TWI810421B - Liquid crystal complex, liquid crystal dimming element and dimming window - Google Patents

Abstract

The present invention provides a liquid crystal composite body suitable for dimming and a liquid crystal dimming element comprising the following liquid crystal composition. At least one of properties such as large anisotropy and positive dielectric anisotropy, or at least two of these properties have an appropriate balance. A liquid crystal composite, comprising a liquid crystal composition and a polymer, the liquid crystal composition contains a specific compound with a large positive dielectric anisotropy and a dichroic pigment, and the liquid crystal composite may further contain a compound with a high upper limit temperature or Specific compounds with low threshold temperatures.

Description

Liquid crystal complex, liquid crystal dimming element and dimming window

The invention mainly relates to a liquid crystal dimming element. More specifically, the present invention relates to a liquid crystal dimming device having a liquid crystal composite composed of a polymer and a liquid crystal composition.

There are methods that utilize light scattering and the like in liquid crystal dimming devices. Such elements are used in building materials such as window panes or room partitions, automotive parts, and the like. In these elements, 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 the substrates, the alignment of the liquid crystal molecules will change by adjusting the applied voltage. By this method, the light passing through the liquid crystal composition can be controlled, so liquid crystal dimming devices are widely used in displays, optical shutters, dimming windows (patent document 1), smart windows (smart window) (patent document 2), etc. middle.

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 fabrication of components is easy. It is easy to control the film thickness over a large area, so it is possible to manufacture large-screen components. Clear display is possible because no polarizer is required. Wide field of view due to light scattering. Since this device has such excellent properties, it is expected to be used in light-controlling glasses, projection displays, large-area displays, and the like.

Another example is a polymer network type liquid crystal dimming element. In this type of device, a liquid crystal composition exists in a three-dimensional network of polymers. This composition is continuous, which is different from the polymer dispersed type. This type of device also has the same features as those of the polymer-dispersed type. 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 in a liquid crystal dimming device. By improving the properties of the composition, devices with good properties can be obtained. The correlation among the characteristics of both is summarized in Table 1 below. The characteristics of the composition will be further described based on elements. The temperature range of the nematic phase correlates with the usable temperature range of the element. A preferable upper limit temperature of the nematic phase is about 70°C or higher, and a preferable lower limit temperature of the nematic phase is about -20°C or lower. The viscosity of the composition correlates with the response time of the component. In order to control the light transmittance, the response time is preferably short. The ideal is a response time that is 1 millisecond shorter than other components. Therefore, it is preferable that the viscosity of a composition is small. More preferably, the viscosity at low temperature is small. The elastic constant of the composition is related to the response time of the element. In order to achieve a short response time in the device, it is more preferable that the elastic constant in the composition is large.

Table 1. Characteristics of liquid crystal composition and liquid crystal dimming element serial number Characteristics of Liquid Crystal Composition Characteristics of liquid crystal dimming components 1 The nematic phase has a wide temperature range Can be used in a wide temperature range 2 low viscosity short response time 3 Large optical anisotropy High haze rate 4 Large positive or negative dielectric anisotropy Low threshold voltage and low power consumption 5 Greater than resistance High voltage retention 6 Stable to light and heat long life 7 Large elastic constant short response time

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

There are normal mode and reverse mode in the liquid crystal dimming element. In normal mode, when no voltage is applied, the device is opaque, and when voltage is applied, the device becomes transparent. In reverse mode, the device is transparent when no voltage is applied and becomes opaque when voltage is applied. Widely used is a normal-mode element, which has the advantage of being inexpensive and easy to manufacture.

Patent documents (Patent Document 3 to Patent Document 6) are referred to in order to improve the liquid crystal dimming element. In Patent Document 7, a device having a black liquid crystal composition prepared by adding at least three dichroic dyes is produced. In Patent Document 8, a liquid crystal material containing a dichroic dye is used for the switching layer. In Patent Document 9, a dichroic dye is used in a guest-host type liquid crystal display element. We have made an attempt to use this dichroic pigment in liquid crystal dimming elements. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 06-273725 [Patent Document 2] International Publication No. 2011-096386 [Patent Document 3] Japanese Patent Application 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 Laid-Open No. 2018-028655 [Patent Document 9] Japanese Patent Laid-Open No. 2006-193742

[Problem to be Solved by the Invention] An object of the present invention is to provide a liquid crystal composite suitable for light adjustment comprising a liquid crystal composition that satisfies a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, a small viscosity, and optical properties. At least one of characteristics such as large anisotropy, large positive dielectric anisotropy, high specific resistance, high stability to light, high stability to heat, and large elastic constant. Another object is to provide a liquid crystal composite suitable for dimming, including a liquid crystal composition having an appropriate balance between at least two of these properties. Another subject is to provide a liquid crystal dimming device having such a liquid crystal composite. Still another subject is to provide a liquid crystal dimming element having characteristics such as short response time, high voltage retention rate, low threshold voltage, high haze ratio, high weather resistance, and long life.

[Means for Solving the Problems] The present invention relates to a liquid crystal composite comprising a liquid crystal composition and a polymer, and the liquid crystal composite containing the liquid crystal composition as a first Components include at least one compound selected from compounds represented by formula (1) and a dichroic dye as a first additive. In formula (1), R ¹ is an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or an alkenyl group with 2 to 12 carbons; Ring A is 1,4-cyclohexylene, 1 ,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ¹ is a single bond, ethylene, vinylene, Ethynyl, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; ^X1 and ^X2 are hydrogen or fluorine; ^Y1 is fluorine, chlorine, cyano, at least one hydrogen through fluorine or chlorine Substituted alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons with at least one hydrogen substituted by fluorine or chlorine, or alkenyloxy with 2 to 12 carbons with at least one hydrogen substituted with fluorine or chlorine ; a is 1, 2, 3, or 4.

[Effect 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 light adjustment. At least one of characteristics such as large anisotropy, large positive dielectric anisotropy, high specific resistance, high stability to light, high stability to heat, and large elastic constant. Another advantage is to provide a liquid crystal composite suitable for dimming comprising a liquid crystal composition having an appropriate balance between at least two of these properties. 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 characteristics such as short response time, high voltage retention 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. "Liquid crystal compound" is a compound having a nematic phase or a smectic liquid crystal phase, and a compound that does not have a liquid crystal phase but is formulated for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. Generic term for compounds added to the composition. This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the liquid crystal composition. A liquid crystal compound having an alkenyl group is not classified as a polymerizable compound in terms of its meaning.

A "liquid crystal composition" is prepared by mixing various liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, and polar compounds are added to the liquid crystal composition as needed. Even when an additive is added, the ratio of the liquid crystal compound is represented by the mass percentage (mass %) based on the liquid crystal composition not including the additive. The ratio of the additives is represented by the mass percentage based on the liquid crystal composition not containing the additives. That is, the ratio of liquid crystal compounds or additives is calculated based on the total amount of liquid crystal compounds. In addition, "mass" in "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. Additives, such as a polymerization initiator and a polymerization inhibitor, are added to a polymeric compound as needed. The ratio of the polymerization initiator and the polymerization inhibitor is represented by the mass percentage based on the polymerizable compound. When an additive is added, the ratio of the polymerizable compound or liquid crystal composition contained in the polymerizable composition is also represented by the mass percentage based on the polymerizable composition not including the additive. "Liquid crystal composite" is produced by polymerization treatment of a polymerizable composition. "Liquid crystal dimming device" is a device 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 simply referred to as the "lower limit temperature". The expression "enhancing the dielectric anisotropy" means that the value increases positively when the dielectric anisotropy is positive, and that the value negatively increases when the dielectric anisotropy is negative. increase to the ground. "Large voltage retention rate" means that the device not only has a large voltage retention rate at room temperature in the initial stage, but also has a large voltage retention rate at a temperature close to the upper limit temperature, and not only has a large voltage retention rate at room temperature after long-term use. It has a large voltage retention rate, and it also has a large voltage retention rate at a temperature close to the upper limit temperature. Sometimes the characteristics of the composition or element are studied by the time-varying test.

The compound (1z) will be described as an example. In formula (1z), the symbols α and β surrounded by a hexagon correspond to ring α and ring β, respectively, and represent rings such as six-membered rings and condensed rings. When the subscript 'x' is 2, there are two loops 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 notations such as the bonding group Z. The oblique line crossing one side of the ring β indicates that any hydrogen on the ring β may be replaced by a substituent (-Sp-P). The subscript 'y' indicates 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 the ring β. In this case, the "may be the same, or may be different" rule also applies. In addition, this rule is also applicable to the case where the symbol of Ra is used for a plurality of compounds.

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

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

The expression "at least one 'A'" means that the number of 'A' is arbitrary. The expression "at least one 'A' may be replaced by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, their positions Unlimited selection is also possible. Sometimes the expression "at least one _-CH2- may be substituted by -O-" is used. In this case, -CH ₂ -CH ₂ -CH ₂ - can be converted to -O-CH ₂ -O- by substituting non-adjacent -CH ₂ - with -O-. However, adjacent _-CH2- will not be substituted with -O-. This is because -OO-CH ₂ - (peroxide) is generated in this substitution.

The alkyl group of the liquid crystal compound is linear or branched, and does not include a cyclic alkyl group. Straight-chain alkyl groups are preferred over branched ones. These conditions are also the same for terminal groups such as alkoxy and alkenyl. In order to increase the upper limit temperature, the stereo configuration related to 1,4-cyclohexylene is that the trans configuration is better than the cis configuration. Since 2-fluoro-1,4-phenylene is left-right asymmetric, there are left (L) and right (R). The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same applies to a bonding group such as carbonyloxy group (-COO- or -OCO-).

The present invention includes the following items and the like.

Item 1. A liquid crystal composite comprising a liquid crystal composition and a polymer, and the liquid crystal composition contains at least one compound selected from the compounds represented by formula (1) as a first component and two compounds as a first additive. Chromatic pigments. In formula (1), R ¹ is an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or an alkenyl group with 2 to 12 carbons; Ring A is 1,4-cyclohexylene, 1 ,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ¹ is a single bond, ethylene, vinylene, Ethynyl, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; ^X1 and ^X2 are hydrogen or fluorine; ^Y1 is fluorine, chlorine, cyano, at least one hydrogen through fluorine or chlorine Substituted alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons with at least one hydrogen substituted by fluorine or chlorine, or alkenyloxy with 2 to 12 carbons with at least one hydrogen substituted with fluorine or chlorine ; a is 1, 2, 3, or 4.

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

In formula (1-1) to formula (1-47), R ¹ is an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or an alkenyl group with 2 to 12 carbons, X ¹ and ^X2 is hydrogen or fluorine; ^Y1 is fluorine, chlorine, cyano, an alkyl group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkyl group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine alkoxy, or an alkenyloxy group having 2 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 Item 2, wherein the proportion of the first component is in the range of 5% to 90% based on the liquid crystal composition.

Item 4. The liquid crystal composite according to any one of Items 1 to 3, wherein the liquid crystal composition contains at least one compound selected from compounds represented by formula (2) as a second component. In formula (2), R ² and R ³ are alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or at least one hydrogen replaced by fluorine or chlorine Alkenyl with 2 to 12 carbons; ring B and ring C are 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene , 2,5-difluoro-1,4-phenylene, or pyrimidine-2,5-diyl; Z ² is a single bond, ethylene, vinylene, ethynyl, methyleneoxy, or carbonyloxy; b is 1, 2, or 3.

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

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

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

Item 7. The liquid crystal composite according to any one of Items 1 to 6, wherein the liquid crystal composition contains at least one compound selected from compounds represented by formula (3) as a third component. In formula (3), R ⁴ and R ⁵ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons Oxygen; Ring D and Ring F are 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted by fluorine or chlorine, naphthalene-2,6-diyl, chromane-2,6- Diyl, or chroman-2,6-diyl with at least one hydrogen replaced by fluorine or chlorine; Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro- 1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-di Fluorochromane-2,6-diyl, 3,4,5,6-tetrafluoro-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4 ,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ³ and Z ⁴ are single bonds, ethyl group, vinylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3, and d is 0 or 1; the sum of c and d is 3 or less.

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

In formula (3-1) to formula (3-35), R ⁴ and R ⁵ are hydrogen, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons , or an alkenyloxy group having 2 to 12 carbon atoms.

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

Item 10. The liquid crystal composite according to any one of Items 1 to 9, wherein the polymer is derived from a mixture of polymerizable compounds containing a compound represented by formula (4) as a main component. In formula (4), P ¹ and P ² are polymerizable groups; Z ⁵ is an alkylene group with 1 to 20 carbons, and in the alkylene group, at least one hydrogen can pass through an alkyl group with 1 to 5 carbons, Fluorine, chlorine, or P ³ substitution, at least one -CH ₂ - may be substituted by -O-, -CO-, -COO-, -OCO-, -NH-, or -N(R ⁶ )-, at least one - CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, at least one -CH ₂ - can be substituted by carbocyclic saturated aliphatic compound, heterocyclic saturated aliphatic compound, A carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, a carbocyclic aromatic compound, or a heterocyclic aromatic compound is substituted with a divalent group formed by removing two hydrogens, the In these divalent groups, the carbon number is 5 to 35, and at least one hydrogen can be replaced by R ⁶ or P ³ , where R ⁶ is an alkyl group with 1 to 12 carbon numbers, and among the alkyl groups, at least one- CH ₂ - may be substituted by -O-, -CO-, -COO-, or -OCO-, and P ³ is a polymerizable group.

Item 11. The liquid crystal composite according to Item 10, wherein P ¹ , P ² , and P ³ are groups selected from the polymeric groups represented by formula (P-1) to formula (P-6). In formula (P-1) to formula (P-6), M ¹ , M ² , and M ³ are hydrogen, fluorine, an alkyl group with 1 to 5 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine or chlorine 1 to 5 alkyl.

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

Item 13. The liquid crystal composite according to any one of Items 1 to 9, wherein the polymer is derived from a mixture of polymerizable compounds containing the compound represented by formula (5) as a main component. In formula (5), M ⁴ and M ⁵ are hydrogen or methyl; Z ⁶ is an alkylene group with 21 to 80 carbons, and in the alkylene group, at least one hydrogen can pass through an alkyl group with 1 to 20 carbons. , fluorine, or chlorine, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, -OCO-, -NH-, or -N(R ⁶ )-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, here, R ⁶ is an alkyl group with 1 to 12 carbons, and in the alkyl group, at least one -CH ₂ - can be substituted by -O -, -CO-, -COO-, or -OCO- substituted.

Item 14. The liquid crystal composite according to any one of Items 1 to 9, wherein the polymer is derived from a mixture of polymerizable compounds containing a compound represented by formula (6) as a main component. In formula (6), M ⁶ is hydrogen or methyl; Z ⁷ is a single bond or an alkylene group with 1 to 5 carbons, in which at least one hydrogen can be substituted by fluorine or chlorine, and at least one - CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-; R ⁷ is an alkyl group 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-, at least one -CH ₂ - can be substituted by carbocyclic saturated aliphatic compound, heterocyclic produced by removing two hydrogens from saturated aliphatic compounds, carbocyclic unsaturated aliphatic compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds, or heterocyclic aromatic compounds Divalent group substitution, in these divalent groups, the carbon number is 5 to 35, and at least one hydrogen can be replaced by an alkyl group with a carbon number of 1 to 12, and in the alkyl group, at least one -CH ₂ - can be replaced by - O-, -CO-, -COO-, or -OCO-substitution.

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

Item 16. The liquid crystal composite according to any one of Items 1 to 9, wherein the polymer is derived from a mixture of polymerizable compounds containing a compound selected from the group consisting of formula (7), formula (8), and formula ( 9) Compounds among the indicated compounds are used as main components. In formula (7), formula (8), and formula (9), ring G, ring I, ring J, ring K, ring L, and ring M are 1,4-cyclohexyl, 1,4-phenylene Base, 1,4-cyclohexenyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or tertiary-2, 7-diyl, where at least one hydrogen can be fluorine, chlorine, cyano, hydroxyl, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons , an alkoxy group with 1 to 5 carbons, an alkoxycarbonyl group with 2 to 5 carbons, or an alkacyl group with 1 to 5 carbons; Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ , and Z ¹⁷ are Single bond, -O-, -COO-, -OCO-, or -OCOO-; Z ⁹ , Z ¹¹ , Z ¹⁴ , and Z ¹⁶ are single bonds, -OCH ₂ -, -CH ₂ O-, -COO- , -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C( CH ₃ )-, -C(CH ₃ )=N-, -N=N-, or -C≡C-; Z ¹⁵ is a single bond, -O- or -COO-; Y ² is hydrogen, fluorine, chlorine , trifluoromethyl, trifluoromethoxy, cyano, alkyl with 1 to 20 carbons, alkenyl with 2 to 20 carbons, alkoxy with 1 to 20 carbons, or alkoxy with 2 to 20 carbons Alkoxycarbonyl; f and h are integers from 1 to 4; k and m are integers from 0 to 3; the sum of k and m is 1 to 4; e, g, i, j, l, and n are 0 to Integer of 20; M ⁷ to M ¹² are hydrogen or methyl.

Item 17. The liquid crystal composite according to any one of Items 1 to 16, wherein the first additive is selected from benzothiadiazoles, diketopyrrolopyrroles, azo At least one dichroic pigment among azo compounds and anthraquinones.

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

Item 19. The liquid crystal composite according to any one of Items 1 to 18, wherein the ratio of the liquid crystal composition is in the range of 50% to 95%, and the ratio of the polymer is in the range of 5% to 50%, based on the liquid crystal composite range.

Item 20. The liquid crystal composite according to any one of Items 1 to 19, wherein the liquid crystal composite is obtained by using a polymerizable composition containing a liquid crystal composition and a polymerizable compound as a precursor, and the polymerizable composition The product contains a photopolymerization initiator as an additive.

Item 21. A liquid crystal dimming element, wherein the dimming layer is the liquid crystal composite as described in any one of Items 1 to 20, and the dimming layer is sandwiched by a pair of transparent substrates, and the transparent substrates have transparent electrodes.

Item 22. The liquid crystal dimming device according to Item 21, wherein the transparent substrate is a glass plate or an acrylic plate.

Item 23. The liquid crystal dimming device according to Item 21, wherein the transparent substrate is a plastic film.

Item 24. A dimming window using the liquid crystal dimming element described in any one of Item 21 to Item 23.

Item 25. A smart window using the liquid crystal dimming element described in any one of Item 21 to Item 23.

Item 26. Use of a liquid crystal composite, the liquid crystal composite being the liquid crystal composite according to any one of Item 1 to Item 20, which is used in a liquid crystal dimming element.

Item 27. Use of a liquid crystal composite, the liquid crystal composite being the liquid crystal composite described in any one of Item 1 to Item 20, which is used in a liquid crystal dimming element whose transparent substrate is a plastic film.

Item 28. Use of a liquid crystal composite, the liquid crystal composite being the liquid crystal composite according to any one of Item 1 to Item 20, which is used in a dimming window.

Item 29. A use of a liquid crystal composite, the liquid crystal composite being the liquid crystal composite described in any one of Item 1 to Item 20, which is used in smart windows.

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

The present invention also includes the following items. (c) The liquid crystal composite as described above, wherein the liquid crystal composition contains, as a first component, compound (1-1), compound (1-2), compound (1-3), Compound (1-9), Compound (1-13), Compound (1-16), Compound (1-21), Compound (1-22), Compound (1-23), Compound (1-24), Compound (1-27), compound (1-28), compound (1-33), compound (1-36), compound (1-41), and compound (1-42).

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

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

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

The present invention also includes the following items. (i) The above-mentioned liquid crystal composite, wherein 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%, based on the liquid crystal composite. (j) The liquid crystal composite as described above, wherein the ratio of the liquid crystal composition is in the range of 80% to 96%, and the ratio of the polymer is in the range of 4% to 20%, based on the liquid crystal composite. (k) The liquid crystal composite as described above, wherein 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%, based on the liquid crystal composite.

The present invention also includes the following items. (l) The above-mentioned liquid crystal composite, containing as the second additive at least A sort of.

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 components in the liquid crystal composition, the preferred ratio of the components and the basis thereof will be described. Fifth, preferred forms of liquid crystal compounds will be described. Sixth, a preferable liquid crystal compound is shown. Seventh, a preferred form of the polymerizable compound and an example thereof will be described. Eighth, a preferred form of a dichroic dye and an example thereof will be described. Ninthly, the synthesis method of the component compounds will be described. Tenth, additives that can be added to the polymerizable composition will be described. Finally, the liquid crystal composite or device will be described.

First, the structure of the liquid crystal composite will be described. A liquid crystal composite is obtained by polymerizing 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 positive. The polymer produced by polymerization of the polymerizable composition undergoes phase separation, thereby providing a liquid crystal composite. That is, a liquid crystal composite in which a polymer and a liquid crystal composition are combined is produced. This liquid crystal composite is suitable for a normal mode device that is opaque when no voltage is applied and becomes transparent when a voltage is applied. The optical anisotropy of the liquid crystal composition is related to the refractive index of the polymer and the transparency of the liquid crystal dimming element. Generally speaking, the larger the optical anisotropy (Δn) of the liquid crystal composition is better. The optical anisotropy is preferably at least 0.15, more preferably at least 0.18.

In the polymer dispersion type device, the liquid crystal composition is dispersed in the polymer like liquid droplets. Individual droplets are separated and discontinuous. On the other hand, in a polymer network type device, the polymer has a three-dimensional network structure, and the liquid crystal composition is surrounded by the network and is continuous. In these devices, in order to efficiently scatter light, the ratio of the liquid crystal composition based on the liquid crystal composite is preferably relatively large. When the droplet or grid is large, the driving voltage is low. Therefore, from the viewpoint of low driving voltage, it is preferable that the ratio of the polymer is small. The response time is short for small droplets or grids. Therefore, from the viewpoint of short response time, it is preferable that the ratio of the polymer is large.

Based on the liquid crystal composite, the preferred 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 more 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 composition and the polymer is 100%, the ratio of the polymer can be easily calculated. In addition, the proportion of the polymer based on the liquid crystal composite is the same as the proportion of the polymerizable compound based on the polymerizable composition.

In order to efficiently scatter light or block sunlight, based on the liquid crystal composite, the preferred proportion of the liquid crystal composition is in the range of about 75% to about 97%. A more preferred 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 and the polymer is within the above-mentioned range, a polymer network-type device is produced. When the ratio of the polymer is large, a polymer-dispersed structure is mixed. On the other hand, when the ratio of the polymer is smaller, a polymer-stabilized alignment device will be produced. It is referred to as a PSA (polymer sustained alignment) element for short. In Example 1 of International Publication No. 2012-050178, it is described that "the monomer is added so as to be 0.5 wt% with respect to the liquid crystal material" (paragraph 0105). As can be seen from this description, in the PSA element, a trace amount of polymerizable compound is added to the liquid crystal material (liquid crystal composition).

In the PSA device, the polymer adjusts the pretilt angle of the 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 normal mode polymer network type device, the refractive index of the polymer is different from that of the liquid crystal molecules, which causes light scattering and the device becomes opaque. When a voltage is applied to the element, the liquid crystal molecules are arranged vertically to the substrate, and the element becomes transparent. Therefore, in the polymer network type element, unlike the PSA element, no polarizing plate is required.

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

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

Third, the main characteristics of the liquid crystal compound and the main effects of the compound on the liquid crystal composition or device will be described. The main properties of the component compounds are summarized in Table 2. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. Symbols L, M, and S are classifications based on qualitative comparisons among component compounds, and 0 (zero) means extremely small.

the Table 2. Characteristics of Liquid Crystalline Compounds the compound Compound (1) Compound (2) Compound (3) upper limit temperature S～L S～L S～L viscosity M~L S~M M~L optical anisotropy M~L S～L M~L Dielectric anisotropy S～L 0 M～L1 ⁾ specific resistance L L L 1) The value of dielectric anisotropy is negative, and the sign indicates the absolute value the

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

Fourth, the combination of components in the liquid crystal composition, the preferred ratio of the components and the basis thereof will be described. A preferable combination of components in the composition is the first component + the second component, the first component + the third component, or the first component + the second component + the third component. A more preferable combination is 1st component+2nd component, or 1st component+2nd component+3rd component.

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

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

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

Fifth, preferred forms of liquid crystal compounds will be described. In formula (1), formula (2), and formula (3), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons. In order to improve the stability to light or heat, preferred R ¹ is an alkyl group having 1 to 12 carbons.

R ² and R ³ are alkyl groups with 1 to 12 carbons, alkoxy groups with 1 to 12 carbons, alkenyl groups with 2 to 12 carbons, or 2 to 12 carbons with at least one hydrogen replaced by fluorine or chlorine Alkenyl. In order to increase the upper limit temperature or lower the lower limit temperature, preferred R ² or R ³ is an alkenyl group with 2 to 12 carbons, and in order to improve the stability to light or heat, preferred R ² or R ³ is a carbon number 1 to 12 alkyl groups.

R ⁴ and R ⁵ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. In order to improve the stability to light or heat, preferred R ⁴ or R ⁵ is an alkyl group with 1 to 12 carbons, and in order to increase the dielectric constant in the minor axis direction of liquid crystal molecules, preferred R ⁴ or R ⁵ is an alkoxy group having 1 to 12 carbon atoms.

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

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More preferable alkoxy group is methoxy group or ethoxy group for reducing viscosity.

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. More preferable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity. The preferred configuration of -CH=CH- in these alkenyl groups depends on the position of the double bond. In order to reduce the viscosity and other reasons, among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl, it is preferred trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferable alkenyloxy group is allyloxy group or 3-butenyloxy group in order to reduce the viscosity.

Preferred examples of alkyl groups in which at least one hydrogen is substituted 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, more preferable examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl.

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

Ring A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6- Difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. In order to increase the optical anisotropy, preferable ring A is 1,4-phenylene or 2-fluoro-1,4-phenylene. In order to increase the upper limit temperature, the stereo configuration related to 1,4-cyclohexylene is that the trans configuration is better than the cis configuration. Tetrahydropyran-2,5-diyl is or , preferably .

Ring B and Ring C are 1,4-cyclohexyl, 1,3-phenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1 , 4-phenylene, or pyrimidine-2,5-diyl. Desirable ring B or ring C is 1,4-cyclohexylene for raising the upper limit temperature or lowering the lower limit temperature, and preferable ring B or ring C is 1,4-cyclohexylene for lowering the lower limit temperature.

Ring D and ring F are 1,4-cyclohexylene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen through fluorine or Chlorine-substituted 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted by fluorine or chlorine naphthalene-2,6-diyl, chroman-2,6-diyl, or A chroman-2,6-diyl group in which at least one hydrogen has been replaced by fluorine or chlorine. Desirable ring D or ring F is 1,4-cyclohexylene for lowering the lower limit temperature or raising the upper limit temperature, and preferable ring D or ring F is 1,4-cyclohexylene for lowering the lower limit temperature.

Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochromane-2,6-diyl, 3,4,5,6-tetrafluoro- 2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2 ), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4). In order to reduce the viscosity, the preferred ring E is 2,3-difluoro-1,4-phenylene, and in order to increase the dielectric constant in the short axis direction of the liquid crystal molecules, the preferred ring E is 4,6-di Fluorodibenzothiophene-3,7-diyl.

Z ¹ is a single bond, ethylidene, vinylene, ethynylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy. Desirable Z ¹ is a single bond in order to increase the upper limit temperature, and a preferred Z ¹ is difluoromethyleneoxy in order to increase the dielectric anisotropy. The best Z ¹ is a single bond. Z ² is a single bond, ethylidene, vinylene, ethynyl, methyleneoxy, or carbonyloxy. In order to improve the stability to light or heat, preferred ^Z2 is a single bond. Z ³ and Z ⁴ are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy. In order to lower the minimum temperature, preferred Z ³ or Z ⁴ is a single bond, and in order to increase the dielectric constant in the short axis direction of liquid crystal molecules, preferred Z ³ or Z ⁴ is methyleneoxy. The extra good Z ³ or Z ⁴ are single bonds.

a is 1, 2, 3, or 4. The preferable a is 2 in order to lower the minimum temperature, and the preferable a is 3 in order to increase the dielectric anisotropy. b is 1, 2, or 3. Desirable b is 1 in order to lower the lower limit temperature, and preferably 2 or 3 in order to increase the upper limit temperature. c is 0, 1, 2, or 3; d is 0 or 1; the sum of c and d is 3 or less. Desirable c is 1 in order to lower the lower limit temperature, and preferably 2 or 3 in order to increase the upper limit temperature. In order to increase the dielectric constant in the minor axis direction of the liquid crystal molecules, the preferred d is 0, and in order to lower the minimum temperature, the preferred d is 1.

^X1 and ^X2 are hydrogen or fluorine. Desirable X ¹ or X ² is hydrogen in order to increase the upper limit temperature, and desirable X ¹ or X ² is fluorine in order to increase the dielectric anisotropy.

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

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

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

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

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

Seventh, a preferred form of the polymerizable compound and an example thereof will be described. Polymers are derived from polymeric compounds. The polymerizable compound may be single or a mixture of plural compounds. A preferable polymerizable compound is compound (4), compound (5), or compound (6). A preferable polymerizable compound is compound (7), compound (8), or compound (9). The polymerizable compound may be a mixture of compounds selected from compound (4) to compound (9). This mixture may contain a polymerizable compound different from compound (4) to compound (9). Such a mixture contains a compound selected from compound (4) to compound (9) as a main component. Here, the main component means the component which occupies the largest ratio in a mixture. For example, in a mixture of 40% of compound (4), 30% of compound (5), and 30% of compound (6), the main component is compound (4). When the polymerizable compound used is only compound (4), compound (4) is also called a main component.

7-1. Compound (4) In formula (4), Z ⁵ is an alkylene group with 1 to 20 carbons, and in the alkylene group, at least one hydrogen can be passed through an alkyl group with 1 to 5 carbons, fluorine, Chlorine, or P ³ substitution, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, -OCO-, -NH-, or -N(R ⁶ )-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, at least one -CH ₂ - can be substituted by carbocyclic saturated aliphatic compound, heterocyclic saturated aliphatic compound, carbocyclic Formula unsaturated aliphatic compound, heterocyclic unsaturated aliphatic compound, carbocyclic aromatic compound, or heterocyclic aromatic compound to remove two hydrogen and generate divalent group substitution, these two In the valence group, the carbon number is 5 to 35, and at least one hydrogen may be replaced by R ⁶ or P ³ . Here, R ⁶ is an alkyl group having 1 to 12 carbons, in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO-, or -OCO-.

Examples of divalent groups formed by removing two hydrogens from carbocyclic or heterocyclic saturated aliphatic compounds are 1,4-cyclohexylene, decahydronaphthalene-2,6-diyl, tetrahydro Pyran-2,5-diyl, 1,3-dioxane-2,5-diyl, etc. Examples of divalent groups formed by removing two hydrogens from carbocyclic or heterocyclic unsaturated aliphatic compounds are 1,4-cyclohexenyl, 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, 1,4-phenylene with at least one hydrogen replaced by fluorine base, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, naphthalene-1,2-diyl, pyrimidine-2,5-diyl, etc.

A preferred Z ⁵ is an alkylene group with 1 to 20 carbons. In the alkylene group, at least one hydrogen may be substituted by an alkyl group with 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. Among these divalent groups, the carbon number 5 to 35. A more preferred ^Z5 is an alkylene group with 1 to 20 carbons, in which at least one hydrogen can be substituted by an alkyl group with 1 to 5 carbons, and at least one _-CH2- can be substituted by -O- .

In order to improve the compatibility with the liquid crystal composition, preferred Z ⁵ includes a ring structure such as 1,4-cyclohexylene or 1,4-phenylene. In order to easily form a network structure, preferred ^Z5 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 a bonding site. More preferable polymerizable groups are formula (P-1) to formula (P-3). P ¹ , P ² , and P ³ may be acryloxy or methacryloxy.

In formula (P-1) to formula (P-6), M ¹ , M ² , and M ³ are hydrogen, fluorine, an alkyl group with 1 to 5 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine or chlorine 1 to 5 alkyl. In order to improve reactivity, preferred M ¹ , M ² , or M ³ is hydrogen or methyl. More preferred ^M1 is hydrogen or methyl, more preferred ^M2 or ^M3 is hydrogen.

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

In the compound (4), when there are many polymerizable groups, the polymer surrounding the droplets becomes firm due to crosslinking, or the network becomes dense. A preferable polymerizable compound has at least one acryloxy group (-OCO-CH=CH ₂ ) or methacryloxy group (-OCO-(CH ₃ )C=CH ₂ ). Compound (4) provides the corresponding polymer by polymerization. When the compound (4) is volatile, its oligomer can be used. A preferred polymer is colorless and transparent, and insoluble in liquid crystal compositions. Desirable polymers have excellent adhesion to the substrate of the device and reduce the driving voltage. In order to enhance this effect, a polymerizable compound different from compound (4) may be used in combination.

7-2. Compound (5) In formula (5), M ⁴ and M ⁵ are hydrogen or methyl. In order to improve reactivity, preferred ^M4 or ^M5 is hydrogen.

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

In order to achieve low-voltage driving, more preferred ^Z6 is an alkylene group in which at least one hydrogen is substituted with an alkyl group. When two hydrogens of an 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.

An example of compound (5) is compound (5-1). In formula (5-1), R ⁸ and R ¹⁰ are alkyl groups with 1 to 5 carbons, R ⁹ and R ¹¹ are alkyl groups with 5 to 20 carbons, and among the alkyl groups, at least one -CH ₂ - Can be substituted by -O-, -CO-, -COO-, or -OCO-, Z ⁸ is an alkylene group with 10 to 30 carbons, and in the alkylene group, at least one -CH ₂ - can be replaced by -O -, -CO-, -COO-, or -OCO- substituted.

An example of compound (5-1) is compound (5-1-1) and compound (5-1-2). In formula (5-1-1) and formula (5-1-2), for example, R ⁸ and R ¹⁰ are ethyl, R ⁹ and R ¹¹ are -CH ₂ OCOC ₉ H ₁₉ , -CH ₂ OCOC ₁₀ H ₂₁ , -CH ₂ OC ₈ H ₁₇ , or -CH ₂ OC ₁₁ H ₂₃ .

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

7-3. Compound (6) In formula (6), M ⁶ is hydrogen or methyl. In order to improve reactivity, preferred ^M6 is hydrogen.

Z ⁷ is a single bond or an alkylene group with 1 to 5 carbons. In the alkylene 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. A preferred Z ⁷ is a single bond or an alkylene group with 1 to 5 carbons. In the alkylene group, at least one -CH ₂ - can be passed through -O-, -CO-, -COO-, or -OCO- replace.

R ⁷ is an alkyl group with 1 to 40 carbons. 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 selected from carbocyclic saturated aliphatic compound, heterocyclic saturated aliphatic compound, carbocyclic unsaturated aliphatic compound, heterocyclic unsaturated fatty Aromatic compounds, carbocyclic aromatic compounds, or heterocyclic aromatic compounds are substituted with divalent groups generated by removing two hydrogens. Among 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-. Preferred R ⁷ is an alkyl group having 5 to 30 carbons. More preferable R ⁷ is a branched alkyl group having 5 to 30 carbon atoms.

An example of compound (6) is compound (6-1) to compound (6-6). In formula (6-1) to formula (6-5), R ¹² is an alkyl group with 5 to 20 carbons, and in the alkyl group, at least one -CH ₂ - can be passed through -O-, -CO-, - COO-, or -OCO-substituted, R ¹³ and R ¹⁴ are alkyl groups with 3 to 10 carbons, and in the alkyl groups, at least one -CH ₂ - can be replaced by -O-, -CO-, -COO-, or -OCO- substitution.

Compound (6) is acrylate or methacrylate. When R ⁷ in the formula (6) has a cyclic structure, the affinity with the liquid crystal composition is improved. When R ⁷ is an alkylene group, the polymer can easily form a network structure. In this polymer, the degree of freedom of molecular movement increases due to the alkylene group, so that the driving voltage decreases. In order to further enhance this effect, a polymerizable compound different from the compound (6) may be used in combination.

7-4. Compound (7) to Compound (9) In formula (7), formula (8), and formula (9), ring G, ring I, ring J, ring K, ring L, and ring M are 1,4-cyclohexyl, 1,4-phenylene Base, 1,4-cyclohexenyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or tertiary-2, 7-diyl, where at least one hydrogen can be fluorine, chlorine, cyano, hydroxyl, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons , an alkoxy group having 1 to 5 carbons, an alkoxycarbonyl group having 2 to 5 carbons, or an alkacyl group having 1 to 5 carbons. In formula (7), formula (8), and formula (9), 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. A more preferable ring is 1,4-cyclohexylene or 1,4-phenylene.

Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ , and Z ¹⁷ are single bonds, -O-, -COO-, -OCO-, or -OCOO-. Z ⁹ , Z ¹¹ , Z ¹⁴ , and Z ¹⁶ are single bonds, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH- , -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N- , or -C≡C-. ^Z15 is a single bond, -O-, or -COO-. Desirable Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ , or Z ¹⁷ is a single bond or -O-. Preferred Z ⁹ , Z ¹¹ , Z ¹⁴ , or Z ¹⁶ are single bonds, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH ₂ -, -CH ₂ CH ₂ COO-, or -OCOCH ₂ CH ₂ -.

^Y2 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 an alkoxycarbonyl group having 2 to 20 carbon atoms. Preferred ^Y2 is cyano, alkyl, or alkoxy.

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

M ⁷ to M ¹² are hydrogen or methyl.

An example of compound (7) is compound (7-1) to compound (7-24).

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

Examples of compound (8) include compound (8-1) to compound (8-31).

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

An example of compound (9) is compound (9-1) to compound (9-10).

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

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

Eighth, a preferred form of a dichroic dye and an example thereof will be described. Liquid crystal dimming elements are sometimes used as room dividers. In this case, a dichroic dye can be added to the liquid crystal composition. Mixtures of colorants may also be added. Liquid crystal dimming elements are sometimes used to block sunlight. In this case, a black (or darkened) dichroic dye is added to the liquid crystal composition. Black is produced by mixing dichroic pigments of cyan, magenta, and yellow. At least two pigments can be mixed. Preferably, two, three, four, five, or six pigments are mixed. It is especially preferred to mix three or four 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 peculiar to a dichroic dye such as a benzothiadiazole ring or a diketopyrrolopyrrole ring exists in the center of the molecule. c) The benzene ring or thiophene ring constituting the molecule together with the unique skeleton are located on the same plane. d) The side chain is an alkyl or alkoxy group. e) It has a conjugated double bond in the central part.

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

Examples of dichroic pigments are: benzothiadiazoles, diketopyrrolopyrroles, azo compounds, azomethine compounds, methine methine compounds, anthraquinones, merocyanines, naphthoquinones, tetrazines, pyrromethenes, and perylenes Or the rylenes of the terylenes. Preferable dichroic dyes are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, anthraquinones, and rylenes. Particularly preferable dichroic dyes 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 proportion of the dichroic dye is in the range of 0.03% to 25%. A more preferable ratio is in the range of 0.03% to 20%. A particularly preferred proportion is in the range of 0.03% to 15%.

Examples of dichroic dyes include compound (10-1) to compound (10-110).

In formula (10-1) to formula (10-110), Et is ethyl, n-Bu and nBu are butyl, n-Pent is pentyl, and n-Hex is hexyl.

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

Ninthly, the synthesis method of the component compounds will be described. These compounds can be synthesized by known methods. Synthetic methods are exemplified. Compound (1-9) and Compound (1-16) were synthesized by the method described in Japanese Patent Application Laid-Open No. 2-233626. Compound (2-1) was synthesized by the method described in JP-A-59-176221. Compound (3-1) was synthesized by the method described in Japanese Patent Application Laid-Open No. Hei 2-503441. Antioxidants are commercially available. Compound (12-1) described later is available from Sigma-Aldrich Corporation. Compound (12-2) and the like were synthesized by the method described in US Pat. No. 3,660,505. The polymerizable compound is commercially available or can be synthesized by a known method.

Compounds whose synthetic methods are not described can be synthesized by the methods described in the following books: "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions (Organic Syntheses)" (John Wiley & Sons, Inc.) Reactions)" (John Wiley & Sons, Inc.), "Comprehensive Organic Synthesis" (Pergamon Press), "Lectures on New Experimental Chemistry" ( Maruzen) etc. The composition is produced from the compound thus obtained by a known method. For example, the component compounds are mixed and then dissolved in each other by heating.

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

The optically active compound is added to the liquid crystal composition for the purpose of imparting a torsion angle by inducing a helical structure of the liquid crystal molecules. Examples of such compounds are compound (11-1) to compound (11-5). A preferred proportion of optically active compounds is about 5% or less. A more preferable ratio is in the range of about 0.01% to about 2%.

Compound (12 -1) Antioxidants such as compound (12-3) are added to the composition.

A compound with low volatility is effective for maintaining a large voltage retention 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 above effect, the preferable ratio of the antioxidant is about 50 ppm or more, and the preferable ratio of the antioxidant is about 600 ppm or less in order not to lower the upper limit temperature or raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferable examples of ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. In addition, light stabilizers such as amines having steric hindrance are also preferable. Preferable examples of the light stabilizer include compound (13-1) to compound (13-16) and the like. In order to obtain said effect, the preferred ratio of these absorbents or stabilizers is more than about 50 ppm, in order not to reduce the upper limit temperature, or in order not to increase the lower limit temperature, the preferred ratio of these absorbents or stabilizers is Below about 10000 ppm. A more 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 light energy absorbed by the liquid crystal compound and converting it into thermal energy. Preferable examples of the matting agent include compound (14-1) to compound (14-7) and the like. In order to obtain the above effects, the preferred ratio of these matting agents is above about 50 ppm, and in order not to increase the lower limit temperature, the preferred ratio of these matting agents is below about 20000 ppm. A more preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

In order 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 above effect, the preferable ratio of the antifoaming agent is about 1 ppm or more, and in order to prevent display defects, the preferable ratio of the antifoaming agent is about 1000 ppm or less. A more preferred ratio is in the range of about 1 ppm to about 500 ppm.

It is preferable to irradiate ultraviolet rays at the time of superposition|polymerization of a polymeric compound. Examples of ultraviolet irradiation lamps are metal halide lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, and the like. When a photopolymerization initiator is used, the wavelength of ultraviolet rays is preferably in the absorption wavelength region of the photopolymerization initiator. Avoid the absorption wavelength range of the liquid crystal composition. The preferred wavelength is above 330 nm. A more preferable wavelength is above 350 nm, such as 365 nm. The reaction can be carried out around room temperature, or can also be carried out under heating.

The polymerization can also be performed in the presence of a polymerization initiator such as a photopolymerization initiator. Appropriate conditions for carrying out the polymerization, or appropriate types and amounts of initiators, are known to those skilled in the art to which this invention pertains and are described in the literature. For example, as a photopolymerization initiator, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF) is suitable for free radical polymerization.

When storing a polymerizable compound, a polymerization inhibitor may be added in order to prevent polymerization. The polymerizable compound is usually mixed in the liquid crystal composition in a state where the polymerization inhibitor is not removed. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenthiazine and the like.

A polar compound is an organic compound having polarity. Here, compounds having ionic bonds are not contained. Atoms such as oxygen, sulfur, and nitrogen are electronegative and tend to have a partial negative charge. Carbon and hydrogen are neutral or tend to have a partial positive charge. Polarity arises from the unequal distribution of partial charges among the different kinds of atoms in a compound. For example, the polar compound has at least one partial structure such as -OH, -COOH, -SH, -NH ₂ , >NH, >N-.

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

Finally, the liquid crystal composite or the light control element will be described. A method for producing a liquid crystal composite from a polymerizable composition is as follows. First, a polymerizable composition is sandwiched between a pair of substrates. 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 produced by these methods, display defects such as flow marks and drop marks may occur. Flow marks are traces of polymeric composition flowing through the device. A drop mark is a mark left by dropping a 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 at the time of polymerization. By polymerization, the polymer is phase-separated from the polymerizable composition. Thereby, a dimming layer (liquid crystal composite) is formed between the substrates. The dimming layer is classified into a polymer dispersion type, a polymer network type, and a mixture of both.

There may be time-dependent changes due to long-term use of components. The haze ratio sometimes changes compared to the initial stage. A smaller change in the haze rate is preferable. When the haze change rate is small, a good state of transparency and opacity can be maintained. The haze change rate is preferably at most 20%. A more preferable haze change rate is 10% or less or 5% or less.

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

In the case of using the device for a long time, the brightness may partially decrease. An example of such a display defect is a line afterimage. This is a phenomenon in which the luminance between electrodes decreases in stripes due to repeated application of different voltages to two adjacent electrodes. This phenomenon is presumed to be caused by the accumulation of ionic impurities contained in the liquid crystal composition on the alignment film near the electrodes.

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

For the alignment film, films such as polyimide or polyvinyl alcohol are suitable. For example, a polyimide alignment film can be coated on a transparent substrate with a polyimide resin composition, and thermally cured at a temperature above about 180° C. Obtained by rubbing.

The pair of substrates were made to face each other with the transparent electrode layer on the inner side. In order to make the thickness between the substrates uniform, spacers may also be placed. Examples of spacers are glass particles, plastic particles, alumina particles, photo spacers, and the like. The preferred thickness of the light-adjusting layer is about 2 μm to about 50 μm, more preferably about 5 μm to about 20 μm. When bonding a pair of substrates, a common sealant can be used. An example of the sealant is an epoxy-based thermosetting composition.

In such an element, a light-absorbing layer, a diffusion reflection plate, and the like may be disposed on the back surface of the element as necessary. Specular reflection, diffuse reflection, retroreflection, holographic reflection and other functions can also be added.

This kind of element has the function of dimming film or dimming glass. In the case of a film, the element can be attached to an existing window, or laminated by sandwiching a pair of glass plates. This type of element is used for the windows installed on the outer wall, or the partition between the meeting room and the corridor. That is, there are applications such as electronic blinds, dimming windows, and smart windows. Furthermore, the function as an optical switch can be used for a liquid crystal shutter or the like. [Example]

The present invention is further described in detail by means of examples. The present invention is not limited by these examples. In the examples, the composition (M1), the composition (M2) and the like are described. In the examples, the mixture of the composition (M1) and the composition (M2) is not described. However, such mixtures are also deemed to be disclosed. A mixture of at least two compositions selected from the examples is also deemed to be disclosed. The synthesized compounds were identified by nuclear magnetic resonance (nuclear magnetic resonance, NMR) analysis and other methods. The properties of compounds, compositions, and devices were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for measurement. In the measurement of ¹ H-NMR, a sample is dissolved in a deuterated solvent such as CDCl ₃ , and the measurement is performed at room temperature at 500 MHz and 16 accumulation times. Tetramethylsilane was used as an internal standard. In the measurement of ¹⁹ F-NMR, CFCl ₃ was used as an internal standard, and the measurement was performed at an accumulated frequency of 24 times. In the explanation of NMR spectrum, s means singlet, d means doublet, t means triplet, q means quartet, quin means quintet, sex means sextet, m means multiplet peak, br means broad peak.

Gas chromatographic analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas was helium (2 mL/min). The sample gasification chamber was set at 280°C, and the detector (flame ionization detector (FID)) was set at 300°C. For the separation of component compounds, a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used; the stationary phase was dimethylpolysiloxane oxane; non-polar). After the column was kept at 200°C for 2 minutes, the temperature was raised to 280°C at a rate of 5°C/min. After the sample was prepared as an acetone solution (0.1%), 1 μL of it was injected into the sample vaporization chamber. The recorder is a chromatography unit (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.

As a solvent for diluting the sample, chloroform, hexane, etc. can be used. In order to separate component compounds, the following capillary columns 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 0.25 μm) 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 was used.

The ratio of the liquid crystal compound contained in the composition can be calculated by the method described below. The liquid crystal compound mixture was analyzed by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio of liquid crystal compounds. When the capillary column described above is used, the correction coefficients of various liquid crystal compounds can be regarded as 1. Therefore, the proportion of the liquid crystal compound can be calculated from the area ratio of the peaks.

Measurement sample: When measuring the characteristics of a composition or an element containing the composition, the composition is used as a sample as it is. When measuring the properties of the compound, a sample for measurement was prepared by mixing the compound (15%) in the mother liquid crystal (85%). From the values obtained by the measurement, the characteristic values of the compound were calculated by extrapolation. (Extrapolated value)={(measured value of sample)−0.85×(measured value of mother liquid crystal)}/0.15. Under this ratio, when the smectic phase (or crystal) is precipitated at 25°C, the ratio of the compound to the mother liquid crystal is changed in the order of 10%:90%, 5%:95%, and 1%:99%. Using this extrapolation method, the values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy related to the compound were obtained.

The following mother liquid crystals were used.

Measuring method: The characteristic was measured by the following method. Most of these methods are the methods described in the JEITA standard (JEITA · ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA) or modified. Methods. In the twisted nematic (twisted nematic, TN) element used for the measurement, no thin film transistor (thin film transistor, TFT) is installed.

(1) Upper limit temperature of the nematic phase (NI; °C): The sample was placed on a heating plate of a melting point measuring device equipped with a polarizing microscope, and heated 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 simply referred to as "upper limit temperature".

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

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

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

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

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

(7) Threshold voltage (Vth; measured at 25° C.; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. The sample was placed in a normally white mode (normally white mode) TN element with an interval (cell gap) between two glass substrates of 0.45/Δn (μm) and a twist angle of 80 degrees. The voltage (32 Hz, rectangular wave) applied to the device was increased from 0 V to 10 V in steps of 0.02 V. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared in which the transmittance was 100% when the amount of light was at its maximum and the transmittance was 0% when the amount of light was at its minimum. The threshold voltage is represented by the voltage at which the transmittance becomes 90%.

(8) Voltage retention rate (VHR; measured at 25°C; %): The TN device used in the measurement has a polyimide alignment film, and the distance (cell gap) between the two glass substrates is 5 μm. A sample is placed in this TN element, and it is sealed with an adhesive hardened by ultraviolet rays. The TN element was placed in a constant temperature bath at 60°C, and charged by applying a pulse voltage (1 V, 60 microseconds, 3 Hz). The attenuated voltage was measured with a high-speed voltmeter during 166.6 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. Area B is the area when not attenuated. The voltage retention rate is represented by the percentage of the area A to the area B.

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

(10) Voltage retention rate (heating VHR; measured at 25°C; %): After heating the TN element with the sample in a constant temperature bath at 120°C for 20 hours, measure the voltage retention rate to evaluate the thermal resistance stability. The configuration of the TN element and the method of measuring the voltage holding ratio are described in item (8). A composition having a large heating VHR has a large stability to heat. The heating VHR is preferably at least 90%, more preferably at least 95%.

(11) Response time (τ; measured at 25° C.; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. Low-pass filter (Low-pass filter) is set to 5 kHz. The sample was placed in a normally white mode TN device with a distance (cell gap) between two glass substrates of 5.0 μm and a twist angle of 80 degrees. Apply a rectangular wave (60 Hz, 5 V, 0.5 sec) to the element. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. The transmittance is regarded as 100% when the amount of light reaches the maximum, and the transmittance is regarded as 0% when the amount of light is at the minimum. Rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. Fall time (τf: fall time; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time is represented by the sum of the rise time and fall time obtained as described above.

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

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

(14) Helical pitch (P; measured at room temperature; μm): The helical pitch was measured by the wedge method. Refer to page 196 of "Liquid Crystal Handbook" (published in 2000, Maruzen). Put the sample into the wedge-shaped unit, and after standing at room temperature for 2 hours, observe the disclination line (disclination line) interval ( d2-d1). The helical pitch (P) is calculated from the following equation in which the angle of the wedge element is expressed as θ. P=2×(d2-d1)×tanθ.

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

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

(17) Alignment stability (liquid crystal alignment axis stability): The change of the liquid crystal alignment axis on the electrode side of a fringe field switching (FFS) element was evaluated. Measure the liquid crystal alignment angle ϕ (before) on the electrode side before stress is applied, then apply a rectangular wave of 4.5 V, 60 Hz to the device for 20 minutes, buffer for 1 second, and measure again after 1 second and 5 minutes. Liquid crystal alignment angle ϕ (after). From these values, the change Δϕ(deg.) of the liquid crystal alignment angle after 1 second and 5 minutes was calculated using the following formula. Δϕ(deg.)=ϕ(after)-ϕ(before) These determinations are based on J. Hilfiker, B. Johs, C. Herzinger, J. F. Elman, E. Mumba Qi (E. Montbach), D. Bryant (D. Bryant) and P. J. Bos (P. J. Bos) "Thin Solid Films (Thin Solid Films)" 455-456 (2004) 596-600 as a reference. It can be said that when Δϕ is small, the change rate of the liquid crystal alignment axis is small, and the stability of the liquid crystal alignment axis is better.

(18) 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 element with the distance (cell gap) between two glass substrates being 3.5 μm and the rubbing direction being antiparallel. The component is sealed with an adhesive that hardens with UV light. A voltage is applied to the element, and the voltage at which the amount of light transmitted through the element becomes the maximum is measured. While applying this voltage to the element, the sensor unit is brought close to the element, and the displayed flicker rate is read.

(19) Line Image Sticking Parameter (LISP; %): Line image sticking is generated by applying electrical stress to the component. The luminance of the area where the line afterimage exists and the luminance of the remaining area (reference area) are measured. The ratio of brightness reduction due to line afterimages is calculated, and the magnitude of the line afterimages is represented by this ratio.

19a) Measurement of brightness: An image of the element was taken using an imaging color photometer (manufactured by Radiant Zemax, PM-1433F-0). The brightness of each region of the device was calculated by analyzing the image using software (Prometric 9.1, manufactured by Radiant Zemax). The light source uses an LED backlight with an average brightness of 3500 cd/m ² .

19b) Stress voltage setting: Put the sample in the FFS element with a cell gap of 3.5 μm and a matrix structure (16 cells of 4 cells in length x 4 cells in width), and use an adhesive that hardens with ultraviolet light to harden the element. seal. Polarizing plates are respectively arranged on the upper surface and the lower surface of the element so that the polarization axes are perpendicular to each other. Light is irradiated to the element and a voltage (rectangular wave, 60 Hz) is applied. The voltage was increased stepwise by 0.1 V in the range of 0 V to 7.5 V, and the luminance of transmitted light at each voltage was measured. The voltage at which the brightness reaches the maximum is referred to as V255 for short. The voltage when the brightness reaches 21.6% of V255 (that is, 127 gray scales) is referred to as V127 for short.

19c) Stress conditions: V255 (rectangular wave, 30 Hz) was applied to the stress area at 60°C for 23 hours, and 0.5 V (rectangular wave, 30 Hz) was applied to the reference area to make it 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.

19d) Calculation of line afterimages: 4 cells in the center of 16 cells (2 cells in length x 2 cells in width) are used for calculation. The 4 units are divided into 25 areas (5 units vertically × 5 units horizontally). The average luminance of the 4 regions (2 vertical cells x 2 horizontal cells) located at the four corners is simply referred to as luminance A. The area obtained by removing the four-corner areas from the 25 areas is cross-shaped. In the four regions obtained by removing the central intersection region from the cross-shaped region, the minimum value of the luminance is simply referred to as luminance B. The line afterimage was calculated by the following formula. (Line afterimage) = (Brightness A - Brightness B) / Brightness A × 100. The line afterimage is preferably small.

(20) Face Image Sticking Parameter (FISP; %): Face image sticking is generated by applying electrical stress to the component. The brightness of the region where the surface afterimage exists and the brightness of the remaining regions were measured at 25°C. The ratio of luminance change due to surface afterimage is calculated, and the size of the surface afterimage is expressed by this ratio.

20a) "Measurement of Brightness", "Setting of Stress Voltage", and "Conditions of Stress" follow the order described in the section of "Line Afterimage".

20b) The surface afterimage was calculated by the following formula. (Surface afterimage) = (Brightness C-Brightness D)/Brightness D×100. Here, the luminance C is the average luminance of 8 cells to which V255 was applied, and the luminance D is the average luminance of 8 cells to which 0.5V was applied. The surface afterimage is preferably smaller. When the dielectric anisotropy of the liquid crystal composition is positive, the afterimage is represented by P-FISP. When the dielectric anisotropy of the liquid crystal composition is negative, surface afterimage is represented by N-FISP.

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

(22) Haze change rate (%): The weather resistance test of the element was carried out. The haze was measured before and after the test, and the haze change rate was calculated. This test was performed 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), temperature in the tank (35°C), and relative humidity in the tank (40%RH).

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

Examples of compositions are shown below. Liquid crystal compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration related to 1,4-cyclohexylene is trans. A number in parentheses following a symbolized compound indicates the formula to which the compound belongs. The mark of (-) means another liquid crystal compound. Finally, the characteristic values of the composition are summarized.

In the examples, it was selected and used from the following compositions. [Composition (M1)] 3-HB-C (1-1) 10% 3-HB(F)-C (1-1) 15% 3-HHB-F (1-9) 4% 2-HHB(F)-F （1-9） 11% 3-HHB(F)-F （1-9） 11% 5-HHB(F)-F （1-9） 10% 3-HHB(F)-C （1-9） 8% 3-BB(F,F)XB(F,F)-F （1-28） 1% 3-HB-O2 (2-2) 10% 3-HHB-1 (2-9) 8% 3-HHB-3 (2-9) 8% 3-HHB-O1 (2-9) 4% NI=95.5℃; Tc>-20℃; η=22.3 mPa･s; Δn=0.100; Δε=8.1; Vth=1.50 V.

[Composition (M2)] 2-HHB(F)-F （1-9） 12% 3-HHB(F)-F （1-9） 12% 5-HHB(F)-F （1-9） 11% 3-HHB(F,F)-F （1-9） 10% 2-HBB(F)-F （1-16） 7% 3-HBB(F)-F （1-16） 7% 5-HBB(F)-F (1-16) 14% 3-HBB(F,F)-F （1-16） 10% 3-BB(F,F)XB(F,F)-F （1-28） 1% 3-HB-O2 (2-2) 3% 3-HHB-1 (2-9) 8% 3-HHB-O1 (2-9) 5% NI=104.8℃; Tc>-20℃; η=25.1 mPa･s; Δn=0.107; Δε=5.9; Vth=1.79 V.

[Composition (M3)] 5-BB-C (1-2) 20% 3-HHB(F)-C （1-9） 10% 2-HBB-F (1-16) 5% 3-HBB-F (1-16) 5% 5-HBB-F (1-16) 5% 2-HBB(F)-F (1-16) 6% 3-HBB(F)-F （1-16） 6% 5-HBB(F)-F (1-16) 13% 3-HBB(F,F)-F （1-16） 10% 3-BB(F,F)XB(F,F)-F （1-28） 1% 3-HB-O2 (2-2) 10% 2-BB(F)B-3 (2-12) 9% NI=86.7℃; Tc>-20℃; η=31.6 mPa･s; Δn=0.162; Δε=8.6; Vth=1.68 V.

[Composition (M4)] 2-HHB(F)-F （1-9） 12% 3-HHB(F)-F （1-9） 12% 5-HHB(F)-F （1-9） 11% 3-HHB(F,F)-F （1-9） 10% 3-HHXB(F,F)-F （1-13） 1% 2-HBB(F)-F （1-16） 4.5% 3-HBB(F)-F (1-16) 4.5% 5-HBB(F)-F (1-16) 9% 3-HBB(F,F)-F (1-16) 18% 3-HB-O2 （2-2） 5% 3-HHB-1 (2-9) 8% 3-HHB-O1 (2-9) 5% NI=101.8℃; Tc>-20℃; η=24.5 mPa･s; Δn=0.105; Δε=6.1; Vth=1.76 V.

[Composition (M5)] 5-BB-C (1-2) 16% 3-HHXB(F,F)-F （1-13） 1% 2-HBB-F (1-16) 5% 3-HBB-F (1-16) 5% 5-HBB-F (1-16) 5% 2-HBB(F)-F (1-16) 6% 3-HBB(F)-F (1-16) 6% 5-HBB(F)-F (1-16) 13% 3-HBB(F,F)-F （1-16） 12% 2-HHBB(F,F)-F （1-29） 3% 3-HHBB(F,F)-F （1-29） 4% 5-HHBB(F,F)-F （1-29） 4% 3-HB-O2 (2-2) 10% 2-BB(F)B-3 (2-12) 10% NI=95.9℃; Tc>-20℃; η=37.4 mPa･s; Δn=0.162; Δε=7.4; Vth=1.87 V.

[Composition (M6)] 5-BB-C (1-2) 16% 3-HHXB(F,F)-F （1-13） 1% 2-HBB-F (1-16) 5% 3-HBB-F (1-16) 5% 5-HBB-F (1-16) 5% 2-HBB(F)-F (1-16) 6% 3-HBB(F)-F (1-16) 6% 5-HBB(F)-F (1-16) 13% 3-HBB(F,F)-F （1-16） 10% 5-HBB(F,F)-F （1-16） 5% 2-HHBB(F,F)-F （1-29） 3% 3-HHBB(F,F)-F （1-29） 4% 5-HHBB(F,F)-F （1-29） 4% 3-HB-O2 (2-2) 10% 2-BB(F)B-3 (2-12) 7% NI=92.9℃; Tc>-20℃; η=33.6 mPa･s; Δn=0.158; Δε=7.5; Vth=1.79 V.

[Composition (M7)] 5-BB-C (1-2) 16% 3-HHXB(F,F)-F （1-13） 1% 2-HBB-F (1-16) 5% 3-HBB-F (1-16) 5% 5-HBB-F (1-16) 5% 2-HBB(F)-F (1-16) 5% 3-HBB(F)-F (1-16) 5% 5-HBB(F)-F (1-16) 10% 3-HBB(F,F)-F （1-16） 10% 5-HBB(F,F)-F （1-16） 5% 2-HHBB(F,F)-F （1-29） 3% 3-HHBB(F,F)-F （1-29） 4% 5-HHBB(F,F)-F （1-29） 4% 3-HB-O2 (2-2) 10% 3-HHB-1 (2-9) 6% 2-BB(F)B-3 (2-12) 6% NI=98.2℃; Tc>-20℃; η=30.8 mPa･s; Δn=0.156; Δε=7.4; Vth=1.94 V.

[Composition (M8)] 5-BB-C (1-2) 20% 3-HHB(F)-C （1-9） 10% 3-BB(F)B(F,F)XB(F,F)-F （1-41） 3% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 6% 5-BB(F)B(F,F)XB(F,F)-F （1-41） 6% 3-HB-O2 (2-2) 12% 3-HHB-1 (2-9) 7% 3-HHB-O1 (2-9) 4% 2-BB(F)B-3 (2-12) 3% 2-BB(F)B-5 (2-12) 10% 3-BB(F)B-5 (2-12) 12% 3-BB(2F,5F)B-3 （2-13） 7% NI=102.9℃; Tc>-20℃; η=75.6 mPa･s; Δn=0.193; Δε=10.8; Vth=2.11 V.

[Composition (M9)] 5-BB-C (1-2) 20% 3-HHB(F)-C （1-9） 10% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 6% 5-BB(F)B(F,F)XB(F,F)-F （1-41） 6% 3-HB-O2 (2-2) 12% 3-HHB-1 (2-9) 8% 3-HHB-O1 (2-9) 5% 2-BB(F)B-3 (2-12) 3% 2-BB(F)B-5 (2-12) 10% 3-BB(F)B-5 (2-12) 12% 3-BB(2F,5F)B-3 （2-13） 8% NI=104.1℃; Tc>-20℃; η=64.6 mPa･s; Δn=0.192; Δε=9.6; Vth=2.09 V.

[Composition (M10)] 3-BB(F,F)XB(F,F)-F （1-28） 15% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 4% 5-BB(F)B(F,F)XB(F,F)-F （1-41） 4% 3-BB(F,F)XB(F)B(F,F)-F （1-42） 4% 3-HB-O2 (2-2) 16% 5-HB-O2 （2-2） 3% 3-HHB-1 (2-9) 8% 3-HHB-O1 (2-9) 5% 3-HBB-2 (2-10) 10% 2-BB(F)B-3 （2-12） 6% 2-BB(F)B-5 (2-12) 10% 3-BB(F)B-5 (2-12) 10% 3-BB(2F,5F)B-3 （2-13） 5% NI=95.4℃; Tc>-20℃; η=50.8 mPa･s; Δn=0.175; Δε=6.4; Vth=2.33 V.

[Composition (M11)] 5-BB-C (1-2) 20% 3-HHB(F)-C （1-9） 10% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 6% 5-BB(F)B(F,F)XB(F,F)-F （1-41） 6% 3-HB-O2 (2-2) 14% 3-HHB-1 (2-9) 6% 3-HHB-O1 (2-9) 4% 2-BB(F)B-3 (2-12) 4% 2-BB(F)B-5 (2-12) 10% 3-BB(F)B-5 (2-12) 12% 3-BB(2F,5F)B-3 （2-13） 8% NI=100.1℃; Tc>-20℃; η=60.0 mPa･s; Δn=0.193; Δε=9.4; Vth=2.07 V.

[Composition (M12)] 3-BB(F,F)XB(F,F)-F （1-28） 15% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 4% 5-BB(F)B(F,F)XB(F,F)-F （1-41） 4% 3-BB(F,F)XB(F)B(F,F)-F （1-42） 4% 3-HB-O2 (2-2) 16% 5-HB-O2 （2-2） 3% 3-HHB-1 (2-9) 8% 3-HHB-3 (2-9) 6% 3-HHB-O1 (2-9) 5% 3-HBB-2 (2-10) 10% 2-BB(F)B-5 (2-12) 10% 3-BB(F)B-5 (2-12) 10% 3-BB(2F,5F)B-3 （2-13） 5% NI=97.7℃; Tc>-20℃; η=52.8 mPa･s; Δn=0.165; Δε=6.3; Vth=2.48 V.

[Composition (M13)] 3-BB(F,F)XB(F,F)-F （1-28） 15% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 3% 5-BB(F)B(F,F)XB(F,F)-F （1-41） 3% 3-BB(F,F)XB(F)B(F,F)-F （1-42） 6% 3-HB-O2 (2-2) 6% 1-BB-3 (2-3) 6% 3-HHB-O1 (2-9) 5% 3-HHB-1 (2-9) 8% 3-HBB-2 (2-10) 12% 2-BB(F)B-3 (2-12) 6% 2-BB(F)B-5 (2-12) 10% 3-BB(F)B-5 (2-12) 12% 3-BB(2F,5F)B-3 （2-13） 8% NI=99.5℃; Tc>-20℃; η=61.7 mPa･s; Δn=0.192; Δε=6.7; Vth=2.77 V.

[Composition (M14)] 5-BB-C (1-2) 20% 3-HHB(F)-C （1-9） 8% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 3% 5-BB(F)B(F,F)XB(F,F)-F （1-41） 3% 3-BB(F,F)XB(F)B(F,F)-F （1-42） 6% 3-HB-O2 (2-2) 12% 3-HHB-1 (2-9) 8% 3-HHB-O1 (2-9) 4% 3-HBB-2 (2-10) 6% 2-BB(F)B-5 (2-12) 10% 3-BB(F)B-5 (2-12) 12% 3-BB(2F,5F)B-3 （2-13） 8% NI=102.1℃; Tc>-20℃; η=54.8 mPa･s; Δn=0.189; Δε=9.0; Vth=2.16 V.

[Composition (M15)] 2-HHB(F)-F （1-9） 11% 3-HHB(F)-F （1-9） 11% 5-HHB(F)-F （1-9） 10% 3-HHB(F,F)-F （1-9） 10% 3-HHXB(F,F)-F （1-13） 3% 2-HBB(F)-F （1-16） 4% 3-HBB(F)-F (1-16) 4% 5-HBB(F)-F (1-16) 8% 3-HBB(F,F)-F （1-16） 15% 5-HBB(F,F)-F （1-16） 6% 3-HB-O2 （2-2） 5% 3-HHB-1 (2-9) 8% 3-HHB-O1 （2-9） 5% NI=101.0℃; Tc>-20℃; η=24.2 mPa･s; Δn=0.105; Δε=6.2; Vth=1.80 V.

[Composition (M16)] 2-HHB(F)-F （1-9） 13% 3-HHB(F)-F （1-9） 13% 5-HHB(F)-F （1-9） 14% 3-HHB(F,F)-F （1-9） 10% 5-HHB(F,F)-F （1-9） 3% 2-HBB(F)-F (1-16) 2% 3-HBB(F)-F (1-16) 2% 5-HBB(F)-F （1-16） 4% 3-HBB(F,F)-F （1-16） 15% 5-HBB(F,F)-F （1-16） 6% 3-HB-O2 （2-2） 5% 3-HHB-O1 (2-9) 5% 3-HBB-2 (2-10) 8% NI=99.9℃; Tc>-20℃; η=23.9 mPa･s; Δn=0.105; Δε=6.0; Vth=1.71 V.

[Composition (M17)] 3-BB(F,F)XB(F,F)-F （1-28） 15% 3-BB(F,F)XB(F)B(F,F)-F （1-42） 12% 3-HB-O2 (2-2) 15% 3-HHB-1 (2-9) 8% 3-HHB-3 (2-9) 10% 3-HHB-O1 (2-9) 5% 3-HBB-2 (2-10) 12% 2-BB(F)B-5 (2-12) 8% 3-BB(F)B-5 (2-12) 8% 3-BB(2F,5F)B-3 （2-13） 7% NI=100.5℃; Tc>-20℃; η=32.3 mPa･s; Δn=0.162; Δε=6.2; Vth=2.28 V.

[Composition (M18)] 3-BB(F,F)XB(F,F)-F （1-28） 15% 3-BB(F,F)XB(F)B(F,F)-F （1-42） 12% 3-HB-O2 (2-2) 6% 1-BB-3 (2-3) 6% 3-HHB-O1 (2-9) 5% 3-HHB-1 (2-9) 8% 3-HBB-2 (2-10) 12% 2-BB(F)B-3 (2-12) 6% 2-BB(F)B-5 (2-12) 10% 3-BB(F)B-5 (2-12) 12% 3-BB(2F,5F)B-3 （2-13） 8% NI=96.9℃; Tc>-20℃; η=41.0 mPa･s; Δn=0.190; Δε=6.5; Vth=2.31 V.

[Composition (M19)] 5-BB-C (1-2) 20% 3-HHB(F)-C （1-9） 8% 3-BB(F,F)XB(F)B(F,F)-F （1-42） 12% 3-HB-O2 (2-2) 12% 3-HHB-1 (2-9) 8% 3-HHB-O1 (2-9) 4% 3-HBB-2 (2-10) 6% 2-BB(F)B-5 (2-12) 10% 3-BB(F)B-5 (2-12) 12% 3-BB(2F,5F)B-3 （2-13） 8% NI=99.6℃; Tc>-20℃; η=43.6 mPa･s; Δn=0.188; Δε=8.9; Vth=1.99 V.

[Composition (M20)] 2-HB(F)-C （1-1） 9% 3-HB(F)-C （1-1） 10% 3-HHB-F (1-9) 4% 2-HHB(F)-F （1-9） 6% 3-HHB(F)-F （1-9） 6% 5-HHB(F)-F （1-9） 6% 2-HHB(F)-C （1-9） 6% 3-HHB(F)-C （1-9） 6% 3-HEB-O4 (2-4) 6% 4-HEB-O2 （2-4） 4% 5-HEB-O1 (2-4) 4% 3-HEB-O2 (2-4) 3% 5-HEB-O2 （2-4） 3% 2-HHB-1 (2-9) 5% 3-HHB-1 (2-9) 8% 3-HHB-3 (2-9) 10% 3-HHB-O1 (2-9) 4% NI=102.2℃; Tc>-20℃; η=25.7 mPa･s; Δn=0.096; Δε=6.7.

[Composition (M21)] 3-HBB-F (1-16) 6% 3-BB(F,F)XB(F,F)-F （1-28） 10% 3-HB-O2 (2-2) 9% 1-BB-3 (2-3) 9% 3-HHB-1 (2-9) 6% 3-HHB-O1 (2-9) 4% 2-BB(F)B-3 (2-12) 10% 2-BB(F)B-5 (2-12) 11% 3-BB(F)B-5 (2-12) 11% 3-BB(2F,5F)B-3 （2-13） 5% 3-BB(F)B(F,F)XB(F,F)-F （1-41） 3% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 4% 3-BB(F,F)XB(F)B(F,F)-F （1-42） 12% NI=90.4℃; Tc>-20℃; Δn=0.193; Δε=7.9.

[Composition (M22)] 3-HB-CL (1-1) 3% 5-HXB(F,F)-F （1-7） 3% 3-HHB-OCF3 (1-9) 3% 3-HHXB(F,F)-F （1-13） 6% 3-HGB(F,F)-F （1-14） 3% 3-HB(F)B(F,F)-F （1-17） 5% 3-BB(F,F)XB(F,F)-F （1-28） 6% 3-HHBB(F,F)-F （1-29） 6% 5-BB(F)B(F,F)XB(F)B(F,F)-F （1-43） 2% 3-BB(2F,3F)XB(F,F)-F （1-44） 4% 3-HHB(F,F)XB(F,F)-F （1） 4% 3-HBB(2F,3F)XB(F,F)-F （1） 5% 3-HH-V (2-1) 22% 3-HH-V1 (2-1) 10% 5-HB-O2 （2-2） 5% 3-HHEH-3 (2-8) 3% 3-HBB-2 (2-10) 7% 5-B(F)BB-3 (2-11) 3% NI=77.2℃; Tc>-20℃; Δn=0.101; Δε=5.8; Vth=1.88 V; η=13.7 mPa･s; γ1=61.3 mPa･s.

[Composition (M23)] 5-HB-CL (1-1) 5% 5-HXB(F,F)-F （1-7） 6% 3-HHXB(F,F)-F （1-13） 6% V-HB(F)B(F,F)-F （1-17） 5% 3-HHB(F)B(F,F)-F （1-30） 7% 2-BB(F)B(F,F)XB(F)-F （1-41） 3% 3-BB(F)B(F,F)XB(F)-F （1-41） 3% 4-BB(F)B(F,F)XB(F)-F （1-41） 4% 2-HH-5 (2-1) 8% 3-HH-V (2-1) 10% 3-HH-V1 (2-1) 7% 4-HH-V (2-1) 10% 4-HH-V1 (2-1) 8% 5-HB-O2 (2-2) 7% 4-HHEH-3 (2-8) 3% V2-BB(F)B-1 （2-12） 3% 1O1-HBBH-3 （-） 5% NI=78.5℃; Tc>-20℃; Δn=0.095; Δε=3.4; Vth=1.50 V; η=8.4 mPa･s; γ1=54.2 mPa･s.

[Composition (M24)] 3-HHEB(F,F)-F （1-10） 5% 3-HHXB(F,F)-F （1-13） 7% 5-HBEB(F,F)-F （1-20） 5% 3-BB(F,F)XB(F,F)-F （1-28） 10% 2-HHB(F)B(F,F)-F （1-30） 3% 5-HHB(F,F)XB(F,F)-F （1） 6% 3-HBB(2F,3F)XB(F,F)-F （1） 5% 2-HH-3 (2-1) 8% 3-HH-V (2-1) 20% 3-HH-V1 (2-1) 7% 4-HH-V (2-1) 6% 5-HB-O2 （2-2） 5% V2-B2BB-1 (2-14) 3% 3-HHEBH-3 (2-19) 5% 3-HHEBH-5 (2-19) 5% NI=90.3℃; Tc>-20℃; Δn=0.088; Δε=5.4; Vth=1.69 V; η=13.7 mPa･s; γ1=60.6 mPa･s.

[Composition (M25)] 7-HB(F,F)-F （1-1） 3% 3-HGB(F,F)-F （1-14） 3% 5-GHB(F,F)-F （1-15） 4% 3-GB(F,F)XB(F,F)-F （1-22） 5% 3-BB(F)B(F,F)-CF3 （1-24） 2% 3-HHBB(F,F)-F （1-29） 4% 3-GBB(F)B(F,F)-F （1-32） 2% 2-dhBB(F,F)XB(F,F)-F （1-35） 4% 3-HGB(F,F)XB(F,F)-F （1） 5% 3-dhB(F,F)B(F,F)XB(F)B(F,F)-F （1） 3% 2-HH-3 (2-1) 14% 2-HH-5 (2-1) 4% 3-HH-V (2-1) 26% 1V2-HH-3 (2-1) 5% 1V2-BB-1 (2-3) 3% 3-BB(2F,5F)B-3 （2-13） 3% 3-HB(F)HH-2 （2-18） 4% 5-HBB(F)B-2 （2-21） 6% NI=78.3℃; Tc>-20℃; Δn=0.094; Δε=5.9; Vth=1.25 V; η=12.8 mPa･s; γ1=61.9 mPa･s.

[Composition (M26)] 3-HHB(F,F)-F （1-9） 8% 3-GB(F)B(F,F)-F （1-21） 3% 3-BB(F,F)XB(F,F)-F （1-28） 10% 3-GB(F)B(F,F)XB(F,F)-F （1-36） 6% 5-GB(F,F)XB(F)B(F,F)-F （1） 5% 3-HH-V (2-1) 30% 3-HH-V1 (2-1) 10% 1V2-HH-3 (2-1) 8% 3-HH-VFF (2-1) 8% V2-BB-1 (2-3) 2% 5-HB(F)BH-3 （2-20） 5% 5-HBBH-3 (2-22) 5% NI=76.6℃; Tc>-20℃; Δn=0.088; Δε=5.5; Vth=1.81 V; η=12.1 mPa･s; γ1=60.2 mPa･s.

[Composition (M27)] 7-HB(F,F)-F （1-1） 6% 3-BB(F,F)XB(F,F)-F （1-28） 14% 3-dhB(F,F)B(F,F)XB(F)B(F,F)-F （1） 7% 2-HH-5 (2-1) 5% 3-HH-V (2-1) 30% 3-HH-V1 (2-1) 3% 3-HH-VFF (2-1) 10% 3-HHB-1 (2-9) 4% 3-HHB-3 (2-9) 5% 3-HHB-O1 (2-9) 3% 3-BB(2F,5F)B-3 （2-13） 3% 3-HHEBH-3 (2-19) 3% 3-HHEBH-4 (2-19) 4% 3-HHEBH-5 (2-19) 3% NI=82.7℃; Tc>-20℃; Δn=0.085; Δε=5.1; Vth=1.70 V; η=8.0 mPa･s; γ1=53.9 mPa･s.

[Composition (M28)] 3-HBB(F,F)-F （1-16） 5% 5-HBB(F,F)-F （1-16） 4% 3-BB(F)B(F,F)-F （1-24） 3% 3-HH2BB(F,F)-F （1-39） 3% 4-HH2BB(F,F)-F （1-39） 3% 3-BB(F)B(F,F)XB(F,F)-F （1-41） 3% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 5% 3-BB(F,F)XB(F)B(F,F)-F （1-42） 3% 5-BB(F)B(F,F)XB(F)B(F,F)-F （1-43） 4% 2-HH-5 (2-1) 8% 3-HH-V (2-1) 28% 4-HH-V1 (2-1) 7% 5-HB-O2 (2-2) 2% 7-HB-1 (2-2) 5% VFF-HHB-O1 （2-9） 8% VFF-HHB-1 (2-9) 3% 3-HBB(2F,3F)-O2 （3-14） 2% 2-BB(2F,3F)B-3 （3-19） 4% NI=81.9℃; Tc>-20℃; Δn=0.109; Δε=4.8; Vth=1.75 V; η=13.3 mPa･s; γ1=57.4 mPa･s.

[Composition (M29)] 5-HB-CL (1-1) 2% 5-HEB(F,F)-F （1-6） 3% 3-HHB-OCF3 (1-9) 4% 3-HHEB(F,F)-F （1-10） 4% 3-HBEB(F,F)-F （1-20） 3% 5-HBEB(F,F)-F （1-20） 3% 3-BB(F)B(F,F)-F （1-24） 3% 3-HBBXB(F,F)-F （1-33） 6% 3-GB(F)B(F,F)XB(F,F)-F （1-36） 5% 4-GB(F)B(F,F)XB(F,F)-F （1-36） 5% 5-HHB(F,F)XB(F,F)-F （1） 3% 3-HGB(F,F)XB(F,F)-F （1） 4% 3-HH-5 (2-1) 4% 3-HH-V (2-1) 21% 3-HH-V1 (2-1) 3% 4-HH-V (2-1) 4% 1V2-HH-3 (2-1) 6% 5-B(F)BB-2 (2-11) 3% 5-B(F)BB-3 (2-11) 2% 3-HB(2F,3F)-O2 （3-1） 3% 3-BB(2F,3F)-O2 （3-6） 2% 3-HHB(2F,3F)-O2 （3-8） 4% F3-HH-V (-) 3% NI=78.1℃; Tc>-20℃; Δn=0.100; Δε=6.6; Vth=1.50 V; η=16.2 mPa･s; γ1=61.8 mPa･s.

[Composition (M30)] 3-HHEB(F,F)-F （1-10） 3% 3-HBEB(F,F)-F （1-20） 3% 3-BB(F,F)XB(F,F)-F （1-28） 4% 3-HHB(F)B(F,F)-F （1-30） 3% 3-BB(F)B(F,F)XB(F,F)-F （1-41） 5% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 5% V-HH-V (2-1) 10% V-HH-2V (2-1) 20% 1V-HH-V (2-1) 10% 3-HH-V (2-1) 15% V2-BB-1 (2-3) 4% 1-BB(F)B-2V （2-12） 7% 2-BB(F)B-2V (2-12) 8% 1O1-HBBH-5 （-） 3% NI=74.3℃; Tc≦-20℃; Δn=0.111; Δε=3.0; Vth=2.39 V; η=11.0 mPa･s; γ1=44.5 mPa･s.

[Composition (M31)] 3-GHB(F,F)-F （1-15） 3% 3-BB(F,F)XB(F,F)-F （1-28） 11% 3-HHBB(F,F)-F （1-29） 4% 3-HBBXB(F,F)-F （1-33） 8% 3-BB(F)B(F,F)XB(F,F)-F （1-41） 3% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 6% 5-BB(F)B(F,F)XB(F,F)-F （1-41） 6% 3-HH-V (2-1) 40% 3-HH-V1 (2-1) 5% 3-HHB-O1 (2-9) 3% 1-BB(F)B-2V （2-12） 3% 3-HDhB(2F,3F)-O2 （3-13） 4% 2-dhBB(2F,3F)-O2 （3-16） 4% NI=85.2℃; Tc>-20℃; Δn=0.114; Δε=7.3; η=15.0 mPa･s.

[Composition (M32)] 3-GB(F,F)XB(F,F)-F （1-22） 3% 3-BB(F)B(F,F)-F （1-24） 9% 3-BB(F)B(F,F)-CF3 （1-24） 4% 3-HBBXB(F,F)-F （1-33） 5% 4-GB(F)B(F,F)XB(F,F)-F （1-36） 3% 3-BB(F)B(F,F)XB(F,F)-F （1-41） 3% 4-BB(F)B(F,F)XB(F,F)-F （1-41） 6% 3-HH-V (2-1) 39% 3-HH-V1 (2-1) 5% V-HHB-1 (2-9) 4% 1-BB(F)B-2V （2-12） 3% 2-BB(F)B-2V （2-12） 3% 3-HHB(2F,3F)-O2 （3-8） 6% 3-HBB(2F,3F)-O2 （3-14） 3% V-HBB(2F,3F)-O2 （3-14） 4% NI=83.2℃; Tc>-20℃; Δn=0.120; Δε=6.2; η=13.6 mPa･s.

In the examples, selected from the following polymeric compounds were used.

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

[Example 1] Production of Liquid Crystal Dimming Element-1 The composition (M1) has positive dielectric anisotropy. A polymeric composition was prepared by mixing 60% of the composition (M1), 32% of the polymeric compound (RM-1), and 8% of the polymeric compound (RM-5). To this composition, the black dichroic dye (A) was added at a ratio of 5% based on the composition (M1). Irgacure 651 (photopolymerization initiator; BASF) was added at a rate of 0.3% based on the polymerizable compound. This polymerizable composition was injected into a device in which the distance (cell gap) between two glass substrates was 3.5 μm. The temperature at the time of injection was 140°C. The element was irradiated with ultraviolet rays of 18 mW/cm ² for 56 seconds by a high-pressure mercury lamp to produce an element having a liquid crystal composite. The element is black. A voltage of 45 V was applied to the element, which became transparent when illuminated with light. This indicates that the component is in normal mode.

[Comparative example 1] In the above experimental operation, a polymerizable composition was prepared without adding the black dichroic dye (A) to the composition. A device having a liquid crystal composite was produced according to the above operation. The element is opaque. However, the surface of the element is bright. A voltage of 45 V was applied to the element, and when light was irradiated, the element became transparent.

[Example 2] Production of liquid crystal dimming element-2 Next, two kinds of polymerizable compounds were combined. A polymeric composition was prepared by mixing 90% of the composition (M1), 5% of the polymeric compound (RM-8), and 5% of the polymeric compound (RM-11). To this composition, the black dichroic dye (A) was added at a ratio of 5% based on the composition (M1). Irgacure 651 (photopolymerization initiator; BASF) was added at a rate of 0.3% based on the polymerizable compound. This polymerizable composition was injected into a device in which the distance (cell gap) between two glass substrates was 3.5 μm. The temperature at the time of injection was 140°C. The element was irradiated with ultraviolet rays of 18 mW/cm ² for 56 seconds by a high-pressure mercury lamp to produce an element having a liquid crystal composite. The element is black. A voltage of 45 V was applied to the element, which became transparent when illuminated with light. This indicates that the component is in normal mode.

[Example 3] Determination of Haze Change Rate 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 element, and the haze rate was measured. Next, the haze ratio after the weather resistance test performed under the conditions described in Measurement (22) was measured, and the haze change rate was calculated. The change rate of haze is small. This indicates that the temporal change of the liquid crystal dimming element is small. [Industrial availability]

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

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Claims (19)

A liquid crystal composite, comprising a liquid crystal composition and a polymer, the liquid crystal composition contains at least one compound selected from the compounds represented by formula (1) as the first component, and at least one compound selected from the compounds represented by formula (2) as the second component ) at least one compound among the compounds represented by ), and a dichroic dye as the first additive,

In formula (1), R ¹ is an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or an alkenyl group with 2 to 12 carbons; ring A is 1,4-cyclohexylene, 1 ,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ¹ is a single bond, ethylene, vinylene, Ethynyl, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; ^X1 and ^X2 are hydrogen or fluorine; ^Y1 is fluorine, chlorine, cyano, at least one hydrogen through fluorine or chlorine Substituted alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons with at least one hydrogen substituted by fluorine or chlorine, or alkenyloxy with 2 to 12 carbons with at least one hydrogen substituted with fluorine or chlorine a is 1, 2, 3, or 4; in formula (2), R ² and R ³ are alkyl groups with 1 to 12 carbons, alkoxy groups with 1 to 12 carbons, alkenes with 2 to 12 carbons , or at least one hydrogen substituted by fluorine or chlorine alkenyl with 2 to 12 carbons; ring B and ring C are 1,4-cyclohexyl, 1,3-phenylene, 1,4-phenylene , 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or pyrimidine-2,5-diyl; Z ² is a single bond, ethylene, vinylene group, ethynyl, methyleneoxy, or carbonyloxy; b is 1, 2, or 3. The liquid crystal composite as described in claim 1, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (1-1) to formula (1-47) as the first component,

In formula (1-1) to formula (1-47), R ¹ is an alkyl group with 1 to 12 carbons, an alkoxyl group with 1 to 12 carbons, or an alkenyl group with 2 to 12 carbons, X ¹ and ^X2 is hydrogen or fluorine; ^Y1 is fluorine, chlorine, cyano, an alkyl group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkyl group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine alkoxy, or an alkenyloxy group having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. The liquid crystal composite as described in item 1 of the patent claims, wherein based on the liquid crystal composition, the proportion of the first component is in the range of 5% to 90%. The liquid crystal composite as described in claim 1, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (2-1) to formula (2-23) as the second component,

In formula (2-1) to formula (2-23), R ² and R ³ are alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or Alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. The liquid crystal complex as described in item 1 of the scope of the patent application, wherein the liquid crystal Crystalline composition, the ratio of the second component is in the range of 5% to 90%. The liquid crystal composite as described in claim 1, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (3) as the third component,

In formula (3), R ⁴ and R ⁵ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons Oxygen; Ring D and Ring F are 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted by fluorine or chlorine, naphthalene-2,6-diyl, chromane-2,6- Diyl, or chroman-2,6-diyl with at least one hydrogen replaced by fluorine or chlorine; Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro- 1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-di Fluorochromane-2,6-diyl, 3,4,5,6-tetrafluoro-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4 ,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ³ and Z ⁴ are single bonds, ethyl group, vinylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3, and d is 0 or 1; the sum of c and d is 3 or less. The liquid crystal composite as described in claim 1, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains a compound represented by formula (4) as a main component, P ¹ -Z ⁵ -P ² ( 4) In formula (4), P ¹ and P ² are polymerizable groups; Z ⁵ is an alkylene group with 1 to 20 carbons, and in the alkylene group, at least one hydrogen can pass through an alkylene group with 1 to 5 carbons. group, fluorine, chlorine, or P ³ substitution, at least one -CH ₂ - may be substituted by -O-, -CO-, -COO-, -OCO-, -NH-, or -N(R ⁶ )-, at least One -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, at least one -CH ₂ - can be substituted by carbocyclic saturated aliphatic compound, heterocyclic saturated aliphatic Compounds, carbocyclic unsaturated aliphatic compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds, or heterocyclic aromatic compounds by removing two hydrogens to generate divalent substituents , in these divalent groups, the carbon number is 5 to 35, and at least one hydrogen can be replaced by R ⁶ or P ³ , where R ⁶ is an alkyl group with 1 to 12 carbon numbers, and in the alkyl group, at least One -CH ₂ - may be substituted by -O-, -CO-, -COO-, or -OCO-, and P ³ is a polymerizable group. The liquid crystal composite as described in claim 7, wherein P ¹ , P ² , and P ³ are groups selected from polymerizable groups represented by formula (P-1) to formula (P-6),

In formula (P-1) to formula (P-6), M ¹ , M ² , and M ³ are hydrogen, fluorine, an alkyl group with 1 to 5 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine or chlorine 1 to 5 alkyl. The liquid crystal composite as described in claim 7, wherein at least one of P ¹ , P ² , and P ³ is acryloxy or methacryloxy. The liquid crystal composite as described in claim 1, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains a compound represented by formula (5) as a main component,

In formula (5), M ⁴ and M ⁵ are hydrogen or methyl; Z ⁶ is an alkylene group with 21 to 80 carbons, and in the alkylene group, at least one hydrogen can pass through an alkylene group with 1 to 20 carbons. , fluorine, or chlorine, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, -OCO-, -NH-, or -N(R ⁶ )-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, here, R ⁶ is an alkyl group with 1 to 12 carbons, and in the alkyl group, at least one -CH ₂ - can be substituted by -O -, -CO-, -COO-, or -OCO- substituted. The liquid crystal composite as described in claim 1, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains a compound represented by formula (6) as a main component,

In formula (6), M ⁶ is hydrogen or methyl; Z ⁷ is a single bond or an alkylene group with 1 to 5 carbons, in the alkylene group, at least one hydrogen can be substituted by fluorine or chlorine, and at least one- CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-; R ⁷ is an alkyl group 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-, at least one -CH ₂ - can be substituted by carbocyclic saturated aliphatic compound, heterocyclic produced by removing two hydrogens from saturated aliphatic compounds, carbocyclic unsaturated aliphatic compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds, or heterocyclic aromatic compounds Divalent group substitution, in these divalent groups, the carbon number is 5 to 35, and at least one hydrogen can be replaced by an alkyl group with a carbon number of 1 to 12, and in the alkyl group, at least one -CH ₂ - can be replaced by - O-, -CO-, -COO-, or -OCO-substitution. The liquid crystal complex as described in item 11 of the scope of the patent application, wherein in formula (6), M ⁶ is hydrogen or methyl; Z ⁷ is a single bond or an alkylene group with 1 to 5 carbon atoms, and the alkylene group is In the group, at least one hydrogen can be substituted by fluorine or chlorine, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, or -OCO-; R ⁷ is an alkyl group with 1 to 40 carbons , 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-. The liquid crystal composite as described in claim 1, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains a compound selected from formula (7), formula (8), and formula (9) The compound in is used as the main component,

In formula (7), formula (8), and formula (9), ring G, ring I, ring J, ring K, ring L, and ring M are 1,4-cyclohexyl, 1,4-phenylene Base, 1,4-cyclohexenyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or tertiary-2, 7-diyl, where at least one hydrogen can be fluorine, chlorine, cyano, hydroxyl, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons , an alkoxy group with 1 to 5 carbons, an alkoxycarbonyl group with 2 to 5 carbons, or an alkacyl group with 1 to 5 carbons; Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ , and Z ¹⁷ are Single bond, -O-, -COO-, -OCO-, or -OCOO-; Z ⁹ , Z ¹¹ , Z ¹⁴ , and Z ¹⁶ are single bonds, -OCH ₂ -, -CH ₂ O-, -COO- , -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C( CH ₃ )-, -C(CH ₃ )=N-, -N=N-, or -C≡C-; Z ¹⁵ is a single bond, -O- or -COO-; Y ² is hydrogen, fluorine, chlorine , trifluoromethyl, trifluoromethoxy, cyano, alkyl with 1 to 20 carbons, alkenyl with 2 to 20 carbons, alkoxy with 1 to 20 carbons, or alkoxy with 2 to 20 carbons Alkoxycarbonyl; f and h are integers from 1 to 4; k and m are integers from 0 to 3; the sum of k and m is 1 to 4; e, g, i, j, l, and n are 0 to Integer of 20; M ⁷ to M ¹² are hydrogen or methyl. The liquid crystal composite as described in item 1 of the scope of the patent application, wherein the first additive is at least one dichroic compound selected from benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and anthraquinones sex pigment. The liquid crystal composite as described in item 1 of the patent application, wherein based on the liquid crystal composition, the proportion of the first additive is in the range of 0.03% to 25%. The liquid crystal composite as described in item 1 of the 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 as described in claim 1, wherein the liquid crystal composite is obtained by using a polymerizable composition comprising a liquid crystal composition and a polymerizable compound as a precursor, and the polymerizable composition contains as an additive Photopolymerization initiator. A liquid crystal light-adjusting element, wherein the light-adjusting layer is the liquid crystal composite described in any one of items 1 to 17 of the scope of the patent application, and the light-adjusting layer is sandwiched by a pair of transparent substrates, and the transparent substrates have transparent electrodes. A dimming window using the liquid crystal described in item 18 of the patent application Dimming element.