature or lower the lower limit temperature, R ³ or R ⁴ is preferably an alkenyl group having 2 to 12 carbons. In order to improve the stability to light or heat, R ³ or R ⁴ is preferably 1 carbon. To 12 alkyl groups.

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, hexyloxy, 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 the alkyl group 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-butene Group, 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 and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or 1,4-phenylene substituted by chlorine, naphthalene-2,6-diyl, naphthalene-2,6-diyl substituted with fluorine or chlorine at least one hydrogen, chroman-2,6-diyl Or Chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine. In order to reduce the lower limit temperature or to increase the upper limit temperature, ring A or ring C is preferably 1,4-cyclohexylene. In order to reduce the lower limit temperature, ring A or ring C is preferably 1,4-phenylene. Tetrahydropyran-2,5-diyl is

or

, Preferably

.

為了降低黏度，較佳的環B為2,3-二氟-1,4-伸苯基，為了提高介電各向異性，較佳的環B為4,6-二氟二苯並噻吩-3,7-二基。Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene- 2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2 ), or 1,1,6,7-tetrafluoroindan-2,5-diyl (InF4).

In order to reduce the viscosity, the preferred ring B is 2,3-difluoro-1,4-phenylene. In order to increase the dielectric anisotropy, the preferred ring B is 4,6-difluorodibenzothiophene- 3,7-diyl.

Ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. In order to increase the upper limit temperature, ring D or ring E is preferably 1,4-cyclohexylene. In order to lower the lower limit temperature, ring D or ring E is preferably 1,4-phenylene.

Z ¹ and Z ² are single bonds, ethylene groups, ethylene groups, methyleneoxy groups, or carbonyloxy groups. In order to lower the lower limit temperature, Z ¹ or Z ² is preferably a single bond or an ethylene group. In order to increase the dielectric anisotropy, Z ¹ or Z ² is preferably a methyleneoxy group. Particularly preferred Z ¹ or Z ² is a single bond. Z ³ is a single bond, ethylene, ethylene, methyleneoxy, or carbonyloxy. In order to improve the stability to light or heat, Z ³ is preferably a single bond.

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

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

Preferred compound (2) is the compound (2-1) to the compound (2-13) described in Item 5. Among these compounds, at least one of the second components is preferably compound (2-1), compound (2-3), compound (2-5), compound (2-6), compound (2-7), Or compound (2-8). Preferably at least two of the second components are compound (2-1) and compound (2-5), compound (2-1) and compound (2-6), compound (2-1) and compound (2- 7), compound (2-1) and compound (2-8), compound (2-3) and compound (2-5), compound (2-3) and compound (2-6), compound (2-3) ) And compound (2-7), or a combination of compound (2-3) and compound (2-8).

Seventh, the preferred form of the polymerizable compound and an example thereof will be described. The polymer is derived from a polymerizable compound. The polymerizable compound may be a single kind or a mixture of multiple compounds. The preferred polymerizable compound is compound (3), compound (4), or compound (5). The preferred polymerizable compound is compound (6), compound (7), or compound (8). The polymerizable compound may be a mixture of compounds selected from compound (3) to compound (8). The mixture may contain a polymerizable compound different from the compound (3) to the compound (8). Such a mixture contains a compound selected from compound (3) to compound (8) as a main component. Here, the main component refers to the component occupying the largest proportion in the mixture. For example, in a mixture of 40% compound (3), 30% compound (4), and 30% compound (5), the main component is compound (3). When the polymerizable compound used is only compound (3), compound (3) is also referred to as the main component.

7-1. Compound (3) In the formula (3), Z ⁴ is an alkylene having 1 to 20 carbons, and in the alkylene, at least one hydrogen may pass through an alkyl having 1 to 5 carbons, fluorine, Chlorine or P ³ substitution, at least one -CH ₂ -can be substituted with -O-, -CO-, -COO-, -OCO-, -NH-, or -N(R ⁵ )-, 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 compound, heterocyclic saturated aliphatic compound, carbocyclic ring Unsaturated aliphatic compounds of formula, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds, or heterocyclic aromatic compounds are substituted with divalent groups generated by removing two hydrogens, these two In the valence group, the carbon number is 5 to 35, and at least one hydrogen may be substituted by R ⁵ or P ³ . Here, R ⁵ 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-.

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 formed 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 replaced by fluorine Base, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, naphthalene-1,2-diyl, pyrimidine-2,5-diyl, etc.

Preferably Z ⁴ is an alkylene having 1 to 20 carbons. In the alkylene, 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 For 5 to 35. Particularly preferred Z ⁴ 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 ⁴ 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 ⁴ 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 represents the bonded position. 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 carbon in which at least one hydrogen is replaced by fluorine or chlorine The number is an alkyl group of 1 to 5. 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（3-1）中，p為1至6的整數，式（3-2）中，q為5至20的整數。Examples of compound (3) are compound (3-1) to compound (3-3).

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

In the compound (3), when there are many polymerizable groups, the polymer surrounding the droplets due to crosslinking becomes firm, or the 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 (3) provides the corresponding polymer by polymerization. When the compound (3) is volatile, its oligomer can be used. The preferred polymer is colorless, transparent, and insoluble in the liquid crystal composition. A preferable polymer has excellent adhesion to the substrate of the element, and lowers the driving voltage. In order to increase this effect, a polymerizable compound different from the compound (3) may be used in combination.

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

Z ⁵ is an alkylene having 20 to 80 carbons. In the alkylene, at least one hydrogen may be substituted by an alkyl having 1 to 20 carbons, fluorine, or chlorine, and at least one -CH ₂ -may be substituted by -O -, -CO-, -COO-, -OCO-, -NH-, or -N(R ⁵ )-substitution, at least one -CH ₂ -CH ₂ -can be replaced by -CH=CH- or -C≡C- Substitution, here, R ⁵ is an alkyl group having 1 to 12 carbons. 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 ⁵ is preferably an alkylene having 20 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 substituted by -O-, -COO-, or -OCO-.

In order to achieve low voltage driving, Z ⁵ is particularly 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 prevent 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（4-1）中，R⁷ 及R⁹ 為碳數1至5的烷基，R⁸ 及R¹⁰ 為碳數5至20的烷基，該些烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、或-OCO-取代，Z⁷ 為碳數10至30的伸烷基，所述伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、或-OCO-取代。An example of compound (4) is compound (4-1).

In the formula (4-1), R ⁷ and R ⁹ are alkyl groups having 1 to 5 carbons, R ⁸ and R ¹⁰ are alkyl groups having 5 to 20 carbons, and in these alkyl groups, at least one -CH _2- It can be substituted by -O-, -CO-, -COO-, or -OCO-. Z ⁷ is an alkylene group having 10 to 30 carbon atoms. In the alkylene group, at least one -CH ₂ -can be substituted by -O -, -CO-, -COO-, or -OCO- substitution.

式（4-1-1）及式（4-1-2）中，例如R⁷ 及R⁹ 為乙基，R⁸ 及R¹⁰ 為-CH₂ OCOC₉ H₁₉ 、-CH₂ OCOC₁₀ H₂₁ 、-CH₂ OC₈ H₁₇ 、或-CH₂ OC₁₁ H₂₃ 。An example of the compound (4-1) is the compound (4-1-1) and the compound (4-1-2).

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

Compound (4) is diacrylate or dimethacrylate. Z ^{5 in the} formula (4) is an alkylene group or the like, so the polymer easily forms a network structure. When the molecular chain of Z ⁵ is short, the cross-linking sites of the polymer are close, so the mesh becomes smaller. At the molecular chain length of Z ⁵ , the cross-linking site of the polymer is far away, and the degree of freedom of molecular motion is increased, so the driving voltage is decreased. When Z ⁵ is branched, the degree of freedom is further increased, and therefore the driving voltage is further decreased. In order to increase this effect, a polymerizable compound different from the compound (4) may be used in combination.

7-3. Compound (5) In formula (5), M ⁶ is hydrogen or methyl. In order to improve the reactivity, preferred M ⁶ is hydrogen.

Z ⁶ is a single bond or an alkylene group having 1 to 5 carbon atoms. In the alkylene 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. Preferably Z ⁶ is a single bond or an alkylene group having 1 to 5 carbon atoms. In the alkylene group, at least one -CH ₂ -can pass through -O-, -CO-, -COO-, or -OCO- replace.

R ⁶ is an alkyl group having 1 to 40 carbon atoms. In the alkyl group, at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH ₂ -may be replaced by -O-, -CO-, -COO-, or- OCO- substituted, at least one -CH ₂ -can be substituted by carbocyclic saturated aliphatic compounds, heterocyclic saturated aliphatic compounds, carbocyclic unsaturated aliphatic compounds, heterocyclic unsaturated fatty compounds Substitution of a divalent group formed by removing two hydrogens from a group compound, a carbocyclic aromatic compound, or a heterocyclic aromatic compound. In these divalent groups, the carbon number is 5 to 35, and at least one hydrogen It may be substituted by an alkyl group having 1 to 12 carbons, and in the alkyl group, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-. Preferable R ⁶ is an alkyl group having 5 to 30 carbon atoms. Particularly preferred R ⁶ is a branched alkyl group having 5 to 30 carbon atoms.

式（5-1）至式（5-5）中，R¹¹ 為碳數5至20的烷基，所述烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、或-OCO-取代，R¹² 及R¹³ 為碳數3至10的烷基，所述烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、或-OCO-取代。Examples of compound (5) are compound (5-1) to compound (5-6).

In formulas (5-1) to (5-5), R ¹¹ is an alkyl group having 5 to 20 carbons. In the alkyl group, at least one -CH ₂ -can be controlled by -O-, -CO-,- Substituted by COO- or -OCO-, R ¹² and R ¹³ are alkyl groups having 3 to 10 carbons. In the alkyl group, at least one -CH ₂ -can be substituted by -O-, -CO-, -COO-, Or -OCO- substitution.

Compound (5) is acrylate or methacrylate. When R ^{6 in the} formula (5) has a cyclic structure, the affinity with the liquid crystal composition is improved. When R ⁶ is an alkylene group, the polymer easily forms a lattice structure. In this polymer, the degree of freedom of molecular motion is increased by alkylation, and therefore the driving voltage is decreased. In order to further increase this effect, a polymerizable compound different from the compound (5) may be used in combination.

7-4. Compound (6) to Compound (8) In formula (6), formula (7), and formula (8), ring F, ring G, ring I, ring J, ring K, and ring L are 1,4-cyclohexylene, 1,4-phenylene Base, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2, 7-diyl group, where at least one hydrogen may be fluorine, chlorine, cyano, hydroxyl, methanoyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, or C1 to C5 alkyl , Alkoxy groups having 1 to 5 carbons, alkoxycarbonyl groups having 2 to 5 carbons, or alkoxycarbonyl groups having 1 to 5 carbons are substituted. In formula (6), formula (7), and formula (8), preferred rings are 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 ⁷ , Z ⁹ , Z ¹¹ , Z ¹² , and Z ¹⁶ are single bonds, -O-, -COO-, -OCO-, or -OCOO-. Z ⁸ , Z ¹⁰ , Z ¹³ , and Z ¹⁵ are single bonds, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH- , -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N- , Or -C≡C-. Z ¹⁴ is a single bond, -O-, or -COO-. In formulas (6) and (7), preferably Z ⁸ , Z ¹⁰ , Z ¹³ , or Z ¹⁵ is a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-,- CH ₂ CH ₂ -, -CH ₂ CH ₂ COO-, or -OCOCH ₂ CH ₂ -.

X is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, Or an alkoxycarbonyl group having 2 to 20 carbons.

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

M ⁷ to M ¹² are hydrogen or methyl.

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

式（6-1）至式（6-24）中，M⁷ 為氫或甲基，d為1至20的整數。

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

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

式（7-1）至式（7-31）中，M⁸ 及M⁹ 為氫或甲基，f及h為1至20的整數。

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

An example of compound (8) is compound (8-1) to compound (8-10).

式（8-1）至式（8-10）中，M¹⁰ 、M¹¹ 、及M¹² 為氫或甲基，i、k、及m為1至20的整數。

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

Compound (6), compound (7), and compound (8) 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 (6), the compound (7), and the compound (8) may be used in combination.

Eighth, the preferred form of the dichroic dye and an example thereof will be described. Liquid crystal dimming elements are sometimes used for room partitions. In this case, a dichroic dye can be added to the liquid crystal composition. Mixtures of pigments can also 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. At least two pigments can be mixed. Preferably, two, three, four, five, or six pigments are mixed. It is particularly preferable to mix three or four kinds of pigments.

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.

Examples of skeletons peculiar to dichroic dyes are as follows. The compound names from the left are benzothiadiazole, diketopyrrolopyrrole, azo compound, and perylene.

Examples of dichroic pigments are: benzothiadiazoles, diketopyrrolopyrroles, azo compounds, azomethine compounds, methine Compounds (methine compounds), anthraquinones, merocyanines, naphthoquinones, tetrazines, pyrromethenes, and perylenes or Rylenes such as terrylenes. The preferred dichroic pigments are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, anthraquinones, and rylenes. Particularly preferred dichroic pigments are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and rylenes. For example, benzothiadiazoles refer to dichroic dyes having a benzothiadiazole ring.

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

Examples of dichroic dyes are compound (9-1) to compound (9-110).

式（9-1）至式（9-110）中，Et為乙基，n-Bu及nBu為丁基，n-Pent為戊基，n-Hex為己基。

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

Examples of commercially available dichroic 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- manufactured by Mitsui Fine Chemicals 426, SI-486, M-412, and M-483.

Ninth, the synthesis method of the component compounds will be explained. These compounds can be synthesized by known methods. Illustrate the synthesis method. Compound (1-1) was synthesized by the method described in Japanese Patent Application Publication No. Hei 2-503441. Compound (2-1) was synthesized by the method described in Japanese Patent Application Laid-Open No. 59-176221. Antioxidants are already commercially available. The compound (11-1) mentioned later can be obtained from Sigma-Aldrich Corporation. Compound (11-2) and the like were 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 Reactions (Organic Reactions) )” (John Wiley & Sons, Inc.), “Comprehensive Organic Synthesis” (Pergamon Press), “New Experimental Chemistry Lecture” (Maruzen )Wait. 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 optically active compounds, 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.

For the purpose of causing the helical structure of liquid crystal molecules to impart a torsion angle, an optically active compound is added to the liquid crystal composition. Examples of such compounds are compound (10-1) to compound (10-5). The preferable ratio of the optically active compound is about 5% or less. A particularly preferable ratio is in the range of about 0.01% to about 2%.

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

A compound with a low volatility is effective for maintaining a high voltage retention rate 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. In addition, light stabilizers such as amines with steric hindrance are also preferable. 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.

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.

It is preferable to irradiate ultraviolet rays during polymerization of the polymerizable compound. 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 range 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 with ordinary knowledge in the technical field to which the present invention belongs, and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 as a photopolymerization initiator (Registered trademark; 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 negative in electrical properties 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 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 composite or the dimming element will be described. 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 sometimes 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. Next, 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 dimming layer (liquid crystal layer) is formed between the substrates. The light control layer is classified into a polymer dispersion type, a polymer network type, and a mixture of both types.

Sometimes it will change over time due to long-term use of components. The haze rate sometimes changes from the initial stage. The change in haze rate is preferably small. When the haze change rate is small, a good state of transparency and opacity can be maintained. The haze change rate is preferably 20% or less. The haze change rate is particularly 10% or less or 5% or less.

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%. The occurrence of flicker can be suppressed by appropriately selecting the component compounds of the polymerizable composition contained in the device.

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 decreases in a stripe pattern. It is estimated that this phenomenon is caused by the accumulation of ionic impurities contained in the liquid crystal composition on the alignment film near the electrode.

Such a light control element has a light control layer (liquid crystal layer) 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. Depending on the application, one of the substrates may also be an opaque material such as silicone resin. The substrate has transparent electrodes on it. 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 180°C, and rubbing with cotton or rayon as necessary Obtained by processing.

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 be sandwiched by a pair of glass plates to make laminated glass. Such elements are used for windows installed on the outer wall, or partitions between conference rooms and corridors. 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. 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 at room temperature under the conditions of 500 MHz and a cumulative number of 16 times. 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 a 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 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 containing 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 values 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) deliberated and formulated by the Japan Electronics and Information Technology Industries Association (JEITA), or modified Methods. 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 at 0℃, -10℃, -20℃, -30℃, and -40℃ After storage in the refrigerator for 10 days, 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): Toyo Technica Co., Ltd. Rotational Viscosity Measurement System LCM-2 was used for measurement. The sample is placed in a vertical alignment (VA) element with a distance (cell gap) of 10 μm between two glass substrates. Apply a rectangular wave (55 V, 1 ms) to the element. Measure the peak current and peak time of the transient current generated by the application. These measured values and dielectric anisotropy are used to obtain the value of rotational viscosity. The dielectric anisotropy is measured by the method described in Measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25°C): Using light with a wavelength of 589 nm, it is measured with an Abbe refractometer with a polarizing plate mounted 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): The value of dielectric anisotropy is calculated according to the formula Δε=ε∥-ε⊥. The dielectric constant (ε∥ and ε⊥) is measured as follows. 1) Measurement of dielectric constant (ε∥): Coat a fully washed glass substrate with a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL). After rotating the glass substrate with a spinner, it was heated at 150°C for 1 hour. A sample was placed in a VA device with a distance (cell gap) of 4 μm between two glass substrates, and the device was sealed with an adhesive that was cured with ultraviolet rays. A sine wave (0.5 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. 2) Measurement of dielectric constant (ε⊥): Coat a polyimide solution on a fully washed glass substrate. After firing the glass substrate, rubbing treatment is performed on the resulting alignment film. A sample was placed in a TN device with a gap between two glass substrates (cell gap) of 9 μm and a twist angle of 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured after 2 seconds.

(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. Place the sample in a normally black mode (normally black mode) VA element with a distance (cell gap) of 4 μm between two glass substrates and an anti-parallel rubbing direction, and use an adhesive that is cured by ultraviolet light. The components are sealed. The voltage (60 Hz, rectangular wave) applied to the device is 0.02 V as the unit, and it is increased stepwise from 0 V to 20 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 minimum is created. The threshold voltage is expressed by the voltage when the transmittance reaches 10%.

(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 3.5 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. The sample is placed in a normally black mode (normally black mode) VA element with a distance (cell gap) of 4 μm between two glass substrates and an anti-parallel rubbing direction. The device is sealed with an adhesive that is cured by ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. 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 the minimum, the transmittance is regarded as 0%. The response time is represented by the time required for the transmittance to change from 90% to 10% (fall time; fall time; milliseconds).

(12) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25°C; pN): Toyo Technica (Toyo Technica) Co., Ltd. was used for measurement EC-1 type elastic constant tester. A sample is placed in a VA device with a distance (cell gap) of 20 μm between two glass substrates. A charge of 20 V to 0 V is applied to the device, and the capacitance and applied voltage are measured. Use the formula (2.98) and formula (2.101) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Kogyo) to fit the measured capacitance (C) and applied voltage (V), according to Equation (2.100) obtains the value of the elastic constant.

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

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

(15) 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. The alignment angle Φ (before) of the liquid crystal on the electrode side before the stress is applied is measured. After applying a rectangular wave of 4.5 V and 60 Hz to the device for 20 minutes, buffer for 1 second, and measure the liquid crystal alignment angle Φ (after) on the electrode side again after 1 second and 5 minutes later. Based on these values, the following formula was used to calculate the change (ΔΦ; deg.) of the liquid crystal alignment angle after 1 second and 5 minutes. ΔΦ(deg.)=Φ(after)-Φ(before) These measurements are based on J. Hilfiker, B. Johs, C. Herzinger, JF Elman, E. Mumba "Thin Solid Films" by Qi (E. Montbach), D. Bryant (D. Bryant) and PJ Bos (PJ Bos) 455-456, (2004) 596-600 are taken as reference . When the change (ΔΦ) is small, the change rate of the liquid crystal alignment axis is small, and it can be said that the liquid crystal molecules are more stable.

(16) Flicker rate (measured at 25°C; %): A multimedia display tester (multimedia display tester) 3298F manufactured by Yokogawa Electric Co., Ltd. was used for 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. The flicker rate is preferably smaller.

(17) 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 brightness drop due to the line afterimage, and use the ratio to express the size of the line afterimage.

17a) 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 Imaging), the image was 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 .

17b) 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 is irradiated to the element and voltage (rectangular wave, 60 Hz) is 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.

17c) Stress conditions: V255 (rectangular wave, 30 Hz) is applied to the stress area at 60°C for 23 hours, and 0.5 V (rectangular wave, 30 Hz) is applied to the reference area to display a checkerboard pattern. Next, V127 (rectangular wave, 0.25 Hz) was applied, and the brightness was measured under the condition of an exposure time of 4000 milliseconds.

17d) Calculation of line afterimage: 4 of the 16 units in the central part (2 units in the vertical x 2 units in the horizontal) 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 according to the following equation. (Line afterimage)=(Brightness A-Brightness B)/Brightness A×100. The line afterimage is preferably smaller.

(18) 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.

18a) "Measurement of brightness", "Setting of stress voltage", and "Conditions of stress" follow the order described in the item "Line afterimage".

18b) The facial afterimage is calculated according to 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 surface afterimage is preferably smaller. 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.

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

(20) Haze change rate (%): conduct weather resistance test of components. 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 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).

(21) Spiral pitch (P; measured at room temperature; μm): The spiral pitch is measured using 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 spiral pitch (P) is calculated from the following equation in which the angle of the wedge unit is expressed as θ. P=2×(d2-d1)×tanθ.

(22) Characteristics of dimming components When measuring the characteristics of a liquid crystal display element, a glass substrate element is generally used. On the other hand, in liquid crystal dimming devices, plastic films are sometimes used as substrates. Therefore, an element with a polycarbonate substrate was produced, 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Example 1] Production of a liquid crystal dimming element-1 The composition (M1) has negative dielectric anisotropy. 95% of the composition (M1) and 5% of the polymerizable compound (RM-1) were mixed to prepare a polymerizable composition. In this composition, the black pigment (A) is added at a ratio of 5% based on the composition (M1). Irgacure 651 (photopolymerization initiator; BASF) was added at a ratio of 0.3% based on the polymerizable compound. This polymerizable composition was injected into an element having a distance (cell gap) between two glass substrates of 3.5 μm. The temperature during injection was 140°C. The device was irradiated with 18 mW/cm ² of ultraviolet rays for 56 seconds with a high-pressure mercury lamp to produce a device having a liquid crystal composite. The element is transparent. A voltage of 45 V was applied to the element, and the element turned black when irradiated with light. This indicates that the component is in reverse mode.

[Comparative Example 1] In the experiment operation, the black pigment (A) was not added to the composition to prepare the polymerizable composition. According to the operation, an element having a liquid crystal composite was produced. The element is transparent. A voltage of 45 V was applied to the element, and when light was irradiated, the element became opaque. However, the surface of the element is bright.

[Example 2] Production of Liquid Crystal Light Control Element-2 Next, two polymerizable compounds were combined. 90% of the composition (M1), 5% of the polymerizable compound (RM-8), and 5% of the polymerizable compound (RM-11) are mixed to prepare a polymerizable composition. In this composition, the black pigment (A) is added at a ratio of 5% based on the composition (M1). Irgacure 651 (photopolymerization initiator; BASF) was added at a ratio of 0.3% based on the polymerizable compound. This polymerizable composition was injected into an element having a distance (cell gap) between two glass substrates of 3.5 μm. The temperature during injection was 140°C. The device was irradiated with 18 mW/cm ² of ultraviolet rays for 56 seconds with a high-pressure mercury lamp to produce a device having a liquid crystal composite. The element is transparent. A voltage of 45 V was applied to the element, and the element turned black when irradiated with light. This indicates that the component is in reverse mode.

[Example 3] Haze change rate determination The elements produced in Example 1 and Example 2 were installed in the haze meter so that the elements were 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 rate after the weather resistance test performed under the conditions described in the measurement (20) was measured, and the haze change rate was calculated. The haze change rate is small. This means that the liquid crystal dimming element has little change over time. [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.

Claims (20)

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

In formula (1), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and alkenyl having 2 to 12 carbons Oxy group, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; ring A and ring C are 1,4-cyclohexenyl, 1,4-cyclohexenyl, tetrahydropyridine Nyl-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen is replaced by fluorine or Chlorine-substituted naphthalene-2,6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; ring B is 2 ,3-Difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-Trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7- Diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoro Indan-2,5-diyl; Z ¹ and Z ² are single bonds, ethylene, ethylene, methyleneoxy, or carbonyloxy; a is 0, 1, 2, or 3, b Is 0 or 1; and the sum of a and b is 3 or less. The liquid crystal composite as described in claim 1, wherein the liquid crystal composition contains as the first component at least one compound selected from the group consisting of compounds represented by formula (1-1) to formula (1-35),

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

In formula (2), R ³ and R ⁴ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, and at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; ring D and ring E are 1,4-cyclohexylene and 1,4-phenylene , 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, ethylene, methyleneoxy, or Carbonyloxy; c is 1, 2, or 3. The liquid crystal composite according to the first item of the patent application, wherein the liquid crystal composition contains as the second component at least one compound selected from the group consisting of compounds represented by formula (2-1) to formula (2-13),

In formulas (2-1) to (2-13), R ³ and R ⁴ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, at least An alkyl group having 1 to 12 carbons in which hydrogen is substituted by fluorine or chlorine, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine. The liquid crystal composite as described in claim 4, wherein the ratio of the second component is in the range of 10% to 80% based on the liquid crystal composition. The liquid crystal composite as described in the first item of the patent application, wherein the polymer is derived from a mixture of polymerizable compounds, the mixture containing the compound represented by formula (3) as a main component,

In formula (3), P ¹ and P ² are polymerizable groups; Z ⁴ is an alkylene group having 1 to 20 carbons. In the alkylene group, at least one hydrogen may be an alkylene group having 1 to 5 carbon atoms, Fluorine, chlorine, or P ³ substitution, at least one -CH ₂ -can be substituted by -O-, -CO-, -COO-, -OCO-, -NH-, or -N(R ⁵ )-, 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 with a divalent group generated by removing two hydrogens, the In these divalent groups, the carbon number is 5 to 35, and at least one hydrogen may be substituted by R ⁵ or P ³ , where R ⁵ 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-, and P ³ is a polymerizable group. The liquid crystal composite according to item 7 of the scope of patent application, 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 carbon in which at least one hydrogen is replaced by fluorine or chlorine The number is an alkyl group of 1 to 5. The liquid crystal composite according to item 7 of the patent application, wherein at least one of P ¹ , P ² , and P ³ is an acryloxy group or a methacryloxy group. The liquid crystal composite as described in item 1 of the scope of the patent application, wherein the polymer is derived from a mixture of polymerizable compounds, the mixture containing the compound represented by formula (4) as a main component,

In formula (4), M ⁴ and M ⁵ are hydrogen or methyl; Z ⁵ is an alkylene having 21 to 80 carbons, and in the alkylene, at least one hydrogen can pass through an alkylene 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 ⁵ )-, at least one -CH ₂ -CH ₂ -may be substituted by -CH=CH- or -C≡C-, where R ⁵ is an alkyl group having 1 to 12 carbons, and in the alkyl group, at least one -CH ₂ -may be substituted by -O -, -CO-, -COO-, or -OCO- substitution. The liquid crystal composite as described in item 1 of the scope of the patent application, wherein the polymer is derived from a mixture of polymerizable compounds, the mixture containing the compound represented by formula (5) as a main component,

In formula (5), M ⁶ is hydrogen or methyl; Z ⁶ 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 ⁶ 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 substituted by carbocyclic saturated aliphatic compound, heterocyclic It is generated by removing two hydrogens from saturated aliphatic compounds, carbocyclic unsaturated aliphatic compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds, or heterocyclic aromatic compounds Substitution with a divalent group. In these divalent groups, the carbon number is 5 to 35, and at least one hydrogen may be substituted by an alkyl group having 1 to 12 carbons. In the alkyl group, at least one -CH ₂ -may be- O-, -CO-, -COO-, or -OCO- substitution. The liquid crystal composite according to item 11 of the scope of patent application, wherein, in formula (5), M ⁶ is hydrogen or methyl; Z ⁶ is a single bond or an alkylene group having 1 to 5 carbon atoms. In the group, 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 ⁶ is an alkyl group with 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-. The liquid crystal composite according to claim 1, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains a compound selected from the group consisting of formula (6), formula (7), and formula (8) As the main component,

In formula (6), formula (7), and formula (8), ring F, ring G, ring I, ring J, ring K, and ring L are 1,4-cyclohexylene, 1,4-phenylene Base, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2, 7-diyl group, where at least one hydrogen may be fluorine, chlorine, cyano, hydroxyl, methanoyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, or C1 to C5 alkyl , An alkoxy group having 1 to 5 carbons, an alkoxycarbonyl group having 2 to 5 carbons, or an alkoxycarbonyl group having 1 to 5 carbons; Z ⁷ , Z ⁹ , Z ¹¹ , Z ¹² , and Z ¹⁶ are Single bond, -O-, -COO-, -OCO-, or -OCOO-; Z ⁸ , Z ¹⁰ , Z ¹³ , and Z ¹⁵ are single bonds, -OCH ₂ -, -CH ₂ O-, -COO- , -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C( CH ₃ )-, -C(CH ₃ )=N-, -N=N-, or -C≡C-; Z ¹⁴ is a single bond, -O- or -COO-; X is hydrogen, fluorine, chlorine, Trifluoromethyl, trifluoromethoxy, cyano, alkyl with 1 to 20 carbons, alkenyl with 2 to 20 carbons, alkoxy with 1 to 20 carbons, or alkane with 2 to 20 carbons Oxycarbonyl; e and g are integers from 1 to 4; j and l are integers from 0 to 3; the sum of j and l is from 1 to 4; d, f, h, i, k, and m are from 0 to 20 M ⁷ to M ¹² are hydrogen or methyl. The liquid crystal composite as described in item 1 of the scope of patent application, wherein the first additive is at least one dichroic selected from the group consisting of benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and anthraquinones Sex pigment. In the liquid crystal composite as described in item 1 of the scope of patent application, the ratio of the first additive is in the range of 0.03% to 25% based on the liquid crystal composition. The liquid crystal composite according to the first item of the scope of patent application, wherein based on the liquid crystal composite, the ratio of the liquid crystal composition is in the range of 50% to 95%, and the ratio of the polymer is in the range of 5% to 50%. The liquid crystal composite according to the first item of the patent application, wherein the liquid crystal composite is obtained by using a polymerizable composition including a liquid crystal composition and a polymerizable compound as a precursor, and the polymerizable composition contains as an additive The photopolymerization initiator of the material. A liquid crystal dimming element, wherein the dimming layer is the liquid crystal composite as described in any one of items 1 to 17 in the scope of patent application, and the dimming layer is sandwiched by a pair of transparent substrates, and the transparent substrate has transparent electrodes. A dimming window using the liquid crystal dimming element described in item 18 of the scope of patent application. A smart window that uses the liquid crystal dimming element described in item 18 of the patent application.