Polymerizable composition for light-adjusting element, liquid crystal light-adjusting element, light-adjusting window, smart window, liquid crystal composite, and use thereof

Abstract

This invention provides a polymeric composition for a dimming element that exhibits good adhesion to a plastic film substrate with transparent electrodes, as well as improved light resistance and weather resistance; a liquid crystal dimming element; a dimming window; a smart window; and a liquid crystal composite with balanced properties suitable for dimming, using the composition, and its applications. The polymer precursors included with the liquid crystal composition contain at least one monofunctional polymeric compound with a non-cyclic structure having a nitrogen atom, a monofunctional polymeric compound with a cyclic structure, and a polyfunctional urethane (meth)acrylate oligomer.

Description

Technical Field

[0001] This invention primarily relates to a polymeric composition for dimming elements, a liquid crystal dimming element, a dimming window, a smart window, a liquid crystal composite, and their uses. More specifically, it relates to a polymeric composition for dimming elements, which is formed by combining a polymeric precursor with a liquid crystal composition having a positive dielectric constant anisotropy, and a liquid crystal dimming element using a liquid crystal composite obtained from said composition, and their uses. Background Technology

[0002] Liquid crystal dimming elements utilize methods such as light scattering. These elements are used in building materials such as window glass or room partitions, and in automotive parts. In addition to rigid substrates such as glass substrates, flexible substrates such as plastic films are also used in these elements.

[0003] In the liquid crystal composition held by these substrates, the arrangement of liquid crystal molecules changes by adjusting the applied voltage. This method allows control of the light transmitted through the liquid crystal composition, and therefore liquid crystal dimming elements are widely used in displays, optical shutters, dimming windows (Patent Document 1), smart windows (Patent Document 2), and the like.

[0004] One example of a liquid crystal dimming element is a polymer-dispersed element based on light scattering. The liquid crystal composition is dispersed within a polymer (liquid crystal composite). This element has the following characteristics: It is easy to fabricate. Film thickness can be easily controlled over a large area, thus enabling the fabrication of large-screen elements. No polarizer is required, thus enabling vivid displays. It has a wide field of view due to the utilization of light scattering. Because of these excellent properties, this element is expected to be used in dimming glass, projection displays, large-area displays, etc.

[0005] Another example is a polymer network type liquid crystal dimming element. In this type of element, a liquid crystal composition exists within a three-dimensional network of polymers. This composition is continuous, unlike the polymer dispersion type. This type of element also possesses the same characteristics as polymer dispersion type elements. Liquid crystal dimming elements that combine polymer network and polymer dispersion types also exist.

[0006] Liquid crystal compositions with appropriate properties are used in liquid crystal dimming elements. By improving the properties of the composition, elements with good properties can be obtained. The correlation between the properties of both is summarized in Table 1 below. The properties of the composition are further explained based on the element. The temperature range of the nematic phase is related to the temperature range in which the element can be used. The preferred upper limit temperature of the nematic phase is about 70°C or higher, and the preferred lower limit temperature of the nematic phase is about -20°C or lower. The viscosity of the composition is related to the response time of the element. In order to control the light transmittance, a short response time is preferred. Ideally, the response time is 1 millisecond shorter than that of other elements. Therefore, a low viscosity of the composition is preferred. Furthermore, a low viscosity at low temperatures is preferred. 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 element, a high elastic constant of the composition is preferred.

[0007] Table 1. Characteristics of Liquid Crystal Compositions and Liquid Crystal Dimming Elements

[0008] serial number Characteristics of liquid crystal compositions Characteristics of liquid crystal dimming elements 1 Nematic phases have a wide temperature range Wide operating temperature range 2 Low viscosity Short response time 3 Large optical anisotropy High haze 4 Positive or negative dielectric constants have greater anisotropy Low threshold voltage and low power consumption 5 High resistivity High voltage retention rate 6 Stable to light and heat Long lifespan 7 Large elastic constant Short response time

[0009] The optical anisotropy of the liquid crystal composition is related to the haze rate of the liquid crystal dimming element. Haze rate is the ratio of diffused light to total transmitted light. A high haze rate is preferred when blocking light. For a high haze rate, high optical anisotropy is preferred. High dielectric constant anisotropy of the composition contributes to a low threshold voltage or low power consumption in the element. Therefore, high dielectric constant anisotropy is preferred. High resistivity of the composition contributes to a high voltage retention rate in the element. Therefore, a composition with high resistivity in the initial stage is preferred. A composition with high resistivity after prolonged use is preferred. The stability or weather resistance of the composition to light or heat is related to the lifespan of the element. Good stability or heat resistance results in a long lifespan. Display defects such as image retention or droplet marks are also related to the lifespan of the element. An element with high weather resistance and low susceptibility to display defects is desirable. (Patent Document 3)

[0010] Liquid crystal dimming elements have a normal mode and a reverse mode. In normal mode, the element is opaque when no voltage is applied and becomes transparent when a voltage is applied. This mode is suitable for room partitions. In reverse mode, the element is transparent when no voltage is applied and becomes opaque when a voltage is applied. This mode is suitable for car windows because it becomes transparent when the element malfunctions. Research has also been conducted on dimming windows or smart windows with liquid crystal dimming elements, where neither the front nor back substrates are rigid substrates (glass or plastic sheets), but rather flexible plastic films are used, manufactured using a roll-to-roll process. (Patent Document 4) A transparent electrode (or further, an alignment film) is formed on the plastic sheet or plastic film, requiring good adhesion to the polymer formed within the liquid crystal layer.

[0011] (Patent Documents 5-8)

[0012] Patent documents 5 through 8 do not disclose or imply any combination of materials used to improve the sealing performance with the weather resistance and light resistance intended for outdoor use.

[0013] [Existing Technical Documents]

[0014] [Patent Literature]

[0015] [Patent Document 1] Japanese Patent Application Publication No. 06-273725

[0016] [Patent Document 2] International Publication No. 2011-096386

[0017] [Patent Document 3] International Publication No. 2019-026621

[0018] [Patent Document 4] Japanese Patent Application Publication No. 2019-105680

[0019] [Patent Document 5] Japanese Patent Application Publication No. 2011-026526

[0020] [Patent Document 6] Japanese Patent Application Publication No. 2011-074304

[0021] [Patent Document 7] Japanese Patent Application Publication No. 2011-105902

[0022] [Patent Document 8] Japanese Patent Application Publication No. 2011-105908 Summary of the Invention

[0023] [The problem the invention aims to solve]

[0024] The objective of this invention is to provide a polymeric composition for a dimming element that exhibits good adhesion to a plastic film substrate with transparent electrodes, as well as improved light resistance and weather resistance.

[0025] Another challenge is to provide a liquid crystal composite with balanced and dimming properties.

[0026] [Technical means to solve the problem]

[0027] The inventors, considering the possibility of further improving the characteristics of liquid crystal dimming elements, conceived of a method of incorporating a liquid crystal compound having a terphenyl structure or a cyano group into a portion of a liquid crystal composition. This is because liquid crystal composites with high optical anisotropy are expected to achieve high haze rates.

[0028] Furthermore, the results of the study on the aforementioned possibilities revealed that by combining specific liquid crystal compounds with specific polymeric compounds, it is possible to achieve both good adhesion and stability for outdoor use (weather resistance and light resistance), thereby obtaining a liquid crystal composite with balanced properties and suitable for dimming, thus completing the present invention.

[0029] This invention relates to a polymeric composition for a dimming element, the polymeric composition for a dimming element comprising a liquid crystal composition and a polymer precursor.

[0030] The liquid crystal composition comprises at least one compound selected from the compounds represented by formula (1) (as component A),

[0031] The polymer precursor contains at least one of a monofunctional polymerizable compound having a nitrogen atom and a noncyclic structure, at least one monofunctional polymerizable compound having a cyclic structure, and at least one polyfunctional urethane (meth)acrylate oligomer.

[0032] In addition, the present invention relates to a liquid crystal composite obtained by polymerizing a precursor, and a liquid crystal dimming element having said liquid crystal composite, etc.

[0033]

[0034] In equation (1), R 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; ring A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z 1It is a single bond, ethylidene, vinylidene, ethynylidene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X 1 and X 2 Each can be independently hydrogen or fluorine; Y 1 It is fluorine, chlorine, cyano, an alkyl group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, an alkoxy group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine; a is 1, 2, 3 or 4.

[0035] [The effects of the invention]

[0036] According to the present invention, by combining a liquid crystal composition with a specific polymeric compound, a polymeric composition for a dimming element can be obtained, which, when used with a plastic film substrate having a transparent electrode formed thereon, exhibits good adhesion between the polymer formed in the liquid crystal layer and the plastic film substrate with the transparent electrode, as well as good light resistance and weather resistance.

[0037] Furthermore, according to the present invention, a liquid crystal composite material can be obtained, which has excellent balanced properties such as high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, large optical anisotropy, large positive dielectric constant anisotropy, large resistivity, high light stability, high thermal stability, and large elastic constant, and also has properties suitable for dimming.

[0038] If the liquid crystal composite is used, 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 can be provided. Attached Figure Description

[0039] Figure 1 This is a schematic diagram of a liquid crystal dimming element (electrode layer not shown) representing the state of light passing through the dimming layer. When a voltage is applied between the upper and lower substrates, the liquid crystal compound aligns, the difference in refractive index between the polymer (which is the transparent material) and the liquid crystal composition decreases, and the scattering of incident light decreases.

[0040] Figure 2 This is a schematic diagram of a liquid crystal dimming element (electrode layer not shown) in the following state: when no voltage is applied between the upper and lower substrates, the liquid crystal compound exists in an unoriented manner, and when light is incident on the dimming layer, strong scattering of the incident light occurs at the interface due to the difference in refractive index between the polymer, which is a transparent material, and the liquid crystal composition.

[0041] Explanation of symbols

[0042] 1: Substrate with electrode layer

[0043] 2: Liquid crystal compounds

[0044] 3: Transparent substances Detailed Implementation

[0045] In this specification, the terms "liquid crystal compound," "polymeric compound," "liquid crystal composition," "polymeric composition," "liquid crystal complex," and "liquid crystal dimming element" are used. "Liquid crystal compound" is a general term for compounds having a liquid crystal phase such as a nematic or smectic phase, as well as compounds that, although not having a liquid crystal phase, are added to a composition for the purpose of adjusting properties such as the temperature range, viscosity, and dielectric anisotropy of the nematic phase. Such compounds, for example, have six-membered rings such as 1,4-cyclohexylene or 1,4-phenylene, and their molecules (liquid crystal molecules) are rod-like. "Polymeric compound" is a compound added for the purpose of forming a polymer in the liquid crystal composition. Liquid crystal compounds containing alkenyl groups are not classified as polymeric compounds in this sense.

[0046] A "liquid crystal composition" is prepared by mixing various liquid crystal compounds. Optically active compounds, antioxidants, UV absorbers, matting agents, pigments, defoamers, polar compounds, and other additives may be added to the liquid crystal composition as needed. Even when additives are added, the proportion of the liquid crystal compounds is expressed as a mass percentage (mass %) based on the liquid crystal composition excluding additives. The proportion of additives is expressed as a mass percentage based on the liquid crystal composition excluding additives. That is, the proportion of liquid crystal compounds or additives is calculated based on the total amount of liquid crystal compounds. Furthermore, sometimes the "mass" in "mass %" is omitted.

[0047] A "polymerizable composition" is prepared by mixing a polymerizable compound into 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 polymerization initiators and polymerization inhibitors may be added to the polymerizable compound as needed. The ratio of polymerization initiators and polymerization inhibitors is expressed as a mass percentage based on the total amount (total quantity) of the liquid crystal composition and the polymer precursor (polymerizable compound). Even when additives are added, the proportion of the polymerizable compound or liquid crystal composition contained in the polymerizable composition is expressed as a mass percentage based on the polymerizable composition without additives.

[0048] "Liquid crystal composite" is a composite of a polymer precursor and a liquid crystal composition, which is produced by polymerizing a polymeric composition.

[0049] "Liquid crystal dimming element" is a component with a liquid crystal composite, and it is a general term for liquid crystal panels and liquid crystal modules used for dimming.

[0050] Sometimes the "upper limit temperature of the nematic phase" is simply referred to as the "upper limit temperature." Sometimes the "lower limit temperature of the nematic phase" is simply referred to as the "lower limit temperature." The expression "increasing dielectric anisotropy" means a positive increase in the dielectric constant value for compositions with positive anisotropy, and a negative increase for compositions with negative anisotropy. "High voltage retention rate" means that the element has a high voltage retention rate not only at room temperature but also near the upper limit temperature in the initial stage, and that after long-term use, the element maintains a high voltage retention rate not only at room temperature but also near the upper limit temperature. Sometimes, the characteristics of a composition or element are studied through time-varying tests.

[0051]

[0052] The following explanation uses compound (1z) as an example. In formula (1z), the notations for α and β, enclosed by hexagons, correspond to ring α and ring β, respectively, and represent six-membered rings, fused rings, etc. When the subscript 'x' is 2, there are two rings α. The two groups represented by the two rings α can be the same or different. The rule applies to any two rings α when the subscript 'x' is greater than 2. The rule also applies to other notations such as bonding group Z. A diagonal line cut across one side of ring β indicates that any hydrogen on ring β can be substituted by a substituent (-Sp-P). The subscript 'y' indicates the number of substituted substituents. When the subscript 'y' is 0, there is no substitution. When the subscript 'y' is 2 or greater, there are multiple substituents (-Sp-P) on ring β. In this case, the rule of "can be the same or different" also applies. Furthermore, the rule also applies when the notation Ra is used in multiple compounds.

[0053] In formula (1z), for example, the statement "Ra and Rb are alkyl, alkoxy, or alkenyl" means that Ra and Rb are independently selected from the group consisting of alkyl, alkoxy, and alkenyl. That is, the group represented by Ra and the group represented by Rb may be the same or different.

[0054] Sometimes, at least one compound selected from the compounds represented by formula (1z) is simply referred to as "compound (1z)". "Compound (1z)" means one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1z). The same applies to compounds represented by other formulas. The statement "at least one compound selected from the compounds represented by formula (1z) and formula (2z)" means at least one compound selected from the group consisting of compounds (1z) and compounds (2z).

[0055] "Principal component" refers to the component that constitutes the largest proportion in a mixture or composition. For example, in a mixture of 40% compound (1z), 35% compound (2z), and 25% compound (3z), the principal component is compound (1z). When the component is only compound (1z), compound (1z) is also referred to as the principal component. When compound (1z) is a single compound, it is also referred to as the principal component.

[0056] The statement "at least one 'A'" means that the number of 'A's is arbitrary. Regarding the statement "at least one 'A' can be substituted by 'B'", when there is only one 'A', the position of the 'A' is arbitrary; when there are two or more 'A's, the positions of these 'A's can be chosen without restriction. Sometimes the statement "at least one -CH2- can be substituted by -O-" is used. In this case, -CH2-CH2-CH2- can be converted to -O-CH2-O- by substituting a non-adjacent -CH2- with -O-. However, the adjacent -CH2- will not be substituted with -O-. This is because the substitution would generate -OO-CH2- (peroxide).

[0057] The alkyl groups of the liquid crystal compounds contained in the liquid crystal composition are either straight-chain or branched, and do not contain cyclic alkyl groups. Straight-chain alkyl groups are preferred over branched alkyl groups. The same applies to terminal groups such as alkoxy and alkenyl groups. To increase the upper temperature limit, the stereoconfiguration associated with 1,4-cyclohexylene is trans configuration preferred over cis configuration.

[0058] Since 2-fluoro-1,4-phenylene is asymmetrical, it can be either left-facing (L) or right-facing (R).

[0059]

[0060] The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same also applies to bonding groups such as carbonyloxy groups (-COO- or -OCO-). In this invention, any of these can be used.

[0061] Furthermore, regarding composition, "based on total mass" refers to the mass ratio of each component in the total mass of all components in the composition or mixture, known as the "internal ratio." On the other hand, "relative to total mass" refers to the mass ratio of said component relative to the total mass of the composition or mixture, known as the "external ratio."

[0062] The present invention includes the following items, etc.

[0063] Item 1.

[0064] A polymeric composition for a dimming element comprises a liquid crystal composition, a polymer precursor, and a photopolymerization initiator.

[0065] The liquid crystal composition contains a liquid crystal compound represented by formula (1) as component A.

[0066] The polymer precursors respectively contain

[0067] At least one monofunctional polymerizable compound selected from the compounds represented by formula (M-1),

[0068] At least one monofunctional polymerizable compound selected from compounds represented by formula (M-2) having a cyclic structure, and

[0069] As a multifunctional polymerizable compound, it is selected from at least one of urethane (meth)acrylate oligomers having two or more (meth)acryloyl groups;

[0070]

[0071] (In equation (1), R) 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; ring A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z 1 It is a single bond, ethylidene, vinylidene, ethynylidene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X 1 and X 2 Each can be independently hydrogen or fluorine; Y 1 It is fluorine, chlorine, cyano, an alkyl group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, an alkoxy group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine; a is 1, 2, 3 or 4.

[0072]

[0073] In equation (M-1),

[0074] M 100 It is hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen-substituted alkyl group having 1 to 5 carbon atoms;

[0075] R 100 and R 101 Each is independently hydrogen or an alkyl or hydroxyalkyl group having 1 to 12 carbon atoms.

[0076] Of these alkyl or hydroxyalkyl groups, at least one -CH2- can be via -O-, -N(R) 102Substitution with -, -CO-, -COO-, or -OCO-, R 102 It is a hydrogen atom and an alkyl group having 1 to 12 carbon atoms;

[0077]

[0078] In equation (M-2),

[0079] M 101 It is hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen-substituted alkyl group having 1 to 5 carbon atoms;

[0080] Z 100 It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one hydrogen atom may be substituted with fluorine or chlorine, and at least one -CH2- may be substituted with -O-, -CO-, -COO- or -OCO-;

[0081] R 103 A monovalent group consisting of 5 to 35 carbon atoms, which is generated by removing a hydrogen atom from a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, or a carbocyclic or heterocyclic aromatic compound, wherein at least one -CH2- in the monovalent group may be substituted with -O-, -CO-, -COO-, or -OCO-.

[0082] Item 2.

[0083] According to the polymeric composition for dimming elements according to item 1, wherein the compound represented by formula (1) is at least one compound selected from the group consisting of compounds represented by formulas (1-1) to (1-48);

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090] (In equations (1-1) to (1-48), R) 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, X 1 and X 2 Each can be independently hydrogen or fluorine; Y 1It is a fluorine, chlorine, cyano group, an alkyl group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, an alkoxy group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine.

[0091] Item 3.

[0092] According to item 1 or item 2, the polymeric composition for a dimming element, wherein the proportion of component A is in the range of 5% to 90% by mass based on the mass of the liquid crystal composition.

[0093] Item 4.

[0094] The polymeric composition for a dimming element according to any one of items 1 to 3, wherein the liquid crystal composition further comprises a liquid crystal compound represented by formula (2) as component B;

[0095]

[0096] (In equation (2), R) 3 R is a group that bonds to the carbon atom of the ring C. 2 and R 3 Each is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine.

[0097] Ring B and ring C are independently 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or pyrimidin-2,5-diyl.

[0098] Z 2 It is a single bond, ethylidene, vinylidene, ethynylidene, methyleneoxy, or carbonyloxy.

[0099] b is 1, 2, or 3).

[0100] Item 5.

[0101] According to the polymeric composition for dimming elements described in claim 4, the liquid crystal composition contains at least one compound selected from the group consisting of liquid crystal compounds represented by formulas (2-1) to (2-23) as component B;

[0102]

[0103]

[0104] In equations (2-1) to (2-23), R 2 and R 3It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine.

[0105] Item 6.

[0106] According to item 4 or 5, the polymeric composition for dimming elements, wherein the proportion of component B is in the range of 5% to 90% by mass based on the mass of the liquid crystal composition.

[0107] Item 7.

[0108] The polymeric composition for a dimming element according to any one of items 1 to 6, wherein the liquid crystal composition contains a liquid crystal compound represented by formula (3) as component C;

[0109]

[0110] (In equation (3), R) 4 and R 5 Each of the following is independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms; ring D and ring F are independently 1,4-cyclohexene, 1,4-cyclohexene-enyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine, naphth-2,6-diyl, naphth-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chromoline-2,6-diyl, or chromoline with at least one hydrogen substituted by fluorine or chlorine. Orthoalkyl-2,6-diyl; 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-trifluoronaphthyl-2,6-diyl, 7,8-difluorochrome orthoalkyl-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z 3 and Z 4 Each is independently a single bond, ethylidene, vinylidene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3, and d is 0 or 1; the sum of c and d is less than 3).

[0111] Item 8.

[0112] According to item 7, the polymeric composition for dimming elements, wherein component C is at least one compound selected from the group consisting of compounds represented by formulas (3-1) to (3-35);

[0113]

[0114]

[0115]

[0116]

[0117] (In equations (3-1) to (3-35), R) 4 and R 5 Each of the following is independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms.

[0118] Item 9.

[0119] According to item 7 or item 8, the polymeric composition for dimming elements, wherein the proportion of component C is in the range of 3% to 25% by mass based on the mass of the liquid crystal composition.

[0120] Item 10.

[0121] According to the polymeric composition for dimming elements described in item 1, wherein the compound represented by formula (M-1) contains,

[0122] M 100 It can be hydrogen or methyl;

[0123] R 100 and R 101 Each is independently hydrogen, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, or a straight-chain hydroxyalkyl group having 1 to 10 carbon atoms, or a branched hydroxyalkyl group having 3 to 10 carbon atoms;

[0124] In these alkyl or hydroxyalkyl groups, at least one -CH2- may be via -O- or -N(R) 102 )- Replacement, R 102 It is a hydrogen or a straight-chain alkyl group having 1 to 10 carbon atoms;

[0125] The compound represented by formula (M-2) is at least one compound selected from the group consisting of compounds represented by formulas (M-2-1) to (M-2-10).

[0126] The urethane (meth)acrylate oligomer is selected from at least one group consisting of polyester-based urethane (meth)acrylate oligomers and polyether-based urethane (meth)acrylate oligomers, and has a weight average molecular weight in the range of 2,000 to 30,000.

[0127]

[0128] (In the formula, M) 101 It is hydrogen or methyl; n 100(where m is 0, 1, or 2, and m100 is an integer from 2 to 6).

[0129] Item 11.

[0130] The polymeric composition for a dimming element according to any one of claims 1 to 10 further comprises at least one polymeric compound having a phosphate site selected from the group consisting of compounds represented by formulas (M-3) and (M-4) as a precursor of the polymer;

[0131]

[0132] (In equations (M-3) to (M-4), M) 102 It is hydrogen or methyl; n 101 n 102 and n 103 (Independently 1 to 4).

[0133] Item 12.

[0134] The polymeric composition for a dimming element according to any one of claims 1 to 11 further comprises at least one polymeric compound selected from the group consisting of compounds represented by formula (M-5-E) and formula (M-5-P), and at least one polymeric compound selected from (meth)acrylate hydroxyalkyl esters as a precursor of said polymer;

[0135]

[0136] (In formulas (M-5-E) and (M-5-P), M) 501 For hydrogen or methyl, R 502 It is an alkyl group having 1 to 6 carbon atoms, and n is 1 to 30;

[0137] The hydrogen atoms in the ethylene glycol structure of formula (M-5-E) and the propylene glycol structure of formula (M-5-P) can be substituted by alkyl groups having 1 to 3 carbon atoms.

[0138] In (meth)acrylate hydroxyalkyl esters, the alkyl group is a straight-chain alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms.

[0139] Item 13.

[0140] The polymeric composition for a dimming element according to any one of items 1 to 12 further comprises at least one polymeric compound selected from the group consisting of compounds represented by formula (7), formula (8) and formula (9) as a precursor of the polymer;

[0141]

[0142] In formulas (7), (8), and (9), rings G, I, J, K, L, and M are independently 1,4-cyclohexene, 1,4-phenylene, 1,4-cyclohexenylene, pyridin-2,5-diyl, 1,3-dioxane-2,5-diyl, naphth-2,6-diyl, or fluorene-2,7-diyl, wherein at least one hydrogen atom in these groups may be substituted by fluorine, chlorine, cyano, hydroxyl, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkoxycarbonyl with 2 to 5 carbon atoms, or alkanoyl with 1 to 5 carbon atoms; Z 8 Z 10 Z 12 Z 13 and Z 17 Each can be independently a single bond, -O-, -COO-, -OCO-, or -OCOO-; Z 9 Z 11 Z 14 and Z 16 Each of these can be independently represented as a single bond, -OCH2-, -CH2O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF2O-, -OCF2-, -CH2CH2-, -CF2CF2-, -CH=CHCOO-, -OCOCH=CH-, -CH2CH2COO-, -OCOCH2CH2-, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH3)-, -C(CH3)=N-, -N=N-, or -C≡C-; Z 15 For single bonds, -O- or -COO-; Y 2 The carbon atoms are hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, straight-chain alkyl with 1 to 20 carbon atoms, straight-chain alkenyl with 2 to 20 carbon atoms, straight-chain alkoxy with 1 to 20 carbon atoms, or straight-chain alkoxycarbonyl with 2 to 20 carbon atoms; f and h are each independently integers from 1 to 4; k and m are each independently integers from 0 to 3; the sum of k and m is 1 to 4; e, g, i, j, l, and n are each independently integers from 0 to 20; M 7 To M 12 Each can be either hydrogen or methyl, independently.

[0143] Item 14.

[0144] The polymeric composition for a dimming element according to any one of items 1 to 13, wherein the proportion of the liquid crystal composition is in the range of 30% to 95% by mass based on the total mass of the liquid crystal composition and the polymer precursor, and the proportion of the polymer precursor is in the range of 5% to 70% by mass.

[0145] Item 15.

[0146] The polymeric composition for a dimming element according to any one of items 1 to 14, wherein the total mass of the liquid crystal composition and the polymer precursor is used as the basis for the composition.

[0147] The proportion of compound (M-1) ranges from 3% to 25% by mass.

[0148] The proportion of compound (M-2) ranges from 3% to 30% by mass.

[0149] The proportion of multifunctional urethane (meth)acrylate oligomers ranges from 5% to 25% by mass, wherein the total proportion of polymer precursors does not exceed 70% by mass.

[0150] The proportion of photopolymerization initiator ranges from 0.1% to 5% by mass, based on the total mass of the liquid crystal composition and the polymer precursor.

[0151] Item 16.

[0152] The polymeric composition for a dimming element according to any one of items 11 to 15, wherein the total mass of the liquid crystal composition and the polymer precursor is used as the basis for the composition.

[0153] The proportions of compounds (M-3) and (M-4) range from 0.001% by mass to 0.5% by mass.

[0154] Item 17.

[0155] The polymeric composition for a dimming element according to any one of items 12 to 16, wherein the total mass of the liquid crystal composition and the polymer precursor is used as the basis for the composition.

[0156] The total proportion of compound (M-5-E) and / or compound (M-5-P) to hydroxyalkyl methacrylate ranges from 2% by mass to 30% by mass.

[0157] Item 18.

[0158] A liquid crystal dimming element, wherein a dimming layer is sandwiched between a pair of transparent substrates having transparent electrodes, the dimming layer being a liquid crystal composite obtained by polymerizing the dimming element according to any one of claims 1 to 17 with a polymeric composition.

[0159] Item 19.

[0160] According to item 18, the liquid crystal dimming element wherein the transparent substrate comprises a glass plate, a plastic plate, or a plastic film.

[0161] Item 20.

[0162] The liquid crystal dimming element according to item 18 or 19, wherein the illuminance (180W / m²) is... 2The haze change rate before and after the weathering test was conducted under the conditions of irradiation time (100 hours) and tank temperature (35℃) was less than 20%.

[0163] Item 21.

[0164] A dimming window using a liquid crystal dimming element according to any one of items 18 to 20.

[0165] Item 22.

[0166] A smart window using a liquid crystal dimming element according to any one of items 18 to 20.

[0167] Item 23.

[0168] A liquid crystal composite is obtained by polymerizing a dimming element according to any one of items 1 to 17 with a polymeric composition.

[0169] Item 24.

[0170] An application of a liquid crystal composite, said liquid crystal composite according to claim 23, for use in a liquid crystal dimming element.

[0171] Item 25.

[0172] Use of a liquid crystal composite, the liquid crystal composite according to claim 23, in a liquid crystal dimming element in which the transparent substrate comprises a plastic plate or a plastic film.

[0173] Item 26.

[0174] An application of a liquid crystal composite, said liquid crystal composite according to claim 23, for use in a dimming window.

[0175] Item 27.

[0176] An application of a liquid crystal composite, said liquid crystal composite according to claim 23, for use in a smart window.

[0177] Item 28.

[0178] Use of a liquid crystal composite obtained by polymerizing a dimming element according to any one of claims 1 to 17 with a polymeric composition, for use in a liquid crystal dimming element in which the transparent substrate comprises a plastic plate or a plastic film.

[0179] This invention also includes the following items.

[0180] (a) A polymeric composition or liquid crystal composite for a dimming element as described above, wherein the liquid crystal composition contains Y in compound (1) of item 1. 1At least one compound of fluorine is used as component A.

[0181] (b) The dimming element polymeric composition or liquid crystal composite as described above, wherein the liquid crystal composition contains Y in compound (1) of item 1. 1 At least one compound with a cyano group is used as component A.

[0182] This invention also includes the following items.

[0183] (c) The polymeric composition or liquid crystal composite for the dimming element as described above, wherein the liquid crystal composition contains at least one compound selected from the compounds (1-1), (1-2), (1-3), (1-9), (1-13), (1-16), (1-21), (1-22), (1-23), (1-24), (1-27), (1-28), (1-33), (1-36), (1-41), (1-42), and (1-48) described in item 2 as component A.

[0184] This invention also includes the following items.

[0185] (d) The polymeric composition or liquid crystal composite for the dimming element as described above, wherein the liquid crystal composition contains at least one compound selected from the compounds (2-1), (2-2), (2-3), (2-4), (2-6), (2-9), (2-10), (2-12), (2-13), (2-14), (2-16), (2-17), (2-19), and (2-21) described in item 5 as component B.

[0186] This invention also includes the following items.

[0187] (e) The polymeric composition or liquid crystal composite for dimming elements as described above, wherein the liquid crystal composition contains at least one compound selected from the compounds (3-1), (3-5), (3-6), (3-7), (3-8), (3-12), (3-14), (3-19), and (3-34) described in item 8 as component C.

[0188] This invention also includes the following items.

[0189] (f) The liquid crystal composite as described above, wherein, based on the liquid crystal composite, the proportion of the polymer is in the range of 5% to 10% by mass, and the proportion of the liquid crystal composition is in the range of 95% to 90% by mass.

[0190] This invention also includes the following items.

[0191] (g) The liquid crystal composite as described above, wherein, based on the liquid crystal composite, the proportion of the polymer ranges from 5% to 70% by mass, and the proportion of the liquid crystal composition ranges from 95% to 30% by mass.

[0192] (h) The liquid crystal composite as described above, wherein, based on the liquid crystal composite, the proportion of the polymer ranges from 20% to 60% by mass, and the proportion of the liquid crystal composition ranges from 80% to 40% by mass.

[0193] (i) The liquid crystal composite as described above, wherein, based on the liquid crystal composite, the proportion of the polymer ranges from 30% to 45% by mass, and the proportion of the liquid crystal composition ranges from 70% to 55% by mass.

[0194] Furthermore, the ratio of polymer to liquid crystal composition in the liquid crystal composite is equivalent to the ratio of polymer precursor to liquid crystal composition in the polymeric composition.

[0195] This invention also includes the following items.

[0196] (j) The liquid crystal composite as described above, wherein the precursor of the liquid crystal composite is a polymeric composition for a dimming element, and the polymeric composition contains a liquid crystal composition, a polymeric compound, and a photopolymerization initiator.

[0197] This invention relates to a liquid crystal composite comprising a polymer and a liquid crystal composition having a nematic phase, and a liquid crystal dimming element having said composite. The liquid crystal composite comprises a nematic liquid crystal composition and a polymer.

[0198] The present invention will be described in the following order.

[0199] First, the polymeric composition will be described.

[0200] Second, the liquid crystal composition will be described.

[0201] Third, the main characteristics of the liquid crystal compound and the main effects of the compound on the liquid crystal composition or element are described.

[0202] Fourth, the combination or preferred ratio of liquid crystal compounds is described.

[0203] Fifth, the preferred morphology of the liquid crystal compound will be described.

[0204] Sixth, the preferred liquid crystal compounds will be described.

[0205] Seventh, a preferred form of the polymer precursor and an example thereof will be described.

[0206] Eighth, the synthesis methods of the constituent compounds are explained.

[0207] Ninth, the photopolymerization initiator added to the polymerizable composition is described.

[0208] Tenth, other additives that may be added to polymeric compositions are described.

[0209] Finally, the liquid crystal composite and liquid crystal dimming element are explained.

[0210] First, the polymeric composition will be described. The polymeric composition of the present invention is a polymeric composition for dimming elements. Hereinafter, it may also be simply referred to as a polymeric composition.

[0211] The polymeric composition is a precursor to a liquid crystal composite, which is generated by the polymerization of the polymer precursor.

[0212] The polymerizable composition is a mixture of a polymer precursor, a liquid crystal composition, and a photopolymerization initiator. When the polymerizable composition is placed into an element and polymerization is carried out, the polymer generated by polymerization undergoes phase separation, providing a liquid crystal composite. The amount of polymer in the liquid crystal composite is equivalent to the amount of the polymerizable precursor in the polymerizable composition. Furthermore, the quality of the photopolymerization initiator does not affect the quality of the polymer.

[0213] Components with liquid crystal complexes are classified into polymer-stabilized orientation type, polymer network type, and polymer dispersion type based on the polymerization of the polymer.

[0214] When the proportion of polymer is small, a polymer-stable alignment (PSA) element is generated. This is simply referred to as a PSA element. Example 1 of International Publication No. 2012-050178 describes the addition of a monomer at a concentration of 0.5 wt% relative to the liquid crystal material (paragraph 0105). According to this description, in a PSA element, a small amount of polymeric compound is added to the liquid crystal material (liquid crystal composition). In the PSA element, 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 element is shortened.

[0215] When the proportion of polymer is high, a polymerically dispersed element is formed. In this type of element, the liquid crystal composition is dispersed in the polymer like droplets. Each droplet is microencapsulated and discontinuous. The liquid crystal molecules are aligned along the inner wall of the capsule, thus in a random state. Because the refractive index of the polymer is different from that of the liquid crystal molecules, incident light is scattered. The element is opaque. When a voltage is applied to the element, the refractive index of the liquid crystal molecules changes. If the refractive index is the same as that of the polymer, the incident light passes through the element, and the element becomes transparent.

[0216] On the other hand, when the proportion of polymer is moderate, a polymer network type element is generated. In this type of element, the polymer has a three-dimensional grid structure, and the liquid crystal composition is surrounded by the grid and is continuous. The liquid crystal molecules are in a random state, and the element is opaque. When a voltage is applied to the element, the liquid crystal molecules align in the direction of the electric field, thus making the element transparent. For efficient light scattering, the proportion of the liquid crystal composition based on the liquid crystal complex is preferably large. When the droplet or grid is large, the driving voltage is low. Therefore, from the viewpoint of low driving voltage, the proportion of polymer is preferably small. When the droplet or grid is small, the response time is short. Therefore, from the viewpoint of short response time, the proportion of polymer is preferably large.

[0217] To scatter incident light and improve the adhesion between the dimming layer (liquid crystal composite) and the substrate, the preferred proportion of the polymer precursor, based on the mass of the polymeric composition, is in the range of 5% to 70% by mass. Further, based on the polymeric composition, the preferred proportion is in the range of 20% to 60% by mass. Particularly preferred, based on the polymeric composition, is in the range of 30% to 50% by mass.

[0218] When the proportion of the polymer precursor ranges from 5% to 70% by mass, polymer network type elements or polymer dispersion type elements are generated. Polymer network type and polymer dispersion type elements are mixed depending on the polymer proportion. Unlike PSA elements, these elements do not require a polarizing plate. In polymer network type elements, an alignment film is used as needed.

[0219] Based on the mass of the polymeric composition, the liquid crystal composition is preferably in the range of 30% to 95% by mass, and the polymer precursor is in the range of 5% to 70% by mass.

[0220] Second, the liquid crystal composition will be described. The composition contains a variety of liquid crystal compounds. The composition may also contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, polymerization initiators, polymerization inhibitors, polar compounds, etc. From the viewpoint of liquid crystal compounds, the composition is classified as composition A and composition B. Composition A may contain liquid crystal compounds selected from those represented by formula (1), and, as needed, those represented by formula (2) and those represented by formula (3) (referred to as compound (1), compound (2), and compound (3) respectively), as well as other liquid crystal compounds, additives, etc. "Other liquid crystal compounds" are liquid crystal compounds that are different from compounds (1), (2), and (3). The compounds are mixed in the composition for the purpose of further adjusting the properties.

[0221] Composition B substantially contains only liquid crystal compounds selected from compound (1), and optionally compounds (2) and (3). "Substantially" means that composition B may contain additives, but does not contain other liquid crystal compounds. Compared to composition A, composition B has fewer components. From the viewpoint of cost reduction, composition B is superior to composition A. From the viewpoint that properties can be further adjusted by mixing with other liquid crystal compounds, composition A is superior to composition B.

[0222] Third, the main characteristics of the liquid crystal compounds and their main effects on liquid crystal compositions or elements are described. The main characteristics of the liquid crystal compounds are summarized in Table 2. In Table 2, L indicates large or high, M indicates moderate, and S indicates small or low. The symbols L, M, and S are classifications based on qualitative comparisons between the component compounds, and 0 (zero) indicates extremely small.

[0223] Table 2. Properties of liquid crystal compounds

[0224] 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 constant anisotropy S~L 0 <![CDATA[M~L 1) ]]> resistivity L L L

[0225] 1) The value of the dielectric constant is negative for anisotropy, and the notation indicates the magnitude of the absolute value.

[0226] The main effects of each liquid crystal compound on the properties of the liquid crystal composition are described below.

[0227] Compound (1) can be used as component A and improves dielectric constant anisotropy.

[0228] Compound (2) can be used as component B and can increase the upper limit temperature or decrease the lower limit temperature.

[0229] Compound (3) can be used as component C and increases the dielectric constant of the short axis of the liquid crystal molecules.

[0230] Fourth, the combination or preferred proportion of the liquid crystal compounds will be described. Preferred combinations are component A + component B, component A + component C, or component A + component B + component C. Further preferred combinations are component A + component B or component A + component B + component C. It is also possible to combine one or two specific compounds selected from component A with component B (or component C). The same applies to component B or component C.

[0231] Based on the quality of the liquid crystal composition, in order to improve the dielectric constant anisotropy, the preferred proportion of component A is 5% by mass or more, and in order to lower the lower limit temperature, the preferred proportion of component A is 90% by mass or less. More preferably, the proportion is in the range of 10% by mass to 85% by mass. Particularly preferred is the proportion in the range of 20% by mass to 80% by mass.

[0232] Based on the mass of the liquid crystal composition, in order to increase the upper limit temperature or decrease the lower limit temperature, the preferred proportion of component B is 5% by mass or more, and in order to improve the dielectric constant anisotropy, the preferred proportion of component B is 90% by mass or less. More preferably, the proportion is in the range of 10% by mass to 85% by mass. Particularly preferred is the proportion in the range of 20% by mass to 80% by mass.

[0233] Based on the quality of the liquid crystal composition, in order to improve the dielectric constant of the liquid crystal molecules along the short axis, the preferred proportion of component C is 3% by mass or more, and in order to lower the lower limit temperature, the preferred proportion of component C is 25% by mass or less. More preferably, the proportion is in the range of 5% to 20% by mass. Particularly preferred is the proportion in the range of 5% to 15% by mass.

[0234] Fifth, the preferred form of the liquid crystal compound will be described. In formula (1), R 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. To improve stability to light or heat, R is preferred. 1 It is an alkyl group having 1 to 12 carbon atoms. In compounds (compounds (1-1) to (1-48), which are preferred examples of compound (1), R 1 The definitions and suitable forms are also the same.

[0235] In equation (2), R 2 and R 3 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms substituted with at least one hydrogen atom by fluorine or chlorine. To increase the upper limit temperature or decrease the lower limit temperature, R is preferred. 2 or R 3 The alkenyl group has 2 to 12 carbon atoms, and R is preferred to improve its stability to light or heat.2 or R 3 It is an alkyl group having 1 to 12 carbon atoms. In compounds (compounds (2-1) to (2-23), etc.) that are preferred examples of compound (2), R 2 and R 3 The definitions and suitable forms are also the same.

[0236] In equation (3), R 4 and R 5 It is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms. To improve stability to light or heat, R is preferred. 4 or R 5 The alkyl group having 1 to 12 carbon atoms is preferred, and R is preferred in order to improve the dielectric constant along the short axis of the liquid crystal molecules. 4 or R 5 It is an alkoxy group having 1 to 12 carbon atoms. In compounds (compounds (3-1) to (3-35), etc.) that are preferred examples of compound (3), R 4 and R 5 The definitions and suitable forms are also the same.

[0237] Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. To further reduce viscosity, methyl, ethyl, propyl, butyl, or pentyl alkyl groups are even more preferred.

[0238] Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, or heptoxy. To further reduce viscosity, methoxy or ethoxy groups are preferred.

[0239] 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. To reduce viscosity, vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl alkenyl groups are further preferred. The preferred stereoconfiguration of -CH=CH- in these alkenyl groups depends on the position of the double bond. For the purpose of reducing viscosity, etc., the trans configuration is preferred among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl. The cis configuration is preferred among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl.

[0240] Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. To reduce viscosity, allyloxy or 3-butenyloxy groups are further preferred.

[0241] Preferred examples of at least one hydrogen-substituted alkyl group are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl, or 8-fluorooctyl. Further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl to improve dielectric anisotropy.

[0242] Preferred examples of an alkenyl group substituted with at least one hydrogen atom 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. For reducing viscosity, 2,2-difluorovinyl or 4,4-difluoro-3-butenyl are further preferred examples.

[0243] Ring A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. To improve optical anisotropy, ring A is preferably 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3-fluoro-1,4-phenylene. To increase the upper temperature limit, the stereoconfiguration associated with 1,4-cyclohexylene is trans configuration preferred over cis configuration. Tetrahydropyran-2,5-diyl is...

[0244]

[0245] Preferred

[0246]

[0247] 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 pyrimidin-2,5-diyl. To increase the upper limit temperature or to decrease the lower limit temperature, ring B or ring C is preferably 1,4-cyclohexylene; to decrease the lower limit temperature, ring B or ring C is preferably 1,4-phenylene.

[0248] Ring D and ring F are 1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine, naphth-2,6-diyl, naphth-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chromoline-2,6-diyl, or chromoline-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine. To lower the lower limit temperature or to raise the upper limit temperature, ring D or ring F is preferably 1,4-cyclohexene; to lower the lower limit temperature, ring D or ring F is preferably 1,4-phenylene.

[0249] The 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-trifluoronaphthyl-2,6-diyl, 7,8-difluorochrome-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4).

[0250]

[0251] To reduce viscosity, the preferred ring E is 2,3-difluoro-1,4-phenylene, and to increase the dielectric constant along the short axis of the liquid crystal molecules, the preferred ring E is 4,6-difluorodibenzothiophene-3,7-diyl.

[0252] Z 1 It can be a single bond, ethylidene, vinylidene, ethynylidene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy. To increase the upper temperature limit, Z is preferred. 1 For single bonds, to improve dielectric anisotropy, Z is preferred. 1 It is a difluoromethyleneoxy group. Z is particularly preferred. 1 It is a single bond. Z 2 It is a single bond, ethylidene, vinylidene, ethynylidene, methyleneoxy, or carbonyloxy. For improved stability to light or heat, Z is preferred. 2 It is a single bond. Z 3 and Z 4 Each can be independently a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. To lower the lower limit temperature, Z is preferred. 3 or Z 4 For single bonds, in order to improve the dielectric constant along the short axis of the liquid crystal molecules, Z is preferred. 3 or Z 4 It is a methylene oxide. Z is particularly preferred. 3 or Z 4 It is a single key.

[0253] Divalent groups such as methyleneoxy groups are asymmetrical. Among methyleneoxy groups, -CH2O- is preferred over -OCH2-. Among carbonyloxy groups, -COO- is preferred over -OCO-. Among difluoromethyleneoxy groups, -CF2O- is preferred over -OCF2-.

[0254] a is 1, 2, 3, or 4. To lower the lower temperature limit, a is preferably 2; to improve dielectric anisotropy, a is preferably 3. b is 1, 2, or 3. To lower the lower temperature limit, b is preferably 1; to improve the upper temperature limit, b is preferably 2 or 3. c is 0, 1, 2, or 3, d is 0 or 1, and the sum of c and d is 3 or less. To lower the lower temperature limit, c is preferably 1; to improve the upper temperature limit, c is preferably 2 or 3. To improve the dielectric constant along the short axis of the liquid crystal molecules, d is preferably 0; to lower the lower temperature limit, d is preferably 1.

[0255] X 1 and X 2 It is either hydrogen or fluorine. To increase the upper temperature limit, X is preferred. 1 or X 2 For hydrogen, in order to improve the anisotropy of the dielectric constant, X is preferred. 1 or X 2 It is fluorine.

[0256] Y 1 It is a fluorine, chlorine, cyano group, an alkyl group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, an alkoxy group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine. For reducing viscosity, Y is preferred. 1 For fluorine, in order to improve dielectric anisotropy or refractive index anisotropy, γ is preferred. 1 It is a cyano group.

[0257] A preferred example of an alkyl group in which at least one hydrogen atom is substituted with fluorine or chlorine is trifluoromethyl. A preferred example of an alkoxy group in which at least one hydrogen atom is substituted with fluorine or chlorine is trifluoromethoxy. A preferred example of an alkenyloxy group in which at least one hydrogen atom is substituted with fluorine or chlorine is trifluorovinyloxy.

[0258] Sixth, a preferred liquid crystal compound is shown. The preferred compound (1) that can be used as component A is the compound represented by formula (1-1) to formula (1-48) as described in item 2 (referred to as compound (1-1) to compound (1-48) respectively).

[0259] The compound (1) that can be used as component A is preferably at least one of the following: compound (1-1), compound (1-2), compound (1-6), 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), compound (1-42), or compound (1-48).

[0260] Furthermore, it is preferred that at least two of the components A are...

[0261] Compounds (1-1) and (1-6),

[0262] Compounds (1-1) and (1-9),

[0263] Compounds (1-2) and compounds (1-9),

[0264] Compounds (1-2) and (1-16),

[0265] Compounds (1-9) and compounds (1-16),

[0266] Compounds (1-9) and compounds (1-24),

[0267] Compounds (1-9) and compounds (1-41),

[0268] Compounds (1-13) and (1-16),

[0269] Compounds (1-16) and (1-24),

[0270] Compounds (1-16) and (1-41),

[0271] Compounds (1-16) and compounds (1-42), or

[0272] Combinations of compounds (1-16) and (1-48).

[0273] Furthermore, multiple compounds (1-6), multiple compounds (1-9), multiple compounds (1-16), multiple compounds (1-29), and multiple compounds (1-41) can also be combined.

[0274] Through the presence of Y in compound (1) 1 When at least one compound containing fluorine is used as component A, there is a tendency for the dielectric constant anisotropy or refractive index anisotropy of the liquid crystal composition to increase. This is achieved by including Y in compound (1). 1 When at least one compound with a cyano group is used as component A, there is a tendency for improved compatibility between polymerizable and liquid crystal compounds.

[0275] The preferred compound (2) as component B is the compound represented by formulas (2-1) to (2-23) as described in item 5 (denoted as compounds (2-1) to (2-23) respectively). Among these compounds, at least one of component B is preferably compound (2-1), compound (2-2), compound (2-3), compound (2-6), compound (2-9), compound (2-10), compound (2-11), compound (2-12), compound (2-13), compound (2-16), compound (2-20), or compound (2-21).

[0276] Preferably, at least two of component B are

[0277] Compounds (2-2) and (2-9),

[0278] Compound (2-2) and compound (2-10),

[0279] Compounds (2-2) and (2-12),

[0280] Compounds (2-9) and (2-10),

[0281] Compounds (2-9) and (2-12),

[0282] Compounds (2-9) and (2-13),

[0283] Compounds (2-10) and (2-12), or

[0284] Compounds (2-12) and (2-13)

[0285] The combination of .

[0286] Furthermore, multiple compounds (2-9) or multiple compounds (2-12) can also be combined.

[0287] By utilizing compounds with a terphenyl structure, there is a tendency to increase the upper limit temperature of the liquid crystal phase. Furthermore, fluorine-substituted terphenyl liquid crystal compounds tend to exhibit improved compatibility with other liquid crystal compounds.

[0288] The preferred compound (3) that can be used as component C is the compound represented by formula (3-1) to formula (3-35) as described in item 8 (referred to as compound (3-1) to compound (3-35) respectively).

[0289] Among these compounds, at least one of component C is preferably compound (3-1), compound (3-3), compound (3-6), compound (3-8), compound (3-10), compound (3-14), or compound (3-34). Preferably, at least two of component C are combinations of 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 compound (3-6) and compound (3-14).

[0290] Seventh, a preferred form of the polymer precursor and an example thereof will be described. The polymer is derived from the polymer precursor through polymerization. The polymer precursor is a polymeric compound.

[0291] The polymer precursor used to ensure the adhesion between the electrode-bearing plastic film and the liquid crystal composite is preferably a combination of any one of the following: a monofunctional polymeric compound without a cyclic structure (M-1), a monofunctional polymeric compound with a cyclic structure (M-2), and a polyfunctional urethane (meth)acrylate oligomer.

[0292] Each polymerizable compound and urethane (meth)acrylate oligomer can be a single compound or a mixture of multiple compounds.

[0293] The preferred monofunctional polymerizable compound is the compound represented by formula (M-1) (compound (M-1)).

[0294]

[0295] In equation (M-1),

[0296] M 100 It is hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, preferably hydrogen or methyl.

[0297] R 100 and R 101 Each is independently hydrogen, a straight-chain alkyl or branched alkyl group having 1 to 12 carbon atoms, or a straight-chain hydroxyalkyl or branched hydroxyalkyl group having 1 to 12 carbon atoms, wherein at least one -CH2- can be emitted via -O- or -N(R) 102 Substitution with -, -CO-, -COO-, or -OCO-, R 102 It is a straight-chain alkyl or branched alkyl group with 1 to 12 carbon atoms.

[0298] Preferred

[0299] Each of the following is independently hydrogen, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, a straight-chain hydroxyalkyl group having 1 to 10 carbon atoms or a branched hydroxyalkyl group having 3 to 10 carbon atoms.

[0300] In these alkyl or hydroxyalkyl groups, at least one -CH2- may be via -O- or -N(R) 102 )- Replacement, R 102 It is a straight-chain alkyl group with hydrogen atoms and 1 to 10 carbon atoms.

[0301] The following are examples of preferred compounds (M-1).

[0302] N,N-dimethylacrylamide,

[0303] N,N-Diethylacrylamide,

[0304] Isopropylacrylamide,

[0305] N-(butoxymethyl)acrylamide,

[0306] N-(2-hydroxyethyl)acrylamide,

[0307] N-[3-(dimethylamino)ethyl]acrylamide,

[0308] N-[3-(dimethylamino)propyl]acrylamide.

[0309] Monofunctional polymerizable compounds with cyclic structures are those represented by formula (M-2) (compound (M-2)).

[0310]

[0311] In equation (M-2),

[0312] M 101 It is hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen-substituted alkyl group having 1 to 5 carbon atoms, Z. 100 It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one hydrogen atom may be substituted with fluorine or chlorine, and at least one -CH2- may be substituted with -O-, -CO-, -COO-, or -OCO-.

[0313] R 103 R is a monovalent group with 5 to 35 carbon atoms generated by removing a hydrogen atom from a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, or a carbocyclic or heterocyclic aromatic compound. 103At least one hydrogen contained therein may be substituted by an alkyl group having 1 to 12 carbon atoms, and at least one -CH2- may be substituted by -O-, -CO-, -COO- or -OCO-.

[0314] Preferably, it is at least one compound selected from the compounds represented by formulas (M-2-1) to (M-2-10).

[0315]

[0316] M 101 It is hydrogen or methyl, n 100 m is 0, 1, or 2. 100 It is an integer between 2 and 6.

[0317] The urethane (meth)acrylate oligomers having two or more (meth)acryloyl groups used as multifunctional polymerizable compounds are preferably polyester-based urethane (meth)acrylate oligomers, polyether-based urethane (meth)acrylate oligomers, and more preferably polyether-based urethane (meth)acrylate oligomers.

[0318] The weight average molecular weight is preferably in the range of 2,000 to 30,000, more preferably in the range of 5,000 to 15,000, and even more preferably in the range of 7,000 to 12,000.

[0319] The reason is that when the weight-average molecular weight is too small, the effect of hardening shrinkage increases and the adhesion tends to decrease. Conversely, when the weight-average molecular weight is too large (the chain length of the single bulk unit becomes too long), the density of the network structure decreases, and liquid crystal molecules easily enter between the molecular chains of oligomers. Therefore, there is a tendency for the interaction between the polymer interface and the liquid crystal compound to decrease, and for the driving voltage of the liquid crystal composition contained in the liquid crystal complex to decrease.

[0320] To further enhance adhesion, polymeric compounds (M-3) or (M-4) with phosphate sites can be added as polymer precursors.

[0321]

[0322] In equations (M-3) to (M-4),

[0323] M 102 It is hydrogen or methyl.

[0324] n 101 n 102 and n 103 Independently, they are 1 to 4.

[0325] Preferred n 101 n 102 and n103 Independently, it is 2.

[0326] Here, the role of polymer precursors will be explained.

[0327] A monofunctional polymerizable compound (M-1) with a nitrogen atom and a non-cyclic structure can control the glass transition temperature of the resulting polymer. When the polymerizable compound (M-1) has linear groups such as straight-chain alkyl or branched-chain alkyl groups, the glass transition temperature of the resulting polymer tends to be lower. A lower glass transition temperature of the polymer can reduce the driving temperature range of the liquid crystal composition contained in the liquid crystal composite. Furthermore, considering the strong interactions with the substrate interface or electrode interface, or with the urethane (meth)acrylate described later, it is envisioned that this will significantly contribute to improving adhesion.

[0328] The glass transition temperature of the resulting polymer can also be controlled by a monofunctional polymeric compound (M-2) with a cyclic structure. Polymeric compound (M-2) tends to increase the glass transition temperature of the resulting polymer. It is believed that the polymer obtained from polymeric compound (M-2) has a tendency to increase the elastic modulus compared to polymers using polymeric compound (M-1). Adhesion was evaluated in a peel test, which included both agglomerated peeling within the dimming layer and interfacial peeling at the interface. It is believed that an increase in elastic modulus can suppress agglomerated peeling within the dimming layer, leading to a tendency for improved adhesion to the supporting substrate.

[0329] For urethane (meth)acrylate oligomers containing monomeric units with linear structures in the polymer, if the chain length of the monomeric unit increases, the interaction between the polymer interface and the liquid crystal compound decreases, and the driving voltage of the liquid crystal composition contained in the liquid crystal composite tends to decrease. Therefore, in this invention, a predetermined molecular weight is used as described above. If the monomeric structure with linear structures contains an ether structure, the driving voltage of the liquid crystal composition contained in the resulting liquid crystal composite tends to decrease.

[0330] When the liquid crystal composite of this application is used as the dimming layer of a liquid crystal dimming element, in particular by combining a monofunctional polymeric compound (M-1) with a non-cyclic structure having nitrogen atoms, a monofunctional polymeric compound (M-2) with a cyclic structure, and a urethane (meth)acrylate oligomer, the adhesion between the dimming layer and the electrode (e.g., a plastic film with indium tin oxide (ITO)) interface tends to increase.

[0331] In addition, to improve the peel strength of the liquid crystal composite at the interface of the support substrate (e.g., the interface with the plastic film with the ITO electrode), a polymeric compound containing a non-liquid crystal phosphate site with a polar group can also be used. This polymeric compound is believed to initiate hydrogen bonds with hydroxyl groups present on the surface of the ITO electrode and enhance the interaction.

[0332] Based on the total mass of the liquid crystal composition and the polymer precursor.

[0333] The proportion of compound (M-1) is from 3% to 25% by mass, preferably from 5% to 25% by mass, and more preferably from 10% to 25% by mass.

[0334] The proportion of compound (M-2) is from 3% to 30% by mass, preferably from 10% to 25% by mass.

[0335] The proportion of multifunctional urethane (meth)acrylate oligomers is preferably in the range of 5% to 25% by mass.

[0336] The total proportion of polymer precursors shall not exceed 70% by mass.

[0337] To improve the adhesion between the dimming layer and the electrode (e.g., a plastic film with ITO (indium tin oxide)), the following mass ratio is ideal.

[0338] The mass ratio of the polymerizable compound (M-1) to the urethane (meth)acrylate oligomer ((M-1) / urethane (meth)acrylate oligomer) is preferably 3 / 1 to 1 / 3, more preferably 2 / 1 to 1 / 2.

[0339] Furthermore, the mass ratio of polymeric compound (M-1) to polymeric compound (M-2) ((M-1) / (M-2)) is preferably 3 / 1 to 1 / 3, more preferably 2 / 1 to 1 / 2. Based on the total mass of the liquid crystal composition and the polymer precursor, the preferred amount of polymeric compound (M-3) or compound (M-4) added (when both are used) is 0.001% by mass to 0.5% by mass, more preferably 0.01% by mass to 0.3% by mass.

[0340] In this invention, monofunctional polymeric compounds with linear or ether structures such as straight-chain alkyl or branched-chain alkyl groups, as represented by formulas (M-5), (M-5-E), and / or (M-5-P), may also be included, unlike compounds (M-1), (M-2), and urethane (meth)acrylate oligomers. Additionally, polyfunctional polymeric compounds with linear structures such as straight-chain alkyl or branched-chain alkyl groups (formula (M-6)) may also be included.

[0341] It can be used alone or with multiple monofunctional polymeric compounds.

[0342] It can be used alone or with a variety of multifunctional polymeric compounds.

[0343] Monofunctional polymeric compounds and polyfunctional polymeric compounds can be used together, or they can be used individually or in combination.

[0344] The main function of monofunctional polymerizable compounds with linear or ether structures such as straight-chain alkyl or branched-chain alkyl side chains is to improve the solubility of compounds (M-1), (M-2), and urethane (meth)acrylate oligomers in liquid crystal compositions. Furthermore, by maintaining the homogeneity of the polymerizable composition, the polymerized liquid crystal composite (e.g., the dimming layer of a liquid crystal dimming element) can have uniform scattering characteristics. The polymerizable compound can control the glass transition temperature of the resulting polymer. Polymers with linear or ether structures such as straight-chain alkyl or branched-chain alkyl side chains tend to have lower glass transition temperatures. If the glass transition temperature of the polymer is low, the driving temperature range of the liquid crystal composition contained in the liquid crystal composite can be reduced. While the reason is unclear, it is believed that if the chain length of the polymer's side chains increases or if it has an ether structure, the interaction between the polymer surface and the liquid crystal compound decreases. Additionally, if the chain length of the polymer's side chains increases or if the side chains contain an ether structure, the driving voltage of the liquid crystal composition contained in the resulting liquid crystal composite tends to decrease. The reason is also unclear, but it is believed to be due to the reduced interaction between the polymer surface and the liquid crystal compound.

[0345]

[0346] In formula (M-5),

[0347] M 501 It is hydrogen or methyl.

[0348] R 501 It is a hydrogen or an alkyl group having 1 to 20 carbon atoms, wherein at least one hydrogen atom may be substituted by an alkyl group having 1 to 12 carbon atoms, fluorine or chlorine, and at least one -CH2- may be substituted by -O-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C-.

[0349] In formulas (M-5-E) and (M-5-P),

[0350] M 501 It is hydrogen or methyl.

[0351] R 502 It is an alkyl group having 1 to 6 carbon atoms.

[0352] n is between 1 and 30.

[0353] The hydrogen atoms in the ethylene glycol structure of formula (M-5-E) and the propylene glycol structure of formula (M-5-P) can be substituted by alkyl groups having 1 to 3 carbon atoms.

[0354] In equation (M-6), M 601 Independently hydrogen or methyl,

[0355] R 601 It is an alkylene group having 1 to 40 carbon atoms, wherein at least one hydrogen atom may be substituted by an alkyl group having 1 to 20 carbon atoms, an alkyl ester of (meth)acrylate having 1 to 20 carbon atoms, an alkoxy ester of (meth)acrylate having 1 to 20 carbon atoms, an alkyl ester of (meth)acrylate having 1 to 20 carbon atoms, fluorine or chlorine, and at least one -CH2- atom may be substituted by -O-, -CO-, -COO- or -OCO-.

[0356] Examples of preferred compounds represented by formula (M-5) are the compounds represented by formulas (M-5-1) to (M-5-5) below.

[0357]

[0358] In the example of the preferred compound represented by formula (M-5-E),

[0359] M 501 Preferably hydrogen or methyl, more preferably hydrogen.

[0360] R 502 Preferably, it is an alkyl group having 1 to 6 carbon atoms, more preferably methyl, ethyl, or propyl.

[0361] n is preferably 1 to 30, more preferably 2 to 25.

[0362] Preferred examples include the following compounds.

[0363]

[0364] Examples of preferred compounds represented by formula (M-6) are the compounds represented by formulas (M-6-1) to (M-6-18) below.

[0365]

[0366]

[0367]

[0368] Here, a and b represent the number of bases recorded on the right side of these characters, respectively. The same meaning is also expressed in the following equations (M-6-17) and (M-6-18).

[0369]

[0370] The main function of polyfunctional polymerizable compounds with linear structures such as straight-chain alkyl or branched-chain alkyl groups is to increase the crosslinking density of the resulting polymer. Increased crosslinking density leads to improved reliability in properties such as moisture resistance, heat resistance, light resistance, and weather resistance.

[0371] Polymers containing polyfunctional polymers with linear structures such as linear alkyl or branched alkyl groups tend to have higher glass transition temperatures. If the crosslinking density increases and the polymer's glass transition temperature also increases, the interaction with the liquid crystal compound may also increase, leading to a rise in the driving voltage of the dimming layer. To maintain reliability while achieving low-voltage driving, it is ideal to avoid excessively high crosslinking densities. From this perspective, polyfunctional polymers with larger molecular weights or those containing a large number of ether bonds that readily result in a lower glass transition temperature after polymerization are preferred.

[0372] The preferred addition amount of monofunctional polymeric compounds having linear structures such as straight-chain alkyl or branched-chain alkyl, and polyfunctional polymeric compounds having linear structures such as straight-chain alkyl or branched-chain alkyl, relative to the total amount of polymer precursors, is 1% to 50% by mass, more preferably 3% to 30% by mass, and even more preferably 3% to 20% by mass.

[0373] In this invention, for the purpose of controlling scattering characteristics or improving heat resistance, a polymeric compound having a liquid crystal structure (mesogen structure) may also be included. The polymeric compound having a liquid crystal structure is copolymerized with the polymer precursor to form a polymer.

[0374] The polymeric compound having a preferred liquid crystal structure is a compound represented by formula (7), formula (8) or formula (9) (referred to as compound (7), compound (8) and compound (9) respectively).

[0375] The polymeric compound having a liquid crystal structure may also be a mixture of compounds selected from compound (7), compound (8) or compound (9).

[0376] The mixture may contain polymeric compounds different from compounds (7), (8) or (9).

[0377] In compounds (7), (8), and (9), rings G, I, J, K, L, and M are 1,4-cyclohexene, 1,4-phenylene, 1,4-cyclohexenylene, pyridin-2,5-diyl, 1,3-dioxane-2,5-diyl, naphth-2,6-diyl, or fluorene-2,7-diyl, wherein at least one hydrogen may be substituted with fluorine, chlorine, cyano, hydroxyl, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkoxycarbonyl with 2 to 5 carbon atoms, or alkanoyl with 1 to 5 carbon atoms. In compounds (7), (8), and (9), the preferred ring is 1,4-cyclohexene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-methoxy-1,4-phenylene, or 2-trifluoromethyl-1,4-phenylene. More preferably, the ring is 1,4-cyclohexene or 1,4-phenylene.

[0378] Z 8 Z 10 Z 12 Z 13 and Z 17 For single bonds, -O-, -COO-, -OCO-, or -OCOO-. Z 9 Z 11 Z 14 and Z 16 For single bonds, -OCH2-, -CH2O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF2O-, -OCF2-, -CH2CH2-, -CF2CF2-, -CH=CHCOO-, -OCOCH=CH-, -CH2CH2COO-, -OCOCH2CH2-, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH3)-, -C(CH3)=N-, -N=N-, or -C≡C-. Z 15 It can be a single bond, -O-, or -COO-. Z is preferred. 8 Z 10 Z 12 Z 13 or Z 17 It is a single bond or -O-. Z is preferred. 9 Z 11 Z 14 or Z 16 It can be a single bond, -OCH2-, -CH2O-, -COO-, -OCO-, -CH2CH2-, -CH2CH2COO-, or -OCOCH2CH2-.

[0379] Y 2It can be hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain alkenyl group having 2 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, or a straight-chain alkoxy carbonyl group having 2 to 20 carbon atoms. Preferred Y 2 It is a cyano, straight-chain alkyl, or straight-chain alkoxy group.

[0380] f and h are integers from 1 to 4; k and m are integers from 0 to 3, and the sum of k and m is from 1 to 4; e, g, i, j, l and n are integers from 0 to 20.

[0381] M 7 To M 12 It can be hydrogen or methyl.

[0382] An example of compound (7) is described below.

[0383]

[0384]

[0385] In equations (7-1) to (7-24), M 7 It is either hydrogen or methyl, and e is an integer from 1 to 20.

[0386] An example of compound (8) is described below.

[0387]

[0388]

[0389]

[0390] In equations (8-1) to (8-31), M 8 and M 9 It is hydrogen or methyl, and g and i are integers from 1 to 20.

[0391] An example of compound (9) is described below.

[0392]

[0393] In equations (9-1) to (9-10), M 10 M 11 and M 12 It is hydrogen or methyl, and j, l and n are integers from 1 to 20.

[0394] Compounds (7), (8), and (9) have at least one acryloyloxy group (-OCO-CH=CH2) or methacryloyloxy group (-OCO-(CH3)C=CH2). The liquid crystal compounds have liquidogens (rigid sites that initiate liquid crystallization), and these compounds also have liquidogens. Therefore, these compounds, together with the liquid crystal compounds, are oriented in the same direction by the action of an alignment film. This orientation is maintained after polymerization.

[0395] The liquid crystal composite obtained by polymerizing the dimming element with a polymeric composition has high transparency. To improve other properties, polymeric compounds different from compounds (7), (8), and (9) may also be used.

[0396] The preferred addition amount of compounds (7) to (9) is 3% to 50% by mass, more preferably 5% to 30% by mass, relative to the total amount of the polymer precursor.

[0397] Eighth, the synthesis methods of the constituent compounds are described. These compounds can be synthesized using known methods. Examples of synthesis methods are given. Compounds (1-9) and (1-16) are synthesized using the method described in Japanese Patent Application Publication No. 2-233626. Compound (2-1) is synthesized using the method described in Japanese Patent Application Publication No. 59-176221. Compound (3-1) is synthesized using the method described in Japanese Patent Application Publication No. 2-503441. Antioxidants are commercially available. Compound (11-1), described later, is available from Sigma-Aldrich Corporation. Compounds (11-2), etc., are synthesized using the method described in US Patent No. 3660505. Polymerizable compounds are commercially available or synthesized using known methods.

[0398] Compounds for which no synthetic method is described can be synthesized using methods described in the following publications: *Organic Syntheses* (John Wiley & Sons, Inc.), *Organic Reactions* (John Wiley & Sons, Inc.), *Comprehensive Organic Synthesis* (Pergamon Press), and *New Lectures in Experimental Chemistry* (Maruzen), etc. The composition is prepared using existing methods from compounds obtained in the manner described. For example, the component compounds are mixed and then dissolved into each other by heating.

[0399] Ninth, the photopolymerization initiator added to the polymerizable composition is described. The polymerizable composition of the present invention contains a photopolymerization initiator as an essential component. Suitable conditions for photopolymerization or suitable types and amounts of initiators are known to those skilled in the art and are described in the literature. For example, Omnirad 651 (registered trademark; IGM Resins), Omnirad 184 (registered trademark; IGM Resins) or Omnirad 1173 (registered trademark; IGM Resins) are suitable for free radical polymerization as photopolymerization initiators.

[0400] Regarding the preferred addition amount, based on the total mass of the liquid crystal composition and the polymer precursor, the proportion of the photopolymerization initiator is 0.1% to 5% by mass, more preferably 0.3% to 3% by mass. Furthermore, when the liquid crystal polymeric compound is contained together with the liquid crystal composition and the polymer precursor, the total amount becomes the total amount of the liquid crystal composition, the polymer precursor, and the liquid crystal polymeric compound.

[0401] Tenth, additives that can be added to polymeric compositions are described.

[0402] The additives include antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, polymerization initiators other than photopolymerization initiators, polymerization inhibitors, polar compounds, etc. The additives may also be pre-added to the liquid crystal composition or polymerizable compound.

[0403] Based on the total amount of the liquid crystal composition and the polymer precursor, the preferred addition amount is 0.1% to 5% by mass, more preferably 0.3% to 3% by mass. Furthermore, in the case of containing a polymeric compound having a liquid crystal structure, it becomes the ratio relative to the total amount of the liquid crystal composition, the polymer precursor, and the polymeric compound having a liquid crystal structure.

[0404] Furthermore, to impart a torsion angle by inducing a helical structure in the liquid crystal molecules, an optically active compound may be added to the polymerizable composition. Examples of such compounds are compounds (10⁻¹⁻¹) to (10⁻⁷⁻¹) represented by the following formulas. The preferred proportion of the optically active compound relative to the liquid crystal composition is 5% by mass or less. More preferably, the proportion is in the range of 0.01% by mass to 2% by mass.

[0405]

[0406]

[0407] To prevent a decrease in resistivity caused by heating in the atmosphere, or to maintain a high voltage retention rate not only at room temperature but also at temperatures close to the upper limit after prolonged use of the component, antioxidants such as compounds (11-1) to (11-3) represented by the following formulas may be added to the polymeric composition.

[0408]

[0409] Compounds with low volatility are effective in maintaining a high voltage retention rate not only at room temperature but also at temperatures close to the upper limit temperature after prolonged use of the component. To achieve this effect, the preferred proportion of the antioxidant relative to the total amount of the liquid crystal composition is 50 ppm by mass or more, and the preferred proportion of the antioxidant is 600 ppm by mass or less to avoid lowering the upper limit temperature or raising the lower limit temperature. More preferably, the proportion is in the range of 100 ppm by mass to 300 ppm by mass.

[0410] Preferred examples of ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, triazole derivatives, etc. Light stabilizers such as amines with steric hindrance are also preferred. Preferred examples of light stabilizers are compounds (12-1) to (12-16) represented by the following formulas. To obtain the aforementioned effect, the preferred proportion of these absorbers or stabilizers relative to the total amount of the liquid crystal composition is 50 ppm by mass or more, and the preferred proportion of these absorbers or stabilizers is 10,000 ppm by mass or less to avoid lowering the upper limit temperature or raising the lower limit temperature. More preferably, the proportion is in the range of 100 ppm by mass to 10,000 ppm by mass.

[0411]

[0412]

[0413] A matting agent is a compound that prevents the decomposition of a liquid crystal compound by accepting the light energy absorbed by the compound and converting it into heat energy. Preferred examples of matting agents are compounds (13-1) to (13-7), etc. To achieve the aforementioned effect, the preferred proportion of these matting agents is 50 ppm by mass or more, and to avoid raising the lower limit temperature, the preferred proportion of these matting agents is 20,000 ppm by mass or less relative to the total amount of the liquid crystal composition. More preferably, the proportion is in the range of 100 ppm by mass to 10,000 ppm by mass.

[0414]

[0415] To suit elements designed for guest-host (GH) mode, a dichroic dye is added to the composition as a pigment. Liquid crystal dimming elements are sometimes used for room partitions. In this case, a pigment is added to the polymeric composition for the purpose of absorbing specific light. Multiple pigments can be added. Liquid crystal dimming elements are sometimes used to block sunlight. In this case, a black (or blackish) dichroic dye is added to the liquid crystal composition. Black is prepared by mixing dichroic dyes of cyan, magenta, and yellow. A black dichroic dye is described in Example 42 of Japanese Patent Application Publication No. 2006-193742. This pigment is prepared by mixing three azo compounds with anthraquinones.

[0416] Examples of dichroic pigments include: benzothiadiazoles, diketopyrrolopyrroles, azo compounds, azomethine compounds, methine compounds, anthraquinones, merocyanines, naphthoquinones, tetrazines, pyrromethenes, and perylenes or rylenes such as terrylenes.

[0417] The dichroic pigment has at least several of the characteristics described below.

[0418] a) Pigment molecules are linear.

[0419] b) The central part of the molecule contains the backbone characteristic of dichroic pigments, such as a benzothiadiazole ring or a diketopyrrolopyrrole ring.

[0420] c) The benzene ring or thiophene ring that together with the unique skeleton of the molecule are located in the same plane.

[0421] d) The side chain is alkyl or alkoxy.

[0422] e) It has conjugated double bonds in the central part.

[0423] Preferred dichroic pigments are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, anthraquinones, and naphthalene-based pigments. Particularly preferred dichroic pigments are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and naphthalene-based pigments. The skeletons of these four pigments are shown below. For example, benzothiadiazoles refer to dichroic pigments having a benzothiadiazole ring.

[0424]

[0425] R and R' represent hydrocarbon groups with 1 to 30 carbon atoms that may have substituents, and may also have an azo group within the structure.

[0426] Examples of commercially available dichroic pigments include G-207, G-241, G-305, G-470, G-471, G-472, LSB-278, LSB-335, NKX-1366, NKX-3538, NKX-3540, NKX-3622, NKX-3739, NKX-3742, NKX-3773, NKX-4010, and NKX-4033 manufactured by Nagase Sangyo, and S-428, SI-426, SI-486, M-412, and M-483 manufactured by Mitsui Fine Chemicals.

[0427] Based on the weight of the liquid crystal composition, the preferred proportion of the dichroic pigment is in the range of 0.01% to 25% by mass. More preferably, it is in the range of 0.02% to 20% by mass. Particularly preferred is the range of 0.03% to 15% by mass.

[0428] To prevent foaming, defoamers such as dimethyl silicone oil and methylphenyl silicone oil can be added to the polymerizable composition. To achieve the desired effect, the preferred proportion of the defoamer relative to the total amount of the polymerizable composition is 1 ppm by mass or more; to prevent poor performance, the preferred proportion of the defoamer is 1000 ppm by mass or less. More preferably, the proportion is in the range of 1 ppm to 500 ppm by mass.

[0429] During the polymerization of polymerizable compounds, ultraviolet (UV) irradiation is preferred. Examples of UV irradiation lamps include metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and UV-LED lamps that can irradiate a single wavelength. When using a photopolymerization initiator, the wavelength of the UV light is preferably within the absorption wavelength region of the photopolymerization initiator, avoiding the absorption wavelength region of the liquid crystal composition. A wavelength of 330 nm or higher is preferred. More preferably, a wavelength of 350 nm or higher, for example, 365 nm, is also preferred. The reaction can be carried out near room temperature or by heating.

[0430] Typically, polymerization inhibitors are added to prevent polymerization when storing polymerizable compounds. Therefore, the polymer precursors used in this invention are usually mixed into the liquid crystal composition in a state where polymerization inhibitors have not been removed. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenanthridine, etc.

[0431] Polar compounds are organic compounds that are polar, distinct from compounds (M-1), (M-2), (M-3), or (M-4). They may also contain polymerizable groups. Compounds with ionic bonds are excluded here. 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 uneven distribution of partial charges among different types of atoms in the compound. For example, polar compounds may have at least one partial structure such as -OH, -COOH, -SH, -NH2, >NH, >N-, or an isocyanurate group or a sulfonate group.

[0432] As preferred compounds, examples include the following compound (14) or hydroxyalkyl methacrylate.

[0433] Specific examples of (meth)acrylate hydroxyalkyl esters can be listed as follows:

[0434] 2-Hydroxyethyl acrylate, 2-Hydroxyethyl methacrylate

[0435] 2-Hydroxypropyl acrylate, 2-Hydroxypropyl methacrylate

[0436] 3-Hydroxypropyl acrylate, 3-Hydroxypropyl methacrylate

[0437] 2-Hydroxybutyl acrylate, 2-Hydroxybutyl methacrylate

[0438] 4-Hydroxybutyl acrylate, 4-Hydroxybutyl methacrylate

[0439] 2-Hydroxypentyl acrylate, 2-Hydroxypentyl methacrylate.

[0440]

[0441] Based on the total mass of the liquid crystal composition and the polymer precursor, the preferred proportion of compound (14) is in the range of 1% to 10% by mass, more preferably in the range of 1% to 7% by mass.

[0442] Based on the total mass of the liquid crystal composition and the polymer precursor, the preferred proportion of (meth)acrylate hydroxyalkyl ester is in the range of 1% to 20% by mass, more preferably in the range of 3% to 15% by mass. It is believed that by combining (meth)acrylate hydroxyalkyl ester with compounds (M-5-E) and / or (M-5-P), the glass transition temperature of the polymer is reduced, and therefore it is expected that it can be driven in lower temperature environments as well.

[0443] The preferred combination of (meth)acrylate hydroxyalkyl esters is

[0444] 2-Hydroxyethyl acrylate, 2-Hydroxyethyl methacrylate, 2-Hydroxypropyl acrylate, 2-Hydroxypropyl methacrylate, 2-Hydroxybutyl acrylate, 2-Hydroxybutyl methacrylate, 4-Hydroxybutyl acrylate or 4-Hydroxybutyl methacrylate, more preferably 2-Hydroxyethyl acrylate, 2-Hydroxypropyl acrylate, 2-Hydroxybutyl acrylate or 4-Hydroxybutyl acrylate.

[0445] When used in combination with (meth)acrylate hydroxyalkyl ester and compound (M-5-E) and / or compound (M-5-P), the (meth)acrylate hydroxyalkyl ester is in the range of 5% to 10% by mass, and the compound (M-5-E) and / or compound (M-5-P) is in the range of 1% to 10% by mass, based on the total mass of the liquid crystal composition and the polymer precursor.

[0446] The polar groups interact non-covalently with the surfaces of glass substrates, metal oxide films, etc. The compounds are adsorbed onto the substrate surface through the action of the polar groups, controlling the orientation of liquid crystal molecules. The polar compounds not only control liquid crystal compounds but sometimes also polymerizable compounds. The aforementioned effects are expected with polar compounds.

[0447] The liquid crystal composite is prepared by polymerizing the polymeric composition.

[0448] When using a liquid crystal composite as the liquid crystal dimming layer of a liquid crystal dimming element, a polymeric composition can be used to prepare the liquid crystal dimming element, for example, as follows: First, the polymeric composition is sandwiched between a pair of substrates. At this time, it is preferable to drop or coat the polymeric composition at a temperature above the upper limit temperature using a vacuum injection method, liquid crystal drop addition method, etc. Preferably, the polymeric composition is in a homogeneous isotropic phase state from the start of the drop addition or coating until the polymeric composition undergoes polymerization. During the drop addition or coating, as a method of sandwiching a polymer-dispersed liquid crystal composition between two substrates, it can be performed by sandwiching the two substrates using a laminator or the like. With the two substrates sandwiched, the polymeric compound is then polymerized by light. At this time, as described above, polymerization is preferably performed by ultraviolet irradiation. Through polymerization, the polymer separates from the polymeric composition. Thus, a dimming layer is formed between the substrates, the dimming layer having the following layers: a layer containing a liquid crystal composition with dimming function; and a layer containing a polymer. The dimming layer is classified as polymer-dispersed, polymer network, or a mixture of both. The mesh size in the network structure is preferably small. A preferred mesh size is 0.2 μm to 2 μm, more preferably 0.2 μm to 1 μm, and especially preferably 0.3 μm to 0.7 μm.

[0449] Finally, the applications of the liquid crystal composite and liquid crystal dimming elements will be described. An example of a preferred application of the liquid crystal composite obtained as described above is a liquid crystal dimming element. The liquid crystal dimming element has a dimming layer comprising the liquid crystal composite and a pair of substrates, the dimming layer being sandwiched between the pair of substrates. The substrates have electrodes, which are typically arranged toward the dimming layer side (inner side). The substrates included in the liquid crystal dimming element are preferably transparent substrates, and it is preferable that the liquid crystal dimming element contains a pair of transparent substrates in a manner that sandwiches the dimming layer. Furthermore, the electrodes on the substrates are preferably transparent electrodes.

[0450] An example of a transparent substrate included in a liquid crystal dimming element is a plate made of a non-deformable material, such as a glass plate, a quartz plate, or a plastic plate (typically a transparent plastic plate), represented by an acrylic plate. Preferred examples of transparent substrates are glass plates and plastic plates (typically transparent plastic plates).

[0451] Other preferred examples of transparent substrates are plastic films such as polyethylene terephthalate (PET) films, acrylic films, and polycarbonate films, typically flexible transparent plastic films. Depending on the application, one of the substrates may also be an opaque material such as silicone.

[0452] The substrate has electrodes thereon, typically transparent electrodes. An alignment film may also be present on the transparent electrodes. Examples of transparent electrodes are indium tin oxide (tin-doped indium oxide, ITO) or conductive polymers.

[0453] Regarding the alignment layer that can be disposed on the substrate, suitable materials are thin films such as polyimide or polyvinyl alcohol. For example, a polyimide alignment film can be obtained by coating a polyimide resin composition onto a transparent substrate, thermosetting it at a temperature above 180°C, and rubbing it with cotton cloth or rayon cloth as needed.

[0454] Typically, a pair of substrates are positioned with the transparent electrode layer facing inward (towards the dimming layer). To ensure uniform thickness between the substrates, spacers may be incorporated. Examples of spacers include glass particles, plastic particles, alumina particles, and photo spacers. These spacers are included in the polymeric composition of the present invention and can be used as raw materials for the liquid crystal dimming element. The preferred thickness of the dimming layer is 2 μm to 50 μm, and more preferably 5 μm to 20 μm. The spacers may be pre-dispersed on the substrate or pre-mixed into the polymeric composition and coated onto the substrate simultaneously with the polymeric composition. When bonding the pair of substrates, a common sealant can be used. Examples of sealants include epoxy-based thermosetting compositions.

[0455] The polymeric composition can be coated onto the film substrate using either a discontinuous batch method or a continuous roll-to-roll method.

[0456] For example, a dimming film can be formed by coating a polymeric composition between film substrates and then polymerizing it under UV irradiation. Coating methods include microgravure coating and slot die coating. By selecting an appropriate coating method, dimming films can be manufactured.

[0457] In addition, substrates can also be produced using flexographic printing, gravure printing, UV offset printing, screen printing, and other printing methods. Furthermore, dimming films with textures such as borders, stripes, fabric patterns, gradients, and dots can be created using masking or other methods.

[0458] The optimal viscosity (at 25°C) of the polymerizable composition varies depending on the coating method, ranging from 10 mPa·s to 1000 mPa·s. When using a film substrate, a viscosity of 50 mPa·s to 500 mPa·s is preferred, and more preferably 100 mPa·s to 300 mPa·s. If the viscosity is too low, it will cause sagging; if the viscosity is too high, it will be difficult to control the film thickness.

[0459] The component may have a light absorption layer, a diffuse reflector, etc., configured on its back side as needed. It may also include additional functions such as specular reflection, diffuse reflection, regressive reflection, and holographic reflection.

[0460] The liquid crystal dimming element of the present invention can be used as an element for switching between transparent and light-scattering states. For example, by switching to a transparent state when no voltage is applied and switching to an opaque (light-scattering state) state when a voltage is applied, the liquid crystal dimming element can be used as a switching element.

[0461] According to the present invention, a liquid crystal dimming element with high durability against external light and low driving voltage can be obtained. The liquid crystal dimming element will be described below with reference to the accompanying drawings. Figure 1 and Figure 2 This is an example of a liquid crystal dimming element driven in normal mode. In normal mode, when... Figure 2 As shown, when no voltage is applied between the substrates, the liquid crystal compound exists in an unoriented form. When light is incident on the dimming layer, strong scattering of the incident light occurs at the interface due to the difference in refractive index between the polymer (which is a transparent material) and the liquid crystal composition. Therefore, light transmission is blocked. When as... Figure 1 As shown, when a voltage is applied between the substrates, the liquid crystal compound aligns. At this time, the difference in refractive index between the polymer (which is a transparent material) and the liquid crystal composition decreases, resulting in less scattering of incident light and light passing through the dimming layer.

[0462] In reverse mode, an alignment film is mounted at the electrode interface, and the liquid crystal compound exhibits an aligned state when no voltage is applied. (This is the state under voltage application in normal mode.) At this time, the difference in refractive index between the polymer (a transparent material) and the liquid crystal composition decreases, resulting in less scattering of light incident on the dimming layer, allowing light to pass through. In reverse mode, when a voltage is applied between the substrates, the liquid crystal alignment is disrupted, creating a difference in refractive index with the polymer, causing scattering of incident light and thus hindering light transmission.

[0463] The element functions as a dimming film or dimming glass. When the element is in film form, it can be applied to an existing window or sandwiched between two glass plates to form laminated glass. The element is used for windows installed on exterior walls or as partitions between conference rooms and corridors. That is, it can be used as electronic blinds, dimming windows, smart windows, etc. Furthermore, it can function as a light switch in applications such as LCD shutters.

[0464] Sometimes, changes occur over time due to prolonged use of the component. Sometimes, the haze rate changes compared to the initial stage. A small change in haze rate is preferable. When the haze rate changes little, a good state of transparency / opaqueness can be maintained. At an illuminance of (180 W / m²) 2The haze change rate before and after the weathering test, conducted under conditions of irradiation time (100 hours) and tank temperature (35°C), is preferably less than 20%. The haze change rate before and after the weathering test is further preferably less than 10%, and particularly preferably less than 5%.

[0465] The haze change rate is a crucial factor in the long lifespan of liquid crystal dimming elements. When testing the weather resistance of these elements, a small haze change rate before and after the change is preferable. To achieve a small haze change rate, it is important to select the type of liquid crystal compound, combine it with a specific polymerizable compound, and study the proportions of each component compound. For even better results, it is useful to investigate the type or amount of additives, polymerization conditions, etc.

[0466] [Example]

[0467] The present invention will be further described in detail through examples. The present invention is not limited to these examples. In the examples, compositions (M1), compositions (M2), etc., are described. Mixtures of compositions (M1) and (M2) are not described in the examples. However, such mixtures are considered to be disclosed. Mixtures selected from at least two compositions in the examples are also considered to be disclosed. The synthesized compounds are identified by methods such as nuclear magnetic resonance (NMR) analysis. The properties of the compounds, compositions, and components are determined by the following methods.

[0468] Measurement Methods: The characteristics were measured using the methods described below. These methods are mostly those described in the JEITA standard (JEITA·ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA), or modified versions thereof. The twisted nematic (TN) element used for measurement does not have a thin-film transistor (TFT) installed.

[0469] (1) Upper limit temperature of the nematic phase (NI; °C): The sample is placed on the heating plate of a melting point measuring apparatus including a polarizing microscope and heated at a rate of 1 °C / min. The temperature at which a portion of the sample changes from a nematic phase to an isotropic liquid is measured. Sometimes the upper limit temperature of the nematic phase is simply referred to as the "upper limit temperature".

[0470] (2) Lower limit temperature of nematic phase (TC; °C): The sample containing the nematic phase is placed in a glass bottle and stored in a freezer at 0 °C, -10 °C, -20 °C, -30 °C, and -40 °C for 10 days, and the liquid crystal phase is observed. For example, if the sample remains in the nematic phase at -20 °C and changes to a crystalline or laminar phase at -30 °C, TC is recorded as ≤-20 °C. Sometimes the lower limit temperature of the nematic phase is simply referred to as "lower limit temperature".

[0471] (3-1) Viscosity of the composition (volume viscosity; η; measured at 20°C; mPa·s): The E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.

[0472] (3-2) Viscosity of polymeric composition (volume viscosity; η; measured at 25°C; mPa·s): The E-type rotational viscometer (VISCOMETER TV-25 type) manufactured by Toki Industries Co., Ltd. was used for the measurement.

[0473] (4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s): The method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, p. 37 (1995), was used. A sample was placed in a TN element with a twist angle of 0° and a spacing (unit gap) of 5 μm between the two glass substrates. A voltage was applied to the element in 0.5 V increments within a range of 16 V to 19.5 V. After 0.2 seconds without voltage application, the voltage was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage application (2 seconds). The peak current and peak time of the transient current generated by the application were measured. The rotational viscosity was obtained based on these measured values ​​and the calculation formula (10) described on p. 40 of M. Imai et al.'s paper. The value of the dielectric constant anisotropy required in the calculation is obtained using an element that measures the rotational viscosity and by the method described below.

[0474] (5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25°C): Measurements were performed using light with a wavelength of 589 nm, employing an Abbe refractometer with a polarizing plate mounted on the eyepiece. The surface of the main prism was rubbed in one direction, and the sample was then dropped onto the prism. The refractive index n∥ was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index n⊥ was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated using the formula Δn = n∥ - n⊥.

[0475] (6) Dielectric constant anisotropy (Δε; measured at 25°C): A sample was placed in a TN element with a 9 μm gap (cell gap) between two glass substrates and a twist angle of 80 degrees. A sine wave (10V, 1kHz) was applied to the element, and the dielectric constant (ε∥) along the long axis of the liquid crystal molecules was measured after 2 seconds. A sine wave (0.5V, 1kHz) was applied to the element, and the dielectric constant (ε⊥) along the short axis of the liquid crystal molecules was measured after 2 seconds. The value of dielectric constant anisotropy was calculated using the formula Δε = ε∥ - ε⊥.

[0476] Methods for measuring the physical properties of liquid crystal dimming elements: The physical properties are measured by the following methods.

[0477] (1) Measurement of haze (%) of unit

[0478] The haze (%) was measured at room temperature by setting up a unit (liquid crystal dimming element) in the NDH5000 haze meter manufactured by NIPPON DENSHOKUINDUSTRIES Co.,LTD with the light source perpendicular to the unit surface.

[0479] (2) Rate of change of haze (%)

[0480] The units obtained in each embodiment and comparative example were placed in a xenon weather meter and irradiated with ultraviolet A under the conditions described below. The haze (%) was measured at room temperature for each unit.

[0481] The rate of change of haze was calculated as follows, based on the haze (%) of the unit before UVA irradiation and the haze (%) after UVA irradiation.

[0482] Haze change rate = (((Haze before UVA irradiation (%)) - (Haze after UVA irradiation (%))) / (Haze before UVA irradiation (%))) * 100

[0483] (3) Color difference change rate (%)

[0484] (3-1) Confirmation of color difference in unit

[0485] Using a JASCO V-650 spectrophotometer manufactured by Japan Spectrophotometer Co., Ltd., the transmittance of the unit was measured at wavelengths from 380 nm to 780 nm. Then, using spectral analysis of a color calculation software program (JASCO V-600 for Windows) conforming to the calculation formula described in Japanese Industrial Standard (JIS) Z8729-2004, the b* value based on the L*a*b* color table was calculated. Furthermore, the color difference value used to calculate the color difference change rate % of the unit described later was the value when a 60V electric field was applied to the unit at room temperature.

[0486] (3-2) Calculation method of color difference change rate (%) of unit

[0487] The units obtained in each embodiment and comparative example were placed in a xenon meteorometer and irradiated with UVA under the conditions described below. The color difference of the unit was measured (room temperature, 60V electric field applied).

[0488] The rate of change of color difference is calculated as follows.

[0489] The rate of change of color difference = (((color difference before UVA irradiation) - (color difference after UVA irradiation)) / (color difference before UVA irradiation)) * 100

[0490] (3-3) Weather resistance test of components: Haze (%) was measured before and after the test, and the haze change rate was calculated. The test was conducted according to Japanese Industrial Standard (JIS) K5600-7-7, Improving Weather Resistance and Improving Light Resistance (Xenon Lamp Method). A super xenon weather meter SX75 manufactured by Suga Testing Machine Co., Ltd. was used for the measurement. The measurement conditions were: illuminance (UVA; 180W / m²). 2 Irradiation time (100 hours), blackboard temperature (63℃±2℃), tank temperature (35℃), and tank relative humidity (40%RH). UVA refers to ultraviolet A.

[0491] (4) Driver confirmation

[0492] Unless otherwise specified, a system is considered capable of operation when a voltage is applied from a state of no voltage application at room temperature (25°C) and the haze (%) is below 100V.

[0493] (5) Evaluation of fit

[0494] The adhesion evaluation test used a STOROGRAPH VESO5D manufactured by Toyo Seiki Co., Ltd. A Nichiban NWBB-N30 film manufactured by Nichiban Co., Ltd. was applied across the entire width of a 25.0 mm wide and 200 mm long plastic sheet. A dimming film measuring 25 mm wide and 350 mm long was then applied as a test piece. The test piece was mounted on a testing machine, and the average peel force was determined when the test piece was peeled off one side in a 180° direction at a tensile speed of 100 mm / min and at 25°C. For each test piece, the average peel force was calculated based on the force-grip movement curve over a peel length of at least 100 mm beyond the initial 25 mm. The test continued until the adhesive length peeled off at least 125 mm, with at least three test pieces used. The average value was calculated and evaluated. Here, if the peel force is above 0.3 N / cm (0.1 N / inch), the adhesion is rated as good.

[0495] Examples of the compositions are shown below. Liquid crystal compounds are indicated by symbols based on the definitions in Table 3 below. In Table 3, the stereoconfiguration associated with 1,4-cyclohexylene is the trans configuration. The number in parentheses following the symbolized compound indicates the chemical formula to which the compound belongs. The symbol (-) refers to other liquid crystal compounds. Finally, the characteristic values ​​of the compositions are summarized.

[0496] Table 3. Representation of compounds using notations

[0497] R-(A1)-Z1-·····-Z n -(A n )-R'

[0498]

[0499] The following composition was used in the examples.

[0500] [Composition (M1)]

[0501]

[0502]

[0503] NI=96.1℃; η=28.3mPa·s; Δn=0.176; Δε=9.8

[0504] [Composition (M2)]

[0505]

[0506] NI=104.5℃; η=41.5mPa·s; Δn=0.216; Δε=12.5

[0507] [Composition (M3)]

[0508]

[0509] NI=95.4℃; η=35.5mPa·s; Δn=0.178; Δε=10.5

[0510] [Composition (M4)]

[0511]

[0512]

[0513] NI=90.4℃; Δn=0.193; Δε=7.9

[0514] [Composition (M5)]

[0515]

[0516] NI=120.9℃; Δn=0.213; Δε=10.2

[0517] [Composition (M6)]

[0518]

[0519] NI=102.2℃; Δn=0.098; Δε=7.1

[0520] [Composition (M7)]

[0521]

[0522] NI=98.2℃; Δn=0.156; Δε=7.4

[0523] [Composition (M8)]

[0524]

[0525] NI=89.3℃; Δn=0.171; Δε=9.5

[0526] [Composition (M9)]

[0527]

[0528]

[0529] NI=89.0℃; Δn=0.199; Δε=18.3

[0530] [Composition (M10)]

[0531]

[0532] NI=119.3℃; Δn=0.201; Δε=8.4

[0533] [Composition (M11)]

[0534]

[0535] NI=134.1℃; Δn=0.199; Δε=15.2

[0536] Polymerizable compounds are suitable to be selected from the following compounds.

[0537] Monofunctional monomers (M-1) can be listed as the following compounds.

[0538] N,N-Dimethylacrylamide, N,N-Diethylacrylamide, N-(Butoxymethyl)acrylamide, N-(2-Hydroxyethyl)acrylamide, N-[3-(Dimethylamino)propyl]acrylamide.

[0539] The following compounds are examples of monofunctional monomers (M-2) with cyclic structures.

[0540]

[0541] In this embodiment, (M-2-2-1), (M-2-7-1), and (M-2-10-1) are used.

[0542] As a multifunctional urethane (meth)acrylate oligomer,

[0543] The polyether-based urethane acrylate oligomer UN6202 (manufactured by Nejou Kogyo Co., Ltd.) with a weight average molecular weight of about 11,000 and the polyether-based urethane acrylate oligomer UN6207 (manufactured by Nejou Kogyo Co., Ltd.) with a weight average molecular weight of 27,000 are used.

[0544] As a polymerizable compound (M-3) having a phosphate group, M is used in formula (M-3), where M... 102 Methyl, n 101 Light Ester P-1M (manufactured by Kyoei Chemical Co., Ltd.) is 2%.

[0545] As polar compounds, hydroxyalkyl (meth)acrylates use 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate.

[0546] As monofunctional polymerizable compounds (formula (M-5-E)) having linear structures such as straight-chain alkyl or branched alkyl, compounds (M-5-E-1), (M-5-E-2), (M-5-E-3), and (M-5-E-4) can be used.

[0547] In this embodiment, Biscoat #190, CBA, and EEEA (manufactured by Osaka Organic Chemical Industry) were used as compound (M-5-E-1), and NK ester AM-130G (manufactured by Shin-Nakamura Chemical Industry) was used as compound (M-5-E-4).

[0548] [Example 1]

[0549] (1) Fabrication of liquid crystal dimming element

[0550] The composition (M4) has positive dielectric anisotropy.

[0551] Take 60% by weight of the composition (M4),

[0552] 10% by mass N,N-diethylacrylamide

[0553] 20% by weight of urethane acrylate oligomer UN6202, and

[0554] A mixture of 10% by mass of a polymeric compound (M-2-7-1)

[0555] Preparation of a polymerizable composition. Based on the total mass of the mixture of the liquid crystal composition and the polymerizable compound, Omnirad 651 (photopolymerization initiator; registered trademark; IGM resin) was added at a ratio of 0.4% by mass to prepare a polymerizable composition for dimming elements. The polymerizable composition for dimming elements is in an isotropic phase at room temperature (25°C). A 15 μm spacer was placed in the polymerizable composition for dimming elements, which was then coated onto a PET film with ITO (film thickness 125 μm) and laminated to another film using a laminator.

[0556] Secondly, a UV-LED irradiator (manufactured by AKS Corporation, LED irradiator AMU-35-DU / LED) was used to irradiate at room temperature (25°C) at 3J / cm². 2 Wavelength 365nm, Illuminance 15mW / cm 2 Ultraviolet light was used to fabricate a device with a liquid crystal composite. The resulting device was opaque. Applying a voltage of 60V to the device caused it to become transparent when exposed to light. Based on this result, the device is in normal mode.

[0557] (2) Evaluation of fit

[0558] Under the conditions described in determination (5), the peel force of the element was measured, and the peel force was 0.6 N / cm.

[0559] (3) Evaluation of the haze change rate after weathering test

[0560] The obtained element was placed inside the haze meter in a position perpendicular to the incident light. A voltage ranging from 0V to 60V was applied to the element, and the haze rate was measured. Next, the haze rate was measured after a weathering test under the conditions described in (3-3), and the haze change rate was calculated, which was approximately 5%.

[0561] [Example 2]

[0562] Take 60% by weight of the composition (M4),

[0563] 10% by mass N,N-diethylacrylamide

[0564] 20% by weight of urethane acrylate oligomer UN6202, and

[0565] A mixture of 10% by mass of a polymeric compound (M-2-2-1)

[0566] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0567] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.3 N / cm.

[0568] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 4%.

[0569] [Example 3]

[0570] Take 60% by weight of the composition (M4),

[0571] 15% by mass N,N-diethylacrylamide

[0572] 15% by weight of urethane acrylate oligomer UN6202, and

[0573] A mixture of 10% by mass of a polymeric compound (M-2-2-1)

[0574] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0575] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.8 N / cm.

[0576] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 5%.

[0577] [Example 4]

[0578] 55% by weight of the composition (M4),

[0579] 22.5% by mass of N,N-diethylacrylamide

[0580] 11.25% by weight of urethane acrylate oligomer UN6202, and

[0581] A mixture of 11.25% by mass of a polymeric compound (M-2-2-1)

[0582] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0583] The peel force of the element was measured using the same method as in Example 1, and the peel force was 2.3 N / cm.

[0584] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 5%.

[0585] [Example 5]

[0586] The composition (M5) has positive dielectric anisotropy.

[0587] Take 60% by weight of the composition (M5),

[0588] 20% by mass N,N-diethylacrylamide

[0589] 10% by weight of urethane acrylate oligomer UN6202, and

[0590] A mixture of 10% by mass of a polymeric compound (M-2-7-1)

[0591] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0592] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.3 N / cm.

[0593] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 5%.

[0594] [Example 6]

[0595] Take 60% by weight of the composition (M5),

[0596] 10% by mass N,N-diethylacrylamide

[0597] 10% by weight of urethane acrylate oligomer UN6202, and

[0598] A mixture of 20% by mass of a polymeric compound (M-2-7-1)

[0599] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0600] The peel force of the element was measured using the same method as in Example 1, and the peel force was 2.3 N / cm.

[0601] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 4%.

[0602] [Example 7]

[0603] Take 60% by weight of the composition (M5),

[0604] 15% by mass N,N-diethylacrylamide

[0605] 15% by weight of urethane acrylate oligomer UN6202, and

[0606] A mixture of 10% by mass of a polymeric compound (M-2-7-1)

[0607] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0608] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.8 N / cm.

[0609] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 5%.

[0610] [Example 8]

[0611] Take 60% by weight of the composition (M5),

[0612] 10% by mass N,N-diethylacrylamide

[0613] 10% by weight of urethane acrylate oligomer UN6202, and

[0614] A mixture of 20% by mass of a polymeric compound (M-2-2-1)

[0615] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0616] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.5 N / cm.

[0617] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 5%.

[0618] [Example 9]

[0619] Take 60% by weight of the composition (M5),

[0620] 20% by mass N,N-diethylacrylamide

[0621] 10% by weight of urethane acrylate oligomer UN6202, and

[0622] A mixture of 10% by mass of a polymeric compound (M-2-2-1)

[0623] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0624] The peel force of the element was measured using the same method as in Example 1, and the peel force was 2.5 N / cm.

[0625] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 4%.

[0626] [Example 10]

[0627] Take 60% by weight of the composition (M4),

[0628] 10% by mass N,N-diethylacrylamide

[0629] 19.8% by weight of urethane acrylate oligomer UN6202

[0630] 10% by mass of the polymeric compound (M-2-7-1), and

[0631] Mixed with 0.2% by weight of Light Ester P-1M.

[0632] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0633] The peel force of the element was measured using the same method as in Example 1, and the peel force was 11.4 N / cm.

[0634] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 5%.

[0635] [Example 11]

[0636] Take 60% by weight of the composition (M4),

[0637] 10% by mass N,N-diethylacrylamide

[0638] 19.8% by weight of urethane acrylate oligomer UN6202

[0639] 10% by mass of the polymeric compound (M-2-2-1), and

[0640] Mixed with 0.2% by weight of Light Ester P-1M.

[0641] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0642] The peel force of the element was measured using the same method as in Example 1, and the peel force was 10.2 N / cm.

[0643] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 4%.

[0644] [Example 12]

[0645] 60% by weight of the composition (M1),

[0646] 15% by mass N,N-diethylacrylamide

[0647] 15% by weight of urethane acrylate oligomer UN6202, and

[0648] A mixture of 10% by mass of a polymeric compound (M-2-7-1)

[0649] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0650] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.9 N / cm.

[0651] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 2%.

[0652] [Example 13]

[0653] Take 60% by weight of the composition (M2),

[0654] 15% by mass N,N-diethylacrylamide

[0655] 15% by weight of urethane acrylate oligomer UN6202, and

[0656] A mixture of 10% by mass of a polymeric compound (M-2-7-1)

[0657] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0658] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.7 N / cm.

[0659] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 3%.

[0660] [Example 14]

[0661] Take 60% by weight of the composition (M3),

[0662] 15% by mass N,N-diethylacrylamide

[0663] 15% by weight of urethane acrylate oligomer UN6202, and

[0664] A mixture of 10% by mass of a polymeric compound (M-2-7-1)

[0665] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0666] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.8 N / cm.

[0667] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 2%.

[0668] [Example 15]

[0669] The composition (M10) has positive dielectric anisotropy.

[0670] Take 60% by weight of the composition (M10),

[0671] 5% by mass N,N-diethylacrylamide

[0672] 10% by weight of urethane acrylate oligomer UN6202

[0673] 15% by mass of a polymeric compound (M-2-2-1),

[0674] 5% by weight of 4-hydroxybutyl acrylate, and

[0675] Mix 5% by mass of the compound (M-5-E-4),

[0676] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for a dimming element was formed. The polymerizable composition for the dimming element was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for the dimming element, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. Applying a voltage of 60V to the element caused it to become transparent upon illumination. Furthermore, by setting the driving temperature to 110°C or -40°C and applying a voltage of 60V to the element, it was confirmed that it also became transparent upon illumination. Based on these results, the element was in normal mode.

[0677] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.5 N / cm.

[0678] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 5%.

[0679] [Example 16]

[0680] Take 60% by weight of the composition (M10),

[0681] 5% by mass N,N-diethylacrylamide

[0682] 10% by weight of urethane acrylate oligomer UN6202

[0683] 15% by mass of a polymeric compound (M-2-2-1),

[0684] 5% by weight of 2-hydroxyethyl acrylate, and

[0685] Mix 5% by mass of the compound (M-5-E-1),

[0686] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for a dimming element was formed. The polymerizable composition for the dimming element was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for the dimming element, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. Applying a voltage of 60V to the element caused it to become transparent upon illumination. Furthermore, by setting the driving temperature to 110°C or -30°C and applying a voltage of 60V to the element, it was confirmed that it also became transparent upon illumination. Based on these results, the element was in normal mode.

[0687] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.9 N / cm.

[0688] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 4%.

[0689] [Example 17]

[0690] Take 60% by weight of the composition (M10),

[0691] 5% by mass N,N-diethylacrylamide

[0692] 10% by weight of urethane acrylate oligomer UN6202

[0693] 7% by mass of the polymeric compound (M-2-2-1),

[0694] 9% by weight of 2-hydroxyethyl acrylate, and

[0695] A mixture of 9% by mass of the compound (M-5-E-1),

[0696] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for a dimming element was formed. The polymerizable composition for the dimming element was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for the dimming element, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. Applying a voltage of 60V to the element caused it to become transparent upon illumination. Furthermore, by setting the driving temperature to 110°C or -40°C and applying a voltage of 60V to the element, it was confirmed that it also became transparent upon illumination. Based on these results, the element was in normal mode.

[0697] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.2 N / cm.

[0698] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 4%.

[0699] [Example 18]

[0700] Take 60% by weight of the composition (M11),

[0701] 5% by mass N,N-diethylacrylamide

[0702] 10% by weight of urethane acrylate oligomer UN6207

[0703] 10% by mass of a polymeric compound (M-2-2-1)

[0704] 5% by mass of the polymeric compound (M-2-10-1),

[0705] 2% by weight of 4-hydroxybutyl acrylate, and

[0706] A mixture of 8% by mass of the compound (M-5-E-1),

[0707] A polymerizable composition was prepared, with a photopolymerization initiator added in the same manner as in Example 1. The polymerizable composition was in an isotropic phase at room temperature (25°C). An element having a liquid crystal composite was fabricated using the same method as in Example 1, except that the polymerizable composition was used. The resulting element was opaque. Applying a voltage of 60V to the element caused it to become transparent upon illumination. Furthermore, by setting the driving temperature to 110°C or -30°C and applying a voltage of 60V to the element, it was confirmed that it also became transparent upon illumination. Based on these results, the element was in normal mode.

[0708] The peel force of the element was measured using the same method as in Example 1, and the peel force was 1.0 N / cm.

[0709] The haze change rate after the weathering test was calculated using the same method as in Example 1, and the result was approximately 3%.

[0710] [Comparative Example 1]

[0711] Take 60% by weight of the composition (M4),

[0712] 20% by weight of urethane acrylate oligomer UN6202, and

[0713] A mixture of 20% by mass of a polymeric compound (M-2-7-1)

[0714] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0715] On the other hand, the peel force of the element was measured using the same method as in Example 1, and the peel force was less than 0.1 N / cm.

[0716] [Comparative Example 2]

[0717] Take 60% by weight of the composition (M4),

[0718] 20% by mass of N,N-diethylacrylamide, and

[0719] A mixture of 20% by mass of a polymeric compound (M-2-7-1)

[0720] A polymerizable composition was prepared by adding a photopolymerization initiator in the same manner as in Example 1, and a polymerizable composition for dimming elements was prepared. The polymerizable composition for dimming elements was in an isotropic phase at room temperature (25°C). Except for using the polymerizable composition for dimming elements, an element having a liquid crystal composite was fabricated using the same method as in Example 1. The resulting element was opaque. When a voltage of 60V was applied to the element, it became transparent upon irradiation with light. Based on the results, the element was in normal mode.

[0721] On the other hand, the peel force of the element was measured using the same method as in Example 1, and the peel force was less than 0.1 N / cm.

[0722] Based on the above results, it can be seen that the elements of Examples 1 to 18 exhibit normal operation, good sealing, and a haze change rate of less than 10% after weathering tests, with minimal change over time. Therefore, we conclude that liquid crystal composites formed by combining specific nematic compositions with specific polymers can be suitable for use in liquid crystal dimming elements.

[0723] [Industry availability]

[0724] Liquid crystal dimming elements containing a liquid crystal composite obtained by polymerizing the dimming element of the present invention with a polymerizable composition can be used in dimming windows, smart windows, etc.

Claims

1. A polymeric composition for a dimming element, comprising a liquid crystal composition, a polymer precursor, and a photopolymerization initiator. The liquid crystal composition contains a liquid crystal compound represented by formula (1) as component A. The polymer precursors respectively contain At least one monofunctional polymerizable compound selected from the compounds represented by formula (M-1), At least one monofunctional polymerizable compound selected from compounds represented by formula (M-2) having a cyclic structure, and As a multifunctional polymerizable compound, it is selected from at least one of urethane (meth)acrylate oligomers having two or more (meth)acryloyl groups; In equation (1), R 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; ring A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z 1 It is a single bond, ethylidene, vinylidene, ethynylidene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X 1 and X 2 Each can be independently hydrogen or fluorine; Y 1 It is fluorine, chlorine, cyano, an alkyl group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, an alkoxy group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine; a is 1, 2, 3 or 4. In equation (M-1), M 100 It can be hydrogen or methyl; R 100 and R 101 Each is independently hydrogen, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, or a straight-chain hydroxyalkyl group having 1 to 10 carbon atoms, or a branched hydroxyalkyl group having 3 to 10 carbon atoms. In these alkyl or hydroxyalkyl groups, at least one -CH2- may be via -O- or -N(R) 102 )- Replacement, R 102 It is a hydrogen or a straight-chain alkyl group having 1 to 10 carbon atoms; In equation (M-2), M 101 It is hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen-substituted alkyl group having 1 to 5 carbon atoms; Z 100 It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one hydrogen atom may be substituted with fluorine or chlorine, and at least one -CH2- may be substituted with -O-, -CO-, -COO- or -OCO-; R 103 The monovalent group consisting of 5 to 35 carbon atoms, which can be substituted by an alkyl group having 1 to 12 carbon atoms, is generated by removing a hydrogen atom from a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, or a carbocyclic or heterocyclic aromatic compound, wherein at least one -CH2- in the monovalent group can be substituted by -O-, -CO-, -COO-, or -OCO-. The compound represented by formula (M-2) is at least one compound selected from the group consisting of compounds represented by formulas (M-2-1) to (M-2-10). The urethane (meth)acrylate oligomer is selected from at least one group consisting of polyester-based urethane (meth)acrylate oligomers and polyether-based urethane (meth)acrylate oligomers, and has a weight average molecular weight in the range of 2,000 to 30,000. In the formula, M 101 It is hydrogen or methyl; n 100 m is 0, 1, or 2. 100 It is an integer between 2 and 6.

2. The polymeric composition for dimming elements according to claim 1, wherein the liquid crystal compound represented by formula (1) is at least one compound selected from the group consisting of compounds represented by formulas (1-1) to (1-48); In equations (1-1) to (1-48), R 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, X 1 and X 2 Each can be independently hydrogen or fluorine; Y 1 It is a fluorine, chlorine, cyano group, an alkyl group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, an alkoxy group having 1 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine.

3. The polymeric composition for a dimming element according to claim 1 or 2, wherein the proportion of component A is in the range of 5% to 90% by mass, based on the mass of the liquid crystal composition.

4. The polymeric composition for a dimming element according to claim 1 or 2, wherein the liquid crystal composition further comprises a liquid crystal compound represented by formula (2) as component B; In equation (2), R 3 R is a group that bonds to the carbon atom of the ring C. 2 and R 3 Each is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine. Ring B and ring C are independently 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or pyrimidin-2,5-diyl. Z 2 It is a single bond, ethylidene, vinylidene, ethynylidene, methyleneoxy, or carbonyloxy. b can be 1, 2, or 3.

5. The polymeric composition for a dimming element according to claim 4, wherein the liquid crystal composition contains at least one compound selected from the group consisting of compounds represented by formulas (2-1) to (2-23) as component B; In equations (2-1) to (2-23), R 2 and R 3 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms that has at least one hydrogen atom substituted with fluorine or chlorine.

6. The polymeric composition for a dimming element according to claim 4, wherein the proportion of component B is in the range of 5% to 90% by mass, based on the mass of the liquid crystal composition.

7. The polymeric composition for a dimming element according to claim 1 or 2, wherein the liquid crystal composition contains a liquid crystal compound represented by formula (3) as component C; In equation (3), R 4 and R 5 Each of the following is independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms; ring D and ring F are independently 1,4-cyclohexene, 1,4-cyclohexene-enyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine, naphth-2,6-diyl, naphth-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chromoline-2,6-diyl, or chromoline with at least one hydrogen substituted by fluorine or chlorine. Orthoalkyl-2,6-diyl; 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-trifluoronaphthyl-2,6-diyl, 7,8-difluorochrome orthoalkyl-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z 3 and Z 4 Each is independently a single bond, ethylidene, vinylidene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3, and d is 0 or 1; the sum of c and d is less than 3.

8. The polymeric composition for a dimming element according to claim 7, wherein component C is at least one compound selected from the group consisting of liquid crystal compounds represented by formulas (3-1) to (3-35); In equations (3-1) to (3-35), R 4 and R 5 Each of the following is independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms.

9. The polymeric composition for a dimming element according to claim 7, wherein the proportion of component C is in the range of 3% to 25% by mass, based on the mass of the liquid crystal composition.

10. The polymeric composition for a dimming element according to claim 1 or 2, further comprising at least one polymeric compound having a phosphate site selected from the group consisting of compounds represented by formula (M-3) and formula (M-4) as a precursor of the polymer; In equations (M-3) to (M-4), M 102 It is hydrogen or methyl; n 101 n 102 and n 103 Independently, they are 1 to 4.

11. The polymeric composition for a dimming element according to claim 1 or 2, further comprising at least one polymeric compound selected from the group consisting of compounds represented by formula (M-5-E) and formula (M-5-P), and at least one polymeric compound selected from hydroxyalkyl methacrylates as a precursor of said polymer; In equations (M-5-E) and (M-5-P), M 501 For hydrogen or methyl, R 502 It is an alkyl group having 1 to 6 carbon atoms, and n is 1 to 30; The hydrogen atoms in the ethylene glycol structure of formula (M-5-E) and the propylene glycol structure of formula (M-5-P) can be substituted by alkyl groups having 1 to 3 carbon atoms. In (meth)acrylate hydroxyalkyl esters, the alkyl group is a straight-chain alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms.

12. The polymeric composition for dimming elements according to claim 1 or 2, further comprising at least one polymeric compound selected from the group consisting of compounds represented by formula (7), formula (8) and formula (9) as a precursor of the polymer; In formulas (7), (8), and (9), rings G, I, J, K, L, and M are independently 1,4-cyclohexene, 1,4-phenylene, 1,4-cyclohexenylene, pyridin-2,5-diyl, 1,3-dioxane-2,5-diyl, naphth-2,6-diyl, or fluorene-2,7-diyl, wherein at least one hydrogen atom in these groups may be substituted by fluorine, chlorine, cyano, hydroxyl, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkoxycarbonyl with 2 to 5 carbon atoms, or alkanoyl with 1 to 5 carbon atoms; Z 8 Z 10 Z 12 Z 13 and Z 17 Each can be independently a single bond, -O-, -COO-, -OCO-, or -OCOO-; Z 9 Z 11 Z 14 and Z 16 Each of these can be independently represented as a single bond, -OCH2-, -CH2O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF2O-, -OCF2-, -CH2CH2-, -CF2CF2-, -CH=CHCOO-, -OCOCH=CH-, -CH2CH2COO-, -OCOCH2CH2-, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH3)-, -C(CH3)=N-, -N=N-, or -C≡C-; Z 15 For single bonds, -O- or -COO-; Y 2 The carbon atoms are hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, straight-chain alkyl with 1 to 20 carbon atoms, straight-chain alkenyl with 2 to 20 carbon atoms, straight-chain alkoxy with 1 to 20 carbon atoms, or straight-chain alkoxycarbonyl with 2 to 20 carbon atoms; f and h are each independently integers from 1 to 4; k and m are each independently integers from 0 to 3; the sum of k and m is 1 to 4; e, g, i, j, l, and n are each independently integers from 0 to 20; M 7 To M 12 Each can be either hydrogen or methyl, independently.

13. The polymeric composition for a dimming element according to claim 1 or 2, wherein the proportion of the liquid crystal composition is in the range of 30% to 95% by mass, and the proportion of the polymeric precursor is in the range of 5% to 70% by mass, based on the total mass of the liquid crystal composition and the polymeric precursor.

14. The polymeric composition for a dimming element according to claim 1 or 2, wherein the composition is based on the total mass of the liquid crystal composition and the polymer precursor. The proportion of compound (M-1) ranges from 3% to 25% by mass. The proportion of compound (M-2) ranges from 3% to 30% by mass. The proportion of multifunctional urethane (meth)acrylate oligomers ranges from 5% to 25% by mass, wherein, The total proportion of polymer precursors shall not exceed 70% by mass. The proportion of photopolymerization initiator ranges from 0.1% to 5% by mass, based on the total mass of the liquid crystal composition and the polymer precursor.

15. The polymeric composition for a dimming element according to claim 10, wherein, based on the total mass of the liquid crystal composition and the polymer precursor, The proportions of compounds (M-3) and (M-4) range from 0.001% by mass to 0.5% by mass.

16. The polymeric composition for a dimming element according to claim 11, wherein, based on the total mass of the liquid crystal composition and the polymer precursor, The total proportion of compound (M-5-E) and / or compound (M-5-P) to hydroxyalkyl methacrylate ranges from 2% by mass to 30% by mass.

17. A liquid crystal dimming element, wherein a dimming layer is sandwiched between a pair of transparent substrates having transparent electrodes, the dimming layer being a liquid crystal composite obtained by polymerizing the dimming element as described in any one of claims 1 to 16 with a polymerizable composition.

18. The liquid crystal dimming element according to claim 17, wherein the transparent substrate comprises a glass plate, a plastic plate, or a plastic film.

19. The liquid crystal dimming element according to claim 17 or 18, wherein the illuminance is 180 W / m². 2 The haze change rate before and after the weathering test was conducted under the conditions of 100 hours of irradiation and 35°C in the tank was less than 20%.

20. A dimming window using a liquid crystal dimming element as claimed in any one of claims 17 to 19.

21. A smart window using a liquid crystal dimming element as described in any one of claims 17 to 19.

22. A liquid crystal composite obtained by polymerizing a dimming element as described in any one of claims 1 to 16 with a polymeric composition.

23. Use of a liquid crystal composite, wherein the liquid crystal composite is the liquid crystal composite as described in claim 22, in a liquid crystal dimming element.

24. Use of a liquid crystal composite, said liquid crystal composite as described in claim 22, in a liquid crystal dimming element in which the transparent substrate comprises a plastic plate or a plastic film.

25. Use of a liquid crystal composite, said liquid crystal composite as described in claim 22, in a dimming window.

26. Use of a liquid crystal composite, said liquid crystal composite as described in claim 22, in a smart window.

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