TW202346546A - Polymer dispersed liquid crystal composition, liquid crystal element and dimming element wherein the polymer dispersed liquid crystal composition includes a polymerizable composition (MA) and a non-polymerizable liquid crystal composition (LB) - Google Patents

Abstract

The present invention provides a polymer dispersed liquid crystal composition, a liquid crystal element and a dimming element that are excellent in adhesion to a base material, reliability, heat resistance, transmittance after being heated, transparency after voltage is applied, high-speed responsiveness in a low-temperature region, and scattering retention in a high-temperature environment. The polymer dispersed liquid crystal composition includes a polymerizable composition (MA) and a non-polymerizable liquid crystal composition (LB). The non-polymerizable liquid crystal composition (LB) has a dielectric anisotropy value with a positive sign, and a rotational viscosity [gamma]1 [mPa.sec] of 400 or less at 25 DEG C.

Description

Polymer dispersed liquid crystal compositions, liquid crystal elements and dimming elements

The present invention relates to a polymer-dispersed liquid crystal composition, a liquid crystal element obtained using the polymer-dispersed liquid crystal composition, and a light modulating element using the liquid crystal element. Dimming components include: dimming components used in smart windows (SW), window glass, doors, partitions, private glass, etc. in buildings such as residences or buildings; used in Dimming components used in glass windows, mirrors, roofs, etc. used in transportation media such as automobiles, airplanes, ships, and trains; optical shutters and light sources for displays used in dimming digital cameras, smartphones, etc. Dimming components in light scattering plates, light guide plates, reflective displays or reflective plates of transparent displays, etc.

Polymer-dispersed liquid crystal elements (PDLC) in which liquid crystal materials are dispersed in a polymer matrix or polymer network-type liquid crystal elements (PNLC) in which liquid crystal materials are interspersed in the gaps of a polymer network are different from ordinary liquid crystal elements. Differently, the degree of transmission/scattering of the element can be adjusted. Based on these characteristics, applications are expected in high value-added displays such as reflective displays, transparent displays, local dimming light diffusion elements, and variable reflective elements. On the other hand, regarding window glass for building materials or transportation, interior decoration, exterior (exterior), private glass (straight glass (SG)) or variable projectors that utilize transmission/diffusion dimming functions Applications in smart glass such as screens and digital signage, or smart windows (SW), etc., due to the development of communication technology in recent years, mobile terminals can be used to control various equipment and machines, whether for industrial or household use. , therefore dimming materials for realizing the application are desired.

In particular, when unfolded on the smart glass or smart window (SW), the entire surface of the polymer-dispersed liquid crystal element or polymer-dispersed liquid crystal element is dimmed. Therefore, generally speaking, a transparent base material, A voltage is applied to the entire surface of a simple structure such as a transparent electrode layer, the liquid crystal element layer, a transparent electrode layer, and a transparent base material layer. When used in a smart window or the like, high scattering properties are required because the situation on the other side is not clear. In addition, in a transparent state, high transparency as if there is nothing is also required. In addition, these states can be electrically switched, but power saving is required, and a low driving voltage for switching on (ON) and off (OFF) is desired. In addition, from the viewpoint of productivity, it is important to use the roll-to-roll method to directly form films such as polyethylene terephthalate (PET) films or polycarbonate (PC) films. Flexible substrate. In order to produce using the roll-to-roll method, the adhesion (adhesion) between the base material and the liquid crystal element has also become an important characteristic, and high adhesion to the base material is also required. In addition, smart windows and the like are sometimes used outdoors, etc., so they are also required to have high light resistance or high heat resistance.

Patent Document 1 shows an example of using a specific monomer compound to achieve low-voltage driving, but there is a problem of insufficient adhesion. In addition, in Patent Document 2, a specific liquid crystal compound is used in order to improve the light resistance. Although a certain effect on the light resistance is observed, there is a problem of insufficient light scattering properties. In Patent Document 3, a specific polymerizable compound is used in order to improve the adhesiveness. Although a certain effect on the adhesiveness is observed, there is a problem of high driving voltage. Thus, a method for improving scattering properties, driving voltage, and adhesion properties in a well-balanced manner is required.

Furthermore, in the case of smart windows used in glass windows used in transportation media, etc., a wide driving temperature range is required to perform dimming operations without problems from the scorching heat of midsummer to the extremely cold temperatures of midwinter. Patent Document 4 proposes a liquid crystal composite containing a liquid crystal composition and a polymerizable compound that can produce a liquid crystal dimming element with improved weather resistance. A certain effect is observed in improving the durability against external light. However, The driveability and high-speed responsiveness in low-temperature regions (for example, -10°C to -30°C) have not been studied.

[Prior art documents] [Patent Document] [Patent Document 1] Japanese Patent Application Laid-Open No. 6-208107 [Patent Document 2] Japanese Patent Application Publication No. 2007-91850 [Patent Document 3] Japanese Patent Application Publication No. 2011-026526 [Patent Document 4] Japanese Patent Application Publication No. 2021-066875

[Problems to be Solved by the Invention] As mentioned above, it is particularly useful in applications that are installed in places that are in contact with outside air, such as windows of buildings, or in transportation media that are exposed to temperatures ranging from the scorching heat of midsummer to the extremely cold temperatures of midwinter. In applications premised on use in a wide range of temperature environments, the characteristics required of various dimming elements need to be exerted in a wide temperature range. That is, it is necessary to satisfy characteristics such as adhesion to the substrate, reliability, driving voltage, transparency when the voltage is turned on, high-speed responsiveness, and scattering properties in a wide temperature range from high temperature to low temperature. Among them, it is necessary to have excellent Realizes transmission and scattering characteristics, driving voltage, and adhesion in low-temperature regions to the highest level.

Therefore, the problem to be solved by the present invention is to obtain a polymer-dispersed liquid crystal composition, and to obtain a liquid crystal element and a light-adjusting element using the polymer-dispersed liquid crystal composition. The polymer-dispersed liquid crystal composition can be made into a special It is a liquid crystal dimming element with high transparency in the transmission state, high scattering property in the scattering state, low driving voltage, and excellent adhesion in the low-temperature region. [Technical means to solve problems]

The inventors of the present invention have conducted diligent research in order to solve the above-mentioned problems, and as a result, they have found that by using a polymer-dispersed liquid crystal composition showing a specific composition and physical property values, it is possible to obtain a product that can be produced in a transmissive state, especially in a low-temperature region. A polymer-dispersed liquid crystal composition for a liquid crystal dimming element with high transparency, high scattering properties in a scattering state, low driving voltage, and excellent adhesion, and a liquid crystal element using the polymer-dispersed liquid crystal composition can be obtained and a light modulating element, thus completing the present invention.

That is, the present invention provides the following polymer-dispersed liquid crystal composition, liquid crystal element, and light control element. [1] A polymer-dispersed liquid crystal composition containing a polymerizable composition (MA) and a non-polymerizable liquid crystal composition (LB). In the polymer-dispersed liquid crystal composition, the non-polymerizable liquid crystal composition The dielectric anisotropy value of (LB) is positive, and the rotational viscosity γ1 [mPa·sec] at 25°C is 400 or less. [2] The polymer-dispersed liquid crystal composition according to [1], wherein the polymerizable composition (MA) contains one or more polymerizable compounds represented by the following general formula (ii). (In the formula, P ⁱⁱ¹ represents a polymerizable group, and Z ⁱⁱ¹ represents a single bond or an alkylene group with 1 to 7 carbon atoms. One or more of the non-adjacent -CH ₂ - groups in the alkylene group may be oxygen. Atoms that are not directly adjacent are independently substituted by -O-, -CO-, -COO- or -OCO-, and A ⁱⁱ¹ represents formula (ii-1) to formula (ii-20); (In the formula, more than one -CH ₂ - can be independently substituted by -O-, -S-, -COO-, -OCO-, -NH-, -NCH ₃ - or -CO-. When in the general formula (ii-1) ~ General formula (ii-20) When there are a total of two or more oxygen atoms and/or sulfur atoms, they are not bonded to each other like -OO-, -OS- or -SS- knot, in addition, one or more -CH ₂ -CH ₂ - may be substituted by -CH=CH- group. In addition, the hydrogen atoms in the general formula (ii-1) to the general formula (ii-20) may be substituted by a carbon atom. Alkyl groups with numbers 1 to 8 are substituted, and one or more of the non-adjacent -CH ₂ - in the alkyl group can be independently replaced by -O-, -CO-, -COO in a manner that the oxygen atoms are not directly adjacent. - or -OCO-substitution; in addition, the black dots in the formula represent the bonds toward Z ⁱⁱ¹ )) [3] The polymer dispersed liquid crystal composition according to [1] or [2], wherein the non- The polymerizable liquid crystal composition (LB) contains one or more compounds represented by the following general formula (iii). (In the formula, R ⁱⁱⁱ¹ are independently n-alkyl, n-alkoxy having 1 to 7 carbon atoms, alkenyl, alkenyloxy or alkoxyalkyl having 2 to 7 carbon atoms, R ⁱⁱⁱ² represents a fluorine atom, a chlorine atom, a cyano group, a CF ₃ group, an OCF ₃ group, an OCHF ₂ group, an NCS group or an alkyl group with 1 to 10 carbon atoms, one or two of the alkyl groups being non-adjacent -CH ₂ - group can be substituted by oxygen atom, -COO-, -OCO-. In addition, one or more -CH ₂ CH ₂ - can be substituted by -CH=CH- or -C≡C-), A ⁱⁱⁱ¹ represents anti- Formula-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1 ,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 3-methyl-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 3,5-dimethyl-1,4-phenylene or 2,6-di Methyl-1,4-phenylene, A ⁱⁱⁱ² and A ⁱⁱⁱ³ each independently represent 1,4-phenylene, 2-fluoro-1,4-phenylene, and 3-fluoro-1,4-phenylene. Phenyl, 2,3-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2- Methyl-1,4-phenylene, 3-methyl-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 3,5-dimethyl-1, 4-phenylene or 2,6-dimethyl-1,4-phenylene, one of Z ⁱⁱⁱ¹ and Z ⁱⁱⁱ² is -C≡C-, and the other one is -C≡C- when present , -CF ₂ O-, -OCF ₂ -, -CH=CH-, -CF=CF-, -COO-, -CH ₂ -CH ₂ -, -CF ₂ -CF ₂ - or single bond, n ⁱⁱⁱ is 0 or 1) [4] The polymer-dispersed liquid crystal composition according to any one of [1] to [3], wherein the polymerizable composition (MA) contains one or more of the following general A polymerizable compound represented by formula (v). (In the formula, P ^v1 represents a polymerizable group, and R ^v1 represents a linear or branched alkyl group with 1 to 22 carbon atoms. One or more -CH ₂ - in the alkyl group may not be directly oxygen atoms. The adjacent modes are independently substituted by -O-, -CO-, -COO-, -OCO- or -P(=O)(-OH)-, and one or more hydrogens present in the alkyl group atoms may be independently substituted with fluorine atoms or -OH) [5] The polymer-dispersed liquid crystal composition according to any one of [1] to [4], wherein the polymerizable composition (MA) contains One or two or more polyfunctional (meth)acrylate oligomers (i) with a weight average molecular weight of 2000 or more. [6] The polymer-dispersed liquid crystal composition according to any one of [1] to [5], wherein the polymerizable composition (MA) contains a weight selected from the group represented by the following general formula (iv) One or more of the group consisting of multifunctional polymerizable oligomers and multifunctional polymerizable monomers with an average molecular weight of less than 2,000. ⁽ In the formula, Y ^iv1 represents a hydrogen atom or a ^methyl group, and The above -CH ₂ - groups can be independently formed by -O-, -NH-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C in such a way that the oxygen atoms are not directly adjacent to each other. -Substituted, one or more hydrogen atoms present in the linear, branched or cyclic hydrocarbon group can be independently substituted by fluorine atoms or -OH, n ^iv1 represents an integer from 2 to 6) [7] According to [ The polymer-dispersed liquid crystal composition according to any one of 1] to [6], wherein the polymerizable composition (MA) further contains an additive represented by the following general formula (X). (In the formula, Y ^X1 represents a hydrogen atom or ^a methyl group, X ^X1 represents an n The above -CH ₂ - groups can be independently formed by -O-, -NH-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C in such a way that the oxygen atoms are not directly adjacent to each other. -Substitution, one or more hydrogen atoms present in the linear, branched or cyclic hydrocarbon group can be independently substituted by fluorine atoms or -OH, n ^X1 represents an integer from 1 to 6, here, X ^X1 At least one -CH ₂ - group in is substituted by the following formula (X-1)) [8] The polymer-dispersed liquid crystal composition according to any one of [1] to [7], further containing a polymerization initiator. [9] The polymer-dispersed liquid crystal composition according to any one of [5] to [8], wherein the polyfunctional (meth)acrylate oligomer (i) having a weight average molecular weight of 2,000 or more ) is one or two or more types selected from the group consisting of urethane-based (meth)acrylate oligomers and polyester-based (meth)acrylate oligomers. [10] The polymer-dispersed liquid crystal composition according to any one of [1] to [9], wherein the polymerizable composition (MA) further contains a polymerization inhibitor, an antioxidant, and a light stabilizer selected from the group consisting of , one or more of the group consisting of particles with a particle size less than 1 μm, pigments and pigments. [11] A liquid crystal element obtained using the polymer-dispersed liquid crystal composition according to any one of [1] to [10]. [12] A light modulating element having: a pair of transparent electrode substrates; and a liquid crystal polymer composite disposed between the transparent electrode substrates and including a polymer network and a liquid crystal compound, in the light modulating element, The polymer network is a polymer network derived from the polymerizable composition (MA) contained in the polymer-dispersed liquid crystal composition according to any one of [1] to [10], so The liquid crystal compound is a non-polymerizable liquid crystal composition (LB) contained in the polymer-dispersed liquid crystal composition according to any one of [1] to [10]. [Effects of the invention]

By the present invention, a polymer-dispersed liquid crystal composition can be obtained, and a liquid crystal element and a light-adjusting element using the polymer-dispersed liquid crystal composition can be obtained. The polymer-dispersed liquid crystal composition can be produced, especially in a low-temperature region. A liquid crystal dimming element with high transparency in the medium transmission state, high scattering properties in the scattering state, low driving voltage, and excellent adhesion.

Embodiments of the polymer-dispersed liquid crystal composition of the present invention and the polymer-dispersed liquid crystal element using the same will be described.

In addition, this embodiment is demonstrated as a specific example in order to better understand the gist of the invention, and does not limit this invention unless otherwise specified.

＜Polymer dispersed liquid crystal composition＞

As described above, the polymer-dispersed liquid crystal composition of the present invention contains the polymerizable composition (MA) and the non-polymerizable liquid crystal composition (LB).

In the polymer-dispersed liquid crystal composition of the present invention, the weight ratio (LB/MA) of the non-polymerizable liquid crystal composition (LB) to the polymerizable composition (MA) is preferably 30/70 to 70/30. The range is preferably 40/60~60/40, further preferably 45/55~60/40, and particularly preferably 50/50. Hereinafter, each component constituting the polymerizable composition (MA) and each component constituting the non-polymerizable liquid crystal composition (LB) will be specifically described.

The non-polymerizable liquid crystal composition (LB) in the present invention has a dielectric anisotropy value with a positive sign, and a rotational viscosity γ1 [mPa·sec] at 25° C. of 400 or less.

In a liquid crystal unit, in order to improve the responsiveness of the liquid crystal material, it is important to reduce the rotational viscosity of the liquid crystal material. This also applies to a polymer-dispersed liquid crystal element using the polymer-dispersed liquid crystal composition of the present invention. The rotational viscosity of the non-polymerizable liquid crystal composition (LB) having a positive dielectric anisotropy value is determined, for example, by the method described in Japanese Patent Application Laid-Open No. 2006-243638. That is, by applying a pulse voltage to a liquid crystal test cell using a nematic liquid crystal material with a positive sign of dielectric constant anisotropy sandwiched between horizontally aligned substrates, and measuring the transition current flowing through the liquid crystal test cell. Find the waveform.

The non-polymerizable liquid crystal compound having a positive dielectric anisotropy has a rotational viscosity γ1 at 25°C of preferably 600 or less, more preferably 500 or less, preferably 450 or less, more preferably 400 or less. , more preferably 350 or less, still more preferably 300 or less, particularly preferably 250 or less.

[Polymerizable composition (MA)]

The polymerizable composition (MA) preferably contains the following second component, first component, fourth component and/or fifth component.

[Second ingredient]

The second component is a cyclic monofunctional polymerizable compound represented by the following general formula (ii). (In the formula, P ⁱⁱ¹ represents a polymerizable group, and Z ⁱⁱ¹ represents a single bond or an alkylene group with 1 to 7 carbon atoms. One or more of the non-adjacent -CH ₂ - groups in the alkylene group may be oxygen. The atoms are independently substituted by -O-, -CO-, -COO- or -OCO- in a manner that is not directly adjacent. A ⁱⁱ¹ represents formula (ii-1) to formula (ii-20), (In the formula, more than one -CH ₂ - can be independently substituted by -O-, -S-, -COO-, -OCO-, -NH-, -NCH ₃ - or -CO-. When in the general formula (ii-1) ~ General formula (ii-20) When there are a total of two or more oxygen atoms and/or sulfur atoms, they are not bonded to each other like -OO-, -OS- or -SS- knot, in addition, one or more -CH ₂ -CH ₂ - may be substituted by -CH=CH- group. In addition, the hydrogen atoms in the general formula (ii-1) to the general formula (ii-20) may be substituted by a carbon atom. Alkyl groups with numbers 1 to 8 are substituted, and one or more of the non-adjacent -CH ₂ - in the alkyl group can be independently replaced by -O-, -CO-, -COO in a manner that the oxygen atoms are not directly adjacent. - or -OCO- substitution; in addition, the black dots in the formula represent the bonding bonds toward Z ⁱⁱ¹ ))

The compound represented by the general formula (ii) is a material excellent in flexibility, and when the compound is used, the white turbidity can be maintained even in a bent state. In addition, the adhesion can be improved and the compatibility of each component in the polymerizable composition can be improved. The compound represented by general formula (ii) is a non-liquid crystal compound.

In the compound represented by general formula (ii), P ⁱⁱ¹ in the formula represents a polymerizable group, and it is preferable that each independently represents any one of the following formulas (P-1) to formula (P-21). In addition, in the following formula (P-1) to formula (P-21), * represents a bond with a carbon atom or other atom.

Among the polymerizable groups represented by formula (P-1) to formula (P-21), from the viewpoint of improving polymerizability and storage stability, formula (P-1) and formula (P- 2), formula (P-7), formula (P-12), formula (P-13) or formula (P-21), preferably formula (P-1), formula (P-2), formula ( P-7), formula (P-21), particularly preferably formula (P-1), formula (P-2), formula (P-21).

In the compound represented by the general formula (ii), Z ⁱⁱ¹ in the formula represents a single bond or an alkylene group with 1 to 7 carbon atoms, and one or more -CH ₂ - in the alkylene group may be an oxygen atom. are independently substituted by -O-, -CO-, -COO- or -OCO- in a non-directly adjacent manner, one or more hydrogen atoms present in the alkylene group can be independently substituted by fluorine atoms . In the formula, Z ⁱⁱ¹ is preferably a single bond or an alkylene group with 1 to 6 carbon atoms, more preferably a single bond or an alkylene group with 1 to 3 carbon atoms, and particularly preferably a single bond or -CH ₂ - group. .

In the compound represented by the general formula (ii), A ⁱⁱ¹ in the formula preferably contains a heterocyclic structure having a nitrogen atom, an oxygen atom, and a sulfur atom in A ⁱⁱ¹ from the viewpoint of further improving the adhesiveness. More specifically, A ii1 , preferably the following formula (ii-a1) to formula (ii-a11). (In the formula, more than one -CH ₂ - can be independently substituted with -CO-. In addition, the hydrogen atoms in the general formula (ii-a1) to the general formula (ii-a11) can be substituted with carbon atoms of 1 to 8. substituted by an alkyl group, one or more of the non-adjacent -CH ₂ - in the alkyl group can be independently substituted by -O-, -CO-, -COO- or -OCO in a manner that the oxygen atoms are not directly adjacent. -Substitution; in addition, the hydrogen atoms in the general formula (ii-a1) to the general formula (ii-a11) can be substituted by an alkyl group with 1 to 8 carbon atoms, and the alkyl group can be a straight chain or a branched chain , one or more non-adjacent -CH ₂ - in the alkyl group can be independently substituted with -O-, -CO-, -COO- or -OCO- in a manner that the oxygen atoms are not directly adjacent; in addition , the black dots in the formula represent the bonding keys toward Z ⁱⁱ¹ )

In particular, when the cyclic structure has nitrogen atoms, the presence of nitrogen atoms in the cyclic structure can further improve the adhesiveness.

Specifically, the compound represented by general formula (ii) is preferably the following compounds (II-34) to (II-51). (X ⁵ in the formula represents a hydrogen atom or methyl group)

Among the structural formulas (II-34) to (II-51), more preferably (II-34), (II-36), (II-38), (II-39), (II-40 ), (II-43), (II-45), (II-47).

From the viewpoint of improving the adhesiveness, and also from the viewpoint of improving the compatibility of each component in the polymerizable composition, relative to the polymerizable composition contained in the polymer-dispersed liquid crystal composition of the present invention The total amount of the substances (MA) is 100% by mass, and the content of the compound represented by the general formula (ii) is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. In addition, from the viewpoint of low voltage, 80 mass% or less is preferred, 70 mass% or less is preferred, 60 mass% or less is preferred, 50 mass% or less is more preferred, and 40 mass% or less is particularly preferred. .

In the present invention, when -CH ₂ - can be substituted with an alkyl group, an alkylene group, etc. with various structures, the number of carbon atoms in the alkyl group or the like refers to the number of carbon atoms before substitution. For example, when it is defined as "alkyl group having 1 to 8 carbon atoms", it may be substituted with a structure containing two carbon atoms so that the total number of carbon atoms becomes 9. This case may also be included. When -CH ₂ CH ₂ - is substituted with various structures, the number of carbon atoms before substitution is also referred to.

[First ingredient]

The first component is a polyfunctional (meth)acrylate oligomer with a weight average molecular weight of 2,000 or more.

The polyfunctional (meth)acrylate oligomer is a compound required to introduce a cross-linked structure into the network structure of the polymer and obtain good adhesion. Among polyfunctional (meth)acrylate oligomers, difunctional acrylate oligomers are preferred. Furthermore, in order to attach importance to the adhesiveness with a base material, a urethane acrylate oligomer or a polyester acrylate oligomer is preferable, and a urethane acrylate oligomer is more preferable. The polyol skeleton structure of the urethane acrylate oligomer includes polyol skeleton structures of polyester series, polyether series, etc., but a polyether series polyol skeleton structure is preferred. As the molecular weight, the weight average molecular weight is 2,000 or more, preferably 2,000 to 60,000, more preferably 2,500 to 40,000, still more preferably 2,800 to 35,000, still more preferably 3,000 to 30,000. This is because if the molecular weight is too small, the cross-linking density increases due to the increase in the (meth)acrylic acid group contained in one molecule, the degree of curing shrinkage increases, and the adhesion deteriorates. On the contrary, if the molecular weight is too large, , the distance between crosslinks becomes longer, so the gap becomes larger and the liquid crystal is easily absorbed, so the scattering property of the polymer-dispersed liquid crystal decreases. That is, if the polymer is placed in a high-temperature environment, the liquid crystal will be absorbed by the polymer, and the characteristics will be greatly changed. In addition, if the molecular weight is large, the degree of decrease in the transition point Tnm of the polymer-dispersed liquid crystal caused by the addition of the polymerizable compound becomes smaller. In order to keep Tnm below room temperature, it is necessary to use a material with a low Tni of the liquid crystal composition itself. As a result, the operating temperature range becomes narrower.

Polyfunctional urethane (meth)acrylate oligomer is obtained by reacting a hydroxyl-containing acrylate with a polyol or polyisocyanate. Examples of the polyol include: polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polybutadiene polyol, etc. Examples of the polyether polyol include: polyethylene glycol alcohol, polypropylene glycol, polytetramethylene glycol, etc.

Examples of polyisocyanates include: 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI), o-toluidine diisocyanate (TODI), naphthylene Diisocyanate (NDI), Xylylene Diisocyanate (XDI), 4,4'-Diphenyl Methane Diisocyanate (MDI), methylene bis(4-cyclohexyl) isocyanate), hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, trans-cyclohexane 1,4-diisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4- Methyloctane isocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate, isocyanate Phorone diisocyanate and carbodiimide modified MDI, polymethylene polyphenyl polyisocyanate, etc.

Examples of the hydroxyl-containing (meth)acrylate include: (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 2-hydroxybutyl ester, (meth)acrylic acid 2-hydroxybutyl ester, (meth)acrylic acid 2-hydroxybutyl ester ) 4-hydroxybutyl acrylate, polypropylene glycol mono(meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate, mono(meth)acrylate modified by ε-caprolactone, etc. .

Specifically, aliphatic urethane (meth)acrylate, aromatic urethane (meth)acrylate, and polyurethane diacrylate oligomer are preferred. Polyols used are preferably polyether polyols, polyester polyols, and polycaprolactone polyols, and particularly preferably polyether polyols and polyester polyols. As the polyisocyanate used, polyisocyanates with cyclic A polyisocyanate with a similar structure, particularly preferably a polyisocyanate with an alicyclic structure. More specifically, o-toluidine diisocyanate (TODI), methylene bis(4-cyclohexyl isocyanate), xylylene diisocyanate, hydrogenated xylylene diisocyanate, and trans-cyclohexane 1,4 are preferred. -Diisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate, isophorone diisocyanate, carbodiimide modified MDI , particularly preferred are methylene bis(4-cyclohexyl isocyanate), xylylene diisocyanate, hydrogenated xylylene diisocyanate, trans-cyclohexane 1,4-diisocyanate, 1,6,11-undecane Triisocyanate, bicycloheptane triisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate, isophorone diisocyanate.

As the hydroxyl-containing (meth)acrylate used, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate, and mono(meth)acrylate modified by ε-caprolactone, especially (meth)acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate.

In addition, the compound of the following general formula (i-1) is also preferred. (In _the ^{formula ,} -CO-, -COO-, -OCO- substituted, b represents 1 to 20, B ² is a group selected from the following (i-2) to (i-6), and by a single group selected from them A structure obtained by repeatedly connecting the bases or combining multiple bases, B ³ is a group selected from the following general formula (i-7), general formula (i-8) or general formula (i-9), and a group in which individual groups selected from these are repeatedly linked, or A structure obtained by combining multiple bases) (In the formula ^, X ⁱ² represents a hydrogen atom ^or a methyl group; Cyclic hydrocarbon group, Y ³ and Y ⁴ represent a hydrogen atom or a methyl group, and when there are multiple X ⁱ¹ , X ⁱ² , X ⁱ³ , B ¹ , B ² , B ³ , Y ³ , Y ⁴ or Y ⁵ , They can be the same or different, t, t1 and t2 independently represent integers from 0 to 300, t+t1+t2 represents integers from 20 to 300)

Here, in the present invention, examples of the divalent aromatic group include 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, and pyrazine-2,5 -Diyl, thiophene-2,5-diyl, 1,2,3,4-tetralin-2,6-diyl, naphthyl-1,4-diyl, naphthyl-1,5 -Diyl, naphthylene-1,6-diyl, naphthylene-2,6-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, Benzothiazolyl, 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2 ,6-diyl, benzo[1,2-b:4,5-b']diselenophene-2,6-diyl, [1]benzothieno[3,2-b]thiophene-2 , 7-diyl, [1]benzoseleneno[3,2-b]selenophene-2,7-diyl or fluorene-2,7-diyl as preferred examples. These groups may be unsubstituted or substituted with more than one ^L1 .

Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopropylene group, 1,3-cyclobutylene group, 2,5-cyclopentylene group, and octahydro-4,7-methyl bridge-1H. -Indene-1,5-diyl, octahydro-4,7-methyl bridge-1H-indene-1,6-diyl, octahydro-4,7-methyl bridge-1H-indene-2,5-diyl base, tricyclo[3.3.1.1 ^3,7 ]-1,3-diyl, 1,4-cyclohexylene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1 ,3-dioxane-2,5-diyl, tetrahydrothiopyran-2,5-diyl, 1,4-bicyclo(2,2,2)octyl, decalin-2,6- Dibase is a preferred example. These groups may be unsubstituted or substituted with more than one ^L1 .

Furthermore, aliphatic urethane acrylate and polyurethane diacrylate oligomer are particularly preferred.

From the viewpoint of improving adhesion, polyfunctional compounds having a weight average molecular weight of 2,000 or more are selected based on 100% by mass of the total amount of the polymerizable composition (MA) contained in the polymer-dispersed liquid crystal composition of the present invention. The content of the polymerizable compound in the (meth)acrylate oligomer is preferably 5 mass% or more, more preferably 15 mass% or more, more preferably 20 mass% or more, and particularly preferably 25 mass% or more. In addition, from the viewpoint of reducing the voltage, the content is preferably 80 mass % or less, more preferably 60 mass % or less, more preferably 50 mass % or less, and particularly preferably 40 mass % or less.

[Fourth ingredient]

The fourth component is a compound selected from the group consisting of a polyfunctional polymerizable oligomer having a weight average molecular weight of less than 2000 and a polyfunctional polymerizable monomer represented by the following general formula (iv). In addition, the molecular weight of the polyfunctional polymerizable oligomer and/or the polyfunctional polymerizable monomer is preferably 2,000 or less, more preferably 1,000 or less. ⁽ In the formula, Y ^iv1 represents a hydrogen atom or a ^methyl group, and The above -CH ₂ - groups can be independently formed by -O-, -NH-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C in such a way that the oxygen atoms are not directly adjacent to each other. -Substitution, one or more hydrogen atoms present in the linear, branched or cyclic hydrocarbon group can be independently substituted by fluorine atoms or -OH, n ^iv1 represents an integer from 2 to 6)

The polyfunctional polymerizable oligomer or polyfunctional polymerizable monomer having a weight molecular weight of less than 2000 represented by the general formula (iv) is preferably a polymerizable compound represented by the general formula (iv-1). (In the formula, Y ^iv2 and ^{Y iv3} represent hydrogen atoms or methyl groups, and The adjacent mode is substituted by -O-, -CO-, -COO-, -OCO-, -CH=CH-, -C≡C- or OH)

Here, in the general formula ( ^iv -1), the linear or branched alkylene group of The range of 60 is particularly preferable from the viewpoint of driving voltage reduction, and the range of 5 to 50 is particularly preferable.

Examples of the polymerizable compound represented by the general formula (iv-1) include compounds having the following structures (iv-1-1) to (iv-1-10). (In the formula, n and m represent n + m is 1 to 10, n ² represents 1 to 18, n ³ and m ² represent n ³ + m ² is the value of 1 to 18, n ⁴ represents 1 to 23, n ⁵ represents 1 to 23, n ⁶ represents 4 to 30, n ⁷ represents 2 to 10, n ⁸ and n ⁹ represent 2 to 10)

From the viewpoint of improvement in heat resistance, the polymerizable composition represented by the general formula (iv) is The content of the compound is preferably 2 mass% or more, more preferably 5 mass% or more, and still more preferably 10 mass% or more. From the viewpoint of maintaining adhesion, it is particularly preferably 50 mass% or less, 40 mass% or less, It is 30 mass % or less and 25 mass % or less.

[Fifth ingredient]

The fifth component is a cyclic monofunctional polymerizable compound represented by the following general formula (v). (In the formula, P ^v1 represents a polymerizable group, and R ^v1 represents a linear or branched alkyl group with 1 to 22 carbon atoms. One or more -CH ₂ - in the alkyl group may not be directly oxygen atoms. The adjacent modes are independently substituted by -O-, -CO-, -COO-, -OCO- or -P(=O)(-OH)-, and one or more hydrogens present in the alkyl group Atoms may be independently substituted by fluorine atoms or -OH)

In the compound represented by the general formula (v), P ^v1 in the formula represents a polymerizable group, and is preferably the same as the polymerizable group represented by P ⁱⁱ¹ in the general formula (ii).

In the compound represented by the general formula (v), R ^v1 in the formula more preferably represents a linear or branched alkyl group having 3 to 20 carbon atoms. Especially in terms of suppressing crystallinity, R v1 preferably represents A linear or branched alkyl group having 6 to 18 carbon atoms, more preferably a branched alkyl group, and still more preferably a branched alkyl group having 9 to 24 carbon atoms.

When R ^v1 represents a linear alkyl group, the compound represented by the general formula (v) is preferably, for example, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) Propyl acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate Ester, decyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate , mono(meth)acrylate with a linear alkyl chain such as stearyl (meth)acrylate, behenyl (meth)acrylate, or a linear alkyl group represented by the following structure chain mono(meth)acrylate.

In addition, as the compound represented by the general formula (v), an acrylate in which R ^v1 in the general formula (v) has a linear ether chain structure is preferred. As the acrylate having the above-mentioned ether chain structure, compounds represented by the structures of the following formulas (v-a1) to (v-a3) are preferred. (In the formula, q represents an integer of 1 to 12, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3)

Among the general formula (v), it is preferable to use an alkyl chain having a linear alkyl chain, especially from the viewpoint of maintaining good transparency when no voltage is applied and making the effect of reducing the driving voltage significant. Mono(meth)acrylate.

When R ^v1 represents a branched alkyl group, the compound represented by the general formula (v) is preferably a mono(meth)acrylate having a branched alkyl chain represented by the following structure. In addition, as the compound represented by the general formula (v), preferred are isobutyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and isobutyl (meth)acrylate. Myristyl, isostearyl (meth)acrylate.

In addition, as the compound represented by the general formula (v), an acrylate in which R ^v1 in the general formula (v) has a linear ether chain structure is preferred. As the acrylate having the above-mentioned ether chain structure, a compound represented by the following structure is preferred. (In the formula, q represents an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3)

Among these compounds, in particular, it is preferable to use a mono(meth)acrylate having a branched alkyl chain in terms of maintaining the transparency when no voltage is applied and making the driving voltage reduction effect significant. .

From the viewpoint of low-voltage driving, and from the viewpoint of improving the compatibility of each component in the polymerizable composition, relative to the polymerizable components contained in the polymer-dispersed liquid crystal composition of the present invention, The total amount of the composition (MA) is 100% by mass, and the content of the chain monofunctional polymerizable compound represented by the general formula (v) is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass. %above. In addition, from the viewpoint of adhesion, the content is preferably 60 mass% or less, more preferably 50 mass% or less, and particularly preferably 40 mass% or less.

[Other polymeric compounds]

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

In the general formulas (2) to (8), P ¹¹ to P ⁷⁴ represent polymerizable groups, and preferably each independently represents any one of the following formulas (P-1) to (P-20). One. In addition, in the following formula (P-1) to formula (P-20), * represents a bond with a carbon atom or other atom.

Among the polymerizable groups represented by formula (P-1) to formula (P-20), from the viewpoint of improving polymerizability and storage stability, formula (P-1) and formula (P- 2).

X ¹¹ to X ⁷² each independently represent -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO -, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH 2 -, -OCO-CH _{2 -} , -CH ₂ -COO-, -CH ₂ -OCO- , -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C- or single bond, when there are multiple X ¹¹ to X ⁷² , they They can be the same or different (each P-(SX)-bond does not include -OO-), especially it is preferably selected from the group consisting of single bonds, -O-, -S-, -CO-, -COO-, The base in -OCO-.

M ¹¹ , M ²¹ , M ³¹ , M ⁵¹ and M ⁷¹ each independently represent a mesogenic group represented by the following general formula (9-a). (In the general formula (9-a), A ⁹¹ , A ⁹² , and A ⁹³ are each independently a divalent group having at least one or more ring structures, and the divalent group represents a group selected from 1,2-cyclopropyl group. , 1,3-cyclobutyl, 2,5-cyclopentyl, octahydro-4,7-methyl bridge-1H-indene-1,5-diyl, octahydro-4,7-methyl bridge- 1H-indene-1,6-diyl, octahydro-4,7-methyl bridge-1H-indene-2,5-diyl, tricyclo[3.3.1.1 ^3,7 ]-1,3-diyl, 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl base, tetrahydrothiopyran-2,5-diyl, 1,4-bicyclo(2,2,2)octyl, decalin-2,6-diyl, pyridine-2,5-diyl, Pyrimidine-2,5-diyl, pyrazine-2,5-diyl, thiophene-2,5-diyl, 1,2,3,4-tetralin-2,6-diyl, naphthylene -1,4-diyl, naphthylene-1,5-diyl, naphthylene-1,6-diyl, naphthylene-2,6-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, benzothiazolyl, 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl, benzo[1, 2-b:4,5-b']dithiophene-2,6-diyl, benzo[1,2-b:4,5-b']diselenophene-2,6-diyl, [1 ]benzothieno[3,2-b]thiophene-2,7-diyl, [1]benzoseleno[3,2-b]selenophene-2,7-diyl or fluorene-2, Groups in 7-diyl, these groups can be unsubstituted or substituted by more than one L ¹ , but in the case of multiple A ⁹¹ and/or A ⁹² , each can be the same or different, Z ⁹¹ and Z ⁹² Each independently represents -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ -, -CO-, -COO-, -OCO-, -CO-S-, -S -CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S -, -SCF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO -CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ - OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, -C≡C- or single bond, However, when multiple Z ⁹¹ and/or Z ⁹² appear, each may be the same or different. j ⁹¹ and j ⁹² each independently represent 0 to 4, j ⁹¹ + j ⁹² represents an integer of 1 to 4, and L ¹ represents Fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfonyl group, nitro group, isocyanate group, amine group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamine group, di Isopropylamine group, trimethylsilyl group, dimethylsilyl group, thioisocyanate group, or one -CH ₂ - or two or more non-adjacent -CH ₂ - can each be independently passed through -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 - or -C≡C-substituted straight-chain alkyl group or branched alkyl group with 1 to 20 carbon atoms. Any hydrogen atom in the alkyl group may be substituted with a fluorine atom. (Furthermore, R ¹ represents 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 fluorine. Atom, one -CH ₂ - or two or more non-adjacent -CH ₂ - in the alkyl group can be independently passed through -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-substitution))

In addition, M ⁴¹ is a trivalent organic group having a ring structure exemplified as A ⁹¹ , A ⁹² , and A ⁹³ , and M ⁶¹ is a tetravalent organic group having a ring structure exemplified as A ⁹¹ , A ⁹² , and A ⁹³ . base.

In the general formulas (2) to (8), R ¹¹ and R ³¹ respectively 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, one -CH ₂ - or two or more non-adjacent ones in the alkyl group -CH ₂ - can each independently be -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- substitution.

m1 to m7, n2 to n7, l4 to l6, and k6 each independently represent an integer from 0 to 5. In the general formulas (2) to (8), S ¹¹ to S ⁷² each independently represents a spacer or a single bond, and the spacer represented by S ¹¹ to S ⁷² represents a carbon number of 1 to 18. Alkylene group (the alkylene group may be substituted by one or more halogen atoms, CN groups, alkyl groups with 1 to 8 carbon atoms, or alkyl groups with 1 to 8 carbon atoms having a polymerizable group, the One CH ₂ group or two or more non-adjacent CH ₂ groups present in the group can be independently formed by -O-, -S-, -NH-, -N( CH ₃ )-, -CO-, -CH(OH)-, CH(COOH), -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-substituted), these Among the spacers, from the viewpoint of alignment, linear alkylene groups having 2 to 8 carbon atoms, alkylene groups having 2 to 6 carbon atoms substituted with fluorine atoms, and alkylene groups having 2 to 6 carbon atoms are preferred. An alkylene group having 5 to 14 carbon atoms partially substituted with -O-. In addition, when there are a plurality of S ¹¹ to S ⁷² , they may be the same or different.

In the general formulas (2) to (8), m1 to m7, n2 to n7, l4 to l6, and k6 each independently represent an integer of 0 to 5, and m1 to m7, n2 to n7, l4 to l6, k6 is preferably 0 or 1 independently.

From the viewpoint of alignment and transparency, the first component, the second component, and the total amount of the polymerizable composition (MA) contained in the polymer-dispersed liquid crystal composition of the present invention are The total content of other polymerizable compounds other than the component, the fourth component, and the fifth component is preferably 2 mass% or more, more preferably 5 mass% or more, and particularly preferably 10 mass% or more. In addition, from the viewpoint of scattering properties and low-voltage driving, the content is preferably 80 mass% or less, more preferably 70 mass% or less, and particularly preferably 60 mass% or less.

[Additive]

In the polymer-dispersed liquid crystal composition of the present invention, in order to achieve a composition that places greater emphasis on adhesion, the polymerizable composition (MA) preferably contains the first component, the second component, the fourth component, and the fifth component in addition to the above-mentioned first component, the second component, the fourth component, and the fifth component. In addition to the other polymerizable compounds mentioned above, it also contains an additive represented by the following general formula (X). (In the formula, Y ^X1 represents a hydrogen atom or ^a methyl group, X ^X1 represents an n The above -CH ₂ - groups can be independently formed by -O-, -NH-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C in such a way that the oxygen atoms are not directly adjacent to each other. -Substitution, one or more hydrogen atoms present in the linear, branched or cyclic hydrocarbon group can be independently substituted by fluorine atoms or -OH, n ^X1 represents an integer from 1 to 6, here, X ^X1 At least one -CH ₂ - group in is substituted by the following formula (X-1))

Specifically, it is preferable to add the following compounds. (In the formula, X ⁶ , X ⁷ and X ⁸ each independently represent a hydrogen atom or a methyl group, and q, r and s represent 1 to 4)

The added amount of the compound having a group represented by the general formula (X-1) is preferably 0.005% by mass or more and 2% by mass or less in the total amount of the polymer-dispersed liquid crystal composition, more preferably 0.01 mass % or more and 0.5 mass % or less, more preferably 0.01 mass % or more and 0.2 mass % or less.

[Non-polymerizable liquid crystal composition (LB)]

[Third ingredient]

The non-polymerizable liquid crystal composition (LB) may contain one, two or more tolane compounds represented by the following general formula (iii) as a third component. (In the formula, R ⁱⁱⁱ¹ are independently n-alkyl, n-alkoxy having 1 to 7 carbon atoms, alkenyl, alkenyloxy or alkoxyalkyl having 2 to 7 carbon atoms, R ⁱⁱⁱ² represents a fluorine atom, a chlorine atom, a cyano group, a CF ₃ group, an OCF ₃ group, an OCHF ₂ group, an NCS group or an alkyl group with 1 to 10 carbon atoms, one or two of the alkyl groups being non-adjacent -CH ₂ - group can be substituted by oxygen atom, -COO-, -OCO-. In addition, one or more -CH ₂ CH ₂ - can be substituted by -CH=CH- or -C≡C-, preferably fluorine atom , cyano group or alkyl group with 1 to 5 carbon atoms (one or two non-adjacent -CH ₂ - groups in the alkyl group can be substituted by oxygen atoms. In addition, more than one -CH ₂ CH ₂ - can be Substituted by -CH=CH- or -CH≡CH-), A ⁱⁱⁱ¹ represents trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3 -Fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, 2-methyl-1,4-phenylene, 3-methyl-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 3, 5-dimethyl-1,4-phenylene or 2,6-dimethyl-1,4-phenylene, A ⁱⁱⁱ² and A ⁱⁱⁱ³ each independently represent 1,4-phenylene, 2- Fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene base, 2,6-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 3-methyl-1,4-phenylene, 2,3-dimethyl -1,4-phenylene, 3,5-dimethyl-1,4-phenylene or 2,6-dimethyl-1,4-phenylene, one of Z ⁱⁱⁱ¹ and Z ⁱⁱⁱ² is -C≡C-, and when the other exists, it is -C≡C-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -CF=CF-, -COO-, -CH ₂ -CH ₂ -, -CF ₂ -CF ₂ - or single bond, n ⁱⁱⁱ is 0 or 1)

Since the non-polymerizable liquid crystal composition (LB) contains one or two or more diphenylene compounds represented by the general formula (iii), a polymer dispersion type including the non-polymerizable liquid crystal composition (LB) is used. The liquid crystal element of the liquid crystal composition has good adhesion and light scattering properties, and can realize low-voltage driving at room temperature and low temperature.

In addition, among the compounds represented by the general formula (iii), A ⁱⁱⁱ¹ is preferably trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3 -Fluoro-1,4-phenyl. From the viewpoint of improving scattering properties, A ⁱⁱⁱ¹ is preferably a 1,4-phenylene group.

In addition, A ⁱⁱⁱ² and A ⁱⁱⁱ³ are preferably 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, or 3,5-difluoro-1 , 4-phenylene, 2,6-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 3-methyl-1,4-phenylene. From the viewpoint of high-speed response, it is preferable to include A ⁱⁱⁱ² and A ⁱⁱⁱ³ . compound of.

The compound represented by the formula (iii) is preferably a compound represented by the following subordinate formula (iii-1) to subordinate formula (iii-8). (In the formula, R ⁱⁱⁱ¹ and R ⁱⁱⁱ² have the meanings shown in the formula (iii), Y ⁱⁱⁱ¹ and Y ⁱⁱⁱ² are 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 general formula (iii) is more preferably a compound represented by the subordinate general formula (iii-6) to the subordinate general formula (iii-8).

The compound represented by the general formula (iii) as the third component is preferably 10 mass% or more and 80 mass% or less relative to 100 mass% of the total amount of the non-polymerizable liquid crystal composition (LB), and more preferably Preferably, it is 25 mass % or more and 70 mass % or less, More preferably, it is 35 mass % or more and 60 mass % or less.

[Sixth ingredient]

The non-polymerizable liquid crystal composition (LB) may further contain one or two or more compounds represented by the following general formula (vi-0) as a sixth component (excluding the third component). (In the formula, R ¹¹ represents an alkyl group with 1 to 10 carbon atoms. One or two non-adjacent -CH ₂ - groups in the alkyl group can be substituted by oxygen atoms, -COO-, -OCO-, and in addition , more than one -CH ₂ CH ₂ - can be substituted by -CH≡CH-, R ¹² represents a fluorine atom, a chlorine atom, a cyano group, a CF ₃ group, an OCF ₃ group, an OCHF ₂ group, an NCS group, a cyano group or a carbon group An alkyl group with 1 to 10 atoms. One or two non-adjacent -CH ₂ - groups in the alkyl group can be substituted by oxygen atoms, -COO-, -OCO-. In addition, one or more -CH ₂ CH _2- can be substituted by -C≡C-, preferably a fluorine atom, a cyano group or an alkyl group with 1 to 5 carbon atoms (one or two non-adjacent CH ₂ groups in the alkyl group can be substituted by an oxygen atom Substitution), Z ¹¹ and Z ¹² independently represent a single bond, -COO-, -OCO-, -CH ₂ -CH ₂ -, -CH=CH-, -CF ₂ O-, -OCF ₂ - or -C ≡C-, when there are multiple Z ^12s , they may be the same or different. A ¹¹ , A ¹² and A ¹³ independently represent 1,4-phenylene group, 1,4-cyclohexylene group, and 1,4 -Cyclohexenyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, decalin-2,6-diyl, pyridine-2,5- Diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl, 1,2,3,4-tetralin-2,6-diyl, 2,6-naphthylene, so The 1,4-phenylene group, 1,2,3,4-tetralin-2,6-diyl group and 2,6-naphthylene group may be unsubstituted or have one or more fluorine atoms, A chlorine atom, CF ₃ group, OCF ₃ group or CH ₃ group serves as a substituent, and when there are multiple A ^13s , they may be the same or different, n ¹¹ is 0, 1 or 2)

As a compound of general formula (vi-0), R ¹¹ in general formula (vi-0) is preferably an alkyl group with 1 to 5 carbon atoms (one or two non-adjacent CH ₂ in the alkyl group group may be substituted by an oxygen atom), R ¹² is preferably a fluorine atom, a cyano group or an alkyl group with 1 to 5 carbon atoms (one or two non-adjacent CH ₂ groups in the alkyl group may be substituted by an oxygen atom ), Z ¹¹ and Z ¹² are preferably each independently a single bond, -COO-, -OCO-, -CH ₂ -CH ₂ -, -CF ₂ O- or -OCF ₂ - (there are multiple bonds in Z ¹¹ may be the same or different), more preferably a single bond, -COO- or -CF ₂ O-, A ¹¹ , A ¹² and A ¹³ are preferably each independently 1,4-phenyl, 1 ,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, 1,2,3,4-tetralin-2,6-diyl or 2,6-naphthylene group (the 1,4-phenylene group, 1,2,3,4-tetralin-2,6-diyl, and 2,6-naphthylene group may be unsubstituted or have One or more fluorine atoms or CH ₃ groups serve as substituents, which may be the same or different when there are multiple A ¹³ groups), more preferably 1,4-phenylene group or 1,4-cyclohexylene group , pyrimidine-2,5-diyl or 2,6-naphthylene group (the 1,4-phenylene group and 2,6-naphthylene group may be unsubstituted or have one or more fluorine atoms or CH ₃ groups serve as substituents, which may be the same or different when there are multiple A ¹³ groups), and n ¹¹ is preferably 0 or 1.

The compound represented by the general formula (vi-0) is more preferably one or two or more liquid crystal compounds represented by the following general formula (vi) (excluding the third component). (In the formula, R ³ represents an alkyl group with 1 to 10 carbon atoms. One or more non-adjacent -CH ₂ - groups in the alkyl group can be separated by an oxygen atom, -CH=CH-, -COO -, -OCO-substituted, A ⁶ represents 1,4-phenylene group, 1,4-cyclohexylene group, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl or Pyrimidine-2,5-diyl, the 1,4-phenylene group may be unsubstituted or have one or more fluorine atoms, chlorine atoms, CF ₃ , OCF ₃ or methyl groups as substituents, A ⁷ Represents 1,4-phenylene group or 1,4-cyclohexylene group. The 1,4-phenylene group may be unsubstituted or have one or more fluorine atoms, chlorine atoms, CF ₃ , OCF ₃ or Methyl is used as a substituent, and A ⁸ represents a 1,4-phenylene group. The 1,4-phenylene group may be unsubstituted or have one or more fluorine atoms, chlorine atoms, CF ₃ , OCF ₃ or Methyl serves as a substituent, and Z ⁶ and Z ⁷ independently represent a single bond, -COO-, -OCO-, -CH ₂ -CH ₂ -, -CH=CH-, -CF ₂ O-, -OCF ₂ -. Or -C≡C-, n ¹² means 0 or 1; among them, the third component is excluded)

In addition, in the general formula (vi), R ³ is more preferably an alkyl group having 1 to 10 carbon atoms, or an alkoxy group. A ⁶ and A ⁷ are more preferably 1,4-phenylene group and 1,4-cyclohexylene group (the 1,4-phenylene group can be unsubstituted or have one or more fluorine atoms as substituents ). It is more preferred that Z ⁶ and Z ⁷ are each independently a single bond, -COO-, -OCO-, -CH ₂ -CH ₂ -, and further preferably a single bond or -COO-.

In addition, in the general formula (vi), R ³ represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 2 to 7 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms, and A ⁷ represents a 1,4-extended alkyl group. Phenyl or 1,4-cyclohexylene group, the 1,4-phenylene group can be unsubstituted or have a fluorine atom as a substituent. In order to reduce the viscosity of the liquid crystal and improve low-temperature driveability, it is best to contain at least n ¹² represents a compound of 0.

From the viewpoint of lowering the voltage, it is preferable to use a compound in which A ⁷ and A ⁸ represent a 1,4-phenylene group in the general formula (vi), and the 1,4-phenylene group is Any one of the groups has at least one fluorine atom as a substituent, Z ⁶ , Z ⁷ and Z ⁸ represent a single bond or -COO-, and A ⁶ represents a 1,4-phenylene group or a 1,4-cyclopentyl group. Hexyl, n ¹² means 0 or 1.

Specific examples include the following compounds (vi-1) to (vi-11). (In the formula, R ⁵¹ represents an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms, Y ¹¹ to Y ⁶⁶ each independently represents a hydrogen atom or a fluorine atom; Y ¹¹ to Y ⁶⁶ can all be Represents a hydrogen atom, or more than one of them may represent a fluorine atom)

Specific examples include the following compounds (vi-A) to (vi-G). (In the formula, R ⁵¹¹ represents an alkyl group having 2 to 7 carbon atoms or an alkoxy group having 2 to 7 carbon atoms, preferably an alkyl group having 2 to 5 carbon atoms or an alkoxy group having 2 to 5 carbon atoms. base)

The compound represented by the general formula (vi-0) is preferably 20 mass% or more and 90 mass% or less, more preferably 30 mass%, based on 100 mass% of the total amount of the non-polymerizable liquid crystal composition (LB) It is more than 75 mass % and less than 75 mass %, and it is more preferable that it is 40 mass % or more and 65 mass % or less.

In addition, the total content of the liquid crystal compound represented by the general formula (vi) is preferably 2 mass% or more and 70 mass% or less based on 100 mass% of the total amount of the non-polymerizable liquid crystal composition (LB), and more preferably Preferably, it is 5 mass % or more and 50 mass % or less, More preferably, it is 10 mass % or more and 30 mass % or less.

Furthermore, the total content of the liquid crystal compounds represented by the general formulas (vi-1) to (vi-11) is preferably 2% with respect to 100% by mass of the total amount of the non-polymerizable liquid crystal composition (LB). It is more than 5 mass % and 70 mass % or less, More preferably, it is 5 mass % or more and 50 mass % or less, More preferably, it is 10 mass % or more and 30 mass % or less.

Furthermore, the total content of the liquid crystal compounds represented by the general formula (vi-A) to the general formula (vi-G) is preferably 100% by mass of the total amount of the non-polymerizable liquid crystal composition (LB). It is 2 mass % or more and 70 mass % or less, more preferably 5 mass % or more and 50 mass % or less, still more preferably 10 mass % or more and 30 mass % or less.

In particular, the general formula (vi-A), general formula (vi-B), general formula (vi-C), general formula ( The total content of the liquid crystal compounds represented by vi-G) is preferably 2 mass % or more and 70 mass % or less, more preferably 5 mass % or more and 50 mass % or less, still more preferably 10 mass % or more and 30 mass % the following.

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, and still more preferably 0.20. Above, the most preferable value is 0.22 or above. The normal light refractive index (no) of the non-polymerizable liquid crystal composition having these Δn is usually about 1.50 to 1.54. When a voltage is applied to a polymer-dispersed liquid crystal element to bring it into a transparent state, if no of the non-polymerizable liquid crystal composition is substantially consistent with the refractive index (np) of the polymer forming the network structure, it can be obtained High transparency. However, when monomers and oligomers are polymerized by ultraviolet (UV) irradiation, etc., they harden as a partially surrounded non-polymerizable liquid crystal composition, so the actual refractive index of the polymer is higher than that of pure The refractive index of polymers is high. Therefore, the refractive index of the monomer and oligomer is preferably less than 1.5, more preferably 1.48 or less, and still more preferably 1.47 or less.

[Polymerization initiator]

The polymer-dispersed liquid crystal composition of the present invention may contain a polymerization initiator. The polymerization initiator used in the present invention is used to polymerize the polymerizable composition (MA) of the present invention. The photopolymerization initiator used when polymerizing by light irradiation is not particularly limited, and a known and commonly used photopolymerization initiator may be used to the extent that it does not inhibit the alignment state of the non-polymerizable liquid crystal composition (LB).

Examples include: 1-hydroxycyclohexylphenyl ketone "Omnirad 184", 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one "Omnirad" Omnirad 1173", 2-methyl-1-[(methylthio)phenyl]-2-morpholinylpropane-1"Omnirad 907", 2,2-di Methoxy-1,2-diphenylethan-1-one "Omnirad BDK", 2-benzyl-2-dimethylamino-1-(4-morpholinobenzene) methyl)-butanone "Omnirad (Omnirad) 369", 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinyl-phenyl)butane- 1-keto "Omnirad (Omnirad) 379", 2,2-dimethoxy-2-phenylacetophenone "Omnirad (Omnirad) 651", 2,2-dimethoxy- 1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl)-diphenylphosphine oxide "Omnirad TOP", 2,4 , 6-trimethylbenzoyl-phenyl-phosphine oxide "Omnirad 819" (manufactured by IGM Resins Co., Ltd.), 1,2-octanedione, 1-[ 4-(phenylthio)-,2-(o-benzoyl oxime)], ethyl ketone "Irgacure OXE01"), 1-[9-ethyl-6-(2-methylbenzene) Formyl)-9H-carbazol-3-yl]-,1-(o-acetyl oxime) "Irgacure OXE02", "Irgacure OXE04" (BASF AG Co., Ltd.), "Adeka cruise (Adeka cruise) NCI-831", "Adeka cruise (Adeka cruise) NCI-930", "Adeka cruise (Adeka cruise) N- 1919" (manufactured by ADEKA), 2,4-diethylthioxanthone ("Kayacure DETX" manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate A mixture of esters ("Kayacure EPA" manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone ("Quantacure ITX manufactured by Ward Blenkinsop") ") and a mixture of p-dimethylaminobenzoic acid ethyl ester, "Esacure ONE", "Esacure KIP150", "Esacure KIP160", "Esacure (Esacure) 1001M", "Esacure A198", "Esacure KIP IT", "Esacure KTO46", "Esacure TZT" (Lamberti ) Co., Ltd.), "SpeedCure BMS", "SpeedCure PBZ", "benzophenone" (manufactured by LAMBSON), etc. Furthermore, as the photocation initiator, a photoacid generator can be used. Examples of the photoacid generator include diazodispene-based compounds, triphenylsulfonium-based compounds, phenylsulfonium-based compounds, sulfonylpyridine-based compounds, triazine-based compounds, diphenyl iodide compounds, and the like.

The content of the photopolymerization initiator is preferably 0.1 mass% or more and 10 mass% or less relative to 100 mass% of the total amount of the polymerizable composition (MA) used in the polymer-dispersed liquid crystal composition of the present invention, and more preferably Preferably, it is 0.2 mass % or more and 6 mass % or less. These may be used individually or in mixture of 2 or more types.

In addition, as the thermal polymerization initiator used in thermal polymerization, well-known and conventional thermal polymerization initiators can be used. For example, methyl acetyl acetate peroxide, cumene hydroperoxide, and benzene peroxide can be used. Formine, bis(4-tert-butylcyclohexyl)peroxydicarbonate, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, 1,1-bis(tert-hexyl peroxide) 3,3 ,5-trimethylcyclohexane, p-pentahydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, isobutyl peroxide, bis(3-methyl-3)dicarbonate peroxide -Methoxybutyl) ester, 1,1-bis(tert-butylperoxy)cyclohexane and other organic peroxides, 2,2'-azobisisobutyronitrile, 2,2'-azobis Azonitrile compounds such as (2,4-dimethylvaleronitrile), azoamidine compounds such as 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2, 2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide} and other azoamide compounds, 2,2'-azo Alkylazo compounds such as bis(2,4,4-trimethylpentane), etc. The content of the thermal polymerization initiator is preferably 0.1% by mass or more and 10% by mass relative to 100% by mass of the total amount of the polymerizable composition (MA) used in the polymerizable composition of the polymer-dispersed liquid crystal composition of the present invention. mass% or less, more preferably 1 mass% or more and 6 mass% or less. These may be used individually or in mixture of 2 or more types.

The polymer-dispersed liquid crystal composition of the present invention can be added with polymerization inhibitors, antioxidants, light stabilizers, and chain transfer agents within the range that does not impair practical electro-optical properties and adhesion when made into a polymer-dispersed liquid crystal element. , pigments, pigments, particles with a particle size less than 1 μm, chiral compounds or alignment materials. Among them, the polymer-dispersed liquid crystal composition preferably contains one or two or more selected from the group consisting of polymerization inhibitors, antioxidants, light stabilizers, particles with a particle size less than 1 μm, dyes and pigments.

[Polymerization inhibitor]

The polymerization inhibitor used in the present invention can be used to adjust the electro-optical properties by controlling the polymerization reaction of the polymer-dispersed liquid crystal composition of the present invention. As such a compound, a well-known and commonly used compound can be used.

Preferred ones are p-methoxyphenol, cresol, tert-butylcatechol, 3,5-di-tert-butyl-4-hydroxytoluene, 2,2'-methylenebis(4-methyl -6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butyl phenol), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol and other phenolic compounds, hydroquinone, methylhydroquinone, 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, diphenoquinone and other quinone compounds, especially p-methoxyphenol, 4-methoxy-1-naphthol, tert-butylhydrogen Quinone, 2-hydroxy-1,4-naphthoquinone.

When a polymerization inhibitor is contained, the content of the polymerization inhibitor is preferably 100% by mass of the total amount of the polymerizable composition (MA) used in the polymerizable composition of the polymer-dispersed liquid crystal composition of the present invention. It is 0.001 mass % or more and 2.0 mass % or less, More preferably, it is 0.01 mass % or more and 0.5 mass % or less.

〔Antioxidants〕

The antioxidant used in the present invention can be used to impart practical durability to the polymer-dispersed liquid crystal element of the present invention. As such compounds, hydroquinone derivatives, nitrosamine-based polymerization inhibitors, hindered phenol-based antioxidants, and the like can be used.

Specifically, preferred are tert-butylhydroquinone, "Q-1300" and "Q-1301" of Wako Pure Chemical Industries, Ltd., and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxy Phenyl)propionate] "IRGANOX 1010", thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] "IRGANOX IRGANOX 1035", octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate "IRGANOX 1076", "IRGANOX""IRGANOX1135","IRGANOX1330", 4,6-bis(octylthiomethyl)-o-cresol "IRGANOX 1520L", "IRGANOX" (IRGANOX) 1726", "IRGANOX (IRGANOX) 245", "IRGANOX (IRGANOX) 259", "IRGANOX (IRGANOX) 3114", "IRGANOX (IRGANOX) 3790", "IRGANOX 5057", "IRGANOX 565" (the above are manufactured by BASF Co., Ltd.), IRGANOX Co., Ltd. and IRGANOX Co., Ltd. (Adekastab) AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, Sumilizer BHT, Sumilizer BBM of Sumitomo Chemical Co., Ltd. -S and Sumilizer GA-80 and compounds having structures represented by the following general formulas (H-1) to (H-4), etc.

In general formula (H-1) to general formula (H-3), R ^H1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. Or an alkenyloxy group with 2 to 10 carbon atoms, one -CH ₂ - or two or more non-adjacent -CH ₂ - present in the group can be independently substituted with -O- or -S-, in addition, One or more hydrogen atoms present in the group may be independently substituted with fluorine atoms or chlorine atoms. More specifically, 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 is preferred. More preferably, it is 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. However, one -CH ₂ - or two or more non-adjacent -CH ₂ - present in the group may be separately are independently substituted with -O- or -S-, and one or more hydrogen atoms present in the group may be independently substituted with fluorine atoms or chlorine atoms.

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

When an antioxidant is contained, the content of the antioxidant is preferably 0.001 mass% or more and 2.0% by mass relative to 100% by mass of the total amount of the polymerizable composition (MA) used in the polymer-dispersed liquid crystal composition of the present invention. mass% or less, more preferably 0.01 mass% or more and 0.5 mass% or less.

[Light stabilizer]

The light stabilizer used in the present invention can be used to impart practical durability to the polymer-dispersed liquid crystal element of the present invention. 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)", "CHIMASSORB (CHIMASSORB) 944LD" (the above are manufactured by BASF Co., Ltd.), "Eddie Costapo" (Adekastab) LA-52", "Adekastab (Adekastab) LA-57", "Adekastab (Adekastab) LA-62", "Adekastab (Adekastab) LA-67", "Adekastab (Adekastab) LA-63P", "Adekastab (Adekastab) LA-68LD", "Adekastab (Adekastab) LA-77", "Adekastab (Adekastab) ) LA-82", "Adekastab LA-87" (the above are manufactured by ADEKA Co., Ltd.), etc.

When a light stabilizer is contained, the added amount of the light stabilizer is preferably 0.001% by mass or more and 2.0% by mass relative to the total amount of the polymerizable composition (MA) used in the polymer-dispersed liquid crystal composition of the present invention. mass% or less, more preferably 0.01 mass% or more and 1.0 mass% or less.

[Chain transfer agent]

The chain transfer agent used in the present invention can be used to further improve the adhesion between the polymer-dispersed liquid crystal composition and the substrate. Examples of the chain transfer agent include: octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, n-dodecyl mercaptan, tert. -Mercaptan compounds such as tetradecylmercaptan and tert-dodecylmercaptan, hexanedithiol, dedecanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol Glycol dithioglycolate, ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropyl Acid ester, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanuric acid Ester, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Thiol compounds, pentaphenylethane, α-methylstyrene dimer, acrolein, allyl alcohol, terpinolene, α-terpene, γ-terpene, dipentene, etc., specifically , preferably compounds represented by the following general formulas (9-1) to (9-8), α-methylstyrene dimer, and α-terpinene. In the formula, R ⁹⁵ represents an alkyl group with 1 to 18 carbon atoms. The alkyl group can be a straight chain or a branched chain. More than one methylene group in the alkyl group can have oxygen atoms and sulfur atoms. The form of direct bonding is substituted by oxygen atom, sulfur atom, -CO-, -OCO-, -COO- or -CH=CH-, R ⁹⁶ represents an alkylene group with 2 to 18 carbon atoms, and the alkylene group More than one methylene group in may be substituted by an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO- or -CH=CH- in a form where the oxygen atom and the sulfur atom are not directly bonded to each other.

When a chain transfer agent is contained, the content of the chain transfer agent is preferably 0.001% by mass or more and 10% by mass relative to 100% by mass of the total amount of the polymerizable composition (MA) of the polymer-dispersed liquid crystal composition of the present invention. mass% or less, more preferably 0.01 mass% or more and 5.0 mass% or less.

〔pigment〕

The pigment used in the present invention can be used to impart color to or control the color of the polymer-dispersed liquid crystal element of the present invention. There is no particular limitation on the pigment, and any known and commonly used pigment can be used within the range of being soluble in liquid crystal or dispersed in a polymer network. Examples of the dye include dichroic dyes, fluorescent dyes, and the like. Examples of such dyes include polyazo dyes, anthraquinone dyes, quinacridone dyes, dioxazine dyes, quinacridone dyes, cyanine dyes, phthalocyanine dyes, perylene dyes, and purpurone dyes. From the viewpoint of adding a squaraine dye or the like, the dye is preferably a dye showing liquid crystallinity. Examples include: Japanese Patent Application Publication No. Sho 51-2885, Japanese Patent Application Publication No. Sho 61-21163, Japanese Patent Application Publication No. Sho 62-555, Japanese Patent Application Publication No. Sho 63-301850, Japanese Patent Application Publication No. Sho 63-301850, Japanese Patent Application Publication No. Japanese Patent Application Publication No. 10-279945, Japanese Patent Application Publication No. 11-172252, Japanese Patent Application Publication No. 2000-239664, Japanese Patent Application Publication The polyazo dye shown in Japanese Patent Application Laid-Open No. 2012-82400, etc., Japanese Patent Application Laid-Open No. Sho 59-20355, Japanese Patent Application Laid-Open No. Sho 59-172549, Japanese Patent Laid-Open No. Sho 61-148291, Anthraquinone pigments shown in Japanese Patent Application Laid-Open No. 1-161086, Japanese Patent Application Laid-Open No. 8-67822, etc., Japanese Patent Application Laid-Open No. 59-51947, Japanese Patent Application Laid-Open No. 61-148292, etc. The quinophthalone dye shown in Japanese Patent Application Laid-Open No. 2000-44825, the dioxazine dye shown in Japanese Patent Application Laid-Open No. 2001-49135, etc.

When a pigment is contained, the content of the pigment is preferably 0.01% by mass or more and 8% by mass relative to 100% by mass of the total amount of the non-polymerizable liquid crystal composition (LB) used in the polymer-dispersed liquid crystal composition of the present invention. mass% or less, more preferably 0.1 mass% or more and 4 mass% or less.

[Pigment]

The pigment used in the present invention can be used to impart color to or control the color of the polymerizable liquid crystal element of the present invention. There is no particular limitation on the pigment, and any known and commonly used pigment can be used within the range of being dispersed in liquid crystal or network polymer. Examples of such pigments include azo pigments, diketopyrrolopyrrole pigments, quinacridone pigments, dioxazine pigments, perylene pigments, phthalocyanine pigments, carbon black pigments, etc., from the viewpoint of effectively imparting coloring properties. Specifically, the pigment is preferably one with good dispersibility in the network polymer.

When a pigment is contained, the content of the pigment is preferably 0.01% by mass or more and 8% by mass relative to 100% by mass of the total amount of the non-polymerizable liquid crystal composition (LB) used in the polymer-dispersed liquid crystal composition of the present invention. mass% or less, more preferably 0.1 mass% or more and 4 mass% or less.

[Particles with a particle size less than 1 μm]

Particles with a particle diameter of less than 1 μm used in the present invention can be used to impart various functions to the polymer-dispersed liquid crystal element of the present invention. Such particles are not particularly limited and can be used within a range that does not impair the electro-optical properties or adhesiveness 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, glass fiber, metal powders such as silver powder and copper powder, or nitrogen Aluminum nitride, boron nitride, silicon nitride, gallium nitride, silicon carbide, magnesium oxide, silicon dioxide, crystalline silicon dioxide (silicon oxide), fused silicon dioxide (silicon oxide), graphite, Thermal conductive fillers such as carbon fibers including carbon nanofibers, silver nanoparticles, quantum dots (QD) luminescent particles, perovskite luminescent particles, etc.

The particles are preferably particles with good dispersibility in the network polymer. When the particles are contained, the content of the particles is preferably 0.001% by mass or more based on 100% by mass of the total amount of the non-polymerizable liquid crystal composition (LB) used in the polymer-dispersed liquid crystal composition of the present invention. And 5 mass % or less, More preferably, it is 0.01 mass % or more and 3 mass % or less.

[Chiral compounds]

The chiral compound used in the present invention can be used to impart various functions to the polymer-dispersed liquid crystal element of the present invention. There is no particular limitation on such a chiral compound, and it can be used within a range that does not impair the electro-optical characteristics or adhesiveness of the liquid crystal element. Specific examples include "CB-15", "C- 15", "S-1082" manufactured by Merck, "CM-19", "CM-20" and "CM" manufactured by Chisso, have 1-methylheptyl group as the "S-811" manufactured by Merck as a chiral group, "CM-21" and "CM-22" manufactured by Chisso, and those with an isosorbide skeleton as a chiral group Polymerizable chiral compounds shown in "LC756" of BASF Corporation, Japanese Patent Application Publication No. 2009-515818, Japanese Patent Application Publication No. 2010-90108, Japanese Patent Application Publication No. 2013-87109, etc. wait.

When a chiral compound is contained, it depends on the use of the polymer in the polymer-dispersed liquid crystal composition of the present invention, but it is preferable to divide the thickness (d) of the polymer obtained by adding the helical pitch in the polymer The value (d/P) obtained by (P) is in the range of 0.1 to 100, and more preferably in the range of 0.1 to 20.

In order to exert the characteristics of the liquid crystal composition, the content of the chiral compound is preferably as small as possible to obtain a desired helical pitch. When a chiral compound is contained, the content of the chiral compound is preferably 0.01 mass % relative to 100 mass % of the total amount of the non-polymerizable liquid crystal composition (LB) used in the polymer-dispersed liquid crystal composition of the present invention. % or more and 8 mass% or less, more preferably 0.1 mass% or more and 4 mass% or less.

[Alignment material]

In order to control the alignment of the liquid crystal element, the polymer-dispersed liquid crystal composition of the present invention may contain an alignment material. The alignment material used in the present invention is a well-known and commonly used alignment material within the range of being insoluble in the liquid crystal composition. Examples of such alignment materials include a polymerizable compound having a polar group at one end of the mesogenic skeleton and a long-chain alkyl group at the other end, or a polymeric compound having polarity at a lateral position of the mesogenic skeleton. A polymerizable liquid crystal compound having a plurality of mesogenic skeletons and a polymerizable compound having a polar group in the side chain of a long-chain alkyl group that bonds one of the mesogenic skeletons to the mesogenic skeleton.

＜Liquid crystal element＞

A liquid crystal element using the polymer-dispersed liquid crystal composition of the present invention includes at least a layer in which liquid crystal and network polymer are phase-separated (phase-separated liquid crystal layer), an electrode, and a base material. Or it includes a phase separation liquid crystal layer, an alignment film phase, an electrode, and a substrate supporting the phase separation liquid crystal layer, alignment film layer, and electrode.

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

Regarding the liquid crystal element of the present invention, for example, when no voltage is applied, the polymer-based network structure and the liquid crystal molecules existing in the gaps can enter a light scattering state. On the other hand, when a voltage is applied, the liquid crystal molecules can be aligned vertically with respect to the substrate, thereby achieving a transparent state. In this way, the liquid crystal element of the present invention changes the light transmission state depending on whether or not a voltage is applied, and therefore can be used as a liquid crystal dimming element incorporated into a device requiring a dimming function or as a liquid crystal used in a display for image display. Display components.

The liquid crystal element of the present invention only needs to be configured so that the alignment of the liquid crystal molecules can be controlled by applying a voltage, but it is preferably 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 as to generate an electric field vertically with respect to the alignment film. In a vertical electric field type liquid crystal element, electrodes are usually provided on two transparent substrates sandwiching a phase-separated liquid crystal layer.

The structure of the vertical electric field type liquid crystal element of the present invention includes a first substrate and a second substrate each including a transparent electrode (layer) made of a transparent conductive material, and is sandwiched between the first substrate and the second substrate. phase separation liquid crystal layer. The phase-separated liquid crystal layer includes a polymer-dispersed liquid crystal material containing liquid crystal molecules and polymer components contained in the liquid crystal composition.

[Substrate]

The substrate used in the liquid crystal element of the present invention is a substrate commonly used in liquid crystal display elements, organic light-emitting display elements, other display elements, optical components, light modulating elements, colorants, markers, printed matter, or optical films. In the liquid crystal element In applications where heat resistance or permeability is important within the temperature range of heating and use in the manufacturing process, there is no particular restriction as long as the material has practical transparency that can withstand it.

Examples of such a substrate include organic materials such as glass substrates, metal substrates, ceramic substrates, plastic substrates, and paper. Especially when the base material is an organic material, examples include cellulose derivatives, polyolefins, polyesters, polycarbonates, polyacrylates, polyarylates, polyether esters, polyimides, and polyphenylene sulfides. Ether, polyphenylene ether, nylon or polystyrene, etc. Among them, it is preferable to use plastic base materials such as polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, polycarbonate, and polyimide.

When there are two substrates, it is only necessary that one of the substrates has transparency that is practical as a liquid crystal element, and the other substrate does not need to have transparency.

As the shape of the substrate, a flat plate shape is shown, but other shapes such as a shape having a curved surface may be used. In addition, the substrate may have an electrode layer, an anti-reflection function, and a reflection function as necessary.

In order to improve the adhesion of the liquid crystal element of the present invention, these substrates may be subjected to surface treatment. Examples of surface treatments include ozone treatment, plasma treatment, corona discharge treatment, silane coupling treatment, and the like. In addition, in order to adjust the transmittance or reflectivity of light, an organic film, an inorganic oxide film or a metal film can be provided on the surface of the base material through evaporation or other methods, or in order to provide added optical value, the base material can be a pickup lens, Rod lenses, optical discs, phase difference films, light diffusion films, microlens sheets, color filters, etc.

[Electrode: Transparent electrode layer]

The electrodes used in the liquid crystal element of the present invention are provided so as to generate an electric field in the liquid crystal element that can control the alignment of liquid crystal molecules in the phase-separated liquid crystal layer. The strength of the electric field is controlled based on how much voltage is applied to the electrodes.

The shape of the electrode is not particularly limited, and the conductive portion may be in a stripe shape, a mesh shape, or a random mesh shape.

As such an electrode material, it is preferable to include a metal material. Specifically, Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni, or an alloy including at least one of them, is preferable. is Al or an alloy containing Al.

In order to improve the transparency of the liquid crystal element, it is preferred that the electrodes be composed of transparent electrode layers. Such a transparent electrode layer may include, for example, a well-known transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (Indium Zinc Oxide, IZO), or indium zinc tin oxide (IZTO). Material. In addition, when one of the substrates contains a non-transparent material, the electrode provided on the non-transparent substrate does not need to be transparent and can be appropriately selected from known metal materials.

[Alignment film layer]

On the substrate, alignment treatment may be performed so that the liquid crystal molecules in the polymer-dispersed liquid crystal element of the present invention are aligned horizontally or vertically, or an alignment film may be provided. Examples of alignment treatments include: stretching treatment, rubbing treatment, polarized ultraviolet and visible light irradiation treatment, ion beam treatment, oblique evaporation treatment of SiO ₂ on the substrate, etc. Examples of such an alignment film include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, and polyethylene terephthalate. Ester, polyether ester, epoxy resin, epoxy acrylate resin, acrylic resin, azo compound, coumarin compound, chalcone compound, cinnamate compound, fulgide compound, anthraquinone compound , arylvinyl compounds and other compounds, or polymers or copolymers of said compounds. In order to impart a tilt angle to the liquid crystal molecules, when a rubbing treatment is performed, the compound that performs the alignment treatment by rubbing is preferably a compound that accelerates crystallization of the material by adding a heating step after the alignment treatment or alignment treatment. Among the compounds subjected to alignment treatment other than rubbing, it is preferable to use a photo-alignment material.

Generally speaking, when a liquid crystal composition is brought into contact with a substrate having an alignment function, liquid crystal molecules are aligned near the substrate in the direction in which the substrate is aligned. The alignment treatment method of the substrate has a great influence on whether the liquid crystal molecules are aligned horizontally, obliquely or vertically with the substrate.

[Example of manufacturing method of liquid crystal element]

From the viewpoint of productivity, the liquid crystal element of the present invention is preferably formed by dripping or coating the polymer-dispersed liquid crystal composition on the substrate using the roll-to-roll method, such as the One Drop Fill (ODF) method. A liquid crystal element is produced by laminating opposing substrates.

In the manufacturing step of the liquid crystal element using the roll-to-roll method, the polymer-dispersed liquid crystal composition is coated on a first electrode, a glass substrate having an alignment film and a first electrode, or a plastic substrate , the second electrode, or the glass substrate having the alignment film and the second electrode, or the electrode side of the plastic substrate, or the alignment film side is bonded to the liquid crystal composition, and The thickness is uniform, so that the liquid crystal element can also be manufactured. Examples of methods for applying the polymer-dispersed liquid crystal composition used in the present invention include an applicator method, a rod coating method, a roller coating method, a direct gravure coating method, a reverse gravure coating method, an inkjet method, and a die coating method. Known and commonly used methods such as cap coating method. In the liquid crystal element manufacturing step of the ODF method, a sealant for a liquid crystal display such as an epoxy-based photothermal combination curable sealant is drawn as a closed-loop bank on either the back plate or the front plate of the hollow element using a dispenser. The liquid crystal element can be manufactured by adding a predetermined amount of the liquid crystal composition dropwise under degassing, and then joining the front plate and the back plate.

The liquid crystal element of the present invention can be produced from a liquid crystal element by interposing a spacer for maintaining a distance between two substrates, like a well-known liquid crystal element. The thickness between the substrates, that is, the thickness of the phase separation layer, is preferably 2 μm to 50 μm, more preferably 10 μm to 30 μm. The spacers may be dispersed on the substrate in advance, or may be mixed into the polymer-dispersed liquid crystal composition in advance and coated on the substrate simultaneously with the polymer-dispersed liquid crystal composition.

The method of 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 using an ODF method or the like. During the period from the dropwise addition or application to the polymerization of the polymerizable composition, the polymer-dispersed liquid crystal composition is preferably in a uniform isotropic state.

When dripping or coating is performed, the polymer dispersion-type liquid crystal composition can be sandwiched between two substrates using a laminator or the like.

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

In this case, the following method is preferred: after applying the polymer-dispersed liquid crystal composition and a composition containing particles that determine the thickness of the liquid crystal element on a plastic base material containing a first electrode, A method of irradiating ultraviolet light immediately after laminating the plastic base material containing the second electrode in such a way that the first electrode and the second electrode face each other; A method of irradiating ultraviolet light while applying pressure to the material; or after applying the liquid crystal composition for a liquid crystal element and a composition containing particles that determine the thickness of the liquid crystal element on the first plastic base material containing the first electrode. , bringing the first plastic base material and the coated liquid crystal composition into a vacuum state, and then laminating the second plastic base material containing the second electrode in such a way that the first electrode and the second electrode face each other. A method of irradiating ultraviolet light in a vacuum state.

[Polymerization method]

As a method for polymerizing the polymer-dispersed liquid crystal composition of the present invention, ultraviolet irradiation is suitable. As a lamp that generates ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, etc. can be used. In addition, the wavelength of the ultraviolet rays to be irradiated is preferably a wavelength range in which the irradiation is an absorption wavelength range of the photopolymerization initiator contained in the polymer-dispersed liquid crystal composition and is not an absorption wavelength range of the contained liquid crystal composition. As for ultraviolet rays, specifically, it is preferable to use ultraviolet rays with a cutoff of 330 nm or less using a metal halide lamp, a high-pressure mercury lamp, or an ultrahigh-pressure mercury lamp. In addition, it is also preferable to use an ultraviolet (UV)-light emitting diode (LED) lamp that can irradiate a single wavelength.

The intensity of the irradiated ultraviolet rays can be appropriately adjusted to obtain the target dimming layer, preferably 1 mW/cm ² to 200 mW/cm ² , and more preferably 5 mW/cm ² to 50 mW/cm ² . The time for irradiating ultraviolet rays is appropriately selected depending on the intensity of ultraviolet rays to be irradiated, but is preferably 10 seconds to 300 seconds.

In addition, the temperature during ultraviolet irradiation is an important factor in determining the characteristics of the light control layer, but is preferably a temperature higher than the isotropic-nematic transition point (Tnm) of the polymer-dispersed liquid crystal composition.

The liquid crystal element of the present invention can be used directly or bonded to other substrates for use. In addition, an adhesive agent or adhesive layer, an adhesive agent or an adhesive layer, a protective film, a polarizing film, etc. may be laminated.

[Other electric field types]

In addition to the vertical electric field type, the liquid crystal element of the present invention can also adopt a lateral electric field type or other electric field types. The fringe electric field used in the fringe field switching (FFS) driving mode can also be used. In this case, a horizontal alignment layer may also be provided. The horizontal alignment layer may include well-known materials.

The liquid crystal element of the present invention is preferably used as a dimming unit in building materials, dimmable glass, smart windows for vehicles, or organic light emitting diode (OLED) displays, for example. The liquid crystal display element of the present invention can be used in the same applications as conventional polymer-dispersed liquid crystal display elements. In particular, it can be suitably used in transmission-type displays, flexible displays, and the like. More specifically, it can be used for architectural dimming elements such as windows, skylights, roofs, walls, partitions, partitions, door leaves, etc., transportation dimming elements for door leaves, windows, doors, helmets, sliding roofs, etc., sunglasses, In articles such as decorative dimming elements such as glasses, sun visors, watches, mirrors, and reflective plates, display components such as flexible liquid crystal display elements, reflective liquid crystal display elements, transparent liquid crystal display elements, and variable diffusion films.

＜Dimming component＞

The light modulating element of the present invention has a pair of transparent electrode substrates; and a composite layer, which is disposed between the pair of transparent electrode substrates and includes a polymer network and a liquid crystal compound. Furthermore, the polymer network is a polymer network derived from the polymerizable composition (MA) contained in the polymer-dispersed liquid crystal composition, and the liquid crystal compound is the polymer-dispersed liquid crystal composition. Non-polymerizable liquid crystal composition (LB) contained in the product.

The light control element may be an element that utilizes the liquid crystal element using a polymer-dispersed liquid crystal composition and electrically controls the light transmittance of the liquid crystal element. This dimming element may be an element in which only a voltage applying device is mounted on the liquid crystal element, but it may also be made of laminated glass with polyvinyl butyral (PVB), ethylene Intermediate films such as Ethyl Vinyl Acetate (EVA), Thermoplastic Urethanes (TPU) (polyurethane series), and ionic interlayer films (Sentry Glas Plus, SGP) are also used. Laminated glass in which a liquid crystal element is sandwiched between two pieces of glass. In addition, functional films such as ultraviolet cutoff and heat ray cutoff can also be added.

[Example]

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 addition, "part" in the composition of the following Examples and Comparative Examples means "part by weight."

The non-polymerizable liquid crystal compositions (LB) used in Examples and Comparative Examples to be described later are shown in Table 1 and Table 2, respectively. Table 3 shows the description of each component of the polymerizable composition (MA) used in Examples and Comparative Examples to be described later.

[Table 1] Liquid crystal composition (parts by weight) Liquid crystal composition No. LC1 LC2 LC3 LC4 Liquid crystal compound in non-polymerizable liquid crystal composition (LB)*1 2-Ph-E-Ph3-CN 8 8 3-Ph-E-Ph3-CN 6 6 3-Cy-Ph-CN 20 14 3-Cy-Ph-O-1 4 10 7 9 3-Ph-Ph3-Ph-CN 4 4 3-Cy-Cy-Ph-1 twenty one 20 20 18 3-Cy-Ph-T-Ph-2 7 7 3-Ph-Ph-T-Ph26-2 twenty three 25 twenty three 25 3-Ph-Ph-T-Ph26-4 15 17 15 18 3-Ph-Ph-T-Ph26-5 10 14 10 12 total 100 100 100 100 Physical property values of liquid crystal compositions Tni[℃] 138 133 141 134 Δn（25℃） 0.243 0.248 0.260 0.270 Δε (25℃) 5.7 4.3 10.1 10.2 γ1[mPa·sec]（25℃） 228 196 273 307 *1 Parts by weight of each compound in total 100 parts by weight of the liquid crystal composition

[Table 2] Liquid crystal composition (parts by weight) Liquid crystal composition No. LC11 LC12 Liquid crystal compound in non-polymerizable liquid crystal composition (LB)*1 2-Ph-E-Ph3-CN 5 3-Ph-E-Ph3-CN 9 2-Ph-Ph-CN 3 5-Ph-Ph-CN 45 3 3-Cy-Ph-CN 9 3-Cy-Ph-O-2 5 1d1-Cy-Ph-CN 9 1OPEP5 5 6OPEP5 7 5-Cy-Ph-Ph-CN 9 3-Ph-Ph3-Ph-CN twenty three 7 2-Cy-Ph-E-Ph3-CN 5 11 3-Cy-Ph-E-Ph3-CN 5 7 4-Cy-Ph-E-Ph3-CN 5 13 5-Cy-Ph-E-Ph3-CN 5 3-Cy-Ph-Ph-1 7 3 total 100 100 Physical property values of liquid crystal compositions Tni[℃] 105.3 109.5 Δn（25℃） 0.241 0.193 Δε (25℃) 18.9 25.5 γ1[mPa·sec]（25℃） 420 608 *1 Parts by weight of each compound in total 100 parts by weight of the liquid crystal composition

The meanings of the symbols indicating the structures of the respective liquid crystal compounds in Tables 1 and 2 are shown below. In addition, "1", "2", "3", "4", and "5" at the end of each component in Table 1 refer to the number of carbon atoms in the side chain.

For example, the correspondence between the structure and expression of a liquid crystal compound is as follows.

[table 3] title Structural formula first ingredient Multifunctional (meth)acrylate oligomer UA-1 (Synthesis example 1) fourth component Multifunctional polymerizable oligomers and multifunctional polymerizable monomers 4-1 4-2 second component cyclic monofunctional polymerizable compound 2-1 2-2 2-3 fifth ingredient Chain monofunctional polymerizable compound 5-1 additives XA polymerization initiator Omnirad 184 Omnirad 651

(Synthesis example 1)

Add 44.4 parts (0.2 mol) of isophorone diisocyanate (IPDI) to a flask equipped with a stirring blade and stir. At the same time, while paying attention to the heat, add 810 parts of polypropylene glycol (average molecular weight Mw: 8100) ( 0.1 mol), then raise the temperature to 70°C. The reaction was carried out for 7 hours at the stated temperature to obtain a urethane polymer having an isocyanate group at the terminal. Next, 23.2 parts (0.2 mol) of 2-hydroxyethyl acrylate (molecular weight: 116) was added, and the reaction was further performed at the temperature for 7 hours. After confirming that the absorption of NCO disappeared using an infrared absorption spectrum, it was taken out to obtain urethane acrylate UA-1 (average molecular weight Mw: 29800).

In addition, in the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured based on gel permeation chromatography (Gel Permeation Chromatography, GPC) and converted to polystyrene. In addition, the measurement conditions of GPC are as follows.

[Measurement conditions for GPC] Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation Column: Protection column "Super (Super) HZ-L" manufactured by Tosoh Co., Ltd. + "Super (Super) HZ2000" manufactured by Tosoh Co., Ltd. × 3 pieces + manufactured by Tosoh Co., Ltd. "T Super (T Super) HZM-M" Detector: Built-in refractive index (Reflective Index, RI) detector Data processing: "EcoSEC-WorkStation Ver2.01" manufactured by Tosoh Corporation Measurement conditions: column temperature 40°C, development solvent tetrahydrofuran, flow rate 1.0 ml/min Standard: Use monodisperse polystyrene of known molecular weight according to the device measurement manual.

(Example 1)

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

Liquid crystal composition LC1 was added to the obtained polymerizable compound ma-1 so that the weight ratio of the polymerizable composition (MA)/non-polymerizable liquid crystal composition (LB) (MA/LB weight ratio) becomes 49/51, It was dissolved while stirring at 50° C. to obtain a polymer-dispersed liquid crystal composition PL1.

After the obtained polymer-dispersed liquid crystal composition PL1 was injected into a glass tank with a thickness of 15 μm at room temperature (the structure is glass substrate/transparent electrode layer/air layer/transparent electrode layer/glass substrate) , irradiating ultraviolet rays at room temperature to obtain a liquid crystal element having a liquid crystal polymer composite. The ultraviolet conditions at this time are that the light source is a UV-LED lamp with a wavelength of 365 nm, the intensity is 15 mW/cm ² , and the time is 60 seconds. The irradiation intensity of ultraviolet rays was measured using an ultraviolet luminance meter UIT-201 and a sensor UVD-365PD manufactured by Ushio Electric (USHIO).

(Transmittance evaluation)

A rectangular wave of 60 Hz and a voltage of 0 V 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 at 0 V was defined as T ₀ , and the transmittance when an alternating current (AC) was applied at 100 V was defined as T ₁₀₀ and evaluated. The respective transmittances under the conditions of 25°C are 0.13% and 87.5%.

(Drive voltage evaluation)

Using a liquid crystal element having the obtained liquid crystal polymer composite, the transmittance (T ₀ ) at 0 V was set to 0% and the transmittance (T ₁₀₀ ) when 100 V was applied at a temperature of 25°C. When it is set to 100%, the voltage at which the transmittance reaches 90% is defined as the driving voltage (V ₉₀ ) and measured. The driving voltage is 37 V.

(Evaluation of low-temperature drivability)

The voltage dependence of the transmittance of a liquid crystal element having the obtained liquid crystal polymer composite using LCD-5200 (manufactured by Otsuka Electronics Co., Ltd.) while lowering the temperature in 5°C increments from 25°C to -30°C. Make a determination. At this time, the lowest measurement temperature at which the change range of transmittance at the measurement temperature (T ₁₀₀ -T ₀ ) is not less than 90% of the change range (T ₁₀₀ -T ₀ ) at the measurement temperature of 25°C is set as the minimum drive Temperature [℃]. The minimum driving temperature is -20℃.

(Tightness evaluation)

The adhesiveness was evaluated according to the following method. First, glass beads with a particle size of 15 μm were spread on one of the transparent electrode surfaces of two PET films with transparent electrodes, the liquid crystal composition was dropped thereon, and applied using an applicator. Then, another PET film was bonded to the coated surface so that the transparent electrode surface was in contact with the coated surface to form a film laminate. By sandwiching the film laminate between two glass plates, pressure is uniformly applied to the entire surface of the film laminate, so that the liquid crystal composition has a substantially uniform thickness. Using a UV-LED lamp with a light source of 365 nm wavelength, the film laminate clamped on the glass plate was irradiated with ultraviolet light with an intensity of 15 mW/cm ² for 60 seconds at room temperature, and then the glass plate was removed, thus obtaining Polymer dispersed liquid crystal element. Furthermore, the UV intensity was measured using the UV luminance meter UIT-201 and sensor UVD-365PD manufactured by Ushio Electric (USHIO).

The obtained polymer-dispersed liquid crystal element was cut into strips so that the width became 25 mm, and a 180° peeling test was performed. Using the force tester MCT2150 manufactured by A&D Company, find out how to pull the ends of two PET films with transparent electrodes at one end of the strip at 180° to each other at a stretching speed of 50 mm in an environment of 25°C. The average peel strength during peeling per minute. The strength is 0.5 N.

(Example 2 to Example 5, Comparative Example 1 to Comparative Example 2)

Polymer-dispersed liquid crystal compositions PL2 to PL5, and polymer-dispersed liquid crystal compositions PL11 to PL1 were prepared in the same manner as PL1 except that each component was used in the mixing ratio shown in Table 4. Molecularly dispersed liquid crystal composition PL12.

Examples were obtained using these polymer-dispersed liquid crystal compositions PL2 to PL5 and polymer-dispersed liquid crystal compositions PL11 to PL12 in the same manner as in Example 1. 2 to Example 5, and the polymer dispersion type liquid crystal element of Comparative Examples 1 to 2.

Each evaluation was performed in the same manner as in Example 1 using the obtained polymer-dispersed liquid crystal element. Table 4 shows the mixing ratio of each component and the evaluation results.

[Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Polymer dispersed liquid crystal composition PL1 PL2 PL3 PL4 PL5 PL11 PL12 Non-polymerizable liquid crystal composition (LB) third component LC1 LC2 LC2 LC3 LC4 LC11 LC12 Polymerizable composition (MA)*2 second component 2-1 20 30 30 20 20 20 2-2 15 20 15 15 2-3 25 first ingredient UA-1 30 30 30 20 30 30 30 fourth component 4-1 5 10 10 5 5 4-2 20 fifth ingredient 5-1 30 30 25 40 30 30 30 mixing ratio MA[mass%] 49 47 47 55 51 37 36 LB[mass%] 51 53 53 45 49 63 64 Others*3 additives XA 0.1 0.1 0.1 0.1 0.1 0.1 0.1 polymerization initiator Omnirad 184 3 3 3 3 3 3 Omnirad 651 2 Dimming characteristics Electro-optical properties T ₀ [%]（25℃） 0.13 0.07 0.16 0.10 0.18 0.12 0.25 T ₁₀₀ [%]（25℃） 87.5 84.4 86.3 84.6 87.9 86.9 87.4 Drive voltage, V ₉₀ [V] (25℃) 37 52 twenty four 38 32 39 32 low temperature drivability Drive voltage, V ₉₀ [V] (-10℃) 33 59 28 34 27 56 43 Drive voltage, V ₉₀ [V] (-20℃) 44 68 40 41 57 77 72 Minimum driving temperature [℃] -20 -20 -20 -20 -20 -5 -5 Tightness [N] (180 degrees, 25 mm width, 25℃) 0.5 0.4 0.3 0.5 0.6 0.3 0.3 *2 Parts by weight out of a total of 100 parts by weight of the first component, the second component, the fourth component, and the fifth component *3 Parts by weight based on a total of 100 parts by weight of the first component, the second component, the fourth component, and the fifth component

According to the above results, the polymer-dispersed liquid crystal elements of Examples 1 to 5 can achieve both low transmittance in the scattering state and high transmittance in the transmission state, and can be driven with a sufficiently low driving voltage. In addition, a sufficiently low driving voltage can be maintained under low temperature conditions, and the lowest driving temperature can be achieved as low as -20°C. Furthermore, it also showed excellent values in the adhesion test.

In contrast, in Comparative Examples 1 to 2, the driving voltage increased under low-temperature conditions, and in particular, the driving voltage at -20° C. increased significantly. In addition, the minimum driving temperature is also -5°C, which is not sufficient.

without

without

Claims (12)

A polymer-dispersed liquid crystal composition, containing a polymerizable composition (MA) and a non-polymerizable liquid crystal composition (LB). In the polymer-dispersed liquid crystal composition, the non-polymerizable liquid crystal composition (LB) The value of dielectric constant anisotropy is positive, and the rotational viscosity γ1 at 25°C is 400 mPa·sec or less. The polymer-dispersed liquid crystal composition according to claim 1, wherein the polymerizable composition (MA) contains one or more polymerizable compounds represented by the following general formula (ii); In the formula, P ⁱⁱ¹ represents a polymerizable group, and Z ⁱⁱ¹ represents a single bond or an alkylene group with 1 to 7 carbon atoms. One or more non-adjacent -CH ₂ - in the alkylene group may be an oxygen atom. The modes that are not directly adjacent are independently substituted by -O-, -CO-, -COO- or -OCO-, A ⁱⁱ¹ represents formula (ii-1) to formula (ii-20); In the formula, more than one -CH ₂ - can be independently substituted by -O-, -S-, -COO-, -OCO-, -NH-, -NCH ₃ - or -CO-. When in the general formula ( ii-1) ~ When there are a total of two or more oxygen atoms and/or sulfur atoms in the general formula (ii-20), they are not bonded to each other like -OO-, -OS- or -SS- , In addition, one or more -CH ₂ -CH ₂ - may be substituted by -CH=CH- group. In addition, the hydrogen atoms in the general formula (ii-1) to the general formula (ii-20) may be substituted by the number of carbon atoms. 1 to 8 alkyl substituted, one or more of the non-adjacent -CH ₂ - in the alkyl group can be independently replaced by -O-, -CO-, -COO- in a manner that the oxygen atoms are not directly adjacent. or -OCO- substitution; in addition, the black dots in the formula represent the bonding bonds toward Z ⁱⁱ¹ . The polymer-dispersed liquid crystal composition according to claim 1 or 2, wherein the non-polymerizable liquid crystal composition (LB) contains one or more compounds represented by the following general formula (iii); In the formula, R ⁱⁱⁱ¹ are independently n-alkyl, n-alkoxy having 1 to 7 carbon atoms, alkenyl, alkenyloxy or alkoxyalkyl having 2 to 7 carbon atoms, R ⁱⁱⁱ² represents a fluorine atom, a chlorine atom, a cyano group, a CF ₃ group, an OCF ₃ group, an OCHF ₂ group, an NCS group or an alkyl group with 1 to 10 carbon atoms, one or two of the non-adjacent alkyl groups - The CH ₂ - group may be substituted by an oxygen atom, -COO-, -OCO-. In addition, one or more -CH ₂ CH ₂ - groups may be substituted by -CH=CH- or -C≡C-. A ⁱⁱⁱ¹ represents trans- 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4 -phenylene, 3,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 3- Methyl-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 3,5-dimethyl-1,4-phenylene or 2,6-dimethyl -1,4-phenylene group, A ⁱⁱⁱ² and A ⁱⁱⁱ³ each independently represent 1,4-phenylene group, 2-fluoro-1,4-phenylene group, or 3-fluoro-1,4-phenylene group , 2,3-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2-methyl -1,4-phenylene, 3-methyl-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 3,5-dimethyl-1,4- Phenylene or 2,6-dimethyl-1,4-phenylene, one of Z ⁱⁱⁱ¹ and Z ⁱⁱⁱ² is -C≡C-, and the other one is -C≡C-, - when present. CF ₂ O-, -OCF ₂ -, -CH=CH-, -CF=CF-, -COO-, -CH ₂ -CH ₂ -, -CF ₂ -CF ₂ - or single bond, n ⁱⁱⁱ is 0 or 1. The polymer-dispersed liquid crystal composition according to claim 1 or 2, wherein the polymerizable composition (MA) contains one or more polymerizable compounds represented by the following general formula (v); In the formula, P ^v1 represents a polymerizable group, and R ^v1 represents a linear or branched alkyl group with 1 to 22 carbon atoms. One or more -CH ₂ - in the alkyl group may not be directly adjacent to oxygen atoms. are independently substituted by -O-, -CO-, -COO-, -OCO- or -P(=O)(-OH)-, one or more hydrogen atoms present in the alkyl group Each may be independently substituted with a fluorine atom or -OH. The polymer-dispersed liquid crystal composition according to claim 1 or 2, wherein the polymerizable composition (MA) contains one or more polyfunctional (meth)acrylates with a weight average molecular weight of 2000 or more. Oligo(i). The polymer-dispersed liquid crystal composition according to claim 1 or 2, wherein the polymerizable composition (MA) contains a polyfunctional polymerizable material selected from the group consisting of a weight average molecular weight of less than 2000 represented by the following general formula (iv) One or more of the group consisting of oligomers and multifunctional polymerizable monomers; In the ^formula , Y ^iv1 represents a hydrogen atom or a ^methyl group, and The -CH ₂ - groups may be independently -O-, -NH-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C- in such a way that the oxygen atoms are not directly adjacent to each other. Substitution: One or two or more hydrogen atoms present in a linear, branched or cyclic hydrocarbon group can be independently substituted with a fluorine atom or -OH, and n ^iv1 represents an integer from 2 to 6. The polymer-dispersed liquid crystal composition according to claim 1 or 2, wherein the polymerizable composition (MA) further contains an additive represented by the following general formula (X); In the formula, Y ^X1 represents a hydrogen atom or ^a methyl group, X ^X1 represents an n The -CH ₂ - groups may be independently -O-, -NH-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C- in such a way that the oxygen atoms are not directly adjacent to each other. Substitution, one or more hydrogen atoms present in the linear, branched or cyclic hydrocarbon group can be independently substituted by fluorine atoms or -OH, n ^X1 represents an integer from 1 to 6, here, in X ^X1 At least one -CH ₂ - group is substituted by the following formula (X-1), . The polymer-dispersed liquid crystal composition according to claim 1 or 2 further contains a polymerization initiator. The polymer dispersed liquid crystal composition according to claim 5, wherein the polyfunctional (meth)acrylate oligomer (i) with a weight average molecular weight of 2000 or more is selected from the group consisting of urethane ( One or more of the group consisting of methacrylate oligomers and polyester-based (meth)acrylate oligomers. The polymer-dispersed liquid crystal composition according to claim 1 or 2, wherein the polymerizable composition (MA) further contains particles selected from the group consisting of polymerization inhibitors, antioxidants, light stabilizers, and particles with a particle size less than 1 μm. One or more of the group consisting of pigments and pigments. A liquid crystal element obtained by using the polymer-dispersed liquid crystal composition according to claim 1 or 2. A dimming component having: a pair of transparent electrode substrates; and A liquid crystal polymer composite is arranged between the transparent electrode substrates and includes a polymer network and a liquid crystal compound, Among the dimming components, The polymer network is a polymer network derived from the polymerizable composition (MA) contained in the polymer-dispersed liquid crystal composition according to claim 1 or 2, The liquid crystal compound is a non-polymerizable liquid crystal composition (LB) contained in the polymer-dispersed liquid crystal composition according to claim 1 or 2.