JP2007092000A - Composition for polymer-stabilized liquid crystal display element and polymer-distributed liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for a polymer-stabilized liquid crystal display element, which can improve thermal stability and mechanical stability and also reduce the driving voltage in a polymer-stabilized liquid crystal display element. <P>SOLUTION: The composition for a polymer-stabilized liquid crystal contains a polymerisable compound at a content ranging from 0.01% to 10%, which is represented by general formula (I-a), wherein the glass transition temperature of a polymerized product of the compound ranges from -100°C to 25°C. The composition also contains a specific liquid crystal compound. The polymer-stabilized liquid crystal display element contains such a composition as a component. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composition useful for a polymer-stabilized liquid crystal display element that can be driven by an active element, and a polymer-stabilized liquid crystal display element using the composition.

As a technique for stabilizing liquid crystal alignment using a polymer, a technique for stabilizing the alignment polymer by adding a photocurable monomer to twisted nematic liquid crystal and irradiating with light is disclosed (Non-patent Document 1). reference). The nematic liquid crystal described in the cited document maintains the twisted structure before polymer stabilization even after photocuring, and by using a liquid crystalline monomer having a liquid crystal skeleton as the photocurable monomer, the display The liquid crystal properties and orientation of the liquid crystal material are not lost.
The cited document shows an example of a polymer stable type liquid crystal element produced by adding a photocurable monomer to a twisted nematic liquid crystal host at a concentration of several percent and then irradiating with light without applying voltage. . Further, in the examples, voltage-dielectric constant characteristics when the liquid crystal monomer is changed by 2%, 3%, 4%, and 5% are shown. According to this result, when the amount of liquid crystal monomer added increases, the saturation dielectric constant decreases, and a higher voltage needs to be applied in order to saturate, resulting in a higher drive voltage and a corresponding increase in device drive voltage. To do. This is a problem in putting a polymer-stabilized liquid crystal element into practical use.

  On the other hand, as an example of applying a polymer-stabilized twisted nematic liquid crystal to a TFT liquid crystal display element, a small amount of photocurable liquid crystalline monomer is added and polymerized in the TFT liquid crystal display element, and the alignment is performed by the action of the formed polymer. Has been disclosed (see Patent Document 1). However, in the cited document, although the response speed of the liquid crystal at the time of falling is improved, the above-described problem of the driving voltage is not solved.

In addition to the twisted nematic liquid crystal display mode in the polymer-stabilized liquid crystal display element, a technique applied to an OCB (Optically compensated birefringence) mode has been proposed (see Non-Patent Document 2). The cited document discloses a technique in which liquid crystal molecules are dispersed in a photoreactive monomer, a desired bend alignment structure is obtained by applying an external electric field, and then the bend alignment is fixed by light irradiation. In the OCB mode, liquid crystal molecules are splayed in the initial state by applying a high voltage when starting up the display device, but an alignment transition operation is required to change this to a bend alignment. By immobilizing with molecules, it is possible to display in the OCB mode at the same time as starting up the display which does not require the alignment transition operation to the bend arrangement, thereby eliminating the disadvantages of the OCB mode.
In addition, liquid crystal molecules are fixed on a single substrate in a polymer liquid crystal matrix to fix the hybrid alignment, and the two substrates are bonded so that the homogeneous alignment portions on the substrate are in contact with each other to form an OCB mode vent alignment. A technique used for manufacturing liquid crystal display elements is disclosed (see Patent Document 2). In this case, a feature is that a vent orientation is formed without applying a voltage.
However, in the inventions disclosed in these cited references, the above-described problem of the driving voltage is not solved.

For polymer-stable ferroelectric liquid crystals (polymer-stable FLC), a technology that uses a monomer together with an FLC material to stabilize the polymer by applying an electric field and irradiating ultraviolet rays while aligning the liquid crystal molecules in one direction. Has been proposed (see Non-Patent Documents 3 and 4).
Further, after injecting a liquid crystal composition containing a ferroelectric liquid crystal and a monofunctional liquid crystalline (meth) acrylate monomer into a liquid crystal cell, the composition is irradiated with ultraviolet rays at a temperature at which the composition exhibits a predetermined liquid crystal phase, and monofunctional. A polymer-stabilized ferroelectric liquid crystal display device obtained by polymerizing a liquid crystalline (meth) acrylate monomer has been disclosed (see Patent Documents 3, 4 and 5). A device using such a monofunctional liquid crystalline (meth) acrylate monomer has a feature that it can display a good halftone, but a polymer obtained by polymerization of a monofunctional liquid crystalline (meth) acrylate monomer. As a result, there was a problem that the reliability of the device at high temperatures was not good.

  A polymer-stabilized ferroelectric liquid crystal display element using a polyfunctional liquid crystalline monomer that gives a polymer having higher heat resistance than a monofunctional liquid crystalline (meth) acrylate monomer is disclosed in Japanese Patent Application Laid-Open No. 2005-228867 (see Patent Document 6). However, many polyfunctional liquid crystalline monomers have a liquid crystallinity that is as high as 80 ° C. or higher, and there is a need to increase the temperature before the irradiation of ultraviolet rays for creating a polymer-stabilized liquid crystal device. There is a problem that undesirable thermal polymerization is induced and the uniformity of liquid crystal alignment deteriorates.

JP 2005-10202 A JP 2003-248226 A JP-A-9-212462 JP-A-9-21463 Japanese Patent Laid-Open No. 11-21554 JP-A-6-194635 Japan Society for the Promotion of Science, Organic Materials for Information Science, 142nd Committee, Section A (Liquid Crystal Materials), 91st Study Group Materials (pages 28-30) IEICE technical report, Vol. 95, (EID95-17), pp. 43-48, 1995 H. Furue, Japan Journal of Applied Physics, 36, L1517 (1997) H. Furue, Japan Journal of Applied Physics, 37, 3417 (1998)

  An object of the present invention is to provide a composition for a polymer stable liquid crystal display device capable of improving the thermal and mechanical stability and reducing the driving voltage in the polymer stable liquid crystal display device. is there.

In order to improve the thermal and mechanical stability in the composition for a polymer stable liquid crystal display element, it is only necessary to have a crosslinked polymer using a bifunctional liquid crystalline acrylate or the like. By using bifunctional liquid crystalline acrylates, the mesogenic groups are arranged in the polymer main chain, and both ends of the mesogenic groups are fixed by cross-linking, so there is little influence of thermal fluctuations and the reliability of alignment stabilization of low-molecular liquid crystals Will improve. However, on the other hand, since the fluctuation of heat is reduced, the interaction with the low-molecular liquid crystal increases, and as a result, the anchoring force at the low-molecular liquid crystal / polymer interface that occurs when the orientation of the low-molecular liquid crystal is fixed. As a result, the drive voltage increases and the drive voltage increases, which makes it difficult to drive with amorphous silicon-TFT or polysilicon TFT.
On the other hand, the polymer stable liquid crystal to which a small amount of monofunctional liquid crystalline acrylate is added is advantageous in terms of driving voltage, but lacks thermal stability and has poor reliability. This is due to the fact that the mesogenic groups bonded to the polymer main chain in a pendant manner are greatly fluctuated by heat and the orientation obtained in the initial state is disturbed.
In order to solve the above problems, the inventors of the present application have studied the composition of various polymerizable liquid crystal compounds and liquid crystal compounds, and have completed the present invention.
The present application is the general formula (Ia)

（式中、Ａ^１及びＡ^９はそれぞれ独立して水素原子又はメチル基を表し、Ａ^２及びＡ^８はそれぞれ独立して単結合又は炭素原子数１から１５のアルキレン基を表し、該アルキレン基中に存在する１個又は２個以上のメチレン基は、酸素原子が相互に直接結合しないものとしてそれぞれ独立に酸素原子、−ＣＯ−、−ＣＯＯ−又は−ＯＣＯ−で置換されていても良く、該アルキレン基中に存在する１個又は２個以上の水素原子はそれぞれ独立にフッ素原子、メチル基、エチル基で置換されていても良く、Ａ^３及びＡ^６はそれぞれ独立して炭素原子数２から２０の直鎖アルキル基を表し、該アルキル基中に存在する１個又は２個以上のメチレン基は、酸素原子が相互に直接結合しないものとしてそれぞれ独立に酸素原子、−ＣＯ−、−ＣＯＯ−又は−ＯＣＯ−で置換されていても良く、Ａ^４及びＡ^７はそれぞれ独立して水素原子、又は炭素原子数１から１０のアルキル基を表し、該アルキル基中に存在する１個又は２個以上のメチレン基は酸素原子が相互に直接結合しないものとしてそれぞれ独立に酸素原子、−ＣＯ−、−ＣＯＯ−又は−ＯＣＯ−で置換されていても良く、該アルキル基中に存在する１個又は２個以上の水素原子はそれぞれ独立にハロゲン原子又は炭素原子数１から９のアルキル基で置換されていても良く、Ａ^５は炭素原子数９から１６のアルキレン基を表し、該アルキレン基中に存在する少なくとも１個以上５個以下のメチレン基の水素原子の一つはそれぞれ独立に炭素原子数１から１０の直鎖又は分岐のアルキル基で置換されており、該アルキレン基中に存在する１個又は２個以上のメチレン基は、酸素原子が相互に直接結合しないものとしてそれぞれ独立に酸素原子、−ＣＯ−、−ＣＯＯ−又は−ＯＣＯ−で置換されていても良い。）で表される重合性化合物であって該化合物の重合物のガラス転移温度が−１００℃から２５℃である化合物を含有し、その含有率が０．０１％から１０％の範囲であり、一般式（II-a）

(In the formula, A ¹ and A ⁹ each independently represent a hydrogen atom or a methyl group; A ² and A ⁸ each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms; One or more methylene groups present therein may be each independently substituted with an oxygen atom, —CO—, —COO— or —OCO— as those in which oxygen atoms are not directly bonded to each other, One or two or more hydrogen atoms present in the alkylene group may be each independently substituted with a fluorine atom, a methyl group, or an ethyl group, and A ³ and A ⁶ are each independently 2 carbon atoms. To 20 straight chain alkyl groups, and one or more methylene groups present in the alkyl group are each independently an oxygen atom, —CO—, —COO on the assumption that oxygen atoms are not directly bonded to each other. Or it may be substituted with -OCO-, A ⁴ and A ⁷ each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, one or two present in the alkyl group The above methylene groups may be each independently substituted with an oxygen atom, —CO—, —COO— or —OCO— as those in which oxygen atoms are not directly bonded to each other, Two or more hydrogen atoms may be each independently substituted with a halogen atom or an alkyl group having 1 to 9 carbon atoms, and A ⁵ represents an alkylene group having 9 to 16 carbon atoms, One of the hydrogen atoms of at least 1 to 5 methylene groups present is independently substituted with a linear or branched alkyl group having 1 to 10 carbon atoms, and is present in the alkylene group. 1 or 2 or more methylene groups may be each independently substituted with an oxygen atom, —CO—, —COO—, or —OCO— as those in which oxygen atoms are not directly bonded to each other. And a compound having a glass transition temperature of −100 ° C. to 25 ° C. of the polymerized product of the compound, the content is in the range of 0.01% to 10%, and the general formula ( II-a)

（式中、Ｒ^１は炭素原子数１から１０のアルキル基又は炭素原子数２から１０のアルケニル基を表し、該アルキル基又はアルケニル基中に存在する１個又は２個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、酸素原子で置換されていてもよく、
Ｃ^１、は１，４−フェニレン基、１，４−シクロヘキシレン基又は１，３−ジオキサン−２，５−ジイル基を表し、該１，４−フェニレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、塩素原子、メチル基又はトリフルオロメチル基又はトリフルオロメトキシ基を有することができ、
Ｃ^２及びＣ^３はそれぞれ独立して１，４−フェニレン基、１，４−シクロヘキシレン基、デカヒドロナフタレン−２，６−ジイル基、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基、２，６−ナフチレン基、又はインダン−２，５−ジイル基、を表し、該１，４−フェニレン基、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基、２，６−ナフチレン基、インダン−２，５−ジイル基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、塩素原子、メチル基又はトリフルオロメチル基又はトリフルオロメトキシ基を有することができ、
Ｚ^１及びＺ^２はそれぞれ独立して、単結合、−ＣＨ_２ＣＨ_２−、−Ｃ≡Ｃ−、−ＣＦ_２Ｏ−、−ＣＯＯ−、又は−ＯＣＯ−を表し、
Ｘ^１はフッ素原子、塩素原子、トリフルオロメチル基、トリフルオロメトキシ基、ジフルオロメチル基、イソシアネート基、シアノ基又はＲ^１と同じ意味を表し、
ｎ^１は、０、１又は２を表す。ただし、ｎ^１が２を表す場合、複数存在するＣ^１及びＺ^１は同じであっても異なっていても良い。）で表される化合物を含有し、その含有率が少なくとも９０％である高分子安定化液晶液晶組成物及び、当該組成物を構成部材とする高分子安定化駅署表示素子を提供する。

(Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one or more methylene groups present in the alkyl group or alkenyl group are: As oxygen atoms that are not directly bonded to each other, they may be substituted with oxygen atoms,
C ¹ represents a 1,4-phenylene group, a 1,4-cyclohexylene group or a 1,3-dioxane-2,5-diyl group, and the 1,4-phenylene group is unsubstituted or substituted. As one or more fluorine atoms, chlorine atoms, methyl groups or trifluoromethyl groups or trifluoromethoxy groups,
C ² and C ³ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6 -Represents a diyl group, a 2,6-naphthylene group, or an indan-2,5-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, indan-2,5-diyl group is unsubstituted or has one or more fluorine, chlorine, methyl, trifluoromethyl or trifluoromethoxy groups as substituents Can have
Z ¹ and Z ² each independently represents a single bond, —CH ₂ CH ₂ —, —C≡C—, —CF ₂ O—, —COO—, or —OCO—,
X ¹ represents the same meaning as a fluorine atom, a chlorine atom, a trifluoromethyl group, a trifluoromethoxy group, a difluoromethyl group, an isocyanate group, a cyano group or R ¹ ;
n ¹ represents 0, 1 or 2. However, when n ¹ represents 2, a plurality of C ¹ and Z ¹ may be the same or different. And a polymer-stabilized liquid crystal liquid crystal composition having a content of at least 90%, and a polymer-stabilized station display device comprising the composition as a constituent member.

  The polymer-stabilized liquid crystal display element comprising the polymer-stabilized liquid crystal composition of the present invention as a constituent member has a low driving voltage and is excellent in thermal and mechanical stability. In addition, since it can be driven by TFT, it is useful as a structural member for plastic liquid crystal cells and the like.

An example of the present invention will be described below. The composition for a polymer-stabilized liquid crystal display element of the present invention is a transparent polymer in which a radical polymerizable compound contained therein is polymerized by active energy rays such as heat or ultraviolet rays, thereby causing phase separation from the liquid crystal composition. It is used to obtain a polymer-stabilized liquid crystal display device comprising a conductive polymer material and a liquid crystal composition.
The polymer-stabilized liquid crystal display element thus formed has a driving voltage that increases in proportion to the content of the polymer precursor added to the composition as described above. When the content of the precursor is very small, the degree of increase in driving voltage is not a problem, but thermal and mechanical stability is poor. In order to increase the reliability, it is necessary to increase the content of the precursor, and at this time, an increase in driving voltage, a decrease in liquid crystal alignment, and the appearance of scattering properties become problems. For example, Japanese Patent Laid-Open No. 6-222320 discloses the relationship of the following equation as an increase in the driving voltage as a description relating to the driving voltage of the polymer dispersed liquid crystal display element. The concept for the driving voltage of the polymer-stabilized liquid crystal element is the same as that of the polymer-dispersed liquid crystal display element and is as follows.

（Ｖthはしきい値電圧を表わし、¹Kii及び²Kiiは弾性定数を表わし、ｉは１、２又は３を表わし、Δεは誘電率異方性を表わし、＜ｒ＞は透明性高分子物質界面の平均空隙間隔を表わし、Ａは液晶組成物に対する透明性高分子物質のアンカリングエネルギーを表わし、ｄは透明性電極を有する基板間の距離を表わす。）

(Vth represents threshold voltage, ¹ Kii and ² Kii represent elastic constants, i represents 1, 2 or 3, Δε represents dielectric anisotropy, and <r> represents a transparent polymer substance. (Indicates the average gap distance of the interface, A indicates the anchoring energy of the transparent polymer substance with respect to the liquid crystal composition, and d indicates the distance between the substrates having transparent electrodes.)

  According to this, the driving voltage of the polymer-stabilized liquid crystal display element includes the average gap distance at the interface of the transparent polymer substance, the distance between the substrates, the elastic constant / dielectric anisotropy of the liquid crystal composition, and the liquid crystal composition. It is determined by the anchoring energy between transparent polymer materials. Of these, in general liquid crystal display elements, the driving voltage is determined by the cell thickness, the dielectric anisotropy, and the elastic constant. It is. It is the anchoring energy between the liquid crystal composition and the transparent polymer material. Therefore, in the polymer-stabilized liquid crystal display device, when the area of the interface between the polymer and the liquid crystal is increased, the anchoring energy of the system is increased and the driving voltage is increased. In other words, it means that when the content of the polymer precursor is increased in the composition of the present invention, the driving voltage is increased. In order to reduce the increase in driving voltage and maintain a low driving voltage, the anchoring energy of the polymer constituting the polymer-stabilized liquid crystal may be lowered. In order to lower the energy, a bifunctional monomer having an alkyl side chain may be used. Particularly, the alkyl side chain preferably has 5 to 15 carbon atoms, and more preferably 8 to 13 carbon atoms. When the alkyl side chain is short, the anchoring energy becomes high, and when it is too long, the influence of the side chain becomes strong and the anchoring energy becomes high. Further, if a mesogenic group having a benzene ring or the like similar to a low-molecular liquid crystal is used as a side chain, the affinity with the low-molecular liquid crystal is increased and the anchoring energy is increased, which is not preferable. Furthermore, the distance between the alkyl side chains is also important, and is preferably 6 to 18 in terms of carbon distance. Although it depends on the liquid crystal composition to be used, if the distance between the alkyl side chains is narrow, the low-molecular liquid crystal is not preferred because it is vertically aligned at the polymer interface.

  The anchoring energy is determined by the balance between the intermolecular interaction that the side chain has on the low-molecular liquid crystal and the intermolecular interaction that the main chain has on the low-molecular liquid crystal. Be minimized. Furthermore, the distance between crosslinks of the polymer affects the thermal mobility of the polymer main chain. When the distance between crosslinks is short and the thermal mobility is low, the molecular interaction with the low-molecular liquid crystal is strong and the anchoring energy is increased. As the distance between crosslinks becomes longer, the thermal mobility of the polymer main chain increases and the fluctuation due to the heat of the main chain increases, and if the fluctuation force becomes larger than the intermolecular interaction force, it acts to cancel the intermolecular interaction Anchoring energy is reduced. However, if the distance between crosslinks is long, the polymerization rate of the polymer precursor is slowed, and the compatibility with the liquid crystal is lowered. As an index representing the thermal mobility of the polymer main chain, a polymer glass transition temperature is generally used. In the present invention, it is preferable to use a polymer precursor having a glass transition temperature of room temperature or lower for the purpose of lowering the anchoring, and more preferably the glass transition temperature is 0 to -100 ° C. In addition, in order to lower the glass transition temperature, it is preferable to lower the glass transition temperature in order to improve mechanical stability. If the glass transition temperature is higher than room temperature, the polymer network structure that stabilizes the liquid crystal alignment with the polymer may be deformed or damaged due to deformation from the outside of the device, etc. . When the glass transition temperature is low, even if the network structure is deformed, the original orientation is restored by the elasticity of the network and the fixed orientation is maintained. That is, by adjusting the main chain length and side chain length of the liquid crystal composition and polymer precursor used in the present invention, and using a polymer precursor having a glass transition temperature of room temperature or less, the driving voltage is low, A highly reliable polymer-stabilized liquid crystal element can be obtained. However, in the polymer-stabilized liquid crystal, it is an important issue to stabilize the initial alignment at the time of manufacturing the liquid crystal display element. When the polymer precursor of the present invention is polymerized in the liquid crystal phase, the order of orientation is not high, but it is observed with a microscope or the like that a network polymer is formed along the liquid crystal molecule director. This is because when the precursor main chain is in contact with the liquid crystal, the precursor main chain tends to be aligned in the direction of the liquid crystal molecule director, and the alignment of the liquid crystal is fixed by polymerizing the precursor. However, when the concentration of the precursor is increased, the phase separation structure by spinodal decomposition or binodal decomposition that occurs in polymerization microphase separation is formed ignoring the alignment of the liquid crystal, so that the target liquid crystal alignment cannot be fixed. . In order to fix the state in which the liquid crystal is aligned by the alignment film or the like without the alignment defect, it is necessary to polymerize the polymer precursor in a network at least in a liquid crystal phase such as a nematic phase or a smectic phase. In order to avoid the formation of the phase separation structure, the polymer precursor is formed so that a network polymer can be formed between the liquid crystal molecules while the content of the polymer precursor is reduced and the liquid crystal is aligned. It is preferable to adjust the content and composition of the precursor, and in the case of photopolymerization, a liquid crystal alignment defect is formed by adjusting the UV exposure time, UV exposure intensity, and temperature to form a network polymer. It is preferable not to have it. In order to obtain a desired liquid crystal alignment when polymerizing the polymer precursor in the composition, a rubbing alignment treatment or a photo-alignment treatment of vertical alignment, parallel alignment, anti-parallel alignment, and twist alignment was performed. A liquid crystal cell having an alignment film is used, a liquid crystal cell in which the upper and lower substrates are a vertical alignment film, or a combination of a vertical alignment film and parallel alignment is used. Furthermore, twisted alignment obtained by applying an external field such as light, heat, voltage, and magnetic field, bent alignment, splay alignment, and the like, and a liquid crystal alignment state that is difficult to obtain with only an alignment film alone are formed. By polymerizing, the alignment state can be fixed and the target polymer stabilized liquid crystal display element can be obtained.

The polymer precursor used in the present invention has arrived as a result of searching for a compound having a greater improvement effect as the polymer precursor as described above. What is necessary is just to contain at least 1 or more types of general formula (Ia), and you may contain multiple, different main chain lengths or alkyl side chain length. Furthermore, you may use a polymerizable liquid crystal compound together as needed. When a polymerizable liquid crystal compound is used, the orientation of the low-molecular liquid crystal can be improved. However, the affinity for the low-molecular liquid crystal is high and the driving voltage is likely to increase, so 5% or less is preferable. Polymer-stabilized liquid crystal display with high mechanical strength and low driving voltage due to the low anchoring energy and low glass transition temperature of general formula (Ia). An element can be obtained.
The two substrates of the liquid crystal cell can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.
The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

  The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. In that case, you may adjust the space | interval of a board | substrate through a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be set to 1-100 micrometers. 2 to 10 μm is more preferable. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates in a form provided with a liquid crystal injection port, the substrates are bonded together, and heated to thermally cure the sealant.

  As a method for sandwiching the polymer-stabilized liquid crystal composition between the two substrates, a normal vacuum injection method, an ODF method, or the like can be used. At this time, the polymer-stabilized liquid crystal composition only needs to be compatible with various liquid crystal compounds and the polymer precursor of the present invention, and is preferably in a uniform isotropic state or a nematic phase. In the smectic phase, handling during device fabrication becomes difficult.

  As a method for polymerizing the radically polymerizable compound, ultraviolet irradiation is suitable. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Further, the wavelength of the ultraviolet rays to be irradiated is an absorption wavelength region of the photopolymerization initiator contained in the polymer dispersion type liquid crystal display element composition, and a wavelength that is not the absorption wavelength region of the contained liquid crystal composition. It is preferable to irradiate ultraviolet rays in the region. Specifically, it is preferable to cut and use ultraviolet rays of 330 nm or less using a metal halide lamp, high-pressure mercury lamp, or ultra-high pressure mercury lamp, and cut ultraviolet rays of 350 nm or less. And more preferably used.

The intensity of the irradiated ultraviolet light can be adjusted as appropriate to obtain the desired light control layer, but it depends on the reactivity of the polymer precursor used, but is preferably 10 to 10,000 mJ / cm @ 2, 50 to 5000 mw / cm. ² is more preferable. The time for irradiation with ultraviolet rays is appropriately selected depending on the intensity of ultraviolet rays to be irradiated, but is preferably 10 to 600 seconds.

The temperature at the time of ultraviolet irradiation is an important factor for stabilizing the desired initial alignment of the liquid crystal by determining the characteristics of the light control layer. When the isotropic phase state is fixed, a temperature slightly higher than the isotropic-nematic transition point of the polymer-stabilized liquid crystal display element composition is preferable, and specifically, the transition point is preferably +0.1 to 10 ° C. The transition point + 0.1 ° C. to 3 ° C. is more preferable. Further, the device can be manufactured at a temperature showing a nematic phase, a smectic phase, or a cholesteric phase.
The alignment state of the liquid crystal that stabilizes the polymer is arranged in multiple directions, such as bend alignment, twist alignment, splay alignment, etc. seen in the smectic phase and nematic phase, and multi-domains combining them in combination, and mono domains with uniaxial alignment. Change the temperature of the required alignment state, such as multi-domain, change the voltage by applying an electric field, or process the alignment processing direction of polyimide alignment film or photo alignment film at the substrate interface in one direction or multiple directions Then, it is preferable to align the liquid crystal, create the desired alignment state by various methods and stabilize the polymer by ultraviolet exposure.

Specific examples of the compound used in the polymer-stabilized liquid crystal composition of the present invention are shown below.
As a preferable structure of the compound represented by the general formula (Ia), both A ¹ and A ⁹ are preferably hydrogen atoms. Although the effect of the present invention is exhibited even in a compound in which these substituents are methyl groups, the compound in which the substituent is a hydrogen atom is advantageous in that the polymerization rate becomes faster. A ² and A ⁸ are preferably each independently a single bond or an alkylene group having 1 to 3 carbon atoms. The distance between the two polymerizable functional groups can be adjusted by changing the length of carbon number independently for A ² and A ⁸ and A ⁵ . The feature of the compound represented by the general formula (Ia) is that the distance between the polymerizable functional groups (distance between the crosslinking points) is long, but if this distance is too long, the polymerization rate becomes extremely slow. Therefore, there is an upper limit on the distance between the polymerizable functional groups. On the other hand, the distance between the two side chains of A ³ and A ⁶ also affects the mobility of the main chain. That is, if the distance between A ³ and A ⁶ is short, the side chains A ³ and A ⁶ will interfere with each other, resulting in a decrease in mobility. Therefore, in the compound represented by the general formula (Ia), the distance between the polymerizable functional groups is determined by the sum of A ² , A ⁸ , and A ⁵ , and among these, A ² and A ⁸ are longer than A. It is preferable to make ⁵ longer.

On the other hand, the following aspect is preferred for the relationship between the lengths of A ³ and A ⁴ , or A ⁶ and A ⁷ , which are side chains. In these substituents, it is preferable that A ³ ≧ A ⁴ and A ⁶ ≧ A ⁷ are satisfied. When this relationship is established, A ³ and A ⁶ which are longer side chains are each independently 2 to 18 carbon atoms which may be substituted with an oxygen atom, —CO—, —COO— or —OCO—. The alkyl group is preferably an alkyl group having 3 to 15 carbon atoms which may be substituted with an oxygen atom, -CO-, -COO- or -OCO-. Since the side chain has higher mobility than the main chain, its presence contributes to improvement of the mobility of the polymer chain at low temperature, but as mentioned above, spatial interference occurs between the two side chains. On the contrary, motility decreases. In order to prevent such spatial interference between the side chains, it is effective to increase the distance between the side chains and to shorten the side chain length within a necessary range. Further, A ⁴ and A ⁷ are each independently preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms which may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, More preferably, it is an alkyl group having 1 to 7 carbon atoms which may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and an oxygen atom, -CO-, -COO- or -OCO The case of an alkyl group having 1 to 5 carbon atoms which may be substituted with-is even more preferable, and the case of an alkyl group having 1 to 3 carbon atoms is most preferable. As for A ⁴ and A ⁷ , too long is not preferable because it induces spatial interference between side chains. On the other hand, when A ⁴ and A ⁷ are alkyl chains having a short length, they can be side chains having high mobility and have a function of inhibiting the proximity of adjacent main chains. It is thought that it acts to prevent interference between the main chains of the polymer, and the mobility of the main chain is considered to be increased, so that the anchoring energy can be prevented from increasing at low temperatures, and the polymer stabilized liquid crystal display This is effective in improving the display characteristics in the low temperature region of the device.

A ⁵ located between the two side chains is preferably longer in terms of changing the distance between the side chains and increasing the distance between the crosslinking points to lower the glass transition temperature. However to come formula compatibility with (I-a) molecular weight becomes large and too liquid crystal composition of the compound represented by decreases when A ⁵ is too long, and the polymerization rate slows down too phase separation The length is naturally set to an upper limit because of adverse effects on the length. Therefore, alkylene chain length of A ⁵ in the present application is a 40 to 2 carbon atoms, preferably 35 carbon atoms 3, carbon atoms 6 18 is more preferred. A ⁵ represents a structural features, have a hydrogen atom in the alkylene group is replaced by an alkyl group having 1 to 10 carbon atoms structures. The number of substitution 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 in the alkyl group to be substituted is preferably 1 to 5, and more preferably 1 to 3.

As described above, A ⁵ is an alkylene group having 3 to 35 carbon atoms, and one of hydrogen atoms of 1 to 5 methylene groups present in the alkylene group is independently selected from 1 to C atoms. It is preferably substituted with 10 alkyl groups, and the methylene group contained in the alkylene group may be substituted with an oxygen atom, -CO-, -COO- or -OCO-,
An alkylene group having 3 to 35 carbon atoms, wherein one of hydrogen atoms of 1 to 3 methylene groups contained in the alkylene group is independently substituted with an alkyl group having 1 to 3 carbon atoms. More preferably, the methylene group contained in the alkylene group may be substituted with an oxygen atom, -CO-, -COO- or -OCO-,
An alkylene group having 3 to 32 carbon atoms, wherein one of hydrogen atoms of 1 to 3 methylene groups contained in the alkylene group is independently substituted with an alkyl group having 1 to 3 carbon atoms; More preferably, the methylene group contained in the alkylene group may be substituted with an oxygen atom, -CO-, -COO- or -OCO-,
A ⁵ is an alkylene group having 3 to 32 carbon atoms, and one of the hydrogen atoms of one or two methylene groups contained in the alkylene group is each independently an alkyl group having 1 to 3 carbon atoms. It is particularly preferred that it is substituted.

The compound represented by the general formula (Ia) is disclosed in Tetrahedoron Letters, Vol. 30, pp 4985, Tetrahedron Letters, Vol. 23, No. 6, pp 681-684, and Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 34, pp217-225 and the like.
For example, in the general formula (Ia), a compound in which A ⁴ and A ⁷ are hydrogen is a compound such as acrylic acid or methacrylic acid having a compound having a plurality of epoxy groups and active hydrogen capable of reacting with the epoxy group. It can be obtained by reacting with a functional compound to synthesize a polymerizable compound having a hydroxyl group and then reacting with a saturated fatty acid.
Furthermore, by reacting a compound having a plurality of epoxy groups with a saturated fatty acid, synthesizing a compound having a hydroxyl group, and then reacting with a polymerizable compound such as an acrylate chloride having a group capable of reacting with a hydroxyl group. Obtainable.

When the radically polymerizable compound is, for example, A ⁴ and A ^{7 in} the general formula (Ia) are alkyl groups, and A ² and A ⁸ are methylene groups having 1 carbon atom, oxetane A method of reacting a compound having a plurality of groups with a fatty acid chloride or a fatty acid capable of reacting with an oxetane group, and further reacting with a polymerizable compound having active hydrogen such as acrylic acid, or a compound having one oxetane group And a polyvalent fatty acid chloride or a fatty acid capable of reacting with an oxetane group, and further reacting with a polymerizable compound having active hydrogen such as acrylic acid.
Further, when A ² and A ⁸ in the general formula (Ia) are propylene groups having 3 carbon atoms, they can be obtained by using a compound having a plurality of furan groups instead of the oxetane groups. Further, when A ² and A ⁸ in the general formula (Ia) are a butylene group having 4 carbon atoms, it can be obtained by using a compound having a plurality of pyran groups instead of an oxetane group.

The compound represented by the general formula (II-a) is specifically described below in terms of a wide liquid crystal temperature range, nematic stability and compatibility in a low temperature range, a high dielectric constant, and a high specific resistance value. Compounds represented by general formula (IV-a), general formula (Va), general formula (Vb), general formula (VI-a) and general formula (VI-b) are preferred.
Formula (IV-a)

(Wherein R ¹¹ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one or more methylene groups present in the alkyl group or alkenyl group are As oxygen atoms that are not directly bonded to each other, they may be substituted with oxygen atoms,
C ¹¹ represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and the 1,4-phenylene group is unsubstituted or has one or more fluorine atoms, chlorine atoms as substituents, It can have a methyl group or a trifluoromethyl group or a trifluoromethoxy group,
Z ¹¹ represents a single bond or —CH ₂ CH ₂ —,
X ¹¹ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms (one or two or more methylene groups present in the alkyl group or alkenyl group have oxygen atoms mutually It may be substituted with an oxygen atom as not directly bonded.), Represents a fluorine atom, a chlorine atom, an isocyanate group, a trifluoromethyl group, a trifluoromethoxy group, a difluoromethoxy group or a general formula (IV-b) ,

(In the formula, C ¹² represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and the 1,4-phenylene group is unsubstituted or has one or more fluorine atoms as a substituent. A chlorine atom, a methyl group or a trifluoromethyl group or a trifluoromethoxy group,
X ¹⁸ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms (one or two or more methylene groups present in the alkyl group or alkenyl group have oxygen atoms mutually It may be substituted with an oxygen atom as not directly bonded.), A fluorine atom, a chlorine atom, an isocyanate group, a trifluoromethyl group, a trifluoromethoxy group, or a difluoromethoxy group. )
X ¹² to X ¹⁷ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group, a trifluoromethoxy group, a methyl group, a methoxy group or an ethyl group,
n ¹¹ represents 0 or 1. )
In the general formula (IV-a), R ¹¹ is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 6 carbon atoms (one or two or more present in the alkyl group or alkenyl group). The methylene group may be substituted with an oxygen atom, assuming that the oxygen atoms are not directly bonded to each other.), Preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. preferable.
Z ¹¹ is preferably a single bond,
X ¹¹ is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a fluorine atom,
X ¹² to X ¹⁷ are preferably a hydrogen atom, a fluorine atom or a methyl group, and more preferably one or more and three or less of X ¹² to X ¹⁷ are a fluorine atom or a methyl group.

  Specifically, from general formula (IV-c) to general formula (IV-i)

(Wherein R ³¹ , R ³² and R ³³ each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms,
X ⁶¹ to X ⁶⁶ each independently represent a hydrogen atom, a fluorine atom, or a methyl group,
X ⁷¹ to X ⁷⁶ each independently represent a hydrogen atom or a fluorine atom. )
Of these, preferred is a compound represented by: at least one of X ⁶¹ to X ⁶⁶ , three or less being a fluorine atom or a methyl group, and at least one or more of X ⁷¹ to X ⁷⁶ , 3 More preferably, no more than one is a fluorine atom. Specifically, from general formula (IV-j) to general formula (I-59)

(Wherein R ³⁵ , R ³⁶ and R ³⁷ each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms,
X ⁸¹ , X ⁸⁴ , X ⁸⁵ and X ⁸⁶ each independently represent a hydrogen atom or a fluorine atom, and X ⁸² and X ⁸³ each independently represent a hydrogen atom, a fluorine atom or a methyl group, (I-55) and in formula (I-56) at least one or more of X ⁸² to X ⁸⁶ represent a fluorine atom or a methyl group,
X ⁸⁷ and X ⁸⁸ each independently represent a hydrogen atom or a fluorine atom. )
Even more preferred is a compound represented by:

  General formula (Va) and general formula (Vb)

(In the formula, each of R ²¹ and R ³¹ independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one or more present in the alkyl group or alkenyl group or Two or more methylene groups may be substituted with oxygen atoms, assuming that the oxygen atoms are not directly bonded to each other,
C ²¹ and C ³¹ each independently represent a 1,4-phenylene group or a 1,4-cyclohexylene group, and the 1,4-phenylene group is unsubstituted or has one or two substituents. It can have the above fluorine atom, chlorine atom, methyl group or trifluoromethyl group or trifluoromethoxy group,
Y represents a ²¹ phenyl group or a cyclohexyl group,
Y ³¹ represents a 1,4-phenylene group or a 1,4-cyclohexylene group,
X ²¹ and X ³¹ each independently represent a fluorine atom, a chlorine atom, an isocyanate group, a trifluoromethyl group, a trifluoromethoxy group or a difluoromethoxy group,
X ²² to X ²⁶ and X ³² to X ³⁶ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group or a trifluoromethoxy group,
Z ²¹ and Z ³¹ each independently represent a single bond or —CH ₂ CH ₂ —;
Z ²² and Z ³² each independently represent a single bond, —CH ₂ CH ₂ — or —CF ₂ O—,
n ²¹ and n ³¹ represent 0 or 1. )
In formulas (Va) and (Vb), R ²¹ and R ³¹ are each an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 6 carbon atoms (the alkyl group or alkenyl group). 1 or 2 or more methylene groups present therein may be substituted with an oxygen atom so that the oxygen atoms are not directly bonded to each other), and the alkenyl group has the formula (Vc)

(The structural formula is assumed to be connected to the ring directly or through an oxygen atom at the right end), and an alkyl group having 1 to 5 carbon atoms is more preferable.
C ²¹ and C ³¹ are preferably 1,4-cyclohexylene groups,
Z ²¹ and Z ³¹ are preferably a single bond,
X ²¹ and X ³¹ are preferably a fluorine atom or a trifluoromethoxy group, and more preferably a fluorine atom.
Specifically, compounds represented by general formula (V-1) to general formula (V-33) are preferable.

(In the formula, R ¹¹ represents an alkyl group having 1 to 5 carbon atoms.)
General formula (VI-a) and general formula (VI-b)

(In the formula, R ⁴¹ and R ⁵¹ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one or more present in the alkyl group or alkenyl group or Two or more methylene groups may be substituted with oxygen atoms, assuming that the oxygen atoms are not directly bonded to each other,
C ⁴¹ and C ⁵¹ each independently represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and the 1,4-phenylene group is unsubstituted or has one or two substituents. It can have the above fluorine atom, chlorine atom, methyl group or trifluoromethyl group or trifluoromethoxy group,
Y ⁴¹ represents a phenyl group or a cyclohexyl group,
Y ⁵¹ represents a 1,4-phenylene group or a 1,4-cyclohexylene group,
X ⁴¹ and X ⁵¹ each independently represent a fluorine atom, a chlorine atom, an isocyanate group, a trifluoromethyl group, a trifluoromethoxy group or a difluoromethoxy group,
X ⁴² to X ⁴⁵ and X ⁵² to X ⁵⁵ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group or a trifluoromethoxy group,
Z ⁴¹ and Z ⁵¹ each independently represent a single bond or —CH ₂ CH ₂ —;
Z ⁴² and Z ⁵² each independently represent a single bond, —CH ₂ CH ₂ — or —CF ₂ O—,
n ⁴¹ and n ⁵¹ represent 0 or 1. )
In the general formula (VI-a) and the general formula (VI-b), R ⁴¹ and R ⁵¹ are each an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 6 carbon atoms (the alkyl group or alkenyl group). 1 or 2 or more methylene groups present therein may be substituted with an oxygen atom so that the oxygen atoms are not directly bonded to each other), and the alkenyl group has the formula (VI-c)

(The structural formula is assumed to be connected to the ring directly or through an oxygen atom at the right end), and an alkyl group having 1 to 5 carbon atoms is more preferable.
C ⁴¹ and C ⁵¹ are preferably 1,4-cyclohexylene groups,
Z ⁴¹ and Z ⁵¹ are preferably a single bond,
X ⁴¹ and X ⁵¹ are preferably a fluorine atom or a trifluoromethoxy group, and more preferably a fluorine atom.
Specifically, compounds represented by general formula (VI-1) to general formula (VI-42) are preferable.

(In the formula, R ¹¹ represents an alkyl group having 1 to 5 carbon atoms.)
Further, in order to obtain further expansion of the liquid crystal temperature region, high dielectric constant, or low viscosity, general formula (IV-a), general formula (Va), general formula (Vb), general formula (VI- In addition to the compound of a) and general formula (VI-b), it is also preferable to contain the compound represented by general formula (VIII-a) or general formula (IX-a).
General formula (VIII-a)

(Wherein R ⁶¹ and R ⁶² each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and Two or more methylene groups may be substituted with oxygen atoms, assuming that the oxygen atoms are not directly bonded to each other,
C ⁶¹ , C ⁶² and C ⁶³ each independently represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and the 1,4-phenylene group is unsubstituted or one or a substituent It can have two or more fluorine atoms, chlorine atoms, methyl groups or trifluoromethyl groups or trifluoromethoxy groups,
Z ⁶¹ and Z ⁶² each independently represent a single bond or —CH ₂ CH ₂ —;
n ⁶¹ represents 0, 1 or 2. However, when n ⁶¹ = 2, a plurality of C ⁶¹ and Z ⁶¹ may be the same or different. )
In General Formula (VIII-a), R ⁶¹ and R ⁶² are each an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 6 carbon atoms (one or 2 present in the alkyl group or alkenyl group). More than one methylene group may be substituted with an oxygen atom so that oxygen atoms are not directly bonded to each other. The alkenyl group is preferably a group represented by the formula (Vc), and a carbon atom Even more preferred are alkyl groups or alkoxy groups of the number 1-5.
In particular, when it is desired to obtain a low viscosity, it is preferable that n ⁶¹ is 0, C ⁶² and C ⁶³ are 1,4-cyclohexylene groups, and Z ⁶² is a single bond.
In particular, to expand the liquid crystal temperature range, n ⁶¹ is 0 or 1, C ⁶¹ and C ⁶² are 1,4-cyclohexylene groups, and C ⁶³ is a 1,4-phenylene group (the 1,4 The -phenylene group is unsubstituted or can have one or more fluorine atoms or methyl groups as substituents), and Z ⁶¹ is a single bond or —CH ₂ CH ₂ —; Z ⁶² is preferably a single bond,
In order to obtain a particularly high refractive index, n ⁶¹ is 1 and C ⁶¹ is 1,4-cyclohexylene group or 1,4-phenylene group (the 1,4-phenylene group is unsubstituted or substituted). 1 or 2 or more fluorine atoms or a methyl group as a group), and C ⁶² and C ⁶³ are 1,4-phenylene groups (is the 1,4-phenylene group unsubstituted)? Alternatively, it may have one or two or more fluorine atoms or methyl groups as a substituent.
Specifically, compounds represented by general formula (VIII-1) to general formula (VIII-5) are preferable.

(Wherein R ¹² and R ¹³ are each independently an alkyl group having 1 to 5 carbon atoms, (one or two or more CH ₂ groups present in the alkyl group have oxygen atoms directly And may be substituted with an oxygen atom as a non-bonded group.), And X ²¹ to X ²⁶ each independently represents a hydrogen atom, a fluorine atom or a methyl group.)
Formula (IX-a)

(Wherein R ⁷¹ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one or more methylene groups present in the alkyl group or alkenyl group are As oxygen atoms that are not directly bonded to each other, they may be substituted with oxygen atoms,
C ⁷¹ , C ⁷² and C ⁷³ each independently represents a 1,4-phenylene group, a 1,4-cyclohexylene group or an indan-2,5-diyl group, and the 1,4-phenylene group, indan-2 , 5-diyl groups can be unsubstituted or have one or more fluorine, chlorine, methyl, trifluoromethyl or trifluoromethoxy groups as substituents;
Z ⁷¹ and Z ⁷² each independently represent a single bond, —CH ₂ CH ₂ — or —CF ₂ O—,
^X71 represents a fluorine atom, a chlorine atom, a trifluoromethyl group or a trifluoromethoxy group, a difluoromethyl group, an isocyanate group,
n ⁷¹ represents 0, 1 or 2. However, when n ⁷¹ = 2, a plurality of C ⁷¹ and Z ⁷¹ may be the same or different. )
R ^{71 in the} general formula (IX-a) is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 6 carbon atoms (one or two or more present in the alkyl group or alkenyl group). The methylene group may be substituted with an oxygen atom, assuming that oxygen atoms are not directly bonded to each other.), And the alkenyl group is preferably represented by the formula (Vc). Even more preferred are 5 alkyl groups or alkoxy groups of 1 to 5 carbon atoms.
X ⁷¹ is preferably a fluorine atom or a trifluoromethoxy group, and more preferably a fluorine atom.
In particular, when it is desired to obtain a high dielectric constant, n ⁷¹ is 0 or 1, C ⁷¹ is a 1,4-cyclohexylene group, C ⁷² is a 1,4-cyclohexylene group, or 1, A 4-phenylene group (the 1,4-phenylene group is unsubstituted or may have one or more fluorine atoms or a methyl group as a substituent), and C ⁷³ is 2-fluoro A 1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 2,6-difluoro-1,4-phenylene group or a 3,5-difluoro-1,4-phenylene group, Z ⁷¹ and Z ⁷² is preferably a single bond.
In particular, to expand the liquid crystal temperature range, n ⁷¹ is 2, C ⁷¹ is a 1,4-cyclohexylene group, and C ⁷² is a 1,4-cyclohexylene group or a 1,4-phenylene group. And C ⁷³ is 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,6-difluoro-1,4-phenylene group or 3,5-difluoro-1,4 - phenylene ^{group, Z 71} and ^{Z 72} is a single bond or _-CH 2 CH ₂ - is preferably.
Specifically, compounds represented by general formula (IX-1) to general formula (IX-4) are preferable.

(Wherein R ¹⁴ represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group, X ³¹ to X ³⁴ represent a hydrogen atom or a fluorine atom, Z ¹¹ represents a single bond, or —CH ₂ CH ₂ —. To express.)
Among these general formulas (IX-1) to (IX-4), compounds represented by general formula (IX-5) to general formula (IX-8) are more preferable.

(In the formula, R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms, and X ³⁵ to X ³⁷ each independently represents a hydrogen atom or a fluorine atom.)
These liquid crystal compositions may be subjected to a purification treatment with silica, alumina or the like for the purpose of removing impurities or the like or further increasing the specific resistance value. The specific resistance value is preferably 10 ¹² Ω · cm or more, and more preferably 10 ¹³ Ω · cm or more.
Furthermore, dopants such as chiral compounds and dyes can be added to the liquid crystal composition according to the purpose.

  As a polymerization method for polymerizing the composition for a polymer-stabilized liquid crystal display element of the present invention, radical polymerization, anion polymerization, cationic polymerization, and the like can be used, but polymerization is preferably performed by radical polymerization.

As the radical polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used, but a photopolymerization initiator is preferable. Specifically, the following compounds are preferable.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 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- Acetophenone series such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone;
Benzoins such as benzoin, benzoin isopropyl ether and benzoin isobutyl ether; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzyl and methylphenylglyoxyesters;
Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4' -Benzophenone series such as tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone;
Thioxanthone systems such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone;
Aminobenzophenone series such as Michler's ketone and 4,4′-diethylaminobenzophenone;
10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like are preferable.
Of these, benzyldimethyl ketal is most preferred.

General formula (II-a) is general formula (IV-a), general formula (Va) and general formula (Vb), general formula (VI-a) and general formula (VI-b), A compound containing 93 to 99.9% by mass of a liquid crystal composition containing a compound represented by the formula (VIII-a) and the general formula (IX-a), and a compound represented by the general formula (Ia) Containing 0.1 to 7% of the polymerizable composition, preferably containing 0.1 to 2% by weight of the polymerization initiator, containing 93 to 99.9% by weight of the liquid crystal composition, More preferably, the content is 22 to 36% by mass, and the polymerization initiator is 0.1 to 2% by mass. As the liquid crystal composition, the content of the compound represented by the general formula (IV-a) is 5 to 90%, the general formula (Va), the general formula (Vb), and the general formula (VI-a). And the content of the compound group represented by the general formula (VI-b) is preferably 5 to 70%, the content of the compound represented by the general formula (IV-a) is 10 to 80%, What has the content rate of the compound group represented by general formula (Va) and general formula (Vb), general formula (VI-a), and general formula (VI-b) being 10 to 50%. More preferred.

In addition, antioxidants, UV absorbers, non-reactive oligomers and inorganic fillers, organic fillers, polymerization inhibitors, antifoaming agents, leveling agents, plasticizers, silane coupling agents, etc. are added as necessary. You may do it.
The polyfunctional liquid crystalline monomer used in the present invention includes, as a polymerizable functional group, acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, epoxy group, vinyl group, vinyloxy group, ethynyl group, mercapto group, maleimide. _{group, ClCH = CHCONH-, CH 2 =} CCl-, CHCl = CH-, RCH = CHCOO- (R is chlorine, fluorine, or a hydrocarbon group having 1 to 10 carbon atoms) but may be mentioned, these Among them, acryloyloxy group, methacryloyloxy group, epoxy group, mercapto group, and vinyloxy group are preferable, methacryloyloxy group and acryloyloxy group are particularly preferable, and acryloyloxy group is most preferable. As the molecular structure of the polyfunctional liquid crystalline monomer, there are at least two liquid crystal skeletons having two or more ring structures, a polymerizable functional group, and a flexible group for connecting the liquid crystal skeleton and the polymerizable functional group. Those having three flexible groups are more preferable. Examples of the flexible group include an alkylene spacer group represented by — (CH ₂ ) _n — (n represents an integer) and — (Si (CH ₃ ) ₂ —O) _n — (n represents an integer). And an alkylene spacer group is preferable. Bonds such as —O—, —COO—, and —CO— may be present in the bonding portion between these flexible groups and the liquid crystal skeleton or polymerizable functional group.

The liquid crystal skeleton can be used without particular limitation as long as it is generally recognized as a liquid crystal skeleton (mesogen) in this technical field, but those having at least two or more ring structures are preferable. Rings that can be used as the ring structure are benzene, pyridine, pyrazine, pyridazine, pyrimidine, 1,2,4-triazine, 1,3,5-triazine, tetrazine, dihydrooxazine, cyclohexane, cyclohexene, cyclohexadiene, cyclohexanone, piperidine , Piperazine, tetrahydropyran, dioxane, tetrahydrothiopyran, dithiane, oxathiane, dioxaborinane, naphthalene, dioxanaphthalene, tetrahydronaphthalene, quinoline, coumarin, quinoxaline, decahydronaphthalene, indane, benzoxazole, benzothiazole, phenanthrene, dihydrophenance Len, perhydrophenanthrene, dioxaperhydrophenanthrene, fluorene, fluorenone, cycloheptane, cycloheptatrienone Examples include cholesterol, bicyclo [2.2.2] octane, bicyclo [2.2.2] octene, 1,5-dioxaspiro (5.5) undecane, 1,5-dithiaspiro (5.5) undecane, triphenylene, torquesen, porphyrin, and phthalocyanine. Among these, benzene, cyclohexane, phenanthrene, naphthalene, tetrahydronephthalene, and decahydronephthalene are preferable. One or more of these rings may be substituted with an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom. As the alkyl group, a methyl group, an ethyl group, an n-propyl group, and an n-butyl group are desirable, and a methyl group and an ethyl group are particularly preferable. As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable. As an alkanoyl group, an acetyl group, a propionyl group, and a butyroyl group are preferable. As a halogen atom, a fluorine atom, a bromine atom, and a chlorine atom are preferable. A fluorine atom and a chlorine atom are particularly preferable. In addition to the polyfunctional liquid crystalline monomer, a monofunctional liquid crystalline monomer may be added.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these examples. In the following examples and comparative examples, “%” means “% by mass” unless otherwise specified.

(Evaluation method for polymer-stabilized liquid crystal display elements)
The polymer dispersion type liquid crystal display elements in the examples were produced by the following method.
A light control layer forming material comprising a liquid crystal composition, a radical polymerizable composition, a photopolymerization initiator and a small amount of a polymerization inhibitor was injected into a glass cell with ITO having a cell gap of 4 μm by a vacuum injection method. The degree of vacuum was set to 2 Pascals. After the injection, the glass cell was taken out, the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond), and then in a nematic phase state at 25 ° C., through a UV cut filter L-37 (manufactured by Hoya Candeo Optronics). A metal halide lamp adjusted to have a surface irradiation intensity of 5 mW / cm ² was irradiated for 300 seconds to obtain a polymer component-stabilized liquid crystal display element.
Abbreviations and meanings of characteristics of the polymer dispersed liquid crystal display elements shown in the examples are as follows.
An AC voltage of 60 Hz is applied to the polymer dispersed liquid crystal display element in an indoor environment of 25 ° C. or a low temperature environment of −20 ° C. The applied voltage is increased stepwise from no application to 5 V under the conditions of 0.2 V / step and 3 seconds / step. When the applied voltage reaches 15 V, this time the applied voltage is lowered to no application under the condition of 0.2 V step and 3 seconds / step. The following characteristic values are defined from the relationship between the applied voltage and the light transmittance when this operation is performed.
T100: Light transmittance (%) when no voltage is applied.
T0: Light transmittance (%) when the light transmittance change with increasing applied voltage reaches saturation and the light transmittance stops changing.
T90: Light transmittance (%) defined by T0 + 0.9 × (T100−T0).
V0: Applied voltage (V) at T0.
Vth: Applied voltage (V) at the transmittance of T90 when the applied voltage is increased from no application.
Voltage holding ratio (VHR): An ideal waveform when there is no voltage drop at a pulse width of 64μsec, a frame period of 200msec, and an applied voltage of 5V, measured using a liquid crystal voltage holding ratio measurement system VHR-A1 (manufactured by Toyo Technica) And area ratio (%).
(Evaluation of glass transition temperature of polymer)
2% of photopolymerization initiator is added to a polymer precursor containing a small amount of a polymerization inhibitor and injected into a glass cell with ITO having a cell gap of 4 μm by a vacuum injection method. A polymer thin film was formed. Connect this cell to an impedance analyzer (1260A) manufactured by Solartron in the United Kingdom via an amplifier and an attenuator, and measure the impedance of a 10Vp-p 1kHz sine wave in the range of 25 ° C to -120 ° C. The dielectric loss factor was obtained from the measurement data. The temperature showing the peak value from the temperature curve of the dielectric loss factor was defined as the glass transition temperature.

Example 1
After forming a polyimide film “SE-7992” (manufactured by Nissan Chemical Co., Ltd.) with a thickness of about 0.03 μm on a glass substrate with an ITO transparent electrode layer, a rubbing treatment was performed to obtain a glass substrate with a polyimide alignment film. The two glass substrate with polyimide alignment film thus obtained were opposed to each other with an interval of 4 μm so that the surface on which the alignment film was formed was on the inner side to form a twist alignment liquid crystal cell. Polymer stabilization with 97 wt% of liquid crystal composition (A), 2.9 wt% of polymer precursor (M-1), and 0.1 wt% of photopolymerization initiator “Irgacure 651” (manufactured by Ciba Specialty Chemicals) For the purpose of adjusting the liquid crystal composition and increasing the specific resistance value by removing impurities and the like, purification treatment with silica was performed to obtain a specific resistance value of 7 × 10 ¹² Ω · cm. The liquid crystal phase was vacuum-injected into the liquid crystal cell. A UV-curable sealing agent was applied to the inlet and a polymer-stabilized liquid crystal device was obtained by the method described above. When the liquid crystal alignment was observed with a polarizing microscope, it was confirmed that the alignment was twisted and there were no alignment defects. When driving characteristics were evaluated by applying a voltage, it was confirmed that Vth operates at 2.13 Vrms. Next, the composition was injected into a liquid crystal cell similar to that described above, and UV exposure was performed under the above-described conditions while applying a voltage of 10 V to obtain a polymer-stabilized liquid crystal element. When the alignment was observed with a polarizing microscope without applying voltage, it was confirmed that the alignment was homeotropic in the dark field, and that the initial alignment of the liquid crystal was stabilized. When this device was allowed to stand at 90 ° C. for 1 hour and the alignment of the liquid crystal was observed with a polarizing microscope, the initial alignment was maintained in the homeotropic alignment. The voltage holding ratio was measured and found to be 99.1%. The glass transition temperature Tg of the polymer thin film of the polymer precursor (M-1) used was −30 ° C.

（実施例２）
ITO透明電極層付きのガラス基板に、みゅポリイミド膜「SE-7992」(日産化学製)を約0.03μmの厚さで形成した後、ラビング処理を施してポリイミド配向膜付きガラス基板を得た。このようにして得た２枚のポリイミド配向膜付きガラス基板を、配向膜が形成された面が内側になるようにして４μmの間隔をもって対向させて捩れ配向液晶セルを作成した。液晶組成物（A）が９７ｗｔ％、高分子前駆体M-２を２．９ｗｔ％、光重合開始剤「イルガキュアー651」(チバスペシャリティケミカルズ製)を０．１ｗｔ％の高分子安定化液晶組成物を調整し、液晶相の状態で上記液晶セルへ真空注入した。注入口に紫外線硬化型の封口剤を塗布して前述の方法で高分子安定化液晶素子を得た。偏光顕微鏡で液晶配向を観察したところ、捩れ配向であり、配向欠陥が無いことを確認した。電圧を印加して駆動特性を評価したところ、Vthは、２．３７Vｒｍｓで動作することを確認した。次に、上述と同様の液晶セルに組成物の注入を行い、電圧１０V印加しながら前述の条件でUV露光を行い高分子安定化液晶素子が得られた。電圧を無印加で、偏光顕微鏡で配向を観察すると暗視野でホメオトロピック配向であり、液晶の初期配向が高分子安定化されたことが確認された。この素子を９０℃、１時間放置して偏光顕微鏡で液晶の配向を観察したところホメオトロピック配向で初期配向が保持されていた。使用した高分子前駆体（M-2）の高分子薄膜のガラス転移温度Tgは、-5℃であった。

(Example 2)
On a glass substrate with an ITO transparent electrode layer, a Mi polyimide film “SE-7992” (Nissan Chemical) was formed to a thickness of about 0.03 μm and then rubbed to obtain a glass substrate with a polyimide alignment film. . The two glass substrate with polyimide alignment film thus obtained were opposed to each other with an interval of 4 μm so that the surface on which the alignment film was formed was on the inner side to form a twist alignment liquid crystal cell. Polymer stabilized liquid crystal composition comprising 97 wt% of liquid crystal composition (A), 2.9 wt% of polymer precursor M-2, and 0.1 wt% of photopolymerization initiator “Irgacure 651” (manufactured by Ciba Specialty Chemicals) The product was prepared and vacuum injected into the liquid crystal cell in the liquid crystal phase. A UV-curable sealing agent was applied to the inlet and a polymer-stabilized liquid crystal device was obtained by the method described above. When the liquid crystal alignment was observed with a polarizing microscope, it was confirmed that the alignment was twisted and there were no alignment defects. When the drive characteristics were evaluated by applying a voltage, it was confirmed that Vth operated at 2.37 Vrms. Next, the composition was injected into the same liquid crystal cell as described above, and UV exposure was performed under the above-mentioned conditions while applying a voltage of 10 V to obtain a polymer-stabilized liquid crystal element. When the voltage was not applied and the alignment was observed with a polarizing microscope, it was confirmed that the alignment was homeotropic in the dark field, and the initial alignment of the liquid crystal was stabilized. When this device was allowed to stand at 90 ° C. for 1 hour and the alignment of the liquid crystal was observed with a polarizing microscope, the initial alignment was maintained in the homeotropic alignment. The glass transition temperature Tg of the polymer thin film of the polymer precursor (M-2) used was −5 ° C.

（比較例１）
ITO透明電極層付きのガラス基板に、ポリイミド膜「SE-7992」(日産化学製)を約0.03μmの厚さで形成した後、ラビング処理を施してポリイミド配向膜付きガラス基板を得た。このようにして得た２枚のポリイミド配向膜 付きガラス基板を、配向膜が形成された面が内側になるようにして４μmの間隔をもって対向させて捩れ配向液晶セルを作成した。液晶組成物（A）が９７ｗｔ％、高分子前駆体M-３（新中村化学工業株式会社製NKエステル A-HD-N）を２．９ｗｔ％、光重合開始剤「イルガキュアー651」(チバスペシャリティケミカルズ製)を０．１ｗｔ％の高分子安定化液晶組成物を調整し、不純物等を除去して比抵抗値を高くする目的で、シリカによる精製処理を施して比抵抗値としては３ｘ１０^１２Ω・cmを得た。液晶相の状態で上述の液晶セルへ真空注入した。注入口に紫外線硬化型の封口剤を塗布して前述の方法で高分子安定化液晶素子を得た。偏光顕微鏡で液晶配向を観察したところ、捩れ配向であり、配向欠陥が無いことを確認した。電圧を印加して駆動特性を評価したところ、Vthは、６．３５Vｒｍｓで動作することを確認した。次に、上述と同様の液晶セルに組成物の注入を行い、電圧１０V印加しながら前述の条件でUV露光を行い高分子安定化液晶素子が得られた。電圧を無印加で、偏光顕微鏡で配向を観察すると完全な暗視野にならず十分なホメオトロピック配向が得られなかった。液晶の初期配向を高分子安定化させることができなかった。電圧保持率を測定したところ98.7％であった。使用した高分子前駆体（M-1）の高分子薄膜のガラス転移温度Tgは、104℃であった。

(Comparative Example 1)
After forming a polyimide film “SE-7992” (manufactured by Nissan Chemical Co., Ltd.) with a thickness of about 0.03 μm on a glass substrate with an ITO transparent electrode layer, a rubbing treatment was performed to obtain a glass substrate with a polyimide alignment film. The two glass substrates with a polyimide alignment film thus obtained were opposed to each other with an interval of 4 μm so that the surface on which the alignment film was formed was on the inner side to form a twisted alignment liquid crystal cell. Liquid crystal composition (A) is 97 wt%, polymer precursor M-3 (NK ester A-HD-N made by Shin-Nakamura Chemical Co., Ltd.) is 2.9 wt%, photopolymerization initiator "Irgacure 651" (Ciba For the purpose of adjusting the 0.1 wt% polymer-stabilized liquid crystal composition and increasing the specific resistance by removing impurities and the like, the specific resistance value is 3 × 10 ^12. Ω · cm was obtained. The liquid crystal phase was vacuum-injected into the liquid crystal cell. A UV-curable sealing agent was applied to the inlet and a polymer-stabilized liquid crystal device was obtained by the method described above. When the liquid crystal alignment was observed with a polarizing microscope, it was confirmed that the alignment was twisted and there were no alignment defects. When the drive characteristics were evaluated by applying a voltage, it was confirmed that Vth operated at 6.35 Vrms. Next, the composition was injected into the same liquid crystal cell as described above, and UV exposure was performed under the above-mentioned conditions while applying a voltage of 10 V to obtain a polymer-stabilized liquid crystal element. When no voltage was applied and the alignment was observed with a polarizing microscope, a complete dark field was not obtained and sufficient homeotropic alignment could not be obtained. The initial alignment of the liquid crystal could not be stabilized. The voltage holding ratio was measured and found to be 98.7%. The glass transition temperature Tg of the polymer thin film of the polymer precursor (M-1) used was 104 ° C.

Claims (4)

General formula (Ia)

(In the formula, A ¹ and A ⁹ each independently represent a hydrogen atom or a methyl group; A ² and A ⁸ each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms; One or more methylene groups present therein may be each independently substituted with an oxygen atom, —CO—, —COO— or —OCO— as those in which oxygen atoms are not directly bonded to each other, One or two or more hydrogen atoms present in the alkylene group may be each independently substituted with a fluorine atom, a methyl group, or an ethyl group, and A ³ and A ⁶ are each independently 2 carbon atoms. To 20 straight chain alkyl groups, and one or more methylene groups present in the alkyl group are each independently an oxygen atom, —CO—, —COO on the assumption that oxygen atoms are not directly bonded to each other. Or it may be substituted with -OCO-, A ⁴ and A ⁷ each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, one or two present in the alkyl group The above methylene groups may be each independently substituted with an oxygen atom, —CO—, —COO— or —OCO— as those in which oxygen atoms are not directly bonded to each other, Two or more hydrogen atoms may be each independently substituted with a halogen atom or an alkyl group having 1 to 9 carbon atoms, and A ⁵ represents an alkylene group having 9 to 16 carbon atoms, One of the hydrogen atoms of at least 1 to 5 methylene groups present is independently substituted with a linear or branched alkyl group having 1 to 10 carbon atoms, and is present in the alkylene group. 1 or 2 or more methylene groups may be each independently substituted with an oxygen atom, —CO—, —COO—, or —OCO— as those in which oxygen atoms are not directly bonded to each other. And a compound having a glass transition temperature of −100 ° C. to 25 ° C. of the polymerized product of the compound, the content is in the range of 0.01% to 10%, and the general formula ( II-a)

(Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one or more methylene groups present in the alkyl group or alkenyl group are: As oxygen atoms that are not directly bonded to each other, they may be substituted with oxygen atoms,
C ¹ represents a 1,4-phenylene group, a 1,4-cyclohexylene group or a 1,3-dioxane-2,5-diyl group, and the 1,4-phenylene group is unsubstituted or substituted. As one or more fluorine atoms, chlorine atoms, methyl groups or trifluoromethyl groups or trifluoromethoxy groups,
C ² and C ³ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6 -Represents a diyl group, a 2,6-naphthylene group, or an indan-2,5-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, indan-2,5-diyl group is unsubstituted or has one or more fluorine, chlorine, methyl, trifluoromethyl or trifluoromethoxy groups as substituents Can have
Z ¹ and Z ² each independently represents a single bond, —CH ₂ CH ₂ —, —C≡C—, —CF ₂ O—, —COO—, or —OCO—,
X ¹ represents the same meaning as a fluorine atom, a chlorine atom, a trifluoromethyl group, a trifluoromethoxy group, a difluoromethyl group, an isocyanate group, a cyano group or R ¹ ;
n ¹ represents 0, 1 or 2. However, when n ¹ represents 2, a plurality of C ¹ and Z ¹ may be the same or different. ), A polymer-stabilized liquid crystal liquid crystal composition having a content of at least 90%. The polymer-stabilized liquid crystal composition according to claim 1, wherein the polymerized polymer of the polymerizable compound has a glass transition temperature of -100 ° C to 0 ° C. 3. The polymer-stabilized liquid crystal composition according to claim 1, which contains a liquid crystal acrylate monomer and has a content of 0.1% to 5%. A polymer-stabilized liquid crystal display element in which a low-molecular liquid crystal is fixed by forming a three-dimensional network polymer chain in a liquid crystal phase, wherein the high-molecular chain and the low-molecular liquid crystal are defined in claims 1 to 3. A polymer-stabilized liquid crystal display element, wherein the polymer-stabilized liquid crystal composition according to any one of the above is formed by polymerized phase separation by ultraviolet exposure.