Polymer-dispersed liquid crystal composition and dimming element

Abstract

To provide a polymer-dispersed liquid crystal composition, a liquid crystal element and a dimming element having excellent adhesion to a base material, reliability, heat resistance, transmittance after heating, transparency at voltage ON and fast response in a low temperature range.SOLUTION: There is provided a polymer-dispersed liquid crystal composition comprising a polymerizable compound (MA) and a nonpolymerizable liquid crystal compound (LB). The polymerizable compound (MA) contains one or two or more chain monofunctional polymerizable compounds as a first component and one or two or more cyclic monofunctional polymerizable compounds as a second component. The copolymer Tg of the polymerizable compound (MA) is -10°C or less. A dye (CR) contains at least one blue dye compound, at least one red dye compound and at least one yellow dye compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymer-dispersed liquid crystal composition, a liquid crystal element obtained by using the polymer-dispersed liquid crystal composition, and a light-adjusting element using the liquid crystal element. The light-adjusting element includes light-adjusting elements used in smart windows, window glass, doors, partitions, private glass, etc. of buildings such as houses and buildings, light-adjusting elements used in glass windows, mirrors, roofs, etc. of automobiles, railroad cars, ships, aircraft, etc., light-adjusting elements used in light-adjusting optical shutters for digital cameras and smartphones, light-scattering plates for light sources for displays, light guide plates, reflectors for reflective displays and transparent displays, etc. [Background technology]

[0002] In the fields of transportation and architecture, various light control methods such as polymer dispersed liquid crystal (PDLC), guest host liquid crystal (GHLC), electrochromic (EC), and suspended particle device (SPD) have been applied as smart windows and smart glass that adjust the degree of transmission of external light to improve the comfort and convenience of spaces. Among them, polymer dispersed liquid crystal elements (PDLC), in which liquid crystal material is dispersed in a polymer matrix as particles, and polymer network liquid crystal elements (PNLC), in which liquid crystal material is interposed as a continuous phase in the voids of a polymer network, can switch the degree of light transmission / scattering by turning on and off the applied voltage using a light control layer (phase-separated liquid crystal layer). Furthermore, it is possible to form the light control layer directly on a transparent substrate with excellent flexibility, such as a plastic film. Here, the light control layer (phase-separated liquid crystal layer) is required to have high adhesion to the substrate, sufficient weather resistance and heat resistance, and to operate without functional degradation in a wide range of environmental temperatures from high to low. In addition, smart windows are required to have light-blocking properties depending on the purpose of improving comfort and the usage environment. In order to impart light-blocking properties to light-control films and light-control elements, light-control elements that have a light-blocking layer or a colored layer laminated on the light-control element have been put to practical use, but the balance between the light-blocking property in the scattering state and the transparency in the transparent state was not sufficient to meet market demands. In addition, conventional polymer-dispersed liquid crystal light-control elements with light-blocking colors that contain dyes in the light-control layer were not sufficient to meet market demands in terms of achieving a high degree of light-blocking of transmitted light in the scattering (light-blocking) state, the contrast between the light-blocking property in the scattering state and the transparency in the transparent state, and the high level of privacy.

[0003] In particular, when applied to the above-mentioned smart glass or smart window (SW), since the light of the polymer dispersed liquid crystal element or the entire surface of the polymer dispersed liquid crystal element is adjusted, generally, a voltage is applied to the entire surface in a simple configuration such as "transparent substrate, transparent electrode layer, phase separation liquid crystal layer (light adjustment layer), transparent electrode layer, transparent substrate" in that order. When used for smart windows, etc., high scattering is desired in the scattering state so that the state on the other side cannot be seen, and high transparency is required in the transparent state so that nothing is visible. In addition, since these states are electrically switched, it is desired that the liquid crystal element can be operated with a low driving voltage, and therefore the power consumption of the light adjustment element is low. In addition, from the viewpoint of productivity, it is important that the liquid crystal element can be directly formed on a flexible plastic substrate such as a polyethylene terephthalate (PET) film or a polycarbonate (PC) film by a roll-to-roll method. In order to produce by the roll-to-roll method, the adhesion (adhesion) between the substrate and the phase separation liquid crystal layer is an important characteristic. In addition, since smart windows, etc. may be used outdoors, high light resistance and high heat resistance are also required.

[0004] Patent Document 1 shows an example of realizing low-voltage driving by using a specific monomer compound, but there is a problem of insufficient adhesion. Patent Document 2 uses a specific liquid crystal compound to improve light resistance, and although a certain effect was observed in light resistance, there was a problem of insufficient light scattering. Patent Document 3 uses a specific polymerizable compound to improve adhesion, and although a certain effect was observed in adhesion, there was a problem of high driving voltage. Thus, a method for improving scattering, driving voltage, and adhesion in a well-balanced manner was required.

[0005] Furthermore, smart windows used in glass windows in automobiles, railroad cars, ships, aircraft, etc., are required to have a wide operating temperature range so that dimming can be performed without problems from the scorching heat of midsummer to the frigid cold of midwinter. Patent Document 4 proposes a liquid crystal composite made of a liquid crystal composition and a polymerizable compound, which can be used to prepare a liquid crystal light control element with improved weather resistance. Although a certain effect was observed in improving durability against external light, the driving properties and high-speed response in low temperature ranges (for example, -10°C to -30°C) were not investigated. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 6-208107 [Patent Document 2] JP 2007-91850 A [Patent Document 3] JP 2011-026526 A [Patent Document 4] Patent Publication No. 2021-066875 Summary of the Invention [Problem to be solved by the invention]

[0007] As described above, it was necessary for the light control element to operate in a wide temperature range, particularly in applications where it is installed in places exposed to the outside air, such as windows in buildings, and in applications where it is used in a wide range of temperature environments, including the scorching heat of midsummer and the extreme cold of midwinter, such as automobiles, railway vehicles, ships, and aircraft. That is, it was necessary for the light control element to satisfy properties such as scattering in the scattering state, transparency in the transparent state, and driveability with a practically acceptable response time, over a wide range of temperatures from practically high to low temperatures, and in particular, it was necessary to achieve excellent levels of scattering, transparency, and response in the low temperature range. In order to achieve excellent response at low temperatures, it was necessary to maintain a low drive voltage at low temperatures.

[0008] Therefore, the problem to be solved by the present invention is to obtain a polymer-dispersed liquid crystal composition capable of producing a liquid crystal light-controlling element having excellent light-blocking properties in a scattered (light-blocking) state, transparency in a transparent state, high-speed response in a practical temperature range, and light resistance, and to obtain a liquid crystal element and a light-controlling element using the same. [Means for solving the problem]

[0009] As a result of extensive investigations aimed at solving the above problems, the present inventors have found that by using a polymerizable compound (MA) exhibiting a specific copolymer Tg, a polymer dispersed liquid crystal composition can be obtained that can be used to fabricate a liquid crystal light control element that has high transparency in the transmitting state at low temperatures, a low driving voltage, and excellent low temperature response and adhesion, and that a liquid crystal element and a light control element using this can be obtained, thereby completing the present invention. That is, the present invention provides the following polymer dispersed liquid crystal composition, liquid crystal device, and light control device.

[0010] [1] A polymer-dispersed liquid crystal composition comprising a polymerizable compound (MA), a non-polymerizable liquid crystal compound (LB), and a dye (CR), the polymerizable compound (MA) contains, as a first component, one or more linear monofunctional polymerizable compounds, and contains, as a second component, one or more cyclic monofunctional polymerizable compounds; The copolymer Tg of the polymerizable compound (MA) is −10° C. or lower, The dye (CR) is a polymer-dispersed liquid crystal composition containing at least one type of blue dye compound, at least one type of red dye compound, and at least one type of yellow dye compound. [2] The polymer dispersed liquid crystal composition according to [1], wherein at least one of the linear monofunctional polymerizable compounds of the first component has a homopolymer Tg value of −30° C. or lower. [3] The polymer dispersed liquid crystal composition according to [1] or [2], wherein at least one of the cyclic monofunctional polymerizable compounds of the second component has a homopolymer Tg value of 40° C. or less. [4] The polymer dispersed liquid crystal composition according to any one of [1] to [3], wherein the nematic-isotropic phase transition point (Tni) of the non-polymerizable liquid crystal compound (LB) is 110° C. or higher and 180° C. or lower. [5] A pair of transparent electrode substrates; A light control element having a liquid crystal polymer composite including a polymer network and a liquid crystal compound, the liquid crystal polymer composite being disposed between the transparent electrode substrates, the polymer network is a polymer network derived from the polymerizable compound (MA) contained in the polymer dispersed liquid crystal composition according to any one of [1] to [4]; A light control element, wherein the liquid crystal compound is a non-polymerizable liquid crystal compound (LB) contained in the polymer dispersion type liquid crystal composition according to any one of [1] to [4]. [6] The light control element according to [5], wherein the pair of transparent electrode substrates are made of a flexible material. [7] The light-adjustable element according to [5], wherein the degree of scattering is 1.5 or less when measured and analyzed based on the detection angle dependency of forward scattered light of straight transmitted light. [8] The light control element according to [5], having a diffuse transmittance of 20% or less according to JIS K7136 (test method for haze of plastic and transparent materials). [9] The light control element according to [5], wherein a contrast ratio of total light transmittance TT [TT (transparent state) / TT (light-shielding state)] is 2.0 or more.

[10] The light control element according to [3], which switches to a light-blocking state when no voltage is applied and to a transparent state when a voltage is applied.

[11] A window comprising the photochromic element according to [5]. Effect of the Invention

[0011] According to the present invention, a polymer dispersed liquid crystal composition is obtained that can be used to prepare a liquid crystal light control element that has high transparency in the transmitting state in the low temperature range, a low driving voltage, and excellent low temperature response and adhesion, and a liquid crystal element and a light control element using the same can be obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The polymer-dispersed liquid crystal composition of the present invention and a polymer-dispersed liquid crystal element using the same will now be described. It should be noted that the present embodiment is described as a specific example to allow a better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

[0013] <Polymer dispersed liquid crystal composition> A polymer-dispersed liquid crystal composition according to an embodiment of the present invention (polymer-dispersed liquid crystal composition according to this embodiment) contains a polymerizable compound (MA), a non-polymerizable liquid crystal compound (LB), and a dye (CR). The polymerizable compound (MA) contains one or more chain-like monofunctional polymerizable compounds as a first component, and one or more cyclic monofunctional polymerizable compounds as a second component. The copolymer Tg of the polymerizable compound (MA) is −10° C. or less, and preferably −50° C. or more and −10° C. or less. The dye (CR) contains at least one blue dye compound, at least one red dye compound, and at least one yellow dye compound. The non-polymerizable liquid crystal compound (LB) preferably has a nematic-isotropic phase transition point (Tni) of 110° C. or more and 180° C. or less. At least one of the linear monofunctional polymerizable compounds of the first component preferably has a homopolymer Tg value of −30° C. or less. At least one of the cyclic monofunctional polymerizable compounds of the second component more preferably has a homopolymer Tg value of 40° C. or less.

[0014] The "copolymer Tg" in the present invention is a value obtained by a known calculation method using the homopolymer Tg of the chain monofunctional polymerizable compound as the first component, which is an essential component contained in the polymer dispersion type liquid crystal composition, the homopolymer Tg of the cyclic monofunctional polymerizable compound as the second component, and, as necessary, the homopolymer Tg of each polymerizable compound other than the first component and the second component described below. The Tg[K] of a copolymer consisting of multiple components can be expressed by the following formula (Formula 1) (called the FOX formula), where the Tg[K] of homopolymers 1, 2, … are Tg1, Tg2, …, respectively, and the weight ratios are C1, C2, ….

[0015] (1 / Tg)=(C1 / Tg1)+(C2 / Tg2)+ (Formula 1)

[0016] Methods for measuring the "homopolymer Tg" of the present invention include dynamic viscoelasticity (DMA), thermomechanical analysis (TMA), differential scanning calorimetry (DSC), and the like. Here, the dynamic viscoelasticity is measured by a resonance oscillation method, that is, the viscoelasticity is measured by using a cured homopolymer as a sample while resonating under a temperature sweep, and the peak top temperature of the loss modulus G" can be regarded as the Tg (glass transition point) of the homopolymer.

[0017] In the polymer dispersion type liquid crystal composition of the present embodiment, the weight ratio (LB / MA) of the non-polymerizable liquid crystal compound (LB) to the polymerizable compound (MA) is preferably in the range of 30 / 70 to 70 / 30, more preferably 40 / 60 to 60 / 40, further preferably 45 / 55 to 60 / 40, and particularly preferably 50 / 50. Each component constituting the polymerizable compound (MA), each component constituting the non-polymerizable liquid crystal compound (LB), and the dye (CR) will be specifically described below.

[0018] [Polymerizable compound (MA)] The polymerizable compound (MA) contains the following first component and the following second component. The polymerizable compound (MA) preferably contains the following fourth component and / or fifth component as necessary.

[0019] [First component] At least one of the linear monofunctional polymerizable compounds of the first component has a homopolymer Tg value of -30°C or less, more preferably -35°C or less, and even more preferably -40°C or less. The homopolymer Tg value is preferably -80°C or more, and may be -70°C or more. When the homopolymer Tg of the first component is in the above range, peeling from the substrate due to insufficient elastic modulus of the polymer matrix or polymer network (hereinafter referred to as polymer network) at high temperatures can be prevented, and dimming operation can be maintained and cracks can be prevented at low temperatures. The first component is preferably a linear monofunctional polymerizable compound represented by the following general formula (v).

[0020] [ka]

[0021] (In the formula, P v1 represents a polymerizable group, R v1 represents a straight-chain or branched alkyl group having 1 to 22 carbon atoms, and one or more -CH2- in the alkyl group may be each independently replaced with -O-, -CO-, -COO-, -OCO- or -P(=O)(-OH)- so that an oxygen atom is not directly adjacent to the alkyl group, and one or more hydrogen atoms in the alkyl group may each independently be replaced with a fluorine atom or -OH. In the compound represented by the general formula (v), v1 represents a polymerizable group, and preferably represents P in formula (ii). ii1 is the same as the polymerizable group represented by

[0022] In the compound represented by the general formula (v), v1 represents a polymerizable group, and preferably each independently represents any one of the following formulae (P-1) to (P-21): In the following formulae (P-1) to (P-21), * represents a bond to a carbon atom or another atom.

[0023] [ka]

[0024] Of the polymerizable groups represented by the above formulas (P-1) to (P-21), from the viewpoint of enhancing polymerizability and storage stability, formula (P-1), formula (P-2), formula (P-7), formula (P-12), formula (P-13) or formula (P-21) is preferred, formula (P-1), formula (P-2), formula (P-7) or formula (P-21) is more preferred, and formula (P-1), formula (P-2) or formula (P-21) is particularly preferred.

[0025] In the compound represented by the general formula (v), v1 more preferably represents a linear or branched alkyl group having 3 to 20 carbon atoms, and more preferably represents a linear or branched alkyl group having 6 to 18 carbon atoms in particular from the viewpoint of suppressing crystallinity, even more preferably represents a branched alkyl group, and even more preferably represents a branched alkyl group having 9 to 24 carbon atoms.

[0026] R v1When represents a linear alkyl group, examples of the compound represented by general formula (v) include ethyl acrylate (homopolymer Tg: -22°C, the same applies below), 2-hydroxyethyl acrylate (-15°C), butyl acrylate (-55°C), pentyl acrylate, hexyl acrylate (-64°C), heptyl acrylate, octyl acrylate (-65°C), nonyl acrylate (-59°C), decyl acrylate, lauryl acrylate (-26°C), tridecyl acrylate (-55°C), tetradecyl acrylate (23°C), hexadecyl acrylate (35°C), stearyl acrylate (35°C), Mono(meth)acrylates having a linear alkyl chain such as ethyl methacrylate (65°C), 2-hydroxyethyl methacrylate (55°C), propyl methacrylate (35°C), butyl methacrylate (20°C), pentyl methacrylate, hexyl methacrylate (3°C), heptyl methacrylate, octyl methacrylate (-16°C), nonyl methacrylate (-29°C), decyl methacrylate, lauryl methacrylate (-65°C), tridecyl methacrylate, tetradecyl methacrylate (-2°C), hexadecyl methacrylate (18°C), and stearyl methacrylate (38°C) are preferred.

[0027] In addition, the compound represented by the general formula (v) is, for example, v1 A (meth)acrylate having a linear ether chain structure is preferred. As the (meth)acrylate having an ether chain structure, compounds represented by the structures of the following formulae (v-a1) to (v-a3) are preferred.

[0028] [ka] (In the formula, q represents an integer of 1 to 12, preferably 1 to 5, and more preferably 1 to 3.)

[0029] Among the above general formula (v), it is preferable to use a mono(meth)acrylate having a linear alkyl chain, from the viewpoint of achieving a remarkable effect of reducing the driving voltage while maintaining good transparency when no voltage is applied.

[0030] R v1 When represents a branched alkyl group, the compound represented by general formula (v) is preferably a mono(meth)acrylate having a branched alkyl chain represented by the following structure.

[0031] [ka]

[0032] [ka]

[0033] Furthermore, preferred examples of the compound represented by general formula (v) include isobutyl acrylate (homopolymer Tg: -26°C, hereinafter the same), tertiary butyl acrylate (14°C), isononyl acrylate (-58°C), isodecyl acrylate (-62°C), isomyristyl acrylate, isostearyl acrylate (-18°C), 2-ethylhexyl methacrylate (-10°C), isobutyl methacrylate (48°C), tertiary butyl methacrylate (107°C), isononyl methacrylate, isodecyl methacrylate (-41°C), isomyristyl methacrylate, isostearyl methacrylate, and 2-ethylhexyl methacrylate (-10°C).

[0034] In addition, the compound represented by the general formula (v) is, for example, v1 The acrylate having a linear ether chain structure is preferably a compound represented by the following structure:

[0035] [ka] (In the formula, q represents an integer of 1 to 10, preferably 1 to 5, and more preferably 1 to 3.)

[0036] Among these, it is particularly preferable to use mono(meth)acrylates having a branched alkyl chain, since they have a significant effect of reducing the driving voltage while maintaining good transparency when no voltage is applied. At least one of the linear monofunctional polymerizable compounds is R v1 is a monoacrylate having a linear alkyl chain, it is preferable that R represents a linear alkyl chain having 3 to 13 carbon atoms, v1 When the monomethacrylate has a linear alkyl chain, it preferably represents a linear alkyl chain having 8 to 13 carbon atoms; when the monoacrylate has a branched alkyl chain, it preferably represents a branched alkyl chain having 4 to 18 carbon atoms; and when the monomethacrylate has a branched alkyl chain, it preferably represents a branched alkyl chain having 9 to 18 carbon atoms.

[0037] The content of the linear monofunctional polymerizable compound represented by formula (v) is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more, based on the total amount (100% by mass) of the polymerizable compound (MA) contained in the polymer dispersion type liquid crystal composition of the present embodiment, from the viewpoint of the copolymer Tg of the polymerizable compound (MA) being −10° C. or less, from the viewpoint of low-voltage driving, and from the viewpoint of improving the compatibility of each component in the polymerizable compound (MA). Also, from the viewpoint of adhesion, it is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, and particularly preferably 40% by mass or less.

[0038] [Second component] At least one of the cyclic monofunctional polymerizable compounds of the second component has a homopolymer Tg value of preferably 40° C. or less, more preferably 30° C. or less, and even more preferably 20° C. or less. It may be −30° C. or more. When the homopolymer Tg of the second component is in the above range, low-temperature responsiveness and substrate adhesion are exhibited. The cyclic monofunctional polymerizable compounds of the second component other than those mentioned above may include those having a homopolymer Tg value of higher than 40° C. These compounds preferably have a homopolymer Tg value of higher than 40° C., more preferably higher than 60° C., and even more preferably higher than 80° C. This is because when the Tg of the cyclic monofunctional polymerizable compound having a homopolymer Tg value of higher than 40° C. is within the above range, the compound exhibits high adhesion to a substrate. The second component is preferably a cyclic monofunctional polymerizable compound represented by the following general formula (ii).

[0039] [ka] (In the formula, P ii1 represents a polymerizable group,

[0040] Z ii1 represents a single bond or an alkylene group having 1 to 7 carbon atoms, in which one or more non-adjacent -CH2- may be each independently replaced by -O-, -CO-, -COO- or -OCO- so that oxygen atoms are not directly adjacent to each other; A ii1 represents formulas (ii-1) to (ii-20).

[0041] [ka]

[0042] (In the formulae, one or more -CH2- may be independently replaced by -O-, -S-, -COO-, -OCO-, -NH-, -NCH3-, or -CO-. However, when a total of two or more oxygen atoms and / or sulfur atoms are present in the general formulae (ii-1) to (ii-20), these do not bond to each other like -OO-, -OS-, or -SS-. In addition, one or more -CH2-CH2- may be replaced by a -CH=CH- group. In addition, the hydrogen atoms in the general formulae (ii-1) to (ii-20) may be replaced by an alkyl group having 1 to 8 carbon atoms, and one or more non-adjacent -CH2- in the alkyl group may be independently replaced by -O-, -CO-, -COO-, or -OCO- so that the oxygen atoms are not directly adjacent to each other. In addition, the black dots in the formulae represent Z. ii1 represents a bond to .)) At least one of the cyclic monofunctional polymerizable compounds is preferably any one selected from the group consisting of (ii-1), (ii-3), (ii-4), (ii-5), (ii-6), (ii-9), (ii-11), (ii-12), (ii-13), and (ii-14).

[0043] The compound represented by the general formula (ii) is a material with excellent flexibility, and when this compound is used, it is possible to maintain opacity even when bent. In addition, it is possible to increase the adhesion and the compatibility of each component in the polymerizable compound (MA). The compound represented by the general formula (ii) is a non-liquid crystal compound. In the compound represented by the general formula (ii), ii1 represents a polymerizable group, and preferably represents P in general formula (v). v1 is the same as the polymerizable group represented by

[0044] In the compound represented by the general formula (ii), ii1represents a single bond or an alkylene group having 1 to 7 carbon atoms, in which one or more -CH2- may be independently replaced with -O-, -CO-, -COO- or -OCO- so that no oxygen atom is directly adjacent, and one or more hydrogen atoms present in the alkylene group may be independently replaced with a fluorine atom. ii1 is preferably a single bond or an alkylene group having 1 to 6 carbon atoms, more preferably a single bond or an alkylene group having 1 to 3 carbon atoms, and particularly preferably a single bond or a -CH2- group.

[0045] In the compound represented by the general formula (ii), ii1 From the viewpoint of further improving adhesion, ii1 It is preferable that the heterocyclic structure has a nitrogen atom, an oxygen atom or a sulfur atom therein, and more specifically, it is preferable that the heterocyclic structure has any of the following formulae (ii-a1) to (ii-a11).

[0046] [ka]

[0047] (In the formulae, one or more -CH2- may be independently replaced by -CO-, and the hydrogen atoms in the general formulae (ii-a1) to (ii-a11) may be substituted by an alkyl group having 1 to 8 carbon atoms, and one or more non-adjacent -CH2- in the alkyl group may be independently replaced by -O-, -CO-, -COO- or -OCO- so that the oxygen atoms are not directly adjacent to each other. In addition, the hydrogen atoms in the general formulae (ii-a1) to (ii-a11) may be substituted by an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be linear or branched, and one or more non-adjacent -CH2- in the alkyl group may be independently replaced by -O-, -CO-, -COO- or -OCO- so that the oxygen atoms are not directly adjacent to each other. In addition, the black dots in the formulae represent Z ii1 ) In particular, when the cyclic structure has a nitrogen atom, the presence of the nitrogen atom in the cyclic structure can further improve the adhesion. Specifically, the compound represented by the general formula (ii) is preferably the following compounds (II-34) to (II-51).

[0048] [ka]

[0049] [ka] (X in the formula 5 represents a hydrogen atom or a methyl group.

[0050] Among the above structural formulas (II-34) to (II-51), (II-34), (II-36), (II-38), (II-39), (II-40), (II-43), (II-45), and (II-47) are more preferred.

[0051] The content of the compound represented by formula (ii) having a homopolymer Tg of 40° C. or less is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more, based on the total amount (100% by mass) of the polymerizable compounds (MA) contained in the polymer dispersion type liquid crystal composition of the present embodiment, from the viewpoint of the copolymer Tg of the polymerizable compounds (MA) being −10° C. or less, from the viewpoint of improving adhesion, and from the viewpoint of enhancing compatibility of each component in the polymerizable compounds (MA). Also, from the viewpoint of reducing the voltage, the content is preferably 80% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. Furthermore, among the compounds represented by general formula (ii), a compound having a homopolymer Tg of more than 40° C. may or may not be contained. When the compound is contained, the content is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more, from the viewpoint of improving adhesion to the substrate, and is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less, from the viewpoint of reducing the voltage.

[0052] In the present invention, when -CH2- of an alkyl group, alkylene group, etc. can be substituted with various structures, the number of carbon atoms of the alkyl group, etc. means the number of carbon atoms before substitution. For example, when an "alkyl group having 1 to 8 carbon atoms" is defined, the total number of carbon atoms becomes 9 as a result of substituting this with a structure containing 2 carbon atoms, and such a case is also included. When -CH2CH2- is substituted with various structures, the number of carbon atoms before substitution is also meant.

[0053] [Fourth component] The fourth component, which is an optional component of the polymer dispersion type liquid crystal composition of the present embodiment, is a polyfunctional (meth)acrylate oligomer having a weight average molecular weight of 2000 or more.

[0054] The polyfunctional (meth)acrylate oligomer is a compound necessary for introducing a crosslinked structure into the network structure of the polymer and for obtaining good adhesion. Among the polyfunctional (meth)acrylate oligomers, bifunctional acrylate oligomers are preferred. Furthermore, in order to emphasize adhesion to the substrate, urethane acrylate oligomers or polyester acrylate oligomers are preferred, and urethane acrylate oligomers are even more preferred. The urethane acrylate oligomers include those having a polyol skeleton structure of polyester type or polyether type, and polyether type is preferred. As for the molecular weight, the weight average molecular weight is 2000 or more, preferably 2000 to 60000, more preferably 2500 to 40000, even more preferably 2800 to 35000, and even more preferably 3000 to 30000. This is because if the molecular weight is too small, the crosslink density increases due to the increase in the (meth)acrylic group contained in one molecule, which increases the degree of cure shrinkage and deteriorates the adhesion, and conversely, if the molecular weight is too large, the distance between crosslinks becomes long, the gap becomes large, and it becomes easier to take in liquid crystal, which reduces the scattering properties of the polymer-dispersed liquid crystal. In other words, if it is left in a high-temperature environment, the polymer absorbs the liquid crystal, and the characteristics change significantly. In addition, if the molecular weight is large, the degree of decrease in the transition point Tnm of the polymer-dispersed liquid crystal by adding a polymerizable compound becomes small, and in order to make Tnm below room temperature, a material with a low Tni of the liquid crystal composition itself must be used, which results in a problem of a narrow operating temperature range.

[0055] Polyfunctional urethane (meth)acrylate oligomers can be obtained by reacting a hydroxyl group-containing acrylate with a polyol and a polyisocyanate. Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, and polybutadiene polyol, and examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0056] Polyisocyanates include 2,4- and 2,6-tolylene diisocyanate (TDI), orthotoluidine diisocyanate (TODI), naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), 4,4'-diphenylmethane diisocyanate (MDI), methylene bis(4-cyclohexyl isocyanate), hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, transcyclohexane 1,4-diisocyanate, and cyclohexane 1,4-diisocyanate. Examples of the isocyanate include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate, isophorone diisocyanate, and carbodiimide-modified MDI, polymethylene polyphenyl polyisocyanate, and the like.

[0057] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate, and mono(meth)acrylate modified with ε-caprolactone.

[0058] Specifically, aliphatic urethane (meth)acrylates, aromatic urethane (meth)acrylates, and polyurethane diacrylate oligomers are preferred, the polyols used are preferably polyether polyols, polyester polyols, and polycaprolactone polyols, with polyether polyols and polyester polyols being particularly preferred, and the polyisocyanates used are preferably polyisocyanates having a cyclic structure, with polyisocyanates having an alicyclic structure being particularly preferred. More specifically, orthotoluidine diisocyanate (TODI), methylene bis(4-cyclohexyl isocyanate), xylylene diisocyanate, hydrogenated xylylene diisocyanate, transcyclohexane 1,4-diisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate, isophorone diisocyanate, and carbodiimide-modified MDI are preferred, and methylene bis(4-cyclohexyl isocyanate), xylylene diisocyanate, hydrogenated xylylene diisocyanate, transcyclohexane 1,4-diisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate, and isophorone diisocyanate are particularly preferred.

[0059] The hydroxyl group-containing (meth)acrylate used is preferably 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate, or a mono(meth)acrylate modified with ε-caprolactone, and more preferably 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate. Also preferred is a compound represented by the following formula (i-1):

[0060] [ka]

[0061] (In the formula, X i1 each independently represents a hydrogen atom or a methyl group; B 1 each independently represents an alkyl group having 1 to 4 carbon atoms, in which one or more -CH2- may be replaced by an oxygen atom, -CO-, -COO- or -OCO-; b represents 1 to 20; B 2 represents a structure obtained by repeatedly linking a group selected from the following (i-2) to (i-6) or a single group selected from these, or by linking a combination of a plurality of groups:

[0062] [ka]

[0063] B 3 is a group selected from the following general formula (i-7), (i-8) or (i-9), a group in which a single group selected from these is repeatedly linked, or a structure obtained by linking a combination of multiple groups.

[0064] [ka]

[0065] [ka]

[0066] (In the formula, X i2 represents a hydrogen atom or a methyl group, and X i3 represents an alkylene group having 1 to 9 carbon atoms, Y 5 represents an alkylene group having 1 to 15 carbon atoms, a divalent aromatic group, or a divalent alicyclic hydrocarbon group, Y 3 and Y 4 represents a hydrogen atom or a methyl group, Xi1 , X i2 , X i3 , B 1 , B 2 , B 3 , Y 3 , Y 4 Or Y 5 When there are multiple, they may be the same or different, t, t1, and t2 each independently represent an integer of 0 to 300, and t+t1+t2 represents an integer of 20 to 300.

[0067] In the present invention, examples of the divalent aromatic group include a 1,4-phenylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a pyrazine-2,5-diyl group, a thiophene-2,5-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, a naphthylene-1,4-diyl group, a naphthylene-1,5-diyl group, a naphthylene-1,6-diyl group, a naphthylene-2,6-diyl group, a phenanthrene-2,7-diyl group, a 9,10-dihydrophenanthrene-2,7 Preferred examples include a -diyl group, a benzothiazole group, a 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, a benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, a benzo[1,2-b:4,5-b']diselenophene-2,6-diyl group, a [1]benzothieno[3,2-b]thiophene-2,7-diyl group, a [1]benzoselenopheno[3,2-b]selenophene-2,7-diyl group, and a fluorene-2,7-diyl group. These groups are unsubstituted or have one or more L 1 may be replaced by:

[0068] Examples of the divalent alicyclic hydrocarbon group include a 1,2-cyclopropylene group, a 1,3-cyclobutylene group, a 2,5-cyclopentylene group, an octahydro-4,7-methano-1H-indene-1,5-diyl group, an octahydro-4,7-methano-1H-indene-1,6-diyl group, an octahydro-4,7-methano-1H-indene-2,5-diyl group, a tricyclo[3.3.1.1 3,7Preferred examples include a 1,3-diyl group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran-2,5-diyl group, a 1,3-dioxane-2,5-diyl group, a tetrahydrothiopyran-2,5-diyl group, a 1,4-bicyclo(2,2,2)octylene group, and a decahydronaphthalene-2,6-diyl group. These groups are unsubstituted or have one or more L 1 may be replaced by: Furthermore, aliphatic urethane acrylate and polyurethane diacrylate oligomer are particularly preferred.

[0069] The content of the polymerizable compound selected from the polyfunctional (meth)acrylate oligomers having a weight average molecular weight of 2000 or more is preferably 5% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more, based on the total amount of the polymerizable compounds (MA) contained in the polymer-dispersed liquid crystal composition of the present embodiment (100% by mass), from the viewpoint of enhancing adhesion. Also, from the viewpoint of reducing the voltage, it is preferably 80% by mass or less, more preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. At least one of the polyfunctional (meth)acrylate oligomers having a weight average molecular weight of 2000 or more has a homopolymer Tg of preferably -30°C or less, more preferably -40°C or less, and even more preferably -50°C or less, from the viewpoint of enhancing adhesion to the substrate.

[0070] [Fifth component] The polymer dispersion type liquid crystal composition of this embodiment preferably contains a fifth component. The fifth component is a compound selected from the group consisting of polyfunctional polymerizable oligomers and polyfunctional polymerizable monomers, each of which has a weight average molecular weight of less than 2000 and is represented by the following general formula (iv). The molecular weight of the polyfunctional polymerizable oligomer and / or polyfunctional polymerizable monomer is preferably 2000 or less, and more preferably 1000 or less.

[0071] [ka] (In the formula, Y iv1 represents a hydrogen atom or a methyl group,

[0072] X iv1 n is a group with 130 or less carbon atoms iv1 one or more -CH2- groups in the linear, branched or cyclic hydrocarbon group may each be independently replaced by -O-, -NH-, -CO-, -COO-, -OCO-, -CH=CH-, or -C≡C- so that the oxygen atoms are not directly adjacent to each other, and one or more hydrogen atoms present in the linear, branched or cyclic hydrocarbon group may each be independently replaced by a fluorine atom or -OH; n iv1 represents an integer from 2 to 6.)

[0073] As the polyfunctional polymerizable oligomer or monomer having a weight molecular weight of less than 2000, represented by general formula (iv), a polymerizable compound represented by general formula (iv-1) is preferably used.

[0074] [ka] (In the formula, Y iv2 and Y iv3 represents a hydrogen atom or a methyl group,

[0075] X iv2 represents a linear or branched alkylene having 2 to 80 carbon atoms, and any carbon atom of the alkylene may be substituted with -O-, -CO-, -COO-, -OCO-, -CH=CH-, -C≡C-, or OH so that an oxygen atom is not directly adjacent to the alkylene.

[0076] In the general formula (iv-1), X iv2 The linear or branched alkylene preferably has 2 to 70 carbon atoms, more preferably 4 to 70 carbon atoms, and even more preferably 5 to 60 carbon atoms, and particularly preferably 5 to 50 carbon atoms, from the viewpoint of reducing the driving voltage. Examples of the polymerizable compound represented by the above general formula (iv-1) include those having the following structures (iv-1-1) to (iv-1-10).

[0077] [ka]

[0078] [ka]

[0079] (In the formula, n and m are each 1 to 10, 2 is 1 to 18, n 3 and m 2 is 3 +m 2 n is a value between 1 and 18 4 is 1 to 23, n 5 is 1 to 23, n 6 is 4 to 30, n 7 is 2 to 10, n 8 and n 9 represents 2 to 10 respectively.)

[0080] Among these, those represented by (iv-1-1), (iv-1-2), and (iv-1-3) 2 is 1 to 5, (iv-1-7) 6 From the viewpoint of ensuring a wide operating temperature range on the high temperature side, it is particularly preferable that the average molecular weight be 4 to 15.

[0081] The content of the polymerizable compound represented by general formula (iv) is, relative to the total amount (100 mass%) of the polymerizable compounds (MA) contained in the polymer dispersion type liquid crystal composition of this embodiment, preferably 2 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more from the viewpoint of improving heat resistance, and particularly preferably 50 mass% or less, 40 mass% or less, 30 mass% or less, or 25 mass% or less from the viewpoint of maintaining adhesion.

[0082] [Other polymerizable compounds] The polymerizable compound (MA) may or may not contain a polymerizable compound having a mesogenic skeleton as another polymerizable compound. Examples of such a polymerizable compound include compounds represented by the following general formulas (2) to (8).

[0083] [ka]

[0084] In the above general formulas (2) to (8), P 11 ~P 74 represents a polymerizable group, and preferably each independently represents any one of the following formulae (P-1) to (P-20): In the following formulae (P-1) to (P-20), * represents a bond to a carbon atom or another atom.

[0085] [ka] Among the polymerizable groups represented by the above formulae (P-1) to (P-20), the formulae (P-1) and (P-2) are preferred from the viewpoint of enhancing polymerizability and storage stability.

[0086] X 11 ~X 72 each independently represents -O-, -S-, -OCH2-, -CHO-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH =CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C- or a single bond, but X 11 ~X 72When a plurality of groups are present, they may be the same or different (however, each P-(SX)- bond does not include -OO-), and a group selected from a single bond, -O-, -S-, -CO-, -COO-, and -OCO- is particularly preferred. M 11 , M 21 , M 31 , M 51 , M 71 each independently represents a mesogenic group represented by the following general formula (9-a).

[0087] [ka]

[0088] (In general formula (9-a), A 91 , A 92 , A 93 are each independently a divalent group having at least one ring structure, and the divalent group is a 1,2-cyclopropylene group, a 1,3-cyclobutylene group, a 2,5-cyclopentylene group, an octahydro-4,7-methano-1H-indene-1,5-diyl group, an octahydro-4,7-methano-1H-indene-1,6-diyl group, an octahydro-4,7-methano-1H-indene-2,5-diyl group, a tricyclo[3.3.1.1 3,7]-1,3-diyl group, 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, naphthylene-1,4-diyl group, naphthylene-1,5-diyl group, naphthylene-1,6-diyl group, naphthylene-2,6-diyl group, represents a group selected from a phenylene-2,6-diyl group, a phenanthrene-2,7-diyl group, a 9,10-dihydrophenanthrene-2,7-diyl group, a benzothiazole group, a 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, a benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, a benzo[1,2-b:4,5-b']diselenophene-2,6-diyl group, a [1]benzothieno[3,2-b]thiophene-2,7-diyl group, a [1]benzoselenopheno[3,2-b]selenophene-2,7-diyl group, or a fluorene-2,7-diyl group, and these groups may be unsubstituted or may contain one or more L 1 may be substituted by, but A 91 and / or A 92 When multiple occurrences occur, they may be the same or different,

[0089] Z 91 and Z 92are each independently -O-, -S-, -OCH2-, -CHO-, -CH2CH2-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=C H-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, -C≡C- or a single bond, but Z 91 and / or Z 92 When multiple occurrences occur, they may be the same or different,

[0090] j 91 and j 92 Each independently represents 0 to 4, 91 +j 92 represents an integer from 1 to 4, and L 1 represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH2- or two or more non-adjacent -CH2- are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, -N=N-, -CR 91 =NN=CR 91 R represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -, -C≡C-, or -C≡C-, and any hydrogen atom in the alkyl group may be substituted by a fluorine atom (R 91represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear or branched, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- in the alkyl group may each independently be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-.

[0091] Also, M 41 A 91 , A 92 , A 93 is a trivalent organic group having a ring structure as exemplified by M 61 A is the above 91 , A 92 , A 93 It is a tetravalent organic group having a ring structure as exemplified above.

[0092] In the general formulas (2) to (8), R 11 , R 31 each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear or branched, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- in the alkyl group may each independently be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-.

[0093] m1 to m7, n2 to n7, l4 to l6, and k6 each independently represent an integer of 0 to 5. In the general formulas (2) to (8), S 11 ~S 72 each independently represents a spacer group or a single bond; 11 ~S 72The spacer group represented by the formula (I) represents an alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with one or more halogen atoms, CN groups, alkyl groups having 1 to 8 carbon atoms, or alkyl groups having 1 to 8 carbon atoms and a polymerizable group, and one CH2 group or two or more non-adjacent CH2 groups present in this group may be independently replaced with -O-, -S-, -NH-, -N(CH3)-, -CO-, -CH(OH)-, CH(COOH), -COO-, -OCO-, -OCOO-, -SCO-, -COS-, or -C≡C- in a form in which oxygen atoms are not directly bonded to each other). Among these spacer groups, from the viewpoint of orientation, a linear alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms substituted with a fluorine atom, and an alkylene group having 5 to 14 carbon atoms in which an alkylene group is partially replaced with -O- are preferred. In addition, S 11 ~S 72 When a plurality of are present, they may be the same or different.

[0094] In the general formulae (2) to (8), m1 to m7, n2 to n7, l4 to l6, and k6 each independently represent an integer of 0 to 5, and it is preferable that m1 to m7, n2 to n7, l4 to l6, and k6 each independently represent 0 or 1.

[0095] The total content of the polymerizable compounds other than the first, second, fourth and fifth components is preferably 2% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, based on 100% by mass of the total amount of the polymerizable compounds (MA) contained in the polymer-dispersed liquid crystal composition of the present embodiment, from the viewpoints of alignment and transparency. Also, from the viewpoints of scattering properties and low-voltage driving, the total content is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less.

[0096] [Additives] In the polymer dispersion type liquid crystal composition of the present embodiment, in order to obtain a composition that places more importance on adhesion, it is preferable that the polymerizable compound (MA) further contains an additive represented by the following general formula (X), in addition to the above-mentioned first component, second component, fourth component, fifth component, and other polymerizable compounds.

[0097] [ka] (In the formula, Y X1 represents a hydrogen atom or a methyl group,

[0098] X X1 n is a group with 130 or less carbon atoms X1 one or more -CH2- groups in the linear, branched or cyclic hydrocarbon group may each be independently replaced by -O-, -NH-, -CO-, -COO-, -OCO-, -CH=CH-, or -C≡C- so that the oxygen atoms are not directly adjacent to each other, and one or more hydrogen atoms present in the linear, branched or cyclic hydrocarbon group may each be independently replaced by a fluorine atom or -OH; n X1 represents an integer from 1 to 6, Here, X X1 At least one -CH2- group is replaced with the following formula (X-1).

[0099] [ka] Specifically, it is preferable to add the following compounds.

[0100] [ka] (X in the formula 6 , X 7 , and X 8 each independently represents a hydrogen atom or a methyl group, and q, r, and s each represent 1 to 4.

[0101] The amount of the compound having a group represented by the general formula (X-1) added is preferably from 0.005% by mass to 2% by mass, more preferably from 0.01% by mass to 0.5% by mass, and even more preferably from 0.01% by mass to 0.2% by mass, of the total amount of the polymer dispersion type liquid crystal composition.

[0102] [Non-polymerizable liquid crystal compound (LB)] [Third component] The non-polymerizable liquid crystal compound (LB) may contain, as a third component, one or more tolan compounds represented by the following general formula (iii).

[0103] [ka]

[0104] (In the formula, R iii1 are each independently an n-alkyl group having 1 to 7 carbon atoms, an n-alkoxy group, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group, or an alkoxyalkyl group,

[0105] R iii2 represents a fluorine atom, a chlorine atom, a cyano group, a CF3 group, an OCF3 group, an OCHF2 group, an NCS group, or an alkyl group having 1 to 10 carbon atoms, in which one or two non-adjacent -CH2- groups may be replaced by an oxygen atom, -COO- or -OCO-, and one or more -CH2CH2- may be replaced by -CH=CH- or -C≡C-, preferably a fluorine atom, a cyano group, or an alkyl group having 1 to 5 carbon atoms (in which one or two non-adjacent -CH2- groups may be replaced by an oxygen atom, and one or more -CH2CH2- may be replaced by -CH=CH- or -CH≡CH-);

[0106] A iii1represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 2,3-difluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group, a 2,6-difluoro-1,4-phenylene group, a 2-methyl-1,4-phenylene group, a 3-methyl-1,4-phenylene group, a 2,3-dimethyl-1,4-phenylene group, a 3,5-dimethyl-1,4-phenylene group, or a 2,6-dimethyl-1,4-phenylene group,

[0107] A iii2 and A iii3 each independently represents a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 2,3-difluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group, a 2,6-difluoro-1,4-phenylene group, a 2-methyl-1,4-phenylene group, a 3-methyl-1,4-phenylene group, a 2,3-dimethyl-1,4-phenylene group, a 3,5-dimethyl-1,4-phenylene group or a 2,6-dimethyl-1,4-phenylene group;

[0108] Z iii1 and Z iii2 one of is -C≡C- and the other, if present, is -C≡C-, -CF2O-, -OCF2-, -CH=CH-, -CF=CF-, -COO-, -CH2-CH2-, -CF2-CF2- or a single bond; n iii is either 0 or 1.)

[0109] By including one or more tolan compounds represented by the above general formula (iii) in the non-polymerizable liquid crystal compound (LB), a liquid crystal element using a polymer-dispersed liquid crystal composition containing the non-polymerizable liquid crystal compound (LB) has good adhesion and light scattering properties, and can be driven at a low voltage at room temperature and at low temperatures.

[0110] In addition, in the compound represented by the general formula (iii), A iii1is preferably a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, or a 3-fluoro-1,4-phenylene group. iii1 is preferably a 1,4-phenylene group.

[0111] Also, A iii2 and A iii3 is preferably a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group, a 2,6-difluoro-1,4-phenylene group, a 2-methyl-1,4-phenylene group, or a 3-methyl-1,4-phenylene group. iii2 and A iii3 but

[0112] [ka] It is preferred that the compound contains a compound represented by the formula: The compound represented by the above formula (iii) may preferably be a compound represented by the following sub-formulae (iii-1) to (iii-8).

[0113] [ka]

[0114] [ka]

[0115] (In the formula, R iii1 and R iii2 has the meaning given in formula (iii) above, and Y iii1 and Y iii2 are each independently H or F, and Y iii3 is a hydrogen atom, a fluorine atom, or a methyl group. Among these, the compound represented by the above general formula (iii) is more preferably the compound represented by the above sub-general formulae (iii-6) to (iii-8).

[0116] The compound represented by the general formula (iii) as the third component is preferably from 10% by mass to 80% by mass, more preferably from 25% by mass to 70% by mass, and even more preferably from 35% by mass to 60% by mass, relative to 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB).

[0117] [Sixth component] The non-polymerizable liquid crystal compound (LB) may further contain, as a sixth component, one or more compounds represented by the following general formula (vi-0) (excluding the third component).

[0118] [ka]

[0119] (In the formula, R 11 represents an alkyl group having 1 to 10 carbon atoms, in which one or two non-adjacent -CH- groups may be replaced by an oxygen atom, -COO- or -OCO-, and one or more -CHCH- may be replaced by -CH≡CH-; R 12 represents a fluorine atom, a chlorine atom, a cyano group, a CF3 group, an OCF3 group, an OCHF2 group, an NCS group, a cyano group, or an alkyl group having 1 to 10 carbon atoms, in which one or two non-adjacent -CH2- groups may be replaced by an oxygen atom, -COO- or -OCO-, and one or more -CH2CH2- may be replaced by -C≡C-, and is preferably a fluorine atom, a cyano group, or an alkyl group having 1 to 5 carbon atoms (in which one or two non-adjacent CH2 groups may be replaced by an oxygen atom);

[0120] Z 11 and Z 12each independently represents a single bond, -COO-, -OCO-, -CH-CH-, -CH=CH-, -CFO-, -OCF-, or -C≡C-; Z 12 When there are multiple, they may be the same or different,

[0121] A 11 , A 12 and A 13 each independently represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran-2,5-diyl group, a 1,3-dioxane-2,5-diyl group, a decahydronaphthalene-2,6-diyl group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a pyrazine-2,5-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or a 2,6-naphthylene group, the 1,4-phenylene group, the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the 2,6-naphthylene group may be unsubstituted or may have one or more fluorine atoms, chlorine atoms, CF3 groups, OCF3 groups, or CH3 groups as substituents, A 13 When there are multiple, they may be the same or different, n 11 is 0, 1 or 2.)

[0122] The compound of general formula (vi-0) includes R 11 is preferably an alkyl group having 1 to 5 carbon atoms (in which one or two non-adjacent CH groups may be replaced by an oxygen atom), and R 12 is preferably a fluorine atom, a cyano group, or an alkyl group having 1 to 5 carbon atoms (in which one or two non-adjacent CH groups may be replaced by an oxygen atom), and Z 11 and Z 12 are each independently a single bond, -COO-, -OCO-, -CH2-CH2-, -CF2O- or -OCF2-(Z 11is preferably a single bond, -COO- or -CF2O-, and when a plurality of A are present, they may be the same or different. 11 , A 12 and A 13 each independently represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,3-dioxane-2,5-diyl group, a pyrimidine-2,5-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or a 2,6-naphthylene group (the 1,4-phenylene group, the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the 2,6-naphthylene group may be unsubstituted or may have one or more fluorine atoms or CH groups as a substituent); 13 is present, they may be the same or different), preferably a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyrimidine-2,5-diyl group or a 2,6-naphthylene group (the 1,4-phenylene group and the 2,6-naphthylene group may be unsubstituted or may have one or more fluorine atoms or CH groups as substituents, and A 13 When there are a plurality of n, they may be the same or different. 11 is preferably 0 or 1.

[0123] The compound represented by the general formula (vi-0) is more preferably one or more liquid crystal compounds represented by the following general formula (vi) (excluding the third component):

[0124] [ka]

[0125] (In the formula, R 3 represents an alkyl group having 1 to 10 carbon atoms, in which one or more non-adjacent -CH- groups may be replaced by an oxygen atom, -CH=CH-, -COO- or -OCO-;

[0126] A 6represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,3-dioxane-2,5-diyl group, a pyridine-2,5-diyl group or a pyrimidine-2,5-diyl group, the 1,4-phenylene group being unsubstituted or may have one or more fluorine atoms, chlorine atoms, CF3, OCF3 or methyl groups as substituents,

[0127] A 7 represents a 1,4-phenylene group or a 1,4-cyclohexylene group, which 1,4-phenylene group may be unsubstituted or may have one or more fluorine atoms, chlorine atoms, CF3, OCF3 or methyl groups as substituents,

[0128] A 8 represents a 1,4-phenylene group, which may be unsubstituted or may bear one or more fluorine atoms, chlorine atoms, CF3, OCF3, or methyl groups as substituents;

[0129] Z 6 and Z 7 each independently represents a single bond, -COO-, -OCO-, -CH-CH-, -CH=CH-, -CFO-, -OCF- or -C≡C-; n 12 represents 0 or 1. However, the third component is excluded.)

[0130] In addition, in the general formula (vi), R 3 A is more preferably an alkyl group or an alkoxy group having 1 to 10 carbon atoms. 6 and A 7 Z is more preferably a 1,4 phenylene group or a 1,4 cyclohexylene group (the 1,4 phenylene group may be unsubstituted or may have one or more fluorine atoms as a substituent). 6 and Z 7 are each independently preferably a single bond, -COO-, -OCO-, or -CH2-CH2-, and more preferably a single bond or -COO-. In addition, in the general formula (vi), R 3represents an alkyl group having 1 to 10 carbon atoms, preferably 2 to 7 carbon atoms, and more preferably 2 to 5 carbon atoms;

[0131] A 7 is a 1,4-phenylene group or a 1,4-cyclohexylene group, which 1,4-phenylene group may be unsubstituted or may have one fluorine atom as a substituent; n 12 It is most preferable that the liquid crystal contains at least a compound which represents 0 in order to reduce the viscosity of the liquid crystal and improve the low-temperature drivability.

[0132] In the general formula (vi), A 7 and A 8 represents a 1,4-phenylene group, one of the 1,4-phenylene groups having at least one fluorine atom as a substituent, and Z 6 , Z 7 and Z 8 represents a single bond or -COO-, A 6 represents a 1,4-phenylene group or a 1,4-cyclohexylene group, n 12 It is preferable to use a compound represented by 0 or 1 from the viewpoint of reducing the voltage. Specifically, the following compounds (vi-1) to (vi-11) can be mentioned.

[0133] [ka]

[0134] [ka]

[0135] (In the formula, R 51 represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; Y 11 ~Y 66 Each of Y independently represents a hydrogen atom or a fluorine atom. 11 ~Y 66 may all represent hydrogen atoms, or one or more of them may represent a fluorine atom.) Specifically, the following compounds (vi-A) to (vi-G) can be mentioned.

[0136] [ka]

[0137] (R in the formula 511 represents an alkyl group having 2 to 7 carbon atoms or an alkoxy group having 2 to 7 carbon atoms, and preferably represents an alkyl group having 2 to 5 carbon atoms or an alkoxy group having 2 to 5 carbon atoms.

[0138] The compound represented by the above general formula (vi-0) is preferably from 20% by mass to 90% by mass, more preferably from 30% by mass to 75% by mass, and even more preferably from 40% by mass to 65% by mass, relative to the total amount of the non-polymerizable liquid crystal compound (LB) (100% by mass).

[0139] The total content of the liquid crystal compounds represented by the general formula (vi) is preferably from 2 to 70% by mass, more preferably from 5 to 50% by mass, and even more preferably from 10 to 30% by mass, relative to 100% by mass of the total amount of the non-polymerizable liquid crystal compounds (LB).

[0140] Furthermore, the total content of the liquid crystal compounds represented by the above general formulas (vi-1) to (vi-11) is preferably from 2 to 70% by mass, more preferably from 5 to 50% by mass, and even more preferably from 10 to 30% by mass, relative to 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB).

[0141] Furthermore, the total content of the liquid crystal compounds represented by the above general formulas (vi-A) to (vi-G) is preferably from 2 to 70% by mass, more preferably from 5 to 50% by mass, and even more preferably from 10 to 30% by mass, relative to 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB).

[0142] In particular, the total content of the liquid crystal compounds represented by the general formulas (vi-A), (vi-B), (vi-C) and (vi-G) is preferably from 2 to 70% by mass, more preferably from 5 to 50% by mass, and even more preferably from 10 to 30% by mass, relative to 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB).

[0143] The nematic-isotropic phase transition point (Tni) of the non-polymerizable liquid crystal compound (LB) according to this embodiment is preferably 110°C or more and 180°C or less, more preferably 120°C or more and 160°C or less, and even more preferably 130°C or more and 140°C or less.

[0144] The refractive index anisotropy (Δn) of the non-polymerizable liquid crystal compound used in the polymer-dispersed liquid crystal element is generally preferably high, and Δn is preferably 0.16 or more, more preferably 0.18 or more, even more preferably 0.20 or more, and most preferably 0.22 or more. The ordinary refractive index (no) of the non-polymerizable liquid crystal compound having these Δn is usually about 1.50 to 1.54. When a voltage is applied to the polymer-dispersed liquid crystal element to make it transparent, high transparency can be obtained if the no of the non-polymerizable liquid crystal compound and the refractive index (np) of the polymer forming the network structure are almost the same. However, when the monomer and oligomer are polymerized by UV irradiation or the like, they are cured in a form that embraces some of the non-polymerizable liquid crystal compound, so that the refractive index of the actual polymer is higher than that of the pure one. Therefore, the refractive index of the monomer and oligomer is preferably lower than 1.5, more preferably 1.48 or less, and even more preferably 1.47 or less.

[0145] [Dye (CR)] The dye (CR) used in this embodiment contains at least one kind of blue dye compound, at least one kind of red dye compound, and at least one kind of yellow dye compound. The blue dye compound, the red dye compound, and the yellow dye compound may each be one kind, but it is preferable that they are two or more kinds. Here, blue refers to a maximum absorption wavelength of 580 to 800 nm, red refers to a maximum absorption wavelength of 490 to 580 nm, and yellow refers to a maximum absorption wavelength of 390 to 490 nm. The maximum absorption wavelength can be measured by the following method. 1.0 part by mass of the dye compound is added to 100 parts by mass of any liquid crystal composition capable of dissolving the dye compound of interest and dissolved. This is poured into a liquid crystal test cell (2 cm x 2 cm, cell thickness 10 μm) in which a glass substrate having an ITO transparent electrode film and a horizontal alignment film faces each other to prepare a liquid crystal element. The absorption spectrum of the liquid crystal cell is measured between 350 and 750 nm at 25°C with no voltage applied using a spectrometer of a liquid crystal characteristic measuring device LCD-5200 (manufactured by Otsuka Electronics Co., Ltd.), and the peak top wavelength of the absorption band of the dye compound can be determined as the maximum absorption wavelength. The dye (CR) used in this embodiment can be used to impart color to the polymer dispersed liquid crystal element of this embodiment or to control the color. There is no particular limitation on such dye (CR), and any known and commonly used dye can be used as long as it is soluble in liquid crystal, can be dispersed in a polymerizable compound, or can be transferred into a polymer network after polymerization phase separation.

[0146] The blue dye compound is preferably one or more compounds having an anthraquinone skeleton, and more preferably one or more compounds selected from the group of compounds represented by the following general formula (11) and general formula (12). It is particularly preferable to include at least a compound represented by general formula (11), and most preferably to include a compound represented by general formula (1A).

[0147] [ka]

[0148] In the above general formula (11), A 1 , A 2 , Z 1 , Z 2 , R 1 , R 2 , R 4 , L 1The meanings are as follows: A 1 and A 2 each independently represents a group selected from the group consisting of the following group (a1), group (b1), group (c1) and group (d1).

[0149] (a1) a 1,4-cyclohexylene group (in which one -CH2- or two or more non-adjacent -CH2- groups may each be independently replaced by -O- or -S-), (b1) a 1,4-phenylene group (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by -N=), (c1) 1,4-cyclohexenylene group, bicyclo[2.2.2]octane-1,4-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene-1,4-diyl group, decahydronaphthalene-2,6-diyl group, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, or phenanthrene- 2,7-diyl group (one -CH= or two or more non-adjacent -CH= present in a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, a 5,6,7,8-tetrahydronaphthalene-1,4-diyl group, an anthracene-2,6-diyl group, an anthracene-1,4-diyl group, an anthracene-9,10-diyl group, or a phenanthrene-2,7-diyl group may be replaced by -N=), (d1) a thiophene-2,5-diyl group, a thiophene-2,4-diyl group, a benzothiophene-2,5-diyl group, a benzothiophene-2,6-diyl group, a dibenzothiophene-3,7-diyl group, a dibenzothiophene-2,6-diyl group, or a thieno[3,2-b]thiophene-2,5-diyl group (in these groups, one -CH= or two or more non-adjacent -CH=s may be replaced by -N=).

[0150] The hydrogen atoms present in the groups (a1), (b1), (c1) and (d1) may each independently be replaced by a methyl group, a fluorine atom or a chlorine atom.

[0151] Z 1 and Z 2 each independently represents -CH2O-, -OCH2-, -CF2O-, -OCF2-, -CH2CH2-, -CF2CF2-, -CH=CH-, -CF=CF-, -N=CH-, -CH=N-, -N=N-, -C≡C-, or a single bond. R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms (a hydrogen atom present in this group may be replaced by a fluorine atom, and one -CH- or two or more non-adjacent -CH- present in this group each independently represents -NR 3 -, -O-, -S-, -CH=CH-, -CF=CF- or -C≡C-. R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (one -CH2- or two or more non-adjacent -CH2- groups in these groups may be each independently replaced by -O-, -S-, -COO-, -OCO- or -CO-, and a hydrogen atom in these groups may be replaced by a fluorine atom). R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L 1 represents -O-, -S-, -COO-, -OCO-, -CO-, or a single bond. R 3 If there are multiple R 3 may be the same or different, provided that no oxygen atom in formula (11) is directly bonded to another oxygen atom.

[0152] The group (b1) is preferably a group having a structure represented by the following formula (b-1), and more preferably a group having a structure represented by the following formula (b-2) or (b-3).

[0153] [ka]

[0154] In formula (b-1), R i1 and R i2 Each of * in formula (b-1), formula (b-2) and formula (b-3) independently represents a hydrogen atom or a methyl group. 1 or Z 2 The wavy line represents the bond to L in the above general formula (11). 1 or represents a bond to a nitrogen atom.

[0155] A in the above general formula (11) 1 and A 2 is preferably a group selected from the group consisting of the groups (a1) and (b1), and more preferably the group (b1). 1 is a group having a structure represented by formula (b-2) or formula (b-3), 2 is preferably a group having a structure represented by formula (b-2), 1 and A 2 It is more preferable that both of the above are groups having a structure represented by formula (b-2). Z in the above general formula (11) 1 and Z 2 is preferably -OCH2- or a single bond. 1 is preferably -OCH2- or a single bond, Z2 is preferably a single bond, Z 1 and Z 2 It is more preferable that both of are single bonds.

[0156] R in the above general formula (11) 1 and R 2 R is preferably an alkyl group (including substituted ones) having 1 to 30 carbon atoms. 1 and R 2The alkyl group represented by the formula (I) may be linear, branched or cyclic, and is preferably linear. The number of carbon atoms in the alkyl group is preferably 2 to 16, and more preferably 4 to 12. When a part of the alkyl group is substituted with any of the above groups, the above carbon number means the total number of carbon atoms including the number of carbon atoms in the substituent. R 1 and R 2 More preferably, R is an unsubstituted alkyl group having 1 to 20 carbon atoms or an unsubstituted alkoxy group having 1 to 19 carbon atoms. 1 It is preferable that R1 is an unsubstituted alkyl group having 1 to 20 carbon atoms or an unsubstituted alkoxy group having 1 to 19 carbon atoms, and R2 is an unsubstituted alkyl group having 1 to 20 carbon atoms, and it is more preferable that both R1 and R2 are unsubstituted alkyl groups having 1 to 20 carbon atoms. 1 When is an alkoxy group, Z 1 is preferably a single bond, R 2 When is an alkoxy group, Z 2 is preferably a single bond.

[0157] Specific examples of unsubstituted alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, etc. Specific examples of unsubstituted alkoxy groups having 1 to 19 carbon atoms include methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyl, etc. L 1 is preferably an oxygen atom.

[0158] A specific preferred example of the compound represented by the general formula (11) (sometimes referred to as compound (11)) is a compound represented by the following formula (11A).

[0159] [ka]

[0160] In general formula (11A), R 5 and R 8 each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, R 6 , R 7 , R 9 and R 10 each independently represents a hydrogen atom or a methyl group; Z 3 and Z 4 each independently represents -OCH2- or a single bond; R 11 represents a hydrogen atom or a methyl group. R 5 and R 8 The details of the alkyl group represented by the formula (11) (including preferred embodiments) are as follows: 1 and R 2 The details of the alkyl group are the same as those of the alkyl group represented by the formula (I).

[0161] R 6 and R 7 One or both of R 9 and R 10 Preferably, both of R 6 , R 7 , R 9 and R 10 It is preferable that all of are hydrogen atoms. Z 3 and Z 4 It is preferred that both of the groups are single bonds.

[0162] [ka]

[0163] In the above general formula (12), A 1 , A 2 , Y 1 , Y2 , Z 1 , Z 2 , R 1 , R 2 The meanings are as follows: A 1 and A 2 each independently represents a group selected from the group consisting of the following groups (a1) and (b1):

[0164] (a1) a 1,4-cyclohexylene group (in which one -CH2- or two or more non-adjacent -CH2- groups may each be independently replaced by -O- or -S-), (b1) a 1,4-phenylene group (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by -N=),

[0165] The hydrogen atoms present in the groups (a1) and (b1) may each be independently replaced by a methyl group, a fluorine atom or a chlorine atom.

[0166] Y 1 and Y 2 each independently represents a hydrogen atom or a hydroxyl group. Z 1 and Z 2 each independently represents -CH2O-, -OCH2-, -CF2O-, -OCF2-, -CH2CH2-, -CF2CF2-, -CH=CH-, -CF=CF-, -N=CH-, -CH=N-, -N=N-, -C≡C-, or a single bond. R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (a hydrogen atom present in this group may be replaced by a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- groups present in this group may each independently be replaced by -NR3-, -O-, -S-, -CH=CH-, -CF=CF- or -C≡C-). R 3represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (one -CH2- or two or more non-adjacent -CH2- groups in these groups may be each independently replaced by -O-, -S-, -COO-, -OCO- or -CO-, and a hydrogen atom in these groups may be replaced by a fluorine atom). R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L 1 represents an oxygen atom or a sulfur atom. R 3 If there are multiple R 3 may be the same or different, provided that no oxygen atom in formula (12) is directly bonded to another oxygen atom. m is 0 or 1, and n is 0, 1, or 2.

[0167] Examples of the blue dye compound represented by the general formula (11A) include the compounds represented by the following formulas (cr-1) and (cr-2).

[0168] [ka]

[0169] In addition to the above, examples of the blue dye compound represented by the general formula (11) include the following formula (cr-3).

[0170] [ka]

[0171] Examples of the blue dye compound represented by the general formula (12) include the compounds represented by the following formulas (cr-4) to (cr-6).

[0172] [ka]

[0173] The red dye compound is preferably one or more compounds having an anthraquinone skeleton, and more preferably one or more compounds selected from the group of compounds represented by the following general formulas (13), (14), and (15). It is particularly preferable to include at least a compound represented by general formula (13), and most preferably to include a compound represented by general formula (13A).

[0174] [ka]

[0175] A in formula (13) a , A b , Z a , Z b , R a , R b The meanings of , m and n are as follows: A a and A b each independently represents a group selected from the group consisting of the following group (a2), group (b2), group (c2) and group (d2).

[0176] (a2) a 1,4-cyclohexylene group (in which one -CH2- or two or more non-adjacent -CH2- groups may each be independently replaced by -O- or -S-), (b2) a 1,4-phenylene group (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by -N=), (c2) 1,4-cyclohexenylene group, bicyclo[2.2.2]octane-1,4-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene-1,4-diyl group, decahydronaphthalene-2,6-diyl group, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, or phenanthrene- 2,7-diyl group (one -CH= or two or more non-adjacent -CH= present in a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, a 5,6,7,8-tetrahydronaphthalene-1,4-diyl group, an anthracene-2,6-diyl group, an anthracene-1,4-diyl group, an anthracene-9,10-diyl group, or a phenanthrene-2,7-diyl group may be replaced by -N=), (d2) a thiophene-2,5-diyl group, a thiophene-2,4-diyl group, a benzothiophene-2,5-diyl group, a benzothiophene-2,6-diyl group, a dibenzothiophene-3,7-diyl group, a dibenzothiophene-2,6-diyl group, or a thieno[3,2-b]thiophene-2,5-diyl group (in these groups, one -CH= or two or more non-adjacent -CH=s may be replaced by -N=).

[0177] The hydrogen atoms present in the groups (a2), (b2), (c2) and (d2) may each independently be replaced by a methyl group, a fluorine atom or a chlorine atom.

[0178] Z a and Z b each independently represents -CH2O-, -OCH2-, -CF2O-, -OCF2-, -COO-, -OCO-, -CH2CH2-, -CF2CF2-, -CH=CH-, -CF=CF-, -N=CH-, -CH=N-, -N=N-, -C≡C-, or a single bond. R a and R beach independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms (a hydrogen atom present in this group may be replaced by a fluorine atom, and one -CH- or two or more non-adjacent -CH- present in this group each independently represents -NR c It may be replaced by -, -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C-. R c represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (one -CH2- or two or more non-adjacent -CH2- groups in these groups may be each independently replaced by -O-, -S-, -COO-, -OCO- or -CO-, and a hydrogen atom in these groups may be replaced by a fluorine atom). n and m each independently represent an integer of 1 to 3. A a and Z a If there are multiple A's, multiple A's a may be the same or different, and multiple Z a may be the same or different from each other. A b and Z b If there are multiple A's, multiple A's b may be the same or different, and multiple Z b may be the same or different from each other. R c If there are multiple R c may be the same or different, provided that no oxygen atom in formula (30) is directly bonded to another oxygen atom.

[0179] A specific preferred example of the compound represented by the general formula (13) (sometimes referred to as compound (13)) is a compound represented by the following formula (13A).

[0180] [ka]

[0181] In formula (13A), R d and R e Each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. Details of the alkyl group and the alkenyl group (including preferred embodiments) are described in R a and R b The details of the alkyl and alkenyl groups are the same as those of the alkyl and alkenyl groups represented by the following formula:

[0182] [ka]

[0183] A in Equation (14) and Equation (15) a , A b , A c , Z a , Z b , R a , R b , R c , R d , R e , L a , L b The meanings are as follows: A a , A b and A c each independently represents a group selected from the group consisting of the following group (a2) and group (b2):

[0184] (a2) a 1,4-cyclohexylene group (in which one -CH2- or two or more non-adjacent -CH2- groups may each be independently replaced by -O- or -S-), (b2) a 1,4-phenylene group (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by -N=),

[0185] The hydrogen atoms present in the groups (a2) and (b2) may each independently be replaced by a methyl group, a fluorine atom or a chlorine atom. R arepresents a hydrogen atom or a methyl group. R b is -NH-R g , a hydrogen atom, or a hydroxyl group. R g represents a hydrogen atom or a methyl group. R c , R d , and R e each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms (a hydrogen atom present in this group may be replaced by a fluorine atom, and one -CH- or two or more non-adjacent -CH- present in this group each independently represents -NR f may be replaced by -, -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C-, R f represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (one -CH2- or two or more non-adjacent -CH2- groups in these groups may be each independently replaced by -O-, -S-, -COO-, -OCO- or -CO-, and a hydrogen atom in these groups may be replaced by a fluorine atom). L a and L b each independently represents an oxygen atom or a sulfur atom. R f If there are multiple R f may be the same or different, provided that no oxygen atom in formula (14) is directly bonded to another oxygen atom.

[0186] An example of the red dye compound represented by the general formula (13A) is the compound represented by the following formula (cr-7).

[0187] [ka]

[0188] Examples of the red dye compounds represented by the general formulas (14) and (15) include the compounds represented by the following formulas (cr-8) to (cr-11).

[0189] [ka]

[0190] The yellow dye compound is preferably at least one selected from the group consisting of compounds represented by the following general formulas (16), (17), (8), and (9).

[0191] [ka]

[0192] [ka]

[0193] In the above general formula (16), R 1 ,R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (one -CH2- or two or more non-adjacent -CH2- in these groups may each be independently replaced by -O-, -S-, -COO-, -OCO-, -CO- or -N=, and a hydrogen atom in these groups may be replaced by a fluorine atom).

[0194] In the above general formula (17), R 1 represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, or an acyloxy group; R 2 represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, a cycloalkyl group, an amino group, an acylamino group, a pyrrolidinyl group, or a hydroxyl group, L 1 , L2 each independently represents a single bond, -O-, -O-CO-, -CO-O-, -O-CH2-, -CH2-O-, -O-C2H5-, -C2H5-O-, or -S-; X 1 , X 2 each independently represents a hydrogen atom or a methyl group; m represents 1 or 2, n represents 0 or 1, and p represents 0 or 1.

[0195] [ka]

[0196] In the above general formula (18), R1 and R2 each independently represent a methyl group, an alkyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a phenyl group, or a benzyl group, and one or more hydrogen atoms in the ring of the phenyl group or the benzyl group may be substituted with a halogen atom, a methyl group, or an alkyl group having 2 to 4 carbon atoms. R3 and R4 each independently represent a methyl group, an alkyl group having 2 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms.

[0197] [ka]

[0198] In the above general formula (19), R1, R2, and R3 each independently represent either unsubstituted or a methyl group, an alkyl group having 2 to 4 carbon atoms, a hydroxyl group, or a benzene ring.

[0199] Examples of the yellow dye compounds represented by the general formula (16), general formula (17), general formula (18), and general formula (19) include the compounds represented by the following formulae (cr-12) to (cr-15).

[0200] [ka]

[0201] [ka] It is preferable that the compound is represented by the following formula:

[0202] The total content of the dye (CR) according to this embodiment is preferably from 0.01% by mass to 12% by mass, and more preferably from 0.1% by mass to 10% by mass, relative to the total amount (100% by mass) of the non-polymerizable liquid crystal compound (LB) used in the polymer dispersed liquid crystal composition of this embodiment. The total content of the blue dye compounds in the dye (CR) according to this embodiment is preferably from 0.01% by mass to 6% by mass, and more preferably from 0.1% by mass to 5% by mass, relative to the total amount (100% by mass) of the non-polymerizable liquid crystal compound (LB) used in the polymer dispersion type liquid crystal composition of this embodiment. The total content of the red dye compounds in the dye (CR) according to this embodiment is preferably from 0.01% by mass to 5% by mass, and more preferably from 0.1% by mass to 4% by mass, relative to the total amount (100% by mass) of the non-polymerizable liquid crystal compound (LB) used in the polymer dispersed liquid crystal composition of this embodiment. The total content of the yellow dye compounds in the dye (CR) according to this embodiment is preferably from 0.01% by mass to 4% by mass, and more preferably from 0.1% by mass to 3% by mass, relative to the total amount (100% by mass) of the non-polymerizable liquid crystal compound (LB) used in the polymer dispersed liquid crystal composition of this embodiment.

[0203] [Other dyes] The dye used in this embodiment is not particularly limited other than the dye (CR), and any known and commonly used dye (sometimes referred to as "other dye") can be used as long as it is soluble in liquid crystal, or can be dispersed in a polymerizable compound, or can be transferred to a polymer network after polymerization phase separation. Examples of the other dye include dichroic dyes and fluorescent dyes. Examples of such dyes include polyazo dyes, anthraquinone dyes, quinacridone dyes, dioxazine dyes, quinophthalone dyes, quinoline dyes, methine dyes, cyanine dyes, phthalocyanine dyes, perylene dyes, perinone dyes, and squarylium dyes. From the viewpoint of addition, the other dyes are preferably dyes exhibiting liquid crystallinity. For example, polyazo dyes disclosed in JP-A-51-2885, JP-A-61-21163, JP-A-62-555, JP-A-63-301850, JP-A-7-48520, JP-A-7-179858, JP-A-10-279945, JP-A-11-172252, JP-A-2000-239664, JP-A-2012-82400, etc., and JP-A-59-20355 Examples of the anthraquinone dyes include those disclosed in JP-A-59-172549, JP-A-61-148291, JP-A-1-161086, JP-A-8-67822, etc.; those disclosed in JP-A-59-51947 and JP-A-61-148292, etc.; and those disclosed in JP-A-2000-44825 and JP-A-2001-49135, etc.

[0204] When the other dyes are contained, the content is preferably from 0.01% by mass to 12% by mass, and more preferably from 0.10% by mass to 10% by mass, relative to the total amount (100% by mass) of the non-polymerizable liquid crystal compound (LB) used in the polymer dispersion type liquid crystal composition of this embodiment.

[0205] [Pigments] The pigment used in this embodiment can be used to impart color to the polymerizable liquid crystal element of this embodiment or to control the color. Such a pigment is not particularly limited, and any known and commonly used pigment can be used as long as it disperses in the liquid crystal or network polymer. Examples of such pigments include azo pigments, diketopyrrolopyrrole pigments, quinacridone pigments, dioxazine pigments, perylene pigments, phthalocyanine pigments, and carbon black pigments. From the viewpoint of effectively imparting coloring properties, the pigment is preferably one that has good dispersibility in the network polymer.

[0206] When the above-mentioned pigment is contained, the content is preferably from 0.01% by mass to 8% by mass, and more preferably from 0.05% by mass to 4% by mass, relative to 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB) used in the polymer dispersion type liquid crystal composition of this embodiment.

[0207] [Polymerization initiator] The polymer dispersion type liquid crystal composition of this embodiment may contain a polymerization initiator. The polymerization initiator used in this embodiment is used to polymerize the polymerizable compound (MA) of this embodiment. The photopolymerization initiator used when polymerization is performed by light irradiation is not particularly limited, and any known and commonly used initiator may be used as long as it does not inhibit the alignment state of the non-polymerizable liquid crystal compound (LB).

[0208] For example, 1-hydroxycyclohexyl phenyl ketone (Omnirad 184), 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one (Omnirad 1173), 2-methyl-1-[(methylthio)phenyl]-2-morpholinopropan-1 (Omnirad 907), 2,2-dimethoxy-1,2-diphenylethan-1-one (Omnirad BDK), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone (Omnirad 369) "), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino-phenyl)butan-1-one "Omnirad 379", 2,2-dimethoxy-2-phenylacetophenone "Omnirad 651", 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl)-diphenylphosphine oxide "Omnirad TPO", 2,4,6-trimethylbenzoyl-phenyl-phosphine oxide "Omnirad 819" (IGM Resins Co., Ltd.), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone "Irgacure OXE01"), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) "Irgacure OXE02", "Irgacure OXE04" (BASF Ltd.), "ADEKA ARCLES NCI-831" Examples of such compounds include "ADEKA ARCLES NCI-930", "ADEKA ARCLES N-1919" (manufactured by ADEKA Corporation), a mixture of 2,4-diethylthioxanthone ("KAYACURE DETX" manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate ("KAYACURE EPA" manufactured by Nippon Kayaku Co., Ltd.), a mixture of isopropylthioxanthone ("CANTACURE-ITX" manufactured by Ward Prexon Co., Ltd.) and ethyl p-dimethylaminobenzoate, "ESACURE ONE", "ESACURE KIP150", "ESACURE KIP160", "ESACURE 1001M", "ESACURE A198", "ESACURE KIP IT", "ESACURE KTO46", "ESACURE TZT" (manufactured by Lamberti Co., Ltd.), "Speedcure BMS", "Speedcure PBZ", and "Benzophenone" (manufactured by LAMBSON Co., Ltd.).Furthermore, as the photocationic initiator, a photoacid generator can be used, such as a diazodisulfone-based compound, a triphenylsulfonium-based compound, a phenylsulfone-based compound, a sulfonylpyridine-based compound, a triazine-based compound, and a diphenyliodonium compound.

[0209] The content of the photopolymerization initiator is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.2% by mass or more and 6% by mass or less, relative to 100% by mass of the total amount of the polymerizable compound (MA) used in the polymer-dispersed liquid crystal composition of the present embodiment. These may be used alone or in combination of two or more kinds.

[0210] In addition, as the thermal polymerization initiator used in the thermal polymerization, a known and commonly used one can be used, for example, methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, isobutyl peroxide, di(3-methyl-3-methoxybutyl)peroxide, Organic peroxides such as dimethyl peroxycarbonate and 1,1-bis(t-butylperoxy)cyclohexane, azonitrile compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile), azoamide compounds such as 2,2'-azobis(2-methyl-N-phenylpropion-amidine) dihydrochloride, azoamide compounds such as 2,2'azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, and alkyl azo compounds such as 2,2'azobis(2,4,4-trimethylpentane) can be used. The content of the thermal polymerization initiator is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 6% by mass or less, based on the total amount (100% by mass) of the polymerizable compound (MA) used in the polymer dispersion type liquid crystal composition of this embodiment. These may be used alone or in combination of two or more.

[0211] The polymer-dispersed liquid crystal composition of the present embodiment may contain a polymerization inhibitor, an antioxidant, a light stabilizer, a chain transfer agent, particles having a particle size of less than 1 μm, a chiral compound, or an alignment material within a range that does not impair practical electro-optical properties and adhesion when made into a polymer-dispersed liquid crystal element. Among these, the polymer-dispersed liquid crystal composition preferably contains one or more selected from the group consisting of polymerization inhibitors, antioxidants, light stabilizers, particles having a particle size of less than 1 μm, dyes, and pigments.

[0212] [Polymerization inhibitor] The polymerization inhibitor used in the present embodiment can be used to adjust the electro-optical properties by controlling the polymerization reaction of the polymer dispersion type liquid crystal composition of the present embodiment. As such a compound, any known and commonly used compound can be used.

[0213] For example, phenolic compounds such as p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis(4-methyl-6-t-butylphenol), 2.2'-methylenebis(4-ethyl-6-t-butylphenol), 4.4'-thiobis(3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, and 4,4'-dialkoxy-2,2'-bi-1-naphthol, hydroquinone, and methylhydroquinone. Preferred are quinone compounds such as tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, and diphenoquinone, and particularly preferred are p-methoxyphenol, 4-methoxy-1-naphthol, tert-butylhydroquinone, and 2-hydroxy-1,4-naphthoquinone.

[0214] When a polymerization inhibitor is contained, the content is preferably from 0.001% by mass to 2.0% by mass, and more preferably from 0.01% by mass to 0.5% by mass, relative to 100% by mass of the total amount of the polymerizable compounds (MA) used in the polymer dispersion type liquid crystal composition of this embodiment.

[0215] [Antioxidants] The antioxidant used in this embodiment can be used to impart practical durability to the polymer dispersed liquid crystal element of this embodiment. Examples of such compounds include hydroquinone derivatives, nitrosamine-based polymerization inhibitors, and hindered phenol-based antioxidants.

[0216] Specifically, tert-butyl hydroquinone, Fujifilm Wako Pure Chemical's "Q-1300" and "Q-1301", pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate "IRGANOX1010", thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate "IRGANOX1035", octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate "IRGANOX1076", "IRGANOX1135", "IRGANOX1330", 4,6-bis(octyl Preferred are (1-methylthiomethyl)-o-cresol "IRGANOX1520L", "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", and "IRGANOX565" (all manufactured by BASF Ltd.), Adeka STAB AO-20, AO-30, AO-40, AO-50, AO-60, and AO-80 manufactured by ADEKA CORPORATION, Sumilizer BHT, Sumilizer BBM-S, and Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd., and compounds having structures represented by the following general formulas (H-1) to (H-4), and the like.

[0217] [ka]

[0218] In general formulas (H-1) to (H-3), R H1represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, and one -CH2- or two or more non-adjacent -CH2- present in the group may be independently substituted with -O- or -S-, and one or more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom. More specifically, it is preferably an alkyl group having 2 to 7 carbon atoms, an alkoxy group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms, and more preferably an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms. In addition, in the general formula (H-4), Sp H1 represents an alkylene group having 1 to 10 carbon atoms, in which one -CH- or two or more non-adjacent -CH- groups may each be independently replaced with -O- or -S-, and one or more hydrogen atoms in the group may each be independently replaced with a fluorine atom or a chlorine atom.

[0219] Among them, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the compounds represented by the general formulae (H-2) to (H-3) are particularly preferred.

[0220] When an antioxidant is contained, the content is preferably from 0.001% by mass to 2.0% by mass, and more preferably from 0.01% by mass to 0.5% by mass, relative to 100% by mass of the total amount of the polymerizable compounds (MA) used in the polymer dispersion type liquid crystal composition of this embodiment.

[0221] [Light stabilizer] The light stabilizer used in this embodiment can be used to impart practical durability to the polymer dispersed liquid crystal element of this embodiment. Examples of such compounds include "TINUVIN 111FDL", "TINUVIN 123", "TINUVIN 144", "TINUVIN 152", "TINUVIN 292", "TINUVIN 622", "TINUVIN 770", "TINUVIN 765", "TINUVIN 780", "TINUVIN 905", "TINUVIN 5100", "TINUVIN 5050", "TINUVIN 5060", "TINUVIN 5151", "CHIMASSORB 119FL", "CHIMASSORB 944FL", and "CHIMASSORB 5151". 944LD" (all manufactured by BASF Ltd.), "ADK STAB LA-52", "ADK STAB LA-57", "ADK STAB LA-62", "ADK STAB LA-67", "ADK STAB LA-63P", "ADK STAB LA-68LD", "ADK STAB LA-77", "ADK STAB LA-82", and "ADK STAB LA-87" (all manufactured by ADEKA Corporation).

[0222] When a light stabilizer is contained, the amount added is preferably from 0.001% by mass to 2.0% by mass, and more preferably from 0.01% by mass to 1.0% by mass, relative to the total amount (100% by mass) of the polymerizable compound (MA) used in the polymer dispersion type liquid crystal composition of this embodiment.

[0223] [Chain transfer agent] The chain transfer agent used in this embodiment can be used to further improve the adhesion between the polymer dispersion type liquid crystal composition and the substrate. Examples of the chain transfer agent include mercaptan compounds such as octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, n-dodecyl mercaptan, t-tetradecyl mercaptan, and t-dodecyl mercaptan, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, and trimethylolpropane tris(3-mercaptobutyrate). , pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine and other thiol compounds, pentaphenylethane, α-methylstyrene dimer, acrolein, allyl alcohol, terpinolene, α-terpinene, γ-terpinene, dipentene, and the like are included, but specifically, the compounds represented by the following general formulas (9-1) to (9-8), α-methylstyrene dimer, and α-terpinene are preferred.

[0224] [ka]

[0225] In the formula, R 95 represents an alkyl group having 1 to 18 carbon atoms, the alkyl group may be linear or branched, one or more methylene groups in the alkyl group may be substituted with an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO-, or -CH=CH-, provided that the oxygen atom and the sulfur atom are not directly bonded to each other, R 96represents an alkylene group having 2 to 18 carbon atoms, and one or more methylene groups in the alkylene group may be substituted with an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO-, or -CH=CH-, provided that the oxygen atoms and sulfur atoms are not directly bonded to each other.

[0226] When a chain transfer agent is contained, the content is preferably from 0.001% by mass to 10% by mass, and more preferably from 0.01% by mass to 5.0% by mass, relative to 100% by mass of the total amount of the polymerizable compound (MA) in the polymer dispersion type liquid crystal composition of this embodiment.

[0227] [Particles with a diameter of less than 1 μm] The particles having a particle diameter of less than 1 μm used in this embodiment can be used to impart various functions to the polymer-dispersed liquid crystal element of this embodiment. There are no particular limitations on such particles, but they can be used within a range that does not impair the electro-optical properties or adhesion of the liquid crystal element. Examples of such particles include inorganic fillers such as alumina, titanium white, titanium black, aluminum hydroxide, talc, clay, mica, barium titanate, zinc oxide, and glass fiber, metal powders such as silver powder and copper powder, thermally conductive fillers such as aluminum nitride, boron nitride, silicon nitride, gallium nitride, silicon carbide, magnesia (magnesium oxide), silica, crystalline silica (silicon oxide), fused silica (silicon oxide), graphite, and carbon fibers including carbon nanofibers, silver nanoparticles, QD luminous particles, and perovskite-type luminous particles.

[0228] The particles are preferably particles having good dispersibility in the network polymer. When the particles are contained, the content is preferably 0.001% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 3% by mass or less, relative to the total amount (100% by mass) of the non-polymerizable liquid crystal compound (LB) used in the polymer-dispersed liquid crystal composition of the present embodiment.

[0229] [Chiral Compounds] The chiral compound used in this embodiment can be used to impart various functions to the polymer-dispersed liquid crystal element of this embodiment. There is no particular limitation on the chiral compound, but it can be used within a range that does not impair the electro-optical properties or adhesion of the liquid crystal element. Specific examples of such chiral compounds include cholesterol pelargonate and cholesterol stearate having a cholesteryl group as a chiral group, BDH's "CB-15" and "C-15" having a 2-methylbutyl group as a chiral group, Merck's "S-1082", Chisso's "CM-19", "CM-20", and "CM", Merck's "S-811" having a 1-methylheptyl group as a chiral group, Chisso's "CM-21" and "CM-22", BASF's "LC756" having an isosorbide skeleton as a chiral group, and polymerizable chiral compounds disclosed in JP-T-2009-515818, JP-A-2010-90108, JP-A-2013-87109, and the like.

[0230] When a chiral compound is contained, it is preferable to add the chiral compound in an amount such that the value (d / P) obtained by dividing the thickness (d) of the resulting polymer by the helical pitch (P) in the polymer is in the range of 0.1 to 100, and more preferably in the range of 0.1 to 20, depending on the application of the polymer in the polymer-dispersed liquid crystal composition of this embodiment.

[0231] The chiral compound is preferably contained in an amount as small as possible that provides a desired helical pitch in order to bring out the characteristics of the liquid crystal composition. When a chiral compound is contained, the amount is preferably 0.01% by mass or more and 8% by mass or less, and more preferably 0.1% by mass or more and 4% by mass or less, relative to the total amount (100% by mass) of the non-polymerizable liquid crystal compound (LB) used in the polymer-dispersed liquid crystal composition of the present embodiment.

[0232] [Alignment material] The polymer dispersion type liquid crystal composition of the present embodiment may contain an alignment material to control the alignment of the liquid crystal element. The alignment material used in the present embodiment may be any known and commonly used material within the range of dissolution in the liquid crystal composition. Examples of such alignment materials include polymerizable compounds having a polar group at one end of a mesogenic skeleton and a long-chain alkyl group at the other end, polymerizable liquid crystal compounds having a polar group at the lateral position of a mesogenic skeleton, and polymerizable compounds having multiple mesogenic skeletons and having a polar group at the side chain of a long-chain alkyl group that bonds one mesogenic skeleton to the other mesogenic skeleton.

[0233] <Liquid crystal element> A liquid crystal element using the polymer-dispersed liquid crystal composition of the present embodiment (sometimes referred to as a polymer-dispersed liquid crystal element) comprises at least a layer in which liquid crystal and a network polymer are phase-separated (phase-separated liquid crystal layer), electrodes, and a substrate, or comprises a phase-separated liquid crystal layer, an alignment film layer, electrodes, and a substrate supporting the electrodes.

[0234] The phase-separated liquid crystal layer is obtained by polymerizing the polymerizable compound (MA) contained in the polymer dispersed liquid crystal composition to form a polymer network derived from each polymerizable component contained in the polymerizable compound (MA).

[0235] The liquid crystal element of this embodiment can be in a light scattering state due to the polymer network structure and the liquid crystal molecules present in the gaps therebetween when no voltage is applied. On the other hand, when a voltage is applied, the liquid crystal molecules are oriented perpendicularly to the substrate, resulting in a transparent state. In this way, the liquid crystal element of this embodiment can change its light transmission state depending on whether or not a voltage is applied, and therefore can be used as a liquid crystal light control element incorporated into a device that requires a light control function, or as a liquid crystal display element used in a display for displaying images.

[0236] The liquid crystal element of the present embodiment may be configured so that the orientation of the liquid crystal molecules can be controlled by applying a voltage, but is preferably configured as a vertical electric field type liquid crystal element. A vertical electric field type liquid crystal element is a liquid crystal element in which electrodes are arranged so that an electric field is generated vertically to the alignment film. In a vertical electric field type liquid crystal element, electrodes are usually provided on both of the two transparent substrates that sandwich the phase-separated liquid crystal layer.

[0237] The vertical electric field type liquid crystal element according to this embodiment has a first substrate and a second substrate each having a transparent electrode (layer) made of a transparent conductive material, and a phase-separated liquid crystal layer sandwiched between the first substrate and the second substrate. The phase-separated liquid crystal layer is made of a polymer-dispersed liquid crystal material composed of liquid crystal molecules and a polymer component contained in the liquid crystal composition.

[0238] In addition, if necessary, an ultraviolet shielding film, an infrared shielding film, a gas barrier film for blocking oxygen and water vapor, a colored film for imparting design with color or pattern, a hard coat layer for preventing scratches, a refractive index adjustment layer formed for the purpose of preventing a decrease in visible light transmittance caused by the refractive index difference between the transparent electrode layer and the flexible substrate, an undercoat layer for ensuring adhesion between the transparent electrode layer and the flexible substrate, an adhesive film or bonding film for fixing the flexible light control element to another transparent support structure, a film having the above-mentioned functions, or an adhesive film or bonding film for bonding these films together to integrate them may be configured in combination. In addition, an easy-adhesion treatment layer may be formed on the outermost surface of the transparent conductive layer on the side in contact with the light control layer.

[0239] 〔substrate〕 The substrate used in the liquid crystal element of this embodiment is a substrate that is commonly used in liquid crystal display elements, organic light-emitting display elements, other display elements, optical components, light control elements, colorants, markings, printed matter, and optical films, and is not particularly limited as long as it is a material that has heat resistance that can withstand the heating in the manufacturing process of the liquid crystal element and the temperature range in which it is used, or has transparency that can withstand practical use in applications where transparency is important.

[0240] Examples of such substrates include glass substrates, metal substrates, ceramic substrates, plastic substrates, and organic materials such as paper. In particular, when the substrate is an organic material, examples of the substrate include cellulose derivatives, polyolefins, polyesters, polycarbonates, polyacrylates, polyarylates, polyethersulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, and polystyrenes. Among these, it is preferable to use plastic substrates such as polyesters, polystyrenes, polyolefins, cellulose derivatives, polyarylates, polycarbonates, and polyimides. In the case where the device has two substrates, it is preferable that both of the pair of substrates have a transparency sufficient for practical use as a liquid crystal element.

[0241] When used in the light control element of the present invention, the substrate is preferably flexible. A transparent flexible substrate having a transparent conductive layer formed on at least one surface thereof is preferably used. Materials for flexible substrates include inorganic materials such as glass that transmit visible light, and organic materials such as plastics. Materials that transmit visible light, are transparent and flexible, and have sufficient heat resistance, weather resistance, light resistance, chemical resistance, and impact resistance to withstand use, can be selected for use. When the substrate is an organic material, a plastic base material is preferable, and examples thereof include biaxially oriented polyester (PET) film, polyethylene naphthalate (PEN) film, PET-G film, cycloolefin (COP) film, acrylic film, polycarbonate (PC) film, triacetate (TAC) film, polyimide (PI) film, polyphenylene sulfide (PPS) film, cellulose derivatives, polyethylene (PE), polypropylene (PP), biaxially oriented polypropylene (OPP), polyethylene-based multilayer film, and nylon-based multilayer film. In order to adjust the difference between the refractive index of the flexible transparent substrate material and the refractive index of the transparent electrode material and ensure the transparency of the flexible transparent conductive substrate, a refractive index adjustment layer may be formed adjacent to the transparent electrode on the surface between the flexible transparent substrate and the flexible transparent substrate, or on the surface opposite to the flexible transparent substrate. Adjacent to the flexible transparent substrate, an easy-adhesion treatment layer or a hard coat layer may be formed on the surface between the transparent electrode or the refractive index adjustment layer, or on the surface opposite to the transparent electrode.

[0242] Although the shape of the substrate is shown as a flat plate, other shapes such as a curved surface may be used. Furthermore, the substrate may have an electrode layer, an anti-reflection function, or a reflection function, as necessary.

[0243] In order to improve the adhesion in the liquid crystal element of this embodiment, the surface of these substrates may be treated. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, and silane coupling treatment. In addition, in order to adjust the light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, or the like may be provided on the surface of the substrate by a method such as deposition, or in order to add optical value, the substrate may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a microlens sheet, a color filter, or the like.

[0244] [Electrode: Transparent electrode layer] The electrodes used in the liquid crystal element of the present embodiment are provided so as to generate an electric field capable of controlling the alignment of liquid crystal molecules in the phase-separated liquid crystal layer in the liquid crystal element. The electric field strength is controlled by the level of voltage applied to the electrodes. The shape of the electrode is not particularly limited, and the conductive portion may be in the form of a uniform surface, stripes or mesh, or a random network.

[0245] In order to enhance the transparency of the liquid crystal element, it is preferable that the electrodes are formed of transparent electrode layers. The electrode material for forming the transparent electrode can be selected from, for example, metals, metal oxides, metal alloys, and organic conductive materials, so long as it is transparent. In the case of metal oxides, a transparent film can be formed by using a known transparent conductive material such as ITO (indium tin oxide), IZO (indium zinc oxide), or IZTO (indium zinc tin oxide) by a method such as sputtering or vapor deposition. Other examples that can be used include a film formed transparently by sputtering or vapor deposition of a metal or metal alloy, a metal or metal alloy arranged in a mesh or wire shape, or a composite film of these. Metal materials include silver, copper, gold, chromium, aluminum, tantalum, titanium, molybdenum, tungsten, nickel, or an alloy containing at least one of these, with silver or an alloy containing silver being preferred. Examples of the organic conductive material include conductive polymers such as polythiophenes such as polyethylenedioxythiophene (PEDOT), polyacetylenes, polyanilines, and polypyrroles. Polythiophenes are preferred because they have a good balance of conductivity, stability, transparency, and film-forming properties, and polyethylenedioxythiophene (PEDOT) is more preferred.

[0246] [Alignment Layer] The substrate may be subjected to an alignment treatment or an alignment film so that the liquid crystal molecules in the polymer-dispersed liquid crystal element of the present embodiment are aligned horizontally or vertically. Examples of the alignment treatment include stretching, rubbing, polarized ultraviolet-visible light irradiation, ion beam treatment, and oblique deposition of SiO2 on the substrate. Examples of such alignment films include compounds such as polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, epoxy acrylate resin, acrylic resin, azo compounds, coumarin compounds, chalcone compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, and arylethene compounds, or polymers or copolymers of the above compounds. When a rubbing treatment is performed to impart a tilt angle to the liquid crystal molecules, it is preferable that the compound to be aligned by rubbing is one in which crystallization of the material is promoted by a heating process during or after the alignment treatment. Among compounds to be aligned other than by rubbing, it is preferable to use a photoalignment material.

[0247] [Refractive index adjusting layer] The refractive index adjusting layer can be made of a transparent metal oxide, for example, a material formed by applying and drying a dispersion of ultrafine particles made of zinc oxide, titanium oxide, zirconium oxide, antimony-doped tin oxide (ATO), aluminum oxide, silicon oxide, or the like, or a material formed by forming a film of such a material on a flexible substrate by sputtering.

[0248] In general, when a liquid crystal composition is brought into contact with a substrate having an alignment function, the liquid crystal molecules are aligned in the direction of the alignment treatment of the substrate near the substrate. Whether the liquid crystal molecules are aligned parallel to the substrate, tilted, or perpendicular is greatly influenced by the alignment treatment method for the substrate.

[0249] [Example of a method for manufacturing a liquid crystal element] From the viewpoint of productivity, the liquid crystal element of the present embodiment is preferably produced by, for example, using a roll-to-roll method, dropping or applying a polymer dispersed liquid crystal composition onto a substrate by an ODF method or the like, and laminating an opposing substrate.

[0250] In the manufacturing process of the liquid crystal element by the roll to roll method, the polymer-dispersed liquid crystal composition is applied onto a first electrode, or a glass substrate having an alignment film and a first electrode, or a plastic substrate, and the polymer-dispersed liquid crystal composition is bonded to a second electrode, or a glass substrate having an alignment film and a second electrode, or a plastic substrate so that the liquid crystal composition is in contact with the electrode side or the alignment film side of the plastic substrate, and the thickness is made uniform, thereby manufacturing the liquid crystal element. The method of applying the polymer-dispersed liquid crystal composition used in the present embodiment includes known and commonly used methods such as an applicator method, a bar coating method, a roll coating method, a direct gravure coating method, a reverse gravure coating method, an inkjet method, a die coating method, and a cap coating method. In the manufacturing process of the liquid crystal element by the ODF method, a liquid crystal display sealant such as an epoxy-based photothermal curing sealant is drawn in a closed-loop bank shape on one of the substrates, the backplane or the frontplane of a hollow element, using a dispenser, and a predetermined amount of the liquid crystal composition is dropped therein under degassing, and then the frontplane and the backplane are joined to manufacture the liquid crystal element.

[0251] The liquid crystal element of this embodiment can be produced from a liquid crystal element by interposing a spacer between two substrates for maintaining a distance, as in the case of known liquid crystal elements. The thickness between the substrates, i.e., the thickness of the phase separation layer, is preferably 2 to 50 μm, more preferably 10 to 30 μm. The spacers may be dispersed on the substrates in advance, or may be mixed in the polymer-dispersed liquid crystal composition in advance and applied to the substrates simultaneously with the polymer-dispersed liquid crystal composition.

[0252] The method for sandwiching the polymer-dispersed liquid crystal composition between two substrates may be a normal vacuum injection method, but is preferably performed by dropping or coating such as the ODF method. It is preferable that the polymer-dispersed liquid crystal composition is in a uniform isotropic state from this dropping or coating until the polymerizable compound (MA) is polymerized. When dropping or coating is performed, the polymer dispersion type liquid crystal composition can be sandwiched between two substrates by a method such as sandwiching the two substrates with a laminator.

[0253] The polymer-dispersed liquid crystal composition of the present embodiment may be mixed with particles for determining the thickness of a liquid crystal element, and the composition may be sandwiched between a hollow element. As such particles, well-known and commonly used glass particles or polymer particles used in general liquid crystal display elements and liquid crystal displays may be used.

[0254] In this case, a preferred method is to apply a composition containing the polymer dispersed liquid crystal composition and particles that determine the thickness of the liquid crystal element onto the plastic substrate having a first electrode, and then bond the plastic substrate having a second electrode to the substrate using a rubber roll, a laminator, or the like so that the first electrode and the second electrode face each other, and then irradiate ultraviolet light in this state; to irradiate ultraviolet light while the bonded first plastic substrate and the second plastic substrate are in close contact by applying pressure to the bonded first plastic substrate and the second plastic substrate; or to irradiate ultraviolet light while the bonded first plastic substrate and the second plastic substrate are in a vacuum state to bond them together, and then irradiate ultraviolet light in the vacuum state.

[0255] [Polymerization method] As a method for polymerizing the polymer-dispersed liquid crystal composition of the present embodiment, ultraviolet irradiation is suitable. As a lamp for generating ultraviolet light, a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like can be used. In addition, as the wavelength of the ultraviolet light to be irradiated, it is preferable to irradiate ultraviolet light having a wavelength range that is within the absorption wavelength range of the photopolymerization initiator contained in the polymer-dispersed liquid crystal composition and is not within the absorption wavelength range of the liquid crystal composition contained therein. Specifically, it is preferable to irradiate light from a metal halide lamp, a high-pressure mercury lamp, or an ultra-high-pressure mercury lamp by cutting ultraviolet light of 330 nm or less through an ultraviolet cut filter or the like. In addition, it is also preferable to use a UV-LED lamp that can irradiate a single wavelength.

[0256] The intensity of the ultraviolet light to be irradiated can be appropriately adjusted to obtain the desired photochromic layer, but is generally in the range of 1 to 200 mW / cm. 2 is preferred, and 5 to 50 mW / cm 2 The time for irradiating with ultraviolet light is appropriately selected depending on the intensity of the ultraviolet light to be irradiated, but is preferably from 10 to 300 seconds.

[0257] In addition, since the temperature of the bonded first plastic substrate and the second plastic substrate during ultraviolet irradiation is an important factor that determines the characteristics of the light control layer of the liquid crystal element, a temperature higher than the isotropic-nematic transition point (T nm) of the polymer dispersed liquid crystal composition is preferable.

[0258] The liquid crystal element of the present embodiment can be used as it is, or can be attached to another substrate for use. In addition, an adhesive or adhesive layer, a pressure sensitive adhesive or adhesive layer, an ultraviolet cut film or an infrared cut film, a protective film, a polarizing film, or the like may be laminated thereon.

[0259] [Other electric field types] The liquid crystal element of this embodiment may adopt a horizontal electric field type or other electric field types in addition to the vertical electric field type. A fringe electric field adopted in the FFS driving mode may be adopted. In this case, a horizontal alignment layer may be provided. The horizontal alignment layer may be made of a known material.

[0260] The liquid crystal element of the present embodiment is preferably used, for example, in building materials, light control glass, smart windows for vehicles, or light control units in OLED displays. The liquid crystal display element of the present embodiment can be used for the same applications as conventional polymer-dispersed liquid crystal display elements, and is particularly preferably used in transmissive displays, flexible displays, and the like. More specifically, it can be used in products such as architectural light control elements such as windows, skylights, roofs, walls, partitions, partitions, and doors; transportation light control elements such as doors, windows, doors, helmets, and sunroofs; decorative light control elements such as sunglasses, glasses, sun visors, watches, mirrors, and reflectors; flexible liquid crystal display elements, reflective liquid crystal display elements, transparent liquid crystal display elements, and display members such as variable diffusion films.

[0261] <Light control element> The light control element of the present embodiment includes a pair of transparent electrode substrates and a composite layer including a polymer network and a liquid crystal compound disposed between the pair of transparent electrode substrates. The polymer network is a polymer network derived from a polymerizable compound (MA) contained in the polymer-dispersed liquid crystal composition, and the liquid crystal compound is a non-polymerizable liquid crystal compound (LB) contained in the polymer-dispersed liquid crystal composition.

[0262] The pair of transparent electrode substrates are preferably made of a flexible material. Examples of the flexible substrate made of a flexible material include the flexible substrate used in the liquid crystal element of the present embodiment and preferred examples thereof.

[0263] This light control element can be switched between a scattering (light blocking) state and a transparent state for visible light by applying or removing a potential difference between a pair of opposing transparent electrodes.

[0264] The light-adjustable element of this embodiment preferably has a scattering degree of 1.5 or less, as determined by a method for measuring and analyzing the detection angle dependency of forward scattered light of straight transmitted light. Using a liquid crystal property measuring device LCD5200 (manufactured by Otsuka Electronics Co., Ltd.), the transmittance to air was set to 100% when quasi-parallel light from a halogen lamp was projected at 25° C. The light was projected from an angle of 15° to the normal to the sample surface, and the transmitted light was received on the opposite surface. The amount of received light was measured by moving the receiver between -15° and 70°, with the receiving angle on the opposite side to the direct projection of the light set to -15°. The degree of scattering was calculated by integrating the transmittance distribution, excluding straight-line light, between receiving angles of -10° and 70° (between 5° and 85°, assuming that the angle of the straight-line opposing side of the projected light is 0°) at 1° intervals for a receiving angle of -15° on the straight-line opposing side. If the scattering degree of a light control element exceeds 1.5, there will be excessive forward scattering at angles other than straight light, so when the light control element is installed in a window and the transmitted light of external light entering the element is observed from the side of the element opposite the incident light, the transmitted light will be strongly scattered, reducing the blackness of the light control element in the light blocking state and appearing to be white-out. By making the scattering degree less than 1.5, the white-out on the light control element surface can be sufficiently suppressed, creating a comfortable space that harmonizes with the design of the light control element and the window in which it is installed.

[0265] The light control element of this embodiment preferably has a diffuse transmittance of 20% or less according to JIS K7136 (test method for haze of plastic / transparent materials). When the diffuse transmittance (the difference between the total light transmittance and the parallel light transmittance) of a photochromic element, measured using a measuring device such as a haze meter in accordance with JIS K7136, exceeds 20%, there is excessive forward scattering at angles other than straight light, so when the photochromic element is installed in a window and the transmitted light from outside incident on the element is observed from the side of the element opposite the incident light, the transmitted light is strongly scattered, reducing the blackness of the photochromic element in the light-blocking state and making it appear whitish. By making the diffuse transmittance less than 20%, the whitish blur on the surface of the photochromic element can be sufficiently suppressed, creating a comfortable space that harmonizes with the design of the photochromic element and the window in which it is installed.

[0266] The light control element of this embodiment has a reflection color in a scattering (light blocking) state that meets the CIE 1976 (L * a * b * ) color system (abbreviation: CIELAB) * Value is 0 to 50, a * (red-green axis) is between -30 and 30, b * It is preferable that (yellow-blue axis) is between -30 and 30. The color can be measured at 25° C. using a liquid crystal characteristic measuring device LCD5200 (manufactured by Otsuka Electronics Co., Ltd.) with the chromaticity measuring function of a spectrophotometer. Alternatively, it may be measured using a commercially available spectrophotometer. *The value ranges from 0 to 100 and indicates the brightness of the color. The higher the value, the brighter the color. To obtain sufficient shading effect, L * The value is preferably equal to or less than 50, more preferably equal to or less than 40, and even more preferably equal to or less than 30. If it exceeds 50, the transmitted light in the scattered (light-shielding) state becomes too bright, and the light-shielding effect becomes insufficient. a * Negative values ​​indicate greenishness, positive values ​​indicate reddishness. * Negative values ​​indicate blueness, and positive values ​​indicate yellowness. The closer to 0, the more neutral the black appears. * b * Each absolute value is preferably 30 or less, more preferably 15 or less, and even more preferably 5 or less.

[0267] In the light control element of this embodiment, the contrast ratio of the total light transmittance TT [TT (transparent state) / TT (light-shielding state)] is preferably 2.0 or more. The total light transmittance TT can be measured using a measuring device such as a haze meter that complies with JIS K7136. TT (transparent state) and TT (light-shielding state) refer to the total light transmittance TT when the light-adjusting element is in a transparent state or a light-shielding (scattering) state by either applying a voltage to the light-adjusting element or cutting it off. The higher this ratio, the greater the light-adjusting effect.

[0268] The light control element of this embodiment preferably switches to a light blocking state when no voltage is applied and to a transparent state when a voltage is applied.

[0269] This light control element may be an element that uses the above-mentioned liquid crystal element using a polymer-dispersed liquid crystal composition and electrically controls the light transmittance of the liquid crystal element. This light control element may simply be the above-mentioned liquid crystal element to which a voltage application device is attached, but may also be a laminated glass in which the liquid crystal element is sandwiched between two pieces of glass via an intermediate film such as PVB (polyvinyl butyral), EVA (ethylene vinyl acetate copolymer resin), TPU (polyurethane-based), or SGP. In addition, functional films such as ultraviolet ray cut and heat ray cut may be added.

[0270] (window) A window can be produced by a known method using the light control element of this embodiment. The window of this embodiment preferably includes the light control element, a flat or curved glass plate or resin plate as a window material, and a resin film such as an adhesive film, a pressure sensitive adhesive film, or an intermediate film that bonds and fixes the light control element and the window material. Examples of producing light control windows and smart windows are described in patent documents: JP-A-06-273725 and WO-2011-096386. EXAMPLES

[0271] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the compositions of the following examples and comparative examples, "parts" means "parts by weight".

[0272] The non-polymerizable liquid crystal compounds (LB) used in the examples and comparative examples described later are shown in Table 1. The components of the polymerizable compounds (MA) used in the examples and comparative examples described later are explained in Table 2. The dyes (CR) used in the examples and comparative examples described later are shown in Table 3.

[0273] [Table 1]

[0274] [Table 2]

[0275] [Table 3]

[0276] In Table 3, dye 1 and dye 2 were synthesized with reference to the synthesis method described in the non-patent document "Journal of Chemical and Engineering Data, 1984, 29(4), 482-483." Dye 3 was synthesized with reference to the synthesis example in the patent document "China Patent Publication No. 106748833". Dye 4 was synthesized with reference to the synthesis example described in JP-A-58-145759. Dye 5 was synthesized with reference to the synthesis method described in Non-Patent Document (Liquid Crystals (2011), 38(11-12), 1683-1698). Dye 6 was synthesized with reference to the synthesis example in the patent document "China Patent Publication No. 106748833". As dye 7, a compound described in an example of the patent document "JP-A 2002-31705" was used. Dye 8 was synthesized with reference to the examples in Japanese Patent Application Laid-Open No. 7-156564. As dye 9, a compound described in the patent document "JP-A-10-111523" was used.

[0277] (Synthesis Example 1) 44.4 parts (0.2 moles) of IPDI (isophorone diisocyanate) was added to a flask equipped with a stirring blade, and 810 parts (0.1 moles) of polypropylene glycol (average molecular weight Mw: 8100) was added while stirring, while being careful not to generate heat, and then the temperature was raised to 70°C. The reaction was carried out at this temperature for 7 hours to obtain a urethane polymer having an isocyanate group at the end. Next, 23.2 parts (0.2 moles) of 2-hydroxyethyl acrylate (molecular weight 116) was added, and the reaction was carried out at this temperature for another 7 hours. After confirming that the absorption of NCO had disappeared in the infrared absorption spectrum, the mixture was taken out to obtain urethane acrylate UA-1 (average molecular weight Mw: 29800).

[0278] In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values ​​calculated based on polystyrene standards based on GPC measurement, the measurement conditions of which are as follows:

[0279] [GPC measurement conditions] Measurement equipment: Tosoh Corporation "HLC-8320 GPC"

[0280] Column: Tosoh Corporation guard column "SuperHZ-L" + Tosoh Corporation "SuperHZ2000" x 3 + Tosoh Corporation "TSuperHZM-M" Detector: Built-in RI detector Data processing: Tosoh Corporation "EcoSEC-WorkStation Ver2.01" Measurement conditions: column temperature 40°C, developing solvent tetrahydrofuran, flow rate 1.0 ml / min Standard: Monodisperse polystyrene with a known molecular weight was used in accordance with the instrument measurement manual.

[0281] Example 1 30 parts by weight of 1-1 was mixed as the first component, 10 parts by weight of 2-1 and 25 parts by weight of 2-2 as the second component, 25 parts by weight of UA-1 (4-1) prepared in Synthesis Example 1 as the fourth component, and 10 parts by weight of 5-1 as the fifth component. Further, 0.1 parts by weight of additive XA and 3 parts by weight of G-1 as a polymerization initiator were added and dissolved with stirring at 50°C, thereby obtaining polymerizable compound ma-1 as the polymerizable compound (MA) of the present invention. In addition, as the non-polymerizable liquid crystal compound (LB), a liquid crystal composition LC1 shown in Table 1 was prepared.

[0282] Relative to 100 parts by mass of liquid crystal composition LC1, 1.5 parts by weight, 1.0 part by weight, and 0.5 parts by weight of dye 1, dye 5, and dye 8, respectively, were added as dyes (CR) and dissolved. The liquid crystal composition LC1 with the dyes mixed therein prepared above was added to the obtained polymerizable compound ma-1 so that the weight ratio of polymerizable compound (MA) / non-polymerizable liquid crystal compound (LB) (MA / LB weight ratio) became 49 / 51, and the mixture was stirred at 50° C. to obtain a uniform liquid, thereby obtaining a polymer-dispersed liquid crystal composition.

[0283] The obtained polymer-dispersed liquid crystal composition was dropped onto the transparent electrode surface of a PET film with a transparent electrode on which resin spacers with a particle size of 20 μm had been dispersed, and another PET film with a transparent electrode was laminated onto the polymer-dispersed liquid crystal composition so that the transparent electrode surfaces faced each other, and the two were pressed together with a rubber roller, after which they were irradiated with ultraviolet light at room temperature to obtain a liquid crystal element having a liquid crystal polymer composite. The ultraviolet light conditions at this time were as follows: a light source was a UV-LED lamp with a wavelength of 365 nm, and an intensity of 20 mW / cm 2 The duration was 60 seconds. The irradiation intensity of the ultraviolet light was measured using an ultraviolet illuminance meter UIT-201 and a sensor UVD-365PD manufactured by Ushio Electric Co., Ltd.

[0284] (Solubility of dyes) 1 g of liquid crystal composition LC1 was placed in a test tube, and the dye (CR) was added and dissolved in the ratio shown in Table 4. This was left to stand at room temperature for 48 hours, and the case where no precipitation was observed was marked with an O, and the case where precipitation progressed was marked with an X.

[0285] (Process resistance) The liquid crystal element having the liquid crystal polymer composite obtained above was compared in appearance color before and after ultraviolet irradiation. The element in which the appearance color was almost the same before and after irradiation was marked with an O, and the element in which fading after irradiation was obvious was marked with an X.

[0286] (colored film overlay) "None" indicates that the physical properties were measured for the liquid crystal light control element alone. The other notations indicate that the physical properties were measured for a liquid crystal light control element that does not contain a dye in the phase-separated liquid crystal layer (light control layer) and a colored film that is laminated together. "Smoke F": This indicates that the commercially available Scotch Tint Window Film Smoke 5 / RE5SMAR (manufactured by 3M) was used as the colored film. "TT: 3%": Indicates that the total light transmittance of the colored film is 3%.

[0287] (Total light transmittance) The measurement was performed at 25° C. using a haze meter (NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7361-1.

[0288] (Hayes) The haze was measured at 25° C. in accordance with JIS K 7136 using a haze meter (NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.).

[0289] (Diffuse transmittance) The haze was measured at 25° C. in accordance with JIS K 7136 using a haze meter (NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.).

[0290] (Scatter degree) Using an LCD5200 liquid crystal property measuring device equipped with a spectroscope, the transmittance relative to air was set to 100% when quasi-parallel light from a halogen lamp was projected at 25° C. The light was projected from an angle of 15° to the normal to the sample surface, and the transmitted light was received on the opposite surface. The amount of received light was measured by moving the receiver between -15° and 70°, with the receiving angle on the opposite side of the projected light set to -15°. The degree of scattering was calculated by integrating the amount of light due to transmitted scattering (forward scattering) at reception angles from -10° to 70° (between 5° and 85° when the direct angle of the light projection is 0°) at 1° intervals.

[0291] (Response time evaluation) "Fall response time" The liquid crystal element having the obtained liquid crystal polymer composite was measured at the target measurement temperature using LCD-5200 (manufactured by Otsuka Electronics Co., Ltd.). The transmittance before applying a square wave 60 Hz, 100 V AC voltage was set as T0, and the transmittance after applying the voltage for 5 minutes was set as T 100 After the voltage is removed, the transmittance is [T 100 The time it takes for the signal to decay to 10% of the original amplitude [T0] was taken as the fall response time [sec] at the measurement temperature. The fall response time was 2.9 seconds at a measurement temperature of -10°C and 29 seconds at -20°C.

[0292] (Adhesion evaluation) The adhesion was evaluated by the following method. First, glass beads with a particle size of 15 μm were scattered on one of the transparent electrode surfaces of two PET films with transparent electrodes, and the liquid crystal composition was dropped on the glass beads and applied with an applicator. Then, the other PET film was attached to the coated surface so that the transparent electrode surface and the coated surface were in contact with each other to form a film laminate. By sandwiching the film laminate between two glass plates, pressure was applied uniformly over the entire surface of the film laminate, so that the liquid crystal composition had a substantially uniform thickness. The film laminate sandwiched between the glass plates was irradiated with a UV-LED lamp with a wavelength of 365 nm at room temperature and with an intensity of 20 mW / cm. 2 After irradiating the glass plate with ultraviolet light for 60 seconds, a polymer dispersed liquid crystal element was obtained by removing the glass plate. The ultraviolet light intensity was measured using an ultraviolet illuminance meter UIT-201 and a sensor UVD-365PD manufactured by Ushio Inc.

[0293] The obtained polymer dispersed liquid crystal element was cut into a strip with a width of 25 mm, and a 180° peel test was performed. Using a Force Tester MCT2150 manufactured by A&D Co., Ltd., the ends of two transparent electrode-attached PET films at one end of the strip were peeled away from each other in a 180° direction at a tensile speed of 100 mm / min in an atmosphere of 25°C, and the average peel strength was determined. The strength was 0.3 N.

[0294] (Examples 2 to 5, Comparative Examples 1 to 2) Polymer-dispersed liquid crystal compositions of Examples 2 to 5 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1, except that the components were used in the blending ratios shown in Table 4.

[0295] Using these polymer dispersed liquid crystal compositions, polymer dispersed liquid crystal elements of Examples 2 to 5 and Comparative Examples 1 and 2 were obtained in the same manner as in Example 1. The obtained polymer dispersed liquid crystal element was subjected to various evaluations in the same manner as in Example 1. The compounding ratio of each component and the evaluation results are shown in Table 4.

[0296] [Table 4] *1 The ratio of each composition to the total of 100% liquid crystal compound (LB) and polymerizable compound (MA) [mass %] *2 The ratio of each compound to the total of 100% of each component in the liquid crystal compound (LB) [mass %] *3 The percentage of each compound when the total of each component in the polymerizable compound (MA) is 100% [mass %] *4 Ratio of each component in the polymerizable compound (MA) to the total of 100% [mass %]

[0297] From the above results, the polymer dispersion type liquid crystal elements of Examples 1 to 5 all had a contrast ratio of total light transmittance of 2.7 or more, and had a sufficient transmittance contrast between high and low transmittance states. The fall response time was 4 seconds or less at -10°C and 35 seconds or less at -20°C or less, maintaining a practically acceptable response time at low temperatures. The light control layer adhesion was 0.2 MPa or more in all cases, showing an acceptable strength.

[0298] In Comparative Example 1, since the Tg of the first component of the polymerizable compound (MA) was higher than -30°C, the response time was 85 seconds at -10°C and 120 seconds or more at -20°C or lower, which is beyond the practical range at low temperatures. In Comparative Example 2, the polymer dispersed liquid crystal composition did not contain any dye, and light-blocking performance was imparted by overlapping colored films. As a result, the contrast ratio was 1.8, and the contrast in transmittance between the high and low transmittance states was insufficient.

Claims

1. A polymer-dispersed liquid crystal composition containing a polymerizable compound (MA), a non-polymerizable liquid crystal compound (LB), and a dye (CR), the polymerizable compound (MA) contains, as a first component, one or more linear monofunctional polymerizable compounds, and contains, as a second component, one or more cyclic monofunctional polymerizable compounds, The copolymer Tg of the polymerizable compound (MA) is −10° C. or less, The dye (CR) is a polymer-dispersed liquid crystal composition containing at least one type of blue dye compound, at least one type of red dye compound, and at least one type of yellow dye compound.

2. 2. The polymer dispersed liquid crystal composition according to claim 1, wherein at least one of said linear monofunctional polymerizable compounds of said first component has a homopolymer Tg value of -30° C. or less.

3. 3. The polymer dispersed liquid crystal composition according to claim 1, wherein at least one of the cyclic monofunctional polymerizable compounds of the second component has a homopolymer Tg value of 40[deg.] C. or less.

4. 3. The polymer-dispersed liquid crystal composition according to claim 1, wherein the non-polymerizable liquid crystal compound (LB) has a nematic-isotropic phase transition point (Tni) of 110° C. or higher and 180° C. or lower.

5. A pair of transparent electrode substrates; A light control element having a liquid crystal polymer composite including a polymer network and a liquid crystal compound, the liquid crystal polymer composite being disposed between the transparent electrode substrates, The polymer network is a polymer network derived from the polymerizable compound (MA) contained in the polymer dispersed liquid crystal composition according to claim 1 or 2, A light control element, wherein the liquid crystal compound is a non-polymerizable liquid crystal compound (LB) contained in the polymer-dispersed liquid crystal composition according to claim 1 .

6. The light control element according to claim 5 , wherein the pair of transparent electrode substrates are made of a flexible material.

7. 6. The light-adjusting element according to claim 5, wherein the degree of scattering determined by a method for measuring and analyzing the detection angle dependency of forward scattered light of straight transmitted light is 1.5 or less.

8. 6. The light control element according to claim 5, which has a diffuse transmittance of 20% or less according to JIS K7136 (test method for haze of plastic and transparent materials).

9. 6. The light control element according to claim 5, wherein a contrast ratio of total light transmittance TT [TT (transparent state) / TT (light-shielding state)] is 2.0 or more.

10. The light control element according to claim 5 , which switches to a light blocking state when no voltage is applied and to a transparent state when a voltage is applied.

11. A window comprising the light control element of claim 5.

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