Polymer-dispersed liquid crystal composition and dimming element

Abstract

To provide a polymer-dispersed liquid crystal composition capable of preparing a liquid crystal dimming element having low drive voltage, low temperature response and excellent adhesion while maintaining scattering properties in the scattering state and transparency in the transmission state in a low temperature range and to provide a liquid crystal element and a dimming element using the same.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.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 trains, automobiles, ships, aircraft, etc., light-adjusting elements used in optical shutters for light control of 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] There are growing expectations for the application of light control elements, which can adjust the degree of light transmission, such as visible light and infrared light, to window glass for architectural, automotive and transportation applications, interior and exterior glass, privacy glass, variable projector screens, digital signage, etc. as smart glass and smart windows (SW), etc. Furthermore, with the recent development of communication technology, it has become possible to control various types of equipment, both industrial and domestic, using mobile terminals, and so light control elements and materials are needed to diversify the functions of these devices. Unlike general liquid crystal elements, polymer dispersed liquid crystal elements (PDLC), in which liquid crystal material is dispersed in the form of particles in a polymer matrix, 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, have the characteristic that they can adjust the degree of transmission / scattering of light, such as visible light and infrared light. This characteristic is expected to lead to applications in high value-added displays, such as reflective displays, transparent displays, local dimming light diffusion elements, and variable reflectors. There is growing expectation that this transmission / scattering light control function can be utilized in the light control elements and materials.

[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 substantially entire surface of the polymer dispersed liquid crystal element is controlled, generally, a voltage is applied to the substantially entire surface in a simple configuration of a transparent substrate, a transparent electrode layer, a phase-separated liquid crystal layer (light control layer), a transparent electrode layer, and a transparent substrate in that order. When used in a smart window, 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 the states are electrically switched between, it is desired that the liquid crystal element can be operated with a low driving voltage, and therefore the power consumption of the light control 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-separated 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, in the case of smart windows used in glass windows for railroads, automobiles, ships, aircraft, etc., a wide operating temperature range is required 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, in particular for applications where the light control element is installed in a place exposed to the outside air, such as windows in buildings, or for applications where the light control element is used in a wide range of temperature environments, including the scorching heat of midsummer and the extreme cold of midwinter, such as railroads, automobiles, ships, and aircraft, it is necessary for the light control element to operate in a wide temperature range. In other words, it is 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 is 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 is 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 control element which maintains scattering properties in the scattering state and transparency in the transmitting state in the low temperature range, has a low driving voltage, and has excellent low temperature response and adhesion, and to obtain a liquid crystal element and a light control 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 containing a polymerizable compound (MA) and a non-polymerizable liquid crystal compound (LB), the polymerizable compound (MA) contains, as a first component, one or more chain monofunctional polymerizable compounds, and contains, as a second component, one or more cyclic monofunctional polymerizable compounds; The polymerizable compound (MA) has a copolymer Tg of -10°C or lower. [2] At least one of the linear monofunctional polymerizable compounds of the first component has a homopolymer Tg value of −30° C. or less; The polymer dispersed liquid crystal composition according to [1], wherein at least one of the cyclic monofunctional polymerizable compounds of the second component has a homopolymer Tg value of 40° C. or less. [3] The polymer dispersed liquid crystal composition according to claim 1 or 2, wherein the polymerizable compound (MA) contains one or more polyfunctional (meth)acrylate oligomers (i) having a weight average molecular weight of 2000 or more as a fourth component. [4] The polymer dispersion type liquid crystal composition according to any one of [1] to [3], wherein the polymerizable compound (MA) further contains, as a fifth component, one or more selected from the group consisting of polyfunctional polymerizable oligomers and polyfunctional polymerizable monomers having a weight average molecular weight of less than 2000, represented by the following general formula (iv): [ka] (In the formula, Y iv1 represents a hydrogen atom or a methyl group, 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.) [5] The polymer dispersed liquid crystal composition according to any one of [1] to [4], wherein the chain monofunctional polymerizable compound of the first component is a polymerizable compound represented by the following general formula (v): [ka] (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. [6] The polymer dispersed liquid crystal composition according to any one of [1] to [5], wherein the cyclic monofunctional polymerizable compound of the second component is a polymerizable compound represented by the following general formula (ii): [ka] (In the formula, P ii1 represents a polymerizable group, Z ii1 represents a single bond or an alkylene group having 1 to 7 carbon atoms, in which one or more non-adjacent -CH- groups may each be 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). [ka] (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 .)) [7] The polymer dispersed liquid crystal composition according to any one of [1] to [6], wherein the polymerizable compound (MA) further contains an additive represented by the following general formula (X): [ka] (In the formula, Y X1 represents a hydrogen atom or a methyl group, 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). [ka] [8] The polymer dispersed liquid crystal composition according to any one of [1] to [7], further comprising a polymerization initiator. [9] The polymer dispersed liquid crystal composition according to [3], wherein the fourth component is a polyfunctional (meth)acrylate oligomer having a weight average molecular weight of 2000 or more, which is one or more selected from the group consisting of urethane-based (meth)acrylate oligomers and polyester-based (meth)acrylate oligomers.

[10] The polymer dispersion type liquid crystal composition according to any one of [1] to [9], further comprising one or more selected from the group consisting of a polymerization inhibitor, an antioxidant, a light stabilizer, particles having a particle diameter of less than 1 μm, a dye, and a pigment.

[11] A liquid crystal device obtained by using the polymer dispersed liquid crystal composition according to any one of [1] to

[10] .

[12] 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, 3. A light control device, 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. Effect of the Invention

[0011] According to the present invention, a polymer-dispersed liquid crystal composition is obtained that can be used to fabricate a liquid crystal light control element that maintains scattering properties in the scattering state and transparency in the transmitting state in the low temperature range, has a low driving voltage, and has excellent low-temperature response and adhesion, and also provides a liquid crystal element and a light control element using the same. 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 one embodiment of the present invention (polymer-dispersed liquid crystal composition according to this embodiment) contains a polymerizable compound (MA) and a non-polymerizable liquid crystal compound (LB). 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 lower, and preferably -50°C or higher and -10°C or lower. If the copolymer Tg of the polymerizable compound (MA) is less than -50°C, the heat resistance of the transparent solid material decreases, and the operation performance of the light control element when exposed to a high temperature environment decreases. If it exceeds -10°C, the response time when exposed to a low temperature (-10°C or lower) becomes long. Therefore, within the above range, the switching between scattering and transparency works well over a wide range of environmental temperatures. It is preferred that at least one of the linear monofunctional polymerizable compounds of the first component has a homopolymer Tg value of −30° C. or less, and at least one of the cyclic monofunctional polymerizable compounds of the second component 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.

[0015] The Tg [K] of a copolymer consisting of multiple components can be expressed by the following formula (Formula 1) (called the FOX formula), where Tg [K] of homopolymer 1, homopolymer 2, … are Tg1, Tg2, …, respectively, and the weight ratios are C1, C2, ….

[0016] (1 / Tg)=(C1 / Tg1)+(C2 / Tg2)+ (Formula 1)

[0017] The Tg of the copolymer in the present invention can be measured by dynamic viscoelasticity (DMA), thermomechanical analysis (TMA), differential scanning calorimetry (DSC), etc., but here the dynamic viscoelasticity is measured by the resonance oscillation method. That is, the viscoelasticity is measured while resonating under a temperature sweep using a cured homopolymer as a sample, and the peak top temperature of the loss modulus G'' can be determined as the Tg (glass transition point) of the homopolymer. The "homopolymer Tg" of the present invention can also be measured in a similar manner.

[0018] 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) and each component constituting the non-polymerizable liquid crystal compound (LB) will be specifically described below.

[0019] [Polymerizable compound (MA)] The polymerizable compound (MA) preferably contains the following first component, second component, and, if necessary, fourth component and / or fifth component.

[0020] [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).

[0021] [ka] (In the formula, P v1 represents a polymerizable group,

[0022] 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.

[0023] In the compound represented by the general formula (v), v1represents 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.

[0024] [ka]

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] [ka] (In the formula, q represents an integer of 1 to 12, preferably 1 to 5, and more preferably 1 to 3.)

[0030] 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.

[0031] 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. Also, the compound represented by general formula (v) is preferably isobutyl acrylate (homopolymer Tg: -26°C, the same applies below), 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, 2-ethylhexyl methacrylate (-10°C).

[0032] [ka]

[0033] [ka]

[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]

[0040] (In the formula, P ii1 represents a polymerizable group; 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 one 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 (meth)acrylate oligomers are preferred. Furthermore, in order to emphasize adhesion to the substrate, urethane-based (meth)acrylate oligomers or polyester-based (meth)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-based or polyether-based, and polyether-based oligomers are 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-based (meth)acrylate oligomers can be obtained by reacting a hydroxyl-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 an integer of 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] (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, X i1 , X i2 , X i3 , B1 , 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.

[0066] 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:

[0067] 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.

[0068] 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.

[0069] [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.

[0070] [ka] (In the formula, Y iv1 represents a hydrogen atom or a methyl group,

[0071] 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.)

[0072] 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.

[0073] [ka] (In the formula, Y iv2 and Y iv3 represents a hydrogen atom or a methyl group,

[0074] 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.

[0075] 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).

[0076] [ka]

[0077] [ka]

[0078] (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 is a value between 1 and 18, n 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.)

[0079] 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.

[0080] 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.

[0081] [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).

[0082] [ka]

[0083] 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.

[0084] [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.

[0085] 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).

[0086] [ka]

[0087] (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,

[0088] 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,

[0089] 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 1 =NN=CR 1 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 1represents 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-.

[0090] 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.

[0091] 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-.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] [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.

[0096] [ka] (In the formula, Y X1 represents a hydrogen atom or a methyl group,

[0097] 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).

[0098] [ka] Specifically, it is preferable to add the following compounds.

[0099] [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.

[0100] 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.

[0101] [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).

[0102] [ka]

[0103] (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,

[0104] 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-);

[0105] 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,

[0106] 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;

[0107] 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.)

[0108] 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.

[0109] 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.

[0110] 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

[0111] [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).

[0112] [ka]

[0113] [ka]

[0114] (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).

[0115] 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).

[0116] [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).

[0117] [ka]

[0118] (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);

[0119] 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,

[0120] 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.)

[0121] 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; 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.

[0122] 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):

[0123] [ka]

[0124] (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-;

[0125] 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,

[0126] 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,

[0127] 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;

[0128] 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.)

[0129] 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;

[0130] 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.

[0131] 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.

[0132] [ka]

[0133] [ka]

[0134] (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.

[0135] [ka]

[0136] (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.

[0137] 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).

[0138] 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).

[0139] 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).

[0140] 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).

[0141] 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).

[0142] The refractive index anisotropy (Δn) of the non-polymerizable liquid crystal composition 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 composition having such 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 composition 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 state in which they embrace a part of the non-polymerizable liquid crystal composition, 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.

[0143] [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).

[0144] 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.

[0145] 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 this embodiment. These may be used alone or in combination of two or more kinds.

[0146] 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 dimethylcarbonate 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 alkylazo 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 of the polymerizable compound (MA) used in the polymer dispersion type liquid crystal composition of this embodiment (100% by mass). These can be used alone or in combination of two or more kinds.

[0147] The polymer-dispersed liquid crystal composition of the present embodiment may contain a polymerization inhibitor, an antioxidant, a light stabilizer, a chain transfer agent, a dye, a pigment, 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 a polymerization inhibitor, an antioxidant, a light stabilizer, particles having a particle size of less than 1 μm, a dye, and a pigment.

[0148] [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.

[0149] 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.

[0150] When a polymerization inhibitor is contained, the content is preferably from 0.001 to 2.0 mass % relative to the total amount (100 mass %) of the polymerizable compounds (MA) used in the polymer dispersion type liquid crystal composition of this embodiment, and more preferably from 0.01 to 0.5 mass %.

[0151] [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.

[0152] 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.

[0153] [ka]

[0154] 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.

[0155] 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.

[0156] When an antioxidant is contained, the content is preferably from 0.001 to 2.0 mass % relative to the total amount (100 mass %) of the polymerizable compound (MA) used in the polymer dispersion type liquid crystal composition of this embodiment, and more preferably from 0.01 to 0.5 mass %.

[0157] [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).

[0158] When a light stabilizer is contained, the amount added is preferably from 0.001 to 2.0 mass % and more preferably from 0.01 to 1.0 mass % based on the total amount of the polymerizable compound (MA) used in the polymer dispersion type liquid crystal composition of this embodiment.

[0159] [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.

[0160] [ka]

[0161] 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.

[0162] When a chain transfer agent is contained, the content is preferably from 0.001 to 10 mass %, and more preferably from 0.01 to 5.0 mass %, relative to 100 mass % of the total amount of the polymerizable compound (MA) in the polymer dispersion type liquid crystal composition of this embodiment.

[0163] [Pigment] The dye 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 are no particular limitations on such dyes, and any known and commonly used dyes can be used as long as they are soluble in liquid crystals or disperse in the polymer network. Examples of the dyes include dichroic dyes and fluorescent dyes. Examples of such dyes include polyazo dyes, anthraquinone dyes, quinacridone dyes, dioxazine dyes, quinophthalone dyes, cyanine dyes, phthalocyanine dyes, perylene dyes, perinone dyes, and squarylium dyes. From the viewpoint of addition, the dye is preferably a dye 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.

[0164] When a dye is contained, the content is preferably from 0.01 to 8% by mass, and more preferably from 0.1 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.

[0165] [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.

[0166] When a pigment is contained, the content is preferably from 0.01 to 8% by mass, and more preferably from 0.1 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.

[0167] [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.

[0168] The particles are preferably particles having good dispersibility in the network polymer. When the particles are contained, the content is preferably 0.001 to 5% by mass, more preferably 0.01 to 3% by mass, based on 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB) used in the polymer-dispersed liquid crystal composition of the present embodiment.

[0169] [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.

[0170] 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.

[0171] 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 to 8% by mass, more preferably 0.1 to 4% by mass, based on 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB) used in the polymer-dispersed liquid crystal composition of the present embodiment.

[0172] [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.

[0173] <Liquid crystal element> A liquid crystal element using the polymer-dispersed liquid crystal composition of the present embodiment includes 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 includes a phase-separated liquid crystal layer, an alignment film layer, electrodes, and a substrate supporting the electrodes.

[0174] The phase-separated liquid crystal phase is obtained by polymerizing the polymerizable compound (MA) contained in the polymerizable liquid crystal composition to form a polymer network derived from each polymerizable component contained in the polymerizable compound (MA).

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] 〔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.

[0180] 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.

[0181] 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. A hard coat layer may be formed adjacent to the flexible transparent substrate on the surface between the flexible transparent substrate and the transparent electrode or the refractive index adjusting layer, or on the surface opposite to the transparent electrode.

[0182] 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.

[0183] 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.

[0184] [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.

[0185] 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.

[0186] [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.

[0187] [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.

[0188] 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.

[0189] [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.

[0190] 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.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] [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.

[0196] 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.

[0197] 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.

[0198] 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 ray cut film or an infrared ray cut film, a protective film, a polarizing film, or the like may be laminated thereon.

[0199] [Other electric field types] In addition to the vertical electric field type, the liquid crystal element of this embodiment may adopt a horizontal electric field type or other electric field types. 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.

[0200] 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 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, the liquid crystal element 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.

[0201] <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 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.

[0202] 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.

[0203] This light-adjusting element can be switched between a scattering state and a transparent state for visible light by applying and removing a potential difference between a pair of opposing transparent electrodes. EXAMPLES

[0204] 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".

[0205] The non-polymerizable liquid crystal compounds (LB) used in the Examples and Comparative Examples described later are shown in Tables 1 and 2, respectively. The components of the polymerizable compounds (MA) used in the Examples and Comparative Examples described later are explained in Tables 3 and 4.

[0206] [Table 1]

[0207] [Table 2]

[0208] [Table 3]

[0209] [Table 4]

[0210] (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).

[0211] 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:

[0212] [GPC measurement conditions] Measurement equipment: Tosoh Corporation "HLC-8320 GPC"

[0213] 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.

[0214] Example 1 30 parts by weight of 1-1 as the first component, 15 parts by weight of 2-1 as the second component, 35 parts by weight of UA-1 (4-1) prepared in Synthesis Example 1 as the fourth component, and 20 parts by weight of 5-1 as the fifth component were mixed, and 0.1 parts by weight of additive XA and 3 parts by weight of Omnirad 184 as a polymerization initiator were added and dissolved while stirring at 50°C to obtain a polymerizable compound ma-1 as the polymerizable compound (MA) of the present invention. In addition, a liquid crystal composition LC1 shown in Table 1 was prepared as a non-polymerizable liquid crystal compound (LB).

[0215] The liquid crystal composition LC1 was added to the obtained polymerizable compound ma-1 so that the weight ratio of the polymerizable compound (MA) / non-polymerizable liquid crystal compound (LB) (MA / LB weight ratio) was 47 / 53, and dissolved with stirring at 50°C to obtain a polymer-dispersed liquid crystal composition PLM1.

[0216] The obtained polymer-dispersed liquid crystal composition PLM1 was injected into a glass cell having a thickness of 15 μm (structure: glass substrate / transparent electrode layer / air layer / transparent electrode layer / glass substrate) at room temperature, and then irradiated with ultraviolet light at room temperature to obtain a liquid crystal device having a liquid crystal polymer composite. The ultraviolet light conditions at this time were as follows: a UV-LED lamp with a wavelength of 365 nm as a light source, and an intensity of 15 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.

[0217] (Storage modulus G') The polymerizable compound ma-1 obtained in Example 1 was applied to one side of a PET film to a thickness of about 1 mm using an applicator, and another PET film was placed on the applied side to create an oxygen-free atmosphere. Using a UV-LED lamp with a wavelength of 365 nm as a light source, ultraviolet rays with an intensity of 15 mW / cm2 were irradiated for 60 seconds at room temperature to form a polymer film. The film thickness after polymerization was measured with a contact film thickness meter, and was between 0.3 mm and 0.8 mm for each sample. The obtained polymer film was cut into strips measuring 5 mm × 20 mm, and the dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring device DVA-205 (manufactured by IT Measurement and Control Co., Ltd.) by applying a sinusoidal tensile stress to the sample to detect the amount of elongation deformation at a measurement temperature of -150°C to 150°C, a heating rate of 4°C / min, and an applied frequency of 10 Hz.

[0218] (rubber plateau) "Minimum temperature in plateau area [℃]" The temperature range where the storage modulus G' shows a steep slope is defined as the glass transition region, and the temperature range on the higher side where it has a gentle slope is defined as the rubbery plateau, and the temperature at which the glass transition region transitions to the rubbery plateau is defined as the minimum temperature in the plateau [°C]. When a graph is drawn with temperature on the horizontal axis and storage modulus G' on the vertical axis, the temperature at which the rate of change in the slope of G' changes from negative to positive in the direction of rising temperature is determined as the minimum temperature in the plateau.

[0219] "Minimum temperature elastic modulus in plateau region [MPa]" The storage modulus G' value at the lowest temperature in the plateau was taken as the plateau minimum temperature modulus [MPa].

[0220] (Drive voltage evaluation) Using the liquid crystal element having the obtained liquid crystal polymer composite, the transmittance at 0V (T0) was measured at 0%, and the transmittance at 100V (T 100 ) is 100%, the voltage at which the transmittance reaches 90% is the driving voltage (V 90 (25)), driving voltage at -20°C (V 90 The driving voltage (V90 (25)), driving voltage at -20°C (V 90 (-20)) were 36.3V and 35.5V, respectively. The ratio: V 90 (-20) / V 90 (25) was 0.98.

[0221] (Transmittance evaluation) A square wave voltage of 60 Hz and 0 to 100 V was applied to the liquid crystal element having the obtained liquid crystal polymer composite using LCD-5200 (manufactured by Otsuka Electronics Co., Ltd.). The transmittance when AC 100 V was applied under the condition of a temperature of 25° C. was measured as T 100 (25), and the transmittance when AC100V is applied under the condition of -20℃ is T 100 The transmittance T 100 (25), T 100 (-20) was 88.2% and 88.4%. The ratio: T 100 (-20) / T 100 (25) was 1.00.

[0222] (Low temperature driveability evaluation) The voltage dependence of transmittance was measured for the liquid crystal element having the obtained liquid crystal polymer composite using LCD-5200 (manufactured by Otsuka Electronics Co., Ltd.) while decreasing the temperature from 25°C to -30°C in 5°C increments. 100 -T0) is the change range at a measurement temperature of 25°C (T 100 The lowest measured temperature that was not below 90% of the T0 was defined as the minimum operating temperature [°C]. The minimum operating temperature was -20°C.

[0223] (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 100The 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 less than 0.1 seconds at measurement temperatures of 10°C, 0°C, and -10°C, and 0.7 seconds at -20°C.

[0224] (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 15 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.

[0225] 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 pulling speed of 50 mm / min in an atmosphere of 25°C, and the average peel strength was determined. The strength was 0.3 N.

[0226] (Examples 2 to 6, Comparative Examples 1 to 4) Polymer dispersed liquid crystal compositions PL2 to PL6 and PLM11 to PLM14 were prepared in the same manner as PLM1, except that the components were used in the blending ratios shown in Table 4.

[0227] Using these polymer dispersed liquid crystal compositions PL2 to PL6 and PLM11 to PLM14, 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 dispersion type 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 Tables 5 and 6.

[0228] [Table 5] *1 The percentage of each compound when the total of each component in the polymerizable compound (MA) is 100% [mass %] *2 Ratio of each component in the polymerizable compound to the total of 100% [mass %] *3 Ratio of each composition to the total of liquid crystal compound and polymerizable composition (100%) [mass %]

[0229] [Table 6] *1 The percentage of each compound when the total of each component in the polymerizable compound (MA) is 100% [mass %] *2 Ratio of each component in the polymerizable compound to the total of 100% [mass %] *3 Ratio of each composition to the total of liquid crystal compound and polymerizable composition (100%) [mass %] *4 ×: Not measured due to insufficient start-up

[0230] From the above results, in the polymer dispersion type liquid crystal elements of Examples 1 to 6, the copolymer of the polymerizable compound (MA) has a Tg of -10°C or less. In this case, the storage modulus G' (25°C) is 20 MPa or less in all cases, so it is presumed that the wettability at the interface with the substrate in the liquid crystal element is good, and therefore the necessary adhesion can be easily maintained. As the storage modulus G' (-20℃) is below 2000MPa in both cases, it is assumed that the mobility at the interface between the polymer and liquid crystal can be maintained even at low temperatures, making it easier to maintain the driveability of the liquid crystal molecules. Furthermore, it is expected that the brittleness of the network polymer will be suppressed when the liquid crystal element or light control element is exposed to low temperatures for long periods of time, and that the occurrence of cracks in the phase-separated liquid crystal layer will be prevented. Since the ratio [G'(-20) / G'(25)] is greater than 20, it is expected to achieve both good wettability at the interface between the network polymer and the substrate when fabricating liquid crystal elements, and good adhesion to the same interface at low temperatures. Since the minimum temperatures of the rubber-like plateau were all below 50°C, close to room temperature, it is assumed that the liquid crystal element has good wettability at the interface with the substrate, making it easy to maintain the necessary adhesion. Since the elastic modulus (G') (rubber elastic modulus) in the rubber-like plateau at that temperature is 20 MPa or less in all cases, it is presumed that the entanglement density of the molecular chains of the network polymer is relatively small, and therefore the mobility of the molecules on the network polymer surface is maintained even at low temperatures, and as a result, the driveability of the liquid crystal is maintained at low temperatures.In addition, during processing such as bonding the liquid crystal element to another curved support or sandwiching it between curved glass plates to produce laminated glass, it is expected to have the effect of easily preventing the occurrence of problems such as cohesive failure of the phase-separated liquid crystal layer or delamination between the phase-separated liquid crystal layer and the substrate, which are caused by the inability to withstand stress due to the brittleness of the network polymer. In this liquid crystal element, the driving voltage ratio was 2.0 or less in all cases, which suppressed the increase in driving voltage at low temperatures and maintained the driving properties of the liquid crystal, ensuring responsiveness at low temperatures. The ratio of rectilinear light transmittance was in the range of 0.97 to 1.04, close to 1, and the transparency of visible light in the transparent state was able to be maintained at low temperatures just as it was at room temperature. The response times for all of the devices were 0.4 seconds or less at 0°C, 1.0 seconds or less at -10°C, and 10 seconds or less at -20°C, maintaining practical response times at low temperatures. The adhesion of the photochromic layer was 0.2 MPa or more in all cases, showing acceptable strength.

[0231] In contrast, in Comparative Examples 1 to 4, the Tg of the copolymer of the polymerizable compound (MA) is higher than -10°C. In this case, the driving voltage of the liquid crystal element at -20°C was significantly higher than that at 25°C, and the ratio [V90(-20) / V90(25)] exceeded 2.0 in all cases. This suggests that the driving properties at low temperatures were significantly reduced. The ratio of rectilinear light transmittance was 0.91 to 0.96 in Comparative Examples 1 to 3, which showed lower transparency of visible light in the transparent state compared to the Examples. The response times were all 1.0 second or more at 0°C, 8 seconds or more or insufficient at -10°C, and insufficient at -20°C, showing a gap compared to the Examples. The adhesion of the photochromic layer was 0.3 MPa or more in all cases, showing sufficient strength.

Claims

1. A polymer-dispersed liquid crystal composition containing a polymerizable compound (MA) and a non-polymerizable liquid crystal compound (LB), 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 polymerizable compound (MA) has a copolymer Tg of −10° C. or lower.

2. At least one of the linear monofunctional polymerizable compounds of the first component has a homopolymer Tg value of −30° C. or less; 2. 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.

3. 3. The polymer dispersed liquid crystal composition according to claim 1, wherein the polymerizable compound (MA) contains, as a fourth component, one or more polyfunctional (meth)acrylate oligomers (i) having a weight average molecular weight of 2000 or more.

4. 3. The polymer dispersion type liquid crystal composition according to claim 1, wherein the polymerizable compound (MA) further contains, as a fifth component, one or more selected from the group consisting of polyfunctional polymerizable oligomers and polyfunctional polymerizable monomers having a weight average molecular weight of less than 2000, and represented by the following general formula (iv): 【Chemistry 1】 (In the formula, Y ｉｖ１ represents a hydrogen atom or a methyl group, X ｉｖ１ is n having 130 or less carbon atoms ｉｖ１ represents a linear, branched or cyclic hydrocarbon group having one or more -CH ２ the - groups may each be independently substituted with -O-, -NH-, -CO-, -COO-, -OCO-, -CH=CH-, or -C≡C- so that oxygen atoms are not directly adjacent to one another, and one or more hydrogen atoms present in the linear, branched or cyclic hydrocarbon group may each be independently substituted with a fluorine atom or -OH; n ｉｖ１ represents an integer from 2 to 6.)

5. 3. The polymer dispersed liquid crystal composition according to claim 1, wherein the linear monofunctional polymerizable compound of the first component is a polymerizable compound represented by the following general formula (v): 【Chemistry 2】 (In the formula, P ｖ１ represents a polymerizable group, R ｖ１ represents a linear or branched alkyl group having 1 to 22 carbon atoms, and one or more -CH ２ Each - may be independently replaced with -O-, -CO-, -COO-, -OCO- or -P(=O)(-OH)- so that no oxygen atom is directly adjacent, and one or more hydrogen atoms present in the alkyl group may be independently replaced with a fluorine atom or -OH.

6. 3. The polymer dispersed liquid crystal composition according to claim 1, wherein the cyclic monofunctional polymerizable compound of the second component is a polymerizable compound represented by the following general formula (ii): 【Chemistry 3】 (In the formula, P ｉｉ１ represents a polymerizable group, Z ｉｉ１ represents a single bond or an alkylene group having 1 to 7 carbon atoms, and one or more non-adjacent —CH ２ - may be 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). 【Chemistry 4】 (Wherein, one or more -CH ２ - is independently -O-, -S-, -COO-, -OCO-, -NH-, or -NCH ３ In the case where a total of two or more oxygen atoms and / or sulfur atoms are present in the general formulae (ii-1) to (ii-20), they are not bonded to each other like -O-O-, -O-S- or -S-S-, and may be substituted by one or more -CH ２ -CH ２ - may be replaced by a -CH=CH- group, and 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 -CH ２ Each - may be independently replaced by -O-, -CO-, -COO- or -OCO- so that the oxygen atom is not directly adjacent. ｉｉ１ It represents a bond to .)

7. 3. The polymer dispersed liquid crystal composition according to claim 1, wherein the polymerizable compound (MA) further contains an additive represented by the following general formula (X): 【Chemistry 5】 (In the formula, Y Ｘ１ represents a hydrogen atom or a methyl group, X Ｘ１ n is a group having 130 or less carbon atoms Ｘ１ represents a linear, branched or cyclic hydrocarbon group having one or more -CH ２ the - groups may each be independently substituted with -O-, -NH-, -CO-, -COO-, -OCO-, -CH=CH-, or -C≡C- so that oxygen atoms are not directly adjacent to one another, and one or more hydrogen atoms present in the linear, branched or cyclic hydrocarbon group may each be independently substituted with a fluorine atom or -OH; n Ｘ１ represents an integer from 1 to 6, Here, X Ｘ１ At least one -CH ２ - group is substituted with the following formula (X-1): 【Chemistry 6】

8. 3. The polymer dispersed liquid crystal composition according to claim 1, further comprising a polymerization initiator.

9. the fourth component, a polyfunctional (meth)acrylate oligomer (i) having an average molecular weight of 2000 or more, is one or more selected from the group consisting of a urethane-based (meth)acrylate oligomer and a polyester-based (meth)acrylate oligomer; 4. The polymer dispersed liquid crystal composition according to claim 3.

10. 3. The polymer dispersion type liquid crystal composition according to claim 1, further comprising one or more selected from the group consisting of a polymerization inhibitor, an antioxidant, a light stabilizer, particles having a particle size of less than 1 μm, a dye, and a pigment.

11. A liquid crystal device obtained by using the polymer dispersed liquid crystal composition according to claim 1 or 2.

12. 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 .

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