JP6501134B2 - Liquid crystal display device - Google Patents

Description

  The present invention relates to a liquid crystal display device.

  Due to the excellent display quality, active matrix liquid crystal display devices are put on the market in portable terminals, liquid crystal televisions, projectors, computers and the like. In the active matrix display method, TFT (thin film transistor) or MIM (metal insulator metal) is used for each pixel, and in combination with a liquid crystal composition having a high voltage holding ratio, TN type (twisted nematic) is used. It is widely used as a general liquid crystal display element to be described at the beginning. Also, in order to obtain wider viewing angle characteristics, VA (vertical alignment: vertical alignment), IPS (In Plane Switching), FFS (Fringe Field Switching) which is an improved version of IPS, etc. are used. In order to cope with such display devices, proposals for new liquid crystal compounds or liquid crystal compositions are currently being made.

On the other hand, since the liquid crystal display element is not a self-luminous type, a light source for emitting light is essential, and a white light source having an emission spectrum in a color reproduction region required as a display is used. As a light source, a cold cathode tube, a white LED (light emitting diode) or the like is used, but from the viewpoint of luminous efficiency, it has become mainstream to use a white LED at present. LEDs can not currently cover the entire visible light range from 380 nm to 750 nm with one element, and several types are known to obtain white light.
1) Combination of blue LED and yellow phosphor 2) Combination of three primary color LEDs (red, green and blue) 3) Combination of near-ultraviolet or purple LED and red, green and blue phosphor From the viewpoint of obtaining white light optimum as a light source of the liquid crystal display device, 3) is the most excellent, 2) and 1) in that order, and 1) is the most excellent in terms of luminous efficiency.

  In liquid crystal display elements, it is important to reduce power consumption, and in order to respond to the power saving program under consideration by developed countries, the light emission efficiency of the light source is emphasized. Therefore, at present, white light is obtained by the combination of the blue LED and the yellow phosphor in 1).

  Although this system is excellent in luminous efficiency, it is inferior in characteristics as a white light source such as a shortage of red light, and has a problem in color reproducibility. In particular, since a liquid crystal display element uses a color filter in combination with a liquid crystal element to realize color display, it is difficult to improve color reproducibility even if the light source portion is improved. Therefore, to improve color reproducibility It has been necessary to increase the color purity by increasing the pigment concentration in the color filter or increasing the thickness of the colored film. However, in this case, there is a problem that the transmittance decreases and the light amount has to be increased, resulting in an increase in power consumption.

  Then, the quantum dot technology (refer to patent documents 1) which is an example of the nanocrystal for light emission attracts attention as a technology for solving the color reproducibility and luminous efficiency of a liquid crystal display element simultaneously. The quantum dots are made of semiconductor microcrystals having particle diameters of several nm to several tens of nm, and energy levels are discretely present due to the confinement effect of electron-hole pairs, and the energy band gap increases as the particle size decreases. Have. By applying this property and controlling the particle diameter to make the band gap uniform, it is possible to obtain a light source with a small half width of the emission spectrum. It is disclosed that a liquid crystal display element with improved color reproducibility can be configured by using quantum dots as a component of a backlight since a wide color gamut display can be realized by obtaining a light source of three primary colors with a small half width. (See Patent Document 2 and Non-Patent Document 1). Furthermore, it has been proposed to use three-color quantum dots as a light source instead of a conventional color filter using short-wavelength visible light such as near-ultraviolet light or blue light (see Patent Document 3). These display elements are, in principle, compatible with high luminous efficiency and color reproducibility.

JP 2001-523758 WO 2004/074739 pamphlet U.S. Pat. No. 8648524 International Publication 2014/045371 Brochure

SID 2012 DIGEST, p 895-896

  However, as described above, when a white light source of a liquid crystal display element is obtained by using a quantum dot which is an example of a light emitting nanocrystal interposed in a light emitting element, as described in FIG. The light from the light source using the light emitting element with the quantum dots interposed therebetween has a smaller half width of each of the three primary colors of red (R), green (G) and blue (B), and the light corresponding to the quantum dot Have a wavelength of Therefore, the emission spectrum is significantly different from common white LEDs (e.g., 1) to 3) described above. As a result, the liquid crystal material used as the light shutter is irradiated with light from the light emitting nanocrystal or light from the light emitting nanocrystal, causing problems such as easy decomposition of the liquid crystal material itself. . For example, Patent Document 4 discloses a technology for optimizing a liquid crystal composition used in a liquid crystal display device using a general white light source and a color filter containing three primary colors, but it is possible to use quantum dots etc. There is no disclosure about maintaining the reliability of the liquid crystal material when light emitting nanocrystals are used as a light source.

  In particular, when a white light source is obtained through light emitting nanocrystals such as quantum dots, if the light emitting nanocrystals deteriorate with time and the light emitting nanocrystals deteriorate due to the external environment, the visible light of the short wavelength used for the light source High energy rays including light rays and ultraviolet rays are less likely to be absorbed by the light emitting nanocrystals, and the liquid crystal layer is directly irradiated with high energy rays for a long time. This causes problems such as the liquid crystal material constituting the liquid crystal layer being easily decomposed. In addition, there is a problem that high energy rays are exposed to a specific region (spot) due to local absence of luminescent nanocrystals, or in the case where the surface of the liquid crystal panel is covered with a film containing luminescent nanocrystals There is a problem that the high energy ray from the periphery of the extension of the panel leaks, so that the liquid crystal is deteriorated from the portion where the high energy ray leaks. In particular, a portion of deterioration is likely to occur partially at the spot or at the edge of the screen, and the partial deterioration is likely to be noticed unlike the overall deterioration. Therefore, the problem to be solved by the present invention is to suppress deterioration of the light emitting nanocrystals due to the deterioration of the light emitting nanocrystals or the partial deterioration of the liquid crystal layer due to the irradiation spot of high energy rays in the liquid crystal display element having the light emitting nanocrystals as the light emitting portion To prevent.

  As a result of intensive studies to solve the above problems, the present inventors have provided a liquid crystal layer containing a liquid crystal composition containing a specific liquid crystal compound in a polymer network, and a light source via a light emitting nanocrystal. It has been found that the above-mentioned problems can be solved by using the element, and the present invention has been completed.

That is, according to the present invention, there is provided a pair of substrates provided with the first substrate and the second substrate facing each other,
A liquid crystal layer sandwiched between the first substrate and the second substrate;
A pixel electrode provided on at least one of the first substrate and the second substrate;
A common electrode provided on at least one of the first substrate and the second substrate;
A color filter composed of three primary color pixel portions of black matrix and red (R), green (G), and blue (B);
A light emitting element that emits ultraviolet or visible light;
A light conversion unit containing a light emitting nanocrystal that emits light by converting incident light from the light emitting element into light of at least one of red (R), green (G), and blue (B);
The liquid crystal layer is a polymer network (A),
The following general formula (i):

(Wherein, R ⁱ¹ and R ⁱ² are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms 8 represents an alkenyloxy group, A ⁱ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and n ⁱ¹ represents 0 or 1. 10 to 50% of a compound represented by The present invention relates to a liquid crystal display element characterized by containing a liquid crystal composition (B) containing%.

  According to the present invention, in a liquid crystal display element having a light emitting nanocrystal as a light emitting portion, it is possible to suppress or prevent the deterioration of the light emitting nanocrystal or the partial deterioration of the liquid crystal layer due to the irradiation spot of high energy light.

FIG. 1 is a perspective view showing an embodiment of the liquid crystal display element of the present invention. FIG. 2 is a perspective view showing another embodiment of the liquid crystal display element of the present invention. FIG. 3 is a schematic view of a cross section obtained by cutting the liquid crystal display element in the direction of the line I-I in FIG. 1, and is an example for showing the configuration of the liquid crystal display element used in this embodiment. FIG. 4 is a diagram showing an example of the configuration of the light conversion unit 103 according to the present invention. FIG. 5 is a schematic view showing an example of a light conversion unit (in particular, a backlight unit) according to the present invention. FIG. 6 is a view showing another embodiment of the preferred backlight according to the present invention. FIG. 7 is a schematic view of a cross section obtained by cutting the liquid crystal display element in the direction of the line I-I in FIG. 1, and is an example for showing the configuration of the liquid crystal display element used in this embodiment. FIG. 8 is a schematic view of a cross section obtained by cutting the liquid crystal display element in the direction of the line I-I in FIG. 1, and is an example for showing the configuration of the liquid crystal display element used in this embodiment. FIG. 9 is a schematic view of a cross section obtained by cutting the liquid crystal display element in the direction of the line II in FIG. 2, and is an example for showing the configuration of the liquid crystal display element used in this embodiment. FIG. 10 is a schematic view of a cross section obtained by cutting the liquid crystal display element in the direction of the line I-I in FIG. 2, and is an example for showing the configuration of the liquid crystal display element used in this embodiment. FIG. 11 is a schematic view showing a pixel portion of the liquid crystal display element of the present invention as an equivalent circuit. FIG. 12 is a schematic view showing an example of the shape of the pixel electrode of the present invention. FIG. 13 is a schematic view showing an example of the shape of the pixel electrode of the present invention. FIG. 14 is a schematic view showing an electrode structure of the IPS type liquid crystal display element of the present invention. FIG. 15 is one of the examples of the cross-sectional view which cut | disconnected the liquid crystal display element shown in FIG. 1 in the III-III line direction in FIG. 12 or FIG. FIG. 16 is a cross-sectional view of an IPS-type liquid crystal panel cut in the direction of the line III-III in FIG. FIG. 17 is an enlarged plan view of a region surrounded by a line II of the electrode layer 3 including the thin film transistor formed on the substrate in FIG. FIG. 18 is a cross-sectional view of the liquid crystal display element shown in FIG. 2 taken along the line III-III in FIG. FIG. 19 is a diagram showing an emission spectrum of a quantum dot. FIG. 20 is a schematic view of an electrode structure of a fishbone type VA liquid crystal cell in an example.

According to the present invention, as described above, a pair of substrates provided with the first substrate and the second substrate facing each other, a liquid crystal layer sandwiched between the first substrate and the second substrate, and A pixel electrode provided on at least one of the first substrate and the second substrate, a common electrode provided on at least one of the first substrate or the second substrate, a black matrix, red (R), green ( G), a color filter composed of three primary color pixel portions of blue (B), a light emitting element for emitting ultraviolet light or visible light, and incident light from the light emitting element is red (R), green (G), blue ( And B) a light conversion portion containing a light emitting nanocrystal that emits light by converting it into light of at least one color,
The liquid crystal layer comprises a polymer network (A) and a compound represented by the general formula (i):

(Wherein, R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms 8 represents an alkenyloxy group, A represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and n represents 0 or 1. 10 to 50% by weight of a compound represented by The liquid crystal display device is characterized by containing the liquid crystal composition (B).

  In the present invention, the color reproduction region is enlarged compared to the conventional liquid crystal display element by providing the light conversion portion having the light emitting nanocrystal, and the display defect due to the deterioration of the light emitting nanocrystal or partial high energy light irradiation spot To provide a liquid crystal display device with reduced

  After the basic structure of a preferred liquid crystal display device according to the present invention is described below with reference to the drawings, each component of the liquid crystal display device will be described.

  FIG. 1 is a perspective view showing the whole of an example of the liquid crystal display element used in the present embodiment, and for convenience of explanation, the respective constituent elements are described separately for convenience.

  The liquid crystal display element 1000 according to the present invention includes the backlight unit 100 and the liquid crystal panel 10. The said backlight unit 100 has the light source part 101 which has the light emitting element L, and the light guide part 102 which has a light-guide plate (not shown). In addition, a light conversion unit 103 that converts incident light from the light emitting element L and emits light is provided as a part of the light source unit 101 or the light guide unit 102. Therefore, for convenience, in FIG. 1, the light conversion unit 103 is provided as a part of the light source unit 101 as the light source unit 101 (103), and the light conversion unit 103 is provided as a part of the light guiding unit 102. As a case, the light guiding unit 102 (103) is shown (the same applies to FIG. 2).

  Moreover, in FIG. 1, 2, the light from the light source part 101 which has the light emitting element L and the light from the liquid crystal panel 10 are represented by the arrow.

  As shown in FIG. 1, in one form of the backlight 100, the light source unit 101 including a plurality of light emitting elements L is disposed on one side of the light guiding unit 102, and in FIG. The liquid crystal panel 10 is arranged in a line on one side. The light source unit 101 including a plurality of light emitting elements L is provided not only on one side of the liquid crystal panel 10 (one side of the light guide 102) but also on the other side of the liquid crystal panel 10 (both sides facing each other) as necessary. A light source unit 101 including a plurality of light emitting elements L may surround three sides of the light guide unit 102 or the entire periphery of the light guide unit 102 so as to surround the light guide unit 102. As such, it may be provided on four sides. Note that the light guide portion 102 may include a light diffusion plate (not shown) instead of the light guide plate as needed.

  In the liquid crystal panel 10, a first substrate 2 and a second substrate 7 are held between a pair of polarizing plates 1 and 8, and a first (transparent insulating) substrate (also referred to as a transparent substrate) disposed opposite to each other. 2) and a second (transparent insulating) substrate 7 having a liquid crystal composition (or liquid crystal layer 5), and the first (transparent insulating) substrate 2 is on the liquid crystal layer 5 side. The electrode layer 3 is formed on the surface. In addition, an alignment layer 4 is provided between the liquid crystal layer 5 and each of the first (transparent insulating) substrate 2 and the second (transparent insulating) substrate 7. Furthermore, in FIG. 1 and FIG. 2, a color filter 6 is provided between the second substrate 7 and the alignment layer 4.

  Although in FIG. 1 the pixel electrode (not shown) and the common electrode (not shown) are provided as the electrode layer 3 on the first substrate 2 side, in another embodiment, the pixel electrode is not The common electrode may be provided on one substrate 2 and the common electrode may be provided on the second substrate 7.

  Further, the liquid crystal molecules in the liquid crystal composition can be aligned in a predetermined direction with respect to the recording substrates 2 and 7 when no voltage is applied by the alignment layer 4.

  Although the form which clamped the said 1st board | substrate 2 and the said 2nd board | substrate 7 with a pair of polarizing plates 1 and 8 is described in FIG.1 and FIG.2, the position which provides the polarizing plates 1 and 8 is this figure. It is not limited to. Furthermore, in FIG. 1 and FIG. 2, the color filter 6 is provided between the second substrate 7 and the alignment layer 4, but as another embodiment of the liquid crystal display element according to the present invention, A filter on array (COA) may be used, and a color filter 6 may be provided between the electrode layer 3 and the liquid crystal layer 5 or a color filter may be provided between the electrode layer 3 and the first substrate 2. It is also good. In addition, if necessary, the substance contained in the color filter layer may be prevented from flowing out to the liquid crystal layer by covering the color filter layer 6 with an overcoat layer (not shown).

  Further, for the sake of convenience in the present specification, for convenience, layers formed on the substrate on the backlight unit side (electrode layer 3 and alignment layer 4 in FIG. 1) and substrate on the backlight unit side (first substrate 2) Is referred to as a first display substrate SUB1 and is formed on a substrate facing the substrate on the backlight unit side (the alignment layer 4 and the color filter 6 in FIG. 1) and the substrate on the backlight unit side The opposing substrate (the second substrate 7) is referred to as a second display substrate SUB2, and according to the embodiment, it faces the layer formed on the backlight unit substrate and the substrate on the backlight unit side. What constitutes the layer formed on the substrate may be different. For example, in the embodiment of the liquid crystal display element according to the present invention shown in FIG. 2, the layer provided on the second substrate side of the second display substrate SUB2 is a second electrode layer 3 '(for example, common electrode) Is provided.

  Furthermore, in the present invention, the alignment layer 4 may be formed on at least one of the first substrate 2 or the second substrate 7. However, as shown in FIGS. An alignment layer 4 is formed on the first substrate and the second substrate so as to be in contact with the liquid crystal layer 5 between the substrate 2 and between the liquid crystal layer 5 and the second substrate 7. Is preferred.

  That is, a liquid crystal panel 1000 according to the present invention includes a first polarizing plate 1, a first substrate 2, an electrode layer 3, an alignment layer 4, a liquid crystal layer 5 containing a liquid crystal composition, and an alignment layer 4. It is preferable that the color filter 6, the second substrate 7, and the second polarizing plate 8 be sequentially laminated.

  In FIG. 1, when the light conversion unit 103 that converts incident light from the light emitting element L and emits light is provided in the light source unit 101, light emitted from the light source unit 101 is converted by the light conversion unit 103. The light emitted from the light source unit 101 is transmitted through the surface of the liquid crystal panel 10 through the light guide unit 102 (for example, a light guide plate).

  On the other hand, when the light conversion unit 103 is provided in the light guide unit 102, the light emitted from the light emitting element L is converted by the light conversion unit 103, and then the light guide plate in the light guide unit 102 is The converted light passes through the surface of the liquid crystal panel 10, or the light emitted from the light emitting element L is converted by the light conversion unit 103 after passing through the light guide plate in the light guide unit 102. Light is transmitted through the surface of the liquid crystal panel 10.

  Under the present circumstances, the shape of the said light-guide plate is a flat body provided with the side which decreases in thickness gradually toward the opposing surface from the side which light emitted from the light emitting element L enters (a form of the side is a tapered shape In the case of a plate, it is possible to convert line light into surface light, so that light can be easily incident into the liquid crystal panel 10. In addition, the line light emitted from the light emitting element L may be converted to surface light by a known means.

  The light guide unit 102 is preferably provided with a light diffusion plate between the liquid crystal panel 10 and the light guide plate from the viewpoint of uniformly scattering light emitted from the light guide plate.

  FIG. 2 is a perspective view showing the whole of an example of a liquid crystal display element in a form in which a plurality of light emitting elements L are arranged in a planar shape with respect to the light guide portion 102. Is described. The embodiment shown in FIG. 2 adopts a direct type backlight structure in which a light source unit 101 is provided immediately below the rear surface of the liquid crystal panel 10. In this structure, the light emitting elements L are arranged substantially equally over substantially the entire rear surface of the liquid crystal panel 10.

  Also in FIG. 2, the light guide portion 102 preferably includes a light diffusion plate between the liquid crystal panel 10 and the light guide plate (which will be described later as an embodiment).

  The liquid crystal panel 10 in FIG. 2 includes a first substrate 2 provided with a first electrode layer 3, a second substrate 7 provided with a second electrode layer 3 ′ (for example, a common electrode), and the first substrate 2. And a liquid crystal composition (or liquid crystal layer 5) sandwiched between the second substrate 7 and the second substrate 7, and the liquid crystal layer 5 is disposed between the first substrate 2 and the liquid crystal layer 5. An alignment layer 4 provided in contact with the liquid crystal layer 5 and an alignment layer 4 provided between the second substrate 7 and the liquid crystal layer 5 to be in contact with the liquid crystal layer 5 are provided. Further, a color filter 6 is provided between the second substrate 7 and the second electrode layer 3 ', and the first substrate 2 and the second substrate 8 are a pair of polarizing plates 1, It is held by eight.

  That is, in the liquid crystal display element 1000 according to the present invention, the first polarizing plate 1, the first substrate 2, the electrode layer (also referred to as thin film transistor layer) 3 including a thin film transistor, the alignment layer 4, the liquid crystal composition The liquid crystal layer 5 including the above, the alignment layer 4, the second electrode layer 3 ', the color filter 6, the first substrate 7, and the first polarizing plate 8 are sequentially stacked.

  Here, the structure of a light conversion unit used in the present invention and a backlight unit including the same will be described with reference to FIGS.

  FIG. 3 shows a liquid crystal display device having a backlight unit in which a plurality of light emitting elements L are arranged in a line on one side of the liquid crystal panel 10 and the light converting portion 103 is provided in a part of the light guiding portion 102. FIG. 2 is a cross-sectional view of the liquid crystal display element cut in the direction of the line I-I in FIG. 1, and is an example for showing the configuration of the liquid crystal display element used in the present embodiment.

  The backlight unit 100 in FIG. 3 includes a light source unit 101 having a light emitting element L attached to one side of the liquid crystal panel 10 and a light guide unit 102 connected to the light source unit 101. The light guide unit 102 includes a light conversion unit 103 and a light guide plate 104.

  Here, the light conversion unit 103 contains a light emitting nanocrystal NC that converts incident light from the light emitting element L into light of at least one of red (R), green (G), and blue (B) and emits light. Do. Therefore, in the liquid crystal display element according to the present invention, the light source unit 101 including the light emitting element L, the light conversion unit 103 and the light guide plate 104 connected to the light source unit 101, and one surface of the light guide plate 104. The first polarizing plate 1, the first display substrate SUB1, the liquid crystal layer 5, the second display substrate SUB2 and the second polarizing plate 8 are sequentially stacked. As described above, in the present embodiment, the light conversion unit 103 is provided in a part of the light guide unit 102.

  FIG. 4 is an example of the light conversion unit 103 according to the present invention. As shown in FIG. 4, the light conversion portion 103 used in the present invention is formed in the inside (hollow portion of the hollow body) of the transparent long hollow body filling container 111 (in FIG. 4, the tubular filling container 111). A light emitting nanocrystal NC is contained (or filled). If necessary, in addition to the light emitting nanocrystals NC, a fluorescent substance or an ultraviolet curable resin may be contained (or filled). Further, in FIG. 4, the shape of the surface cut perpendicular to the long axis direction of the filling container 111 is a “0” shape, but the shape of the cross section is not particularly limited.

  Although a specific method of manufacturing the light conversion unit 103 will be described in detail later, the opening portion at one end of a transparent tubular filling container 111 such as glass, quartz or acrylic is sealed, and light emitting nanocrystals NC, For example, a mixture of a quantum dot and an ultraviolet curable resin is injected into the inside of the tube 111, irradiated with ultraviolet radiation to cure the resin, and the other opening of the tube is sealed if necessary. Thus, the light conversion portion 103 in which the light emitting nanocrystals NC are sealed can be formed in the filling container 111.

  FIG. 5 shows an example of a backlight unit having a light conversion unit, and more specifically, the light source unit 101 and a light emitting nanocrystal NC inside a transparent elongated hollow body as shown in FIG. 4. It is a figure which shows the back light which uses the member (light conversion part 103) accommodated and the light-guide plate 104 as an essential component. Here, in the embodiment of FIG. 5, the light conversion unit 103 and the light guide plate 104 form the light guide unit 102.

  The light emitting element L of the light source unit 101 is a point light source. Specifically, the light source unit 101 is configured of a light emitting element L including a light emitting diode 105 (LED). For example, the light emitting diode 105 is mounted on the light source substrate 110, and is disposed opposite to the light incident surface (for example, the left side surface in FIG. 5) of the light guide plate 104. In addition, as shown in FIG. 5, a tube (light conversion unit 103) in which light emitting nanocrystals NC are accommodated is disposed between the light source unit 101 including the light emitting element L and the light guide plate 104. ing.

  In the light source unit 101, the light source substrate 110 has a long rectangular parallelepiped shape, and the light emitting elements L are arranged in a line in the longitudinal direction of the light source substrate 110 (see FIGS. 1 and 5). In addition, the light conversion unit 103 connected to the light source unit 101 is a long hollow body like the light source substrate 110, and the light emitting nanocrystals NC are accommodated inside the transparent long hollow body. Configuration. Furthermore, since the light guide plate 104 is connected to the light conversion unit 103, the light from the light source unit 101 is at least one of red (R), green (G), and blue (B) in the light conversion unit 103. And is guided to the light guide plate 104 and enters the liquid crystal panel 10. Here, a light diffusion plate may be provided between the light guide plate 104 and the first polarizing plate 1. Thus, the light passing through the light guide plate 104 is scattered and supplied as planar light to the liquid crystal panel 10, for example, the first polarizing plate 1 (see FIGS. 3 and 5). Therefore, in this case, the light guide unit 102 is configured by the light conversion unit 103, the light guide plate 104, and the light diffusion plate.

  The light emitting element L (or the light emitting diode 105) according to the present invention is not particularly limited as far as it is a wavelength range that is absorbed by the light emitting nanocrystals included in the light conversion part in the wavelength range. It is preferable to have a main emission peak. For example, a light emitting diode having a main emission peak in a wavelength range of 420 nm to 480 nm can be suitably used. The light emitting diode having a main emission peak in the blue region includes, for example, a seed layer made of AlN formed on a sapphire substrate, an underlayer formed on the seed layer, and a laminated semiconductor layer mainly composed of GaN. The thing provided with at least etc. is mentioned as an example. In addition, the laminated semiconductor layer includes a substrate (for example, one in which an underlayer, an n-type semiconductor layer, a light emitting layer, and a p-type semiconductor layer are laminated in order from the light source substrate 110 side in FIG.

  Examples of the light source of ultraviolet light include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, electrodeless lamps, metal halide lamps, xenon arc lamps, LEDs, etc. L is preferably an LED that generates ultraviolet light, as well as an LED having a main emission peak in the wavelength region of 420 nm or more and 480 nm or less described above.

  In the present invention, light having an emission center wavelength in a wavelength band of 420 to 480 nm is referred to as blue light, light having an emission center wavelength in a wavelength band of 500 to 560 nm is referred to as green light, and a wavelength band of 605 to 665 nm The light having a light emission center wavelength is called red light. Moreover, the ultraviolet light of this specification means the light which has a light emission center wavelength in the wavelength range of 300 to 420 nm. Furthermore, in the present specification, the "half width" refers to the width of the peak at a peak height of 1/2.

  The light conversion unit 103 is for converting the wavelength of the light from the light emitting element L, and includes a light emitting nanocrystal NC for converting the wavelength of the light from the light emitting element L. The light emitting nanocrystals have discrete energy levels, and the emission wavelength can be freely selected by changing the particle size of the primary particles of the nanocrystals. Therefore, the color reproduction area is expanded as compared with the light emitting device in which the conventional white LED and the fluorescent substance are combined.

  The light conversion unit 103 shown in FIGS. 4 to 6 includes a transparent hollow tube and a hollow portion of the hollow tube that absorbs light emitted from the light emitting diode 105 and emits longer wavelength light. It is preferable to include more than type, preferably two or more types of light emitting nanocrystals NC and a transparent resin containing the light emitting nanocrystals NC uniformly dispersed. In this case, the light emitting nanocrystals NC are one or more types, preferably two or more types of light emitting nanocrystals NC, which absorb light emitted by the light emitting diode 105 and emit light of longer wavelength, and light emitting nanocrystals NC. And a transparent resin containing the resin in a uniformly dispersed state. In this case, the light emitting nanocrystals NC absorb blue light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 and emit blue light. Blue light emitting nanocrystals NC emitting light, light emitted by the light emitting diode 105 (preferably Red light emitting nanocrystals NC that absorb blue light to ultraviolet light and emit green light and emit light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 Preferably containing at least one light emitting nanocrystal NC selected from the group consisting of: blue light emitting nanocrystal NC, green light emitting nanocrystal NC and red light emitting nanocrystal NC It is more preferable to include two luminescent nanocrystals NC. In particular, it is particularly preferable to include green light emitting nanocrystals NC and red light emitting nanocrystals NC that emit red light.

  Thus, the spectra of red light and green light obtained through the light conversion unit have narrow half-widths and sharp peaks. Therefore, the color purity of red light and green light is increased, and light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105, green light emitted by the nanocrystals NC for green light emission, and nanocrystals NC similarly for red light emission Because the three primary colors of blue, green, and red are aligned by the red light emitted by the light source, and the color gamut of these combined lights is broadened, the color reproduction area is expanded compared to the conventional white LED and light emitting device combining phosphors. Ru.

  In addition, if necessary, the light conversion unit 103 according to the present invention may include, for example, a fluorescent material, in addition to the light emitting nanocrystals NC and the transparent resin containing the light emitting nanocrystals NC uniformly dispersed. Specifically, the light source 101 is preferably light including blue light having a peak at 450 nm, and more preferably a blue light source. The light conversion unit 103 preferably includes a fluorescent material that converts the wavelength of blue light from the light source unit 101 into red light or green light as necessary. Thus, the backlight unit can generate light of various color tones by combining the red light and the green light whose wavelengths are converted by the light conversion unit 103.

  FIG. 6 is a specific example of the backlight unit of FIG. 5 and is a view showing one form of a preferred backlight according to the present invention.

  The light emitting diode 105 is, for example, sealed in the recess container 113 (not shown in FIG. 6) and mounted on the light source substrate 110, and the light incident surface of the light guide plate 104 (in FIG. It is arranged opposite to. Further, as shown in FIG. 6, a tube 111 (a light conversion unit 103 in which a light emission nanocrystal NC is accommodated between the light emitting element L and the light guide plate 104 via the fixing members 112 a and 112 b. ) Are connected to the light source unit 101.

  Thus, in the liquid crystal display element according to the present invention, the light conversion portion 103 containing the light emitting nanocrystals NC is provided in the light path until the light from the light emitting element L is supplied to the liquid crystal panel. The portion 103 can emit light obtained by converting incident light from the light emitting element L into light of at least one of red (R), green (G), and blue (B).

  7A is a cross-sectional view of the liquid crystal display element shown in FIG. 1 cut in the direction of the line I-I in FIG. 1, and a plurality of light emitting elements L are arranged in a line on one side of the liquid crystal panel 10. An embodiment having a different structure is shown.

  Here, the light emitting element L is integrally configured so that the light conversion unit 103 covers the light emitting diode 105, and the backlight unit 100 includes a light source unit 101 including the light emitting element L, a light guide plate 104, It is comprised from the light guide part (not shown) which contains a light-diffusion plate (not shown) as needed. Further, in the present embodiment, a light diffusion plate (not shown) may be provided between the light guide plate 104 and the liquid crystal panel 10 (for example, the polarizing plate 1) to be in contact with the light guide plate 104 if necessary.

  In addition, the light conversion unit 103 present in the light emitting element L includes the light emitting nanocrystals NC (for example, quantum dots) and a resin (not shown) as essential components.

  Therefore, the liquid crystal display element according to the embodiment of FIG. 7A includes the light source unit 101 having the light emitting element L including the light emitting diode 105 and the light converting unit 103, the light guide plate 104, and one of the light guide plates 104. A first polarizing plate 1, a first display substrate SUB1, a liquid crystal layer 5, a second display substrate SUB2 and a second polarizing plate 8 are sequentially stacked on the surface. Further, in the liquid crystal display element, the light source unit 101 having the light emitting element L including the light conversion unit 103 and the light guide unit including the light guide plate 104 are connected. It is attached to one side of the outside.

  Further, the light emitting element L in FIG. 7A is configured by a light emitting diode 105 (LED), and becomes a point light source. As an example of the light emitting element L, a description will be given using the enlarged part in FIG. 7B as a concave container 113 (transparent filling container) for housing a light emitter having a concave formed on the upper side, and a light source integrated with the container. Substrate 110 (lead for anode (not shown) including lead frame and lead for cathode (not shown)), light emitting LED (light emitting diode) 105 attached to the bottom of the recess, and the recess And a resin layer containing light emitting nanocrystals NC.

  The light emitting diode 105 in FIG. 7B is bonded and fixed on the cathode lead exposed on the bottom of the recess. The light emitting diode 105 has an n-type electrode and a p-type electrode, and the p-type electrode is connected to the anode lead portion via the bonding wire and the n-type electrode is connected to the cathode lead portion. ing. In the light source unit 101 used in the present embodiment, the light emitting diode 105 is attached to a substantially central portion of the bottom surface, but is not particularly limited. The light source substrate 110 (anode lead portion and cathode lead portion, in other words, a lead frame) is a metal plate, and is a metal conductor such as a copper alloy having a silver plating layer formed on the surface, so a transparent filling container In the bottom of the concave portion, the silver plating layer of a part (conductor part) of the lead for the anode which is a metal conductor and a part (conductor part) of the lead for the cathode is exposed.

  The light emitting diode 105 in FIG. 7B is not particularly limited in the wavelength range, but preferably has a main emission peak in the blue range. For example, a light emitting diode 105 having a main emission peak in a wavelength range of 420 nm to 480 nm can be suitably used. The light emitting diode 105 includes, for example, at least a seed layer made of AlN formed on a sapphire substrate, an underlayer formed on the seed layer, and a laminated semiconductor layer mainly composed of GaN. Are mentioned as an example. In addition, the laminated semiconductor layer includes a substrate (for example, one in which an underlayer, an n-type semiconductor layer, a light emitting layer, and a p-type semiconductor layer are laminated in order from the light source substrate 110 side in FIG.

  The light conversion portion 103 in FIGS. 7A and 7B is at least one type, preferably two or more types of nanocrystals NC for light emission that absorbs light emitted from the light emitting diode 105 and emits light of longer wavelength. And a transparent resin containing the light emitting nanocrystals NC uniformly dispersed. In this case, the light emitting nanocrystals NC absorb blue light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 and emit blue light. Blue light emitting nanocrystals NC emitting light, light emitted by the light emitting diode 105 (preferably Red light emitting nanocrystals NC that absorb blue light to ultraviolet light and emit green light and emit light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 Preferably containing at least one light emitting nanocrystal NC selected from the group consisting of: blue light emitting nanocrystal NC, green light emitting nanocrystal NC and red light emitting nanocrystal NC It is more preferable to include two luminescent nanocrystals NC. In particular, it is particularly preferable to include a green light emitting nanocrystal NC and a red light emitting nanocrystal NC that emits red light. The red light emitting nanocrystals NC are also excited by the light emitted from the green light emitting nanocrystals NC, so the light emitting wavelength of the light emitting diode 105, the ratio of the green and red light emitting nanocrystals NC, and the light conversion portion 103 It is preferable to adjust the content of the nanocrystals NC for light emission appropriately.

  The three primary colors of blue, green and red are aligned by the blue light emitted by the light emitting diode 105, the green light emitted by the green light emitting nanocrystal NC, and the red light emitted by the red light emitting nanocrystal NC similarly. For this reason, white light is emitted from the light emission surface of the light conversion unit 103. The color reproduction range using this white light as a backlight of the liquid crystal display element depends on the wavelength and half width of the main emission peak of the light emitting diode 105 and the wavelength and half width of the emission peak of the light emitting nanocrystals NC.

  FIG. 8 shows a liquid crystal display having a backlight unit in which a plurality of light emitting elements L are arranged in a line on one side of the liquid crystal panel 10, and a sheet-like light conversion unit 103 is provided in a part of the light guide unit 102. FIG. 2 is a cross-sectional view of the liquid crystal display element taken along the line I-I in FIG.

  The liquid crystal display element in the present embodiment of FIG. 8 includes a light guide plate 104 and a light guide portion 102 including a light conversion portion 103 including a light emitting nanocrystal NC formed on one surface of the light guide plate 104; The first polarizing plate 1, the first display substrate SUB 1, the liquid crystal layer 5, the second display substrate SUB 2, and the second polarizing plate 8 are sequentially stacked, and a light source is provided on one side of the light guide plate 104. It is the structure where the part 101 was attached. Therefore, in the present embodiment, the light conversion unit 103 is included in the light guide unit 102. In addition, if necessary, a light diffusion plate may be provided between the light guide plate 104 and the liquid crystal panel 10 (for example, the polarizing plate 1) so as to abut on the light guide plate 104.

  Furthermore, the light source unit 101 having the light emitting element L is connected to the light guide plate 104.

  In the embodiment of FIG. 8, the light conversion portion 103 including the light emitting nanocrystals NC is in a sheet form, and in this structure, the light conversion portion 103 is disposed to abut against substantially the entire back surface of the liquid crystal panel 10. It is done. In addition, the light conversion portion 103 including the light emitting nanocrystals NC has a structure in which colloidal light emitting nanocrystals are dispersed in a film and sandwiched between protective films. In addition, as the light conversion unit 103, one or more types, preferably two or more types of nanocrystals NC for light emission, which absorb light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 and emit longer wavelength light. And a transparent resin containing the light emitting nanocrystals NC uniformly dispersed. In this case, the light emitting diode 105 according to the present invention is not particularly limited with respect to the wavelength region as in the other embodiments, but preferably has a main emission peak in the blue region. For example, a light emitting diode 105 having a main emission peak in a wavelength range of 420 nm to 480 nm can be suitably used.

  The light conversion part 103 in FIG. 8 absorbs light emitted from the light emitting diode 105 and uniformly emits at least one type, preferably two or more types of light emitting nanocrystals NC and light emitting nanocrystals NC. And the transparent resin contained in the dispersed state. In this case, the light emitting nanocrystals NC absorb blue light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 and emit blue light. Blue light emitting nanocrystals NC emitting light, light emitted by the light emitting diode 105 (preferably Red light emitting nanocrystals NC that absorb blue light to ultraviolet light and emit green light and emit light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 Preferably containing at least one light emitting nanocrystal NC selected from the group consisting of: blue light emitting nanocrystal NC, green light emitting nanocrystal NC and red light emitting nanocrystal NC It is more preferable to include two luminescent nanocrystals NC. In particular, it is particularly preferable to include a green light emitting nanocrystal NC and a red light emitting nanocrystal NC that emits red light.

  As shown in FIG. 8, planar blue light passing from the light emitting element L through the light guide plate 104 is converted into green light by the green light emitting nanocrystals NC in the light conversion unit 103 including the light emitting nanocrystals NC. It is preferable that red light is converted to red light by the red light emission nanocrystal NC, and blue light is transmitted as it is. Therefore, the liquid crystal display element according to the present invention can provide a bright color to an image by expanding the color reproduction region by becoming a planar light source having sharp peaks of red, green and blue.

  Next, FIG. 9 has a flat plate-like backlight unit 100 in which a plurality of light emitting elements L are disposed in a plane just below the back of the liquid crystal panel, and the sheet-like light conversion part 103 is 7 is an example of a cross-sectional view of the liquid crystal display element having a backlight unit provided in a part of 102, the liquid crystal display element being cut in the direction of the line I-I in FIG.

  The backlight unit 100 in the embodiment shown in FIG. 9 includes the light source unit 101 in which a plurality of light emitting elements L are disposed in a plane relative to the light diffusion plate 106, the light diffusion plate 106, and the light diffusion plate 106. It is comprised from the light conversion part 103 containing the nanocrystal for light emission NC provided so that contact | connected might be carried out. Here, in the present embodiment, the light guiding portion 102 is formed of the light diffusing plate 106 and the light converting portion 103. Therefore, the liquid crystal display element in this embodiment includes the light source unit 101, the light diffusion plate 106, the light conversion unit 103, the first polarizing plate 1, the first display substrate SUB1, the liquid crystal layer 5, the second display substrate SUB2 and The second polarizing plate 8 is stacked in order. The light diffusion plate 106 has a role of uniformly scattering the light emitted from the light emitting element L.

  As shown in FIG. 9, the light conversion portion 103 including the light emitting nanocrystals NC is in the form of a sheet, and this structure is light so as to abut on substantially the entire back surface of the liquid crystal panel 10 as in FIG. A converter 103 is arranged.

  The light conversion portion 103 in the present embodiment includes one or more types, preferably two or more types of light emission nanos, which absorb light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 and emit light of a longer wavelength. It is composed of a crystal NC and a transparent resin containing the light emitting nanocrystals NC uniformly dispersed. In this case, the light emitting diode 105 according to the present invention is not particularly limited with respect to the wavelength region as in the other embodiments, but preferably has a main emission peak in the blue region. For example, a light emitting diode 105 having a main emission peak in a wavelength range of 420 nm to 480 nm can be suitably used.

  Here, the light conversion unit 103 uniformly absorbs one or more, preferably two or more, light emitting nanocrystals NC and light emitting nanocrystals NC by absorbing light emitted from the light emitting diode 105 and emitting light of a longer wavelength. It is comprised from the transparent resin contained in the disperse | distributed state. In this case, the light emitting nanocrystals NC absorb blue light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 and emit blue light. Blue light emitting nanocrystals NC emitting light, light emitted by the light emitting diode 105 (preferably Red light emitting nanocrystals NC that absorb blue light to ultraviolet light and emit green light and emit light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 Preferably containing at least one light emitting nanocrystal NC selected from the group consisting of: blue light emitting nanocrystal NC, green light emitting nanocrystal NC and red light emitting nanocrystal NC It is more preferable to include two luminescent nanocrystals NC. In particular, it is particularly preferable to include a green light emitting nanocrystal NC and a red light emitting nanocrystal NC that emits red light.

  As shown in FIG. 9, the planar blue light diffused from the plurality of light emitting elements L by the light diffusion plate 106 is converted into green light emitting nanocrystals NC in the sheet-like light conversion portion 103 including light emitting nanocrystals NC. The red light is converted to green light by the red light emission nanocrystal NC, and the blue light is transmitted as it is. Therefore, the liquid crystal display element according to the present invention can provide a bright color to an image by expanding the color reproduction region by becoming a planar light source having sharp peaks of red, green and blue.

  FIG. 10 (a) is a cross-sectional view of the liquid crystal display element shown in FIG. 2 cut in the direction of the line II of FIG. 14 shows an embodiment of a liquid crystal display device having a flat plate-like backlight unit 100 and having a backlight unit provided with a light conversion unit 103 in a part of the light source unit 101. FIG.

  In the embodiment of FIG. 10 (a), the light emitting element L is integrally configured so that the light conversion unit 103 covers the light emitting diode 105 as shown in FIG. 10 (b). The light source unit 101 is disposed in a planar shape with respect to the light diffusion plate 106.

  Therefore, the liquid crystal display element in the present embodiment has a plurality of light emitting elements L including the light conversion section 103, and the light source section 101 in which the plurality of light emitting elements L are arranged in a planar shape; The first polarizing plate 1, the first display substrate SUB1, the liquid crystal layer 5, the second display substrate SUB2, and the second polarizing plate 8 are sequentially stacked.

  The light emitting diode 105 in the present embodiment is not particularly limited in the wavelength range, but preferably has a main emission peak in the blue range. For example, a light emitting diode 105 having a main emission peak in a wavelength range of 420 nm to 480 nm can be suitably used.

  The light conversion portion 103 in FIGS. 10A and 10B is one or more types, preferably two or more types of nanocrystals NC for light emission that absorbs light emitted from the light emitting diode 105 and emits light of longer wavelength. And a transparent resin containing the light emitting nanocrystals NC uniformly dispersed. In this case, the light emitting nanocrystals NC absorb blue light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 and emit blue light. Blue light emitting nanocrystals NC emitting light, light emitted by the light emitting diode 105 (preferably Red light emitting nanocrystals NC that absorb blue light to ultraviolet light and emit green light and emit light (preferably blue light to ultraviolet light) emitted by the light emitting diode 105 Preferably containing at least one light emitting nanocrystal NC selected from the group consisting of: blue light emitting nanocrystal NC, green light emitting nanocrystal NC and red light emitting nanocrystal NC It is more preferable to include two luminescent nanocrystals NC. In particular, it is particularly preferable to include a green light emitting nanocrystal NC and a red light emitting nanocrystal NC that emits red light. The red light emitting nanocrystals NC are also excited by the light emitted from the green light emitting nanocrystals NC, so the light emitting wavelength of the light emitting diode 105, the ratio of the green and red light emitting nanocrystals NC, and the light conversion portion 103 It is preferable to adjust the content of the nanocrystals NC for light emission appropriately.

  The three primary colors of blue, green and red are aligned by the blue light emitted by the light emitting diode 105, the green light emitted by the green light emitting nanocrystal NC, and the red light emitted by the red light emitting nanocrystal NC similarly. For this reason, white light is emitted from the light emission surface of the light conversion unit 103. The color reproduction range using this white light as a backlight of the liquid crystal display element depends on the wavelength and half width of the main emission peak of the light emitting diode 105 and the wavelength and half width of the emission peak of the light emitting nanocrystals NC.

  As described above, the layers (the electrode layer 3 and the alignment layer 4 in FIG. 1) formed on the substrate on the backlight unit side and the substrate (first substrate 2) on the backlight unit side are the first display substrate SUB1. And a layer formed on the substrate facing the substrate on the backlight unit side (the alignment layer 4 and the color filter 6 in FIG. 1) and a substrate facing the substrate on the backlight unit side (second The substrate 7) is referred to as a second display substrate SUB2 and, according to the embodiment, is formed on a layer formed on the substrate on the backlight unit side or on a substrate facing the substrate on the backlight unit side What constitutes a layer may be different.

  Next, a light conversion unit and a liquid crystal layer which are components of the liquid crystal display device according to the present invention will be described.

  In each embodiment of the liquid crystal display element of the present invention, as described above, the light conversion portion 103 contains light emitting nanocrystals. The term "nanocrystal" as used herein preferably refers to particles having at least one length of 100 nm or less. The shape of the nanocrystals may have any geometric shape, and may be symmetrical or unsymmetrical. Specific examples of the shape of the nanocrystal include elongated, rod-like, circular (spherical), elliptical, pyramidal, disc-like, branch-like, net-like or any irregular shape. In some embodiments, the nanocrystals are preferably quantum dots or quantum rods.

  The light emitting nanocrystal preferably has a core containing at least one first semiconductor material, and a shell covering the core and containing a second semiconductor material which is the same as or different from the core.

  Therefore, the light-emitting nanocrystal according to the present invention comprises a core containing at least a first semiconductor material and a shell containing a second semiconductor material, and the first semiconductor material and the second semiconductor material may be the same or different. It is good. In addition, both the core and / or the shell may include a third semiconductor material other than the first semiconductor and / or the second semiconductor. In addition, covering a core here should just cover at least one part of a core.

  Furthermore, the luminescent nanocrystals need a core comprising at least one first semiconductor material, a first shell covering the core and comprising a second semiconductor material identical or different to the core. Preferably has a second shell covering the first shell and including a third semiconductor material that is the same as or different from the first shell.

  Therefore, the luminescent nanocrystal according to the present invention has a form comprising a core comprising a first semiconductor material and a shell covering the core and comprising a second semiconductor material identical to the core, ie one or two An aspect (= a structure with only a core (also referred to as a core structure)) composed of semiconductor materials of a kind or more, and a second semiconductor material which covers the core including the first semiconductor material and the core and which is different from the core A core / shell structure, a core including a first semiconductor material, and a first shell including a core including the first semiconductor material and covering the core and including a second semiconductor material different from the core; Only a few of the three structures in the form having a second shell covering a first shell and comprising a third semiconductor material different from said first shell, ie a core / shell / shell structure It is preferred to have one Kutomo.

  Furthermore, as described above, it is preferable that the light emitting nanocrystal according to the present invention includes three forms of core structure, core / shell structure and core / shell / shell structure, in which case the core is a semiconductor of two or more types. A mixed crystal containing a material may be used (for example, CdSe + CdS, CIS + ZnS, etc.). Furthermore, the shell may also be a mixed crystal containing two or more semiconductor materials.

  In the light conversion part according to the present invention, in the light emitting nanocrystal, a molecule having an affinity for the light emitting nanocrystal may be in contact with the light emitting nanocrystal.

  The above-mentioned molecules having affinity are small molecules and polymers having a functional group having an affinity to the nanocrystal for light emission, and there is no particular limitation on the functional group having an affinity, but nitrogen It is preferable that it is a group containing one kind of element selected from the group consisting of oxygen, sulfur and phosphorus. For example, organic sulfur group, organic phosphoric acid pyrrolidone group, pyridine group, amino group, amide group, isocyanate group, carbonyl group, hydroxyl group and the like can be mentioned.

  The semiconductor material according to the present invention is one selected from the group consisting of II-VI semiconductors, III-V semiconductors, I-III-VI semiconductors, IV semiconductors and I-II-IV-VI semiconductors. Or it is preferable that it is 2 or more types. Preferred examples of the first semiconductor material, the first semiconductor material and the third semiconductor material according to the present invention are the same as the above-mentioned semiconductor materials.

Specifically, the semiconductor material according to the present invention is CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSe, HgSeS, HgSeTe, HgSTe. , CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe; GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs , AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaP s, GaPSb, AlNP, AlNAs, AlSb, AlPAs, AlPSb, InPS, InNAs, InNAs, InNSb, InPAs, InPSb, InPSb, GaAlNs, GaAlNAs, GaAlNs, GaAlPAs, GaAlPSb, GaAlPSb, GaInNAs, GaInNSb, GaInNSb, GaInPSb, InAlNPInAlNs, InAlPAs, InAlPSb; SnS, SnSe, SnTe, PbS, PbSe, PbSe, SnSeTe, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbSe, SnPbTe, SnPbSSe, SnPbSe, SnPbSTe; Si, Ge, SiC, SiGe, AgInSe2, CuGaSe2, CuInS2, At least one compound selected from the group consisting of uGaS2, CuInSe2, AgInS2, AgGaSe2, AgGaS2, C, Si and Ge is selected, and these compound semiconductors may be used alone or in combination of two or more. is good, CdS, CdSe, CdTe, ZnS , ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, InP, InAs, InSb, GaP, GaAs, GaSb, AgInS 2, AgInSe 2, AgInTe 2, AgGaS 2, AgGaSe 2, At least one selected from the group consisting of AgGaTe ₂ , CuInS ₂ , CuInSe ₂ , CuInTe ₂ , CuGaS ₂ , CuGaS ₂ , CuGaSe ₂ , CuGaTe ₂ , Si, C, Ge, and Cu ₂ ZnSnS ₄ can be selected. More preferably, these compound semiconductors may be used alone or in combination of two or more.

  The light emitting nanocrystal according to the present invention is at least selected from the group consisting of a red light emitting nanocrystal that emits red light, a green light emitting nanocrystal that emits green light, and a blue light emitting nanocrystal that emits blue light. It is preferred to include one nanocrystal. Generally, the luminescent color of the luminescent nanocrystal depends on the particle size according to the solution of the Schrodinger wave equation of the well potential model, but it also depends on the energy gap of the luminescent nanocrystal. The emission color is selected by adjusting the crystals and their particle sizes.

  In the present invention, the upper limit of the wavelength peak of the fluorescence spectrum of the red light emitting nanocrystal that emits red light is 665 nm, 663 nm, 660 nm, 658 nm, 655 nm, 653 nm, 651 nm, 650 nm, 647 nm, 645 nm, 643 nm, 640 nm, 637 nm, 635 nm The lower limit of the wavelength peak is preferably 628 nm, 625 nm, 623 nm, 620 nm, 615 nm, 610 nm, 607 nm or 605 nm.

  In the present invention, the upper limit of the wavelength peak of the fluorescence spectrum of the green light-emitting nanocrystal emitting green light is 560 nm, 557 nm, 555 nm, 550 nm, 547 nm, 545 nm, 543 nm, 540 nm, 537 nm, 535 nm, 532 nm or 530 nm Preferably, the lower limit of the wavelength peak is 528 nm, 525 nm, 523 nm, 520 nm, 515 nm, 510 nm, 507 nm, 505 nm, 503 nm or 500 nm.

  In the present invention, the upper limit of the wavelength peak of the fluorescence spectrum of the blue light emitting nanocrystal that emits blue light is 480 nm, 477 nm, 475 nm, 470 nm, 467 nm, 465 nm, 463 nm, 460 nm, 457 nm, 455 nm, 452 nm or 450 nm Preferably, the lower limit of the wavelength peak is 450 nm, 445 nm, 440 nm, 435 nm, 430 nm, 428 nm, 425 nm, 422 nm or 420 nm.

  The semiconductor material used for the red light-emitting nanocrystal that emits red light in the present invention preferably has a peak emission wavelength in the range of 635 nm ± 30 nm. Similarly, it is desirable that the semiconductor material used for the green light emitting nanocrystal that emits green light has a light emission peak wavelength falling within the range of 530 nm ± 30 nm, and is used for the blue light emitting nanocrystal that emits blue light Preferably, the semiconductor material to be used has a peak emission wavelength in the range of 450 nm ± 30 nm.

  The lower limit value of the fluorescence quantum yield of the nanocrystal for light emission according to the present invention is preferably in the order of 40% or more, 30% or more, 20% or more, and 10% or more.

  The upper limit of the half value width of the fluorescence spectrum of the light emitting nanocrystals according to the present invention is preferably in the order of 60 nm or less, 55 nm or less, 50 nm or less, and 45 nm or less.

The upper limit of the particle diameter (primary particle) of the light emitting nanocrystals according to the present invention is preferably 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less in order of peak wavelength of light emission of red light emitting nanocrystals according to the present invention The upper limit of is 665 nm, the lower limit is 605 nm, and the compound and its particle size are selected to fit this peak wavelength. Similarly, the upper limit of emission peak wavelength of the green light emitting nanocrystal is 560 nm, the lower limit is 500 nm, the upper limit value of emission peak wavelength of the blue light emitting nanocrystal is 480 nm, and the lower limit is 420 nm, respectively. Select the compound and its particle size to fit.

  The light conversion part according to the present invention includes a light emitting nanocrystal, and the light emitting nanocrystal emits a red light emitting nanocrystal, a green light emitting nanocrystals and a blue light. It is preferable to include at least one nanocrystal selected from the group consisting of blue light emitting nanocrystals. Specifically, red (for example, light emitting nanocrystals of CdSe, rod light emitting nanocrystals of CdSe, rod light emitting nanocrystals having a core-shell structure, the shell portion is CdS, and the inner core is A rod-like luminescent nanocrystal having a core-shell structure with CdSe, the shell portion being CdS, the inner core portion being a ZnSe, a luminescent nanocrystal having a core-shell structure, the shell portion being a CdS Light emitting nanocrystals having an inner core portion of CdSe and a core-shell structure, the shell portions being CdS and an inner core portion being a mixed crystal light emitting nanocrystal of ZnSe, CdSe and ZnS, Nanocrystals for rod-like emission of mixed crystals of CdSe and ZnS, Nanocrystals for luminescence of InP, Nanocrystals for luminescence of InP, Nanocrystals for rod-like luminescence of InP, Mixed light emitting nanocrystals of dSe and CdS, rod-shaped light emitting nanocrystals of mixed crystals of CdSe and CdS, mixed nanocrystals of mixed crystals of ZnSe and CdS, mixed rods of ZnSe and CdS Light emitting nanocrystals, green light emitting nanocrystals (CdSe light emitting nanocrystals, CdSe rod light emitting nanocrystals, mixed crystal light emitting nanocrystals of CdSe and ZnS, rod shapes of mixed crystals of CdSe and ZnS Light emitting nanocrystals etc. and blue (ZnSe light emitting nanocrystals, ZnSe rod light emitting nanocrystals, ZnS light emitting nanocrystals, ZnS rod light emitting nanocrystals, light emitting nanocrystals with core-shell structure The shell portion is ZnSe, the inner core portion is ZnS, a rod-like light emitting nanocrystal having a core-shell structure, and the shell portion is ZnSe. Including the core portion ZnS, light emitting nanocrystals CdS, different nanocrystals that emit in the CdS rod light emitting nanocrystals). Other colors (for example, yellow may also be contained in the light conversion part as needed.

  The particle size (primary particle) of the light-emitting nanocrystal according to the present invention in the present specification can be measured by TEM observation. Generally, as a method of measuring the average particle size of nanocrystals, a light scattering method, a sedimentation type particle size measurement method using a solvent, and a method of observing particles directly by an electron microscope to measure the average particle size can be mentioned. Since light emitting nanocrystals are easily degraded by moisture and the like, in the present invention, arbitrary plural crystals are directly observed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM), and the long and short of projected two-dimensional images It is preferable to calculate each particle diameter from the diameter ratio and obtain the average. Therefore, in the present invention, the above method is applied to calculate the average particle diameter. The primary particle of the light emitting nanocrystal is a single crystal having a size of several to several tens of nm or a crystallite close thereto, and the size and shape of the primary particle of the light emitting nanocrystal is the primary particle It depends on the chemical composition, structure, manufacturing method, manufacturing conditions, etc.

  The light conversion unit according to the present invention may mix the light emitting nanocrystals described above and, if necessary, a resin.

  When the light conversion unit according to the present invention is connected to the light source unit as shown in the embodiment of FIG. 3 and installed on the side surface of the first substrate or the second substrate, more specifically, the present invention In the case where the light conversion unit according to is connected to the light source unit and has the hollow tube and the light emitting nanocrystal housed inside the hollow tube, the light emitting nanocrystal may be mixed with the transparent resin if necessary. Good. The transparent resin in this case may be a known one, such as acrylic resin, silicone resin, epoxy resin, polyamide resin, polyimide resin, polyester resin, polycarbonate resin, polyether resin, polythioether resin, polyacrylonitrile resin, Polyether ether ketone resin, linear structure and cyclic structure polyolefin resin etc. are mentioned. The transparent resin is preferably a transparent resin having a total light transmittance of 80% or more in the visible light range (360 nm to 830 nm).

  Furthermore, in the light conversion part according to the present invention, if necessary, in addition to the transparent resin and the nanocrystals for light emission, scattering of phosphors, polymerization initiators, catalysts, alumina, silica, titanium oxide beads, zeolite or zirconia, etc. The composition may contain known additives such as additives.

  The upper limit of the content of the light emitting nanocrystals to the transparent resin in the case where the light conversion unit according to the present invention is connected to the light source unit and has the hollow tube and the light emitting nanocrystal housed inside the hollow tube. Is preferably 20 parts by mass, preferably 17 parts by mass, preferably 15 parts by mass, and preferably 13 parts by mass, with respect to 100 parts by mass of the transparent resin. It is preferably 10 parts by mass, preferably 8 parts by mass, preferably 6 parts by mass, and more preferably 5 parts by mass, and 4.5 parts by mass. Is preferable, 4 parts by mass is preferable, 3.5 parts by mass is preferable, and 3 parts by mass is preferable. The lower limit of the content of the light emitting nanocrystals is preferably 0.05 parts by mass, preferably 0.07 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the transparent resin. Is preferable, 0.15 parts by mass is preferable, 0.2 parts by mass is preferable, 0.3 parts by mass is preferable, 0.5 parts by mass is preferable, and 0.7 parts by mass 1 part by mass is preferable, 1.2 parts by mass is preferable, 1.5 parts by mass is preferable, 1.7 parts by mass is preferable, and 2 parts by mass is preferable. It is preferably 2.5 parts by mass, preferably 2.7 parts by mass, and more preferably 3 parts by mass. In addition, when multiple types of light emitting nanocrystals are contained in the light conversion part, the above content represents the total amount.

  When the light conversion unit according to the present invention is integrated with the light emitting element as shown in the embodiments of FIGS. 7 and 10, more specifically, the light conversion unit according to the present invention comprises the light emitting element and the nanocrystal for light emission. If necessary, the light emitting nanocrystal may be used as a mixture with a transparent resin, in the case of including a light conversion portion containing A transparent resin in this case can be a known one, and since a resin similar to the transparent resin of Embodiment 1 can be used, the description thereof is omitted here. Further, in the light conversion unit according to the present invention, additives added as necessary are also the same as those described above.

  The upper limit of the content of the nanocrystals for light emission to the transparent resin in the case of including the light conversion part containing the light emitting element and the nanocrystal for light emission is preferably 25 parts by mass with respect to 100 parts by mass of the transparent resin. 23 parts by mass is preferable, 20 parts by mass is preferable, 17 parts by mass is preferable, 15 parts by mass is preferable, 13 parts by mass is preferable, and 12 parts by mass 10 parts by mass is preferable, 8 parts by mass is preferable, 6 parts by mass is preferable, 5 parts by mass is preferable, and 4.5 parts by mass is preferable. 4 parts by mass, preferably 3.5 parts by mass, and more preferably 3 parts by mass. The lower limit of the content of the light emitting nanocrystals is preferably 0.05 parts by mass, preferably 0.07 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the transparent resin. Is preferable, 0.15 parts by mass is preferable, 0.2 parts by mass is preferable, 0.3 parts by mass is preferable, 0.5 parts by mass is preferable, and 0.2 parts by mass is preferable. 7 parts by mass is preferable, 1 part by mass is preferable, 1.2 parts by mass is preferable, 1.5 parts by mass is preferable, and 1.7 parts by mass is preferable 2 parts by mass, preferably 2.5 parts by mass, preferably 2.7 parts by mass, preferably 3 parts by mass, and 3.5 parts by mass Preferably, 4 parts by mass is preferableIn the case where the light conversion portion contains a plurality of luminescent nanocrystals, the content represents the total amount.

  When the light conversion unit according to the present invention is connected to the light source unit as shown in the embodiments of FIGS. 8 and 9 and installed on the entire surface with respect to the first substrate or the second substrate, more detailed When the light conversion part according to the present invention is in the form of a sheet, and is disposed on the entire surface of the first substrate or the second substrate relative to the substrate on the light source part side, nanocrystals for light emission as necessary May be used as a mixture with a transparent resin. A transparent resin in this case can be a known one, and since a resin similar to the transparent resin of Embodiment 1 can be used, the description thereof is omitted here. Further, in the light conversion unit according to the present invention, additives added as necessary are also the same as those described above.

  When the light conversion unit according to the present invention is connected to the light source unit and the light conversion unit is disposed on the entire surface with respect to the first substrate or the second substrate, the upper limit of the content of nanocrystals for light emission relative to the transparent resin is the transparent resin It is preferable that it is 19 mass parts with respect to 100 mass parts, It is preferable that it is 17 mass parts, It is preferable that it is 15 mass parts, It is preferable that it is 13 mass parts, It is 12 mass parts Preferably, 10 parts by mass is preferable, 8 parts by mass is preferable, 6 parts by mass is preferable, 5 parts by mass is preferable, and 4.5 parts by mass is preferable. It is preferable that it is a mass part, it is preferable that it is 3.5 mass parts, and it is preferable that it is 3 mass parts. The lower limit of the content of the light emitting nanocrystals is preferably 0.05 parts by mass, preferably 0.07 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the transparent resin. Is preferable, 0.15 parts by mass, 0.2 parts by mass is preferable, 0.3 parts by mass is preferable, 0.5 parts by mass is preferable, and 0.7 parts by mass 1 part by mass is preferable, 1.2 parts by mass is preferable, 1.5 parts by mass is preferable, 1.7 parts by mass is preferable, and 2 parts by mass is preferable. And 2.5 parts by mass, preferably 2.7 parts by mass, preferably 3 parts by mass, and more preferably 3.5 parts by mass. In the case where the light conversion portion contains a plurality of luminescent nanocrystals, the content represents the total amount.

  Furthermore, in the light conversion part according to the present invention, if necessary, in addition to the transparent resin and the nanocrystals for light emission, scattering of phosphors, polymerization initiators, catalysts, alumina, silica, titanium oxide beads, zeolite or zirconia, etc. The composition may contain known additives such as additives.

  Next, the liquid crystal layer in the liquid crystal display device, for example, the liquid crystal layer 5 in each of the above-mentioned embodiments, as described above, comprises the polymer network (A),

(Wherein, R ⁱ¹ and R ⁱ² are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms 8 represents an alkenyloxy group, A ⁱ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and n ⁱ¹ represents 0 or 1. 10 to 50% of a compound represented by It is characterized in that the liquid crystal composition (B) is contained.

  The polymer network constituting such a liquid crystal layer is preferably one having uniaxial optical anisotropy, or uniaxial refractive index anisotropy or easy alignment axis direction, and the optical axis or alignment of the polymer network. It is more preferable that the easy axis and the alignment easy axis of the low molecular liquid crystal constituting the liquid crystal composition (B) be substantially aligned. The polymer network also includes a polymer binder in which a plurality of polymer networks are aggregated to form a polymer thin film. The polymer binder has refractive index anisotropy exhibiting uniaxial orientation, and a low molecular weight liquid crystal is dispersed in the thin film, and the uniaxial optical axis of the thin film and the optical axis of the low molecular weight liquid crystal are substantially the same direction It is a feature that is aligned to.

  Therefore, unlike the polymer dispersed liquid crystal or polymer network liquid crystal which is a light scattering type liquid crystal, light scattering does not occur, and high contrast display can be obtained in a liquid crystal display element using polarized light. It is characterized in that the response time of the liquid crystal element is improved by shortening the down time. Furthermore, in the liquid crystal layer constituting the liquid crystal display element of the present invention, the polymer network layer is formed on the entire liquid crystal display element, so a polymer thin film layer is formed on the liquid crystal element substrate to induce pretilt. It can be distinguished from a sustained alignment) liquid crystal composition.

  Such a liquid crystal layer can be produced, for example, by polymerizing a polymerizable liquid crystal composition containing the polymerizable monomer component (A) and the liquid crystal composition (B) as essential components. Specifically, the molecular weight is increased by polymerizing the polymerizable monomer component (A) in the polymerizable liquid crystal composition in a state where the polymerizable liquid crystal composition exhibits a liquid crystal phase, and thus the liquid crystal composition The liquid crystal layer can be formed by phase separation of the substance (B) and the polymer (or copolymer).

Here, the form of separation into two phases depends on the type of liquid crystal composition (B) contained and the type of monomer. For example, in the liquid crystal composition (B), a number of monomer phases may be generated as island-like nuclei and grow to form a phase separation structure by bimodal decomposition, and the liquid crystal composition (B) may form a phase separation structure. The phase separation structure may be formed by spinodal decomposition in which phase separation occurs from concentration fluctuations. In order to form a polymer network by bimodal decomposition, by using a compound having a high reaction rate of monomers, it is possible to generate an infinite number of nuclei of monomers having a size smaller than the wavelength of visible light and link them linearly. It is preferable because a phase separation structure is formed. As a result, when polymerization in the monomer phase proceeds, a polymer network having a gap distance shorter than the wavelength of visible light is formed depending on the phase separation structure. On the other hand, the voids of the polymer network are due to phase separation of the liquid crystal composition (B) phase, and if the size of the voids is smaller than the wavelength of visible light, there is no light scattering and high contrast, and anchors from the polymer network The influence of the ring force is intensified, the fall time is shortened, and a liquid crystal display element with high response speed can be obtained, which is particularly preferable. Nucleation of the monomer phase in bimodal decomposition is preferably adjusted as necessary, affected by the change in compatibility depending on the kind and combination of compounds, reaction rate, temperature and other parameters. In the case of ultraviolet polymerization, the reaction rate depends on the functional group of the monomer, the type and content of the polymerization initiator, and the ultraviolet irradiation intensity, and the ultraviolet irradiation conditions may be appropriately adjusted to promote the reactivity, at least 2 mW / Ultraviolet radiation intensity of cm ² or more is preferred. Spinodal decomposition is preferable because a phase separation microstructure can be obtained due to fluctuations in the concentration of two phases having periodicity, and a uniform gap spacing smaller than the visible light wavelength can be easily formed. When the content of the polymerizable monomer component (A) is increased, there is a phase transition temperature at which two phases of liquid crystal composition (B) high concentration phase and monomer high concentration phase separate under the influence of temperature. If the temperature is higher than the two-phase separation transition temperature, an isotropic phase is exhibited. When two-phase separation occurs due to temperature change, it is preferable to form a phase separation structure at a temperature higher than the two-phase separation temperature. In any of the cases described above, the polymer network can be formed while maintaining the same alignment state as the alignment state of the liquid crystal composition (B).

  Here, the above-mentioned polymerizable liquid crystal composition includes the polymerizable monomer component (A), the liquid crystal composition (B), and, if necessary, the polymerization initiator, the polymerizable monomer component When (A) is used in a proportion of 0.5 to 20% by mass, preferably 1 to 10% by mass in the polymerizable liquid crystal composition, the phase separation of the liquid crystal composition (B) and the polymer net are well formed. It is preferable from the point of being Therefore, in the present invention, the liquid phase layer contains 0.5 to 20% by mass, particularly 1 to 10% by mass of the polymer network (A) based on the total mass of the polymer network (A) and the liquid crystal composition (B). It is preferable to exist in the ratio used as mass%.

  When polymerizing a polymerizable liquid crystal composition, two phases of a monomer high concentration phase and a liquid crystal high concentration phase are formed in the process of forming a polymer phase separation structure, but the polymerization initiator is usually a monomer or a liquid crystal Concentration localization tends to occur, as it tends to collect in any of the higher affinity groups.

  Here, when the polymerization initiator is localized in the monomer high concentration phase, the polymerization of the monomer is promoted, but the polymerization of the monomer remaining in the liquid crystal high concentration phase is difficult to proceed. In this case, the remaining monomer in the liquid crystal high concentration phase in which the photoinitiator concentration is lowered is crosslinked by being collected to the monomer high concentration phase by the action of aggregation and the like.

  On the contrary, when the polymerization initiator is localized in the liquid crystal high concentration phase, the polymerization of the residual monomer in the liquid crystal high concentration phase is promoted, and the molecular weight of the residual monomer in the liquid crystal is increased. In the case of forming a polymer phase separation structure or in the case of aggregation into a monomer high concentration phase, the remaining monomer in the liquid crystal high concentration phase is preferable because polymerization tends to proceed by the effect of the photoinitiator dissolved in the liquid crystal phase. It is also preferable that the residual monomer of the liquid crystal high concentration phase proceed with the polymerization phase separation by the effect of the photoinitiator to newly form a polymer network.

  The formed polymer network exhibits optical anisotropy so as to follow the orientation of the liquid crystal composition (B). As a form of the liquid crystal layer in the polymer network, a structure in which the liquid crystal composition (B) forms a continuous layer in a three-dimensional network structure of the polymer, and a structure in which droplets of the liquid crystal composition (B) are dispersed in the polymer Or a structure in which both are mixed, and further, a structure in which a polymer network layer exists from both substrate surfaces and is only a liquid crystal layer in the vicinity of the center with the facing substrate. In any structure, it is preferable that a pretilt angle of 0 to 90 ° is induced to the liquid crystal element substrate interface by the action of the polymer network. The structure in which the product (B) forms a continuous layer is preferable from the viewpoint of the stability of the pretilt of liquid crystal molecules. Here, the polymer network constituting the liquid phase layer preferably has a function of orienting the coexisting liquid crystal composition (B) in the orientation direction indicated by the orientation film of the liquid crystal cell, and further, low relative to the polymer interface direction It is also preferable to have a function of pretilting the molecular liquid crystal. It is useful and preferable to introduce a monomer for pretilting the low molecular weight liquid crystal with respect to the polymer interface for improving the transmittance and lowering the driving voltage of the liquid crystal element. Moreover, it may have refractive index anisotropy, and it is preferable to use a monomer having a mesogen group for the function of aligning liquid crystals in the alignment direction. Alternatively, a pretilt may be formed by forming a polymer network by ultraviolet irradiation or the like while applying a voltage.

  From such a viewpoint, it is preferable to use a liquid crystalline monomer as the polymerizable monomer component (A). That is, the liquid crystal display device of the present invention has a structure in which a polymer network layer is formed on the entire surface of the liquid crystal display device in the liquid crystal phase and the liquid crystal phase is continuous, and the alignment easy axis or uniaxial optical axis of the polymer network is It is preferable to form a polymer network so as to induce the pretilt angle of the low molecular weight liquid crystal, because the speed of the off response can be increased, and therefore, it is preferable that the direction is substantially the same as the alignment easy axis of the low molecular weight liquid crystal. The polymerizable monomer constituting the polymerizable monomer component (A) is preferably a liquid crystalline monomer having a mesogenic structure in its molecular structure. In the liquid crystal display element according to the present invention, it is preferable that the polymer network layer has a size in which the average gap distance of the polymer network is smaller than the wavelength of visible light, that is, the average gap distance is less than 450 nm. It is preferable because it does not occur.

  As such a liquid crystalline monomer, the following general formula (P1)

What is represented by

Here, Z ^p11 may be a fluorine atom, a cyano group, a hydrogen atom, an alkyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted by a halogen atom, or a hydrogen atom may be substituted by a halogen atom Alkoxy group having 1 to 15 carbon atoms, alkenyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, 1 to 15 carbon atoms in which a hydrogen atom may be substituted for a halogen atom or alkenyloxy group represents an ^-Sp p12 ^{-R p12.} Among these, using a fluorine atom or an alkyl group having 1 to 15 carbon atoms in which an oxygen atom may be substituted by a halogen atom as Z ^p11 can increase the voltage holding ratio of the liquid crystal display element. preferably from the viewpoint of it becomes possible and is preferably ^-Sp p12 ^{-R p12} from the viewpoint of the stability of the tilt.

Here, R ^p11 and R ^p12 are each independently from the following formula (RP11-1) to the formula (PP11-8)

In the formulas (RP11-1) to (RP11-8), R ^{P111 to} R ^P112 independently of one another represent a hydrogen atom or a carbon atom number. 1 to 5 alkyl groups, t ^M11 represents 0, 1 or 2; Among them, it is particularly preferable to use a (meth) acryloyl group which is represented by the above-mentioned formula (RP11-1) and which is a hydrogen atom or a methyl group as R ^{P111 in} the formula at the time of producing a liquid crystal display element It is possible to reduce the amount of UV irradiation when polymerizing the monomer, to keep the UV irradiation amount to the liquid crystal material to the minimum necessary, and to prevent the deterioration of the liquid crystal material and the liquid crystal display element preferable.

Among the formulas (RP11-1) to (PP11-8) listed as R ^p11 and R ^p12 , in particular, the following formula (RP11-1) to the formula (RP11-4)

Are preferred from the viewpoint of excellent reactivity, and in particular, those represented by the formula (RP11-1).

Sp ^p11 and Sp ^p12 are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a carbon atom of this linear or branched alkylene structure is adjacent to an oxygen atom And a structural moiety having a chemical structure substituted with an oxygen atom or a carbonyl group under the conditions not described. Among them, in particular, a linear or branched alkylene group having 1 to 12 carbon atoms is preferable because it enhances the compatibility with the liquid crystal material (B), and the number of carbon atoms is about the same as the alkyl group possessed by liquid crystal molecules. Those of 1 to 6 are particularly preferred. Here, when the compatibility between the polymerizable monomer component (A) and the liquid crystal material (B) is not sufficient, or when the compatibility of the polymerization initiator (C) with the liquid crystal material (B) is not sufficient. In this case, since the polymer network has a portion where the density of the polymer network is rough and a portion where it is dense, the device properties are affected and the in-plane characteristics tend to be uneven. However, in the present invention, the polymerizable monomer component (A) and When the compatibility with the liquid crystal material (B) is good, the uniform polymerization phase is combined with the good compatibility between the polymerization initiator (C) and the liquid crystal material (B). The separation structure is formed, and a uniform polymer network in the liquid crystal is formed to make the characteristics of the liquid crystal display element constant in the plane. Here, in the case of having Sp ^p11 and Sp ^p12 which are linear or branched alkylene groups having 1 to 12 carbon atoms, it is easy for the production of the monomer that they are identical, and It is preferable from the point which physical-property adjustment becomes easy by adjusting the use ratio of several types of compounds in which alkylene chain length differs. On the other hand, when Sp ^p11 and Sp ^p12 are single bonds, the monomers tend to be collected on the substrate surface, and the tendency to form a thin film on the surface of the vertical alignment film is stronger than the tendency to form a polymer network. The effect of applying pretilt to the alignment film and immobilizing it becomes stronger than the effect of high-speed response by.

When the content of the polymerizable monomer component (A) in the polymerizable liquid crystal composition is less than 0.5% by mass, a pretilt angle is given to the above-mentioned alignment film and fixed. Sp ^p11 and Sp ^p12 are preferably single bonds, while when the content is in the range of 0.5% by mass to 20% by mass, Sp ^p11 and Sp ^p12 have 1 to 12 carbon atoms. A linear or branched alkylene group is preferable because it can form a polymer network that accelerates the off response speed. In particular, the range of 1% by mass to 10% by mass is preferable in terms of the off response speed and the low drive voltage. Moreover, as a carbon atom number, 2-8 are preferable and, as for the linear or branched alkylene group mentioned above, 2-6 are more preferable. Moreover, it is preferable to substitute the carbon atom on an alkylene group by an oxygen atom or a carbonyl group on the conditions which an oxygen atom does not adjoin. In particular, it is preferable to introduce an oxygen atom at a position bonded to ^{MP 11} or ^{MP 13} from the viewpoint that it is possible to expand the liquid crystal upper limit temperature of the whole liquid crystal material and to increase the ultraviolet sensitivity at the time of polymerization.

Next, in the general formula (P1), L ^p11 and L ^p12 are each independently a single bond, -O-, -S-, -CH _2- , -OCH _2- , -CH ₂ O-,- _{CO -, - C 2 H 4} -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO-NR P113 -, - NR P113 -CO- , -SCH _2- , -CH ₂ S-, -CH = CR ^P113 -COO-, -CH = CR ^{P113 -OCO-} , -COO-CR ^P113 = CH-, -OCO-CR ^aP113 = CH-, -COO -CR ^P113 = CH- ^COO- , -COO-CR ^P113 = CH-OCO-, -OCO-CR ^P113 = CH-COO-, -OCO-CR ^P113 = CH-OCO-,-(CH ₂ ) _tm12 -C ( _{O) -O -, - (CH} 2) tm12 -O- (C = O) -, - O- (C = O) - (CH 2) tm12 -, - (C = O) -O- (CH 2 _{) tm12 -, - CH = CH} -, - CF = CF -, - CF = CH -, - CH = CF -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 - _{, -CH 2 CF 2 -, -} CF 2 CF 2 -, - C≡C -, - N = N -, - CH = in N- or -C = N-N = C- ^{(wherein, R P113} each And independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein tm12 represents an integer of 1 to 4).

Liquid crystal is high in these within any polymerizable monomer component (A), in view of the irregular alignment deterrence in the liquid crystal display device, a single _{bond, -C 2 H 4 -, -} COO -, - OCO -, - CH _{= CH-COO -, - OCO} -CH = CH -, - (CH 2) 2 -C (= O) -O -, - (CH 2) 2 -O- (C = O) -, - O- ( _{C = O) - (CH 2} ) 2 -, - (C = O) -O- (CH 2) 2 -, - CH = CH -, - CF = CF -, - CF = CH -, - CH = CF _{-, - CF 2 O -,} - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - C≡C -, - N = N-, or -C = N-N = C- is preferable.

  In addition, since the photoalignment function by light using the Weigert effect can be used by providing the monomer with a function of photoisomerization, -CH = CH-, -CF = CF-, -CF = CH-, -CH = It is preferable to select CF- or -N = N-, and to select -CH = CH- and -N = N-, in particular -N = N-. Further, from the viewpoint of enhancing the orientation of the polymer network, it is particularly preferable that -N = N-.

Next, M ^p11 , M ^p12 and M ^p13 in the general formula (P1) are each independently 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-cyclohexylene Group, 1,3-cyclohexylene group, 1,2-cyclohexylene group, 1,4-cyclohexenylene group, 1,3-cyclohexenylene group, 1,2-cyclohexenylene group, anthracene-2, 6 -Diyl group, phenanthrene-2,7-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, indane -2,5-diyl group, fluorene-2,6-diyl group, fluorene-1,4-diyl group, phenanthrene-2,7-diyl group, anthracene-2,6-diyl group, anthrase The number of carbon atoms in these aromatic nuclei is preferably selected from the group consisting of benzene-1,4-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl and 1,3-dioxane-2,5-diyl. 1 to 12 alkyl group, halogenated alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, halogenated alkoxy group having 1 to 12 carbon atoms, halogen atom, cyano group, or nitro group And a structure substituted by

Further, it is preferable that M ^p11 , M ^p12 and M ^{p13 be} those in which the aromatic nucleus of these structures is substituted with -S ^p11 -R ^p11 from the viewpoint of becoming a radical polymerizable monomer excellent in reactivity. At this time, it is preferable that R ^p11 be a formula (RP 11-1), and R ^{p 111} be a hydrogen atom or a (meth) acryloyl group which is a methyl group.

  Among these, 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, anthracene-2,6-diyl, phenanthrene-2,7-diyl, pyridine-2 3,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, indane-2,5-diyl group, fluorene-2,6-diyl group, fluorene-1,4-diyl group Phenanthrene-2,7-diyl group, anthracene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, A 2,3-difluoro-1, 4-phenylene group and a 2-fluoro-1, 4-phenylene group are preferable from the point of compatibility with a liquid crystal.

Further, in the general formula (P1), mp12 represents 1 or 2, mp13 and mp14 each independently represent 0, 1, 2 or ^{3, m pi 1} and ^{m p15} is 1, 2, or independently Represents 3 Here, when a plurality of Z ^p11 are present, they may be the same or different, and when a plurality of R ^p11 are present, they may be the same or different, and R ^p12 is When a plurality of Sp ^p11 are present, they may be the same or different; when a plurality of Sp ^p11 are present, they may be the same or different; when a plurality of Sp ^p12 is present They may be the same or different, and when a plurality of L ^p11 are present, they may be the same or different, and when a plurality of L ^p12 are present, they are the same. ^May also be different, and when there are a plurality of M ^p12 , they may be the same or different, and when there are a plurality of M ^p13 , they may be the same or different so It is preferably a compound that is. Moreover, it is preferable that the said material contains 1 type or 2 types or more.

Further, ^m p12 ^{~m p14} described above is preferably their sum is in the range of 1-6, 2-4 in the range, and particularly preferably among them 2. When two or more types of monomers are used, the average number calculated by multiplying the concentration of the monomers in the entire monomer and the sum of m ^{p12 to} m ^p14 is set to 1.6 to 2.8. Is more preferably 1.7 to 2.4, and particularly preferably 1.8 to 2.2.

1-6 are preferable, as for the sum of ^mp11 and ^mp15 , 2-4 are more preferable, and 2 is especially preferable. When two or more types of monomers are used, the average number calculated by multiplying the concentration of the monomers in the entire monomer and the sum of m ^p1 and ^p15 may be set to 1.6 to 2.8. Preferably, it is more preferably 1.7 to 2.4, and particularly preferably 1.8 to 2.2. When the average number is close to 1, the drive voltage of the liquid crystal display element tends to be reduced, and when the average number is high, the off-response tends to be quick.

Substitution of M ^p11 , M ^p12 and M ^p13 with fluorine atoms can control the size and solubility of the interaction between the liquid crystal material and the polymer or copolymer without deteriorating the voltage holding ratio of the liquid crystal display device Because it is preferable. The preferred substitution number is 1 to 4.

  Use of the compounds represented by the following formulas (P2-1) to (P2-11) among the formulas (P1) described in detail above is effective for suppressing the temporal change of the tilt angle.

(Wherein, R ^P21 and R ^P22 each independently represent a hydrogen atom or a methyl group)
Although such compounds are useful, their solubility in liquid crystal materials may not be good. Accordingly, the content of such a compound is preferably 90% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less, based on the total amount of monomers used.

  Moreover, using the compounds represented by the following formulas (P3-1) to (P3-11) among the formula (P1) is to suppress the temporal change of the tilt angle and to ensure the solubility in the liquid crystal material. It is preferable because coexistence can be achieved.

(Wherein R ^P31 and R ^P32 each independently represent a hydrogen atom or a methyl group, mP 31 represents an integer of 0 or 1, and mP 32 represents an integer of 1 to 6 when mP 31 is 0, and mp 31 is In the case of 1, mP32 represents an integer of 2 to 6)

  It is preferable to use compounds represented by the following formulas (P4-1) to (P4-11) among the formula (P1) because they are useful for effectively improving the off response.

(Wherein R ^P41 and R ^P42 each independently represent a hydrogen atom or a methyl group, mP42 and mP43 each independently represent an integer of 0 or 1, and when mP42 is 0, mP41 is 1 to 6) MP41 represents an integer of 2 to 6 when mp42 is 1, mP44 represents an integer of 1 to 6 when mP43 is 0, and mp44 an integer of 2 to 6 when mP43 is 1. Represent)
Such a compound is preferably contained in an amount of 40% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more, in the whole monomer to be used.

  Among the compounds of formula (P1), compounds represented by formulas (P5-1) to (P5-11) having an aryl ester structure in mesogen have the ability to initiate polymerization by irradiation with ultraviolet light, and thus the addition of a polymerization initiator It is preferable because the amount can be reduced.

(Wherein R ^P51 and R ^P52 each independently represent a hydrogen atom or a methyl group, mP52 and mP53 each independently represent an integer of 0 or 1, and when mP52 is 0, mP51 is 1 to 6) Represents an integer, when mp52 is 1, mP51 represents an integer of 2 to 6, when mP53 is 0, mP54 represents an integer of 1 to 6, and when mP53 is 1, mp54 is an integer of 2 to 6 Represent)
When the addition amount of such a compound is large, the voltage holding ratio of the liquid crystal display element tends to deteriorate, so the content is preferably 30% by mass or less in the whole monomer to be used, and further preferably 20% by mass or less. Preferably, 10% by mass or less is particularly preferable.

  Moreover, it is also preferable to introduce | transduce a cinnamate ester group in mesogen like compounds represented by Formula (P6-1)-(P6-11) among Formula (P1).

(Wherein, R ^P61 and R ^P62 each independently represent a hydrogen atom or a methyl group, mP62 and mP63 each independently represent an integer of 0 or 1, and when mP62 is 0, mP61 is 1 to 6) Represents an integer, when mp62 is 1, mP61 represents an integer of 2 to 6; when mP63 is 0, mP64 represents an integer of 1 to 6; when mP63 is 1, mp64 represents an integer of 2 to 6 Represent)

  In addition, compounds having a condensed ring as represented by the following formulas (P7-1) to (P7-5) among the formula (P1) may shift the ultraviolet absorption area to the visible light side from the single ring compound As it can be, it is preferable from the viewpoint of the sensitivity control of a monomer.

(Wherein, R ^P71 and R ^P72 each independently represent a hydrogen atom or a methyl group, mP72 and mP73 each independently represent an integer of 0 or 1, and when mP72 is 0, mP71 is 1 to 6) Represents an integer, when mp72 is 1, mP71 represents an integer of 2 to 6, when mP73 is 0, mP74 represents an integer of 1 to 6, and when mP73 is 1, mp74 represents an integer of 2 to 6 Represent)
Although the bifunctional monomer was illustrated as a preferable compound in the above, use of trifunctional monomers like the compound represented by Formula (P5-1)-(P5-11) among Formula (P1) is also preferable. The mechanical strength of the polymer or copolymer can be improved. Moreover, since what has an ester bond in mesogen has the ability to start a superposition | polymerization by ultraviolet irradiation, since the addition amount of a polymerization initiator can be reduced, it is more preferable.

(Wherein, R ^P81 and R ^P83 each independently represent a hydrogen atom or a methyl group, mP72 and mP73 each independently represent an integer of 0 or 1, and when mP72 is 0, mP71 is 1 to 6) MP71 represents an integer of 2 to 6 when mp72 is 1, mP74 represents an integer of 1 to 6 when mP73 is 0, and mp74 is an integer of 2 to 6 when mP73 is 1 Represents

  Moreover, in order to adjust the drive voltage of a liquid crystal display element also in Formula (P1), use of monofunctional monomers like the compound represented by following formula (P9-1)-(P9-11) is also preferable.

(Wherein, R ^P91 represents a hydrogen atom or a methyl group, and R ^P92 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms)

  Further, among the formula (P1), it is preferable to impart the photoisomerization function as a monomer, because the photoalignment function by light using the Weigert effect can be utilized. From such a viewpoint, compounds represented by (P10-1) to (P10-11) are preferable.

(Wherein, R ^P101 and R ^P102 each independently represent a hydrogen atom or a methyl group, mP102 and mP103 each independently represent an integer of 0 or 1, and when mP102 is 0, mP101 is 1 to 6) MP101 represents an integer of 2 to 6 when mp102 is 1, mP104 represents an integer of 1 to 6 when mP103 is 0, and mp104 an integer of 2 to 6 when mP103 is 1. Represent)

  The polymerizable monomer component (A) described in detail above is a compound represented by the above-mentioned various specific examples, and is represented by the following general formula (V)

(Wherein, X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or -O- (CH ₂ ) _s — (wherein, s represents an integer of 1 to 11, and an oxygen atom is bonded to an aromatic ring), and U represents a linear or branched C 2-20 carbon atom Group represents a polyvalent aliphatic hydrocarbon group or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and the polyvalent aliphatic hydrocarbon group may be substituted by an oxygen atom within the range where the oxygen atoms are not adjacent to each other And an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted by an oxygen atom within the range where the oxygen atom is not adjacent) or may be substituted by a cyclic substituent, k is 1 Represents an integer of 5 to 5. All 1,4-phenylenes in the formula Is any hydrogen atom _-CH 3, -OCH _3, fluorine atom, or may be substituted by a cyano group.)
Or the following general formula (VI)

(Wherein, X ³ represents a hydrogen atom or a methyl group, and Sp ³ is a single bond, an alkylene group having 1 to 12 carbon atoms, or -O- (CH ₂ ) _t- (wherein t is 2 to 2) Represents an integer of 11 and an oxygen atom is bonded to an aromatic ring), and V represents a linear or branched alkylene group having 2 to 20 carbon atoms or a polyvalent ring having 5 to 30 carbon atoms A cyclic substituent, a structural moiety substituted by an oxygen atom within the range where the oxygen atom in the linear or branched alkylene structure having 2 to 20 carbon atoms is not adjacent, and the chemical structure of these is a carbon constituting the structure The hydrogen atom on the atom is substituted by an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted by an oxygen atom within the range where the oxygen atom is not adjacent) or a cyclic substituent W is a hydrogen atom or a halogen atom Represents an alkyl group having 1 to 15 carbon atoms. In addition, all 1,4-phenylene group in the formula, any hydrogen atom is _-CH 3, -OCH _3, substituted by fluorine atoms, or a cyano group May be
It can also be represented by

Here, when Sp ¹ and Sp ² in the general formula (V) are the same, for example, when they are a linear or branched alkylene group having 1 to 12 carbon atoms, It is preferable from the viewpoint of easy synthesis and easy adjustment of physical properties by adjusting the use ratio of a plurality of compounds having different alkylene chain lengths.

  As described above, the polymerizable monomer component (A) described in detail above is in the range of 0.5% by mass to 20% by mass, particularly in the range of 1% by mass to 10% by mass, in the polymerizable liquid crystal composition. It is preferable to use it in proportions, but it is preferable to adjust at least two kinds of polymerizable monomer components (A) having different Tg at any concentration within the range and adjust the Tg as necessary. . The polymerizable monomer component (A) which is a precursor of a polymer having a high Tg is a polymerizable monomer component (A) having a molecular structure in which the crosslink density is high, and the number of functional groups is 2 or more. Is preferred. The polymer precursor having a low Tg preferably has one or two or more functional groups, and preferably has a structure having an alkylene group or the like as a spacer between the functional groups and having a long molecular length. When adjusting the Tg of the polymer network in order to cope with the thermal stability and impact resistance improvement of the polymer network, it is preferable to appropriately adjust the ratio of the polyfunctional monomer and the monofunctional monomer. In addition, Tg is also associated with molecular-level thermal mobility in the main chain and side chain of the polymer network, and also affects the electro-optical properties. For example, when the crosslinking density is increased, the molecular mobility of the main chain is reduced, the anchoring force with the low molecular weight liquid crystal is increased, the driving voltage is increased, and the falling time is shortened. On the other hand, when the crosslinking density is lowered so as to lower the Tg, the thermal mobility of the polymer main chain is increased, whereby the anchoring force with the low molecular weight liquid crystal is lowered and the driving voltage tends to be lowered. The anchoring force at the polymer network interface is influenced by the molecular mobility of the polymer side chain in addition to the above-mentioned Tg, is monovalent or divalent, and is an acrylate of an alcohol compound having 8 to 18 carbon atoms Alternatively, by using methacrylate as the polymerizable monomer component (A), the anchoring force at the polymer interface can be reduced. In addition, such a polymerizable monomer component (A) is effective for inducing a pretilt angle at the substrate interface and acts in the direction of reducing the anchoring force in the polar angle direction.

  Next, as described above, the liquid crystal composition (B) constituting the liquid crystal layer or the polymerizable liquid crystal composition has the following general formula (i):

(Wherein, R ⁱ¹ and R ⁱ² are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms 8 represents an alkenyloxy group, A ⁱ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and n ⁱ¹ represents 0 or 1. 10 to 50% of a compound represented by % Is contained.

  The compound represented by the general formula (i) is preferably a compound selected from the group of compounds represented by the following general formulas (i-1) to (i-2).

  The compounds represented by General Formula (i-1) are the following compounds.

( ^Wherein , R ⁱ¹¹ and R ⁱ¹² each independently represent the same meaning as R ^L1 and R ^L2 in general formula (i).)
R ⁱ¹¹ and R ⁱ¹² are preferably linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms, and linear alkenyl groups having 2 to 5 carbon atoms. .

  Although the compound represented by general formula (i-1) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

  The lower limit value of the preferable content is 1% by mass, 2% by mass, 3% by mass, 5% by mass, and 7% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 10% by mass, 15% by mass, 20% by mass, 25% by mass, 30% by mass, 35% by mass, 40% by mass, 45% by mass Yes, it is 50% by mass and 55% by mass. The upper limit of the preferable content is 95% by mass, 90% by mass, 85% by mass, and 80% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass Yes, it is 30% by mass and 25% by mass.

  Within the above preferable range, deterioration by light such as a blue LED is less likely to occur.

In the case where a composition having a high response speed while keeping the viscosity of the liquid crystal composition (B) used in the present invention low is required, it is preferable that the above lower limit is high and the upper limit is high. Additionally, keeping the liquid crystal composition used in the present invention the T _NI of (B) high, it is preferred if good composition temperature stability is required is the upper limit value in the lower limit of the above is moderate is moderate. When it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is low and the upper limit value is low.

  The compound represented by general formula (i-1) is preferably a compound selected from the group of compounds represented by general formula (i-1-1).

( ^Wherein , R ⁱ¹² represents the same meaning as in the general formula (i-1).)
The compound represented by General Formula (i-1-1) is a compound selected from the compound group represented by Formula (i-1-1. 1) to Formula (i- 1-1. 3) It is preferable that it is a compound represented by formula (i-1-1. 2) or formula (i- 1-1. 3), and in particular, it is represented by formula (i- 1-1. 3) It is preferable that it is a compound.

  The lower limit of the preferable content of the compound represented by the formula (i-1-1.3) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, and 2% by mass. Yes, 3% by mass, 5% by mass, 7% by mass, and 10% by mass. The upper limit value of the preferable content is 20% by mass, 15% by mass, 13% by mass, and 10% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 7% by mass, 6% by mass, 5% by mass, and 3% by mass.

  The compound represented by the general formula (i-1) is a compound selected from the group of compounds represented by the general formula (i-1-2) as a light having a wavelength of 200 to 400 nm in the ultraviolet region as a backlight. Is preferable in that it has excellent durability even when it is irradiated and can exhibit a voltage holding ratio.

( ^Wherein , R ⁱ¹² represents the same meaning as in the general formula (i-1).)
The lower limit of the preferable content of the compound represented by the formula (i-1-2) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass and 5% by mass, 10 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 35 mass %. The upper limit value of the preferable content is 60 mass%, 55 mass%, 50 mass%, and 45 mass% with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 40% by mass, 38% by mass, 35% by mass, 33% by mass, 30% by mass, 20% by mass, 15% by mass, 10% by mass is there. Among these, from the viewpoint of preventing the deterioration of the liquid crystal layer with respect to blue visible light, the upper limit value of the content is preferably 15% by mass, and particularly preferably 10% by mass.

Furthermore, the compound represented by the general formula (i-1-2) is a compound selected from the compound group represented by the formula (i-2.1) to the formula (i-1-2.4) It is preferable that it is a compound represented by Formula (i-1-2.2) to Formula (i-1-2.4). In particular, the compound represented by the formula (i-1-2.2) is preferable in order to particularly improve the response speed of the liquid crystal composition (B) used in the present invention. Further, when obtaining the high _{T NI} than the response speed, it is preferable to use a compound represented by the formula (i-1-2.3) or the formula (i-1-2.4). It is unpreferable to make content of the compound represented by Formula (i-1-2.3) and Formula (i-1-2.4) into 30 mass% or more, in order to improve the solubility in low temperature .

  The lower limit of the preferable content of the compound represented by the formula (i-1-2.2) to the total amount of the liquid crystal composition (B) used in the present invention is 10% by mass, and 15% by mass Yes, 18% by mass, 20% by mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, 33% by mass, 35% by mass, It is 38% by mass and 40% by mass. The upper limit of the preferable content is 60% by mass, 55% by mass, 50% by mass, and 45% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 40% by mass, 38% by mass, 35% by mass, 32% by mass, 30% by mass, 27% by mass, 25% by mass, and 22% by mass is there.

  The total of the compound represented by the formula (i-1-1.3) and the compound represented by the formula (i-1-2.2) with respect to the total amount of the liquid crystal composition (B) used in the present invention The lower limit value of the preferable content is 10% by mass, 15% by mass, 20% by mass, 25% by mass, 27% by mass, 30% by mass, and 35% by mass, It is 40% by mass. The upper limit of the preferable content is 60% by mass, 55% by mass, 50% by mass, and 45% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 40% by mass, 38% by mass, 35% by mass, 32% by mass, 30% by mass, 27% by mass, 25% by mass, and 22% by mass is there.

  The compound represented by General Formula (i-1) is preferably a compound selected from the group of compounds represented by General Formula (i-1-3).

( ^Wherein , R ⁱ¹³ and R ⁱ¹⁴ each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ⁱ¹³ and R ⁱ¹⁴ are preferably linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms, and linear alkenyl groups having 2 to 5 carbon atoms. .

The lower limit of the preferable content of the compound represented by the formula (i-1-3) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass and 5% by mass, It is 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, and 30 mass%. The upper limit of the preferable content is 60% by mass, 55% by mass, 50% by mass, and 45% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 37% by mass, 35% by mass, 33% by mass, 30% by mass, 27% by mass, 25% by mass, 23% by mass, 20% by mass Yes, 17% by mass, 15% by mass, 13% by mass, and 10% by mass.
Furthermore, the compound represented by the general formula (i-1-3) is a compound selected from the group of compounds represented by the formula (i-3.1. 1) to the formula (i-1.3.1. 2) The compound is preferably a compound represented by the formula (i-3.1), the formula (i-1-3. 3) or the formula (i-1-3.4). In particular, the compound represented by the formula (i-3.1) is preferable in order to particularly improve the response speed of the liquid crystal composition (B) used in the present invention. Further, when obtaining the high _{T NI} than the response speed, the formula (i-1-3.3), the formula (i-1-3.4), the formula (L-1-3.11) and formula (i It is preferable to use the compound represented by -1-3.12). The total of the compounds represented by the formula (i-1.3.3), the formula (i1-3.4), the formula (i-1.3.1.1) and the formula (i-1.3.12.) It is not preferable to make the content of 20% by mass or more in order to improve the solubility at low temperature.

  The lower limit of the preferable content of the compound represented by the formula (i-3.1) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, and 2% by mass Yes, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 20% by mass, 17% by mass, 15% by mass, and 13% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 8% by mass, 7% by mass, and 6% by mass.

  The compound represented by general formula (i-1) is preferably a compound selected from the group of compounds represented by general formula (i-1-4) and / or (i-1-5).

( ^Wherein , R ⁱ¹⁵ and R ⁱ¹⁶ each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ⁱ¹⁵ and R ⁱ¹⁶ are preferably linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms, and linear alkenyl groups having 2 to 5 carbon atoms. .

  The lower limit of the preferable content of the compound represented by the formula (i-1-4) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass and 5% by mass, It is 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. The upper limit value of the preferable content is 25% by mass, 23% by mass, 20% by mass, and 17% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 13% by mass, and 10% by mass.

  The lower limit of the preferable content of the compound represented by the formula (i-1-5) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass and 5% by mass, It is 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. The upper limit value of the preferable content is 25% by mass, 23% by mass, 20% by mass, and 17% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 13% by mass, and 10% by mass.

  Furthermore, the compounds represented by general formulas (i-1-4) and (i-1-5) are represented by formulas (i-4.1) to (i-1-5.3): It is preferable that it is a compound chosen from the compound group which is, and it is preferable that it is a compound represented by Formula (i-1-4.2) or Formula (i-1-5.2).

  The lower limit of the preferable content of the compound represented by the formula (i-1-4.2) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, and 2% by mass. Yes, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 20% by mass, 17% by mass, 15% by mass, and 13% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 8% by mass, 7% by mass, and 6% by mass.

Formula (i-1-1.3), Formula (i-1-2.2), Formula (i-1-3.1), Formula (i-1-3.3), Formula (i-1-1.3) 3.4), It is preferable to combine 2 or more types of compounds chosen from the compound represented by Formula (i-1-3.11) and Formula (i-1-3.12), It is preferable -1.3), the formula (i-1-2.2), the formula (i-3.1), the formula (i-1-3.3), the formula (i-1-3.4) and It is preferable to combine two or more compounds selected from the compounds represented by the formula (i-1-4.2), and the lower limit of the preferable content of the total content of these compounds is the liquid crystal used in the present invention 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, and 13% by mass with respect to the total amount of the composition (B) And at 15% by mass 18% by mass 20% by mass 23% by mass 25% by mass 27% by mass 30% by mass 33% by mass 35% by mass The upper limit is 80% by mass, 70% by mass, 60% by mass, 50% by mass, and 45% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. 40 mass%, 37 mass%, 35 mass%, 33 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass %. When importance is attached to the reliability of the composition, compounds represented by Formula (i-3.1), Formula (i-1.3) and Formula (i-1-3.4)) It is preferable to combine two or more compounds selected from the above, and when importance is attached to the response speed of the composition, it is represented by the formula (i-1-1. 3) and the formula (i- 1 -2.2) It is preferable to combine two or more compounds selected from
The compound represented by general formula (i-1) is preferably a compound selected from the group of compounds represented by general formula (i-1-6).

( ^Wherein , each of ^{Ri 17} and ^{Ri 18} independently represents a methyl group or a hydrogen atom).
The lower limit of the preferable content of the compound represented by the formula (i-1-6) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, and 5% by mass, 10 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 35 mass %. The upper limit value of the preferable content is 60 mass%, 55 mass%, 50 mass%, and 45 mass% with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 40% by mass, 38% by mass, 35% by mass, 33% by mass, and 30% by mass.

  Furthermore, the compound represented by General Formula (i-1-6) is a compound selected from the compound group represented by Formula (i-1-6.1) to Formula (i-1-6.3) Is preferred.

  The compounds represented by the general formula (i-2) are the following compounds.

( ^Wherein , R ⁱ²¹ and R ⁱ²² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in general formula (i).)
R ⁱ²¹ is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and R ^L22 is an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or a carbon atom The alkoxy group of the number 1-4 is preferable.

  The compounds represented by General Formula (i-2) can be used alone, or two or more compounds can be used in combination. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

  When importance is given to solubility at low temperature, setting the content higher is more effective, and conversely, when importance is placed on response speed, setting the content smaller is more effective. Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

  The lower limit of the preferable content of the compound represented by the formula (i-2) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, and 3% %, 5% by mass, 7% by mass, and 10% by mass. The upper limit value of the preferable content is 20% by mass, 15% by mass, 13% by mass, and 10% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 7% by mass, 6% by mass, 5% by mass, and 3% by mass.

  Furthermore, the compound represented by General Formula (i-2) is preferably a compound selected from the group of compounds represented by Formula (i-2.1) to Formula (i-2.6), It is preferable that it is a compound represented by (L-2.1), Formula (i-2.3), Formula (i-2.4), and Formula (i-2.6).

  The liquid crystal composition (B) used in the present invention further contains one or two or more compounds selected from the compounds represented by the general formulas (N-1), (N-2) and (N-3) Is preferred. These compounds correspond to dielectrically negative compounds (the sign of Δε is negative and its absolute value is larger than 2).

[In the general formulas (N-1), (N-2), (N-3) and (N-4), R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 , R ^N32 , R ^N41 and R N ⁴² is each independently an alkyl group having 1 to 8 carbon atoms, or one or two non-adjacent two or more -CH ₂ -in the alkyl chain having 2 to 8 carbon atoms are each independently- Structural moiety having a chemical structure substituted by CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 , A ^N32 , A ^N41 and A ^N42 are each independently (a) 1,4-cyclohexylene group (one -CH present in this group ₂ -or 2 or more non-adjacent -CH _2- may be replaced by -O-) and (b) 1,4-phenylene group (one -CH = present in this group Or two or more non-adjacent -CH = may be replaced by -N =)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH = or two or more non-adjacent —CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by —N =. )
(D) represents a group selected from the group consisting of 1,4-cyclohexenylene groups, and the above groups (a), (b), (c) and (d) are hydrogen atoms in the structure Each may be independently substituted with a cyano group, a fluorine atom or a chlorine atom,
^{Z N11, Z N12, Z N21} , Z N22, Z N31, Z N32, Z N41 and ^{Z N42} are each independently a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH _{2 -, - CH 2 O -} , - COO -, - OCO -, - OCF 2 -, - CF 2 O -, - CH = N-N = CH -, - CH = CH -, - CF = CF- or Represents -C≡C-,
X ^N21 represents a hydrogen atom or a fluorine atom, T ^N31 represents a -CH ₂ -or oxygen atom, X ^N41 represents an oxygen atom, a nitrogen atom or -CH _2- , and Y ^N41 represents a single bond or -CH ₂ - ^{represents, n N11, n N12, n} N21, n N22, n N31, n N32, n N41, and ^{n N42} is an integer of independently ^{0~3, n} N11 ⁺ n ^N12 , N N ²¹ + n N ²² and n ^{N 31} + n ^{N 32} are each independently 1, 2 or 3, and when there are a plurality of A ^{N11 to} A ^N32 and Z ^{N11 to} Z ^N32 , they are identical or different. at ^best, n N41 ^{+ n N42} represents an integer of 0 to ^{3, if a N41} and ^{a N42, Z N41} and ^{Z N42} there are multiple, they differ even for the same Even though it may. ]
The compounds represented by general formulas (N-1), (N-2), (N-3) and (N-4) are preferably compounds in which Δε is negative and the absolute value is larger than 2 .

In the general formulas (N-1), (N-2) and (N-3), R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 each independently have 1 to 8 carbon atoms Alkyl group, alkoxy group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms or alkenyloxy group having 2 to 8 carbon atoms are preferable, and alkyl group having 1 to 5 carbon atoms, the number of carbon atoms An alkoxy group of 1 to 5, an alkenyl group of 2 to 5 carbon atoms or an alkenyloxy group of 2 to 5 carbon atoms is preferable, and an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms is preferable. More preferably, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is further preferable, and an alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable.

  When the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and carbon Alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain Preferred is an alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, preferably linear.

  The alkenyl group is preferably selected from the groups represented by any one of formulas (R1) to (R5). (The black dot in each formula represents a carbon atom in the ring structure.)

A ^{N 11} , A ^{N 12} , A ^{N 21} , A ^{N 22} , A ^{N 31} and A ^{N 32} are each preferably aromatic when it is required to increase Δn independently, and in order to improve the response speed, it is preferable to use fat Group is preferred, and trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5 -Difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1 Be 2,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl Preferred, it is more preferable that represents the following structures,

More preferably, it represents a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group.

^{Z N11, Z N12, Z N21} , Z N22, Z N31 and ^{Z N32} _-CH 2 each _{independently O -, - CF 2 O -} , - CH 2 CH 2 -, - CF 2 CF 2 - or a single bond preferably represents _{an, -CH 2 O -, - CH} 2 CH 2 - or a single bond is more preferable, _-CH 2 O-or a single bond is particularly preferred.

X ^N21 is preferably a fluorine atom.

T ^N31 is preferably an oxygen atom.

n ^{N 11} + n ^{N 12} , n N ²¹ + n N ²² and n ^{N 31} + n ^{N 32} are preferably 1 or 2, and combinations in which n ^{N 11} is 1 and n ^{N 12} is 0, n ^{N 11} is 2 and n ^{N 12} is 0, n ^A combination in which ^{N 11} is 1 and n ^{N 12} is 1, a combination in which n ^{N 11} is 2 and n ^{N 12} is 1, a combination in which n N ²¹ is 1 and n N ²² is 0, n N ²¹ is 2 and n N ²² is A combination of 0, a combination of n ^N31 of 1 and n ^N32 of 0, and a combination of n ^N31 of 2 and n ^N32 of 0 is preferred.

  The lower limit of the preferable content of the compound represented by the formula (N-1) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 10% by mass, and 20% %, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass Yes, 80% by mass. The upper limit value of the preferable content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, and 35% by mass, It is 25% by mass and 20% by mass.

  The lower limit of the preferable content of the compound represented by the formula (N-2) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 10% by mass, and 20% by mass. %, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass Yes, 80% by mass. The upper limit value of the preferable content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, and 35% by mass, It is 25% by mass and 20% by mass.

  The lower limit of the preferable content of the compound represented by the formula (N-3) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 10% by mass, and 20% %, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass Yes, 80% by mass. The upper limit value of the preferable content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, and 35% by mass, It is 25% by mass and 20% by mass.

When a composition having a high response speed while keeping the viscosity of the liquid crystal composition (B) used in the present invention low is required, it is preferable that the above lower limit is low and the upper limit is low. Additionally, keeping the liquid crystal composition used in the present invention the T _NI of (B) high, it is preferred if good composition temperature stability is required a low upper limit lower the lower limit of the above. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value be high and the upper limit value be high.

  Among the compounds represented by the general formulas (N-1) to (N-4), in the liquid crystal composition (B) according to the present invention, in particular, the compound represented by the general formula (N-1) is a liquid crystal display It is preferable from the point which is excellent in the voltage holding ratio in an element, and has low rotational viscosity.

  As a compound represented by general formula (N-1), the compound group represented by the following general formula (N-1a)-(N-1h) can be mentioned.

^{(Wherein, R N11} and ^{R N12} are as defined ^{R N11} and ^{R N12} in the general formula ^{(N-1), n Na11} represents 0 or ^{1, n NB11} is 1 or ^{2, n NC11} is 0 or 1; n ^Nd11 represents 1 or 2; n ^Ne11 represents 1 or 2; n ^Nf11 represents 1 or 2; n ^Ng11 represents 1 or 2; A ^Ne11 represents trans-1, 4 ^{-Represents a} cyclohexylene group or a 1,4-phenylene group, and A ^Ng11 represents a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group, but at least one of them Represents a 1,4-cyclohexenylene group, and Z ^{Ne 11} represents a single bond or ethylene, but at least one represents ethylene).
The liquid crystal composition (B) used in the present invention preferably further contains one or two or more compounds represented by General Formula (J). These compounds correspond to dielectrically positive compounds (Δε is greater than 2).

(Wherein, R ^J1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH ₂ -in the alkyl group are each independently -CH = CH-,- It may be substituted by C≡C-, -O-, -CO-, -COO- or -OCO-,
n ^J1 represents 0, 1, 2, 3 or 4;
A ^J1 , A ^J2 and A ^J3 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , And one or more non-adjacent -CH = present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by -N =).
Group (a), group (b) and group (c) are each independently a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoro group It may be substituted by a methoxy group,
Z ^J1 and ^{Z J2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O-, -COO-, -OCO- or -C≡C-
When n ^J1 is 2, 3 or 4 and there are a plurality of A ^J2 , they may be the same or different, and n ^J1 is 2, 3 or 4 and a plurality of Z ^J1 is present If they are identical or different,
X ^J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )
In the general formula (J), R ^J1 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy having 2 to 8 carbon atoms Group is preferable, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferable. An alkyl group of 1 to 5 or an alkenyl group of 2 to 5 carbon atoms is more preferable, an alkyl group of 2 to 5 carbon atoms or an alkenyl group of 2 to 3 carbon atoms is further preferable, and an alkenyl group of 3 carbon atoms (Propenyl group) is particularly preferred.

When importance is attached to reliability, R ^J1 is preferably an alkyl group, and when importance is attached to decrease in viscosity, it is preferably an alkenyl group.

  When the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and carbon Alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain Preferred is an alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, preferably linear.

  The alkenyl group is preferably selected from the groups represented by any one of formulas (R1) to (R5). (The black dot in each formula represents a carbon atom in a ring structure to which an alkenyl group is bonded.)

A ^J1 , A ^J2 and A ^J3 are each preferably aromatic when it is required to increase Δn independently, and in order to improve the response speed, it is preferably aliphatic, and trans- 1,4-cyclohexylene group, 1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene It is preferable to represent a 2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, which are substituted by a fluorine atom It is more preferable to represent the following structure.

It is more preferable to represent the following structure.

Z ^J1 and Z ^J2 each preferably independently represent -CH ₂ O-, -OCH _2- , -CF ₂ O-, -CH ₂ CH _2- , -CF ₂ CF ₂ -or a single bond,- More preferred is OCH ₂ —, —CF ₂ O—, —CH ₂ CH ₂ — or a single bond, and particularly preferred is —OCH ₂ —, —CF ₂ O— or a single bond.

X ^J1 is preferably a fluorine atom or a trifluoromethoxy group, more preferably a fluorine atom.

n ^J1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, and if emphasis is placed on improvement of Δε, then 0 or 1 is preferred, and if emphasis is placed on T _NI , 1 or 2 is preferred. preferable.

  There is no particular limitation on the types of compounds that can be combined, but they are used in combination according to the desired properties such as low temperature solubility, transition temperature, electrical reliability, birefringence and the like. The types of compounds to be used are, for example, one type, two types, and three types in one embodiment of the present invention. Furthermore, in another embodiment of the present invention, there are four types, five types, six types, and seven or more types.

  In the liquid crystal composition (B) used in the present invention, the content of the compound represented by the general formula (J) is low temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, It is necessary to appropriately adjust according to the required performance such as drip marks, burn-in, dielectric anisotropy and the like.

  The lower limit of the preferable content of the compound represented by the general formula (J) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 10% by mass, and 20% by mass 30% by mass 40% by mass 50% by mass 55% by mass 60% by mass 65% by mass 70% by mass 75% by mass And 80% by mass. The upper limit of the preferable content is, for example, 95% by mass, 85% by mass, and 75% by mass in one embodiment of the present invention, based on the total amount of the liquid crystal composition (B) used in the present invention. It is 65 mass%, 55 mass%, 45 mass%, 35 mass%, and 25 mass%.

It is preferable to keep the viscosity of the liquid crystal composition (B) used in the present invention low and lower the above lower limit and lower the upper limit when a composition having a high response speed is required. Furthermore, it is preferable to keep _TNI of the liquid crystal composition (B) used in the present invention high, and lower the above lower limit value and lower the upper limit value when a composition having good temperature stability is required. When it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the lower limit and raise the upper limit.

When importance is attached to reliability, R ^J1 is preferably an alkyl group, and when importance is attached to decrease in viscosity, it is preferably an alkenyl group.

  As a compound represented by General formula (J), the compound represented by General formula (M) and the compound represented by General formula (K) are preferable.

(Wherein, R ^M1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH ₂ -in the alkyl group are each independently -CH = CH-,- It may be substituted by C≡C-, -O-, -CO-, -COO- or -OCO-,
n ^M1 represents 0, 1, 2, 3 or 4 and
A ^M1 and A ^M2 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- And (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =)
And hydrogen atoms on the above groups (a) and (b) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^M1 and ^{Z M2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O-, -COO-, -OCO- or -C≡C-
When n ^M1 is 2, 3 or 4 and there are a plurality of ^{AM 2} , they may be the same or different, and n ^M1 is 2, 3 or 4 and a plurality of Z ^M1 is present If they are identical or different,
X ^M1 and X ^M3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,
X ^M2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )

(Wherein, R ^K1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH ₂ -in the alkyl group are each independently -CH = CH-,- It may be substituted by C≡C-, -O-, -CO-, -COO- or -OCO-,
n ^K1 represents 0, 1, 2, 3 or 4;
A ^K1 and A ^K2 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- And (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =)
And hydrogen atoms on the above groups (a) and (b) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^K1 and ^{Z K2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O-, -COO-, -OCO- or -C≡C-
When n ^K1 is 2, 3 or 4 and there are a plurality of ^{AK 2} , they may be the same or different, and n ^K1 is 2, 3 or 4 and a plurality of Z ^K1 is present If they are identical or different,
X ^K1 and X ^K3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,
X ^K2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )

In general formula (M), R ^M1 is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy having 2 to 8 carbon atoms Group is preferable, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferable. An alkyl group of 1 to 5 or an alkenyl group of 2 to 5 carbon atoms is more preferable, an alkyl group of 2 to 5 carbon atoms or an alkenyl group of 2 to 3 carbon atoms is further preferable, and an alkenyl group of 3 carbon atoms (Propenyl group) is particularly preferred.

When importance is attached to reliability, R ^M1 is preferably an alkyl group, and when importance is attached to decrease in viscosity, it is preferably an alkenyl group.

  When the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and carbon Alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain Preferred is an alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, preferably linear.

  The alkenyl group is preferably selected from the groups represented by any one of formulas (R1) to (R5). (The black dot in each formula represents a carbon atom in a ring structure to which an alkenyl group is bonded.)

A ^M1 and A ^M2 are each preferably aromatic when it is required to increase Δn independently, and in order to improve the response speed, it is preferably aliphatic, and trans-1,4 -Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group 2, 3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It is preferable to represent a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferable to represent the following structure,

It is more preferable to represent the following structure.

Z ^M1 and ^{Z M2} each _{independently -CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CF 2 O-, -CH ₂ CH ₂ - or a single bond is more preferable, _-CF 2 O-or a single bond is particularly preferred.

n ^M1 is preferably 0, 1, 2 or 3 and is preferably 0, 1 or 2; 0 or 1 is preferred when emphasis is placed on improvement of Δε, and 1 or 2 is preferred when T _NI is emphasized preferable.

  There is no particular limitation on the types of compounds that can be combined, but they are used in combination according to the desired properties such as low temperature solubility, transition temperature, electrical reliability, birefringence and the like. The types of compounds to be used are, for example, one type, two types, and three types in one embodiment of the present invention. Furthermore, in another embodiment of the present invention, there are four types, five types, six types, and seven or more types.

  In the liquid crystal composition (B) used in the present invention, the content of the compound represented by the general formula (M) is the solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, It is necessary to appropriately adjust according to the required performance such as drip marks, burn-in, dielectric anisotropy and the like.

  The lower limit value of the preferable content of the compound represented by the formula (M) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 10% by mass, and 20% by mass Yes, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, It is 80% by mass. The upper limit of the preferable content is, for example, 95% by mass, 85% by mass, and 75% by mass in one embodiment of the present invention, based on the total amount of the liquid crystal composition (B) used in the present invention. It is 65 mass%, 55 mass%, 45 mass%, 35 mass%, and 25 mass%.

It is preferable to keep the viscosity of the liquid crystal composition (B) used in the present invention low and lower the above lower limit and lower the upper limit when a composition having a high response speed is required. Furthermore, it is preferable to keep _TNI of the liquid crystal composition (B) used in the present invention high, and lower the above lower limit value and lower the upper limit value when a composition having good temperature stability is required. When it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the lower limit and raise the upper limit.

  The liquid crystal composition of the present invention preferably further contains one or more compounds represented by General Formula (L). The compounds represented by the general formula (L) correspond to dielectric substantially neutral compounds (the value of Δε is −2 to 2).

(Wherein, R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH ₂ -in the alkyl group are independently of each other It may be substituted by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,
n ^L1 represents 0, 1, 2 or 3;
A ^L1 , A ^L2 and A ^L3 are each independently (a) 1,4-cyclohexylene group (one -CH _2- present in this group or two or more non-adjacent -CH _2- May be replaced by -O-) and (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = is -N May be replaced by =.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH = or two or more non-adjacent —CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by —N =. )
And the group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and ^{Z L2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 _{-, - CF 2 O -,} - CH = N-N = CH -, - CH = CH -, - represents CF = CF- or -C≡C-,
When n ^L1 is 2 or 3 and a plurality of A ^L2 is present, they may be the same or different, and when n ^L1 is 2 or 3 and a plurality of Z ^L2 is present, they may be May be the same or different, but the compounds represented by formulas (N-1), (N-2), (N-3), (J) and (i) are excluded. )
The compounds represented by formula (L) may be used alone or in combination. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the desired performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of compound used is, for example, one type in one embodiment of the present invention. Or in another embodiment of the present invention, there are 2 types, 3 types, 4 types, 5 types, 5 types, 6 types, 7 types, 8 types, 9 types and 10 It is more than kind.

  In the liquid crystal composition (B) used in the present invention, the content of the compound represented by the general formula (L) is the solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, It is necessary to appropriately adjust according to the required performance such as drip marks, burn-in, dielectric anisotropy and the like.

  The lower limit of the preferable content of the compound represented by the formula (L) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 10% by mass, and 20% by mass Yes, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, It is 80% by mass. The upper limit value of the preferable content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, and 35% by mass, It is 25% by mass.

In the case where a composition having a high response speed while keeping the viscosity of the liquid crystal composition (B) used in the present invention low is required, it is preferable that the above lower limit is high and the upper limit is high. Additionally, keeping the liquid crystal composition used in the present invention the T _NI of (B) high, it is preferable if the temperature stability with good composition is required upper limit higher the lower limit of the above is high. When it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value be low and the upper limit value be low.

When reliability is important, both R ^L1 and R ^L2 are preferably alkyl groups, and when importance is given to reducing the volatility of the compound, alkoxy groups are preferable, and viscosity reduction is important When doing, at least one is preferably an alkenyl group.

    The number of halogen atoms present in the molecule is preferably 0, 1, 2 or 3 and is preferably 0 or 1. When importance is attached to compatibility with other liquid crystal molecules, 1 is preferred.

R ^L1 and R ^L2 are, when the ring structure to which they are bonded is a phenyl group (aromatic), a linear alkyl group of 1 to 5 carbon atoms, or a linear alkyl group of 1 to 4 carbon atoms Alkoxy groups and alkenyl groups having 4 to 5 carbon atoms are preferred, and in the case where the ring structure to which they are attached is a saturated ring structure such as cyclohexane, pyran and dioxane, a straight chain having 1 to 5 carbon atoms The alkyl group, the linear alkoxy group having 1 to 4 carbon atoms, and the linear alkenyl group having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, preferably linear.

  The alkenyl group is preferably selected from the groups represented by any one of formulas (R1) to (R5). (The black dot in each formula represents a carbon atom in the ring structure.)

n ^L1 is preferably 0 when importance is attached to the response speed, 2 or 3 is preferable to improve the upper limit temperature of the nematic phase, and 1 is preferable to balance them. Moreover, in order to satisfy the characteristics required as a composition, it is preferable to combine compounds of different values.

A ^{L 1} , A ^{L 2} and A ^{L 3} are preferably aromatic when it is required to increase Δn, and are preferably aliphatic to improve the response speed, and each of them is independently trans- 1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group 1,4-cyclohexenylene group 1,4-bicyclo [2.2.2] octyrene group piperidine-1,4-diyl group naphthalene-2,6-diyl group decahydronaphthalene-2,6 -Preferably represents a diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, more preferably represents the following structure,

More preferably, it represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

It is preferable that Z ^L1 and Z ^L2 be a single bond when the response speed is important.

  The compound represented by formula (L) preferably has 0 or 1 halogen atoms in the molecule.

  The compound represented by Formula (L) is preferably a compound selected from the group of compounds represented by Formulas (L-3) to (L-8).

  The compounds represented by General Formula (L-3) are the following compounds.

(Wherein, R ^L31 and R ^L32 each independently represent the same meaning as R ^L1 and R ^L2 in general formula (L).)
Each of R ^L31 and R ^L32 is preferably independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

  Although a compound denoted by a general formula (L-3) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

  The lower limit of the preferable content of the compound represented by the formula (L-3) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, and 3% %, 5% by mass, 7% by mass, and 10% by mass. The upper limit value of the preferable content is 20% by mass, 15% by mass, 13% by mass, and 10% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 7% by mass, 6% by mass, 5% by mass, and 3% by mass.

When obtaining a high birefringence highly effective when larger amount to set the content, on the contrary, when importance is attached to high T _NI highly effective when fewer to set the content. Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

  The compounds represented by General Formula (L-4) are the following compounds.

(Wherein, R ^L41 and R ^L42 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L).)
R ^L41 is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and R ^L42 is an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or a carbon atom The alkoxy group of the number 1-4 is preferable. )
Although a compound denoted by a general formula (L-4) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

  In the liquid crystal composition (B) used in the present invention, the content of the compound represented by the general formula (L-4) is the solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility It is necessary to appropriately adjust according to the required performance such as the polarity, the dripping mark, the burn-in, and the dielectric anisotropy.

  The lower limit of the preferable content of the compound represented by the formula (L-4) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, and 3% %, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, 20% by mass, 23% by mass, and 26% by mass Present, 30% by mass, 35% by mass, and 40% by mass. The upper limit of the preferable content of the compound represented by the formula (L-4) to the total amount of the liquid crystal composition (B) used in the present invention is 50% by mass, 40% by mass, and 35% by mass %, 30% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass.

  The compounds represented by General Formula (L-5) are the following compounds.

(Wherein, R ^L51 and R ^L52 each independently represent the same meaning as R ^L1 and R ^L2 in general formula (L).)
R ^L51 is preferably an alkenyl group having 2 to 5 alkyl groups or carbon atoms of 1 to 5 carbon ^{atoms, R L52} is an alkyl group having 1 to 5 carbon atoms, an alkenyl group or a carbon atom of the carbon atoms 4-5 The alkoxy group of the number 1-4 is preferable.

  Although the compound represented by general formula (L-5) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

  In the liquid crystal composition (B) used in the present invention, the content of the compound represented by the general formula (L-5) is the solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility It is necessary to appropriately adjust according to the required performance such as the polarity, the dripping mark, the burn-in, and the dielectric anisotropy.

  The lower limit of the preferable content of the compound represented by the formula (L-5) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, and 3% %, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, 20% by mass, 23% by mass, and 26% by mass Present, 30% by mass, 35% by mass, and 40% by mass. The upper limit of the preferable content of the compound represented by the formula (L-5) to the total amount of the liquid crystal composition (B) used in the present invention is 50% by mass, 40% by mass, and 35% %, 30% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass

  The compounds represented by General Formula (L-6) are the following compounds.

(Wherein, R ^L61 and R ^L62 each independently represent the same as R ^L1 and R ^L2 in General Formula (L), and X ^L61 and X ^L62 each independently represent a hydrogen atom or a fluorine atom. )
Each of R ^L61 and R ^L62 is preferably independently an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and one of X ^L61 and X ^L62 is a fluorine atom, and the other is a hydrogen atom Is preferred.

  Although a compound denoted by a general formula (L-6) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

  The lower limit of the preferable content of the compound represented by the formula (L-6) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, and 3% %, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, 20% by mass, 23% by mass, and 26% by mass Present, 30% by mass, 35% by mass, and 40% by mass. The upper limit of the preferable content of the compound represented by the formula (L-6) to the total amount of the liquid crystal composition (B) used in the present invention is 50% by mass, 40% by mass, and 35% %, 30% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass. When emphasis is placed on increasing Δn, it is preferable to increase the content, and when emphasis is put on precipitation at low temperature, it is preferable to reduce the content.

  The compounds represented by General Formula (L-7) are the following compounds.

(Wherein, R ^L71 and R ^L72 each independently represent the same as R ^L1 and R ^L2 in the general formula (L), and A ^L71 and A ^L72 are each independently A ^L2 and A ^L2 in the general formula (L) A hydrogen having the same meaning as A ^L3 is represented, but each of hydrogen atoms on A ^L71 and A ^L72 may be independently substituted by a fluorine atom, and Z ^L71 has the same meaning as Z ^L2 in formula (L), X ^L71 and X ^L72 each independently represent a fluorine atom or a hydrogen atom.)
^{Wherein, R L71} and ^{R L72} are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms 2 to 5 carbon atoms ^{preferably, A L71} and ^{A L72} each independently 1,4-cyclohexylene group or a 1,4-phenylene group is preferably ^a hydrogen atom on ^{a L71} and ^{a L72} may be substituted by fluorine atoms ^{independently, Z L71} is a single A bond or COO- is preferable, a single bond is preferable, and X ^L71 and X ^L72 are preferably hydrogen atoms.

  There is no particular limitation on the types of compounds that can be combined, but they are combined according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of compound used is, for example, one type, two types, three types, and four types according to one embodiment of the present invention.

  In the liquid crystal composition (B) used in the present invention, the content of the compound represented by the general formula (L-7) is the solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility It is necessary to appropriately adjust according to the required performance such as the polarity, the dripping mark, the burn-in, and the dielectric anisotropy.

  The lower limit of the preferable content of the compound represented by the formula (L-7) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, and 3% %, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, and 20% by mass. The upper limit of the preferable content of the compound represented by the formula (L-7) to the total amount of the liquid crystal composition (B) used in the present invention is 30% by mass, 25% by mass, and 23% %, 20% by mass, 18% by mass, 15% by mass, 10% by mass and 5% by mass.

When a liquid crystal composition (B) to be used in the present invention is desired to have a high _TNI embodiment, it is preferable to increase the content of the compound represented by formula (L-7), and a low viscosity embodiment If desired, it is preferable to reduce the content.

  The compounds represented by General Formula (L-8) are the following compounds.

(Wherein, R L ⁸¹ and R L ⁸² each independently represent the same meaning as R ^{L 1} and R ^{L 2} in general formula (L), and A L ⁸¹ represents the same meaning or single bond as A ^{L 1} in general formula (L) However, each hydrogen atom on ^{AL 81} may be independently substituted by a fluorine atom, and X ^{L81 to} X ^L86 each independently represent a fluorine atom or a hydrogen atom.)
^{Wherein, R L81} and ^{R L82} are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms 2 to 5 carbon atoms ^{preferably, A L81} is 1, 4-cyclohexylene group or 1,4-phenylene group is preferable, a hydrogen atom on a ^L71 and a ^L72 may be substituted independently by fluorine atoms, the general formula (L-8) in the same of The number of fluorine atoms on the ring structure is preferably 0 or 1, and the number of fluorine atoms in the molecule is preferably 0 or 1.

  There is no particular limitation on the types of compounds that can be combined, but they are combined according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of compound used is, for example, one type, two types, three types, and four types according to one embodiment of the present invention.

  In the liquid crystal composition (B) used in the present invention, the content of the compound represented by the general formula (L-8) is the solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility It is necessary to appropriately adjust according to the required performance such as the polarity, the dripping mark, the burn-in, and the dielectric anisotropy.

  The lower limit of the preferable content of the compound represented by the formula (L-8) to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, and 3% %, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, and 20% by mass. The upper limit of the preferable content of the compound represented by the formula (L-8) to the total amount of the liquid crystal composition (B) used in the present invention is 30% by mass, 25% by mass, and 23% %, 20% by mass, 18% by mass, 15% by mass, 10% by mass and 5% by mass.

When a liquid crystal composition (B) used in the present invention is desired to have a high _TNI embodiment, the content of the compound represented by formula (L-8) is preferably increased, and a low viscosity embodiment is used. If desired, it is preferable to reduce the content.

  In general formula (i), general formula (L), (N-1), (N-2), (N-3) and (J) with respect to the total amount of liquid crystal composition (B) used by this invention The lower limit of the preferable content of the total of the compounds represented is 80% by mass, 85% by mass, 88% by mass, 90% by mass, 92% by mass and 93% by mass 94% by mass, 95% by mass, 96% by mass, 97% by mass, 98% by mass, 99% by mass and 100% by mass. The upper limit value of the preferable content is 100% by mass, 99% by mass, 98% by mass, and 95% by mass. However, from the viewpoint of obtaining a composition having a large absolute value of Δε, any one of the compounds represented by the general formulas (N-1), (N-2), (N-3) or (J) is 0 It is preferable that it is mass%.

  The general formula (i), the general formulas (L-1) to (L-7), and the general formulas (M-1) to (M-8) with respect to the total amount of the liquid crystal composition (B) used in the present invention The lower limit of the preferable content of the total of the compounds represented by the general formulas (N-1) to (N-4) is 80% by mass, 85% by mass, and 88% by mass, and 90% by mass 92% by mass 93% by mass 94% by mass 95% by mass 96% by mass 97% by mass 98% by mass 99% by mass , 100% by mass. The upper limit value of the preferable content is 100% by mass, 99% by mass, 98% by mass, and 95% by mass.

  The liquid crystal composition (B) used in the present invention preferably does not contain a compound having a structure in which oxygen atoms such as a peracid (-CO-OO-) structure are bonded to each other in the molecule.

  In the liquid crystal composition (B) used in the present invention, when importance is placed on the reliability and long-term stability of the composition, the content of the compound having a carbonyl group is 5% by mass or less based on the total mass of the composition. It is preferable that the content be 3% by mass or less, still more preferably 1% by mass or less, and most preferably substantially non-containing.

  In the liquid crystal composition (B) used in the present invention, when importance is placed on stability due to UV irradiation, the content of the compound substituted by chlorine atoms is 15% by mass or less based on the total mass of the composition. Is preferably 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, and preferably 3% by mass or less. Is more preferred.

  In the liquid crystal composition (B) used in the present invention, it is preferable to increase the content of the compound in which all the ring structures in the molecule are 6-membered rings, and include the compound in which the ring structures in the molecules are all 6-membered rings. The amount is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, based on the total mass of the composition, and the ring in the molecule is substantially preferable. Most preferably, the composition is composed only of compounds which are all six-membered rings in structure.

  In the liquid crystal composition (B) used in the present invention, in order to suppress deterioration due to oxidation of the composition, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and has a cyclohexenylene group The content of the compound is preferably 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less based on the total mass of the composition. It is preferable to do, and it is further preferable not to contain substantially.

In the liquid crystal composition (B) used in the present invention, when importance is attached to improvement of viscosity and improvement of _TNI, a 2-methylbenzene-1,4-diyl group in which a hydrogen atom may be substituted by halogen is selected. It is preferable to reduce the content of the compound having in the molecule, and the content of the compound having the 2-methylbenzene-1,4-diyl group in the molecule is 10% by mass or less based on the total mass of the composition. The content is preferably 8% by mass or less, more preferably 5% by mass or less, preferably 3% by mass or less, and still more preferably substantially non-containing.

  In the present application, "not substantially contained" means that it is not contained except for unintentionally contained substances.

  When the compound contained in the composition of the first embodiment of the present invention has an alkenyl group as a side chain, when the alkenyl group is bonded to cyclohexane, the number of carbon atoms of the alkenyl group is 2 to 5 When the alkenyl group is bonded to benzene, the number of carbon atoms of the alkenyl group is preferably 4 to 5, and the unsaturated bond of the alkenyl group and benzene are directly bonded. Preferably not.

  The polymerizable liquid crystal composition used in the present invention proceeds with polymerization even in the absence of a polymerization initiator, but may contain a polymerization initiator in order to accelerate the polymerization.

  Here, as the polymerization method, radical polymerization, anionic polymerization, cationic polymerization and the like can be used, but polymerization by radical polymerization is preferable, radical polymerization by light fleece rearrangement, radical polymerization by a photopolymerization initiator More preferable.

  As a radical polymerization initiator, although a thermal polymerization initiator and a photoinitiator can be used, a photoinitiator is preferable. Specifically, the following compounds are preferred.

Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (4- 2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- Acetophenones such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4'-phenoxyacetophenone, 4'-ethoxyacetophenone;
Benzoins such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, benzoin ethyl ether;
Acyl phosphine oxides such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide;
Benzyl, methyl phenylglyoxy ester type;
Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4' Benzophenones such as tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone and the like;
Thioxanthones such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and the like;
Amino benzophenones such as Michler's ketone, 4,4'-diethylamino benzophenone;
Preferred are 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like. Among these, benzyl dimethyl ketal is most preferable.

  It is also preferable to use a plurality of polymerization initiators in consideration of the lifetime and reactivity of the radical.

  When forming a liquid crystal layer from the polymerizable liquid crystalline composition detailed above, for example, in the case of applying a vertical alignment cell such as VA mode, vertical alignment is performed together with the above-mentioned polymerizable monomer component (a) as a monomer. An acrylate or methacrylate of an alcohol compound which has no inducing mesogenic group, is monovalent or divalent, and has 8 to 18 carbon atoms may be used as a monomer, and is preferably used in combination with a monomer having a mesogenic group .

  When a polymer network (A) is formed in a vertically aligned cell by phase separation polymerization using a polymerizable liquid crystal composition for manufacturing a liquid crystal display element, a fibrous or columnar polymer network (A) is a liquid crystal cell substrate On the other hand, it is preferable that the liquid crystal composition (B) is formed in substantially the same direction as the vertical direction. In addition, when a vertical alignment film in which a pre-tilt angle is induced by using a rubbing process or the like so that liquid crystal induces tilt alignment to the vertical alignment film on the cell substrate surface is used, pretilt alignment is performed. It is preferable that the fibrous or columnar polymer network (A) is formed to be inclined in the same direction as the liquid crystal composition (B). The tilt of the polymer network (A) may be chosen to occur spontaneously at the substrate interface. Alternatively, the polymer network (A) may be formed by applying a voltage to bring the liquid crystal into a tilted alignment state and irradiating ultraviolet light or the like.

  Furthermore, as a method of inducing a pretilt angle while applying a voltage, polymerization is performed while applying a voltage in a range of about 0.9 V lower than a threshold voltage of liquid crystal for manufacturing a liquid crystal display element to about 2 V higher. Alternatively, a voltage higher than the threshold voltage may be applied for a short time of several seconds to several tens of seconds during the formation of the polymer network (A), and then may be made lower than the threshold voltage to form a polymer network.

  The fibrous or columnar polymer network is preferably formed to be inclined to induce a pretilt angle of 90 to 80 degrees with respect to the transparent substrate plane, and the pretilt angle is 90 to 85 degrees. The range of 89.9 degrees to 85 degrees, the range of 89.9 degrees to 87 degrees, and the range of 89.9 degrees to 88 degrees are particularly preferable. The fibrous or columnar polymer network formed by any method is characterized in connecting between two cell substrates. As a result, the thermal stability of the pretilt angle can be improved, and the reliability of the liquid crystal display element can be enhanced.

  In addition, as a method of inducing the pretilt angle of the liquid crystal composition (B) by forming the fibrous or columnar polymer network (A) by tilt alignment, alkylene located between the polymerizable functional group and the mesogen group A bifunctional acrylate having a small pretilt angle induction angle of 6 or more carbon atoms and a functional group, and a bifunctional acrylate having a large pretilt angle induction angle of 5 or more carbon atoms of an alkylene group between mesogen groups And combinations thereof. A desired pretilt angle can be induced near the interface by adjusting the compounding ratio of these compounds.

  Furthermore, there is a method of forming a fibrous or columnar polymer network (A) by adding a monomer having a reversible photoalignment function in the range of at least 0.01% by mass to 1% by mass. In this case, in the trans form, it has a rod-like form similar to the low molecular weight liquid crystal, and affects the alignment state of the low molecular weight liquid crystal. The transformer contained in the polymerizable liquid crystal composition for producing a liquid crystal display device is aligned so that the direction in which the ultraviolet light travels and the long axis direction of the rod-like molecule become parallel when irradiated with ultraviolet light from the top of the cell as parallel light. At the same time, low molecular weight liquid crystal is also aligned so as to align in the molecular long axis direction of the trans form. When the cell is inclined and irradiated with ultraviolet light, the long molecular axis of the transformer body is oriented in the inclined direction so that the liquid crystal is oriented in the inclined direction of the ultraviolet light. That is, a pretilt angle is induced to exhibit a photoalignment function. At this stage, crosslinking of the monomers induces the pretilt angle to be immobilized by the fibrous or columnar polymer network formed by polymerization phase separation. Therefore, the induction of the important pretilt angle in the VA mode can be achieved by a method of causing polymer phase separation while applying a voltage, a method of adding a plurality of monomers having different induced pretilt angles and polymer phase separation, a monomer having a reversible photoalignment function And a method of aligning the liquid crystal composition (B) and the monomer in the direction in which the ultraviolet light travels using the photoalignment function exhibited by the liquid crystal to separate the polymer phase, and the liquid crystal element of the present invention is selected from these as needed. Can be made.

  Here, the monomer having a photoalignment function may be a photoisomer compound which absorbs ultraviolet rays to be in a trans form, or may be a photoisomerization compound which absorbs ultraviolet rays to be a cis form. Furthermore, it is preferable that the reaction rate of the monomer having the photoalignment function is slower than the reaction rate of monomers other than the monomer having the photoalignment function. When irradiated with ultraviolet light, the monomer having a photoalignment function immediately becomes a trans form, and when it is oriented in the direction in which light travels, surrounding monomers and non-polymerized liquid crystal compositions are also oriented in the same direction. At this time, polymerization phase separation proceeds, and the orientation easy axis direction of the liquid crystal composition (B) and the polymer network is aligned in the same direction as the orientation easy axis of the monomer having a photoalignment function and the pretilt angle is induced Be done.

  Furthermore, in the case of applying a parallel alignment cell such as IPS or FFS mode, the surface of the liquid crystal cell substrate is formed of a fibrous or columnar polymer network (A) by phase separation polymerization using a liquid crystal composition for manufacturing a liquid crystal display element. The liquid crystal composition (B) is parallel-aligned to the alignment direction of the alignment film in the liquid crystal composition (B) and the refractive index anisotropy or alignment easy axis direction of the formed fibrous or columnar polymer network Preferably, it is formed in substantially the same direction as the orientation direction of. Furthermore, it is more preferable that the fibrous or columnar polymer network is present substantially throughout the cells except for the voids in which the liquid crystal composition (B) is dispersed. For the purpose of inducing the pretilt angle with respect to the polymer interface direction, a monomer having a mesogenic group is used as a monomer having a monohydric or bivalent alcohol compound having 8 to 18 carbon atoms as a monomer. It is preferred to use.

  Furthermore, although the electro-optical properties are influenced by the surface area of the polymer network interface and the void spacing of the polymer network, it is important not to cause light scattering, and it is preferable to make the mean void spacing smaller than the wavelength of visible light. For example, there is a method of increasing the content of the monomer composition in order to widen the surface area of the interface and reduce the gap spacing. Thus, the polymer network is formed such that the surface area of the interface is increased by changing the polymerization phase separation structure and the gap spacing becomes fine, and the driving voltage and the fall time become short. The polymerization phase separation structure is also influenced by the polymerization temperature.

  In the present invention, it is preferable to obtain a phase separation structure having fine voids by polymerizing at a high phase separation rate. The phase separation speed is greatly influenced by the compatibility between the low molecular liquid crystal and the monomer and the polymerization speed. Since the composition largely depends on the molecular structure and the content of the compound, it is preferable to use it by appropriately adjusting the composition. When the compatibility is high, it is preferable to use a monomer having a high polymerization rate, and in the case of ultraviolet polymerization, it is preferable to increase the ultraviolet intensity. Moreover, it is also preferable to increase the content of the monomer in the liquid crystal composition for manufacturing a device. When the compatibility is low, the phase separation speed is sufficiently fast, which is preferable for producing the liquid crystal element of the present invention. As a method of reducing the compatibility, a method of polymerizing at a low temperature can be mentioned. When the temperature is low, the degree of alignment order of the liquid crystal is increased, and the compatibility between the liquid crystal composition (B) and the monomer is reduced, so that the separation speed of the polymer phase can be increased. As another method, there may also be mentioned a method of polymerizing a liquid crystal composition for producing a liquid crystal display element at a temperature showing a supercooling state. In this case, the temperature may be slightly lower than the melting point of the liquid crystal composition for manufacturing a liquid crystal display element, and it is possible to accelerate the phase separation only by lowering the temperature by several degrees, which is preferable. Thus, the polymer phase separation structure corresponding to the case where a monomer content of several tens of mass% is added to the liquid crystal, that is, the surface area of the polymer network interface which is a structure acting to shorten the fall time A fine polymer network structure is formed. Therefore, it is preferable to appropriately adjust the composition of the liquid crystal composition for manufacturing a liquid crystal display element in consideration of the alignment function, the crosslink density, the anchoring force and the gap distance so that the fall time is short.

  In the liquid crystal display device, it is necessary to prevent light scattering in order to obtain a high contrast display, but in view of the method described above, it is possible to obtain the target voltage-transmittance characteristics and switching characteristics. It is important to control the separation structure to form a suitable polymer network layer structure.

  More specifically, the liquid crystal layer having such a polymer network layer structure has a structure in which the polymer network layer is formed on the entire surface of the liquid crystal display element in the liquid crystal phase and the liquid crystal phase is continuous. Preferably, the alignment easy axis or uniaxial optical axis of the polymer network (A) is substantially in the same direction as the alignment easy axis of the low molecular weight liquid crystal, and the polymer network is formed to induce the pretilt angle of the low molecular weight liquid crystal. It is preferable that light scattering does not occur by reducing the average gap distance of the polymer network to at least 450 nm smaller than the wavelength of visible light. Furthermore, in order to make the falling time of the response shorter than the response time of the low molecular liquid crystal alone by the interaction effect (the anchoring force) of the polymer network (A) and the low molecular liquid crystal, it may be in the range of 50 nm to 450 nm. preferable. In order for the falling time to be reduced by the influence of the cell thickness of the liquid crystal and to show the falling time as thin as possible even if the cell thickness is large, at least the lower limit is about 200 nm and the upper limit is about 450 nm. It is preferable that the If the average gap distance is reduced, the increase in drive voltage becomes an issue, but to suppress the increase in drive voltage to 25 V or less and shorten the fall response time, it is better to fall within the range of around 250 nm to 450 nm. The falling response time can be improved to about 5 msec to about 1 msec, which is preferable. In order to suppress the increase in drive voltage to about 5 V or less, the average gap distance is preferably in the range of about 300 nm to 450 nm. Furthermore, it is also possible to control the average gap interval of the polymer network (A) to make the falling response time a high-speed response of 1 msec or less.

  When such a high-speed response is used, the driving voltage may be increased to 30 V or more, but the average gap distance may be between 50 nm and 250 nm to be 0.5 msec or less. It is preferable to make it near. The mean diameter of the polymer network is preferably in the range of 20 nm to 700 nm, contrary to the mean void spacing. The average diameter tends to increase as the monomer content increases. If the reactivity is increased to increase the polymerization phase separation speed, the density of the polymer network will increase and the average diameter of the polymer network will decrease, so the phase separation conditions may be adjusted as necessary. When the monomer content is 10% by mass or less, the average diameter is preferably in the range of 20 nm to 160 nm, and in the range of 200 nm to 450 nm, the average diameter is preferably in the range of 40 nm to 160 nm. . When the monomer content is more than 10% by mass, the range of 50 nm to 700 nm is preferable, and the range of 50 nm to 400 nm is more preferable.

  In contrast to the structure in which the polymer network layer is formed on the entire surface of the liquid crystal display element and the liquid crystal phase is continuous, when the monomer content is low and the amount necessary for the polymer network layer to cover the entire cell is insufficient It is formed discontinuously. When the polarity of the substrate surface such as polyimide alignment film is high, the monomer tends to gather near the liquid crystal cell substrate interface, and a polymer network layer is formed to grow a polymer network from the substrate surface and adhere to the substrate interface, from the cell substrate surface The polymer network layer, the liquid crystal layer, the polymer network layer, and the counter substrate are sequentially stacked. A laminated structure of polymer network layer / liquid crystal layer / polymer network layer is shown, and a polymer having a thickness of at least 0.5% or more, preferably 1% or more, more preferably 5% or more of the cell thickness in the cell cross section direction When the network layer is formed, the effect of shortening the falling time is exhibited by the action of the anchoring force between the polymer network and the low molecular weight liquid crystal, which is preferable. However, since the influence of the cell thickness becomes large, if the fall time becomes longer as the cell thickness is increased, the thickness of the polymer network layer may be increased as necessary. The structure of the polymer network in the polymer network layer may be such that the low molecular weight liquid crystal induces a pretilt angle as long as the low molecular weight liquid crystal and the alignment easy axis or the uniaxial optical axis are aligned in substantially the same direction. Just do it. The average gap spacing is preferably in the range of 90 nm to 450 nm.

  For example, when the monomer content is less than 6% by mass, it is preferable to use a bifunctional monomer having a mesogen group with high anchoring power, and a bifunctional monomer having a short distance between functional groups and a high polymerization rate It is preferable to use, and it is preferable to form a polymer phase separation structure at a low temperature of 0 ° C. or less. When the monomer content is 6% by mass to less than 10% by mass, a combination of the bifunctional monomer and a monofunctional monomer having low anchoring power is preferable, and polymerization is performed in the range of 25 ° C. to −20 ° C. as necessary. It is preferable to form a phase separation structure. Furthermore, if the melting point is higher than room temperature, it is preferable to lower the melting point by about 5 ° C. because the same effect as low temperature polymerization can be obtained. The higher the monomer concentration in the liquid crystal composition for manufacturing a liquid crystal display element, the larger the anchoring force between the liquid crystal composition (B) and the polymer interface, and the faster τd. On the other hand, when the anchoring force between the liquid crystal composition (B) and the polymer interface increases, τr slows down. In order to set the sum of τd and τr to less than 1.5 ms, the concentration of the monomer in the liquid crystal composition for producing a liquid crystal display element is 1% by mass or more and less than 10% by mass, and 1.5% by mass or more and 8%. % By mass or less is preferable, and 1.8% by mass or more and 5% by mass or less is more preferable.

In the case of using it in a TFT drive liquid crystal display element, it is necessary to improve the reliability of suppression of flicker, residual image due to baking and the like, and the voltage holding ratio becomes an important characteristic. The cause of lowering the voltage holding ratio is the presence of ionic impurities contained in the liquid crystal composition for producing a liquid crystal display element, particularly mobile ions, so that at least a specific resistance of 10 ¹⁴ Ω · cm or more can be obtained. As described above, it is preferable to perform purification treatment etc. to remove mobile ions. In addition, when a polymer network is formed by radical polymerization, the voltage holding ratio may decrease due to ionic impurities generated from a photopolymerization initiator etc. However, a polymerization initiator with a small amount of generated organic acid and low molecular weight byproducts It is preferable to select

  Furthermore, when the liquid crystal display element of the present invention has an alignment film, it is preferable that the alignment easy axis direction of the alignment film and the alignment easy axis direction of the polymer network (A) be the same. In this case, by providing a polarizing plate, a retardation film, or the like, it is possible to display using this orientation state.

  As described above, the content of the polymer network in the liquid crystal layer 5 is preferably 0.5% by mass or more and 20% by mass or less of the total mass of the liquid crystal composition (B) and the polymer network. 0.7% by mass or more is preferable, 0.9% by mass or more, and particularly 1% by mass is preferable, and 10% by mass or less and 9% by mass or less is preferable as the upper limit, and 7% by mass or less Is preferable from the point of being excellent in the balance of off-response speed and drive voltage.

  In the PSA type liquid crystal display device, alignment processing is omitted by providing a plurality of slits each having a width of 3 to 5 μm on the electrode instead of rubbing alignment processing, and performing tilt alignment of the liquid crystal in the slit direction. In mass-production technology, when ultraviolet light is applied while applying a voltage of several tens of volts, the orientation of the liquid crystal is polymer-stabilized so that a pretilt angle (tilt angle to the substrate normal) is obtained at the substrate interface. Thin film is formed. It is used in the manufacture of a PSVA (polymer-stabilized vertical alignment) LCD or PSA LCD by utilizing the fact that the pretilt angle is induced by the action of this polymer thin film. Further, in order to improve the viewing angle, the pretilt angle direction in one pixel is divided into a plurality of parts using pattern electrodes designed to form multi-domains.

  However, when this method is applied to a liquid crystal display element capable of forming a polymer network or the like in the entire cell and improving the relaxation time of response, a voltage of several tens of volts higher than the saturation voltage is applied to irradiate ultraviolet light. Therefore, the polymer network will stabilize the liquid crystal in the horizontal alignment state. Therefore, in this method, since the refractive anisotropy or easy alignment axis of the polymer network is formed to hold the liquid crystal molecules in the horizontal alignment state, vertical alignment can not be obtained.

  On the other hand, when a low voltage near the threshold voltage is applied to form the refractive anisotropy or easy alignment axis of the polymer network, the transmittance is lowered because the tilt alignment direction of the liquid crystal is not determined.

  Therefore, in the present invention, a high voltage equal to or higher than the threshold voltage is applied to the polymerizable liquid crystal composition to partially form a polymer network, and then the voltage is made lower than the threshold voltage during ultraviolet irradiation. It is preferable to continue the That is, first, a high voltage equal to or higher than the threshold voltage is applied to polymerize a part of the monomers to partially form the polymer network so that the tilt alignment orientation of the liquid crystal is stabilized. By making the voltage less than the voltage, the liquid crystal returns to the substantially vertical alignment, and further, when the ultraviolet irradiation is continued in this state, the refractive anisotropy or easy alignment axis of the polymer network is formed so as to become the substantially vertical alignment. Can be left as a locus in the polymer network, and it is possible to achieve both orientation control at the time of voltage application and vertical orientation at the time of no voltage application.

  Therefore, in the method of producing the liquid crystal display element of the present invention, the polymerizable liquid crystal composition for producing a liquid crystal display element sandwiched between two transparent substrates having an electrode on at least one side is a threshold of liquid crystal for producing the element. It is preferable to include a step of irradiating the ultraviolet light to apply a voltage higher than the voltage to separate the polymer phase, and a step of setting the voltage below the threshold voltage while irradiating the ultraviolet light and further irradiating the ultraviolet light.

  Here, in the case of a vertical alignment mode liquid crystal display element including a pattern electrode cell or the like, in the step of irradiating ultraviolet rays while applying a voltage higher than the threshold voltage of liquid crystal for liquid crystal display element manufacture And aligning the liquid crystal molecules in the liquid crystal of the liquid crystal at an angle of 0 ° to 30 ° with respect to the plane of the transparent substrate, and then irradiating the ultraviolet light while making the voltage less than the threshold voltage. Preferably, the liquid crystal molecules are aligned at an angle of 80 degrees to 90 degrees with respect to the plane of the transparent substrate.

  The state in which the liquid crystal molecules are aligned at an angle of 0 ° to 30 ° with respect to the transparent substrate plane indicates that the birefringence of the liquid crystal is increased by voltage application, and the alignment state of the liquid crystal is in the transparent substrate plane. On the other hand, the birefringence is preferably maximized at 0 °, but it is preferred that the alignment be 30 ° inclined with respect to the plane of the substrate. In particular, in the PVA cell, the inclination direction can be made constant, which is preferable. In any case, it is preferable to form a polymer network in which the alignment is stabilized so that the tilt alignment direction of the liquid crystal by voltage application is in a constant direction.

  When the liquid crystal molecules are aligned at an angle of 80 degrees to 90 degrees with respect to the transparent substrate plane, the birefringence is minimized when the liquid crystal is oriented at 90 degrees with respect to the transparent substrate plane when no voltage is applied. Although it is useful and preferable for increasing the contrast of the liquid crystal display element, it is more preferable to be inclined within 89.9 ° to 85 ° with respect to the plane of the substrate in order to tilt in a fixed direction when applying a voltage. . If the angle exceeds 80 degrees with respect to the substrate plane, the birefringence increases and the amount of transmitted light increases, and the display contrast is undesirably lowered. The display black level becomes good at 85 degrees or more with respect to the substrate plane and high. It is preferable because contrast can be obtained.

  Further, in a liquid crystal display element of an IPS (In-plane switching) display mode or FFS mode, a step of irradiating an ultraviolet ray while applying a voltage higher than a threshold voltage of a liquid crystal composition for manufacturing a liquid crystal display element Liquid crystal molecules in a liquid crystal composition for manufacturing a liquid crystal display element are aligned at an angle of 0 ° to 90 ° with respect to the plane of the transparent substrate, and the voltage is made lower than the threshold voltage while being irradiated with ultraviolet light. Preferably, in the step of irradiating ultraviolet light, the liquid crystal molecules are aligned at an angle of 0 ° to 30 ° with respect to the plane of the transparent substrate.

  The liquid crystal molecules are inclined in the range of 0 degrees to 90 degrees with respect to the transparent substrate plane, and the alignment forms a polymer network so as to stabilize the alignment state of the liquid crystal to which a voltage is applied. In the case of the IPS mode, the tilt angle of the property of the alignment film used in the element largely depends on it, and may be in the range of 1 degree to 2 degrees, and the tilt angle of liquid crystal molecules including twisted orientation is 0 5 degrees to 3 degrees are preferable, and 0 degrees to 2 degrees are preferable.

  In the case of the FFS mode, when a voltage higher than the threshold voltage is applied, the alignment state of the liquid crystal depends on the electric field distribution in the element, and splay alignment, bend alignment, and twist alignment state coexist, but mainly splay alignment and twist alignment state Indicates The tilt angle of the alignment state of the liquid crystal molecules in this state is preferably in the range of 0 ° to 45 °, and the same range is preferably stabilized when the alignment is stabilized by the polymer network. In the TN mode, the inclination angle is preferably in the range of 45 degrees to 90 degrees.

  On the other hand, a polymer network is formed to stabilize the alignment state of the liquid crystal by applying a voltage less than the threshold voltage, but in the case of IPS mode, FFS mode, and TN mode, the pretilt angle is formed at the substrate interface by rubbing alignment processing. Since it is about 1 to 3 degrees, it is preferable to form a polymer network so as to stabilize the alignment state of the liquid crystal to which a voltage less than the threshold voltage is applied, and the alignment angle of the liquid crystal is inclined to this range The tilt angle of the liquid crystal molecules including twisted orientation is preferably 0.5 degrees to 3 degrees, and the wide viewing angle is within 0 degrees to 2 degrees using other alignment processing methods such as a photo alignment film. Useful and preferred to obtain.

  Moreover, it is preferable that the voltage to be applied is an alternating current waveform, and has a frequency in a range where the liquid crystal composition (B) for producing a liquid crystal display element exhibits dielectric anisotropy. The waveform is preferably a rectangular wave that can increase the effective voltage when the peak voltage is constant. The upper limit of the frequency may be a frequency at which the signal transmitted to the pixel by the drive circuit used for the liquid crystal display element is not attenuated, and at least the frequency is preferably 2 kHz or less. The frequency dependency of the dielectric constant of the liquid crystal composition for producing a liquid crystal display element before ultraviolet irradiation may be 10 kHz or less at the frequency indicated by the dielectric anisotropy. The lower limit value may be a frequency at which flicker may occur when the element is driven, and in this case, the frequency is preferably at least 20 Hz or more.

  In the method for producing a liquid crystal display device of the present invention, it is preferable to form a polymer network so as to maintain two liquid crystal alignment states as described above, but a polymer network formed so as to maintain each liquid crystal alignment state Is formed such that the refractive index anisotropy or easy alignment axis of the polymer network coincides with the liquid crystal alignment direction equal to or higher than the threshold voltage or the liquid crystal alignment direction smaller than the threshold voltage. As a result, a polymer network that stabilizes the alignment of the liquid crystal when voltage is applied and a polymer network that stabilizes the alignment of the liquid crystal when no voltage is applied coexist to create a liquid crystal alignment when no voltage is applied. It becomes possible to suppress the orientation distortion which occurs when the orientation is deformed by applying a voltage from the state, and to improve the display characteristics such as the improvement of the contrast. On the other hand, only the polymer network formed so as to maintain the liquid crystal alignment state when no voltage is applied is formed so as to maintain the liquid crystal alignment below the threshold voltage when transitioning to the liquid crystal alignment state when voltage is applied. Since the influence of the polymer network is strong, when it shifts to the liquid crystal alignment state above the threshold voltage, it causes an orientation distortion to lower the transmittance. By forming a polymer network that stabilizes the alignment of the liquid crystal when a voltage is applied to a part of the polymer network, distortion of the alignment transition caused by switching is suppressed, and the originally required transition of the liquid crystal alignment can be obtained. Improve the rate. The polymer network formed to stabilize the alignment state of each liquid crystal at the time of voltage application and at the time of no voltage application has the refractive index anisotropy or the alignment of the polymer network along the alignment of two different liquid crystals. The feature is that the easy axis is formed.

  Furthermore, the influence of the polymer network formed to stabilize the liquid crystal state above the threshold voltage is changed by the application time of the voltage above the threshold voltage during ultraviolet irradiation, and the electro-optical characteristics can be changed. Become. For example, when the polymer network is formed as a parallel alignment in which the alignment state of the liquid crystal at the time of voltage application includes a tilt alignment of 0 ° to 30 ° with respect to the substrate plane, the application time of the voltage higher than the threshold voltage during ultraviolet irradiation If it is shortened, the effect of maintaining the parallel alignment is small, so that the liquid crystal tends to align according to the action of the polymer network that attempts to maintain the vertical alignment. Furthermore, the influence of both orientations from the polymer network holding two different orientations is balanced to induce a small angle of pretilt within 1 degree with respect to the direction of the transparent substrate normal. As the application time of voltage above the threshold voltage during UV irradiation increases, the influence of the polymer network to maintain the horizontal orientation is enhanced, so that the balance between the force to maintain the vertical orientation and the force to maintain the parallel orientation is derived from the pretilt. The angle is increased, and the pretilt angle is increased to be 10 degrees or more with respect to the transparent substrate normal direction. Also, the application time of the voltage higher than the threshold voltage during ultraviolet irradiation largely depends on the reactivity of the polymerizable liquid crystal composition for manufacturing the liquid crystal display element used, so that the desired pretilt angle can be obtained by appropriate adjustment. It is preferable to In particular, it is preferable to obtain a pretilt angle in the range of 80 degrees to 90 degrees with respect to the substrate plane, more preferably 85 degrees to 89.9 degrees, and 87 degrees to 89.9 degrees. Is more preferred.

  The polymer network formed to maintain the alignment state of the liquid crystal obtained by applying a voltage higher than the threshold voltage has a horizontal alignment state in the liquid crystal display element of the vertical alignment mode using negative dielectric anisotropy. Or inclined orientation with a constant azimuthal angle is desirable. The alignment state obtained below the threshold voltage is preferably substantially vertical alignment, and particularly preferably substantially perpendicular alignment at 80 to 90 degrees with respect to the substrate plane, and a good black level such that high contrast can be obtained. It is preferable that it is an orientation state which shows.

  In the IPS display mode with a transverse electric field using negative dielectric anisotropy or positive dielectric anisotropy, the alignment state of the liquid crystal obtained by applying a voltage higher than the threshold voltage during ultraviolet irradiation is twisted. It is preferable that it is orientation. The orientation state obtained below the threshold voltage is preferably a parallel orientation with a constant azimuthal angle. In the FFS mode, it is preferable that the alignment state obtained by applying a voltage higher than the threshold voltage during ultraviolet irradiation is at least one of a bend alignment, a splay alignment, a tilt alignment, or a plurality of alignment states. Below the threshold voltage, it is preferable to have a substantially parallel orientation. After forming a polymer network so as to maintain the alignment state of the liquid crystal at the time of voltage application, the liquid crystal when a voltage is applied after the polymer network formation is completed by stabilizing the alignment state of the liquid crystal below the threshold voltage. It can be easily oriented and deformed to the orientation state of (1), and both high transmittance and high speed response can be achieved.

  The applied voltage at the time of ultraviolet irradiation is preferably adjusted appropriately so that the display of the liquid crystal display element after formation of the polymer network has high contrast, and the electro-optical effect of the liquid crystal composition for manufacturing the liquid crystal display element before ultraviolet irradiation is Because it depends largely on the characteristics, it is necessary to match with the voltage-transmittance characteristic exhibited by the liquid crystal for manufacturing the liquid crystal display element. The voltage higher than the threshold voltage is preferably a voltage V10 or higher which is 10% or higher with respect to the total change of the transmittance in the voltage-transmittance characteristic voltage of the liquid crystal for manufacturing liquid crystal display elements. The voltage V20 or more at which the change amount is 20% or more is more preferable, and the voltage V50 or more at which the total change amount of the transmittance is 50% or more is more preferable. However, the voltage is preferably 6 times or less of the threshold voltage. It is preferable to apply an alternating voltage, and it is preferable to apply a rectangular wave as the voltage higher than the threshold voltage applied during ultraviolet irradiation. The frequency is preferably a frequency at which the flicker can not be recognized visually, and in the case where an electronic circuit such as a TFT substrate is formed on a glass substrate, it may be a frequency at which the attenuation of the polymerization voltage does not occur. It is preferable to have a degree.

  The voltage applied in the middle of ultraviolet irradiation is made higher than or equal to the threshold voltage and lower than the threshold voltage, but a voltage less than the threshold voltage may be within a range where the alignment of the liquid crystal does not change with voltage. Voltages of less than 10% are preferred, voltages of less than 80% are preferred, and 70% or less is more preferred. In addition, the applied voltage is made to be equal to or lower than the threshold voltage during irradiation with ultraviolet light, but at this time, it is preferable to return to the liquid crystal alignment state at the time of OFF in the liquid crystal display element. It is sufficient to return to the vertical alignment, and in the FFS mode and the IPS mode, to be parallel alignment. In order to return to the liquid crystal alignment state when the liquid crystal display element is turned off, it is preferable to lower the voltage to less than the threshold voltage while the influence of the polymer network that stabilizes the alignment of the liquid crystal is small.

  After applying a voltage higher than the threshold voltage, UV light is irradiated, but if the voltage application time is prolonged during UV irradiation, the influence of the polymer network that stabilizes the alignment of the liquid crystal at the time of voltage application during UV irradiation increases. It becomes unpreferable because it does not return to the liquid crystal alignment state at the time of the liquid crystal display element OFF which is required. Therefore, it is preferable to appropriately optimize the voltage during the optimal ultraviolet irradiation to manufacture the liquid crystal display device of the present invention. In addition, when the voltage during ultraviolet irradiation is made less than the threshold voltage, the voltage is gradually lowered during the irradiation of ultraviolet light for the purpose of adjusting the relaxation time of the response in the liquid crystal of the liquid crystal composition for device manufacture. The effect of backflow that occurs in the response relaxation process may be minimized by making the fall time of the response longer than the response relaxation time in the liquid crystal during UV irradiation, and the drop time of the applied voltage is 10 ms or more. Preferably within 1000 ms. On the other hand, it may be lowered quickly, preferably at least shorter than the relaxation time of the liquid crystal composition for producing a liquid crystal display element, and is preferably 100 ms or less.

  As described above, the polymer network of the horizontal alignment component is partially formed by ultraviolet irradiation in a state where a voltage higher than the threshold voltage is applied, and the liquid crystal is vertical by keeping the voltage below the threshold voltage while continuing the ultraviolet irradiation. The polymerization phase separation is completed by returning to the orientation. In the fishbone type electrode liquid crystal cell, the pretilt angle can be changed by the ratio of the above-mentioned parallel alignment component and vertical alignment component, and when the voltage is cut in the initial process of polymer network formation, the tilt alignment direction is fixed, vertical alignment By forming the remaining monomer with the residual monomer, it is possible to simultaneously achieve vertical alignment and inclined alignment orientation, and this is an alignment control technology in nanophase-separated liquid crystals.

  The parallel alignment state means that a negative dielectric anisotropic liquid crystal is in a substantially parallel alignment state when a voltage is applied, and a range of 0.1 to 30 degrees with respect to the substrate surface is preferable, 0 It is preferable that the inclined orientation is in the range of 1 degree to 10 degrees. The vertical alignment when no voltage is applied means that the liquid crystal is in a substantially vertical alignment state by the action of the vertical alignment film, and the alignment of the liquid crystal is inclined at 80 to 89.9 degrees with respect to the substrate plane. It is preferable that the angle be 85 degrees to 89.9 degrees.

  In the case of a positive dielectric anisotropic liquid crystal, vertical alignment is obtained when a voltage is applied, but the liquid crystal is inclined and oriented in the range of 45 degrees to 89.9 degrees with respect to the substrate plane. Is included. The parallel alignment when no voltage is applied means that the liquid crystal is approximately parallel aligned by the action of the parallel alignment film, and the alignment of the liquid crystal is inclined at 0.1 to 30 degrees with respect to the substrate plane. Included.

  The distance (d) between the substrates in the liquid crystal display element of the present invention is preferably in the range of 2 to 5 μm, and more preferably 3.5 μm or less. In general, the birefringence is adjusted so that the product of the birefringence of the liquid crystal composition and the cell thickness is around 0.275, but in the liquid crystal composition for device production used in the present invention, the polymer network is separated after polymerization phase separation Liquid crystal composition, and a polymer composition, or a liquid crystal display device, because the birefringence of the liquid crystal display device when an electric field is applied is lowered due to the anchoring force action of the polymer network and the optical properties of the polymer network. The product of the birefringence (Δn) of the liquid crystal composition contained in the liquid crystal composition for production and the distance (d) between the substrates is 0.3 to 0. When the drive voltage increases within 5 V or so by polymer network formation. The range of 4 μm is particularly preferable, the range of 0.30 to 0.35 μm is more preferable in the increase of about 3 V, and the range of 0.29 to 0.33 μm in the increase of the drive voltage of 1 V or less. It is particularly preferred. By making the product of the distance (d) between the substrates of the liquid crystal display element and the birefringence (Δn) of the liquid crystal composition and the distance (d) between the substrates within the above ranges, the transmittance is limited to only low molecular liquid crystals. It is possible to obtain a display that is relatively high, and has a fast response and a favorable color reproducibility. The product of the cell thickness (d) and the birefringence (Δn) of the liquid crystal composition used for the liquid crystal composition for manufacturing a liquid crystal display element is 1 to 1.9 times the value of 0.275 It is preferable to

  The driving voltage of the liquid crystal display device of the present invention is not determined only by the dielectric anisotropy or elastic constant of the liquid crystal composition, but is largely influenced by the anchoring force acting between the liquid crystal composition and the polymer interface.

  For example, as a description relating to the drive voltage of a polymer dispersed liquid crystal display element, the relationship of the following equation is shown in JP-A-6-222320.

(Vth represents a threshold voltage, 1 Kii and 2 Kii represent elastic constants, i represents 1, 2 or 3, Δε represents dielectric anisotropy, and <r> is the transparent polymer material interface Represents the average gap spacing, A represents the anchoring power of the transparent polymeric material to the liquid crystal composition, and d represents the distance between the substrates having the transparent electrode.)

According to this, the driving voltage of the light scattering type liquid crystal display element is the average gap distance of the interface of the transparent polymer substance, the distance between the substrates, the elastic constant and dielectric anisotropy of the liquid crystal composition, and the liquid crystal composition and the transparent It is determined by the anchoring energy between the macromolecular substances. Among these, the parameters that can be controlled by the liquid crystal display device of the present invention are the physical properties of the liquid crystal and the anchoring force between the polymers. Since the anchoring force largely depends on the molecular structure of the polymer and the molecular structure of the low molecular weight liquid crystal, it is possible to accelerate the response time to 1.5 ms or less by selecting a monomer having a strong anchoring force. At the same time, since the drive voltage is increased to 30 V or more, it is preferable to select the liquid crystal compound and the monomer appropriately to adjust the composition so that the response speed becomes 1.5 ms or less at 30 V or less. It is preferable to adjust the composition so as to balance the drive voltage and the response speed by appropriately blending the polymer precursor having a strong anchoring force and the polymer precursor having a weak anchoring force. On the other hand, as the physical properties of the liquid crystal composition required to lower the driving voltage, it is particularly preferable to set the dielectric anisotropy to 6 or more in the P-type liquid crystal and to -3 or less in the N-type liquid crystal. . Further, it is preferable to make the birefringence be 0.09 or more. Furthermore, it is more preferable if the birefringence of the liquid crystal composition and the refractive index of the fibrous or columnar polymer network are as close as possible to eliminate light scattering. However, since the retardation of the liquid crystal element is affected by the concentration of the polymer precursor, it is preferable to appropriately increase or decrease the birefringence of the liquid crystal composition so as to obtain the necessary retardation.

  In the liquid crystal display element of the present invention, energy rays are irradiated while the above-mentioned liquid crystal composition is kept at -50 ° C to 30 ° C to polymerize the monomer, and the refractive index anisotropy or alignment easy axis direction is obtained in the liquid crystal composition. It is preferable that it is obtained by forming the polymer network which it has. The upper limit of the polymerization temperature is 30 ° C, preferably 20 ° C to -10 ° C. As will be described later in the examples, the inventor has found that τ d is further accelerated by low temperature polymerization and normal temperature polymerization depending on the monomer composition. The reason is that 1) polymerization is carried out with the degree of alignment of liquid crystal molecules increased at low temperature, and 2) the compatibility between the polymer polymerized by low temperature polymerization and the liquid crystal composition is reduced, so that phase separation becomes easy, The phase separation speed is increased, and the gap spacing of the polymer network is reduced, and 3) even if a monomer with a relatively low anchoring force is used, the gap spacing is fine, so that the influence of the anchoring force becomes strong It is considered to be due to the formation of a rate anisotropic polymer network and the like.

  Furthermore, in the liquid crystal display device of the present invention, the direction of the optical axis or easy axis of the polymer network or polymer binder having uniaxial refractive index anisotropy or easy axis direction forms a pretilt angle with respect to the transparent substrate. The alignment of the low molecular weight liquid crystal is controlled by adjusting the strength of the electric field, and the energy beam is applied while applying a voltage to the liquid crystal layer described above by tilting the liquid crystal layer with respect to the substrate surface. The configuration is preferably such that the monomer is polymerized by irradiation to obtain a polymer having the refractive index anisotropy in the liquid crystal composition or the orientation easy axis direction. In the VA mode with vertical alignment, the voltage used is applied so that the pretilt angle is within 20 degrees with respect to the normal direction of the substrate, and polymerization is performed. It is particularly preferable because it has not only an effect equivalent to fine polymer protrusions of PSA liquid crystal, etc., but also a high-speed response that can not be realized with PSA. In addition, by applying an electric field direction from a plurality of directions to cause polymerization, a multi-domain can be formed, and the viewing angle can be improved, which is more preferable. Furthermore, the alignment direction of the low molecular liquid crystal alignment is defined by subjecting the alignment film to photo alignment processing, rubbing alignment processing or the like so that the low molecular liquid crystal induces a pretilt angle at the substrate interface vertical alignment film interface. It is preferable to suppress the occurrence of alignment defects of the above, and it is also preferable to use a pattern electrode which tilts in a plurality of directions or to perform the alignment treatment. The liquid crystal layer appropriately applies an alternating electric field in a temperature range of −50 ° C. to 30 ° C. to a polymerizable liquid crystal composition containing a monomer, and irradiates ultraviolet light or an electron beam, thereby exhibiting refractive index anisotropy. Is formed in the liquid crystal such that the optical axis direction of the polymer network having a pretilt angle with respect to the substrate surface. This pretilt angle is a liquid crystal element in which the optical axis of the polymer network after polymerization is inclined with respect to the substrate surface when the polymer phase is separated in the alignment state induced by applying an electric field by the dielectric anisotropy of low molecular liquid crystal. It is more preferable that the monomer is polymerized. Furthermore, it is also preferable to induce a pretilt angle by combining the polymer network obtained by stabilizing the alignment state to which a voltage is applied and the polymer network obtained by stabilizing the alignment state to which a voltage is not applied.

  The two substrates used in the liquid crystal display device of the present invention can use a flexible transparent material such as glass or plastic. 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 produced, for example, by a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method or the like. A method of producing a color filter by the pigment dispersion method will be described by way of example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to a patterning treatment, and cured by heating or light irradiation. By performing this process for each of three colors of red, green, and blue, it is possible to create a pixel portion for a color filter. In addition, on the substrate, a pixel electrode provided with an active element such as a TFT or a thin film diode may be provided.

  The substrate is opposed with the transparent electrode layer on the inside. At this time, the distance between the substrates may be adjusted through the spacer. At this time, it is preferable to adjust the thickness of the obtained light control layer to 1 to 100 μm. When the polarizing plate is used, the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d is adjusted so as to maximize the contrast, and 1/550 nm according to the display mode. It is preferable to make it 2 or 1⁄4. When two polarizing plates are provided, the polarizing axis of each polarizing plate can be adjusted to adjust the viewing angle and contrast to be good. Furthermore, retardation films for widening the viewing angle can also be used. Examples of the spacer include columnar spacers made of glass particles, plastic particles, alumina particles, photoresist materials and the like. Thereafter, a sealing agent such as an epoxy-based thermosetting composition is screen-printed on the substrate in a form provided with a liquid crystal injection port, the substrates are bonded to each other, and heating is performed to thermally cure the sealing agent.

  As a method of holding a liquid crystal composition for manufacturing a liquid crystal display element between two substrates, a normal vacuum injection method or an ODF method can be used. In the liquid crystal display device manufacturing process of the ODF method, a sealing agent such as an epoxy-based combination heat and light curing property is drawn on a back plane or front plane substrate in a closed loop shape using a dispenser, and removed therefrom. The liquid crystal display element can be manufactured by bonding a front plane and a back plane after dropping a predetermined amount of a liquid crystal display element manufacturing liquid under air. The liquid crystal composition for producing a device used in the present invention can be suitably used because the liquid crystal / monomer composite material can be stably dropped in the ODF process.

  As a method of polymerizing a monomer, in order to obtain a good alignment performance of liquid crystal, an appropriate polymerization rate is desirable. Therefore, polymerization is carried out by irradiating the active energy ray ultraviolet ray or electron beam singly or in combination or in order. The preferred method is When ultraviolet light is used, a polarized light source may be used or a non-polarized light source may be used. In addition, when polymerization is carried out in a state where a liquid crystal composition for manufacturing a liquid crystal display element is held between two substrates, at least the substrate on the irradiation surface side is given appropriate transparency to active energy rays. Must be Moreover, it is preferable to irradiate an ultraviolet-ray or an electron beam while applying an alternating current electric field to the liquid crystal composition for liquid crystal display element manufacture in the temperature range of -50 degreeC-20 degreeC with respect to the liquid crystal composition containing a monomer. The alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 100 Hz to 5 kHz, and the voltage is selected depending on the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the liquid crystal display element in the transverse electric field type MVA mode, it is preferable to control the pretilt angle to 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.

The temperature at the time of irradiation is preferably in the temperature range of -50 ° C to 30 ° C for the liquid crystal composition for producing a liquid crystal display element. Furthermore, 20 ° C to -10 ° C is more preferable. Depending on the composition of the liquid crystal composition for manufacturing a device, low temperature polymerization and room temperature polymerization tend to further increase the speed of τd. The reason is that 1) polymerization is carried out with the degree of alignment of liquid crystal molecules increased at low temperature, and 2) the compatibility between the polymer polymerized by low temperature polymerization and the liquid crystal composition is reduced, so that phase separation becomes easy, The effect of the anchoring force is enhanced because the phase separation speed is increased and the gap spacing of the polymer network is reduced, and 3) the gap spacing is reduced even if a polymerizable compound having a relatively low anchoring force is used. It is considered that this is due to the formation of a refractive index anisotropic polymer network.

As a lamp that generates ultraviolet light, a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-ray to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not an absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use the ultraviolet ray less than 365 nm as needed. 0.1 mW / cm ^{2 to} 100 W / cm ² is preferable, and ² mW / cm ^{2 to} 50 W / cm ² is more preferable. Energy of ultraviolet light irradiation, can be appropriately adjusted, preferably 500 J / cm ² from 10 mJ / cm ^2, from 100mJ / cm ² 200J / cm ² is more preferable. When irradiating ultraviolet light, the intensity may be changed. The irradiation time of the ultraviolet light is appropriately selected depending on the intensity of the ultraviolet light to be irradiated, preferably 10 seconds to 3600 seconds, and more preferably 10 seconds to 600 seconds.

  The entire structure including the electrode structure in the liquid crystal display device having the light conversion portion and the liquid crystal layer described in detail above will be further described with reference to FIGS. FIG. 11 is a schematic view of the structure of the electrode layer 3 of the liquid crystal display unit, and more specifically, FIG. 11 is a schematic view showing the pixel portion by an equivalent circuit, and FIGS. It is a schematic diagram which shows an example of. Moreover, FIGS. 12-13 is a schematic diagram which shows the electrode structure of the FFS type liquid crystal display element as an example of this embodiment. FIG. 14 is a schematic view showing an electrode structure of an IPS type liquid crystal display element as an example of the present embodiment. Furthermore, FIG. 17 is a schematic view showing an electrode structure of a VA liquid crystal display element as an example of the present embodiment. As shown in FIG. 1 and FIG. 2, the liquid crystal panel 10 is driven as a liquid crystal display element by providing the above-mentioned backlight unit as illumination means for illuminating from the back side.

  In FIG. 11, the electrode layer 3 according to the present invention includes a common electrode and a plurality of pixel electrodes. The pixel electrode is disposed on the common electrode via an insulating layer (for example, silicon nitride (SiN) or the like). The pixel electrode is disposed for each display pixel, and a slit-like opening is formed. The common electrode and the pixel electrode are, for example, transparent electrodes formed of ITO (Indium Tin Oxide), and the electrode layer 3 is a gate bus line GBL (along the row in which a plurality of display pixels are arranged in the display portion). GBL1, GBL2... GBLm), a source bus line SBL (SBL1, SBL2... SBLm) extending along a column in which a plurality of display pixels are arranged, and a position near the intersection of a gate bus line and a source bus line Thin film transistors as pixel switches. The gate electrode of the thin film transistor is electrically connected to the corresponding gate bus line GBL, and the source electrode of the thin film transistor is electrically connected to the corresponding signal line SBL. Furthermore, the drain electrode of the thin film transistor is electrically connected to the corresponding pixel electrode.

  The electrode layer 3 includes a gate driver and a source driver as drive means for driving a plurality of display pixels, and the gate driver and the source driver are disposed around the liquid crystal display unit. The plurality of gate bus lines are electrically connected to the output terminal of the gate driver, and the plurality of source bus lines are electrically connected to the output terminal of the source driver. The gate driver sequentially applies the on voltage to the plurality of gate bus lines, and supplies the on voltage to the gate electrode of the thin film transistor electrically connected to the selected gate bus line. Electrical conduction is established between the source and drain electrodes of the thin film transistor in which the on voltage is supplied to the gate electrode.

  The source driver supplies an output signal corresponding to each of the plurality of source bus lines. The signal supplied to the source bus line is applied to the corresponding pixel electrode through the thin film transistor in which the source and drain electrodes are conducted. The operation of the gate driver and the source driver is controlled by a display processing unit (also referred to as a control circuit) disposed outside the liquid crystal display element.

The display processing unit according to the present invention may have a low frequency driving function and an intermittent driving function to reduce driving power in addition to normal driving, and an LSI for driving a gate bus line of a TFT liquid crystal panel. The operation of the gate driver and the operation of the source driver which is an LSI for driving the source bus line of the TFT liquid crystal panel are controlled. In addition, the common voltage V _COM is supplied to the common electrode to control the operation of the backlight.

  FIG. 12 is a view showing a comb-shaped pixel electrode as an example of the shape of the pixel electrode, and is a plan view enlarging a region surrounded by a line II of the electrode layer 3 formed on the substrate 2 in FIG. . As shown in FIG. 12, the electrode layer 3 including the thin film transistor formed on the surface of the first substrate 2 has a plurality of gate bus lines 26 for supplying a scanning signal and a plurality of display signals. The source bus lines 25 and the source bus lines 25 cross each other and are arranged in a matrix. An area surrounded by the plurality of gate bus lines 26 and the plurality of source bus lines 25 forms a unit pixel of the liquid crystal display device, and the pixel electrode 21 and the common electrode 22 are formed in the unit pixel. ing. Near the intersection where the gate bus line 26 and the source bus line 25 cross each other, a thin film transistor including the source electrode 27, the drain electrode 24 and the gate electrode 28 is provided. The thin film transistor is connected to the pixel electrode 21 as a switch element for supplying a display signal to the pixel electrode 21. Further, in parallel with the gate bus line 26, a common line 29 is provided. The common line 29 is connected to the common electrode 22 in order to supply a common signal to the common electrode 22.

  A common electrode 22 is formed on the back surface of the pixel electrode 21 via an insulating layer 18 (not shown). Then, the shortest separation distance between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance (cell gap) between the alignment layers. The surface of the pixel electrode is preferably covered with a protective insulating film and an alignment film layer. A storage capacitor may be provided in a region surrounded by the plurality of gate bus lines 26 and the plurality of source bus lines 25 for storing a display signal supplied via the source bus line 25.

  FIG. 13 is a modification of FIG. 12 and is a view showing a slit-like pixel electrode as an example of the shape of the pixel electrode. In the pixel electrode 21 shown in FIG. 13, the electrode of a substantially rectangular flat plate is hollowed out at the central portion and both ends of the flat plate with a triangular notch, and the other portion is a substantially rectangular frame notch. It is a hollowed out part. In addition, the shape in particular of a notch part is not restrict | limited, The notch part of well-known shapes, such as ellipse, circular, rectangular shape, a rhombus, a triangle, or a parallelogram, can be used.

  12 and 13 show only the pair of gate bus lines 26 and the pair of source bus lines 25 in one pixel.

  FIG. 15 is one of the examples of the cross-sectional view which cut | disconnected the liquid crystal display element shown in FIG. 1 in the III-III line direction in FIG. 12 or FIG. The first substrate 2 on the surface of which the alignment layer 4 and the electrode layer 3 including the thin film transistor are formed, and the second substrate 7 on the surface of which the alignment layer 4 is formed are separated such that the alignment layers face each other at a predetermined gap G The space is filled with a liquid crystal layer 5 containing a liquid crystal composition. The gate insulating film 12, the common electrode 22, the passivation film 18, the pixel electrode 21 and the alignment layer 4 are laminated in this order on a part of the surface of the first substrate 2.

  For example, as shown in FIG. 15, the gate electrode 11 formed on the surface of the substrate 2 and the gate electrode 11 are provided so as to cover substantially the entire surface of the substrate 2, as shown in FIG. The gate insulating layer 12, the semiconductor layer 13 formed on the surface of the gate insulating layer 12 so as to face the gate electrode 11, and the protective film provided to cover a part of the surface of the semiconductor layer 13 14, a drain electrode 16 covering one side end of the protective layer 14 and the semiconductor layer 13 and in contact with the gate insulating layer 12 formed on the surface of the substrate 2, and the protection A source electrode 17 covering the film 14 and the other side end of the semiconductor layer 13 and provided to be in contact with the gate insulating layer 12 formed on the surface of the substrate 2; It has a passivation film 18 provided to cover the electrode 16 and the source electrode 17, a. An anodized film (not shown) may be formed on the surface of the gate electrode 11 for the purpose of eliminating the difference in level with the gate electrode.

  In the embodiment shown in FIGS. 12 and 13, the common electrode 22 is a flat plate-like electrode formed on almost the entire surface of the gate insulating layer 12, while the pixel electrode 21 covers the common electrode 22. It is a comb-shaped electrode formed on top.

  That is, the common electrode 22 is disposed at a position closer to the first substrate 2 than the pixel electrode 21, and these electrodes are disposed so as to overlap with each other via the insulating protective layer 18. The pixel electrode 21 and the common electrode 22 are formed of, for example, a transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), IZTO (Indium Zinc Tin Oxide) or the like. Since the pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material, the area of the unit pixel area is increased, and the aperture ratio and the transmittance are increased.

  Further, in order to form a fringe electric field between the pixel electrode 21 and the common electrode 22, an inter-electrode distance (also referred to as a minimum separation distance) R between the pixel electrode 21 and the common electrode 22 is equal to It is formed to be smaller than the thickness G of the liquid crystal layer 5 between the first substrate 2 and the second substrate 7. Here, the inter-electrode distance R represents the distance between the electrodes in the horizontal direction. In FIG. 12, since the flat common electrode 22 and the comb-shaped pixel electrode 21 overlap, an example in which the minimum separation distance (or the distance between the electrodes): R = 0 is shown, and the minimum separation distance R is Thickness of the liquid crystal layer between the first substrate 2 and the second substrate 7 (also referred to as cell gap): smaller than G, an electric field E of fringes is formed. Therefore, the FFS liquid crystal display device can use a horizontal electric field formed in a direction perpendicular to the line forming the comb shape of the pixel electrode 21 and a parabolic electric field. The electrode width of the comb-like portion of the pixel electrode 21: l and the width of the gap of the comb-like portion of the pixel electrode 21: m are such widths that all liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. It is preferable to form.

  An example of an IPS type liquid crystal display element which is a modified example of the FFS type of the liquid crystal panel of the liquid crystal display element according to the present invention will be described with reference to FIG. 1, FIG. 14 and FIG. The configuration of the liquid crystal panel 10 of the IPS type liquid crystal display element is a structure in which an electrode layer 3 (including a common electrode, a pixel electrode and a TFT) is provided on one substrate as in the FFS type of FIG. A first polarizing plate 1, a first substrate 2, an electrode layer 3, an alignment layer 4, a liquid crystal layer 5 containing a liquid crystal composition, an alignment layer 4, a color filter 6, and a second substrate 7 And the second polarizing plate 8 are sequentially stacked.

FIG. 14 is an enlarged plan view of a part of a region surrounded by the II line of the electrode layer 3 formed on the first substrate 2 of FIG. 1 in the IPS type liquid crystal display unit. As shown in FIG. 14, in a region (within a unit pixel) surrounded by a plurality of gate bus lines 26 for supplying a scanning signal and a plurality of source bus lines 25 for supplying a display signal, a comb shape is formed. State in which the first electrode (for example, pixel electrode) 21 and the comb-shaped second electrode (for example, common electrode) 22 are loosely fitted to each other. Provided). In the unit pixel, a thin film transistor including a source electrode 27, a drain electrode 24, and a gate electrode 28 is provided in the vicinity of an intersection where the gate bus line 26 and the source bus line 25 intersect with each other. The thin film transistor is connected to the first electrode 21 as a switch element for supplying a display signal to the first electrode 21. Also, in parallel with the gate bus line 26, a common line (V _com ) 29 is provided. The common line 29 is connected to the second electrode 22 in order to supply a common signal to the second electrode 22.

  FIG. 16 is a cross-sectional view of an IPS-type liquid crystal panel cut in the direction of the line III-III in FIG. A gate insulating layer 32 is provided on the first substrate 2 so as to cover the gate bus lines 26 (not shown) and to cover substantially the entire surface of the first substrate 2, and a surface of the gate insulating layer 32. The formed insulating protective layer 31 is provided, and the first electrode (pixel electrode) 21 and the second electrode (common electrode) 22 are provided on the insulating protective film 31 separately from each other. The insulating protective layer 31 is a layer having an insulating function, and is formed of silicon nitride, silicon dioxide, a silicon oxynitride film, or the like.

  In the embodiment as shown in FIGS. 14 and 16, the first electrode 21 and the second electrode 22 are comb-shaped electrodes formed on the insulating protection layer 31, that is, on the same layer, It is provided in a state of being separated and engaged. In the IPS type liquid crystal display unit, the inter-electrode distance G between the first electrode 21 and the second electrode 22 and the thickness of the liquid crystal layer between the first substrate 2 and the second substrate 7 Cell gap): H satisfies the relationship G ≧ H. The inter-electrode distance: G represents the shortest distance in the horizontal direction to the substrate between the first electrode 21 and the second electrode 22. In the example shown in FIGS. 14 and 16, the first electrode 21 is used. And the second electrode 22 loosely fit and represent a horizontal distance with respect to alternately formed lines. The distance H between the first substrate 2 and the second substrate 7 represents the thickness of the liquid crystal layer between the first substrate 2 and the second substrate 7. Specifically, the first distance The distance between the alignment layers 4 (the outermost surface) provided on each of the substrate 2 and the second substrate 7 (that is, the cell gap), and the thickness of the liquid crystal layer are shown.

  On the other hand, in the above-described FFS liquid crystal display portion, the thickness of the liquid crystal layer 5 between the first substrate 2 and the second substrate 7 is between the first electrode 21 and the second electrode 22. The IPS type liquid crystal display unit has a thickness of the liquid crystal layer 5 between the first substrate 2 and the second substrate 7 that is greater than or equal to the shortest distance in the horizontal direction to the substrate. Between the two electrodes 22 and less than the shortest distance horizontal to the substrate. Therefore, the difference between IPS and FFS does not depend on the positional relationship between the first electrode 21 and the second electrode 22 in the thickness direction.

  The IPS type liquid crystal display element drives liquid crystal molecules using an electric field in the horizontal direction with respect to the substrate surface formed between the first electrode 21 and the second electrode 22. The electrode width: Q of the first electrode 21 and the electrode width: R of the second electrode 22 are preferably formed to such a width that all liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field.

  Another preferred embodiment of the liquid crystal panel of the present invention is a vertical alignment liquid crystal display device. FIG. 17 is an enlarged plan view of the region surrounded by the II line of the electrode layer 3 (also referred to as the thin film transistor layer 3) including the thin film transistor formed on the substrate in FIG. FIG. 18 is a cross-sectional view of the liquid crystal display element shown in FIG. 2 taken along the line III-III in FIG. Hereinafter, a vertical alignment liquid crystal display unit according to the present invention will be described with reference to FIGS. 2 and 17 to 18.

  The configuration of the liquid crystal panel 10 in the liquid crystal display element according to the present invention is the second one having a transparent electrode (layer) 3 '(also referred to as a common electrode 3') made of a transparent conductive material as described in FIG. Between the first substrate 2 and the second substrate 7, the first substrate 2 including the substrate 7 and the electrode layer 3 on which the thin film transistor for controlling the pixel electrode and the pixel electrode provided in each pixel is formed. A liquid crystal composition (or liquid crystal layer 5) sandwiched between the liquid crystal molecules and the alignment of liquid crystal molecules in the liquid crystal composition when no voltage is applied is substantially perpendicular to the substrates 2 and 7. The liquid crystal composition of the present invention is used as the liquid crystal composition. Further, as shown in FIG. 18, the first substrate 2 and the second substrate 7 may be sandwiched by a pair of polarizing plates 1 and 8. Furthermore, in FIG. 18, a color filter 6 is provided between the second substrate 7 and the common electrode 3 '. Furthermore, a pair of alignment layers 4 are formed on the surface of the transparent electrodes (layers) 3, 3 'so as to be adjacent to the liquid crystal layer 5 according to the present invention and in direct contact with the liquid crystal composition constituting the liquid crystal layer 5. It is also good.

  FIG. 17 is a view showing an inverted L-shaped pixel electrode as an example of the shape of the pixel electrode 21 and an enlarged region of the electrode layer 3 formed on the substrate 2 in FIG. It is a top view. The pixel electrode 21 is formed in an inverted L shape substantially over the entire area surrounded by the gate bus line 26 and the source bus line 25 as in FIGS. 12, 13 and 14 described above. The shape is not limited.

  Unlike the above-described IPS type or FFS type, the liquid crystal display portion of the vertical alignment type liquid crystal display element is formed such that a common electrode 22 (not shown) is opposed to and spaced apart from the pixel electrode 21. In other words, the pixel electrode 21 and the common electrode 22 are formed on another substrate. On the other hand, in the above-mentioned FFS or IPS type liquid crystal display element, the pixel electrode 21 and the common electrode 22 are formed on the same substrate.

  Further, from the viewpoint of preventing light leakage, the color filter 6 is preferably formed with a black matrix (not shown) in a portion corresponding to the thin film transistor and the storage capacitor.

  FIG. 18 is a cross-sectional view of the liquid crystal display element shown in FIG. 2 cut along the line III-III in FIG. That is, the liquid crystal panel 10 of the liquid crystal display element according to the present invention vertically aligns the liquid crystal with the first polarizing plate 1, the first substrate 2, the electrode layer (also referred to as thin film transistor layer) 3 including thin film transistors An alignment layer 4, a layer 5 containing a liquid crystal composition, the alignment layer 4, a common electrode 3 ', a color filter 6, a second substrate 7, and a first polarizing plate 8 are sequentially stacked. Configuration.

In order to improve the viewing angle dependency, the vertically aligned liquid crystal display element described in detail above is preferably one in which the divided alignment is performed with a multi-domain in which the pixel is divided into two to eight. Such divisional orientation may be produced by mask rubbing the alignment film 4, but
1) means for forming ribs on both the first substrate 2 side and the second substrate 7;
2) means for forming a rib on the second substrate 7 by using an electrode slit for the first pixel electrode 21;
3) means for forming ribs on the second substrate 7 using fine slit electrodes for the first pixel electrodes 21;
4) using slit electrodes for the first pixel electrode 21 and the second common electrode 22;
5) A means for forming a pretilt in liquid crystal by using a fine slit electrode for the first pixel electrode 21 and a polymer
6) It is a multi-domain type VA device in which the alignment orientation of the liquid crystal is defined by a means using a so-called photo alignment film capable of providing uniform alignment orientation to the liquid crystal by linearly polarized ultraviolet irradiation as the alignment film. Is preferred because it is easy. Among them, in particular, the polymer network of the liquid crystal layer 5 can be easily formed, and the optical axis direction or the easy axis direction of the polymer network (A) in the liquid phase layer 5 and the liquid crystal composition (B) Obtained by means of forming a pretilt in the liquid crystal by the 5) polymer or by using the photoalignment film of the 6) because it is easy to control the direction of easy axis of alignment in the same or substantially the same direction. It is preferable that it is a liquid crystal display element.

  Here, when a fine slit electrode is used as the pixel electrode 22 described above, a so-called fishbone type electrode as shown in FIG. 20 is preferable from the viewpoint of the stability of the orientation. If this fishbone type electrode is explained in full detail based on FIG. 20, this electrode is comprised from transparent electrodes, such as ITO, and the slit part 512c which extracted a part of the electrode material (ITO) is provided. A cross section connecting middle points of opposite sides of a rectangular cell, and a slit portion 512c with a width of about 3 to 5 μm functions as a structure for alignment control, extends from the slit 512 c in a 45 ° diagonal direction and has a width of 5 μm A plurality of 512 c are formed at a pitch of 8 μm, and these function as auxiliary alignment control factors for suppressing disturbance in the azimuthal direction at the time of inclination. The width of the display pixel electrode is, for example, 3 μm. In FIG. 20, while the pixel trunk electrode 512a and the pixel branch electrode 512b have an angle of 45 degrees, the branch electrodes are extended in four directions different by 90 degrees with respect to the pixel center as a symmetry center. There is. The liquid crystal molecules are tilt-aligned by voltage application, but since the tilt alignment is performed so that the orientation of the tilt alignment coincides with these four directions, four divided domains are formed in one pixel to make the viewing angle of display It can be made wider.

In addition, when the photoalignment film of the above 6) is used, the photoalignment film may be composed of a photoresponsive molecule or a photoresponsive polymer as a main component. As such a photoresponsive molecule or photoresponsive polymer,
(1) A photoresponsive isomerization type molecule or a polymer thereof which is isomerized in response to light and oriented substantially perpendicular or parallel to the polarization axis
(2) Photoresponsive dimerized molecules that form a crosslinked structure by dimerization in response to light, and (3) Photoresponsive degradable polymers in which polymer chains are cut in response to light. Among these, a photoresponsive isomerization type molecule or a polymer thereof (3) is particularly preferable in terms of sensitivity and alignment controllability.

Specifically as the above-mentioned photoresponsive isomerization type molecule or its polymer,
An azo compound represented by the general formula (A) or a polymer thereof is particularly preferred.
(General formula (A))

(In the general formula (A), R ¹ and R ² each independently represent a hydroxy group, or (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinyl group, vinyloxy group and maleimide group Wherein A ¹ and A ² each independently represent a divalent hydrocarbon group which may be substituted by a single bond or an alkoxy group, B ¹ and Each B ² independently represents a single bond, -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -NH-CO-O- or -O-CO -NH-, but in the bond of R ¹ and R ² , does not form -O-O- bond, and m and n each independently represent an integer of 0 to 4 (provided that m or n when is 2 or more, a plurality of ^{a 1,} B 1, ^{a 2} and ^{B 2} Flip the A be different at best, represent the two B ¹ or A ¹ or A ² is sandwiched between B ² is which may be optionally divalent hydrocarbon group substituted by an alkoxy group.) Each of R ^{3 to} R ⁶ independently represents a hydrogen atom, a halogen atom, a halogenated alkyl group, an allyloxy group, a cyano group, a nitro group, an alkyl group, a hydroxyalkyl group, an alkoxy group, a carboxyl group or an alkali metal salt thereof, an alkoxy A carbonyl group, a halogenated methoxy group, a hydroxy group, a sulfo group or an alkali metal salt thereof, an amino group, a carbamoyl group, a sulfamoyl group, -OR ⁷ (wherein R ⁷ represents a lower alkyl group having 1 to 6 carbon atoms, a carbon atom C1-C6 lower alkyl group substituted by C3-C6 cycloalkyl group or C1-C6 lower alkoxy group Represented), a hydroxyalkyl group or -CONR 1 to 4 carbon atoms ⁸ R ^{9 (R 8} and ^{R 9} represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms each independently), or ( Represents a polymerizable functional group selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinyl group, vinyloxy group and maleimide group, and X represents a single bond, -CH = CH -, - ^{NR 10} - ^{(where, R 10} represents a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms), - NH-CO-NH -, - S-, or -CH ₂ - represents, ^{G 1} and G ² are each independently 1,4-phenylene group such as phenylene group; represents a 2,6 such arylene groups naphthalene diyl group, one or two or more present in the phenylene group or an arylene group Each hydrogen atom is independently substituted by a hydroxy group, a halogen group, a cyano group, a nitro group, an amino group, a sulfo group, an alkali metal salt of a sulfo group, an alkyl group of 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group It may be done.

In the general formula (A), when at least one of R ^{1 and} R ² is a polymerizable functional group, the stability to light and heat is preferably increased. Among the polymerizable functional groups, (meth) acryloyloxy group is particularly preferable. Also, the maleimide group is preferable because a polymerization initiator is not required. When R ¹ is a hydroxy group, m is preferably 0, and when R ¹ is a polymerizable functional group, m is preferably an integer of 1 to 3, and 1 or 2 is more preferable. When R ² is a hydroxy group, n is preferably 0, and when R ² is a polymerizable functional group, n is preferably an integer of 1 to 3 and more preferably 1 or 2.

  The weight average molecular weight of the polymer of the compound represented by the above general formula (A) is the viscosity of the solution which is easy to apply, from the viewpoint of maintaining the heat resistance of the dry film after application and increasing the orientation control force. 5000-100000 are preferable and 10000-500000 are especially preferable.

  Next, as a light responsive dimerization type molecule, the following general formula (3):

(In the above general formula (3), X is 6 to 12, Y is 0 to 2, and R ^{1 to} R ⁴ are each independently a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms And R ³⁰ is a group represented by the formula (2-a) or the formula (2-b):

R ³¹ in the formula (2-a) is a polymerizable group, an alkoxy group having 1 to 10 carbon atoms, a cyano group or a fluorinated alkyl group having 1 to 12 carbon atoms, j is 0 It is an integer of 6 or more and 6 or less. The photoresponsive dimerization type polymer represented by these is mentioned.

  The photoresponsive degradable polymer is preferably a condensation product of tetracarboxylic acid dianhydride and a diamine compound.

  The liquid crystal display device of the present invention described in detail above can be applied to operation modes such as TN, STN, ECB, VA, VA-TN, IPS, FFS, π cell, OCB, cholesteric liquid crystal and the like. Among these, VA, IPS, FFS, VA-TN, TN and ECB are particularly preferable. The liquid crystal display device of the present invention can be distinguished from a PSA (Polymer Sustained Alignment) liquid crystal display device having a polymer or copolymer on an alignment film in that a polymer network is formed in the liquid crystal layer.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. The following abbreviations are used for the descriptions of compounds in each example. Also, n represents a natural number.

"N-type compound"
(Side chain)
-N-C _n H _{2 n + 1} straight-chain alkyl group having n carbon atoms n-C _n H _{2 n + 1-} straight-chain alkyl group having n carbon atoms-On-OC _n H _{2 n + 1} straight chain having n carbon atoms Jo alkoxyl group nO- C _n H _2n + 1 O- carbon atoms n linear alkoxyl group -V -CH = CH ₂
V- CH ₂ = CH-
-V1 -CH = CH-CH ₃
1V- CH ₃ -CH = CH-
_{-2V -CH 2 -CH 2 -CH = CH} 3
_{V2- CH 2 = CH-CH 2} -CH 2 -
-2V 1 -CH ₂ -CH ₂ -CH = CH-CH _{3
1V2- CH 3 -CH = CH-CH} 2 -CH 2
(Linking group)
-N--C _n H ₂ n-
-NO--C _n H _{2 n-} O-
-On--O-C _n H _{2 n-}
-COO- -C (= O) -O-
-OCO- -O-C (= O)-
-CF2O- -CF ₂ -O-
-OCF2- -O-CF ₂ -

  (Ring structure)

  (Ring structure)

  The polymerizable monomers used in each example are as follows.

  The polymerization initiator used in Examples 19 to 27 is Irgacure 651.

  The properties measured in each example are as follows.

T _NI : Nematic phase-isotropic liquid phase transition temperature (° C.)
Δn: refractive index anisotropy at 25 ° C. Δε: dielectric anisotropy at 25 ° C. :: viscosity at 25 ° C. (mPa · s)
γ ₁ : rotational viscosity (mPa · s) at 25 ° C
VHR measurement (voltage holding ratio (%) at 333 K under the conditions of frequency 60 Hz and applied voltage 1 V)
LED light fastness test with main emission peak at 450 nm:
The visible light LED light source having a main emission peak in 20,000 cd / ^{m 2} of 450nm was measured VHR before and after exposing 1 week with respect to the liquid crystal panel.

LED light fastness test with main emission peak at 385 nm:
The VHR before and after irradiation for 60 seconds and 130 J was measured with a monochromatic LED having a peak at 385 nm.

(Preparation of polymerizable liquid crystal composition)
The liquid crystal composition is adjusted according to the composition of the following Tables 1 to 15 as an N-type liquid crystal composition, and then heated to 60 ° C., and the polymerizable monomers [(P2-1M), (P2- 2M) or (P4-4M)] was mixed and dissolved. It was confirmed by a polarization microscope that each polymerizable liquid crystal composition was uniformly dissolved at room temperature to show a nematic liquid crystal phase. In Examples 19 to 27, this solution was further mixed with a polymerization photoinitiator (IRGACURE 651) to prepare a polymerizable liquid crystal composition.

(Liquid crystal panel, backlight unit, and method of manufacturing liquid crystal display device)
(1) Preparation of liquid crystal panel (VA type liquid crystal panel)
An alignment film solution was formed by spin coating on the transparent electrode formed on the first substrate to form an alignment film having a dry thickness of 0.1 μm. An alignment film was similarly formed on the second substrate on which the color filter was formed. The first substrate on which the comb-shaped transparent electrode and the alignment film are formed and the second electrode substrate on which the color filter is formed are opposed to each alignment film and irradiated with linearly polarized light or the rubbed direction is the antiparallel direction It arrange | positioned so that it might become (180 degrees), and the peripheral part was bonded together with the sealing agent in the state which maintained a fixed gap | interval (4 micrometers) between 2 board | substrates. Next, the above-described various polymerizable liquid crystal compositions (compositions 1 to 9) are filled by vacuum injection into the cell gap partitioned by the alignment film surface and the sealing agent, and the pair of polarizing plates is A VA type liquid crystal panel was manufactured by bonding on a substrate and a second substrate.

While applying a rectangular wave voltage of 2.43 V at a frequency of 1 kHz to this liquid crystal panel, after irradiating an ultraviolet ray with an irradiation intensity of 15 mW / cm ² for 12 seconds using an ultraviolet LED light source of wavelength 365 nm, the ultraviolet irradiation is continued. In this state, the voltage was returned to the vertical alignment by setting the voltage to 0 V, and ultraviolet light was irradiated for 68 seconds from the time the voltage was returned to 0 V. The liquid crystal panel manufactured in this manner was used as an evaluation element, and VHR measurement and evaluation of display quality with respect to UV were performed.

  The results are shown in the following table.

  In Tables 1 to 15 above, the change rate at the main emission peak at 450 nm is “VHR value of initial (= 1 week before light resistance test) / VHR value after 1 week light resistance test”, change at main emission peak at 385 nm The rate is “initial (= 60 seconds before VHR value before light resistance test) / VHR value after 60 seconds light resistance test”. Therefore, as the rate of change is closer to 1, it is more stable to light having a main emission peak at 450 nm or light having a main emission peak at 385 nm. According to the above experimental results, it is considered that the liquid crystal display element is excellent in light resistance, and can suppress or prevent the deterioration of the light emitting nanocrystals and the deterioration of the liquid crystal layer due to the partial irradiation spots of high energy rays.

  From the above experimental results, when the light having a main emission peak at 450 nm is irradiated for one week, the liquid crystal display elements of Example 2, Example 11, and Example 20 have the largest change in VHR value (the change rate is low) ) Was confirmed. It was also confirmed that the liquid crystal display elements of Example 2, Example 11, and Example 20 had the lowest rate of change in VHR value even when light having a main emission peak at 385 nm was irradiated.

  On the other hand, it is confirmed that Example 3, Example 12, and Example 21 are the highest in view of γ1 related to the high-speed response of the liquid crystal display element. The cause of the former is considered to be related to easy absorption of light because it contains a liquid crystal compound of two or more rings including a fused ring (naphthalene). Moreover, as a cause of the latter, since it is a liquid crystal compound having two or more rings containing a chroman ring, it is considered that the viscosity becomes high.

  In Examples 8, 17, and 26, 0.05 parts by mass of an antioxidant represented by the following formula (III-22) is added to 100 parts by mass of the liquid crystal composition to obtain a VA type The liquid crystal panel of the present invention may be prepared and evaluated for light resistance test with light having a main emission peak at 450 nm and light resistance test with light having a main emission peak at 385 nm.

(2) Preparation of back light unit (Preparation of nanocrystal film for light emission)
3 parts by mass of light emitting nanocrystals (InP / ZnS core shell nanocrystal (red light emitting property), InP / ZnS core shell nanocrystal (green light emitting property) all of which are oleic acid ligands) when the nonvolatile component is 100% by mass A mixture of a toluene dispersion of each of green and red light emitting nanocrystals, a photocurable acrylic resin and a photo initiator so that the photocurable acrylic resin is 93 parts by mass and the photo initiator is 4 parts by mass, and the evaporator is A nanocrystal-containing resin composition for light emission is prepared by removing toluene by this method. After this resin composition was coated on a PET film so as to have a film thickness of 100 μm, a PET film was further laminated. The light conversion part (the nanocrystal film for light emission) was obtained by implementing UV irradiation to 5000 mJ of integrated UV irradiation amount.

(Production of Backlight Unit 1)
A blue LED light source is installed at the end of one side of the light guide plate, the reflection sheet covers the portion excluding the irradiation surface, the light emitting nanocrystal film sheet is arranged on the irradiation surface of the light guide plate, and the diffusion sheet is further It arrange | positioned and the backlight unit 1 was produced.

(Production of backlight unit 2)
A blue LED is arranged in a lattice shape on the lower reflection plate that scatters and reflects light, and a diffusion plate is further arranged immediately above the irradiation side, and the above-mentioned nanocrystalline film sheet for light emission is arranged on the diffusion plate A diffusion sheet was disposed on the irradiation side to produce a backlight unit 2.

(Fabrication of a light emitting device including a light emitting nanocrystal)
8 parts by mass of light emitting nanocrystals (InP / ZnS core shell nanocrystal (red light emitting property), InP / ZnS core shell nanocrystal (green light emitting property) all of which are oleic acid ligands) when the nonvolatile component is 100% by mass A mixture of a toluene dispersion of green and red light emitting nanocrystals and an epoxy resin so that the amount of the epoxy resin curing agent and the curing catalyst mixture is 92 parts by mass, and the toluene is removed by an evaporator to obtain a nanocrystal containing resin for light emission Adjust the composition. After the curing agent and the curing catalyst were mixed with the above, the above composition was applied on the LED element so as to have a thickness of about 1 mm. By curing the resin under the condition of 110 ° C. × 3 hours, an LED element provided with a light conversion part was obtained.

(Production of backlight unit 3)
The blue LED element containing the light emitting nanocrystals is installed at the end of one side of the light guide plate, the reflection sheet covers the portion excluding the irradiation surface, and the diffusion sheet is disposed on the irradiation surface of the light guide plate to back light unit 3 was produced.

(Production of backlight unit 4)
A blue LED element containing the above-mentioned light emitting nanocrystals is disposed in a lattice shape on the lower reflection plate that scatters and reflects light, and a diffusion sheet is disposed on the diffusion plate and the diffusion plate directly above the irradiation side to further back light unit 4 was produced.

(Preparation of transparent tube containing light emitting nanocrystals)
1 part by mass of light emitting nanocrystals (InP / ZnS core shell nanocrystal (red light emitting property), InP / ZnS core shell nanocrystal (green light emitting property), all of which are oleic acid ligands) when the nonvolatile component is 100% by mass , Toner dispersion of green and red light emitting nanocrystals and epoxy resin are mixed so that the mixture of epoxy resin, curing agent and curing catalyst is 99 parts by mass, and by removing the toluene by an evaporator, the light emitting nanocrystals are contained. A resin composition was prepared. Thereafter, the above resin composition is filled in a glass tube sealed at one end, the epoxy resin is cured under the condition of 110 ° C. for 3 hours, and the unsealed end is finally sealed. A light-emitting nanocrystal-containing transparent tube was obtained.

(Production of Backlight Unit 5)
A blue LED light source is placed at one end of the light guide plate, and the nanocrystal-containing transparent tube is placed between the blue LED light source and the light guide plate. Furthermore, the part except an irradiation surface was covered with a reflective sheet, the diffusion sheet was arrange | positioned on the irradiation surface of a light-guide plate, and the backlight unit 5 was produced.

(3) Preparation of Liquid Crystal Display Element and Measurement of Color Reproduction Area The backlight units 1 to 5 prepared above were attached to the obtained VA type liquid crystal panel, and the color reproduction area was measured. As a result, when the liquid crystal display element provided with the light conversion part is compared with the conventional liquid crystal display element not provided with the light conversion part, the liquid crystal display element provided with the light conversion part has a color reproduction region It was confirmed to expand.

1000: liquid crystal display element 100: backlight unit (101: light source unit, 102: light guide unit, 103: light conversion unit)
101: light source unit (L: light emitting element (105: light emitting diode, 110: light source substrate), 112a, b: fixing member)
102: light guide part (106: diffusion plate, 104: light guide plate)
103: light conversion part 110: light source substrate 111: transparent filling container 112a, b: fixing member 113: recess container SUB1: (transparent) electrode substrate SUB2: (transparent) substrate (including the case of including electrodes)
SUB3: (transparent) substrate NC: nanocrystals for light emission (compound semiconductor)
1, 8: polarizing layer 2, 7: transparent substrate 3: first electrode layer 3 ': second electrode layer 4: alignment film 5: liquid crystal layer 6: color filter (including the case where the resin contains a dye) )
11: gate electrode 12: gate insulating film 13: semiconductor layer 14: protective layer 16: drain electrode 17: source electrode 18: passivation film 21: pixel electrode 22: common electrode 33: flat film 35: insulating film 510: liquid crystal display device 512: pixel electrode 512a: pixel trunk electrode 512b: pixel branch electrode 512c: pixel slit 516: scanning wiring 517: signal wiring

Claims (20)

A pair of substrates provided with the first substrate and the second substrate facing each other;
A liquid crystal layer sandwiched between the first substrate and the second substrate;
A pixel electrode provided on at least one of the first substrate and the second substrate;
A common electrode provided on at least one of the first substrate and the second substrate;
A color filter composed of three primary color pixel portions of black matrix and red (R), green (G), and blue (B);
A light emitting element that emits ultraviolet or visible light;
A light conversion unit containing a light emitting nanocrystal that emits light by converting incident light from the light emitting element into light of at least one of red (R), green (G), and blue (B);
The liquid crystal layer is a polymer network (A),
The following general formula (i):

(Wherein, R ⁱ¹ and R ⁱ² are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms 8 represents an alkenyloxy group, A ⁱ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and n ⁱ¹ represents 0 or 1. 10 to 50% of a compound represented by % Containing a liquid crystal composition (B) and contained in the liquid crystal composition (B)

Content of less than 30% by weight, or the general formula (N-2)

(Wherein, R ^N21 and R ^N22 are each independently an alkyl group having 1 to 8 carbon atoms, or one or two or more non-adjacent —CH ₂ — in the alkyl chain having 2 to 8 carbon atoms Each independently represents a structural moiety having a chemical structure substituted by —CHCHCH—, —C≡C—, —O—, —CO—, —COO— or —OCO—;
A ^{N 21} and A ^{N 22} are each independently
(A) 1,4-cyclohexylene group,
(B) 1,4-cyclohexylene structure present in one -CH ₂ - or nonadjacent two or more -CH ₂ - 2 monovalent organic group having a has been replaced by -O- structure
as well as
(C) 1,4-phenylene group
(D) a divalent organic group having a structure in which one —CH = or two or more non-adjacent —CH = present in the 1,4-phenylene structure are replaced by —N =;
(E) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group
(F) One —CH = or two or more non-adjacent —CH present in the naphthalene-2,6-diyl structure or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure = Is a divalent organic group having a structure replaced by -N =, and
(G) 1,4-cyclohexenylene group
Represents a group selected from the group consisting of
The above groups (a), (b), (c), (d), (e), (f) and (g) are each independently a cyano group, a fluorine atom or chlorine It may be substituted by an atom,
Z ^N21 and ^{Z N22} are each independently a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 _{-, - CF 2 O -,} - CH = N-N = CH -, - CH = CH -, - represents CF = CF- or -C≡C-,
X ^N21 represents a hydrogen atom or a fluorine atom,
n ^N21 and n ^N22 each independently represent an integer of 0 to 3,
n ^N21 + n ^N22 is 1, 2 or 3, and when a plurality of ^{AN 21} and ^{AN 22} are present, they may be the same or different. )
The content of <10% by weight of the liquid crystal display element. The light converting portion, the red (R) and green (G) region in a light-emitting spectrum, the liquid crystal display device according to claim 1, wherein said light emitting element is closed the emission spectrum in the blue region. The light converting portion, the red (R), has an emission spectrum in the green (G) and blue (B) region, the liquid crystal display device according to claim 1, wherein said light emitting element is closed the emission spectrum in the ultraviolet region.   The liquid crystal display element according to claim 2 or 3, wherein the half width of the emission spectrum of at least one of red (R), green (G) and blue (B) regions is 20 to 60 nm.   The light conversion unit according to any one of claims 1 to 4, wherein the light conversion unit is provided between the light emitting element and the substrate on the light emitting element side in either the first substrate or the second substrate. Liquid crystal display device.   The said light conversion part is a sheet-like thing, And either of said 1st board | substrate or a 2nd board | substrate is arrange | positioned over the whole surface with respect to the board | substrate by the side of a light emitting element. The liquid crystal display element as described in 1 or 2. The liquid crystal display element according to any one of claims 1 to 5, wherein the light conversion portion is provided on a side surface portion of the first substrate or the second substrate.   The liquid crystal display element according to any one of claims 1 to 5, wherein the light emitting element and a light conversion part containing the light emitting nanocrystal are disposed as a light source part integrally laminated. The luminescent nanocrystal comprises a core comprising at least one first semiconductor material;
The liquid crystal display element according to any one of claims 1 to 8, further comprising: a shell that covers the core and includes a second semiconductor material that is the same as or different from the core.   The first semiconductor material is one selected from the group consisting of II-VI semiconductors, III-V semiconductors, I-III-VI semiconductors, IV semiconductors and I-II-IV-VI semiconductors. The liquid crystal display element according to claim 9, which is at least two types.   The liquid crystal display according to claim 1, wherein in the liquid crystal layer, the optical axis direction or the alignment easy axis direction of the polymer network (A) and the alignment easy axis direction of the liquid crystal composition (B) are in the same direction. element.   12. The liquid crystal display according to claim 1, wherein the liquid crystal layer is formed by polymerizing a polymerizable liquid crystal composition containing a polymerizable monomer component (a) and the liquid crystal composition (B) as essential components. element.   The liquid crystal layer is formed by polymerizing a polymerizable liquid crystal composition containing a polymerization initiator (c) as an essential component in addition to the polymerizable monomer component (a) and the liquid crystal composition (B). The liquid crystal display device according to claim 12.     14. The liquid crystal display element according to claim 13, wherein the polymerizable liquid crystal composition contains the polymerizable monomer component (a) in a proportion of 0.5 to 20% by mass in the polymerizable liquid crystal composition. 12. The liquid crystal display according to claim 11, wherein liquid crystal molecules constituting the liquid crystal composition (B) with respect to a transparent substrate are formed to form a pretilt angle of 0.1 to 30 ° with respect to the substrate normal direction. element.   12. The liquid crystal display element according to claim 1, wherein a polymer network layer having a thickness of 0.5% or more of the cell thickness is formed in the cell cross section. The polymerizable monomer component (a) has the following general formula (P1)

( ^Wherein , Z ^p11 is a fluorine atom, a cyano group, a hydrogen atom, an alkyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted by a halogen atom, or a hydrogen atom is substituted by a halogen atom Alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted by a halogen atom, or a carbon atom having a carbon atom in which a hydrogen atom may be substituted by a halogen atom 15 represents an alkenyloxy group or -Sp ^p12 -R ^p12 ,
R ^p11 and R ^p12 are each independently the following formula (RP11-1) to the formula (RP11-8)

In the formulas (RP11-1) to (RP11-8), R ^{P111 to} R ^P112 independently of one another represent a hydrogen atom or a carbon atom number. 1 to 5 alkyl groups, t ^M11 represents 0, 1 or 2;
Sp ^p11 and Sp ^p12 are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a carbon atom of this linear or branched alkylene structure is not adjacent to an oxygen atom Represents a structural moiety having a chemical structure substituted with an oxygen atom or a carbonyl group under the conditions,
L ^p11 and L ^p12 each independently represent a single bond, -O-, -S-, -CH _2- , -OCH _2- , -CH ₂ O-, -CO-, -C ₂ H ₄ -,- _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO-NR P113 -, - NR P113 -CO -, - SCH 2 -, - CH 2 S- ^{, -CH = CR P113 -COO -,} - CH = CR P113 -OCO -, - COO-CR P113 = CH-, -OCO-CR P113 = CH-, -COO-CR P113 = CH-COO -, - COO -CR ^P113 = CH-OCO-, -OCO-CR ^P113 = CH-COO-, -OCO-CR ^P113 = CH-OCO-,-(CH ₂ ) _tm12 -C (= O) -O-,-(CH _{2) m12 -O- (C = O) -} , - O- (C = O) - (CH 2) tm12 -, - (C = O) -O- (CH 2) tm12 -, - CH = CH -, - _{CF = CF -, - CF =} CH -, - CH = CF -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 _{CF 2 -, - C≡C -,} - N = N -, - CH = N- or -C = N-N = C- ^{(wherein, R P113} is the number of hydrogen atoms or carbon atoms 1 independently 4 represents an alkyl group, wherein tm12 represents an integer of 1 to 4);
M ^p11 , M ^p12 and M ^p13 each independently represent a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, 1,2-cyclohexylene group, 1,4-cyclohexenylene group, 1,3-cyclohexenylene group, 1,2-cyclohexenylene group, anthracene-2,6-diyl group, phenanthrene-2,7- Diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, indan-2,5-diyl group, fluorene- 2,6-diyl group, fluorene-1,4-diyl group, phenanthrene-2,7-diyl group, anthracene-2,6-diyl group, anthracene-1,4-diyl group, 1, Represents a 2,3,4-tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group,
M ^p11 , M ^p12 and M ^p13 are each independently unsubstituted or an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, It may be substituted by a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, a nitro group or a group having the same meaning as -Sp ^p11 -R ^p11 , mp12 represents 1 or 2, mp13 to mp14 Each independently represents 0, 1, 2, or 3, and mp11 and mp15 each independently represent 1, 2 or 3, but when there are a plurality of Z ^p11 , they are identical even though they are identical When there are a plurality of R ^p11 , they may be the same or different, and when there are a plurality of R ^p12 , they may be the same or different. When there are a plurality of Sp ^p11 , they may be the same or different, and when there are a plurality of Sp ^p12 , they may be the same or different, When a plurality of L ^p11 are present, they may be the same or different, and when a plurality of L ^p12 are present, they may be the same or different, and a plurality of M ^p12 is present In the case where they are the same or different, in the case where there are a plurality of M ^{p13 's} , they may be the same or different. The liquid crystal display element according to claim 12, which is represented by The liquid crystal composition (B) is added to the compound represented by the general formula (i), and the following general formulas (N-1), (N-2), (N-3) and (N-4)

(Wherein, R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 , R ^N32 , R ^N41 and R ^N42 are each independently an alkyl group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms One or two or more non-adjacent -CH ₂ -in the alkyl chain are each independently -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO. Represents a structural moiety having a chemical structure substituted by-,
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 , A ^N32 , A ^N41 and A ^N42 are each independently (a) 1,4-cyclohexylene group,
(B) 1,4-cyclohexylene structure present in one -CH ₂ - or nonadjacent two or more -CH ₂ - 2 monovalent organic group having a has been replaced by -O- structure And (c) 1,4-phenylene group (d) a structure in which one -CH = or two or more non-adjacent -CH = present in the 1,4-phenylene structure is replaced by -N = A divalent organic group having
(E) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (f) Naphthalene-2,6-diyl Structure or a structure in which one -CH = or two or more non-adjacent -CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure is replaced by -N = And a group selected from the group consisting of (g) 1,4-cyclohexenylene groups, and
The above groups (a), (b), (c), (d), (e), (f) and (g) are each independently a cyano group, a fluorine atom or chlorine It may be substituted by an atom,
^{Z N11, Z N12, Z N21} , Z N22, Z N31, Z N32, Z N41 and ^{Z N42} are each independently a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 - _{, -CH 2 O -, - COO} -, - OCO -, - OCF 2 -, - CF 2 O -, - CH = N-N = CH -, - CH = CH -, - CF = CF- or -C Represents ≡C-,
X ^N21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents -CH ₂ -or an oxygen atom,
X ^N41 represents an oxygen atom, a nitrogen atom or -CH _2- ,
Y ^N41 represents a single bond or -CH _2- ;
n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 , n ^N32 , n ^N41 and n ^N42 each independently represent an integer of 0 to 3, but
n ^{N 11} + n ^{N 12} , n N ²¹ + n N ²² and n ^{N 31} + n ^{N 32} are each independently 1, 2 or 3, and A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 , A ^N32 , Z ^N11 , Z ^N12 And Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32 may be the same or different.
n ^N41 + n ^N42 represents an integer of 0 to 3, but when there are a plurality of A ^N41 and A ^N42 , Z ^N41 and Z ^N42 , they may be the same or different. )
The liquid crystal display element according to claim 1, comprising one or more compounds selected from the group consisting of compounds represented by and wherein the anisotropy of the dielectric constant is negative. The liquid crystal composition (B) is added to the compound represented by the general formula (i), and the following general formula (J)

(Wherein, R ^J1 is an alkyl group having 1 to 8 carbon atoms, or one or two non-adjacent two or more —CH ₂ — in the alkyl chain having 2 to 8 carbon atoms are each independently — Structural moiety having a chemical structure substituted by CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,
n ^J1 represents 0, 1, 2, 3 or 4;
A ^J1 , A ^J2 and A ^J3 are each independently
(A) 1,4-cyclohexylene group (b) 1,4-cyclohexylene structure present in one -CH ₂ - or nonadjacent two or more -CH ₂ - is replaced by -O- A divalent organic group having a defined chemical structure,
(C) 1,4-phenylene group (d) Chemical structure in which one -CH = or two or more non-adjacent -CH = in the 1,4-phenylene structure are replaced by -N = A divalent organic group having
(E) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (f) Naphthalene-2,6-diyl Structure or a structure in which one -CH = or two or more non-adjacent -CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure is replaced by -N = Represents a group selected from the group consisting of divalent organic groups having a group represented by the above-mentioned groups (a), (b), (c), (d), (d), and (f) And each may be independently substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
Z ^J1 and ^{Z J2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O-, -COO-, -OCO- or -C≡C-
When n ^J1 is 2, 3 or 4 and there are a plurality of A ^J2 , they may be the same or different, and n ^J1 is 2, 3 or 4 and a plurality of Z ^J1 is present If they are identical or different,
X ^J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )
The liquid crystal display element according to claim 1, wherein the liquid crystal display element is a compound represented by the following formula and one or more compounds having positive dielectric anisotropy.   The liquid crystal display element of any one of Claims 1-19 whose (DELTA) n of the liquid crystal composition in the said liquid crystal layer is 0.05-0.15.

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