JP7083990B2 - Polymer-dispersed liquid crystal element and its manufacturing method - Google Patents

Description

The present invention relates to a polymer-dispersed liquid crystal device and a method for manufacturing the same.

Since the polymer-dispersed liquid crystal element does not require a polarizing plate, it has an advantage that a brighter display can be realized as compared with a TN, STN, IPS or VA mode liquid crystal display element using a conventional polarizing plate. Since the configuration is simple, it is applied to optical shutter applications such as dimming glass and segment display applications such as clocks.

There are several types of this polymer-dispersed liquid crystal element, for example, a type called NCAP (Patent Document 1), a type called PDLC (Polymer Dispersed LC) (Patent Document 2, Patent Document 3), and PNLC (Patent Document 3). A type (Patent Document 4) and the like called Polymer Network LC) have been proposed.

Here, among the polymer-dispersed liquid crystals, types called PDLC and PNLC will be briefly described. These liquid crystal compositions for a polymer-dispersed liquid crystal element are usually composed of a non-polymerizable nematic liquid crystal composition, one or more kinds of polymerizable compounds, and a photopolymerization initiator, and a mixture thereof (polymer). A liquid crystal composition for a dispersed liquid crystal element) is made uniform, sandwiched between glass cells or a plastic film, and irradiated with ultraviolet rays to polymerize the polymerizable compound or its composition, and at the same time, the polymer and the liquid crystal composition are polymerized. The substance is phase-separated to form a structure in which the liquid crystal composition forms a continuous layer in the three-dimensional network structure of the polymer, a structure in which the droplets of the liquid crystal composition are dispersed in the polymer, or a structure in which both are mixed. ..

The polymer-dispersed liquid crystal element obtained by sandwiching the liquid crystal composition for a polymer-dispersed liquid crystal element between glass or a film and irradiating with ultraviolet rays, the liquid crystal composition is randomly oriented in a state where no voltage is applied. It takes a state and becomes a state in which light is scattered due to the difference in refractive index between the cured polymer and the liquid crystal composition and the random orientation of the liquid crystal composition itself, that is, a cloudy state. On the other hand, when a sufficiently high voltage is applied, the liquid crystal composition is oriented in the electric field direction, and the scattering property of the liquid crystal composition itself is lost. Here, if the difference between the refractive index of the polymer and the no (normal light refractive index) of the liquid crystal composition is sufficiently small, light scattering does not occur and the liquid crystal composition becomes transparent.

Further, a polymer-dispersed liquid crystal element called a reverse mode type, which is transparent when no voltage is applied and scatters light when a voltage is applied, has also been proposed (Patent Documents 5 and 6).

Special Table No. 58-501631 Japanese Unexamined Patent Publication No. 2-15236 Japanese Unexamined Patent Publication No. 63-271233 Japanese Unexamined Patent Publication No. 1-198725 Japanese Unexamined Patent Publication No. 5-119302 Japanese Unexamined Patent Publication No. 2008-58374

However, since these conventionally known polymer-dispersed liquid crystal elements have a large surface area in contact with the polymer component and the liquid crystal component, they are strongly bound to the liquid crystal at the interface and have a large drive voltage.

An object of the present invention is to provide a polymer-dispersed liquid crystal element having excellent low-voltage driveability and a method for manufacturing the same.

The present invention includes the following aspects.
[1] A pair of substrates having electrodes on at least one of the substrates and a composite layer of a liquid crystal component and a polymer compound component are provided between the pair of substrates.
A polymer-dispersed liquid crystal element in which the composite layer forms a slippery interface between the liquid crystal component and the polymer compound component.

[2] The polymer-dispersed liquid crystal element according to the above [1], wherein the drive voltage is 5 to 25 V.
[3] The polymer compound component has the following general formula (I).
In the polymer-dispersed liquid crystal device according to the present invention, the polymer compound component is represented by the following general formula (I).

(In general formula (I),
A ¹ represents a hydrogen atom or a methyl group.
Y ¹ is a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups present in the alkylene group are independently oxygen atoms, assuming that the oxygen atoms do not directly bond to each other. , -CO-, -COO- or -OCO-, and one or more hydrogen atoms present in the alkylene group are independently substituted with a fluorine atom, a methyl group or an ethyl group, respectively. It may have been done.)
A and B independently have a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, a 3,6-cyclohexenylene group, and a 1,4-silacyclohexylene group, respectively. , Tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,3-ditian-2,5-diyl group, 1, 4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group , 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthren-2,7-diyl group, 9,10-dihydrophenantren-2,7-diyl group, 1 , 2,3,4,4a, 9,10a-Octahydrophenanthrene-2,7-diyl group or fluorene-2,7-diyl group, the 1,4-phenylene group, 1,2,3,4 -Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a , 9,10a-Octahydrophenanthrene-2,7-diyl group and fluorene-2,7-diyl group are unsubstituted or one or more as substituents F, Cl, CF ₃ , OCF ₃ Or it can have CH ₃ .

m independently represents 0, 1, 2, or 3, respectively.
X ¹ and X ² independently represent a single bond, -O-, -COO-, -OCO- or -CO-, assuming that the oxygen atoms do not bond directly to each other.
Z ⁴ represents an alkyl group having 4 to 18 carbon atoms, and the alkyl group is unsubstituted or has one or more F, Cl, CN, CH ₃ or CF ₃ as a substituent. The one or more CH ₂ groups present in the alkyl group may be substituted with O, CO or COO so that the O atoms do not directly bond to each other. )
The polymer-dispersed liquid crystal element according to the above [1] or [2], which is a polymer compound component obtained by polymerizing a polymerizable compound component containing at least one compound represented by.
[4] The polymer compound component has the following general formula (Ia).

(In the formula (IA), A ¹ represents a hydrogen atom or a methyl group, and A ² is a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more alkylene groups present in the alkylene group). The methylene group may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, assuming that the oxygen atoms are not directly bonded to each other, and one or one present in the alkylene group. Two or more hydrogen atoms may be independently substituted with a fluorine atom, a methyl group or an ethyl group, respectively.) ^, And A3 and ^A6 are independently hydrogen atoms or carbon atoms 1 to 18 respectively. Alkyl group (one or more methylene groups present in the alkyl group are independently substituted with oxygen atom, -CO-, -COO- or -OCO- as if the oxygen atom does not directly bond to each other. One or two or more hydrogen atoms present in the alkyl group may be independently substituted with a halogen atom or an alkyl group having 1 to 17 carbon atoms.) A ⁴ and A ⁷ are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms (one or two or more methylene groups present in the alkyl groups are assumed that oxygen atoms do not directly bond to each other. Each may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms present in the alkyl group are independently halogen atoms or carbon atoms, respectively. It may be substituted with an alkyl group of numbers 1 to 9), k represents 1 to 40, and B ¹ , B ² and B ³ are independently hydrogen atoms and carbon atoms 1 to 10, respectively. Linear or branched alkyl group (one or more methylene groups present in the alkyl group are independently oxygen atoms, -CO-, -COO- as if the oxygen atoms do not directly bond to each other. Or it may be replaced with -OCO-), or the general formula (Ib).

(In the formula (Ib), A ⁹ represents a hydrogen atom or a methyl group, and A ⁸ is a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more alkylene groups present in the alkylene group). The methylene group may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, assuming that the oxygen atoms are not directly bonded to each other, and one or one present in the alkylene group. Two or more hydrogen atoms may be independently substituted with a fluorine atom, a methyl group or an ethyl group, respectively.) However, among 2k + 1 B ¹ , B ² and B ³ . The number of basic substances represented by the general formula (Ib) is 0 to 3.) A polymer compound obtained by polymerizing a polymerizable compound component containing at least one compound represented by the above formula (Ib). The polymer-dispersed liquid crystal element according to any one of the above [1] to [3], which is a component.

[5] The liquid crystal component is the following general formula (I-1).

(In the formula, R ⁰¹ represents a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, and one or two or more non-adjacent −CH _2- in the alkyl group is an oxygen atom, —CH = CH. -, -COO-, may be replaced with -OCO-,
R ⁰² represents a hydrogen atom, 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 having 1 to 15 carbon atoms, and is a non-alkyl group among the alkyl groups. One adjacent or two or more non-adjacent -CH ₂ -may be replaced with an oxygen atom, -CH = CH-, -COO-, -OCO-.
A ⁰¹ , A ⁰² , A ⁰³ , and A ⁰⁴ independently have a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, and a 3,6-cyclohexenylene, respectively. Group, 1,4-silacyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, decahydronaphthalene-2,6-diyl group, pyridine-2,5 -Diyl group, pyrimidin-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, 1,3 -Representing a dithian-2,5-diyl group or a tetrahydrothiopyran-2,5-diyl group, said 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or The 2,6-naphthylene group is unsubstituted or can have one or more fluorine atoms, chlorine atoms, ₃ CFs, ₃ ^OCFs or ₃ CHs as substituents, provided that A03. And / or ^A04 may be a single bond.
Z ⁰¹ , Z ⁰² , and Z ⁰³ are independently single-bonded, -COO-, -OCO-, -CH ₂ -CH _2- , -CF ₂ -CF _2- , -CH = CH-,-, respectively. CF = CF-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , or -C≡C-. The polymer-dispersed liquid crystal device according to any one of [1] to [4] above, which contains at least one liquid crystal compound represented by ().
[6] The liquid crystal component is the following general formula (III).

(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a halogen atom, CN and NCS, and the alkyl group and the alkenyl group are unsubstituted. Alternatively, it can have one or more F, Cl, CN, CH ₃ , CF ₃ as a substituent and one or more CH ₂ groups present in the alkyl or alkenyl group. Assuming that the O atoms do not directly bond to each other, they may be substituted with O, CO, and COO, and the rings F, G, and H are independently 1,4-phenylene groups and 1,4-cyclohexyl, respectively. Siren group, 1,4-cyclohexenylene group, 3,6-cyclohexenylene group, 1,4-silacyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5- Diyl group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydro Represents a naphthalene-2,6-diyl group, a 2,6-naphthylene group, a 1,3- ^{dithian -} 2,5-diyl group or a tetrahydrothiopyran-2,5-diyl group, Y7, Y8 and ^Y9 . Are independently single-bonded, -COO-, -OCO-, -C≡C-, -CH ₂ CH _{2-, -CH 2 CH 2 CH 2 CH 2-} , -CH ₂ CH ₂ CH ₂ O- , -OCH ₂ CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CF = CF-, -CH = CH-, -CH ₂ CH ₂ CH = CH-, -CH = CHCH ₂ CH _2- , -CH ₂ CH = CHCH _2- , -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , Y ¹⁰ is a single bond, -O-, -CO-, -COO-, -OCO-, -CH _{2-, -CH 2 O-} , -OCH _2- , -CH ₂ COO- or -CH ₂ OCO- , Z ³ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a halogen atom, and the alkyl group or the alkenyl group is unsubstituted or has one or one as a substituent. It can have two or more F, Cl, CN, CH ₃ or CF ₃ , and one or two or more CH ₂ groups present in the alkyl or alkenyl group is an O atom. May be substituted with O, CO or COO so that they do not bind directly to each other, r and s independently represent 0, 1, 2, or 3, but r + s is 0, 1, 2, or 3. be. The polymer-dispersed liquid crystal device according to any one of [1] to [5] above, which contains at least one compound represented by (1).

[7] The polymer-dispersed liquid crystal element precursor mixture containing the liquid crystal component and the polymerizable compound component is injected between a pair of substrates having electrodes on at least one of the substrates to obtain the polymerizable compound component. The method for producing a polymer-dispersed liquid crystal element according to any one of [1] to [6] above, wherein the polymerization reaction is carried out.

The polymer-dispersed liquid crystal device of the present invention is excellent in low voltage driveability.

It is a schematic sectional drawing which shows the example of the polymer dispersion type liquid crystal element which concerns on this invention. It is a schematic diagram which shows the experimental setting at the time of measuring the electro-optic characteristic. It is a graph which shows the example of the measurement result of the VT characteristic (voltage-light transmittance characteristic) of the polymer dispersion type liquid crystal element of this invention. It is a graph which compares and shows the measurement result of the VT characteristic (voltage-light transmittance characteristic) in the voltage increase process of the polymer dispersion type liquid crystal element of an Example and a comparative example. It is a schematic sectional drawing which shows the example of the polymer dispersion type liquid crystal element of 1st Embodiment of this invention. It is a schematic sectional drawing which shows the example of the polymer dispersion type liquid crystal element of the 2nd Embodiment of this invention. It is a schematic sectional drawing which shows the example of the polymer dispersion type liquid crystal element of the 3rd Embodiment of this invention. ^{1 1} H-NMR chart of compound A3B2DA. It is a graph which shows the square wave AC voltage of the frequency of 1 kHz applied at the time of measuring the electro-optic characteristic.

Hereinafter, the polymer-dispersed liquid crystal device according to the present invention will be described with reference to the drawings. The diagram of the polymer-dispersed liquid crystal device according to the present invention conceptually represents each configuration, and the present invention is not limited to the following embodiments.

In FIG. 1, the polymer-dispersed liquid crystal element 10 of the present invention has a liquid crystal component 13 and a height between a pair of substrates 11 and 12 having an electrode 18 on at least one of the substrates 11 and the pair of substrates 11 and 12. A composite layer 15 of the molecular compound component 14 is provided, and the composite layer 15 forms a slippery interface having a lubricating interface induction region between the liquid crystal component 13 and the polymer compound component 14.

As used herein, the slippery interface refers to a slippery interface formed between a liquid crystal component and a polymer compound component.
As used herein, the lubrication interface induction region is a region that induces the lubrication interface and is a region that is less ordered than the liquid crystal phase.

As a method for forming a slippery interface having a lubricating interface induction region between the liquid crystal component and the polymer compound component, for example, the polymer compound component is appropriately similar to the structure of the liquid crystal molecule of the liquid crystal component. However, it is possible to introduce a structure that does not exhibit liquid crystallinity or reduces liquid crystallinity.

By forming a slippery interface between the liquid crystal component and the polymer compound component, it becomes possible to exhibit the effect that the liquid crystal molecule easily responds to an external field. As a result, after removing the external field, a small external field force (low electric field in the case of an electric field) due to the easy response of the liquid crystal molecules while maintaining the force to restore the original orientation by the elastic force of the liquid crystal. It is possible to obtain a function such as a response or a high-speed response that responds to an external field at a high speed.

In the polymer-dispersed liquid crystal element of the present invention, when the liquid crystal molecules of the liquid crystal component react to the change of the external field of the external electric field or the external magnetic field, the composite layer is formed between the liquid crystal component and the polymer compound component. By forming a slippery interface, it is excellent in low voltage driveability.

In the conventional polymer-dispersed liquid crystal, the interaction between the liquid crystal composition and the polymer compound is used to orient the liquid crystal, and the resulting difference in refractive index between the liquid crystal composition and the polymer compound is used to emit light. It was scattered. However, when the liquid crystal composition is driven by applying a voltage due to the interaction between the liquid crystal composition and the polymer compound, a higher voltage is required.

In the polymer-dispersed liquid crystal element of the present invention, the polymer compound component has, for example, moderately similar to the structure of the liquid crystal molecule of the liquid crystal component represented by the general formula (I), but does not exhibit liquid crystal property or has liquid crystal property. It is considered that the driving voltage could be reduced by forming a slippery interface having a lubricating interface induction region between the liquid crystal component and the polymer compound component by introducing a structure that reduces the temperature. Be done.

The drive voltage of the polymer-dispersed liquid crystal element according to the present invention is preferably adjusted to 25 V or less, more preferably 1 to 23 V, and particularly preferably 4 to 16 V. When a low voltage is preferred, it is preferably 4 to 12V, more preferably 4 to 10V, and particularly preferably 4 to 8V. When contrast is important, it is preferably 6 to 20 V, more preferably 7 to 18 V.

A first embodiment of the polymer-dispersed liquid crystal device according to the present invention will be described with reference to FIG.
The polymer-dispersed liquid crystal element 10'according to the first embodiment is a normal mode type polymer-dispersed liquid crystal element using a positive liquid crystal composition as the liquid crystal component 13.

In the polymer-dispersed liquid crystal element 10'according to the first embodiment, a liquid crystal component 13 and a polymer compound component 14 are formed between a substrate 11 having an electrode 18 and a substrate 12 having an electrode 19 facing the substrate 11. The composite layer 15 is provided, and the composite layer 15 forms a slippery interface having a lubricating interface induction region between the liquid crystal component 13 and the polymer compound component 14.

In the polymer-dispersed liquid crystal element 10'according to the first embodiment, in the state where no voltage is applied (FIG. 5A), the liquid crystal component 13 takes a random orientation state, and the polymer compound component 14 and the liquid crystal component 13 are combined. The composite layer 15 can be made cloudy by scattering light due to the difference in refractive index of the liquid crystal component 13 and the random orientation of the liquid crystal component 13 itself. When a sufficiently high voltage is applied between the electrodes 18 and 19 (FIG. 5B), the liquid crystal molecules of the liquid crystal component 13 are oriented in the electric field direction. Here, if the difference between the refractive index of the polymer compound component 14 and the no (normal light refractive index) of the liquid crystal component 13 is sufficiently small, light scattering does not occur and the liquid crystal component 13 becomes transparent.

In the polymer-dispersed liquid crystal element 10'according to the first embodiment, the polymer compound component 14 is a polymer that has a moderately similar structure to the liquid crystal molecules of the liquid crystal component 13, but does not exhibit liquidity or reduces liquidity. Therefore, a lubrication interface induction region having a lower order than that of the liquid crystal phase is formed between the liquid crystal phase of the liquid crystal component 13 and the solid phase of the polymer compound component 14, and the liquid crystal component 13 and the polymer are used. By forming a slippery interface having a lubricating interface induction region between the compound component 14 and the compound component 14, the driving voltage can be reduced.

In the normal mode type polymer dispersion type liquid crystal element, even if the liquid crystal component 13 is surrounded by the polymer compound component 14 like a droplet, the liquid crystal component 13 is continuously connected to the network of the polymer compound component 14. It may exist, or it may be in a mixed state of both.

A second embodiment of the polymer-dispersed liquid crystal device according to the present invention will be described with reference to FIG.
The polymer-dispersed liquid crystal element 100 according to the second embodiment is a reverse mode type polymer-dispersed liquid crystal element that uses a negative liquid crystal composition as the liquid crystal component 13.

The polymer-dispersed liquid crystal element 100 according to the second embodiment includes a substrate 11 having a vertical alignment film 16 and an electrode 18, a substrate 12 facing the substrate 11 and having a vertical alignment film 17 and an electrode 19, and a pair of substrates 11. , 12 is provided with a composite layer 15 of a liquid crystal component 13 and a polymer compound component 14, and the composite layer 15 has a lubricating interface induction region between the liquid crystal component 13 and the polymer compound component 14. It forms a slippery interface.

A negative liquid crystal composition is used as the liquid crystal component 13, and in a voltage-free state (FIG. 6A), the liquid crystal component 13 is oriented perpendicular to the pair of substrates 11 and 12, and the composite layer 15 is formed. It can be made transparent. When a sufficiently high voltage is applied between the electrodes 18 and 19 (FIG. 6 (b)), the liquid crystal molecules of the liquid crystal component 13 are oriented in the direction perpendicular to the electric field direction, but the polymer compound component 14 and the liquid crystal component are oriented. Light is scattered due to the difference in refractive index from 13 and the random orientation of the liquid crystal component 13 itself, and the composite layer 15 becomes cloudy. Also in the polymer-dispersed liquid crystal element 100 according to the second embodiment, as the polymer compound component 14, a polymer that has a moderately similar structure to the liquid crystal molecules of the liquid crystal component 13 but does not exhibit liquid crystal properties or reduces the liquid crystal properties. Therefore, the driving voltage can be reduced by forming a slippery interface having a lubricating interface induction region between the liquid crystal component 13 and the polymer compound component 14.

A third embodiment of the polymer-dispersed liquid crystal device according to the present invention will be described with reference to FIG. 7.
The polymer-dispersed liquid crystal element 101 according to the third embodiment is a reverse mode type polymer-dispersed liquid crystal element using a positive liquid crystal composition as the liquid crystal component 13.

The polymer-dispersed liquid crystal element 101 according to the third embodiment faces a substrate 11 having an electrode 18 and an electrode 19, an insulating layer 21 for insulating the electrode 18 and the electrode 19, and a vertical alignment film 16. A substrate 12 having a vertically oriented film 17 and a composite layer 15 of a liquid crystal component 13 and a polymer compound component 14 are provided between the pair of substrates 11 and 12, and the composite layer 15 is the liquid crystal component 13 and the polymer. A slippery interface having a lubricating interface induction region is formed between the compound component 14 and the compound component 14.

In the polymer-dispersed liquid crystal element 101 according to the third embodiment, in a voltage-free state (FIG. 7A), the liquid crystal component 13 takes an orientation state perpendicular to the pair of substrates 11 and 12, and the composite layer 15 is formed. It can be made transparent. When a sufficiently high voltage is applied between the electrodes 18 and 19 (FIG. 7 (b)), some liquid crystal molecules of the liquid crystal component 13 are oriented in a direction parallel to the pair of substrates 11 and 12, but are high. Light can be scattered by the difference in refractive electrode between the molecular compound component 14 and the liquid crystal component 13 and the random orientation of the entire liquid crystal component 13, so that the composite layer 15 becomes cloudy.

Also in the polymer-dispersed liquid crystal element 101 according to the third embodiment, as the polymer compound component 14, a polymer that has a moderately similar structure to the liquid crystal molecules of the liquid crystal component 13, but does not exhibit liquidity or reduces liquidity. Therefore, a lubrication interface induction region having a lower order than that of the liquid crystal phase is formed between the liquid crystal phase of the liquid crystal component 13 and the solid phase of the polymer compound component 14, and the liquid crystal component 13 and the polymer are used. By forming a slippery interface having a lubricating interface induction region between the compound component 14 and the compound component 14, the driving voltage can be reduced.

In the reverse mode type polymer dispersion type liquid crystal element, it is necessary to define the initial orientation of the liquid crystal component 13, and it is generally the alignment film on the surface of the substrate that defines the initial orientation, and at least the liquid crystal component. It is necessary that 13 is in contact with the alignment film. Further, in order to permeate the restricting force of the alignment film into the inside, the liquid crystal component 13 does not exist in a closed space such as a droplet, but the liquid crystal component 13 near the alignment film and the liquid crystal component 13 inside do not exist. It is preferably a continuum having some elastic interaction.

[Polymer compound component]
In the polymer-dispersed liquid crystal device according to the present invention, the polymer compound component is a polymer compound component obtained by polymerizing a polymerizable compound component containing at least one compound represented by the following general formula (I). Is preferable.

In general formula (I),
A ¹ represents a hydrogen atom or a methyl group.
Y ¹ is a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups present in the alkylene group are independently oxygen atoms, assuming that the oxygen atoms do not directly bond to each other. , -CO-, -COO- or -OCO-, and one or more hydrogen atoms present in the alkylene group are independently substituted with a fluorine atom, a methyl group or an ethyl group, respectively. It may be.).

The number of carbon atoms of Y ¹ is 1 to 15, preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 5.

A and B independently have a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, a 3,6-cyclohexenylene group, and a 1,4-silacyclohexylene group, respectively. , Tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,3-ditian-2,5-diyl group, 1, 4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group , 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthren-2,7-diyl group, 9,10-dihydrophenantren-2,7-diyl group, 1 , 2,3,4,4a, 9,10a-Octahydrophenanthrene-2,7-diyl group or fluorene-2,7-diyl group, the 1,4-phenylene group, 1,2,3,4 -Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a , 9,10a-Octahydrophenanthrene-2,7-diyl group and fluorene-2,7-diyl group are unsubstituted or one or more as substituents F, Cl, CF ₃ , OCF ₃ Or can have CH ₃
m independently represents 0, 1, 2, or 3, respectively.
X ¹ and X ² independently represent a single bond, -O-, -COO-, -OCO- or -CO-, assuming that the oxygen atoms do not directly bond to each other.

The following structures are preferable for A and B independently of each other.

As A and B, the following structures are more preferable.

As A and B, the following structures are particularly preferable.

Z ⁴ represents an alkyl group having 4 to 18 carbon atoms, and the alkyl group is unsubstituted or has one or more F, Cl, CN, CH ₃ or CF ₃ as a substituent. The one or more CH ₂ groups present in the alkyl group may be substituted with O, CO or COO so that the O atoms do not directly bond to each other.

The number of carbon atoms of Z ⁴ is preferably 4 to 18, more preferably 8 to 16, and particularly preferably 10 to 14.

Preferred compounds represented by the general formula (I) include the following.

In the polymer dispersion type liquid crystal element of the present invention, the high amount obtained by polymerizing the compound represented by the general formula (I) when the mass of the whole composite layer of a liquid crystal component and a polymer compound component is 100% by mass. The ratio of the molecular compound component is preferably 0.1 to 20% by mass, may be 0.2 to 20% by mass, may be 0.4 to 19% by mass, and may be 0.8 to 0.8. It may be 18% by mass, 1 to 17% by mass, 2 to 16% by mass, 4 to 15% by mass, or 6 to 14% by mass. It may be 7 to 13% by mass, or 8 to 12% by mass. When it is at least the lower limit value, a slippery interface can be formed between the liquid crystal component and the polymer compound component, and more excellent low voltage driveability is exhibited. If the upper limit is exceeded, the response may be delayed.
When the mass of the entire composite layer of the liquid crystal component and the polymer compound component is 100% by mass, the proportion of the polymer compound component obtained by polymerizing the compound represented by the general formula (I) is high, which will be described later. It can be obtained from the ratio of the compound represented by the general formula (I) when the mass of the precursor mixture for the molecular dispersion type liquid crystal element is 100% by mass.

<Polymerizable compound>
In the polymer-dispersed liquid crystal device according to the present invention, the polymer compound component is represented by the following general formula (Ia).

(In formula (Ia),
A ¹ represents a hydrogen atom or a methyl group.
A ² is a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups present in the alkylene group are independently oxygen atoms, assuming that the oxygen atoms do not directly bond to each other. , -CO-, -COO- or -OCO-, and one or more hydrogen atoms present in the alkylene group are independently substituted with a fluorine atom, a methyl group or an ethyl group, respectively. It may have been done.)
A ³ and A ⁶ are independent hydrogen atoms or alkyl groups having 1 to 18 carbon atoms (one or two or more methylene groups present in the alkyl groups are those in which oxygen atoms do not directly bond to each other. As each of them may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or two or more hydrogen atoms present in the alkyl group are independently halogen atoms or carbons, respectively. It may be substituted with an alkyl group having 1 to ¹⁷ atoms), and ^A4 and A7 are independently present in a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (in the alkyl group). One or more methylene groups may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO- as if the oxygen atoms do not directly bond to each other, and may be substituted in the alkyl group. One or two or more hydrogen atoms present may be independently substituted with a halogen atom or an alkyl group having 1 to 9 carbon atoms.)
k represents 1 to 40
B ¹ , B ² and B ³ are independently hydrogen atoms and linear or branched alkyl groups having 1 to 10 carbon atoms (one or two or more methylene groups present in the alkyl groups are It may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO- as if the oxygen atoms do not directly bond to each other), or the general formula (Ib).

(In the formula (Ib), A ⁹ represents a hydrogen atom or a methyl group, and A ⁸ is a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more alkylene groups present in the alkylene group). The methylene group may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, assuming that the oxygen atoms are not directly bonded to each other, and one or one present in the alkylene group. Two or more hydrogen atoms may be independently substituted with a fluorine atom, a methyl group or an ethyl group, respectively.) However, among 2k + 1 B ¹ , B ² and B ³ . The number of the bases represented by the general formula (Ib) is 0 to 3), which is obtained by polymerizing a polymerizable compound component containing at least one compound. It is preferable that it is a polymer compound component to be used.

Here, the "alkylene group" is a divalent group "-(CH ₂ ) _n- " obtained by removing one hydrogen atom from each of the carbon atoms at both ends of the aliphatic linear hydrocarbon, unless otherwise specified. However, n is an integer of 1 or more), and there is a substitution from the hydrogen atom to a halogen atom or an alkyl group, or a substitution from a methylene group to an oxygen atom, -CO-, -COO- or -OCO-. In that case, the fact shall be specifically refused. Further, the "alkylene chain length" means n in the general formula "-(CH ₂ ) _n- " of the "alkylene group".

As a preferable structure of the polymerizable compound represented by the general formula (Ia), the following general formula (Ic) is used.

(In the formula (IC), A ¹¹ and A ¹⁹ each independently represent a hydrogen atom or a methyl group, and A ¹² and A ¹⁸ independently represent a single bond or an alkylene group having 1 to 15 carbon atoms (1 to 15). One or more methylene groups present in the alkylene group are independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, assuming that the oxygen atoms do not directly bond to each other. Alternatively, one or two or more hydrogen atoms present in the alkylene group may be independently substituted with a fluorine atom, a methyl group or an ethyl group), and A13 and ^A16 are represented by ^A13 and A16. A linear alkyl group having 2 to 20 carbon atoms independently (one or two or more methylene groups present in the linear alkyl group are independently bonded to each other as oxygen atoms do not directly bond to each other. It may be substituted with an oxygen atom, -CO-, -COO- or -OCO-), and A ¹⁴ and A ¹⁷ are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms (the said). Even if one or more methylene groups present in the alkyl group are independently substituted with an oxygen atom, -CO-, -COO- or -OCO- as if the oxygen atoms do not directly bond to each other. It is preferable that one or two or more hydrogen atoms present in the alkyl group are independently substituted with a halogen atom or an alkyl group having 1 to ⁹ carbon atoms.), And A15 represents carbon. An alkylene group having 9 to 16 atoms (in at least 1 or more and 5 or less methylene groups existing in the alkylene group, one of the hydrogen atoms in the methylene group is an independent direct sequence of 1 to 10 carbon atoms. Substituted with a chain or branched alkyl group, the one or more methylene groups present in the alkylene group are independently oxygen atoms, -CO-, assuming that the oxygen atoms do not directly bond to each other. , -COO- or may be substituted with -OCO-).), A compound represented by the general formula (Id).

(In the formula (Id), A ²¹ and A ²² each independently represent a hydrogen atom or a methyl group, and a represents an integer of 6 to 22), a compound represented by the general formula (I-). e)

(In the formula (Ie), A ³¹ and A ³² independently represent a hydrogen atom or a methyl group, b and c independently represent an integer of 1 to 10, and d is an integer of 1 to 10. Represents, e represents an integer of 0 to 6), and the general formula (If).

(In the formula (If), A ⁴¹ and A ⁴² each independently represent a hydrogen atom or a methyl group, and m, n, p and q each independently represent an integer of 1 to 10). One or more selected from the group consisting of the compounds to be used is mentioned. Among these, it is preferable to include the compound represented by the formula (Ic).

As a preferable structure of the polymerizable compound represented by the general formula (Ic), it is preferable that both A ¹¹ and A ¹⁹ are hydrogen atoms. The effect of the present invention is exhibited even in a compound in which these substituents A ¹¹ and A ¹⁹ are methyl groups, but a compound in which a hydrogen atom is an advantage is advantageous in that the polymerization rate becomes faster.

It is preferable that A ¹² and A ¹⁸ are independently single bonds or alkylene groups having 1 to 3 carbon atoms. The distance between the two polymerizable functional groups can be adjusted independently for ^A12 and ^A18 and ^A15 by changing the length of each carbon number. The characteristic of the compound represented by the general formula (Ic) is that the distance between the polymerizable functional groups (distance between the cross-linking points) is long, but if this distance is too long, the polymerization rate becomes extremely slow. Therefore, there is an upper limit to the distance between the polymerizable functional groups because it adversely affects the phase separation. On the other hand, the distance between the two side chains of A ¹³ and A ¹⁶ also affects the motility of the main chain. That is, if the distance between A ¹³ and A ¹⁶ is short, the side chains A ¹³ and A ¹⁶ will interfere with each other, resulting in a decrease in motility. Therefore, in the compound represented by the general formula (Ic), the distance between the polymerizable functional groups is determined by the sum of A ¹² , A ¹⁸ , and A ¹⁵ , of which A is not longer than A ¹² and A ¹⁸ . It is preferable to lengthen ¹⁵ .

On the other hand, in the side chains A ¹³ , A ¹⁴ , A ¹⁶ and A ¹⁷ , it is preferable that the lengths of these side chains have the following aspects.

In the general formula (I-c), A ¹³ and A ¹⁴ are bonded to the same carbon atom in the main chain, but when these lengths are different, the longer side chain is called A ^13. ( If the length of A ¹³ and the length of A ¹⁴ are equal, whichever is A ¹³ ). Similarly, when the length of A ¹⁶ and the length of A ¹⁷ are different, the longer side chain shall be called A ¹⁶ (if the length of A ¹⁶ and the length of A ¹⁷ are equal, which one is used. A ¹⁶ ).

In the present application, such A ¹³ and A ¹⁶ are independently linear alkyl groups having 2 to 20 carbon atoms (one or two or more methylene groups present in the linear alkyl groups are oxygen. Assuming that the atoms do not bond directly to each other, they may be independently substituted with oxygen atoms, -CO-, -COO- or -OCO-.)
Preferably, the linear alkyl groups each independently having 2 to 18 carbon atoms (one or more methylene groups present in the linear alkyl group do not directly bond oxygen atoms to each other). Each may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-).
More preferably, a linear alkyl group having 3 to 15 carbon atoms independently (one or two or more methylene groups present in the linear alkyl group do not directly bond oxygen atoms to each other. , Each may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-).

Since the side chain has higher motility than the main chain, its presence contributes to the improvement of the motility of the polymer chain at low temperature, but as mentioned above, spatial interference occurs between the two side chains. In the situation, on the contrary, motility decreases. In order to prevent such spatial interference between side chains, it is effective to increase the distance between the side chains and shorten the side chain length within a necessary range.

Further, regarding A ¹⁴ and A ¹⁷ , in the present application, hydrogen atoms or alkyl groups having 1 to 10 carbon atoms (one or two or more methylene groups existing in the alkyl groups have oxygen atoms mutually. They may be independently substituted with oxygen atoms, -CO-, -COO- or -OCO- as those that do not directly bond to, and one or more hydrogen atoms present in the alkyl group are independent of each other. Although it may be substituted with a halogen atom or an alkyl group having 1 to 9 carbon atoms (the alkyl group may be substituted), it is preferable that each of them independently has a hydrogen atom or an alkyl group having 1 to 7 carbon atoms (the alkyl group). The one or more methylene groups present therein may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, assuming that the oxygen atoms do not directly bond to each other. ), More preferably, each independently has a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (one or two or more methylene groups present in the alkyl group do not directly bond oxygen atoms to each other. Each of them may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-), and more preferably, each independently has a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. (One or more methylene groups present in the alkyl group are independently substituted with oxygen atoms, -CO-, -COO- or -OCO- as if the oxygen atoms do not directly bond to each other. It may be.).

As for A ¹⁴ and A ¹⁷ , it is not preferable that the length is too long because it induces spatial interference between the side chains. On the other hand, when A ¹⁴ and A ¹⁷ are alkyl chains having a short length, they can be side chains with high motility and have a function of inhibiting the approach between adjacent main chains. It is considered that it has the effect of preventing interference between polymer main chains and enhances the motility of the main chains, and it is possible to suppress the increase of anchoring energy at low temperatures, and the polymer is stable. It is effective in improving the characteristics of the polymerized liquid crystal optical element in the low temperature range.

The length of ^A15 located between the two side chains is preferably long from the viewpoint of changing the distance between the side chains and from the viewpoint of widening the distance between the cross-linking points and lowering the glass transition temperature. However, if A ¹⁵ is too long, the molecular weight of the compound represented by the general formula (Ic) becomes too large, the compatibility with the liquid crystal composition decreases, and the polymerization rate becomes too slow, resulting in phase separation. An upper limit is naturally set for the length because of adverse effects on the liquid crystal.

Therefore, in the present invention, A15 is an alkylene group having 9 to ¹⁶ carbon atoms (in at least 1 or more and 5 or less methylene groups existing in the alkylene group, one of the hydrogen atoms in the methylene group is each. It is independently substituted with a linear or branched alkyl group having 1 to 10 carbon atoms. One or two or more methylene groups present in the alkylene group assume that oxygen atoms do not directly bond to each other. , Each may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-).

That is, in the present invention, the alkylene chain length of A15 is preferably 9 to ¹⁶ carbon atoms. As a structural feature, A ¹⁵ has a structure in which a hydrogen atom in an alkylene group is replaced with an alkyl group having 1 to 10 carbon atoms. The number of substitutions of the alkyl group is 1 or more and 5 or less, preferably 1 to 3, and more preferably 2 or 3 substitutions. The number of carbon atoms of the alkyl group to be substituted is preferably 1 to 5, more preferably 1 to 3.

The compound represented by the general formula (Ia) is described in Tetrahedron Letters, Vol. 30, pp4895, Tetrahedron Letters, Vol. 23, No6, pp681-684, and Journal of Polymer Science: PartA: Polymer Chemistry, Vol. It can be synthesized by a known method such as 34, pp217-225.

For example, in the general formula (Ic), the compound in which A ¹⁴ and A ¹⁷ are hydrogen is polymerizable between a compound having a plurality of epoxy groups and acrylic acid or methacrylic acid having active hydrogen capable of reacting with the epoxy group. It can be obtained by reacting with a compound to synthesize a polymerizable compound having a hydroxyl group, and then reacting with a saturated fatty acid.
Further, by reacting a compound having a plurality of epoxy groups with a saturated fatty acid to synthesize a compound having a hydroxyl group, and then reacting with a polymerizable compound such as an acrylate product having a group capable of reacting with the hydroxyl group. Obtainable.

Further, when the radically polymerizable compound is, for example, A ¹⁴ and A ¹⁷ of the general formula (Ic) are alkyl groups, and A ¹² and A ¹⁸ are methylene groups having 1 carbon atom, an oxetane group is used. A method of reacting a compound having a plurality of compounds with a fatty acid chloride or fatty acid that can react with an oxetane group, and further reacting with a polymerizable compound having an active hydrogen such as acrylic acid, or a compound having one oxetane group. It can be obtained by a method of reacting with a polyvalent fatty acid chloride or fatty acid capable of reacting with an oxetane group, and further reacting with a polymerizable compound having active hydrogen such as acrylic acid.

When A ¹² and A ¹⁸ of the general formula (Ic) are alkylene groups having 3 carbon atoms (propylene group; -CH ₂ CH ₂ CH _2- ), a plurality of furan groups are used instead of the oxetane group. It can be obtained by using the compound having. Further, when A ¹² and A ¹⁸ of the general formula (Ic) are an alkylene group having 4 carbon atoms (butylene group; -CH ₂ CH ₂ CH ₂ CH _2- ), a pyran group is used instead of the oxetane group. It can be obtained by using a compound having a plurality of.

In the polymer-dispersed liquid crystal element according to the present invention, the polymer compound component is a polymerizable compound component containing a compound represented by the general formula (I) and a compound represented by the general formula (Ia). It is more preferable that the polymer compound component is obtained by polymerizing the above, and B ¹ of the general formula (I) and the general formula (Ia) is the general formula (Ib). ) Is particularly preferable, it is a polymer compound component obtained by polymerizing a polymerizable compound component containing a cross-linking agent as a base.

In the polymer dispersion type liquid crystal element of the present invention, it is obtained by polymerizing the compound represented by the general formula (Ia) when the mass of the entire composite layer of the liquid crystal component and the polymer compound component is 100% by mass. The proportion of the polymer compound component to be obtained is preferably 0.1 to 20% by mass, may be 0.2 to 20% by mass, may be 0.4 to 19% by mass, and may be 0. It may be 8 to 18% by mass, 1 to 17% by mass, 2 to 16% by mass, 4 to 15% by mass, or 6 to 14% by mass. It may be 7 to 13% by mass, or 8 to 12% by mass.
The proportion of the polymer compound component obtained by polymerizing the compound represented by the general formula (Ia) when the mass of the entire composite layer of the liquid crystal component and the polymer compound component is 100% by mass will be described later. It can be obtained from the ratio of the compound represented by the general formula (Ia) when the mass of the precursor mixture for the polymer-dispersed liquid crystal element is 100% by mass.

<Polymer initiator>
The polymerizable compound component may contain a polymerization initiator, if necessary. For example, when the polymerizable compound is polymerized by radical polymerization, a thermal polymerization initiator and a photopolymerization initiator can be added as the radical polymerization initiator.

Specifically, the following compounds are preferably used;
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-( 2-Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -acetophenone such as butanone;
Benzoins such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether;
Acylphosphine oxide system such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;
Benzyl, methylphenylgrioxy ester type;
Benzophenone, o-Methyl benzoyl benzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylicized benzophenone, 3,3', 4,4' -Benzophenone series such as tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone;
Thioxanthone series such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichloromethanexanthone, 2,4-dichlorothioxanthone;
Aminobenzophenone systems such as Michler ketone, 4,4'-diethylaminobenzophenone;
10-Butyl-2-chloroacrydone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like.

Among these compounds, benzyldimethyl ketal is preferable as the radical polymerization initiator contained in the mixture.

[Liquid crystal component]
The liquid crystal component preferably contains at least one liquid crystal compound represented by the following general formula (I-1).

In the formula, R ⁰¹ represents a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, and one or two or more non-adjacent -CH _2- in the alkyl group is an oxygen atom, and -CH = CH-. , -COO-, -OCO- may be replaced,
R ⁰² represents a hydrogen atom, 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 having 1 to 15 carbon atoms, and is a non-alkyl group among the alkyl groups. One adjacent or two or more non-adjacent -CH ₂ -may be replaced with an oxygen atom, -CH = CH-, -COO-, -OCO-.
A ⁰¹ , A ⁰² , A ⁰³ , and A ⁰⁴ independently have a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, and a 3,6-cyclohexenylene, respectively. Group, 1,4-silacyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, decahydronaphthalene-2,6-diyl group, pyridine-2,5 -Diyl group, pyrimidin-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, 1,3 -Representing a dithian-2,5-diyl group or a tetrahydrothiopyran-2,5-diyl group, said 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or The 2,6-naphthylene group is unsubstituted or can have one or more fluorine atoms, chlorine atoms, ₃ CFs, ₃ ^OCFs or ₃ CHs as substituents, provided that A03. And / or ^A04 may be a single bond.
Z ⁰¹ , Z ⁰² , and Z ⁰³ are independently single-bonded, -COO-, -OCO-, -CH ₂ -CH _2- , -CF ₂ -CF _2- , -CH = CH-,-, respectively. CF = CF-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , or -C≡C-.

The liquid crystal compound represented by the general formula (I-1) in the liquid crystal component is a so-called neutral compound having a dielectric anisotropy (Δε) value of -2 to 2 and a dielectric anisotropy (Δε). It is preferably a so-called positive compound having a value of 2 or more.
As the neutral compound contained in the liquid crystal component, it is preferable that R ⁰² has an alkyl group having 1 to 15 carbon atoms, and one non-adjacent one or two or more non-adjacent ones in the alkyl group. -CH _2- may be replaced with an oxygen atom, -CH = CH-, -COO-, -OCO-, an alkyl group having 1 to 8 carbon atoms, an alkyloxy group having 1 to 8 carbon atoms, or carbon. Compounds having those substituted with an alkenyl group having 2 to 8 atoms are preferable.
As the positive compound contained in the liquid crystal component, a compound having a fluorine atom, a chlorine atom, a cyano group, a CF ₃ group, an OCF ₃ group, an OCHF ₂ group or an NCS group is preferable, and a fluorine atom, a chlorine atom and a cyano group are used. Those having ₃ groups or OCFs are more preferable, and those having a cyano group are further preferable. As the positive compound having a cyano group, compounds represented by the following formulas (I-1-1) to (I-1-2) are preferable.

In formulas (I-1-1) to (I-1-2), R ⁰¹¹ and R ⁰¹² are the same as R ⁰¹ . R ⁰¹¹ and R ⁰¹² are preferably an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. The number of carbon atoms of the alkyl group and the alkoxy group of R ⁰¹¹ and R ⁰¹² is preferably 1 to 12, more preferably 2 to 10, further preferably 3 to 9, and 4 to 9. It is more preferably present, and particularly preferably 5 to 8. The alkyl and alkoxy groups of R ⁰¹¹ and R ⁰¹² are preferably linear.
The liquid crystal component includes a compound represented by the following formula (I-1-10), a compound represented by the formula (I-1-11), a compound represented by the formula (I-1-12), and a formula ( It is particularly preferable to contain the compound represented by I-1-13). The compound represented by the following formula (I-1-10), the compound represented by the formula (I-1-11), the compound represented by the formula (I-1-12) and the formula (I-1-13). ), Examples of the liquid crystal component containing the compound represented by) include the liquid crystal composition E7, which will be described later.

Of the general formula (I-1) in the liquid crystal component, the content of the compound having a cyano group of ^R02 is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and 80 to 100% by mass. More preferably, 90 to 100% by mass is particularly preferable.

When the liquid crystal component contains a compound represented by the formula (I-1-1) and a compound represented by the formula (I-1-2), the formula (I-1-) with respect to the mass of the liquid crystal component. 1) The ratio of the total content of the compounds represented by the formula (I-1-2) is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, still more preferably 80 to 100% by mass. , 90-100% by mass is particularly preferable.

The liquid crystal component is a compound represented by the formula (I-1-10), a compound represented by the formula (I-1-11), a compound represented by the formula (I-1-12), and a compound represented by the formula (I-1-12). When the compound represented by -1-13) is contained, the total content of the compounds represented by the formulas (I-1-10) to (I-1-13) with respect to the mass of the liquid crystal component. The ratio is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, further preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass.

The liquid crystal component may be a positive liquid crystal component in which the liquid crystal compound represented by the general formula (I-1) has a positive dielectric anisotropy (Δε), and is represented by the general formula (I-1). The represented liquid crystal compound may be a negative type liquid crystal component having a negative dielectric anisotropy (Δε).

The liquid crystal component may be a negative type liquid crystal component containing at least one compound represented by the following general formula (III).

In the formula, R represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a halogen atom, CN and NCS, and are the alkyl groups and alkenyl groups unsubstituted? Alternatively, it can have one or two or more F, Cl, CN, CH ₃ , CF ₃ as a substituent, and one or two or more CH ₂ groups present in the alkyl group or alkenyl group is O. Assuming that the atoms do not directly bond to each other, they may be substituted with O, CO, and COO, and ring F, ring G, and ring H are independently 1,4-phenylene group and 1,4-cyclohexylene, respectively. Group, 1,4-cyclohexenylene group, 3,6-cyclohexenylene group, 1,4-silacyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl Group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidin-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene Represents a -2,6-diyl group, a 2,6-naphthylene group, a 1,3- ^{dithian -} 2,5-diyl group or a tetrahydrothiopyran-2,5-diyl group, where Y7, Y8 and Y9 are respectively. Independently, single bond, -COO-, -OCO-, -C≡C-, -CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ O-,- OCH ₂ CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CF = CF-, -CH = CH-, -CH ₂ CH ₂ CH = CH -, -CH = CHCH ₂ CH _2- , -CH ₂ CH = CHCH _2- , -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , Y ¹⁰ represents a single bond, -O-, -CO-, -COO-, -OCO-, -CH _{2-, -CH 2 O-} , -OCH _2- , -CH ₂ COO- or -CH ₂ OCO-. , Z ³ represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a halogen atom, and the alkyl group or alkenyl group is unsubstituted or has one or two substituents. The above F, Cl, CN, CH ₃ or CF ₃ can be possessed, and one or two or more CH ₂ groups present in the alkyl group or alkenyl group have an O atom as a phase. It may be substituted with O, CO or COO as not directly bound to each other, where r and s independently represent 0, 1, 2 or 3, but r + s is 0, 1, 2 or 3. ..

[Manufacturing method of polymer dispersion type liquid crystal element]
In the polymer-dispersed liquid crystal element of the present invention, the precursor mixture for a polymer-dispersed liquid crystal element containing the liquid crystal component and the polymerizable compound component is injected between a pair of substrates having electrodes on at least one substrate. Then, it can be produced by subjecting the polymerizable compound component to a polymerization reaction.
The polymerizable compound component preferably contains a polymerizable compound, a cross-linking agent, and a photopolymerization initiator.

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.
In addition, "%" and "wt%" in the compositions of the following Examples and Comparative Examples mean "mass%".

(Synthesis of compound A0)
Acroyl chloride (9.05 g) in a solution of 4-hydroxybenzoic acid (13.14 g, 0.095 mol) and NaOH (7.7 g, 0.193 mol) in 50 ml of water and 25 ml of dioxane (0.01 mol). , 0.1 mol) was added at 10-15 ° C. The resulting mixture was stirred at room temperature for 4 hours and then neutralized with dilute HCl. The precipitate was filtered and washed with warm water, dilute hydrochloric acid and water. The product was recrystallized from ethanol. The yield was 72%.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C., TMS, ppm in δ): 6.06-6.09 (d, 1H), 6.31-6.38 (dd, 1H), 6.63-6 .68 (d, 1H), 7.26-7.28 d, 2H), 8.16-8.18 (d, 2H).

(Synthesis of compound A0DA)
Compound A0 (0.01 mol), dodecyl alcohol (0.01 mol) and 4-dimethylaminopyridine (DMAP, 0.0002 mol) were dissolved in anhydrous THF. The solution was cooled in an ice bath and then N, N'-dicyclohexylcarbodiimide (DCC, 0.014 mol) was added to the solution over 15 minutes. The reaction mixture was stirred at room temperature for 24 hours. The resulting mixture was filtered to remove the precipitated dicyclohexylurea and the THF was evaporated. The residue was purified by column chromatography (SiO ₂ ; ethyl acetate / heptane, 1: 4) CH ₃ Cl) to obtain a white solid. The yield was 60%.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C, TMS, ppm in δ): 0.86-0.89 (t, 3H), 1.26-1.80 (m, 20H), 4.30-4 .33 (t, 2H) 6.07 (d, 1H), 6.30-6.37 (dd, 1H), 6.62-6.66 (d, 1H), 7.21-7.23 (d, 1H) d, 2H), 8.08-8.10 (d, 2H, aromatic).

(Synthesis of compound A1)
In a stirred solution (3 ml) of 4-hydroxybenzoic acid (1.38 g, 0.1 mol), KOH (15 g, 0.27 mol) and KI (1.6 g, 0.01 mol) in 35 ml ethanol and 15 ml water. 3-Chloropropanol was added slowly with stirring and heating. The reaction mixture was heated to reflux for 48 hours. The solvent was evaporated, the solid residue was dissolved in water, washed with chloroform and strongly acidified with HCl. The precipitate was filtered, washed with water, dried in vacuo and then recrystallized from ethanol. The yield was 78%.
¹ H-NMR (400 MHz, DMSO-d6, 25 ° C, TMS, ppm in δ): 1.86-1.91 (m, 2H), 3.53-3.58 (m, 2H), 4.09- 4.12 (t, 2H), 4.57 (s, 1H), 6.99-7.01 (d, 2H, aromatic), 7.86-7.89 (d, 2H), 12.61 (S, 1H, COOH).

(Synthesis of compound A2)
N, N-dimethylaniline (5.08 g, 0.04 mol) and Al (10 g, 0.04 mol) were added to 210 ml of 1,4-dioxane. After heating the mixture to 60 ° C., acroyl chloride (4 g, 0.06 mol) was added dropwise. After stirring for 3 hours, the solution was poured into 1000 ml of water and stirred. The precipitate thus formed was filtered, washed with water, recrystallized from isopropanol and purified to obtain a white solid. The yield was 78%.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C., TMS, ppm in δ): 2.19-2-22 (m, 2H), 4.13-4.16 (t, 2H), 4.37-4 .40 (t, 2H), 5.84-5.86 (d, 1H), 6.10-6.17 (dd, 1H), 6.40-6.45 (d, 1H, CH ₂ = CH) ), 6.94-6.96 (d, 2H), 8.06-8.08 (d, 2H).

(Synthesis of compound A3DA)
Compound A2 (0.01 mol), dodecyl alcohol (0.01 mol) and 4-dimethylaminopyridine (0.0002 mol) were dissolved in anhydrous THF. The solution was cooled in an ice bath and then N, N'-dicyclohexylcarbodiimide (DCC, 0.014 mol) was added to the solution over 15 minutes. The reaction mixture was stirred at room temperature for 24 hours. The resulting mixture was filtered to remove the precipitated dicyclohexylurea and the THF was evaporated. The residue was purified by column chromatography (SiO ₂ ; ethyl acetate / heptane, 1: 4) CH ₃ Cl) to obtain a white solid. The yield was 75%.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C., TMS, ppm in δ): 0.86-0.89 (t, 3H), 1.26-2.21 (m, 22H), 4.11-4 .14 (t, 2H) (d, 1H), 6.40-6.44 (d, 1H), 6.90-6.92 (d, 2H), 4.36-4.39), 7. 98-8.10 (d, 2H, aromatic).

(Synthesis of compound A3B2DA)
Of 4'-hydroxybiphenyl-4-carboxylic acid (7.8 g, 0.04 mol), KOH (5.05 g, 0.09 mol) and KI (0.8 g, 0.005 mol) in 15 ml ethanol and 5 ml water. 3-Chloropropanol (4.25 g, 0.04 mol) was slowly added to the stirred solution while stirring and heating. The reaction mixture was heated to reflux for 48 hours. The solvent was evaporated, the solid residue was dissolved in water, washed with chloroform and strongly acidified with HCl. Product 1 was precipitated from the solution with chloroform and then dried in vacuo. The yield was 51%.

N, N-dimethylaniline (0.73 g, 0.006 mol) and product 1 (1.5 g, 0.006 mol) were added to 30 ml of 1,4-dioxane. After heating the mixture to 60 ° C., acrylic chloride (0.54 g, 0.006 mol) was added dropwise. After stirring for 3 hours, the solution was poured into 200 ml of water and stirred. The precipitate thus formed was filtered, washed with water and dried in vacuo to give product 2 as a white solid. The yield was 91%.

Product 2 (0.005 mol), dodecyl alcohol (0.005 mol) and 4-dimethylaminopyridine (0.0001 mol) were dissolved in anhydrous THF. The solution was cooled in an ice bath and then DCC (0.005 mol) was added to the solution over 15 minutes. The reaction mixture was stirred at room temperature for 24 hours. The resulting mixture was filtered to remove the precipitated dicyclohexylurea and the THF was evaporated. The residue was purified by column chromatography (SiO ₂ ; CH ₂ Cl ₂ ) to obtain compound A3B2DA as a white solid. The yield was 30%. A ¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C., TMS, ppm in δ) chart of compound A3B2DA is shown in FIG.

(Example 1)
As a precursor mixture for a polymer-dispersed liquid crystal element, a liquid crystal composition E7 (100 mg, 80 wt%), a monofunctional monomer compound A3DA (12 mg, 9.6 wt%), and a cross-linking agent compound HDDA (12 mg, 9). .6 wt%) and the photopolymerization initiator DMCAP (1 mg, 0.8 wt%) were dissolved at 30 ° C. for 30 minutes and then injected into an ITO-coated liquid crystal cell (cell thickness 10 μm, EHC Co., Ltd). Then, polymerization was carried out at 30 ° C. for 30 minutes under the irradiation of ultraviolet rays having an intensity of 1.5 to ² mWcm-2 at 365 nm to produce the polymer-dispersed liquid crystal device of Example 1.

(Observation with an optical microscope)
The composite layer of the polymer dispersed liquid crystal element sample was observed using a Nikon Eclipse LV 100 POL optical microscope equipped with a Nikon DS-Ri1 CCD camera. The temperature of the sample was precisely controlled by a hot plate and a temperature controller (Linkam hot stage (10013L)) at a heating rate of 1 ° C./min. A polydomain-like non-uniform structure, which seems to be formed by phase separation of the polymer and the liquid crystal, was observed.

The electro-optic characteristics were measured with the experimental settings shown in FIG. For the permeability calculation, the permeability of the sample cell in the isotropic state was calibrated to T = 100%. The transmittance of the polymer-dispersed liquid crystal element sample placed on the hot stage at 303K is shown in the graph of FIG. 9, and the square wave AC voltage with a frequency of 1 kHz is used as the voltage increasing process (1st step to 50th step). , The voltage reduction process (51st step to 100th step) was determined by applying the voltage separately, and the VT characteristic (voltage-light transmittance characteristic) was measured. The applied time and the no-voltage time of each step are both 100 ms.

FIG. 3 shows the measurement results of the VT characteristics (voltage-light transmittance characteristics) of the polymer-dispersed liquid crystal element of Example 1. The driving voltage of the polymer-dispersed liquid crystal element of Example 1 was 6.2V.

(Comparative Example 1)
Among the precursor mixtures for polymer-dispersed liquid crystal elements, the high molecular weight of Comparative Example 1 is the same as that of Example 1 except that the compound A3DA (9.6 wt%) is changed to the compound TMHA (9.6 wt%). A molecular dispersion type liquid crystal element was manufactured, and VT characteristics (voltage-light transmission characteristics) were measured. The drive voltage of the polymer-dispersed liquid crystal element of Comparative Example 1 was 34.5 V.

FIG. 4 shows the measurement results of the voltage increasing process of the VT characteristics (voltage-light transmittance characteristics) of the polymer-dispersed liquid crystal elements of Example 1 and Comparative Example 1. In the polymer-dispersed liquid crystal element of Comparative Example 1, since the polymer component and the liquid crystal component are in contact with each other on a large surface surface, the binding to the liquid crystal at the interface is strong and the driving voltage is large, whereas the polymer dispersion of Example 1 is performed. In the type liquid crystal element, the presence of a structural unit derived from the compound A3DA in the polymer component reduces the liquid crystal property of the liquid crystal component in the vicinity thereof, and lubricates between the liquid crystal component and the polymer compound component. As a result of having an interface-inducing region and forming a slippery interface between the liquid crystal component and the lubricating interface-inducing region, the driving voltage can be reduced.

(Example 2)
Among the precursor mixtures for polymer-dispersed liquid crystal elements, compound A3DA (9.6 wt%) and compound HDDA (9.6 wt%) are added to compound A3DA (12.8 wt%) and compound HDDA (6.4 wt%). The polymer-dispersed liquid crystal element of Example 2 was produced in the same manner as in Example 1 except for the changed points, and the VT characteristics (voltage-light transmission characteristic) were measured. The driving voltage of the polymer-dispersed liquid crystal element of Example 2 was 10.5V.

(Example 3)
Among the precursor mixtures for polymer-dispersed liquid crystal elements, compound A3DA (9.6 wt%) and compound HDDA (9.6 wt%) are added to compound A3DA (11.2 wt%) and compound HDDA (8.0 wt%). The polymer-dispersed liquid crystal element of Example 3 was produced in the same manner as in Example 1 except for the changed points, and the VT characteristics (voltage-light transmission characteristic) were measured. The driving voltage of the polymer-dispersed liquid crystal element of Example 3 was 5.5V.

(Example 4)
The precursor mixture for the polymer-dispersed liquid crystal element is the liquid crystal composition E7 (78.8 wt%), the monofunctional monomer compound A3DA (11.0 wt%), and the cross-linking agent compound HDDA (9.4 wt%). The polymer-dispersed liquid crystal element of Example 4 was produced in the same manner as in Example 1 except that the photopolymerization initiator was changed to DMPAP (0.8 wt%), and the VT characteristics (voltage-light transmission rate). (Characteristics) was measured. The driving voltage of the polymer-dispersed liquid crystal element of Example 4 was 6.2V.

(Example 5)
Among the precursor mixtures for polymer-dispersed liquid crystal elements, compound A3DA (9.6 wt%) and compound HDDA (9.6 wt%) are added to compound A3DA (8.0 wt%) and compound HDDA (11.2 wt%). The polymer-dispersed liquid crystal element of Example 5 was produced in the same manner as in Example 1 except for the changed points, and the VT characteristics (voltage-light transmission characteristic) were measured. The driving voltage of the polymer-dispersed liquid crystal element of Example 5 was 10.5V.

(Example 6)
Among the precursor mixtures for polymer-dispersed liquid crystal elements, compound A3DA (9.6 wt%) and compound HDDA (9.6 wt%) are added to compound A3DA (8.8 wt%) and compound HDDA (10.4 wt%). The polymer-dispersed liquid crystal element of Example 6 was produced in the same manner as in Example 1 except for the changed points, and the VT characteristics (voltage-light transmission characteristic) were measured. The driving voltage of the polymer-dispersed liquid crystal element of Example 6 was 8.4V.

(Example 7)
Among the precursor mixtures for polymer-dispersed liquid crystal elements, compound A3DA (9.6 wt%) and compound HDDA (9.6 wt%) are added to compound A3DA (10.4 wt%) and compound HDDA (8.8 wt%). The polymer-dispersed liquid crystal element of Example 6 was produced in the same manner as in Example 1 except for the changed points, and the VT characteristics (voltage-light transmission characteristic) were measured. The driving voltage of the polymer-dispersed liquid crystal element of Example 6 was 8.4V.

(Example 8)
The polymer of Example 8 in the same manner as in Example 1 except that A3DA (9.6 wt%) was changed to compound A0DA (9.6 wt%) in the precursor mixture for the polymer-dispersed liquid crystal element. A distributed liquid crystal element was manufactured, and the VT characteristic (voltage-light transmission characteristic) was measured. The driving voltage of the polymer-dispersed liquid crystal element of Example 8 was 6.5V.

(Comparative Example 2)
Of the precursor mixture for the polymer-dispersed liquid crystal element, the polymer dispersion of Comparative Example 2 is the same as in Example 1 except that A3DA (9.6 wt%) is changed to DA (9.6 wt%). A type liquid crystal element was manufactured, and the VT characteristic (voltage-light transmission characteristic) was measured. The drive voltage of the polymer-dispersed liquid crystal element of Comparative Example 2 was 35 V or more, and was not saturated in the range up to 35 V.

(Comparative Example 3)
In the polymer dispersion type liquid crystal element precursor mixture, the polymer dispersion of Comparative Example 3 is the same as in Example 1 except that A3DA (9.6 wt%) is changed to A3B (9.6 wt%). A type liquid crystal element was manufactured, and the VT characteristic (voltage-light transmission characteristic) was measured. The driving voltage of the polymer-dispersed liquid crystal element of Comparative Example 3 was 35V, and it was not saturated in the range up to 35V.

(Comparative Example 4)
Among the precursor mixtures for polymer-dispersed liquid crystal elements, the height of Comparative Example 4 is the same as that of Example 1 except that the compound A3DA (9.6 wt%) is changed to the compound A6OC6H13 (9.6 wt%). A molecular dispersion type liquid crystal element was manufactured, and VT characteristics (voltage-light transmission characteristics) were measured. The drive voltage of the polymer-dispersed liquid crystal element of Comparative Example 4 was 35 V or more, and was not saturated in the range up to 35 V.

(Example 9)
The polymer of Example 9 in the same manner as in Example 1 except that A3DA (9.6 wt%) was changed to compound A3B2DA (9.6 wt%) in the precursor mixture for the polymer-dispersed liquid crystal element. A distributed liquid crystal element was manufactured, and the VT characteristic (voltage-light transmission characteristic) was measured. The driving voltage of the polymer-dispersed liquid crystal element of Example 8 was 18.4V.

10,10', 100,101 ... Polymer-dispersed liquid crystal element, 11,12 ... Substrate, 13 ... Liquid crystal component, 14 ... Polymer compound component, 15 ... Composite layer, 16 , 17 ... Alignment film, 18, 19 ... Electrodes, 21 ... Insulation layer

Claims (5)

A pair of substrates having electrodes on at least one substrate and a composite layer of a liquid crystal component and a polymer compound component are provided between the pair of substrates.
The composite layer forms a slippery interface between the liquid crystal component and the polymer compound component, which has a lubrication interface induction region having a lower order than the liquid crystal phase of the liquid crystal component .
A polymer-dispersed liquid crystal element , wherein the polymer compound component is a polymer compound component obtained by polymerizing a polymerizable compound component containing at least one compound represented by the following .

The polymer-dispersed liquid crystal device according to claim 1, wherein the drive voltage is 5 to 25 V. The liquid crystal component is the following general formula (I-1).

(In the formula, R ⁰¹ represents a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, and one or two or more non-adjacent −CH _2- in the alkyl group is an oxygen atom, —CH = CH. -, -COO-, may be replaced with -OCO-,
R ⁰² represents a hydrogen atom, 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 having 1 to 15 carbon atoms, and is a non-alkyl group among the alkyl groups. One adjacent or two or more non-adjacent -CH ₂ -may be replaced with an oxygen atom, -CH = CH-, -COO-, -OCO-.
A ⁰¹ , A ⁰² , A ⁰³ , and A ⁰⁴ independently have a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, and a 3,6-cyclohexenylene, respectively. Group, 1,4-silacyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, decahydronaphthalene-2,6-diyl group, pyridine-2,5 -Diyl group, pyrimidin-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, 1,3 -Representing a dithian-2,5-diyl group or a tetrahydrothiopyran-2,5-diyl group, said 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or The 2,6-naphthylene group is unsubstituted or can have one or more fluorine atoms, chlorine atoms, ₃ CFs, ₃ ^OCFs or ₃ CHs as substituents, provided that A03. And / or ^A04 may be a single bond.
Z ⁰¹ , Z ⁰² , and Z ⁰³ are independently single-bonded, -COO-, -OCO-, -CH ₂ -CH _2- , -CF ₂ -CF _2- , -CH = CH-,-, respectively. CF = CF-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , or -C≡C-. The polymer-dispersed liquid crystal element according to claim 1 or 2 , which contains at least one liquid crystal compound represented by). The liquid crystal component is the following general formula (III).

(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a halogen atom, CN and NCS, and the alkyl group and the alkenyl group are unsubstituted. Alternatively, it can have one or more F, Cl, CN, CH ₃ , CF ₃ as a substituent and one or more CH ₂ groups present in the alkyl or alkenyl group. Assuming that the O atoms are not directly bonded to each other, they may be substituted with O, CO, and COO, and the rings F, G, and H are independently 1,4-phenylene groups and 1,4-cyclohexyl, respectively. Siren group, 1,4-cyclohexenylene group, 3,6-cyclohexenylene group, 1,4-silacyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5- Diyl group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydro Represents a naphthalene-2,6-diyl group, a 2,6-naphthylene group, a 1,3- ^{dithian -} 2,5-diyl group or a tetrahydrothiopyran-2,5-diyl group, Y7, Y8 and ^Y9 . Are independently single-bonded, -COO-, -OCO-, -C≡C-, -CH ₂ CH _{2-, -CH 2 CH 2 CH 2 CH 2-} , -CH ₂ CH ₂ CH ₂ O- , -OCH ₂ CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CF = CF-, -CH = CH-, -CH ₂ CH ₂ CH = CH-, -CH = CHCH ₂ CH _2- , -CH ₂ CH = CHCH _2- , -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , Y ¹⁰ is a single bond, -O-, -CO-, -COO-, -OCO-, -CH _{2-, -CH 2 O-} , -OCH _2- , -CH ₂ COO- or -CH ₂ OCO- , Z ³ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a halogen atom, and the alkyl group or the alkenyl group is unsubstituted or has one or one as a substituent. It can have two or more F, Cl, CN, CH ₃ or CF ₃ , and one or two or more CH ₂ groups present in the alkyl or alkenyl group is an O atom. May be substituted with O, CO or COO so that they do not bind directly to each other, r and s independently represent 0, 1, 2, or 3, but r + s is 0, 1, 2, or 3. be. The polymer-dispersed liquid crystal device according to any one of claims 1 to 3 , which contains at least one compound represented by (). A precursor mixture for a polymer-dispersed liquid crystal element containing the liquid crystal component and the polymerizable compound component is injected between a pair of substrates having electrodes on at least one substrate, and the polymerizable compound component is polymerized. The method for manufacturing a polymer-dispersed liquid crystal element according to any one of claims 1 to 4 .

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