WO2018105439A1

WO2018105439A1 - Liquid crystal display element

Info

Publication number: WO2018105439A1
Application number: PCT/JP2017/042547
Authority: WO
Inventors: 英彦山口; 芳典岩下; 小川　真治; 崇之三木; 穣田淵
Original assignee: Dic株式会社
Priority date: 2016-12-05
Filing date: 2017-11-28
Publication date: 2018-06-14
Also published as: JPWO2018105439A1

Abstract

[Problem] To provide a liquid crystal display element which balances light-emission efficiency and color reproducibility, and is capable of suppressing or preventing deterioration of the liquid crystal layer thereof caused by high energy light ray irradiation. [Solution] A liquid crystal display element which is depicted in fig. 3 and equipped with a pair of substrates provided in a manner such that a first substrate and a second substrate face one another, a liquid crystal layer sandwiched between the pair of substrates, a pixel electrode provided on the first or second substrate, a common electrode provided on the other of the substrates, a light source unit, and a photoconversion layer which contains a light-emitting nanocrystal that has a light-emitting spectrum which is red (R), green (G) or blue (B) depending on the light from the light source unit, wherein the liquid crystal layer contains a polymer network (A), and a liquid crystal composition (B) containing a compound represented by general formula (i) (In the formula, Rⁱ¹ and Rⁱ² represent a C1-8 alkyl group or the like, Aⁱ¹ represents a 1,4-phenylene group or the like, and nⁱ¹ represents 0 or 1.) in the amount of 10-50 wt%.

Description

Liquid crystal display element

The present invention relates to a liquid crystal display element.

Because of its excellent display quality, active matrix liquid crystal display devices are put on the market for mobile terminals, liquid crystal televisions, projectors, computers and the like. In the active matrix display system, TFT (thin film transistor) or MIM (metal insulator metal) is used for each pixel. In combination with a liquid crystal composition having a high voltage holding ratio, a TN type (twisted nematic) is used. It is widely used as the first general liquid crystal display element. In order to obtain wider viewing angle characteristics, VA (vertical alignment: vertical alignment), IPS (In Plane Switching: in-plane switching), IPS improved FFS (Fringe Field Switching: fringe field switching), etc. are used. In order to deal with such display elements, new liquid crystal compounds or liquid crystal compositions have been proposed at present.

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 for a display is used. As the light source, a cold cathode tube, a white LED (light emitting diode), or the like is used. From the viewpoint of light emission efficiency, at present, the white LED is mainly used. LEDs cannot currently cover the entire visible light range from 380 nm to 750 nm with a single element, and several forms are known for obtaining 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 Among these three methods, From the viewpoint of obtaining white light optimal as a light source for a liquid crystal display element, 3) is the best, and 2) and 1) are in order, and from the viewpoint of luminous efficiency, 1) is the best.

In a liquid crystal display element, reduction of power consumption is important, and in order to respond to a power saving program under study by advanced countries, the light emission efficiency of the light source is emphasized. Therefore, at present, white light is obtained by the combination of 1) blue LED and yellow phosphor.

Although this method is excellent in luminous efficiency, it has poor characteristics as a white light source, such as lack of red light, and has a problem in color reproducibility. In particular, liquid crystal display elements use color filters in combination with liquid crystal elements to realize color display, so it is difficult to improve color reproducibility even if the light source section is improved. It has been necessary to increase the color purity by increasing the pigment concentration in the color filter or by increasing the color film thickness. However, in this case, there is a problem that the light transmittance is reduced, and the amount of light must be increased, resulting in an increase in power consumption.

Therefore, as a technique for simultaneously solving the color reproducibility and the light emission efficiency of the liquid crystal display element, a quantum dot technique (see Patent Document 1), which is an example of a nanocrystal for light emission, has attracted attention. Quantum dots are composed of semiconductor microcrystals with a particle size of several nanometers to several tens of nanometers. The energy levels are discrete due to the confinement effect of electron-hole pairs, and the energy band gap increases as the particle diameter decreases. is doing. By applying this property and controlling the particle diameter to make the band gap uniform, a light source with a small half-value width of the emission spectrum can be obtained. Since a wide color gamut display can be realized by obtaining a light source of three primary colors with a small half-value width, it is disclosed that a liquid crystal display element with improved color reproducibility can be configured by using quantum dots as a constituent member of a backlight. (See Patent Document 2 and Non-Patent Document 1). Further, a proposal has been made to use three-color quantum dots in place of conventional color filters by using short-wavelength visible light such as near ultraviolet light or blue light as a light source (see Patent Document 3). In principle, these display elements can achieve both high luminous efficiency and color reproducibility.

JP-T-2001-523758 International Publication No. 2004/074739 Pamphlet U.S. Pat. No. 8,648,524

However, as described above, when quantum dots, which are examples of light-emitting nanocrystals, are used in a liquid crystal display element as in

Patent Documents

2 and 3 and Non-Patent Document 1, a short light source is used to cause excitation of the quantum dots. Since a visible light source with a wavelength or ultraviolet light is required, the light transmitted through the liquid crystal layer is mainly in a short wavelength region, unlike the case of using conventional white light.

Therefore, short-wavelength visible light and ultraviolet light used as a light source for light emission from the light-emitting nanocrystal are high-energy light, and the liquid crystal layer functioning as an optical switch can withstand long-time exposure to these high-energy light. It is demanded. In particular, it has been confirmed that the liquid crystal material itself is decomposed when the liquid crystal layer is exposed to a high-energy light beam such as short-wavelength visible light or ultraviolet light.

Therefore, the problem to be solved by the present invention is that, when a light conversion layer containing nanocrystals for light emission is used instead of a color filter, a high energy light beam while achieving both high luminous efficiency and excellent color reproducibility. An object of the present invention is to provide a liquid crystal display element capable of suppressing or preventing the deterioration of the liquid crystal layer due to the irradiation.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present application have used a liquid crystal layer containing a specific liquid crystal compound in a polymer network as a member corresponding to a color filter using light-emitting nanocrystals such as quantum dots. The present invention was completed by finding that the above-mentioned problems can be solved by using the liquid crystal display device.

That is, 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 light source unit including a light emitting element;
It has three primary color pixels of red (R), green (G), and blue (B), and red (R), green (G), and blue (B) by light from the light source unit incident on at least one of the three primary colors. A light conversion layer containing a light-emitting nanocrystal having an emission spectrum,
The liquid crystal layer comprises a polymer network (A) and a 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 an alkyl group having 2 to 8 carbon atoms. A alkenyloxy group, A represents a 1,4-phenylene group or trans-1,4-cyclohexylene group, and n represents 0 or 1). The present invention relates to a liquid crystal display element comprising the composition (B).

According to the present invention, when a light conversion layer containing nanocrystals for light emission is used in place of a color filter, the liquid crystal layer is irradiated with a high-energy beam while achieving both high light emission efficiency and excellent color reproducibility. An object of the present invention is to provide a liquid crystal display element capable of suppressing or preventing deterioration. Therefore, the liquid crystal display element of the present invention can maintain the color reproduction region for a long time.

FIG. 1 is a perspective view showing an embodiment of a 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 perspective view showing another embodiment of the liquid crystal display element of the present invention. FIG. 4 is a perspective view showing another embodiment of the liquid crystal display element of the present invention. FIG. 5 is a schematic view of a cross section of the liquid crystal display element cut along the line II in FIGS. 1 to 4, and is a schematic view showing an example of a light conversion layer in the liquid crystal display element of the present invention. FIG. 6 is a schematic view of a cross section of the liquid crystal display element taken along the line II in FIGS. 1 to 4, and is a schematic view showing another example of the light conversion layer in the liquid crystal display element of the present invention. FIG. 7 is a schematic view of a cross section of the liquid crystal display element taken along the line II in FIGS. 1 to 4, and is a schematic view showing another example of the light conversion layer in the liquid crystal display element of the present invention. FIG. 8 is a schematic cross-sectional view of the liquid crystal display element cut along the line II in FIGS. 1 to 4, and is a schematic view showing another example of the light conversion layer in the liquid crystal display element of the present invention. FIG. 9 is a schematic view of a cross section of the liquid crystal display element cut along the line II in FIGS. 1 to 4, and is a schematic view showing another example of the light conversion layer in the liquid crystal display element of the present invention. FIG. 10 is a schematic cross-sectional view of the liquid crystal display element cut along the line II in FIGS. 1 to 4, and is a schematic view showing another example of the light conversion layer in the liquid crystal display element of the present invention. FIG. 11 is a schematic cross-sectional view of the liquid crystal display element cut along the line II in FIGS. 1 to 4, and is a schematic view showing another example of the light conversion layer in the liquid crystal display element of the present invention. FIG. 12 is a schematic diagram showing the pixel portion of the liquid crystal display element of the present invention in an equivalent circuit. FIG. 13 is a schematic diagram showing an example of the shape of the pixel electrode of the present invention. FIG. 14 is a schematic diagram showing an example of the shape of the pixel electrode of the present invention. FIG. 15 is a schematic view showing an electrode structure of the IPS liquid crystal display element of the present invention. 16 is one example of a cross-sectional view of the liquid crystal display element shown in FIG. 2 cut along the line III-III in FIG. 13 or FIG. FIG. 17 is a cross-sectional view of the IPS liquid crystal panel taken along the line III-III in FIG. FIG. 18 is an enlarged plan view of a region surrounded by the II line of the electrode layer 3 including the thin film transistor formed on the substrate in FIGS. 19 is a cross-sectional view of the liquid crystal display element shown in FIGS. 3 and 4 taken along the line III-III in FIG. FIG. 20 is a schematic diagram illustrating an example of the light conversion layer 6. FIG. 21 is a schematic diagram illustrating an example of the light conversion layer 6. FIG. 22 is a schematic diagram illustrating an example of the light conversion layer 6. FIG. 23 is a diagram showing an emission spectrum of a quantum dot. FIG. 24 is a schematic diagram of an electrode structure of a fishbone type VA liquid crystal cell.

As described above, the liquid crystal display element of the present invention includes a pair of substrates provided with the first substrate and the second substrate facing each other, and 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 or the second substrate, a common electrode provided on at least one of the first substrate or the second substrate, and a light source including a light emitting element And
The apparatus includes three primary color pixels of red (R), green (G), and blue (B). Red (R), green (G), and blue (B) are generated by incident light from the light source unit that is incident on at least one of the three primary colors. And a light conversion layer containing a light-emitting nanocrystal having an emission spectrum.
The liquid crystal layer comprises a polymer network (A) and a 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 an alkyl group having 2 to 8 carbon atoms. A alkenyloxy group, A represents a 1,4-phenylene group or trans-1,4-cyclohexylene group, and n represents 0 or 1). It contains the composition (B).

In the present invention, a highly reliable liquid crystal display element having a liquid crystal layer capable of withstanding long-time exposure to high-energy light rays such as short-wavelength visible light and ultraviolet light used for a light source by configuring the liquid crystal layer as a characteristic configuration Can provide.

A preferred liquid crystal display element according to the present invention will be described below with reference to the drawings, and then each component of the liquid crystal display element will be described.

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

The liquid crystal display element 1000 according to the present invention includes a backlight unit 100 and a liquid crystal panel 10. The backlight unit 100 includes a light source unit 101 having a light emitting element L, and a light guide unit 102 serving as a light guide plate (not shown) or a light diffusion plate (not shown). As shown in FIG. 1, in one form of the backlight 100, a light source unit 101 including a plurality of light emitting elements L is disposed on one side surface of the light guide unit 102. If necessary, the light source unit 101 including the plurality of light emitting elements L is not only provided on one side surface of the liquid crystal panel 10 (one side surface of the light guide unit 102) but also on the other side surface side (opposite side surfaces) of the liquid crystal panel 10. The 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 side surfaces. The light guide unit 102 may include a light diffusion plate (not shown) instead of the light guide plate as necessary.

In the liquid crystal panel 10 shown in FIG. 1, the first (transparent insulating) substrate 2 is provided with a polarizing layer 1 on one surface and an electrode layer 3 on the other surface. In addition, a second (transparent insulating) substrate 7 is disposed so as to face the first substrate 2 with the liquid crystal layer 5 interposed therebetween, and a light conversion layer (so-called color layer) 6 and a polarized light are disposed on the substrate 7. The layers 8 are provided in this order. Here, the light conversion layer (color layer) 6 includes three primary color pixels of red (R), green (G), and blue (B), and pixels of at least one of the three primary colors are emitted from the light source unit. It contains light-emitting nanocrystals having an emission spectrum in any of red (R), green (G), and blue (B) by incident light.

FIG. 1 shows a mode in which a pixel electrode (not shown) and a common electrode (not shown) are provided on the first substrate 2 side as the electrode layer 3, but another embodiment (for example, 3 and 4), the pixel electrode may be provided on the first substrate 2 and the common electrode 3 ′ may be provided on the second substrate 7.

In FIG. 1, a light conversion layer 6 is provided between the second substrate 7 and the liquid crystal layer 5. As another embodiment of the liquid crystal display element according to the present invention, FIG. 11, the light conversion layer 6 may be provided on the first substrate 2 side as in the so-called color filter on array (COA) type, and in this case, between the electrode layer 3 and the liquid crystal layer 5. The light conversion layer 6 may be provided, or the light conversion layer 6 may be provided between the electrode layer 3 and the first substrate 2. Further, if necessary, an overcoat layer (not shown) may be provided so as to cover the light conversion layer 6 to prevent a substance contained in the light conversion layer from flowing out to the liquid crystal layer.

Next, the liquid crystal display element 1000 shown in FIG. 2 is a view showing an embodiment in which an alignment layer 4 is further provided in the liquid crystal panel 10 of FIG. Specifically, in the liquid crystal panel 10 of FIG. 2, the polarizing layer 1 is provided on one surface of the first (transparent insulating) substrate 2, and the electrode layer 3 is provided on the other surface. Further, an alignment layer 4 is formed on the electrode layer 3. In addition, a light conversion layer 6 containing nanocrystals for light emission is provided on a second (transparent insulating) substrate 7 so as to face the first substrate 2 with the liquid crystal layer 5 interposed therebetween. Further, a polarizing layer 8 is provided on the first substrate 2 side of the light conversion layer 6, and an alignment layer 4 is further provided on the first substrate 2 side of the polarizing layer 8.

In FIG. 2, a pixel electrode (not shown) and a common electrode (not shown) are provided on the first substrate 2 side as the electrode layer 3, but another embodiment (for example, FIG. 3 and FIG. 4). ), The pixel electrode 3 may be provided on the first substrate 2, and the common electrode may be provided on the second substrate 7.

The alignment layer 4 can align liquid crystal molecules in the liquid crystal composition in a predetermined direction with respect to the

substrates

2 and 7 when no voltage is applied. Although FIG. 2 shows an example in which the liquid crystal layer 5 is sandwiched between the pair of alignment layers 4, the alignment layer 4 may be provided only on one side of the first substrate 2 or the second substrate.

In FIG. 2, the light conversion layer 6 is provided between the second substrate 7 and the alignment layer 4. As in the case of FIG. 1, similar to the so-called color filter on array (COA) type. The light conversion layer 6 may be provided on the first substrate 2 side. Further, in FIG. 2 and FIG. 4 described later, the alignment layer 4 is provided on the first substrate 2 side and the second substrate 7 side so as to be in contact with the liquid crystal layer 5, but only one of them may be provided.

As described above, the liquid crystal panel 10 according to the present invention includes the first polarizing layer 1, the first substrate 2, the electrode layer 3, the liquid crystal layer 5, the second polarizing layer 8, and the light conversion layer 6. And the second substrate 7 are sequentially laminated, or the first polarizing layer 1, the first substrate 2, the electrode layer 3, the alignment layer 4, and a liquid crystal layer containing a liquid crystal composition 5, the alignment layer 4, the second polarizing layer 8, the light conversion layer 6, and the second substrate 7 are preferably laminated in sequence.

1 and 2, the light emitted from the light emitting element L passes through the light guide 102 (for example, via a light guide plate or a light diffusion plate) and enters the surface of the liquid crystal panel 10. The light incident on the liquid crystal panel 10 is polarized in a specific direction by the first polarizing layer 1, and then the light whose polarization direction is changed by the liquid crystal layer 5 is blocked by the second polarizing layer 8. After being polarized in a specific direction, it enters the light conversion layer 6. In the light conversion layer 6, the light incident on the light conversion layer 6 is absorbed by the light-emitting nanocrystals and converted into an emission spectrum into one of red (R), green (G), and blue (B). Thus, any one of red (R), green (G), and blue (B) can be displayed.

At this time, the shape of the light guide portion 102 (particularly, the light guide plate) is a flat plate having a side surface whose thickness gradually decreases from the side surface on which the light emitted from the light emitting element L is incident toward the opposing surface (side surface Is preferable because it is easy to make light incident on the liquid crystal panel 10 because the line light can be converted into surface light (which will be described later as an embodiment).

FIG. 3 shows an example of the entire liquid crystal display element having a so-called direct-type backlight structure in which the backlight unit 100 has a plurality of light emitting elements L arranged in a plane with respect to the flat light guide 102. It is a perspective view. In addition, for convenience of explanation, each component is illustrated separately.

In the direct backlight structure, the light from the light emitting element L is surface light, and therefore the shape of the light guide 102 need not be tapered unlike FIGS.

A liquid crystal panel 10 in FIG. 3 includes a first substrate 2 having a first electrode layer 3 (for example, a pixel electrode) on one surface and a first polarizing layer 1 on the other surface; The second substrate 7 having the electrode layer 3 ′ (for example, a common electrode), and the liquid crystal layer 5 sandwiched between the first substrate 2 and the second substrate 7 are provided. In addition, a light conversion layer 6 is provided between the second substrate 7 and the second electrode layer 3 ′, and a second electrode layer 3 ′ on the light conversion layer 6 is disposed on the second electrode layer 3 ′ side. The polarizing layer 8 is provided.

That is, in the embodiment of FIG. 3, the liquid crystal display element 1000 includes the backlight unit 100, the first polarizing plate 1, the first substrate 2, and an electrode layer including a thin film transistor (or a thin film transistor layer or a pixel electrode). ) 3, a layer 5 containing a liquid crystal composition, a second electrode layer 3 ′, a second polarizing plate 8, a light conversion layer 6, and a second substrate 7 are sequentially laminated. Become.

Next, the liquid crystal display element 1000 shown in FIG. 4 is a view showing an embodiment in which an alignment layer 4 is further provided in the liquid crystal panel 10 of FIG. That is, the liquid crystal panel 10 in FIG. 4 includes a first substrate 2 having a first electrode layer 3 (for example, a pixel electrode) on one surface and a first polarizing layer 1 on the other surface; A liquid crystal composition (or liquid crystal layer 5) sandwiched between a second substrate 7 having a second electrode layer 3 ′ (for example, a common electrode) and the first substrate 2 and the second substrate 7. Between the first substrate 2 and the liquid crystal layer 5 so as to be in contact with the liquid crystal layer 5, and between the second substrate 7 and the liquid crystal layer 5. An alignment layer 4 provided in contact with the liquid crystal layer 5. In addition, a light conversion layer 6 is provided between the second substrate 7 and the second electrode layer 3 ′, and a second electrode layer 3 ′ on the light conversion layer 6 is disposed on the second electrode layer 3 ′ side. The polarizing layer 8 is provided.

That is, in the embodiment of FIG. 4, the liquid crystal display element 1000 includes a backlight unit 100, a first polarizing plate 1, a first substrate 2, and an electrode layer (or a thin film transistor layer) 3 including a thin film transistor. , Alignment layer 4, layer 5 containing a liquid crystal composition, alignment layer 4, second electrode layer 3 ′, second polarizing plate 8, light conversion layer 6, second substrate 7, It is preferable that are sequentially stacked.

3 and 4, the light emitted from the light emitting element L passes through the light guide 102 (through the light diffusion plate or the light diffusion plate) and enters the surface of the liquid crystal panel 10. The light incident on the liquid crystal panel 10 is polarized in a specific direction by the first polarizing layer 1, and then the light whose polarization direction is changed by the liquid crystal layer 5 is blocked by the second polarizing layer 8. After being polarized in a specific direction, it enters the light conversion layer 6. In the light conversion layer 6, the light incident on the light conversion layer 6 is absorbed by the light-emitting nanocrystals and converted into an emission spectrum into one of red (R), green (G), and blue (B). Thus, any one of red (R), green (G), and blue (B) can be displayed.

Moreover, it is preferable that a light diffusing plate is provided between the liquid crystal panel 10 and the light guide unit 102 as the light guide unit 102 (described as an embodiment below).

Hereinafter, a cross-sectional structure of a liquid crystal panel portion in a preferable liquid crystal display element of the present invention, in particular, a laminated mode of a polarizing layer, a light conversion layer, a liquid crystal layer, and the like will be described.

5 to 11 are schematic views of cross-sectional views of the liquid crystal display device in which a portion of the liquid crystal panel 10 is cut to show the configuration of the liquid crystal panel used in the present embodiment. It is the schematic which shows the lamination | stacking aspect of a liquid crystal layer. 5 to 11, for convenience of description of the positional relationship among the polarizing layer, the light conversion layer, and the liquid crystal layer, the electrode layer 3 (including the TFT), the electrode layer 3 ′, and the electrode layer 3 ′ shown in FIGS. The alignment layer 4 and the like are omitted schematically.

Further, in FIGS. 5 to 11, a substrate on the backlight unit (light source) side and a laminate laminated on the substrate are array substrate (A-SUB), and the array substrate and liquid crystal layer 5 are connected to the liquid crystal layer 5. A substrate opposed to the substrate and a stacked body stacked on the substrate are referred to as a counter substrate (O-SUB). The configurations and preferred embodiments of the array substrate (A-SUB) and the counter substrate (O-SUB) will be described in detail in the description of the electrode structure in FIGS. 5 to 11 show an example in which TFTs are formed on the array substrate side, the array substrate and the counter substrate may be interchanged.

In the embodiment of FIG. 5, the light conversion layer 6 is provided on the counter substrate (O-SUB), and the light conversion layer 6 and the second polarizing layer 8 include a pair of substrates (the first substrate 2 and the second substrate 2). In this embodiment, a so-called in-cell polarizing layer is provided between the second substrates 7).

In general liquid crystal display elements, light from a white light source is wavelength-selected in a color filter, and each color is displayed by absorbing a part of the light. One of the features is that the light conversion layer containing crystals is used as an alternative member of the color filter. Therefore, the light conversion layer 6 in the present invention includes the three primary color pixels of red (R), green (G), and blue (B), and plays the same role as a so-called color filter.

Specifically, the light conversion layer 6 includes, for example, a red (R) pixel portion (red color layer portion) including a light conversion pixel layer (NC-Red) including a red light emitting nanocrystal, and a green ( The pixel portion (green color layer portion) of R) includes a light conversion pixel layer (NC-Green) containing nanocrystals for green light emission, and the blue (R) pixel portion (blue color layer portion) An optical conversion pixel layer (NC-Blue) including a blue light emitting nanocrystal is provided. An example of such a single layer type light conversion layer 6 is shown in FIG.

That is, when the light conversion layer 6 uses light having a main peak near 450 nm, such as a blue LED, as a light source, the blue light emitted from the blue LED can be used as blue. Therefore, when the light from the light source is blue light, the light conversion pixel layer (NC-Blue) is omitted from the light conversion pixel layers (NC-Red, NC-Green, NC-Blue) of the respective colors. However, for blue, the backlight may be used as it is. In this case, the color layer displaying blue can be constituted by a transparent material or a color material layer (so-called blue color filter) containing a blue color material. Therefore, in FIGS. 5 and 22, since the blue light emitting nanocrystal can be an arbitrary component, the blue light emitting nanocrystal is indicated by a one-dot broken line.

In the liquid crystal display element of the present invention shown in FIG. 5, a black matrix may be provided for the purpose of preventing color mixing between the color layers. In FIG. 5, a color layer containing a blue color material (so-called “blue”) between the light conversion layer 6 and the second polarizing layer 8 according to the type of light source used (blue LED as a light emitting element). It is preferable to provide a color filter “) between them in order to prevent the intrusion of unnecessary light from the outside and suppress deterioration in image quality. A structure in which such a blue color filter is arranged is shown in FIG.

When the embodiment shown in FIG. 5 is applied to a VA type liquid crystal display element, in the counter substrate side O-SUB, between the liquid crystal 5 and the second polarizing layer 8 or between the second polarizing layer 8 and the light conversion layer. 6 is provided with an electrode layer 3 ′ (common electrode), and the electrode layer 3 (pixel electrode) is preferably formed on the first substrate 2. The alignment layer 4 is preferably formed on the surface in contact with at least one liquid crystal layer on the counter substrate side (O-SUB) and the array substrate side (A-SUB). Further, in FIG. 5, when the liquid crystal display element is an FFS type or an IPS type, the pixel electrode and the common electrode are preferably formed on the first base 2.

Next, in the embodiment of FIG. 6, the light conversion layer 6 is provided on the counter substrate (O-SUB), and the light conversion layer 6 includes a pair of substrates (first substrate 2 and second substrate 7). ) Is provided outside. Therefore, a support substrate 9 that supports the second polarizing layer 8 and the light conversion layer 6 is provided. The support substrate 9 is preferably a transparent substrate.

In the light conversion layer 6 in FIG. 6, the red (R) pixel portion (red color layer portion) is a light conversion pixel layer (NC-Red) containing red light emitting nanocrystals, as in the embodiment of FIG. The green (R) pixel portion (green color layer portion) includes a light conversion pixel layer (NC-Green) including a green light emitting nanocrystal, and the blue (R) pixel portion (blue color) The layer portion) includes a light conversion pixel layer (NC-Blue) that optionally includes blue light emitting nanocrystals. Further, the preferred form of the red (R) pixel portion, the green (G) pixel portion, and the blue (B) pixel portion in the light conversion layer 8 in FIG. 6 is the same as the embodiment shown in FIG. It is omitted here.

When the embodiment shown in FIG. 6 is applied to a VA liquid crystal display element, an electrode layer 3 ′ (common electrode) is provided between the liquid crystal 5 and the second polarizing layer 8 on the counter substrate side O-SUB, and The electrode layer 3 (pixel electrode) is preferably formed on the first substrate 2. The alignment layer 4 is preferably formed on the surface in contact with at least one liquid crystal layer on the counter substrate side (O-SUB) and the array substrate side (A-SUB). Further, in FIG. 6, when the liquid crystal display element is an FFS type or an IPS type, it is preferable that the pixel electrode and the common electrode are formed on the first substrate 2.

Next, in the embodiment of FIG. 7, the light conversion layer 6 is provided on the counter substrate side O-SUB, and the light conversion layer 6 and the second polarizing layer 8 are formed of a pair of substrates (the first substrate 2 and the second substrate 2). And an in-cell polarizing plate provided between the substrates 7), and in each of the red and green color layer portions constituting the light conversion layer 6, the red color layer portion is a red light emitting nano-layer. It has a two-layer structure in which a light conversion pixel layer (NC-Red) containing crystals and a color material layer (so-called red color filter) (CF-Red) containing a red color material are stacked, and the green color The layer part is composed of a light conversion pixel layer (NC-Green) containing nanocrystals for green light emission that emits green light and a color material layer (so-called green color filter) (CF-Green) containing a green color material. It has a two-layer structure.

That is, such a two-layer structure of the color layer portion transmits the remaining excitation light when all of the incident light (light from the light source, preferably blue light) cannot be converted by the light conversion pixel layer containing nanocrystals. A color filter (CFL) is laminated for the purpose of absorption without absorption.

According to FIG. 7, in the liquid crystal panel portion of the liquid crystal display element according to the present invention, the second polarizing layer 8 and the light conversion layer 6 having a red color layer, a green color layer, and a blue color layer are provided as a backlight. It is provided on the substrate side O-SUB opposite to the unit (light source) side substrate A-SUB. In FIG. 7, the second polarizing layer 8 includes an in-cell polarizing plate provided between a pair of substrates (first substrate 2 and second substrate 7). The embodiment in FIG. 7 is a form in which the light conversion layer 6 in FIG. 5 is laminated in two layers. More specifically, the light conversion layer 6 has a red color layer portion, a green color layer portion, and a blue color layer portion, and the red (R) pixel portion (red color layer portion) is red. A light conversion pixel layer (NC-Red) including a light emitting nanocrystal and a color material layer (CF-Red) including a red color material are configured as a two-layer structure. The green (R) pixel portion (green color layer portion) includes a light conversion pixel layer (NC-Green) including a green light emitting nanocrystal and a color material layer (CF-Green) including a green color material. Configured as a layered structure. In this case, in FIG. 7, the green color layer portion includes a light conversion pixel layer (NC-Green) including a green light emitting nanocrystal and a yellow color material in order to perform color correction in consideration of transmission of excitation light. It may be combined with a color material layer (CF-Yellow) containing The blue (R) pixel portion (blue color layer portion) is composed of a color layer (NC-Blue) that optionally includes blue light emitting nanocrystals.

If necessary, a light conversion pixel layer (NC-Red) including a red light emitting nanocrystal, a light conversion pixel layer (NC-Green) including a green light emitting nanocrystal, and a blue light emitting nanocrystal in the light conversion layer 6 in FIG. A preferable form of the color layer (NC-Blue) to be included is the same as that of the embodiment shown in FIG. In FIG. 7, the red color layer portion, the green color layer portion, and the blue color layer portion are shown as being in contact with each other, but in order to prevent color mixing, a light shielding layer is provided between them. A black matrix may be arranged.

When a blue LED or the like is used as the light emitting element to be used, a color material layer containing a blue color material (so-called blue color filter) between the light conversion layer 6 and the second polarizing layer 8 in FIG. Is preferably provided between them in order to prevent intrusion of unnecessary light from the outside and suppress deterioration in image quality. An example of a layer structure having such a two-layer light conversion layer 6 and a blue color filter as essential components is the structure shown in FIG.

When the embodiment shown in FIG. 7 is applied to a VA liquid crystal display element, an electrode layer 3 ′ (common electrode) is provided between the liquid crystal 5 and the second polarizing layer 8 on the opposite substrate side O-SUB, The electrode layer 3 (pixel electrode) is preferably formed on the first substrate 2. Further, in FIG. 7, when the liquid crystal display element is an FFS type or an IPS type, it is preferable that the pixel electrode and the common electrode are formed on the first substrate 2. In the VA-type, FFS-type, or IPS-type liquid crystal display element, an alignment layer 4 is formed on a surface in contact with at least one liquid crystal layer on the counter substrate side (O-SUB) and the array substrate side (A-SUB). Preferably it is.

Next, the embodiment of FIG. 8 is a mode in which the second polarizing layer 8 includes an in-cell polarizing plate provided between a pair of substrates (first substrate 2 and second substrate 7). It has a two-layer light conversion layer 6 in which a layer containing nanocrystals and a color filter are laminated. Specifically, the light conversion layer 6 includes a red (R) pixel portion (red color layer portion) of a layer (NCL) including a light emitting nanocrystal and a color material layer including a red color material. It is composed of a layer structure, and the green (R) pixel portion (green color layer portion) is composed of a two-layer structure of a layer (NC) containing a light emitting nanocrystal and a color material layer containing a green color material. The blue (R) pixel portion (blue color layer portion) has a two-layer structure of a layer (NC) containing nanocrystals for light emission and a color material layer containing a blue color material.

In this case, the light-emitting nanocrystal in the layer including the light-emitting nanocrystal NC absorbs incident light (light from the light source, preferably blue light) and emits blue light, and incident light (from the light source). Of light emission, preferably blue light) and emits green light, and green light emission nanocrystals that emit incident light (light from a light source, preferably blue light) and emit red light. It is preferable that 1 type or 2 types selected from a group are included. In the present embodiment, a black matrix may be provided for the purpose of preventing color mixing between the color layers.

Further, in the embodiment of FIG. 8, it is preferable that a blue color filter is provided on one side so as to be adjacent to the liquid crystal layer side of the light conversion layer 6 from the viewpoint that unnecessary light can be prevented from entering and image quality deterioration can be suppressed. A structure in which such a blue color filter is arranged can be shown in FIG.

When the embodiment shown in FIG. 8 or FIG. 9 is applied to a VA liquid crystal display element, an electrode layer 3 ′ (common electrode) is provided between the liquid crystal 5 and the second polarizing layer 8 in the counter substrate side O-SUB. Preferably, the electrode layer 3 (pixel electrode) is provided on the first display substrate SUB1. The alignment layer 4 is preferably formed on the surface in contact with at least one liquid crystal layer on the counter substrate side (O-SUB) and the array substrate side (A-SUB). In FIG. 8, when the liquid crystal display element is an FFS type or IPS type, it is preferable that the pixel electrode and the common electrode are formed on the first display substrate SUB1.

In the embodiment shown in FIGS. 5 to 9 described in detail above, light using a high energy light source such as short wavelength visible light or ultraviolet light is converted into light through a liquid crystal layer and a polarizing layer functioning as an optical switch. The light-emitting nanocrystal contained in the layer absorbs the light, and the absorbed light is converted into light of a specific wavelength by the light-emitting nanocrystal to emit light, thereby displaying a color.

Next, in the embodiment of FIG. 10, the light conversion layer 6 is provided on the array substrate side (A-SUB) side, and the second polarizing layer 8 is provided outside the second substrate 7, The first polarizing layer 1 is a color filter on array type liquid crystal panel including an in-cell polarizing plate provided between a pair of substrates (first substrate 2 and second substrate 7).

When the embodiment shown in FIG. 10 is applied to a VA liquid crystal display element, an electrode layer 3 ′ (common electrode) is provided between the liquid crystal 5 and the second substrate 7 on the opposite substrate side O-SUB, and The electrode layer 3 (pixel electrode) is preferably formed on the first substrate 2.

For example, the pixel electrode 3 is formed between the first substrate 2 and the light conversion layer 6, between the first polarizing layer 1 and the light conversion layer 6, or between the first polarizing layer 1 and the liquid crystal layer 5. It is preferable that

Further, it is preferable that an alignment layer 4 is formed on the surface in contact with at least one liquid crystal layer on the counter substrate side (O-SUB) and the array substrate side (A-SUB).

In addition, in FIG. 10, when the liquid crystal display element is an FFS type or an IPS type, the pixel electrode and the common electrode are arranged on the first substrate 2, for example, between the first substrate 2 and the light conversion layer 6, It is preferably formed between the one polarizing layer 1 and the light conversion layer 6 or between the first polarizing layer 1 and the liquid crystal layer 5. In addition, it is preferable that a blue color filter is provided between the light conversion layer 6 and the first substrate 2 so as to prevent unnecessary light from entering and suppress deterioration in image quality. Further, when the incident light is blue light, the color layer for displaying blue does not have to use a nanocrystal for blue light emission. In this case, a color layer containing a transparent resin or a blue color material (so-called blue color filter). ) Or the like.

In the embodiment shown in FIG. 11, the light conversion layer 6 is provided on the array substrate (A-SUB) side on the backlight unit (light source) side, and the first polarizing layer 1 and the second polarizing layer 8 are a pair. It is the form provided in the outer side between the board | substrates (the 1st board | substrate 2 and the 2nd board | substrate 7). Therefore, a support substrate 9 that supports the first polarizing layer 1 and the light conversion layer 6 is provided closer to the light source unit (backlight unit) than the first substrate 2.

When the embodiment shown in FIG. 11 is applied to a VA type liquid crystal display element, an electrode layer 3 ′ (common electrode) is provided between the liquid crystal 5 and the second substrate 7 on the opposite substrate side O-SUB, and The electrode layer 3 (pixel electrode) is preferably formed on the first substrate 2. For example, a common electrode 3 ′ is preferably formed between the first substrate 2 and the liquid crystal layer 5. The alignment layer 4 is preferably formed on the surface in contact with at least one liquid crystal layer on the counter substrate side (O-SUB) and the array substrate side (A-SUB). 11, when the liquid crystal display element is an FFS type or an IPS type, the pixel electrode and the common electrode are arranged on the first substrate 2, for example, between the first substrate 2 and the liquid crystal layer 5. It is preferable that a common electrode is formed. In addition, it is preferable to provide a blue color filter between the light conversion layer 6 and the support substrate 9 so as to prevent unnecessary light from entering and suppress deterioration in image quality. In addition, when the incident light is blue light, the color layer for displaying blue does not have to use a blue light emitting nanocrystal. In this case, a color material layer containing a transparent resin or a blue color material (so-called blue color) Filter) or the like.

As described in detail above, in the embodiments shown in FIGS. 10 to 11, light emitted from a nanocrystal for light emission contained in the light conversion layer out of light using a high-energy light source such as short-wavelength visible light or ultraviolet light is absorbed. The light that has not passed, particularly the light that has passed through the blue color layer, displays the color through a liquid crystal layer that functions as an optical switch.

Among the embodiments shown in FIGS. 5 to 11, in particular, the light conversion layer 6 shown in FIGS. 5 to 9 is placed on the substrate side O− facing the substrate A-SUB on the backlight unit (light source) side. The structure provided on the SUB side is preferable in that the effect of the present invention that the deterioration of the liquid crystal layer due to irradiation with high-energy rays can be suppressed or prevented is significantly exhibited.

Next, a light conversion layer, a color filter, a liquid crystal layer, an alignment layer, a light source part, a light source part, a polarizing layer, and a substrate, which are main components in the liquid crystal display element of the present invention, will be described in detail.

[Light conversion layer]
The light conversion layer in the liquid crystal display element of the present invention has a pixel portion that includes a light-emitting nanocrystal as an essential component, a resin component, and other molecules having an affinity for the light-emitting nanocrystal if necessary, It may contain known additives and other coloring materials. Further, as described above, it is preferable from the viewpoint of contrast that a black matrix is provided at the boundary between the color layers.

(Nanocrystals for light emission)
The light-emitting nanocrystal constituting the light conversion layer preferably refers to a particle having at least one length of 100 nm or less. The shape of the nanocrystal may have any geometric shape and may be symmetric or asymmetric. Specific examples of the shape of the nanocrystal include an elongated shape, a rod shape, a circle shape (spherical shape), an ellipse shape, a pyramid shape, a disk shape, a branch shape, a net shape, or any irregular shape. In some embodiments, the nanocrystals are preferably quantum dots or quantum rods.

The light-emitting nanocrystal preferably has a core including at least one first semiconductor material and a shell that covers the core and includes a second semiconductor material that is the same as or different from the core.

Therefore, the light-emitting nanocrystal includes at least a core including the first semiconductor material and a shell including the second semiconductor material, and the first semiconductor material and the second semiconductor material may be the same or different. Further, the core and / or the shell may contain a third semiconductor material other than the first semiconductor and / or the second semiconductor. In addition, what is necessary is just to coat | cover at least one part of a core with the core covering here.

The light-emitting nanocrystal further includes a core including at least one first semiconductor material, a first shell covering the core and including a second semiconductor material that is the same as or different from the core, and It is preferable to have a second shell that covers the first shell and includes a third semiconductor material that is the same as or different from the first shell.

Therefore, the nanocrystal for light emission according to the present invention has a form having a core containing a first semiconductor material and a shell covering the core and containing the same second semiconductor material as the core, that is, one type or two An embodiment composed of more than one kind of semiconductor material (= core-only structure (also referred to as core structure)), a core containing a first semiconductor material, and a second semiconductor material that covers the core and is different from the core Including a core / shell structure, a core including a first semiconductor material, and a first shell covering the core and including a second semiconductor material different from the core; Of the three structures of a core / shell / shell structure in a form having a second shell covering the first shell and containing a third semiconductor material different from the first shell It is preferred to have one even without.

Further, as described above, the light-emitting nanocrystal according to the present invention preferably includes three forms of a core structure, a core / shell structure, and a core / shell / shell structure. In this case, the core has two or more kinds of semiconductors. 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 layer 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 low molecules and polymers having a functional group having affinity for the nanocrystals for light emission, and the functional group having affinity is not particularly limited. And a group containing one element selected from the group consisting of oxygen, sulfur and phosphorus. Examples include organic sulfur groups, organic phosphate groups pyrrolidone groups, pyridine groups, amino groups, amide groups, isocyanate groups, carbonyl groups, and hydroxyl groups.

The semiconductor material according to the present invention is one selected from the group consisting of II-VI group semiconductors, III-V group semiconductors, I-III-VI group semiconductors, IV group semiconductors, and I-II-IV-VI group semiconductors. Or it is preferable that they are 2 or more types. Preferable 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 semiconductor materials described above.

Specifically, the semiconductor material according to the present invention includes 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 , AgGaTe ₂ , CuInS ₂ , CuInSe ₂ , CuInTe ₂ , CuGaS ₂ , CuGaSe ₂ , CuGaTe ₂ , Si, C, Ge, Cu ₂ ZnSnS ₄ Two or more may be mixed.

The luminescent nanocrystal according to the present invention preferably includes at least one nanocrystal selected from the group consisting of a red luminescent nanocrystal, a green luminescent nanocrystal, and a blue luminescent nanocrystal. In general, the emission color of a light-emitting nanocrystal depends on the particle size according to the Schrodinger wave equation of the well-type potential model, but also depends on the energy gap of the light-emitting nanocrystal. The emission color is selected by adjusting the crystal and its particle size.

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

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

The upper limit of the half-value width of the fluorescence spectrum of the luminescent nanocrystal 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 red light emitting nanocrystal according to the present invention is preferably in the order of 50 nm or less, 40 nm or less, 30 nm or less, and 20 nm or less.

The upper limit value of the peak wavelength of the nanocrystal for red light emission according to the present invention is 665 nm, and the lower limit value is 605 nm, and the compound and its particle size are selected so as to match this peak wavelength. Similarly, the upper limit value of the peak wavelength of the green light emitting nanocrystal is 560 nm, the lower limit value is 500 nm, the upper limit value of the peak wavelength of the blue light emitting nanocrystal is 420 nm, and the lower limit value is 480 nm. Select the compound and its particle size.

The liquid crystal display element according to the present invention includes at least one pixel. The color constituting the pixel is obtained by three adjacent pixels, and each pixel is red (for example, CdSe light-emitting nanocrystal, CdSe rod-shaped light-emitting nanocrystal, and rod-shaped light-emitting device having a core-shell structure) It is a nanocrystal, the shell portion is CdS, the inner core portion is CdSe, and a rod-shaped light emitting nanocrystal having a core-shell structure. The shell portion is CdS, the inner core portion is ZnSe, and the core shell. A light-emitting nanocrystal having a structure, wherein the shell portion is CdS, an inner core portion is CdSe, and a light-emitting nanocrystal having a core-shell structure is formed, and the shell portion is CdS and an inner core portion ZnSe, mixed crystal luminescent nanocrystals of CdSe and ZnS, mixed crystal rod-shaped luminescent nanocrystals of CdSe and ZnS, InP luminescent nanocrystals, I P light-emitting nanocrystals, InP rod-shaped light-emitting nanocrystals, CdSe and CdS mixed crystal light-emitting nanocrystals, CdSe and CdS mixed crystal rod-shaped light-emitting nanocrystals, ZnSe and CdS mixed Luminescent nanocrystals, ZnSe and CdS mixed crystal rod-shaped luminescent nanocrystals, etc.), green (CdSe luminescent nanocrystals, CdSe rod-shaped luminescent nanocrystals, CdSe and ZnS mixed crystals) Luminescent nanocrystals, mixed crystal rod-like luminescent nanocrystals of CdSe and ZnS, etc. and blue (ZnSe luminescent nanocrystals, ZnSe luminescent nanocrystals, ZnS luminescent nanocrystals, ZnS luminescent nanocrystals) Rod-shaped nanocrystal for light emission, light-emitting nanocrystal having a core-shell structure, the shell portion is ZnSe, the inner core portion is ZnS, and the rod-shaped light-emitting nanocrystal having a core-shell structure A use nanocrystals comprises a core portion inside of the shell portion is a ZnSe is ZnS, light emitting nanocrystals CdS, different nanocrystals that emit in the CdS rod light emitting nanocrystals). Other colors (for example, yellow) may be contained in the light conversion layer as necessary, and different colors of four or more adjacent pixels may be used.

The average particle size (primary particles) of the luminescent nanocrystal according to the present invention can be measured by TEM observation. In general, examples of the method for measuring the average particle size of nanocrystals include a light scattering method, a sedimentation type particle size measurement method using a solvent, and a method of actually observing particles with an electron microscope and measuring the average particle size. In the present invention, any number of crystals are directly observed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM), and the length of the nanocrystals for light emission is reduced by projection two-dimensional images. A method is preferred in which the particle diameters are calculated from the diameter ratio and the average is obtained. Therefore, in the present invention, the average particle diameter is calculated by applying the above method. The primary particle of the light emitting nanocrystal is a single crystal having a size of several to several tens of nanometers or a crystallite close thereto, and the size and shape of the primary particle of the light emitting nanocrystal is the primary particle. It is considered that it depends on the chemical composition, structure, manufacturing method and manufacturing conditions.

The light conversion layer in the present invention preferably contains a resin component for appropriately dispersing and stabilizing the light-emitting nanocrystals in addition to the light-emitting nanocrystals described above.

Such a resin component is preferably a polymer of a photopolymerizable compound and alkali-developable, since the light conversion layer is mainly produced by a photolithography method. Such as 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, etc. Polymer of bifunctional monomer: trimethylol propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacyl Polymers of relatively low molecular weight small polyfunctional monomers rate, etc., polyester acrylate, polyurethane acrylate, a polymer of a large multi-functional monomer of relatively low molecular weight such as polyether acrylate.

In addition, some thermoplastic resins may be used in combination with these polymers. Examples of the thermoplastic resins include urethane resins, acrylic resins, polyamide resins, polyimide resins, and styrene maleic acid resins. And styrene maleic anhydride resin.

Furthermore, in the light conversion layer according to the present invention, if necessary, in addition to the transparent resin and the luminescent nanocrystal, a polymerization initiator, a catalyst, alumina, silica, titanium oxide beads, a scattering agent such as zeolite or zirconia, Known additives may be included.

In the light conversion layer in the present invention, the upper limit of the content of the light-emitting nanocrystals with respect to the transparent resin is preferably 80 parts by mass, 70 parts by mass, 60 parts by mass, or 50 parts by mass with respect to 100 parts by mass of the transparent resin. On the other hand, the lower limit is preferably 1.0 part by weight, 3.0 parts by weight, 5.0 parts by weight, or 10.0 parts by weight with respect to 100 parts by weight of the transparent resin. In the case where a plurality of kinds of light-emitting nanocrystals are contained in the light conversion layer, the above content represents the total amount.

In the case where a plurality of kinds of light-emitting nanocrystals are contained in the light conversion layer, the above content represents the total amount.

(Color material)
The light conversion layer in the liquid crystal display element of the present invention includes three color pixel portions of red (R), green (G), and blue (B), and may include a color material as necessary as described above. As the color material, a known color material can be used. For example, a diketopyrrolopyrrole pigment and / or an anionic red organic dye is used in a red (R) pixel portion, and a green (G) pixel portion. At least one selected from the group consisting of a halogenated copper phthalocyanine pigment, a phthalocyanine green dye, and a mixture of a phthalocyanine blue dye and an azo yellow organic dye, and an ε-type copper phthalocyanine pigment in a blue (B) pixel portion And / or a cationic blue organic dye.

The preferred colorant optionally added together with the luminescent nanocrystals in the red color layer according to the present invention preferably contains a diketopyrrolopyrrole pigment and / or an anionic red organic dye. Specific examples of the diketopyrrolopyrrole pigment include C.I. I. One or more selected from Pigment Red 254, 255, 264, 272, Orange 71 and 73 are preferred, and one or more selected from Red 254, 255, 264 and 272 Is more preferred, and C.I. I. Pigment Red 254 is particularly preferable. Specific examples of the anionic red organic dye include C.I. I. One or more selected from Solvent Red 124, Acid Red 52 and 289 are preferred. I. Solvent Red 124 is particularly preferred.

In the red color layer according to the present invention, C.I. I. Pigment Red 177, 242, 166, 167, 179, C.I. I. Pigment Orange 38, 71, C.I. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. Solvent Red 89, C.I. I. Solvent Orange 56, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, 162.

Preferred colorants optionally added together with the light emitting nanocrystals in the green color layer according to the present invention are metal halide phthalocyanine pigments, phthalocyanine green dyes and mixtures of phthalocyanine blue dyes and azo yellow organic dyes. It is preferable to contain at least one selected from the group consisting of Examples of the metal halide phthalocyanine pigment include the following two groups of metal halide phthalocyanine pigments.

(First group)
It has a metal selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn and Pb as a central metal, and phthalocyanine A halogenated metal phthalocyanine pigment in which 8 to 16 halogen atoms per molecule are bonded to the benzene ring of the phthalocyanine molecule. When the central metal is trivalent, the central metal contains one halogen atom, hydroxyl group Or when a sulfonic acid group (—SO ₃ H) is bonded and the central metal is a tetravalent metal, the central metal has one oxygen atom or two halogens which may be the same or different. A halogenated metal phthalocyanine pigment to which any one of an atom, a hydroxyl group and a sulfonic acid group is bonded.

(Second group)
2 of halogenated metal phthalocyanine having a trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In as a central metal and having 8 to 16 halogen atoms bonded to the benzene ring of the phthalocyanine molecule per phthalocyanine molecule. Halogen having molecules as structural units and each central metal of these structural units bonded through a divalent atomic group selected from the group consisting of oxygen atom, sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO ₂ —) A pigment comprising a metal halide phthalocyanine dimer.

In the halogenated metal phthalocyanine pigment used in the present invention, all the halogen atoms bonded to the benzene ring may be the same or different. Different halogen atoms may be bonded to one benzene ring.

Here, the halogenated metal phthalocyanine pigment used in the present invention in which 9 to 15 bromine atoms out of 8 to 16 halogen atoms per phthalocyanine molecule are bonded to the benzene ring of the phthalocyanine molecule is yellowish. It exhibits a bright green color and is optimal for use in the green pixel portion of the color filter. The metal halide phthalocyanine pigment used in the present invention is insoluble or hardly soluble in water or an organic solvent. The halogenated metal phthalocyanine pigment used in the present invention includes both a pigment that has not been subjected to a finishing treatment described later (also referred to as a crude pigment) and a pigment that has been subjected to a finishing treatment.

The halogenated metal phthalocyanine pigments belonging to the first group and the second group can be represented by the following general formula (PIG-1).

The halogenated metal phthalocyanine pigment belonging to the first group is as follows in the general formula (PIG-1).

In the general formula (PIG-1), X ₁ to X _{16 each} represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. The four X atoms bonded to one benzene ring may be the same or different. Of X ₁ to X ₁₆ bonded to four benzene rings, 8 to 16 are chlorine, bromine or iodine atoms. M represents a central metal. In the range of Y and the number of halogenated metal phthalocyanine pigments having the same number m, a pigment having a total of less than 8 chlorine atoms, bromine atoms and iodine atoms out of ₁₆ X ₁ to X ₁₆ is blue. Similarly, among the ₁₆ X ₁ to X ₁₆ pigments, the total of chlorine atom, bromine atom and iodine atom is 8 or more, and the yellow color becomes stronger as the total value is larger. Y bonded to the central metal M is a monovalent atomic group selected from the group consisting of a halogen atom of any one of fluorine, chlorine, bromine or iodine, an oxygen atom, a hydroxyl group and a sulfonic acid group, and m is bonded to the central metal M. Represents the number of Y to be represented, and is an integer of 0-2.

The value of m is determined by the valence of the central metal M. When the central metal M is trivalent like Al, Sc, Ga, Y, and In, m = 1, and is selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl group, and sulfonic acid group. One of the groups is attached to the central metal. When the central metal M is tetravalent like Si, Ti, V, Ge, Zr, Sn, m = 2 and one of oxygen is bonded to the central metal or fluorine, chlorine, Two of the groups selected from the group consisting of bromine, iodine, hydroxyl group and sulfonic acid group are bonded to the central metal. When the central metal M is divalent like Mg, Fe, Co, Ni, Zn, Zr, Sn, and Pb, Y does not exist.

The halogenated metal phthalocyanine pigment belonging to the second group is as follows in the general formula (PIG-1).

In the general formula (PIG-1), X ₁ to X ₁₆ are as defined above, and the central metal M represents a trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In, m represents 1. Y represents the following atomic group.

In the chemical structure of the atomic group Y, the central metal M has the same definition as described above, and X ₁₇ to X ₃₂ have the same definition as X ₁ to X _{16 in} the general formula (PIG-1). is there. A represents a divalent atomic group selected from the group consisting of an oxygen atom, a sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO ₂ —). M in the general formula (PIG-1) and M in the atomic group Y are bonded via the divalent atomic group A.

That is, the halogenated metal phthalocyanine pigment belonging to the second group is a halogenated metal phthalocyanine dimer in which two molecules of metal halide phthalocyanine are structural units and these are bonded via the divalent atomic group.

Specific examples of the metal halide phthalocyanine pigment represented by the general formula (PIG-1) include the following (1) to (4).

(1) Mainly divalent metals selected from the group consisting of Mg, Fe, Co, Ni, Zn, Zr, Sn, and Pb, such as halogenated tin phthalocyanine pigment, halogenated nickel phthalocyanine pigment, and halogenated zinc phthalocyanine pigment. A halogenated metal phthalocyanine pigment which is a metal and has 8 to 16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule. Of these, chlorinated brominated zinc phthalocyanine pigments include C.I. I. Pigment Green 58, which is particularly preferable.

(2) As a central metal, a trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In, such as a halogenated chloroaluminum phthalocyanine, has one halogen atom, hydroxyl group or sulfonic acid as the central metal. A halogenated metal phthalocyanine pigment having any of the groups and having 8 to 16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule.

(3) A central metal is a tetravalent metal selected from the group consisting of Si, Ti, V, Ge, Zr and Sn, such as halogenated oxytitanium phthalocyanine and halogenated oxyvanadium phthalocyanine. 8 to 16 halogen atoms bonded to four benzene rings per one phthalocyanine molecule, having one oxygen atom or two halogen atoms which may be the same or different, a hydroxyl group or a sulfonic acid group Halogenated metal phthalocyanine pigment.

(4) Three selected from the group consisting of Al, Sc, Ga, Y and In, such as a halogenated μ-oxo-aluminum phthalocyanine dimer and a halogenated μ-thio-aluminum phthalocyanine dimer. The valence metal is the central metal, and the halogenated metal phthalocyanine is composed of two molecules of 8-16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule. Each central metal of these structural units is an oxygen atom. And a pigment comprising a metal halide phthalocyanine dimer bonded through a divalent atomic group selected from the group consisting of sulfur atom, sulfinyl and sulfonyl.

Other color materials include C.I. in the green color layer. I. Solvent Blue 67 and C.I. I. A mixture with Solvent Yellow 162, or C.I. I. Preferably, Pigment Green 7 and / or 36 are optionally contained.

In the green color layer according to the present invention, C.I. I. Pigment Yellow 150, 215, 185, 138, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, and 33.

The preferred colorant optionally added together with the light emitting nanocrystals in the blue color layer according to the present invention preferably contains an ε-type copper phthalocyanine pigment and / or a cationic blue organic dye. The ε-type copper phthalocyanine pigment is C.I. I. Pigment Blue 15: 6. Specific examples of the cationic blue organic dye include C.I. I.

Solvent Blue

2, 3, 4, 5, 6, 7, 23, 43, 72, 124, C.I. I.

Basic Blue

7 and 26 are preferred, and C.I. I. Solvent Blue 7 and Basic Blue 7 are more preferable, and C.I. I. Solvent Blue 7 is particularly preferable.

In the blue color layer according to the present invention, C.I. I. Pigment Blue 1, C.I. I. Pigment Violet 23, C.I. I. Basic Blue 7, C.I. I. Basic Violet 10, C.I. I. Acid Blue 1, 90, 83, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Direct Blue 86.

In addition, when a yellow color material is used in the light conversion layer or the color filter according to the present invention, the color material may be C.I. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. Solvent Yellow 21, 82, 83: 1, 33, or 162 is preferably at least one yellow organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, and 162.

In the light conversion layer in the present invention, the upper limit of the content of the light-emitting nanocrystals with respect to the transparent resin is preferably 80 parts by mass, 70 parts by mass, 60 parts by mass, or 50 parts by mass with respect to 100 parts by mass of the transparent resin. As for the minimum of content of the nanocrystal for light emission, 1.0 mass part, 3.0 mass part, 5.0 mass part, and 10.0 mass parts are preferable with respect to 100 mass parts of transparent resin. In the case where a plurality of kinds of light-emitting nanocrystals are contained in the light conversion layer, the above content represents the total amount.

The aforementioned light conversion layer can be formed by a method such as a photolithography method, an electrodeposition method, a transfer method, a micellar electrolysis method, a PVED (Photovoltaic Electrodeposition) method, an ink jet method, a reverse printing method, a thermosetting method, etc. Among these, the photolithography method is preferable from the viewpoint of excellent productivity.

Specifically, such a photolithographic method involves applying a photoluminescent composition containing a light-emitting nanocrystal, which will be described later, to the surface of the transparent substrate on which the black matrix is provided, heating and drying (prebaking), and then photomasking. After pattern exposure is performed by irradiating ultraviolet rays through the film, the photocurable compound at a location corresponding to the pixel portion is cured, and then the unexposed portion is developed with a developer, and the non-pixel portion is removed to remove the pixel. This is a method of fixing the part to the transparent substrate.

A photocurable composition is prepared for each of other color pixels such as a red (R) pixel, a green (G) pixel, a blue (B) pixel, and a yellow (Y) pixel as necessary. By repeating the above-described operation, a light conversion layer having colored pixel portions of red (R) pixels, green (G) pixels, blue (B) pixels, and yellow (Y) pixels at a predetermined position can be manufactured. .

In this manner, a pixel portion composed of a cured colored film of the light-emitting nanocrystal-containing photocurable composition is formed on the transparent substrate.

Here, examples of the method for applying the light-emitting nanocrystal-containing photocurable composition onto a transparent substrate such as glass include a spin coating method, a roll coating method, and an inkjet method.

The drying conditions of the coating film of the light-emitting nanocrystal-containing photocurable composition applied to the transparent substrate vary depending on the type of each component, the blending ratio, etc., but usually at 50 to 150 ° C. for about 1 to 15 minutes. is there. In addition, as light used for photocuring of the light-emitting nanocrystal-containing photocurable composition, it is preferable to use ultraviolet rays or visible light in a wavelength range of 200 to 500 nm. Various light sources that emit light in this wavelength range can be used.

Examples of the developing method include a liquid filling method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the necessary color pixel portion is formed is washed with water and dried. The color filter thus obtained is subjected to a heat treatment (post-baking) at 90 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven, thereby removing volatile components in the colored coating film and simultaneously emitting light. The unreacted photocurable compound remaining in the cured colored film of the photocurable composition containing the nanocrystals for use is thermally cured to complete the light conversion layer.

In the light conversion layer of the present invention, by using the colorant and the resin together with the light-emitting nanocrystal, the voltage holding ratio (VHR) of the liquid crystal layer is lowered, the blue light or the ultraviolet light is deteriorated, and the ion density (ID) is reduced. It is possible to prevent the increase and to remarkably improve problems of display defects such as white spots, alignment unevenness, and burn-in.

As a method for producing the light-emitting nanocrystal-containing photocurable composition described above, a light-emitting nanocrystal and an organic solvent are mixed, and if necessary, an affinity molecule, a dispersant, a colorant (= Dye and / or pigment composition), and stirring and dispersing so as to be uniform. First, a dispersion liquid for forming the pixel portion of the light conversion layer is prepared, and then the photo-curing property is prepared there. Examples include a method of adding a light emitting nanocrystal-containing photocurable composition containing a light emitting nanocrystal by adding a compound and, if necessary, a thermoplastic resin or a photopolymerization initiator.

Examples of the organic solvent used here include aromatic solvents such as toluene, xylene, methoxybenzene, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol methyl ether acetate. , Acetate solvents such as diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl Ether, diethylene glycol dimethyl ether Ether solvents such as tellurium, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline And nitrogen compound solvents such as pyridine, lactone solvents such as γ-butyrolactone, and carbamate esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate.

Dispersants used here include, for example, Big Chemie's Dispersic 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 170, Dispersic 171, Dispersic 174, Dispersic 180, Dispersic 182, Dispersic 183, Dispersic 184, Dispersic 185, Dispersic 2000, Dispersic 2001, Dispersic 2020, Dispersic 2050, Dispersic 2070, Dispersic 2096, Dispersic 2150, Dispersic LPN21116, Dispersic LPN6919 Efka EFKA 46, EFKA 47, EFKA 452, EFKA LP4008, EFKA 009, Efka LP4010, Efka LP4050, LP4055, Efka400, Efka401, Evka402, Efka403, Efka450, Efka451, Efka453, Evka4540, Efka4550, EfkaLP4560, Efka120, Efka150, Evka1501, Evka1501, 1502, Efka 1503, Lubrizol's Sol Sparse 3000, Sol Sparse 9000, Sol Sparse 13240, Sol Sparse 13650, Sol Sparse 13940, Sol Sparse 17000, 18000, Sol Sparse 20000, Sol Sparse 21000, Sol Sparse 20000, Sol Sparse 24000, Sol Sparse 26000, Sol Sparse 28000, Sol Sparse 28000, Sol Sparse 32000, Sol Sparse 3 000, Solsperce 37000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajinomoto Co., Ltd. Agents, natural rosin such as acrylic resin, urethane resin, alkyd resin, wood rosin, gum rosin, tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, modified rosin such as maleated rosin, Rosin derivatives such as rosinamine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenol A synthetic resin that is liquid and water-insoluble at room temperature can be contained. Addition of these dispersants and resins also contributes to reduction of flocculation, improvement of pigment dispersion stability, and improvement of viscosity characteristics of the dispersion.

Further, as a dispersion aid, organic pigment derivatives such as phthalimidomethyl derivatives, sulfonic acid derivatives, N- (dialkylamino) methyl derivatives, N- (dialkylaminoalkyl) sulfonic acid amide derivatives, etc. You can also. Of course, two or more of these derivatives can be used in combination.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4 ′ -Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid, and the like. Commercially available photopolymerization initiators include, for example, “Irgacure (trade name) -184”, “Irgacure (trade name) -369”, “Darocur (trade name) -1173” manufactured by BASF, “Lucirin- "TPO", Nippon Kayaku Co., Ltd. "Kayacure (trade name) DETX", "Kayacure (trade name) OA", Stofer "Bicure 10", "Bicure 55", Akzo "Trigonal PI", Sand "Sandray 1000" manufactured by Upjohn, "Deep" manufactured by Upjohn, and "Biimidazole" manufactured by Kurokin Kasei.

Also, a known and commonly used photosensitizer can be used in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles or other compounds having a nitrogen atom. These can be used alone or in combination of two or more.

The blending ratio of the photopolymerization initiator is not particularly limited, but is preferably in the range of 0.1 to 30% by mass with respect to the compound having a photopolymerizable or photocurable functional group. If it is less than 0.1% by mass, the photosensitivity at the time of photocuring tends to decrease, and if it exceeds 30%, crystals of the photopolymerization initiator are precipitated when the pigment-dispersed resist coating film is dried. May cause deterioration of physical properties of coating film.

Using each of the materials as described above, on a mass basis, 300 to 100,000 parts of an organic solvent and 1 to 500 parts of an affinity molecule or dispersant per 100 parts of the light-emitting nanocrystal of the present invention. The dye / pigment solution can be obtained by stirring and dispersing so as to be uniform. Then, per 100 parts of this pigment dispersion, a total of 0.125 to 2500 parts of thermoplastic resin and photocurable compound, 0.05 to 10 parts of photopolymerization initiator per 1 part of photocurable compound, and if necessary In addition, an organic solvent is further added, and the light-curable nanocrystal-containing photocurable composition for forming a pixel portion by stirring and dispersing so as to be uniform can be obtained.

As the developer, a known and commonly used organic solvent or alkaline aqueous solution can be used. In particular, when the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and exhibits alkali solubility, the color filter can be washed with an alkaline aqueous solution. It is effective for forming the pixel portion.

Here, although the manufacturing method of the colored pixel part of R pixel, G pixel, B pixel, and Y pixel by the photolithography method was described in detail, the pixel part prepared by using the nanocrystal-containing composition for light emission of the present invention Forming each color pixel portion by other electrodeposition method, transfer method, micellar electrolysis method, PVED (Photovoltaic Electrodeposition) method, ink jet method, reversal printing method, thermosetting method, etc. to produce a light conversion layer Also good.

[Color filter]
In the present invention, the color material layer (CF-Green, CF-Red) laminated on the light conversion pixel layer in FIG. 7, the color filter (CFL) in FIG. 8 or FIG. 9, and the blue color filter (CF-Blue) in FIG. A color filter containing a color material as shown in FIG.

As the blue, red, green, and yellow color materials that can be used here, any of the above-mentioned color materials can be used. Among them, as the blue (B) color material, an ε-type copper phthalocyanine pigment or a cationic blue organic material can be used. Dye, red (R) colorant as diketopyrrolopyrrole pigment or anionic red organic dye, green (G) colorant as halogenated copper phthalocyanine pigment, phthalocyanine green dye, or phthalocyanine blue dye and azo A mixture with a yellow organic dye is preferred. In addition, the color filter may contain the above-described transparent resin, a photocurable compound described later, a dispersant, and the like, if necessary, and the color filter can be produced by a known photolithography method or the like.

[Liquid crystal layer]
Next, as described above, the liquid crystal layer in the liquid crystal display element, for example, the liquid crystal layer 5 in each of the above embodiments, includes the polymer network (A) and 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 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.) % Liquid crystal composition (B).

(Polymer network (A))
The polymer network (A) constituting such a liquid crystal layer preferably has a uniaxial optical anisotropy, a uniaxial refractive index anisotropy, or an orientation easy axis direction. It is more preferable that the axis or the easy alignment axis is formed so that the easy alignment axis of the low-molecular liquid crystal constituting the liquid crystal composition (B) substantially coincides. The polymer network includes a polymer binder in which a polymer thin film is formed by aggregating a plurality of polymer networks. The polymer binder has refractive index anisotropy indicating uniaxial orientation, low molecular 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 liquid crystal are substantially in the same direction. The feature is that they are aligned.

Therefore, unlike a polymer dispersion type liquid crystal or polymer network type liquid crystal which is a light scattering type liquid crystal, light scattering does not occur and a high contrast display can be obtained in a liquid crystal display element using polarized light. A characteristic is that the response time of the liquid crystal element is improved by shortening the down time. Further, in the liquid crystal layer constituting the liquid crystal display element of the present invention, since the polymer network layer is formed on the entire liquid crystal display element, a thin film layer of polymer is formed on the liquid crystal element substrate to induce pretilt (Polymer). It can be distinguished from a Sustained Alignment) type 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, 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, the molecular weight is increased and the liquid crystal composition is increased. The liquid crystal layer can be formed by phase separation of the product (B) and the polymer (or copolymer).

Here, the form of separation into two phases depends on the type of the liquid crystal composition (B) to be contained and the type of the polymerizable monomer component (a) (hereinafter sometimes simply referred to as “monomer”). To do. For example, the phase of the polymerizable monomer component (a) (hereinafter abbreviated as “monomer phase”) in the liquid crystal composition (B) is generated by innumerable island-like nuclei and grows by binodal decomposition. A separated structure may be formed, or a phase separated structure may be formed in the liquid crystal composition (B) by spinodal decomposition in which phase separation is performed based on concentration fluctuations with the monomer phase. In order to form a polymer network by binodal decomposition, by using a compound with a high monomer reaction rate, a structure of nano-order is generated by generating innumerable monomer nuclei smaller than the wavelength of visible light and connecting them linearly. This is preferable because a phase separation structure is formed. As a result, when the polymerization in the monomer phase proceeds, a polymer network having a void interval shorter than the wavelength of visible light is formed depending on the phase separation structure. On the other hand, the voids in the polymer network are due to the phase separation of the liquid crystal composition (B) phase. When 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 are used. This is particularly preferable because the influence of the ring force is increased, the fall time is shortened, and a high-speed response liquid crystal display element can be obtained. The nucleation of the monomer phase in the binodal decomposition is preferably adjusted as necessary as affected by parameters such as the change in compatibility depending on the type and combination of the compounds, the reaction rate, and the temperature. In the case of UV polymerization, the UV irradiation conditions may be appropriately adjusted so as to promote the reactivity depending on the type and content of the functional group of the monomer, the polymerization initiator, the UV irradiation intensity, and at least 2 mW / An ultraviolet irradiation intensity of cm ² or more is preferable. Spinodal decomposition is preferable because a phase-separated microstructure can be obtained by fluctuations in the concentration of two phases having periodicity, and uniform gaps smaller than the visible light wavelength can be easily formed. When the monomer content is increased, there is a phase transition temperature at which the liquid crystal composition (B) high-concentration phase and the monomer high-concentration phase are separated into two phases due to the temperature. An isotropic phase is exhibited at a temperature higher than the two-phase separation transition temperature, but if it is low, separation occurs and a uniform phase separation structure cannot be obtained. When two-phase separation is performed due to a temperature change, it is preferable to form a phase separation structure at a temperature higher than the two-phase separation temperature. In any case described above, a polymer network can be formed while maintaining the same alignment state as that of the liquid crystal composition (B).

(Polymerizable liquid crystal composition)
The polymerizable liquid crystal composition described above includes a polymerizable monomer component (a), the liquid crystal composition (B), and a polymerization initiator as necessary. The use of (A) in the polymerizable liquid crystal composition in a proportion of 0.5 to 20% by mass, preferably 1 to 10% by mass, results in good phase separation of the liquid crystal composition (B) and polymer net formation. This is preferable. Therefore, in the present invention, the liquid phase layer has a polymer network (A) of 0.5 to 20% by mass, particularly 1 to 10%, based on the total mass of the polymer network (A) and the liquid crystal composition (B). It is preferable that it exists in the ratio used as the mass%.

When polymerizing a polymerizable liquid crystal composition, in the process of forming a polymer phase separation structure, two phases of a monomer high concentration phase and a liquid crystal high concentration phase are formed. Concentration tends to occur in any of the higher affinity areas.

Here, when the polymerization initiator is unevenly distributed in the monomer high concentration phase, the polymerization of the monomer is promoted, while the polymerization of the monomer remaining in the liquid crystal high concentration phase is difficult to proceed. In this case, the residual monomer in the liquid crystal high-concentration phase having a low photoinitiator concentration is cross-linked by collecting into the monomer high-concentration phase by an action such as aggregation.

On the contrary, when the polymerization initiator is unevenly distributed 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 increases. For example, a polymer phase separation structure may be formed or the monomer may be agglomerated into a high concentration phase of the monomer, and the residual monomer in the high concentration phase of the liquid crystal is preferable because the polymerization is facilitated by the effect of the photoinitiator dissolved in the liquid crystal phase. It is also preferable that the residual monomer in the high-concentration liquid crystal phase undergoes separation of the polymerization phase by the effect of the photoinitiator and forms a new polymer network.

The formed polymer network (A) exhibits optical anisotropy so as to follow the orientation of the liquid crystal composition (B). The form of the liquid crystal layer in the polymer network includes a structure in which the liquid crystal composition (B) forms a continuous layer in the three-dimensional network structure of the polymer, and a structure in which the droplets of the liquid crystal composition (B) are dispersed in the polymer. Or a structure in which both are mixed, and a structure in which a polymer network layer is present starting from both substrate surfaces and only a liquid crystal layer is provided near the center of the facing substrate. In any structure, it is preferable that a pretilt angle of 0 to 90 ° is induced with respect to the liquid crystal element substrate interface by the action of the polymer network. Among these structures, the liquid crystal composition is particularly included in the three-dimensional network structure of the polymer. A structure in which the product (B) forms a continuous layer is preferable from the viewpoint of excellent pretilt stability of liquid crystal molecules. Here, the polymer network constituting the liquid phase layer preferably has a function of aligning the coexisting liquid crystal composition (B) in the alignment direction indicated by the alignment film of the liquid crystal cell, and is further low in the polymer interface direction. It is also preferable to have a function of pretilting the molecular liquid crystal. Introducing a monomer that pre-tilts a low-molecular liquid crystal with respect to the polymer interface is useful and preferable 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 mesogenic group for the function of aligning the liquid crystal in the alignment direction. Alternatively, a pretilt may be formed by forming a polymer network by applying ultraviolet rays or the like while applying a voltage.

From such a viewpoint, the polymerizable monomer component (a) is preferably a liquid crystalline monomer. That is, the liquid crystal display element of the present invention 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, and the polymer network has an easy alignment axis and a single optical axis. It is preferable that the orientation direction of the low-molecular liquid crystal is substantially the same direction as that of the low-molecular liquid crystal, and that the polymer network is formed so as to induce the pretilt angle of the low-molecular liquid crystal because the off-response speed can be increased. The polymerizable monomer component (a) is preferably a liquid crystalline monomer having a mesogenic structure in the molecular structure. In the liquid crystal display element according to the present invention, the polymer network layer has a polymer network having an average gap interval smaller than the wavelength of visible light, that is, an average gap interval of less than 450 nm. This is preferable because it does not occur.

As such a liquid crystalline monomer, that is, a polymerizable monomer component (a) exhibiting liquid crystallinity, the following general formula (P1)

The thing represented by is mentioned.

Here, 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 with a halogen atom, or a hydrogen atom in which a hydrogen atom is substituted. An 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 with a halogen atom, and 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom The alkenyloxy group of — or —Sp ^p12 —R ^p12 . Among these, as Z ^p11 , the use of an alkyl group having 1 to 15 carbon atoms in which a fluorine atom or an oxygen atom may be substituted with a halogen atom increases the voltage holding ratio of the liquid crystal display device. From the viewpoint of enabling tilting, it is preferable to be -Sp ^p12 -R ^p12 from the viewpoint of tilt stability.

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

(Wherein, * represents a bonding point), and in the formulas (RP11-1) to (RP11-8), R ^P111 to R ^P112 are independently of each other a hydrogen atom or a carbon atom number. 1 to 5 alkyl groups, and t ^M11 represents 0, 1 or 2. It represented especially by the formula (RP11-1) Among these, and, as the R ^P111 in formula is a hydrogen atom or a methyl group, a (meth) acryloyl group, at the time of manufacturing the liquid crystal display device It is possible to reduce the amount of UV irradiation when polymerizing the monomer, the amount of UV irradiation to the liquid crystal material can be kept to the minimum necessary, and the deterioration of the liquid crystal material and the liquid crystal display element can be avoided. preferable.

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

In view of excellent reactivity, those represented by the formula (RP11-1) are particularly preferred.

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. A structural moiety having a chemical structure substituted with an oxygen atom or a carbonyl group. Among these, in particular, a linear or branched alkylene group having 1 to 12 carbon atoms is preferable because it increases compatibility with the liquid crystal material (B), and has the same number of carbon atoms as the alkyl group of the liquid crystal molecule. 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 the compatibility of the polymerization initiator (C) with the liquid crystal material (B) is not sufficient. In the present invention, since the density of the polymer network is increased and the density is increased, the device characteristics are affected and the in-plane characteristics are likely to be uneven. 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). A separation structure is formed, and a uniform polymer network in the liquid crystal is formed, so that the characteristics of the liquid crystal display element are 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 to produce the monomer that they are the same, It is preferable from the viewpoint that the physical properties can be easily adjusted by adjusting the use ratio of a plurality of kinds of compounds having different alkylene chain lengths. On the other hand, when Sp ^p11 and Sp ^p12 are single bonds, the monomer tends to collect 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 the polymer network. The effect of imparting a pretilt to the alignment film and fixing it is stronger than the effect of the high-speed response due to.

Further, when the content of the polymerizable monomer component (a) in the polymerizable liquid crystal composition is less than 0.5% by mass, from the point of imparting a pretilt angle to the alignment film and fixing it, Sp ^p11 and Sp ^p12 are preferably single bonds. On the other hand, 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 preferred from the viewpoint of forming a polymer network that increases the off-response speed. In particular, it is preferably in the range of 1% by mass to 10% by mass from the viewpoint of off-response speed and low driving voltage. In addition, the linear or branched alkylene group described above preferably has 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms. Further, it is preferable to substitute a carbon atom on the alkylene group with an oxygen atom or a carbonyl group under the condition that the oxygen atom is not adjacent. In particular, it is preferable to introduce an oxygen atom at a position where it binds to M ^P11 or M ^P13 from the viewpoint that the liquid crystal material as a whole can increase the upper limit temperature of the liquid crystal and increase the ultraviolet sensitivity during polymerization.

Next, in the general formula (P1), 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 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═N— or —C═N— ^N═C— (wherein R ^P113 represents Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein tm12 represents an integer of 1 to 4).

Among these, the polymerizable monomer component (a) has high liquid crystallinity, and from the viewpoint of suppressing alignment unevenness in the liquid crystal display element, 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 preferred.

In addition, since the photo-alignment function by light using the Weigert effect can be used by imparting a photoisomerization function to the monomer, —CH═CH—, —CF═CF—, —CF═CH—, —CH═ CF— or —N═N— is preferred, and —CH═CH— and —N═N— are preferably selected, and in particular, —N═N— is preferred. Further, from the viewpoint of increasing 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, anthrace 1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, or the number of carbon atoms in the aromatic nucleus 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, a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, or a nitro group And a structure substituted with.

Further, M ^p11 , M ^p12 and M ^p13 are preferably those in which —Sp ^p11 —R ^p11 is substituted on the aromatic nucleus of these structures from the viewpoint of becoming a radically polymerizable monomer having excellent reactivity. In this case, R ^p11 is preferably the formula (RP11-1), and R ^P111 is preferably a hydrogen atom or a (meth) acryloyl group which is a methyl group.

Among these, in particular, 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-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, 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, 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 preferred from the viewpoint of compatibility with liquid crystals.

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 3 is represented. Here, may be those in the case where Z ^{pi 1} there are a plurality have the same or different and when R ^{pi 1} there exist a plurality they may be the same or different and is R ^p12 When a plurality of Sp ^p11 are present, they may be the same or different. When there are a plurality of Sp ^p11 , they may be the same or different. 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. When there are a plurality of L ^p12 , they are the same. They may be the same or different when a plurality of M ^p12 are present, and they may be the same or different when a plurality of M ^p13 are present. so It is preferably a compound that is. Moreover, it is preferable to contain the said material 1 type (s) or 2 or more types.

Further, the total of m ^p12 to m ^p14 described above is preferably in the range of 1 to 6, particularly preferably in the range of 2 to 4, particularly 2. When two or more types of monomers are used, the average number calculated by multiplying the concentration of the monomers in the whole monomer and the sum of m ^p12 to m ^p14 is set to 1.6 to 2.8. It is preferably 1.7 to 2.4, more preferably 1.8 to 2.2.

The total of m ^p11 and m ^p15 is preferably 1 to 6, more preferably 2 to 4, and particularly preferably 2. When using two or more monomers, the average number calculated by multiplying the density and m ^p1 and ^p15 sum of the monomers in the total monomer, may be set to be 1.6 to 2.8 It is preferably 1.7 to 2.4, more preferably 1.8 to 2.2. When the average number is close to 1, the driving 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 with fluorine atoms for M ^p11 , M ^p12 and M ^p13 can control the magnitude 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 element. Therefore, it is preferable. The preferred number of substitution is 1 to 4.

Among the formulas (P1) detailed above, the use of compounds represented by the following formulas (P2-1) to (P2-11) is effective in suppressing the change in tilt angle with time.

(Wherein R ^P21 and R ^P22 each independently represents a hydrogen atom or a methyl group)
Although such a compound is useful, the solubility in a liquid crystal material may not be good. Accordingly, such a compound is preferably contained in an amount of 90% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less in the whole monomer to be used.

Further, among the formulas (P1), the use of compounds represented by the following formulas (P3-1) to (P3-11) can suppress the change in tilt angle with time and ensure solubility in liquid crystal materials. It is preferable because both can be achieved.

(In the formula, R ^P31 and R ^P32 each independently represent a hydrogen atom or a methyl group, mP31 represents an integer of 0 or 1, and when mP31 is 0, mP32 represents an integer of 1 to 6; In the case of 1, mP32 represents an integer of 2 to 6)

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

(In the formula, 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 1-6. When mp42 is 1, mP41 represents an integer of 2 to 6, when mP43 is 0, mP44 represents an integer of 1 to 6, and when mP43 is 1, mp44 represents an integer of 2 to 6. To express)
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 formulas (P1), the compounds represented by the formulas (P5-1) to (P5-11) having an aryl ester structure in the mesogen have the ability to initiate polymerization by ultraviolet irradiation. This is preferable because the amount can be reduced.

(In the formula, 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 1-6. 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 represents an integer of 2 to 6. To express)
If the amount of such a compound added is large, the voltage holding ratio of the liquid crystal display element tends to deteriorate. Therefore, it is preferably contained in an amount of 30% by mass or less and more preferably 20% by mass or less in the whole monomer used. It is preferably 10% by mass or less.

It is also preferable to introduce a cinnamic ester group into a mesogen such as the compounds represented by formulas (P6-1) to (P6-11) among formula (P1).

(In the formula, 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 1-6. When mp62 is 1, mP61 represents an integer from 2 to 6, when mP63 is 0, mP64 represents an integer from 1 to 6, and when mP63 is 1, mp64 represents an integer from 2 to 6. To express)

Further, among the compounds of formula (P1), compounds having a condensed ring represented by the following formulas (P7-1) to (P7-5) can shift the ultraviolet absorption region from the monocyclic compound to the visible light side. This is preferable from the viewpoint of adjusting the sensitivity of the monomer.

(In the formula, 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 1-6. 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. To express.)
In the above, a bifunctional monomer is exemplified as a preferred compound, but among the formula (P1), the use of a trifunctional monomer such as the compounds represented by the formulas (P5-1) to (P5-11) is also preferred. The mechanical strength of the polymer or copolymer can be improved. Moreover, what has an ester bond in a mesogen has the capability to start superposition | polymerization by ultraviolet irradiation, Therefore Since the addition amount of a polymerization initiator can be reduced, it is more preferable.

(In the formula, 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 1-6. 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 is an integer of 2 to 6 Represents.)

In addition, among the formula (P1), it is also preferable to use a monofunctional monomer such as a compound represented by the following formulas (P9-1) to (P9-11) for the purpose of adjusting the driving voltage of the liquid crystal display element.

(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, in the formula (P1), it is preferable to provide a function of photoisomerization as a monomer because a light alignment function by light using the Weigert effect can be used. From such a viewpoint, the compounds represented by (P10-1) to (P10-11) are preferable.

(In the formula, 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 1-6. When mp102 is 1, mP101 represents an integer from 2 to 6, when mP103 is 0, mP104 represents an integer from 1 to 6, and when mP103 is 1, mp104 represents an integer from 2 to 6 To express)

The polymerizable monomer component (a) detailed above is a compound represented by the various specific examples described above, 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), U represents a linear or branched group having 2 to 20 carbon atoms 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 with an oxygen atom within a range in which the oxygen atoms are not adjacent to each other. , An alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom within the range in which the oxygen atom is not adjacent) or a cyclic substituent, and k is 1 Represents an integer of up to 5. All 1,4-phenylene 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, Sp ³ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _t — (wherein t is 2 to Represents an integer of 11 and an oxygen atom is bonded to an aromatic ring), and V is a linear or branched alkylene group having 2 to 20 carbon atoms or a polyvalent having 5 to 30 carbon atoms. A cyclic substituent, a structural site in which an oxygen atom in a linear or branched alkylene structure having 2 to 20 carbon atoms is not adjacent to each other, and these chemical structures are the carbons constituting the structure. A 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 a range not adjacent to the oxygen atom) or a cyclic substituent; W may be 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 expressed as

Here, when Sp ¹ and Sp ² in the general formula (V) are the same, when these are, for example, a linear or branched alkylene group having 1 to 12 carbon atoms, It is preferable because it is easy to synthesize and the physical properties can be easily adjusted by adjusting the proportions of a plurality of compounds having different alkylene chain lengths.

As described above, the polymerizable monomer component (A) detailed 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 preferably used in proportion, but at any concentration within the range, it is preferable to contain at least two kinds of polymerizable monomer components (A) having different Tg and adjust 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 that increases the crosslinking density, and has two or more functional groups. Is preferred. The precursor of the polymer having a low Tg preferably has a structure in which the number of functional groups is 1 or 2 or more, and an alkylene group or the like is provided as a spacer between the functional groups to increase the molecular length. When adjusting the Tg of the polymer network for the purpose of improving the thermal stability and impact resistance of the polymer network, it is preferable to appropriately adjust the ratio of the polyfunctional monomer to the monofunctional monomer. Tg is also related to thermal mobility at the molecular level in the main chain and side chain of the polymer network, and has an influence on electro-optical properties. For example, when the crosslink density is increased, the molecular mobility of the main chain is lowered, the anchoring force with the low molecular liquid crystal is increased, the drive voltage is increased, and the fall time is shortened. On the other hand, when the crosslinking density is lowered so that Tg is lowered, the thermal mobility of the polymer main chain is increased, so that the anchoring force with the low-molecular liquid crystal is lowered, the driving voltage is lowered, and the fall time is increased. 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, and is monovalent or divalent, and an acrylate of an alcohol compound having 8 to 18 carbon atoms. Alternatively, the anchoring force at the polymer interface can be lowered by using methacrylate as the polymerizable monomer component (a). Further, such a polymerizable monomer component (A) is effective in inducing a pretilt angle at the substrate interface and acts in the direction of lowering the polar anchoring force.

(Liquid crystal composition (B))
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 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.) % Content.

Thereby, the retardation of the liquid crystal layer can be adjusted. Moreover, since the liquid crystal layer containing a compound having high reliability with respect to light resistance can be constituted by the above compound, deterioration due to light from the light source, in particular, blue light (from the blue LED) can be suppressed / prevented.

In the liquid crystal layer or the polymerizable liquid crystal composition of the present invention, the lower limit of the preferable content of the compound represented by the general formula (i) is based on the total amount of the liquid crystal layer of the present invention or the polymerizable liquid crystal composition. 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 15% by mass, 20% by mass, It is 25% by mass, 30% by mass, 35% by mass, 40% by mass, 45% by mass, 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 layer of the present invention or the polymerizable liquid crystal composition. 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, and 35% by mass %, 30% by mass, and 25% by mass.

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 compound represented by the general formula (i-1) is the following compound.

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

The compound represented by the general formula (i-1) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit 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, and 45% by mass. Yes, 50% by mass, 55% by mass. The upper limit of the preferable content is 95% by mass, 90% by mass, 85% by mass, 80% by mass, and 75% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 70% by weight, 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, 40% by weight, and 35% by weight. Yes, 30% by mass and 25% by mass.

When the composition of the liquid crystal composition (B) used in the present invention needs to maintain a low viscosity and has a fast response speed, it is preferable that the above lower limit value is high and the upper limit value 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 driving voltage low, it is preferable that the lower limit value is low and the upper limit value is low.

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

( ^Wherein R ⁱ¹² represents the same meaning as in general formula (i-1).)
The compound represented by the general formula (i-1-1) is a compound selected from the group of compounds represented by the formula (i-1-1.1) to the formula (i-1-1.3). And is preferably a compound represented by formula (i-1-1.2) or formula (i-1-1.3), and particularly 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) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, Yes, 3% by mass, 5% by mass, 7% by mass, and 10% by mass. The upper limit of the preferable content is 20% by mass, 15% by mass, 13% by mass, 10% by mass, and 8% 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), and the light having a wavelength of 200 to 400 nm in the ultraviolet region as a backlight. Even when it is irradiated, it is preferable in that it has excellent durability and can express a voltage holding ratio.

( ^Wherein R ⁱ¹² represents the same meaning as in general formula (i-1).)
The lower limit of the preferable content of the compound represented by the formula (i-1-2) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 5% by mass, 10% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, and 35% by mass %. The upper limit of the preferable content is 60% by mass, 55% by mass, 50% by mass, 45% by mass, and 42% 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, 33% by mass, 30% by mass, 20% by mass, 15% by mass, 10% by mass is there. Among these, from the viewpoint of preventing deterioration of the liquid crystal layer with respect to blue visible light, the upper limit of the content is preferably 15% by mass, particularly 10% by mass.

Further, the compound represented by the general formula (i-1-2) is a compound selected from the group of compounds represented by the formula (i-1-2.1) to the formula (i-1-2.4). Preferably, it is a compound represented by the formula (i-1-2.2) to the formula (i-1-2.4). In particular, the compound represented by the formula (i-1-2.2) is preferable because the response speed of the liquid crystal composition (B) used in the present invention is particularly improved. Further, when obtaining a T _NI higher 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). The content of the compounds represented by the formulas (i-1-2.3) and (i-1-2.4) is preferably not more than 30% by mass in order to improve the solubility at low temperatures. .

The lower limit of the preferable content of 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 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, 38% by mass and 40% by mass. The upper limit of the preferable content is 60% by mass, 55% by mass, 50% by mass, 45% by mass, and 43% 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, 22% by mass is there.

The total amount of the compound represented by formula (i-1-1.3) and the compound represented by 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 of the preferred content is 10% by mass, 15% by mass, 20% by mass, 25% by mass, 27% by mass, 30% by mass, and 35% by mass, 40% by mass. The upper limit of the preferable content is 60% by mass, 55% by mass, 50% by mass, 45% by mass, and 43% 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, 22% by mass is there.

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

(In the formula, 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 a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

The lower limit of the preferable content of the compound represented by the formula (i-1-3) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass, and 30% by mass. The upper limit of the preferable content is 60% by mass, 55% by mass, 50% by mass, 45% by mass, and 40% by mass with respect to the total amount of the liquid crystal composition (B) used in the present invention. %, 37% by weight, 35% by weight, 33% by weight, 30% by weight, 27% by weight, 25% by weight, 23% by weight, 20% by weight Yes, 17% by mass, 15% by mass, 13% by mass, and 10% by mass.
Further, the compound represented by the general formula (i-1-3) is a compound selected from the group of compounds represented by the formula (i-1-3.1) to the formula (i-1-3.12). Preferably, it is a compound represented by formula (i-1-3.1), formula (i-1-3.3) or formula (i-1-3.4). In particular, the compound represented by the formula (i-1-3.1) is preferable because the response speed of the liquid crystal composition (B) used in the present invention is particularly improved. Further, when obtaining T _NI higher than the response speed, the equation (i-1-3.3), the equation (i-1-3.4), the equation (L-1-3.11), and the equation (i It is preferable to use a compound represented by (1-3.12). Sum of compounds represented by formula (i-1-3.3), formula (i-1-3.4), formula (i-1-3.11) and formula (i-1-3.12) The content of is not preferably 20% by mass or more in order to improve the solubility at low temperatures.

The lower limit of the preferable content of the compound represented by the formula (i-1-3.1) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% 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, 13% by mass, and 10% 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 the general formula (i-1) is preferably a compound selected from the group of compounds represented by the general formula (i-1-4) and / or (i-1-5).

(In the formula, R ⁱ¹⁵ and R ⁱ¹⁶ each independently represents 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 a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

The lower limit of the preferable content of the compound represented by the formula (i-1-4) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 5% by mass, It is 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferable content is 25% by mass, 23% by mass, 20% by mass, 17% by mass, and 15% 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) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 5% by mass, It is 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferable content is 25% by mass, 23% by mass, 20% by mass, 17% by mass, and 15% 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 the general formulas (i-1-4) and (i-1-5) are represented by the formulas (i-1-4.1) to (i-1-5.3). Are preferably selected from the group of compounds represented by formula (i-1-4.2) or (i-1-5.2).

The lower limit of the preferable content of the compound represented by the formula (i-1-4.2) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% 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, 13% by mass, and 10% 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- 3.4), it is preferable to combine two or more compounds selected from the compounds represented by formula (i-1-3.11) and formula (i-1-3.12). -1.3), formula (i-1-2.2), formula (i-1-3.1), formula (i-1-3.3), formula (i-1-3.4) and It is preferable to combine two or more compounds selected from the compounds represented by 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% by weight, 37% by weight, 35% by weight, 33% by weight, 30% by weight, 28% by weight, 25% by weight, 23% by weight, 20% by weight %. When emphasizing the reliability of the composition, compounds represented by formula (i-1-3.1), formula (i-1-3.3) and formula (i-1-3.4)) It is preferable to combine two or more compounds selected from the group consisting of formulas (i-1-1.3) and (i-1-2.2) when the response speed of the composition is important. It is preferable to combine two or more compounds selected from the following compounds.
The compound represented by the general formula (i-1) is preferably a compound selected from the group of compounds represented by the general formula (i-1-6).

(In the formula, R ⁱ¹⁷ and R ⁱ¹⁸ each independently represent a methyl group or a hydrogen atom.)
The lower limit of the preferable content of the compound represented by the formula (i-1-6) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 5% by mass, 10% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, and 35% by mass %. The upper limit of the preferable content is 60% by mass, 55% by mass, 50% by mass, 45% by mass, and 42% 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, 33% by mass, and 30% by mass.

Further, the compound represented by the general formula (i-1-6) is a compound selected from the compound group represented by the formula (i-1-6.1) to the formula (i-1-6.3). Preferably there is.

The compound represented by the general formula (i-2) is the following compound.

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

The compound represented by the general formula (i-2) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

When emphasizing solubility at low temperatures, it is highly effective to set a large amount of content. Conversely, when emphasizing response speed, setting a small amount of content is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

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

Further, the compound represented by the general formula (i-2) is preferably a compound selected from the group of compounds represented by the formulas (i-2.1) to (i-2.6) A compound represented by formula (L-2.1), formula (i-2.3), formula (i-2.4) and formula (i-2.6) is preferred.

(N-type compound)
The liquid crystal composition (B) used in the present invention further contains one or more compounds selected from compounds represented by formulas (N-1), (N-2) and (N-3). It is preferable. These compounds correspond to dielectrically negative compounds (the sign of Δε is negative and the absolute value is greater 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 ^N42 each independently represents 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 A 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 each independently represents (a) a 1,4-cyclohexylene group (one —CH present in this group) ₂ or two or more non-adjacent —CH ₂ — may be replaced by —O—) and (b) a 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═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
(D) represents a group selected from the group consisting of 1,4-cyclohexenylene groups, and the group (a), the group (b), the group (c) and the group (d) are each a hydrogen atom in the structure Each independently may be 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 -C≡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 —, and Y ^N41 represents a single bond, or —CH ₂ — and 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 ^N11 + n ^N12 N ^N21 + n ^N22 and n ^N31 + n ^N32 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 the same or different. at ^best, the 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 the general formulas (N-1), (N-2), (N-3) and (N-4) are preferably compounds whose Δε is negative and whose 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 represent 1 to 8 carbon atoms. An alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, preferably 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, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 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 more preferable, and an alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable.

Further, 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 An alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which the alkenyl group 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 A straight-chain alkoxy group having 1 to 4 carbon atoms and a straight-chain alkenyl group having 2 to 5 carbon atoms are preferred. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from groups represented by any of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31, and A ^N32 are preferably aromatic when it is required to increase Δn independently, and in order to improve the response speed, fat Preferably a 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-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group 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.

^XN21 is preferably a fluorine atom.

T ^N31 is preferably an oxygen atom.

n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are preferably 1 or 2, a combination in which n ^N11 is 1 and n ^N12 is 0, a combination in which n ^N11 is 2 and n ^N12 is 0, n ^A combination in which ^N11 is 1 and n ^N12 is 1, a combination in which n ^N11 is 2 and n ^N12 is 1, a combination in which n ^N21 is 1 and n ^N22 is 0, n ^N21 is 2 and n ^N22 is n A combination in which n ^N31 is 1 and n ^N32 is 0, and a combination in which n ^N31 is 2 and n ^N32 is 0 are preferable.

The lower limit of the preferable content of the compound represented by the formula (N-1) 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. %, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, and 75% by mass. Yes, 80% by mass. The upper limit 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, 25% by mass and 20% by mass.

The lower limit of the preferable content of the compound represented by the formula (N-2) 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. %, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, and 75% by mass. Yes, 80% by mass. The upper limit 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, 25% by mass and 20% by mass.

The lower limit of the preferable content of the compound represented by the formula (N-3) 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. %, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, and 75% by mass. Yes, 80% by mass. The upper limit 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, 25% by mass and 20% by mass.

When the viscosity of the liquid crystal composition (B) used in the present invention is kept low and a composition having a high response speed is required, the above lower limit value is preferably low and the upper limit value is preferably 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 is increased and the upper limit value is high.

In the liquid crystal composition according to the present invention, among the compounds represented by the general formulas (N-1) to (N-4), the compound represented by the general formula (N-1) is particularly a voltage in a liquid crystal display device. This is preferable from the viewpoint of excellent retention and low rotational viscosity.

(P-type compound)
It is preferable that the liquid crystal composition (B) used in the present invention further contains one or more compounds represented by the 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—, — Optionally 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) a 1,4-phenylene group (one —CH═ present in the 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 , 3,4-tetrahydronaphthalene-2,6-diyl group, one —CH═ or two or more non-adjacent —CH═ may be replaced by —N═.
The group (a), the group (b) and the group (c) are each independently selected from the group consisting of cyano group, fluorine atom, chlorine atom, methyl group, trifluoromethyl group or trifluoro May be substituted with a methoxy group,
Z ^J1 and Z ^J2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents —COO—, —OCO— or —C≡C—,
When n ^J1 is 2, 3 or 4 and a plurality of A ^J2 are present, 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 the same 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 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 alkenyloxy having 2 to 8 carbon atoms. A 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 having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms. (Propenyl group) is particularly preferred.

R ^J1 is preferably an alkyl group when emphasizing reliability, and is preferably an alkenyl group when emphasizing a decrease in viscosity.

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

A ^J1 , A ^J2 and A ^J3 are preferably aromatic when it is required to independently increase Δn, and are preferably aliphatic to improve the response speed. 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 -2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, preferably 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 independently preferably represent —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond, OCH ₂ —, —CF ₂ O—, —CH ₂ CH ₂ — or a single bond is more preferred, and —OCH ₂ —, —CF ₂ O— or a single bond is particularly preferred.

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

n ^J1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when emphasizing the improvement of Δε, and 1 or 2 when emphasizing _TNI. preferable.

There are no particular restrictions on the types of compounds that can be combined, but they are used in combination according to desired properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. For example, in one embodiment of the present invention, there are one kind, two kinds, and three kinds of compounds to be used. 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 suitability, It is necessary to adjust appropriately according to required performance such as dripping marks, image sticking, and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the general formula (J) 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. 30% by mass 40% by mass 50% by mass 55% by mass 60% by mass 65% by mass 70% by mass 75% by mass 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 with respect to the total amount of the liquid crystal composition (B) used in the present invention. 65% by mass, 55% by mass, 45% by mass, 35% by mass, and 25% by mass.

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

As the compound represented by the general formula (J), a compound represented by the general formula (M) and a compound represented by the 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—, — Optionally substituted by C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^M1 represents 0, 1, 2, 3 or 4;
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) a 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═).
A hydrogen atom on the group (a) and the group (b) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^M1 and Z ^M2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents —COO—, —OCO— or —C≡C—,
When n ^M1 is 2, 3 or 4 and a plurality of A ^M2 are present, 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 the same 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—, — Optionally 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) a 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═).
A hydrogen atom on the group (a) and the group (b) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^K1 and Z ^K2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents —COO—, —OCO— or —C≡C—,
When n ^K1 is 2, 3 or 4 and a plurality of A ^K2 are present, 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 the same 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 the general formula (M), R ^M1 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. A 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 having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms. (Propenyl group) is particularly preferred.

R ^M1 is preferably an alkyl group when emphasizing reliability, and is preferably an alkenyl group when emphasizing a decrease in viscosity.

A ^M1 and A ^M2 are preferably aromatic when it is required to independently increase Δn, and are preferably aliphatic for improving the response speed, 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 preferably represents a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents 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, and —CF ₂ O— or a single bond is particularly preferable.

n ^M1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when emphasizing the improvement of Δε, and 1 or 2 when emphasizing T _NI preferable.

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

The lower limit of the preferable content of the compound represented by the formula (M) 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 weight, 40% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 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 with respect to the total amount of the liquid crystal composition (B) used in the present invention. 65% by mass, 55% by mass, 45% by mass, 35% by mass, and 25% by mass.

(Np compound)
The liquid crystal composition of the present invention preferably further contains one or more compounds represented by the general formula (L). The compound represented by the general formula (L) corresponds to a dielectrically neutral compound (Δε value is −2 to 2).

(Wherein R ^L1 and R ^L2 each independently 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 Optionally 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 each independently represent (a) a 1,4-cyclohexylene group (one —CH ₂ — present in the group or two or more —CH ₂ — not adjacent to each other). May be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or two or more —CH═ not adjacent to each other —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═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
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 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 = NN-CH-, -CH = CH-, -CF = CF- or -C≡C-
When n ^L1 is 2 or 3, and a plurality of A ^L2 are present, they may be the same or different, and when n ^L1 is 2 or 3, and a plurality of Z ^L2 are present, May be the same or different, but excludes compounds represented by general formulas (N-1), (N-2), (N-3), (J) and (i). )
Although the compound represented by general formula (L) may be used independently, it can also be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to desired properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention. Alternatively, in another embodiment of the present invention, there are two types, three types, four types, five types, six types, seven types, eight types, nine types, 10 types, More than types.

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

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 weight, 40% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by mass. The upper limit 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, 25% by mass.

When the composition of the liquid crystal composition (B) used in the present invention needs to maintain a low viscosity and has a fast response speed, it is preferable that the above lower limit value is high and the upper limit value 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. Further, 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 is lowered and the upper limit value is low.

When importance is attached to reliability, R ^L1 and R ^L2 are preferably both alkyl groups, and when importance is placed on reducing the volatility of the compound, it is preferably an alkoxy group, and importance is placed on viscosity reduction. In this case, at least one is preferably an alkenyl group.

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

R ^L1 and R ^L2 are each a linear alkyl group having 1 to 5 carbon atoms or a linear alkyl group having 1 to 4 carbon atoms when the ring structure to which R ^L1 is bonded is a phenyl group (aromatic). When the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a straight-chain C 1-5 carbon atom is preferred. Alkyl groups, linear alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferred. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

n ^L1 is preferably 0 when importance is attached to the response speed, 2 or 3 is preferred for improving the upper limit temperature of the nematic phase, and 1 is preferred for balancing these. In order to satisfy the properties required for the composition, it is preferable to combine compounds having different values.

A ^L1 , A ^L2, and A ^L3 are preferably aromatic when it is required to increase Δn, and are preferably aliphatic for improving the response speed, and are each 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] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 -It preferably represents a diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents the following structure:

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

Z ^L1 and Z ^L2 are preferably single bonds when the response speed is important.

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

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

The compound represented by the general formula (L-3) is the following compound.

(In the formula, R ^L31 and R ^L32 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L).)
R ^L31 and R ^L32 are each independently preferably 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.

The compound represented by the general formula (L-3) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (L-3) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, 3% by mass %, 5% by mass, 7% by mass, and 10% by mass. The upper limit of the preferable content is 20% by mass, 15% by mass, 13% by mass, 10% by mass, and 8% 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 a high birefringence is obtained, the effect is high when the content is set to be large. On the other hand, when the high _TNI is emphasized, the effect is high when the content is set low. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The compound represented by the general formula (L-4) is the following compound.

(In the formula, 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 having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L42 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable. )
The compound represented by the general formula (L-4) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

In the liquid crystal composition (B) used in the present invention, the content of the compound represented by the general formula (L-4) is low temperature solubility, transition temperature, electrical reliability, birefringence, process suitability. It is necessary to adjust appropriately according to required properties such as property, dripping marks, image sticking, and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, 3% by mass %, 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. Yes, 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) with respect 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 compound represented by the general formula (L-5) is the following compound.

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

The compound represented by the general formula (L-5) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

In the liquid crystal composition (B) used in the present invention, the content of the compound represented by the general formula (L-5) is low temperature solubility, transition temperature, electrical reliability, birefringence, process suitability. It is necessary to adjust appropriately according to required properties such as property, dripping marks, image sticking, and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, 3% by mass %, 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. Yes, 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) with respect 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 compound represented by the general formula (L-6) is the following compound.

(In the formula, R ^L61 and R ^L62 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L), and X ^L61 and X ^L62 each independently represent a hydrogen atom or a fluorine atom. )
R ^L61 and R ^L62 are each independently preferably 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.

The compound represented by the general formula (L-6) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the liquid crystal composition (B) used in the present invention is 1% by mass, 2% by mass, 3% by mass %, 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. Yes, 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) with respect 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. When emphasizing to increase Δn, it is preferable to increase the content, and when emphasizing the precipitation at low temperature, it is preferable to decrease the content.

The compound represented by the general formula (L-7) is the following compound.

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

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

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 suitability It is necessary to adjust appropriately according to required properties such as property, dripping marks, image sticking, and dielectric anisotropy.

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

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

The compound represented by the general formula (L-8) is the following compound.

(In the formula, R ^L81 and R ^L82 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L), and A ^L81 represents the same meaning or single bond as A ^L1 in General Formula (L)). However, each hydrogen atom on A ^L81 may be independently substituted with 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 of 2 to 5 carbon atoms ^{preferably, A L81} is 1, A 4-cyclohexylene group or a 1,4-phenylene group is preferable, and the hydrogen atoms on A ^L71 and A ^L72 may be each independently substituted with a fluorine atom, and the same in general formula (L-8) The number of fluorine atoms in the ring structure is preferably 0 or 1, and the number of fluorine atoms in the molecule is preferably 0 or 1.

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 suitability It is necessary to adjust appropriately according to required properties such as property, dripping marks, image sticking, and dielectric anisotropy.

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

When an embodiment of _TNI having a high liquid crystal composition (B) used in the present invention is desired, the content of the compound represented by formula (L-8) is preferably increased, and an embodiment having a low viscosity 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 in the present invention. The lower limit of the preferable total content 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 of 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 formula (N-1), (N-2), (N-3) or (J) is 0. It is preferable that it is mass%.

General formula (i), general formulas (L-1) to (L-7), 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 total content of the compounds represented by the general formulas (N-1) to (N-4) is 80% by mass, 85% by mass, 88% by mass, 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 of 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 in the molecule.

In the liquid crystal composition (B) used in the present invention, when emphasizing 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. Preferably, the content is 3% by mass or less, more preferably 1% by mass or less, and most preferably not substantially contained.

In the liquid crystal composition (B) used in the present invention, when importance is attached to the stability by UV irradiation, the content of the compound substituted with 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, and substantially does not contain. Is more preferable.

In the liquid crystal composition (B) used in the present invention, it is preferable to increase the content of a compound whose ring structure in the molecule is a 6-membered ring, and the inclusion of a compound whose ring structure in the molecule is a 6-membered ring. The amount is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and substantially the ring in the molecule. Most preferably, the composition is composed of only compounds having a 6-membered ring 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 a compound having a cyclohexenylene group as a ring structure, and to have a cyclohexenylene group. The content of the compound is preferably 10% by mass or less with respect to the total mass of the composition, preferably 8% by mass or less, more preferably 5% by mass or less, and 3% by mass or less. Preferably, it is more 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 with a halogen is substituted. The content of the compound having in the molecule is preferably reduced, 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, further preferably 3% by mass or less, and still more preferably substantially not contained.

“Substantially not contained” in the present application means that it is not contained except for an unintentionally contained product.

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 alkenyl group has 2 to 5 carbon atoms. 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.

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

Here, radical polymerization, anionic polymerization, cationic polymerization, and the like can be used as the polymerization method. Polymerization is preferably performed by radical polymerization, and radical polymerization by photo-Fries rearrangement, radical polymerization by a photopolymerization initiator is used. More preferred.

As the radical polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used, but a photopolymerization initiator is preferable. Specifically, the following compounds are preferable.

Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- ( 2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- Acetophenone series such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4′-phenoxyacetophenone, 4′-ethoxyacetophenone;
Benzoins such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, benzoin ethyl ether;
Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;
Benzyl, methylphenylglyoxyesters;
Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4' -Benzophenone series such as tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone;
Thioxanthone systems such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone;
Aminobenzophenone series such as Michler's ketone and 4,4'-diethylaminobenzophenone;
10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like are preferable. Of these, benzyldimethyl ketal is most preferred.

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

The polymerizable liquid crystal composition in the present invention can further contain a compound represented by the general formula (Q) as an antioxidant or a light stabilizer.

(Wherein, R ^Q represents a straight-chain alkyl group or branched alkyl group having from 1 22 carbon atoms, one or two or more CH ₂ groups in the alkyl group, so that the oxygen atoms are not directly adjacent a, -O -, - CH = CH -, - CO -, - OCO -, - COO -, - C≡C -, - CF 2 O -, - OCF 2 - may be replaced by, ^{M Q} is trans Represents a 1,4-cyclohexylene group, a 1,4-phenylene group or a single bond.)
^RQ represents a straight-chain alkyl group or a branched-chain alkyl group having 1 to 22 carbon atoms, and one or more CH ₂ groups in the alkyl group are —O—so that oxygen atoms are not directly adjacent to each other. —, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O—, —OCF ₂ — may be substituted. Linear alkyl group, linear alkoxy group, linear alkyl group in which one CH ₂ group is substituted with —OCO— or —COO—, branched alkyl group, branched alkoxy group, one CH ₂ group is —OCO— Or a branched alkyl group substituted with —COO—, a linear alkyl group having 1 to 20 carbon atoms, a linear alkyl group in which one CH ₂ group is substituted with —OCO— or —COO—, branched Chain alkyl group, branched alkoxy group, one CH ₂ group Is more preferably a branched alkyl group substituted with —OCO— or —COO—. ^MQ represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a single bond, and a trans-1,4-cyclohexylene group or a 1,4-phenylene group is preferred.

As the compound represented by the general formula (Q), more specifically, compounds represented by the following (III-1) to (III-38) are preferable.

(In the formula, n represents an integer of 0 to 20.)
The polymerizable liquid crystal composition of the present invention preferably contains one or more compounds represented by general formula (Q) or compounds selected from general formulas (III-1) to (III-38). It is more preferable to contain 1 to 5 types, and the content is preferably 0.001 to 1%, more preferably 0.001 to 0.1%, and 0.001 to 0.05%. Particularly preferred.

The above-described method for forming the liquid crystal layer will be described in more detail. The two substrates are opposed so that the transparent electrode layer is on the inside, the distance between the substrates is adjusted via a spacer, and the polymerizable property is maintained between the substrates. Examples include a method of sandwiching the liquid crystal composition and polymerizing the polymerizable monomer component (a) in the composition.

Here, the thickness of the liquid crystal layer is preferably adjusted to be 1 to 100 μm, more preferably 1.5 to 10 μm. When a polarizing plate is used, the refractive index of the liquid crystal is maximized so that the contrast is maximized. It is preferable to adjust the product of the anisotropy Δn and the cell thickness d. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used.

Here, examples of the spacer include columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like.

As a method for sandwiching the polymerizable liquid crystal composition between two substrates, a normal vacuum injection method, an ODF method, or the like can be used. In the ODF liquid crystal display device manufacturing process, a sealant such as epoxy photothermal curing is drawn on a backplane or frontplane substrate using a dispenser in a closed-loop bank shape, and then removed. A liquid crystal display element can be produced by bonding a front plane and a back plane after dropping a predetermined amount of the polymerizable liquid crystal composition under air. The polymerizable liquid crystal composition used in the present invention can be preferably used because it can stably drop the composite material of the liquid crystal and the polymerizable monomer component (a) in the ODF process.

As a method for polymerizing the polymerizable monomer component (a), in order to obtain good alignment performance of the liquid crystal, an appropriate polymerization rate is desirable. Therefore, ultraviolet rays or electron beams which are active energy rays are used singly or in combination. Or the method of superposing | polymerizing by irradiating in order is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. In addition, when polymerization is performed in a state where a liquid crystal composition for manufacturing a liquid crystal display element is sandwiched between two substrates, at least the substrate on the irradiation surface side is given appropriate transparency to active energy rays. Must be. In addition, it is preferable to apply an alternating electric field in the temperature range of −50 ° C. to 20 ° C. and irradiate the polymerizable liquid crystal composition containing the polymerizable monomer component (a) with ultraviolet rays or electron beams. 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 a 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 a horizontal electric field type MVA mode liquid crystal display element, the pretilt angle is preferably controlled from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.

The temperature during irradiation is preferably such that the temperature of the polymerizable liquid crystal composition is in the range of −50 ° C. to 30 ° C. Furthermore, the range of 20 ° C. to −10 ° C. allows polymerization with an increased degree of orientation of the liquid crystal molecules, lowers the compatibility between the polymer and the liquid crystal composition, and facilitates phase separation, thereby causing voids in the polymer network. Since the interval becomes fine, it is preferable from the point that the off-response speed is further improved.

As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate ultraviolet rays in a wavelength region other than the absorption wavelength region of the liquid crystal composition, and it is preferable to cut and use ultraviolet rays of less than 365 nm as necessary. Intensity of ultraviolet irradiation is ^preferably from 0.1mW / cm 2 ~ 100W / cm 2, 2mW / cm 2 ~ 50W / cm 2 is more preferable. The amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² . When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiated ultraviolet rays, but is preferably from 10 seconds to 3600 seconds, and more preferably from 10 seconds to 600 seconds.

When a liquid crystal layer is formed using a vertically aligned cell, a fibrous or columnar polymer network (A) is formed in a direction substantially the same as the vertical direction of the liquid crystal composition (B) with respect to the liquid crystal cell substrate. It is preferable. In addition, when a vertical alignment film that induces a pretilt angle by rubbing the liquid crystal on the cell substrate surface so as to induce a tilted alignment is used, the liquid crystal is pretilted and aligned. 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 inclination of the polymer network (A) may be such that a monomer is selected so as to spontaneously occur at the substrate interface, or a spontaneous orientation agent and a photo-alignment film described later are used. Alternatively, the polymer network (A) may be formed by applying a voltage to place the liquid crystal in an inclined alignment state and irradiating with ultraviolet rays or the like.

Furthermore, as a method for inducing the pretilt angle while applying a voltage, a method of polymerizing while applying a voltage in a voltage range of about 0.9 V to 2 V higher than a threshold voltage of a liquid crystal for manufacturing a liquid crystal display element. Alternatively, a method of forming a polymer network by applying a voltage higher than the threshold voltage for a short time of several seconds to several tens of seconds during the process of forming the polymer network (A) and then forming the polymer network below the threshold voltage.

The fibrous or columnar polymer network (A) formed in the liquid crystal layer is preferably formed to be inclined so as to induce a pretilt angle of 90 to 80 degrees with respect to the transparent substrate plane. The pretilt angle is particularly preferably in the range of 90 ° to 85 °, in the range of 89.9 ° to 85 °, in the range of 89.9 ° to 87 °, and in the range of 89.9 ° to 88 °. The fibrous or columnar polymer network formed by any method is characterized in that the two cell substrates are connected to each other. As a result, the thermal stability of the pretilt angle can be improved and the reliability of the liquid crystal display element can be increased.

In addition, as a method for inducing the pretilt angle of the liquid crystal composition (B) by forming the fibrous or columnar polymer network (A) by tilting orientation, an alkylene between the polymerizable functional group and the mesogenic group is used. Bifunctional acrylates having a small pretilt angle induction angle with 6 or more carbon atoms and functional groups, and bifunctional acrylates having a large pretilt angle induction angle with 5 or more carbon atoms in the alkylene group between the mesogenic groups A method using a combination of A desired pretilt angle can be induced in the vicinity of the interface by adjusting the compounding ratio of these compounds.

Furthermore, a method of forming a fibrous or columnar polymer network (A) by adding a monomer having a reversible photo-alignment function in a range of at least 0.01% by mass to 1% by mass.

In this case, the transformer body has a rod-like shape similar to that of the low-molecular liquid crystal, which affects the alignment state of the low-molecular liquid crystal. The trans isomer contained in the polymerizable liquid crystal composition for producing a liquid crystal display element is aligned so that the direction of ultraviolet light travels parallel to the direction of the long axis of the rod when irradiated with ultraviolet light as parallel light from the top surface of the cell. The low-molecular liquid crystals are also aligned so as to be aligned in the molecular major axis direction of the trans form at the same time. When the cell is tilted and irradiated with ultraviolet rays, the molecular long axis of the trans body is oriented in the tilt direction and the liquid crystal is oriented in the tilt direction of the ultraviolet rays. That is, a pre-tilt angle is induced and a photo-alignment function is exhibited. When the monomer is crosslinked at this stage, the pretilt angle induced is fixed by a fibrous or columnar polymer network formed by polymerization phase separation. Therefore, the pretilt angle that is important in the VA mode is induced by a method of separating the polymerization phase while applying a voltage, a method of adding a plurality of monomers with different pretilt angles to induce polymerization phase separation, and a monomer having a reversible photo-alignment function. The liquid crystal composition (B) and the monomer are aligned in the direction in which ultraviolet rays travel using the photo-alignment function shown in FIG. Can be produced.

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

Further, when a parallel alignment cell such as IPS or FFS mode is applied, a fibrous or columnar polymer network (A) is formed on the surface of the liquid crystal cell substrate by phase separation polymerization using a liquid crystal composition for manufacturing a liquid crystal display element. Although the liquid crystal composition (B) is aligned in parallel with the alignment direction of the alignment film in the liquid crystal composition (B), the refractive index anisotropy or the easy axis direction of the formed fibrous or columnar polymer network and the liquid crystal composition (B ) In the direction substantially the same as the orientation direction. Furthermore, it is more preferable that the fibrous or columnar polymer network is present in substantially the entire cell 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 using a monovalent or divalent acrylate or methacrylate of an alcohol compound having 8 to 18 carbon atoms as a monomer; It is preferable to use it.

Furthermore, although the electro-optical characteristics are affected by the surface area of the polymer network interface and the gap spacing of the polymer network, it is important not to cause light scattering, and the average gap spacing is preferably smaller than the wavelength of visible light. For example, there is a method of increasing the monomer composition content in order to increase the surface area of the interface and reduce the gap interval. As a result, the polymer phase is formed so that the surface area of the interface is increased by changing the polymerization phase separation structure and making the gap interval fine, and the drive voltage and the fall time are shortened. The polymerization phase separation structure is also affected by the polymerization temperature.

In order to obtain a high contrast display in a liquid crystal display element, it is necessary to prevent light scattering. However, in consideration of the above-described method, it is necessary to obtain a desired voltage-transmittance characteristic and switching characteristic. It is desirable to control the separation structure to form a suitable polymer network layer structure.

The liquid crystal layer having such a polymer network (A) will be described in more detail. The liquid crystal layer has a structure in which a 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. In addition, it is preferable that the easy axis of alignment of the polymer network (A) and the uniaxial optical axis are substantially in the same direction as the easy alignment axis of the low molecular liquid crystal, and the polymer network is formed so as to induce the pretilt angle of the low molecular liquid crystal. Preferably, the light scattering is less likely to occur by making the average gap distance of the polymer network (A) smaller.

Furthermore, in order to make the fall time of the response shorter than the response time of the low molecular liquid crystal alone due to the interaction effect (anchoring force) between the polymer network (A) and the low molecular liquid crystal, the average gap interval of the polymer network (A) Is preferably in the range of 50 nm to 450 nm. In order that the influence of the cell thickness of the liquid crystal is small and the fall time is as long as the cell thickness is large, at least the average gap interval is in the range of around 200 nm and the upper limit is around 450 nm. It is preferable to enter. Increasing the drive gap increases the average gap spacing. However, in order to suppress the increase in drive voltage to 25 V or less and shorten the fall response time, it is sufficient to enter the range from about 250 nm to 450 nm. The fall response time can be improved in the range of about 5 msec to about 1 msec, which is preferable. Further, in order to suppress the drive voltage from increasing within about 5V, it is preferable that the average gap interval is 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.

In order to achieve such a high-speed response, the drive voltage may be increased to 30 V or more, but the average gap interval may be set between about 50 nm and about 250 nm, and in order to make 0.5 msec or less, from about 50 nm to 200 nm. It is preferable to make it near. The average diameter of the polymer network is in the range of 20 nm to 700 nm, contrary to the average gap spacing. The average diameter tends to increase as the monomer content increases. Increasing the polymerization phase separation rate by increasing the reactivity increases the density of the polymer network and decreases the average diameter of the polymer network. Therefore, the phase separation conditions may be adjusted as necessary. When the monomer content is 10% by mass or less, the average diameter is preferably from 20 nm to 160 nm, and when the average gap distance is from 200 nm to 450 nm, the average diameter is preferably from 40 nm to 160 nm. . When the monomer content is larger 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, the content of the polymerizable monomer component (a) is low and the polymer network layer is required to cover the entire cell. When the amount is insufficient, the polymer network layer is formed discontinuously. When the polarity of the substrate surface is high, the polymerizable monomer component (a) tends to gather near the liquid crystal cell substrate interface, and a polymer network layer is formed so that the polymer network grows from the substrate surface and adheres to the substrate interface. The polymer network layer, the liquid crystal layer, the polymer network layer, and the counter substrate are stacked in this order from the cell substrate surface. Polymer having a laminated structure of polymer network layer / liquid crystal layer / polymer network layer and having a thickness of at least 0.5%, preferably 1%, more preferably 5% or more of the cell thickness in the cell cross-sectional direction When the network layer is formed, the effect of shortening the fall time due to the action of the anchoring force between the polymer network and the low-molecular liquid crystal is exhibited and a favorable tendency is exhibited. However, since the influence of the cell thickness increases, 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 polymer network structure in the polymer network layer is such that the low-molecular liquid crystal and the easy-orientation axis or uniaxial optical axis are aligned in substantially the same direction, and the low-molecular liquid crystal is formed so as to induce a pretilt angle. Just do it. The average gap distance 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 mesogenic group having a high anchoring force, and a bifunctional monomer having a structure with 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 lower. When the monomer content is from 6% by mass to less than 10% by mass, a combination of the bifunctional monomer and a monofunctional monomer having a low anchoring force 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 room temperature or higher, 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 producing a liquid crystal display element, the greater the anchoring force between the liquid crystal composition (B) and the polymer interface, and the higher the τd. On the other hand, when the anchoring force between the liquid crystal composition (B) and the polymer interface increases, τr decreases. In order to make the sum of τd and τr 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. % By mass or less is preferable, and 1.8% by mass or more and 5% by mass or less is more preferable.

When used in a TFT drive liquid crystal display element, it is necessary to improve the reliability such as suppression of flicker and afterimages caused by printing, and the voltage holding ratio is 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. Thus, it is preferable to remove the mobile ions by performing a purification treatment or the like. In addition, when a polymer network is formed by radical polymerization, the voltage holding ratio may decrease due to ionic impurities generated from the photopolymerization initiator, etc., but the polymerization initiator generates a small amount of organic acid and low-molecular byproducts. Is preferably selected.

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 is the same as the alignment easy axis direction of the polymer network (A). In this case, by providing a polarizing plate, a retardation film, etc., it is possible to display using this orientation state.

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, as described above. Is preferably 0.7% by mass or more, 0.9% by mass or more, particularly preferably 1% by mass, and the upper limit is preferably 10% by mass or less, 9% by mass or less, and preferably 7% by mass or less. Is preferable from the viewpoint of excellent balance between the off-response speed and the drive voltage.

In the PSA-type liquid crystal display element, the alignment treatment is omitted by providing a plurality of slits with a width of 3 to 5 μm in the electrode instead of the rubbing alignment treatment and tilting the liquid crystal in the slit direction. In mass production technology, when UV irradiation is applied while applying a voltage of several tens of volts, the alignment of the liquid crystal is stabilized so that a pretilt angle (tilt angle with respect to the substrate normal) is obtained at the substrate interface, and the polymer is stabilized. A thin film is formed. Utilizing the fact that the pretilt angle is induced by the action of the polymer thin film, it is used for the production of PSVA (polymer-stabilized vertical alignment) LCD or PSALCD. Further, for the purpose of improving the viewing angle, a pattern electrode designed so that a multi-domain can be formed is used to divide the pretilt angle direction in one pixel into a plurality of parts.

However, when this method is applied to a liquid crystal display element that can improve the response relaxation time by forming a polymer network or the like in the entire cell, it is irradiated with ultraviolet rays by applying a voltage of several tens of volts above the saturation voltage. Therefore, the polymer network stabilizes the liquid crystal in the horizontal alignment state. Therefore, in this method, since the refractive anisotropy or the easy alignment axis of the polymer network is formed so as to hold the liquid crystal molecules in the horizontal alignment state, the vertical alignment cannot be obtained.

On the other hand, when a low voltage in the vicinity of the threshold voltage is applied to form the refractive anisotropy of the polymer network or the easy alignment axis, the transmittance decreases because the tilted orientation of the liquid crystal is not determined.

Therefore, in the present invention, a voltage higher than the threshold voltage is applied to the polymerizable liquid crystal composition to form a part of the polymer network, and then the voltage is set to be lower than the threshold voltage during the ultraviolet irradiation. Is preferably continued. That is, first, a voltage higher than the threshold voltage is applied, a part of the monomer is polymerized to form a part of the polymer network so that the tilt alignment orientation of the liquid crystal is stabilized, and then the voltage is set to the threshold during ultraviolet irradiation. When the voltage is lower than the voltage, the liquid crystal returns to a substantially vertical alignment. Further, when UV irradiation is continued in this state, the refractive anisotropy of the polymer network or the easy alignment axis is formed so that the substantially vertical alignment is formed, and the tilted alignment orientation is formed. Can be left in the polymer network as a trajectory, and it is possible to achieve both orientation control when a voltage is applied and vertical orientation when no voltage is applied.

Therefore, the method for producing a liquid crystal display element of the present invention includes a polymerizable liquid crystal composition for producing a liquid crystal display element sandwiched between two transparent substrates having electrodes on at least one side, and a liquid crystal threshold value for producing the element. A method comprising a step of irradiating ultraviolet rays while applying a voltage higher than the voltage to cause polymerization phase separation, and a step of further irradiating with ultraviolet rays by setting the voltage below the threshold voltage while irradiating with ultraviolet rays is preferable.

Here, in the case of a vertical alignment mode liquid crystal display element including a pattern electrode cell, etc., in the process of polymerizing phase separation by applying ultraviolet rays while applying a voltage higher than the threshold voltage of the liquid crystal for liquid crystal display element manufacture, The liquid crystal molecules in the liquid crystal are aligned with an inclination in the range of 0 ° to 30 ° with respect to the transparent substrate plane, and then the above-mentioned voltage is made lower than the threshold voltage while irradiating with ultraviolet rays, and further irradiating with ultraviolet rays In the above, it is preferable that the liquid crystal molecules are aligned with an inclination of 80 to 90 degrees with respect to the transparent substrate plane.

The state in which the liquid crystal molecules are aligned with an inclination in the range of 0 to 30 degrees with respect to the transparent substrate plane indicates a state in which the birefringence of the liquid crystal is increased by voltage application, and the alignment state of the liquid crystal is in the plane of the transparent substrate. On the other hand, when it is 0 degree, the birefringence is maximized, which is preferable. However, an orientation inclined by 30 degrees with respect to the substrate plane is also preferable. In particular, the PVA cell is preferable because the tilt direction can be made constant. In any case, it is preferable to form a polymer network in which the orientation is stabilized so that the tilt orientation direction of the liquid crystal by voltage application becomes a constant direction.

When the liquid crystal molecules are aligned at an angle of 80 to 90 degrees with respect to the transparent substrate plane, the birefringence becomes minimum when the liquid crystal is aligned at 90 degrees with respect to the transparent substrate plane when no voltage is applied. It is useful and preferable for increasing the contrast of the liquid crystal display element, but it is more preferable that the liquid crystal display device is tilted within 89.9 degrees to 85 degrees with respect to the substrate plane in order to tilt and align in a certain direction when a voltage is applied. . If the angle exceeds 80 degrees with respect to the substrate plane, the birefringence increases and the amount of transmitted light increases, which is not preferable because the display contrast is lowered. Since contrast is obtained, it is preferable.

In the IPS (In-plane switching) display mode and FFS mode liquid crystal display element, a process of polymerizing phase separation by irradiating ultraviolet rays while applying a voltage higher than a threshold voltage of a liquid crystal composition for liquid crystal display element production. The liquid crystal molecules in the liquid crystal composition for manufacturing a liquid crystal display element are aligned with an inclination in the range of 0 to 90 degrees with respect to the transparent substrate plane, and the voltage is set to be lower than the threshold voltage while being irradiated with ultraviolet rays. In the step of further irradiating with ultraviolet rays, it is also preferable that the liquid crystal molecules are aligned with an inclination of 0 to 30 degrees with respect to the transparent substrate plane.

The liquid crystal molecules are tilted in the range of 0 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 properties of the alignment film used in the element greatly depends on the tilt angle, and may be in the range of 1 to 2 degrees. The tilt angle of the liquid crystal molecules including the twisted orientation is 0. .5 to 3 degrees is preferable, and 0 to 2 degrees is preferable.

In 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 device, and the splay alignment, bend alignment, and twist alignment states coexist. Indicates. The inclination angle of the alignment state of the liquid crystal molecules in this state is preferably in the range of 0 to 45 degrees, and the same range is preferably stabilized when the alignment is stabilized by the polymer network. In the TN mode, the tilt angle is preferably in the range of 45 degrees to 90 degrees.

On the other hand, a polymer network is formed so as to stabilize the alignment state of the liquid crystal by applying a voltage lower than the threshold voltage. In the IPS mode, FFS mode, and TN mode, the pretilt angle is applied to the substrate interface by rubbing alignment treatment. Therefore, 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, even if the liquid crystal alignment angle is inclined within this range. The tilt angle of the liquid crystal molecules including the twist orientation is preferably 0.5 to 3 degrees using other alignment processing methods such as a photo-alignment film, and a wide viewing angle is within 0 to 2 degrees. Useful and more preferred to obtain.

Further, it is preferable that the voltage to be applied is an alternating current waveform and has a frequency in a range in which 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 that does not attenuate the signal transmitted to the pixel by the driving circuit used for the liquid crystal display element, and it is preferable that the frequency is at least 2 kHz or less. The frequency shown by the dielectric anisotropy in the frequency dependence of the dielectric constant exhibited by the liquid crystal composition for producing a liquid crystal display element before ultraviolet irradiation may be 10 kHz or less. The lower limit value may be a frequency at which flicker occurs when the element is driven. In this case, the frequency may be any frequency that minimizes flicker, and is preferably at least 20 Hz or more.

In this way, it is preferable to form a polymer network so as to maintain two liquid crystal alignment states. However, the polymer network formed so as to maintain each liquid crystal alignment state has a refractive index anisotropy or alignment of the polymer network. It is formed so that the easy axis coincides with the liquid crystal alignment direction not less than the threshold voltage or the liquid crystal alignment direction less than the threshold voltage. This creates a state in which the polymer network that stabilizes the alignment of the liquid crystal when a voltage is applied and the polymer network that stabilizes the alignment of the liquid crystal when no voltage is applied coexist, and the liquid crystal alignment when no voltage is applied It is possible to improve display characteristics such as an improvement in contrast by suppressing orientation distortion that occurs when orientation deformation is caused by voltage application from the state. 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 changing to the liquid crystal alignment state when the voltage is applied. Since the influence of the polymer network is strong, when the liquid crystal alignment state is shifted to a threshold voltage or higher, an alignment strain is applied to cause a decrease in 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 change caused by switching is suppressed, and the originally required change in liquid crystal alignment can be obtained and transmitted. The rate can be improved. The polymer network formed so as to stabilize the alignment state of each liquid crystal when a voltage is applied and when no voltage is applied is the refractive index anisotropy or alignment of the polymer network along the alignment of two different liquid crystals. It is characterized by forming an easy axis.

Furthermore, the influence of the polymer network formed to stabilize the liquid crystal state above the threshold voltage changes depending on the application time of the voltage above the threshold voltage during UV irradiation, making it possible to change the electro-optical characteristics. Become. For example, when the polymer network is formed with the alignment state of the liquid crystal at the time of voltage application as a parallel alignment including a tilted alignment of 0 to 30 degrees with respect to the substrate plane, the voltage application time equal to or higher than the threshold voltage during ultraviolet irradiation is set. When shortened, the action to maintain the parallel alignment is small, so that the liquid crystal tends to align according to the action of the polymer network to maintain the vertical alignment. Furthermore, the influence of both orientations from the polymer network holding two different orientations is balanced, and a small pre-tilt angle of less than 1 degree is induced with respect to the normal direction of the transparent substrate. As the application time of the voltage exceeding the threshold voltage during UV irradiation is increased, the influence of the polymer network that tries to maintain the horizontal alignment becomes stronger, so the pretilt is based on the balance between the force that maintains the vertical alignment and the force that maintains the parallel alignment. The angle increases and the pretilt angle increases, and it becomes possible to make it 10 degrees or more with respect to the normal direction of the transparent substrate. In addition, since 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 used for manufacturing the liquid crystal display element used, it can be adjusted appropriately to obtain a desired pretilt angle. It is preferable to make it. In particular, it is preferable to obtain a pretilt angle in the range of 80 to 90 degrees with respect to the substrate plane, more preferably 85 to 89.9 degrees, and 87 to 89.9 degrees. Is more preferable.

The polymer network formed to maintain the alignment state of the liquid crystal obtained by applying a voltage higher than the threshold voltage is the horizontal alignment state in the vertical alignment mode liquid crystal display element using negative dielectric anisotropy. Alternatively, a tilted orientation with a constant azimuth is desirable. The alignment state obtained at a voltage lower than the threshold voltage is preferably a substantially vertical alignment, and in particular, a substantially vertical alignment of 80 to 90 degrees with respect to the substrate plane is preferable, and a good black level that provides high contrast is obtained. It is preferable that it is the orientation state which shows.

In the IPS display mode by a lateral 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. The orientation is preferable. The alignment state obtained at a voltage lower than the threshold voltage is preferably parallel alignment with a constant azimuth angle. In the FFS mode, the alignment state obtained by applying a voltage equal to or higher than the threshold voltage during ultraviolet irradiation is preferably at least one of bend alignment, splay alignment, inclined alignment, or a mixed alignment state. When the voltage is lower than the threshold voltage, it is preferable to have a substantially parallel orientation. After forming the polymer network to maintain the alignment state of the liquid crystal when a voltage is applied, the polymer is stabilized after the formation of the polymer network by stabilizing the alignment state of the liquid crystal below the threshold voltage. The alignment state can be easily changed to the alignment state, and both high transmittance and high-speed response can be achieved.

The applied voltage at the time of ultraviolet irradiation is preferably adjusted as appropriate so that the display of the liquid crystal display element after the formation of the polymer network has a high contrast, and the electro-optic effect of the liquid crystal composition for manufacturing the liquid crystal display element before the ultraviolet irradiation Since it greatly depends on the characteristics, it is necessary to match the voltage-transmittance characteristics exhibited by the liquid crystal for manufacturing the liquid crystal display element. The voltage above the threshold voltage is preferably a voltage V10 or higher, which is 10% or higher with respect to the total change in transmittance in the voltage-transmittance characteristic voltage of the liquid crystal for manufacturing a liquid crystal display element. 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 in transmittance is 50% or more is more preferable. However, the voltage is preferably not more than 6 times the threshold voltage. As the voltage that is equal to or higher than the threshold voltage applied during the ultraviolet irradiation, an alternating voltage is preferably applied, and a rectangular wave is preferably applied. The frequency is preferably a frequency that cannot be visually recognized by the flicker, and when an electronic circuit such as a TFT substrate is formed on a glass substrate, it may be a frequency at which the polymerization voltage does not attenuate, and is 30 Hz to 5 kHz. It is preferable that there is a degree.

The voltage applied in the middle of the ultraviolet irradiation is changed from the threshold voltage to less than the threshold voltage, but the voltage less than the threshold voltage may be in a range where the orientation of the liquid crystal does not change with the voltage. The voltage is preferably less than 80%, more preferably less than 80%, and even more preferably 70% or less. In addition, the applied voltage is set to the threshold voltage or lower during the ultraviolet irradiation, but at this time, it is preferable to return to the liquid crystal alignment state at the OFF time in the liquid crystal display element. For example, in the vertical alignment mode as described above. In other words, it may be returned to the vertical alignment, and in the FFS mode or the IPS mode, the parallel alignment may be used. In order to return to the liquid crystal alignment state when the liquid crystal display element is OFF, it is preferable that the influence of the polymer network that stabilizes the liquid crystal alignment during voltage application is lowered to a voltage lower than the threshold voltage in a slight state.

The ultraviolet rays are irradiated after applying a voltage higher than the threshold voltage. However, if the voltage application time becomes longer during the ultraviolet irradiation, the influence of the polymer network that stabilizes the orientation of the liquid crystal during voltage application during the ultraviolet irradiation increases. It becomes unpreferable because it does not return to the liquid crystal alignment state when the required liquid crystal display element is OFF. Therefore, it is preferable to produce the liquid crystal liquid crystal display element of the present invention by appropriately optimizing the optimum voltage during ultraviolet irradiation. In addition, when the voltage during ultraviolet irradiation is made lower than the threshold voltage, the voltage is gradually lowered during the ultraviolet irradiation in order to adjust the response relaxation time in the liquid crystal of the liquid crystal composition for device manufacture. It is possible to minimize the influence of backflow that occurs in the response relaxation process by making the fall time of the liquid crystal longer than the response relaxation time in the liquid crystal during ultraviolet irradiation. The fall time of the applied voltage is 10 ms or more. Is preferably within 1000 ms. On the contrary, it may be lowered quickly, and it is preferably at least shorter than the relaxation time indicated by the liquid crystal composition for producing a liquid crystal display element, and preferably 100 ms or less.

In this way, a polymer network of the horizontal alignment component is partially formed by irradiating with ultraviolet rays in a state where a voltage equal to or higher than the threshold voltage is applied, and the liquid crystal is vertically aligned 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 liquid crystal cell, the pretilt angle can be changed by the ratio of the above-mentioned parallel alignment component and vertical alignment component. When the voltage is turned off in the initial stage of polymer network formation, the tilt alignment direction is determined and the vertical alignment is determined. By using the residual monomer, it becomes possible to achieve both the vertical alignment and the tilt alignment orientation, which is an alignment control technique in the nanophase separation liquid crystal.

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 is preferably in the range of 0.1 to 30 degrees with respect to the substrate surface. It is preferable that the tilt orientation is in the range of 1 to 10 degrees. The vertical alignment when no voltage is applied means that the vertical alignment film is brought into a substantially vertical alignment state. 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 is inclined from 85 degrees to 89.9 degrees.

In the case of a positive dielectric anisotropic liquid crystal, a vertical alignment is obtained when a voltage is applied, but the liquid crystal is tilted and aligned in the range of 45 to 89.9 degrees with respect to the substrate plane. It is also included. The parallel alignment when no voltage is applied means that the parallel alignment film is brought into a substantially parallel alignment state. The alignment of the liquid crystal is tilted from 0.1 to 30 degrees with respect to the substrate plane. It is 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, 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 close to 0.275. In the liquid crystal composition for manufacturing an element used in the present invention, the polymer network is separated after the polymerization phase separation. Since the birefringence of the liquid crystal display element 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 liquid crystal composition, the polymer composition, or the liquid crystal display element 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 0.00 when the driving voltage is increased within about 5 V due to the formation of the polymer network. The range of 4 μm is particularly preferable, the range of 0.30 to 0.35 μm is more preferable when the increase is within about 3 V, and the range of 0.29 to 0.33 μm when the drive voltage is within 1 V. It is particularly preferred. By making the product of the distance (d) between the substrates of the liquid crystal display element and the product of 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 high-speed response and favorable color reproducibility. The birefringence of the liquid crystal composition used in the liquid crystal composition for manufacturing the liquid crystal display element is such that the product of the cell thickness (d) and the birefringence (Δn) is 1 to 1.9 times with respect to 0.275. It is preferable to make it.

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

For example, Japanese Patent Laid-Open No. 6-222320 discloses the relationship of the following formula as a description regarding the driving voltage of a polymer dispersion type liquid crystal display element.

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

According to this, the driving voltage of the light-scattering liquid crystal display element is determined by the average gap spacing at the interface of the transparent polymer material, the distance between the substrates, the elastic constant / dielectric anisotropy of the liquid crystal composition, and the transparency with the liquid crystal composition. Determined by the anchoring energy between the conductive polymer materials. Among these, parameters that can be controlled by the liquid crystal display device of the present invention are liquid crystal properties and anchoring force between polymers. Since the anchoring force largely depends on the molecular structure of the polymer and the molecular structure of the low-molecular liquid crystal, if a monomer having a strong anchoring force is selected, the response time can be shortened to 1.5 ms or less. At the same time, since the drive voltage increases to 30 V or more, it is preferable to adjust the composition by appropriately selecting the liquid crystal compound and the monomer so that the drive voltage is 30 V or less and the response speed is 1.5 ms or less. It is preferable to adjust the composition so that the driving voltage and the response speed are balanced by appropriately blending a polymer precursor having a strong anchoring force and a polymer precursor having a weak anchoring force. On the other hand, as the physical properties of the liquid crystal composition required for lowering the driving voltage, it is particularly preferable that the dielectric anisotropy is 6 or more for the P-type liquid crystal and -3 or less for the N-type liquid crystal. . The birefringence is preferably 0.09 or more. Furthermore, it is more preferable to make the birefringence of the liquid crystal composition and the refractive index of the fibrous or columnar polymer network 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 use the liquid crystal composition with an increased or decreased birefringence so that the necessary retardation can be obtained.

The liquid crystal layer described in detail above has a retardation (Re) defined by the following mathematical formula (1) when the wavelength of incident light from the light source unit in the liquid crystal display element is 450 nm and 25 ° C.
Re = Δn × d
(In the above formula (1), Δn represents the refractive index anisotropy at 589 nm, and d represents the cell thickness (μm) of the liquid crystal layer of the liquid crystal display element.)
It is preferably 220 to 300 nm.

In other words, a liquid crystal display element using a normal white light source and a liquid crystal display element that switches transmission of blue visible light (so-called short wavelength region light) or ultraviolet light of about 500 nm or less that causes excitation of the quantum dots are transmitted. Since the optical properties of the transmitted light and the transmitted light are different, the characteristics required for each element are also different. However, the difference between a light source used in a conventional liquid crystal display element using a light emitting nanocrystal such as a quantum dot as a light emitting element and a light source used in a normal liquid crystal display element not including a light emitting nanocrystal such as a quantum dot. The optical characteristics of the liquid crystal material resulting from the above have not been optimized, and there has been a problem that the optical characteristics of display elements using light emitting nanocrystals such as quantum dots cannot be utilized to the maximum. Therefore, by satisfying the retardation condition, the transmittance of the liquid crystal display element can be improved when blue visible light (so-called short wavelength region light) of 500 nm or less or ultraviolet light is used as incident light. Therefore, it is possible to suppress or prevent a decrease in transmittance of the liquid crystal display element.

[Alignment layer]
The liquid crystal display element of the present invention may have the alignment layer 4 as described above. For example, in the case of a VA liquid crystal display element, when the liquid crystal compound is vertically aligned, without providing an alignment layer, A self-aligning agent is included in the polymerizable liquid crystal composition so that the liquid crystal is self-supported without an alignment film, or is aligned using a solvent-soluble vertical alignment polyimide, or a photo-alignment film, particularly a non-polyimide. It is preferable from the viewpoint that the liquid crystal display element can be easily manufactured by aligning the liquid crystal with the photo alignment film of the system.

As the spontaneous alignment agent that can be used here, the alignment direction of the liquid crystal molecules contained in the liquid crystal composition (B) constituting the liquid crystal layer can be controlled. It is considered that the alignment direction of the liquid crystal molecules can be controlled by accumulating or adsorbing the components of the spontaneous alignment agent at the interface of the liquid crystal layer. Thereby, when a spontaneous orientation agent is included in the polymerizable liquid crystal composition, the orientation layer of the liquid crystal panel can be eliminated.

The content of the spontaneous alignment agent in the polymerizable liquid crystal composition according to the present invention is preferably 0.1 to 10% by mass in the entire polymerizable liquid crystal composition.

The spontaneous alignment agent is preferably the following general formula (al-1) and / or general formula (al-2).

(In the formula, ^Ral1 , ^Ral2 , ^Zal1 , ^Zal2 , ^Lal1 , ^Lal2 , ^Lal3 , ^Spal1 , ^Spal2 , ^Spal3 , ^Xal1 , ^Xal2 , ^Xal3 , ^mal1 , ^mal2 ^al3 , ^nal1 , ^nal2 , ^nal3 , ^pal1 and ^pal2 are each independently of each other,
R ^al1 represents a hydrogen atom, a halogen, a straight chain, branched or cyclic alkyl having 1 to 20 carbon atoms, wherein in the alkyl group, one or two or more non-adjacent CH ₂ The group is substituted by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— so that the O and / or S atoms are not directly bonded to each other. In addition, one or more hydrogen atoms may be replaced by F or Cl.
R ^al2 represents a group having any of the following partial structures:

^Spal1 , ^Spal2 and ^Spal3 each independently represent an alkyl group having 1 to 12 carbon atoms or a single bond,
^Xal1 , ^Xal2 and ^Xal3 each independently represent an alkyl group, an acrylic group, a methacrylic group or a vinyl group,
Z ^al1 is —O—, —S—, ^—CO— , ^—CO—O— , ^—OCO— , —O—CO—O—, —OCH ₂ —, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, — (CH ₂ ) _n ^al —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ — , — (CF ₂ ) _n ^al —, ^{—CH═CH—,} ^{—CF═CF—,} ^—C≡C—, ^{—CH═CH—} ^COO—, ^—OCO— ^CH═CH— , — (CR ^al3 R ^al4 _{^{^{^{) n a1 -, - CH (}}}} -Sp al1 -X al1) -, - CH 2 CH (-Sp al1 -X al1) -, - CH (-Sp al1 -X al1) CH (-Sp al1 -X al1) -
Z ^al2 is each independently a single bond, —O—, —S—, —CO—, ^{—CO—O—, —OCO—} , —O—CO—O—, —OCH ₂ —, —CH _2. O—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, — (CH ₂ ) n1-, —CF ₂ CH ₂ — , —CH ₂ CF ₂ —, — (CF ₂ ) _n ^al —, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— ^{^{_{^{, - (CR al3 R al4)}}}} na1 -, - CH (-Sp al1 -X al1) -, - CH 2 CH (-Sp al1 -X al1) -, - CH (-Sp al1 -X al1) CH (- Sp ^al1 -X ^al1 )-
L ^al1 , L ^al2 and L ^al3 are each independently a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, —CN, —NO ₂ , —NCO, —NCS, —OCN, —SCN, — C (═O) N (R ^al3 ) ₂ , —C (═O) R ^al3 , an optionally substituted silyl group having 3 to 15 carbon atoms, an optionally substituted aryl group or cycloalkyl group, or Represents 1 to 25 carbon atoms, wherein one or more hydrogen atoms may be replaced by halogen atoms (fluorine atoms, chlorine atoms),
The ^{R AL3} represents an alkyl group having 1 to 12 carbon atoms, the ^{R AL4} represents an alkyl group having a hydrogen atom or 1 to 12 carbon atoms, the ^{n al} is 1-4 Represents an integer,
^pal1 and ^pal2 each independently represent 0 or 1, ^mal1 , ^mal2 and ^mal3 each independently represent an integer of 0 to 3, and ^nal1 , ^nal2 and ^nal3 are Each independently represents an integer of 0 to 3. )
General formula (Al-2):

^Wherein Z ⁱ¹ and Z ⁱ² are each independently a single bond, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —OCOO—, —OOCO. _{_{-, - CF 2 O -,}} - OCF 2 -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 -CH 2 COO -, - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO—, —OCOC (CH ₃ ) ═CH—, —CH ₂ —CH (CH ₃ ) COO—, —OCOCH (CH ₃ ) —CH ₂ —, —OCH ₂ CH ₂ O—, or 2 to 20 represents an alkylene group, and one or two or more non-adjacent —CH ₂ — in the alkylene group may be substituted with —O—, —COO— or —OCO—, provided that K ⁱ¹ is (K In the case of -11), at least —CH ₂ is added to the mesogenic group. —CH ₂ COO—, —OCOCH ₂ —CH ₂ —, —CH═C (CH ₃ ) COO—, —OCOC (CH ₃ ) ═CH—, —CH ₂ —CH (CH ₃ ) COO—, —OCOCH ( Including any one of CH ₃ ) —CH ₂ —, —OCH ₂ CH ₂ O—,
A ^AL21 and Aa ¹²² each independently represents a divalent 6-membered ring aromatic group or a divalent 6-membered ring aliphatic group, a divalent unsubstituted 6-membered ring aromatic group, a divalent An unsubstituted 6-membered cycloaliphatic group or a hydrogen atom in these ring structures is unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom It is preferable that a divalent unsubstituted 6-membered aromatic group, a group in which a hydrogen atom in the ring structure is substituted with a fluorine atom, or a divalent unsubstituted 6-membered cyclic aliphatic group Preferably, the hydrogen atom on the substituent is preferably a 1,4-phenylene group, a 2,6-naphthalene group or a 1,4-cyclohexyl group, which may be substituted by a halogen atom, an alkyl group or an alkoxy group, one of the substituents is ^P i1 -Sp ⁱ - it has been replaced by,
If Z ^i1, ^{A AL21} and ^{Aa 122} is present in plural may each also being the same or different,
Sp ⁱ¹ preferably represents a linear alkylene group or a single bond having 1 to 18 carbon atoms, more preferably a linear alkylene group or a single bond having 2 to 15 carbon atoms, and more preferably a carbon atom. Represents a linear alkylene group or a single bond of several 3 to 12,
R ^al21 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group, or P ⁱ¹ —Sp ⁱ¹ —, and —CH ₂ — in the alkyl group represents —O —, —OCO—, or —COO— is preferable (where —O— is not continuous), more preferably a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or P ⁱ¹ —. Sp ⁱ¹ — represents —CH ₂ — in the alkyl group represents —O— or —OCO— (however, —O— is not continuous).

K ⁱ¹ represents a substituent represented by the following general formula (K-1) to general formula (K-11),

P ⁱ¹ represents a polymerizable group, and represents a substituent selected from the group represented by the following general formulas (P-1) to (P-15) (in the formula, the black dot on the right end represents a bond). To express.),

When there are a plurality of Z ⁱ¹ , Z ⁱ² , A ^al21 , m ⁱⁱⁱ¹ and / or A ^al22 , they may be the same or different from each other, provided that any one of A ⁱ¹ and A ⁱ² is at least When substituted with one P ⁱ¹ —Sp ⁱ¹ — and K ⁱ¹ is (K-11), Z ⁱⁱ¹ is at least —CH ₂ —CH ₂ COO—, —OCOCH ₂ —CH ₂ —, —CH ₂ Including —CH (CH ₃ ) COO—, —OCOCH (CH ₃ ) —CH ₂ —, —OCH ₂ CH ₂ O—,
m ⁱⁱⁱ¹ represents an integer of 1 to 5,
m ⁱⁱⁱ² represents an integer of 1 to 5,
G ⁱ¹ represents a divalent, trivalent or tetravalent branched structure, or a divalent, trivalent or tetravalent aliphatic or aromatic ring structure;
m ⁱⁱⁱ³ represents an integer smaller than the valence of G ⁱ¹ . )
Specifically, the following compounds are mentioned.

In addition, as a means for eliminating the alignment layer of the liquid crystal panel, when the liquid crystal composition containing the polymerizable compound is filled between the first substrate and the second substrate, the crystal composition is filled in a state of Tni or higher. And a method of curing the polymerizable compound by irradiating the liquid crystal composition containing the polymerizable compound with UV.

On the other hand, when a photo-alignment film is used as the alignment film 4, the photo-alignment 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 isomerized molecule or polymer thereof that isomerizes in response to light and is oriented substantially perpendicularly or parallel to the polarization axis;
(2) Photoresponsive dimerization-type molecules that form a crosslinked structure by dimerization in response to light, and (3) Photoresponsive decomposable polymers in which a polymer chain is cleaved in response to light. Among these, the photoresponsive isomerized molecule or the polymer (3) is particularly preferable from the viewpoints of sensitivity and orientation regulating ability.

[Light source]
Next, the light source part which comprises the liquid crystal display element of this invention has a light emitting element which light-emits ultraviolet or visible light. The light-emitting element is not particularly limited with respect to the wavelength region, but preferably has a main light emission peak in the blue region. For example, a light emitting diode (blue light emitting diode) having a main light emission peak in a wavelength region of 420 nm or more and 480 nm or less can be suitably used.

The light-emitting element (or light-emitting diode) according to the present invention is not particularly limited in the wavelength region, but preferably has a main light emission peak in the blue region. For example, a light emitting diode having a main emission peak in a wavelength region of 430 nm to 500 nm (420 nm to 480 nm) can be suitably used. A known light emitting diode having a main light emission peak in the blue region can be used. As a light emitting diode having a main light emission peak in a blue region, for example, a seed layer made of AlN formed on a sapphire substrate, an underlayer formed on the seed layer, a laminated semiconductor layer mainly composed of GaN, The thing provided with at least etc. is mentioned as an example. In addition, the stacked semiconductor layer may be configured by stacking a base layer, an n-type semiconductor layer, a light emitting layer, and a p-type semiconductor layer in this order from the substrate side.

Examples of the ultraviolet light source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, an electrodeless lamp, a metal halide lamp, a xenon arc lamp, and an LED. L is preferably an LED that generates ultraviolet light other than the LED having the main emission peak in the wavelength region of 420 nm to 480 nm.

In this specification, light having an emission center wavelength in the wavelength band of 420 to 480 nm is referred to as blue light, light having an emission center wavelength in the wavelength band of 500 to 560 nm is referred to as green light, and wavelength of 605 to 665 nm. The light having the emission center wavelength in the band is referred to as red light. Further, the ultraviolet light in this specification refers to light having an emission center wavelength in a wavelength band of 300 nm or more and less than 420 nm. Further, in the present specification, the “half-value width” refers to the width of the peak at the peak height ½.

(Polarizing layer)
As the polarizing layer used in the liquid crystal display element of the present invention, a known polarizing plate (polarizing layer) can be used. Examples thereof include a dichroic organic dye polarizer, a coating type polarizing layer, a wire grid type polarizer, or a cholesteric liquid crystal type polarizer. For example, the wire grid polarizer is formed on the first substrate, the second substrate, and the color filter, and is formed by any one of nanoimprint method, block copolymer method, E-beam lithography method, and glansing angle deposition method. It is preferable. Moreover, when forming a coating type polarizing layer, you may further provide the orientation layer demonstrated by this specification below. Therefore, when the polarizing layer which concerns on this invention is a coating type polarizing layer, it is preferable to have a coating type polarizing layer and an orientation layer.

(substrate)
The two substrates used in the liquid crystal display element of the present invention, specifically, the first substrate 2 and the second substrate 7 are made of a transparent material having flexibility such as glass or plastic. it can. 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 specific structure of the liquid crystal display element of the present invention composed of the elements described above will be described with reference to FIGS.

FIG. 12 shows a schematic diagram of a structure diagram of the electrode layer 3 of the liquid crystal display unit. More specifically, FIG. 12 is a schematic diagram showing the pixel portion in an equivalent circuit, and FIGS. 13 and 14 show the shape of the pixel electrode. It is a schematic diagram which shows an example. 13 to 14 are schematic views showing electrode structures of FFS type liquid crystal display elements as an example of the present embodiment. FIG. 15 is a schematic diagram showing an electrode structure of an IPS liquid crystal display element as an example of the present embodiment. Further, FIG. 18 is a schematic diagram showing an electrode structure of a VA liquid crystal display element as an example of the present embodiment. As shown in FIGS. 1 to 4, a liquid crystal display element is driven by providing the backlight unit as illumination means for illuminating the liquid crystal panel 10 from the back side.

In FIG. 13, 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)). The pixel electrode is disposed for each display pixel, and a slit-shaped opening is formed. The common electrode and the pixel electrode are transparent electrodes formed of, for example, ITO (Indium Tin Oxide), and the electrode layer 3 has a gate bus line GBL (extending along a row in which a plurality of display pixels are arranged in the display unit. 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 vicinity of a position where the gate bus line and the source bus line intersect. In addition, a thin film transistor is provided as a pixel switch. 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. Further, 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 driving means for driving a plurality of display pixels, and the gate driver and the source driver are arranged 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 an 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. 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 a thin film transistor in which the source and drain electrodes are electrically connected. The operations of the gate driver and the source driver are controlled by a display processing unit (also referred to as a control circuit) arranged 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 for reducing 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. . For example, the display processing unit according to the present invention includes a local dimming unit that divides the entire display screen into a plurality of sections and adjusts the intensity of the backlight light according to the brightness of the image displayed in each section. Also good.

FIG. 13 is a diagram illustrating a comb-shaped pixel electrode as an example of the shape of the pixel electrode, and is an enlarged plan view of a region surrounded by the II line of the electrode layer 3 formed on the substrate 2 in FIG. . As shown in FIG. 13, the electrode layer 3 including the thin film transistor formed on the surface of the first substrate 2 includes a plurality of gate bus lines 26 for supplying scanning signals and a plurality of gate bus lines 26 for supplying display signals. The source bus lines 25 are arranged in a matrix so as to cross each other. A unit pixel of the liquid crystal display device is formed by a region surrounded by the plurality of gate bus lines 26 and the plurality of source bus lines 25, and a pixel electrode 21 and a common electrode 22 are formed in the unit pixel. ing. A thin film transistor including a source electrode 27, a drain electrode 24, and a gate electrode 28 is provided in the vicinity of the intersection where the gate bus line 26 and the source bus line 25 intersect each other. The thin film transistor is connected to the pixel electrode 21 as a switch element that supplies a display signal to the pixel electrode 21. A common line 29 is provided in parallel with the gate bus line 26. 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 through an insulating layer 18 (not shown). 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. The “horizontal component of the shortest separation path” here means that the shortest separation path connecting the adjacent common electrode and the pixel electrode is decomposed into a horizontal direction with respect to the substrate and a vertical direction (= thickness direction) with respect to the substrate. Among the components, the component in the horizontal direction with respect to the substrate. Note that a storage capacitor for storing a display signal supplied through the source bus line 25 may be provided in a region surrounded by the plurality of gate bus lines 26 and the plurality of source bus lines 25.

FIG. 14 is a modification of FIG. 13 and shows a slit pixel electrode as an example of the shape of the pixel electrode. The pixel electrode 21 shown in FIG. 13 is formed by cutting out a substantially rectangular flat plate electrode at the center and both ends of the flat plate with a triangular cutout, and the other portions are cut out in a substantially rectangular frame shape. The shape is hollowed out at the part. The shape of the notch is not particularly limited, and a notch having a known shape such as an ellipse, a circle, a rectangle, a rhombus, a triangle, or a parallelogram can be used.

13 and 14 show only a pair of gate bus lines 26 and a pair of source bus lines 25 in one pixel.

FIG. 16 is one example of a cross-sectional view of the liquid crystal display element shown in FIG. 1 cut along the line III-III in FIG. 13 or FIG. The first substrate 2 having the alignment layer 4 and the electrode layer 3 including the thin film transistor formed on the surface thereof is separated from the second substrate 7 having the alignment layer 4 formed on the surface so that the alignment layers face each other with a predetermined gap G. This space is filled with a liquid crystal layer 5 containing a liquid crystal composition. A gate insulating film 12, a common electrode 22, a passivation film 18, a pixel electrode 21, and an alignment layer 4 are sequentially stacked on a part of the surface of the first substrate 2.

A preferred embodiment of the structure of the thin film transistor is provided, for example, as shown in FIG. 16 so as to cover the gate electrode 11 formed on the surface of the substrate 2 and the gate electrode 11 and cover the substantially entire surface of the substrate 2. A gate insulating layer 12, a semiconductor layer 13 formed on the surface of the gate insulating layer 12 so as to face the gate electrode 11, and a protective film provided so as to cover a part of the surface of the semiconductor layer 13 14, a drain electrode 16 provided so as to cover one side end of the protective layer 14 and the semiconductor layer 13 and to be in contact with the gate insulating layer 12 formed on the surface of the substrate 2, and the protection A source electrode 17 which covers the film 14 and the other side edge of the semiconductor layer 13 and is in contact with the gate insulating layer 12 formed on the surface of the substrate 2; It has a passivation film 18 provided so as to cover the electrode 16 and the source electrode 17, a. An anodic oxide film (not shown) may be formed on the surface of the gate electrode 11 for reasons such as eliminating a step with the gate electrode.

In the embodiment shown in FIGS. 13 and 14, the common electrode 22 is a flat electrode formed on almost the entire surface of the gate insulating layer 12, while the pixel electrode 21 is an insulating protective layer 18 covering the common electrode 22. It is a comb-shaped electrode formed on the 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 each other via the insulating protective layer 18. The pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), IZTO (Indium Zinc Tin Oxide), and the like. Since the pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material, the area opened by the unit pixel area increases, and the aperture ratio and transmittance increase.

Further, the pixel electrode 21 and the common electrode 22 have an interelectrode distance (also referred to as a minimum separation distance) R between the pixel electrode 21 and the common electrode 22 in order to form a fringe electric field between these electrodes. 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 in the horizontal direction on the substrate between the electrodes. In FIG. 12, since the flat common electrode 22 and the comb-shaped pixel electrode 21 are overlapped, an example in which the minimum separation distance (or interelectrode distance): R = 0 is shown, and the minimum separation distance R is The thickness of the liquid crystal layer between the first substrate 2 and the second substrate 7 (also referred to as a cell gap): smaller than G, and thus a fringe electric field E is formed. Therefore, the FFS type liquid crystal display element can use a horizontal electric field formed in a direction perpendicular to a line forming the comb shape of the pixel electrode 21 and a parabolic electric field. The electrode width of the comb-shaped portion of the pixel electrode 21: l and the width of the gap of the comb-shaped portion of the pixel electrode 21: m are such that all the 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 liquid crystal display element, which is a modification 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 FIGS. 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. First polarizing plate 1, first substrate 2, electrode layer 3, alignment layer 4, liquid crystal layer 5 containing a liquid crystal composition, alignment layer 4, color filter 6, and second substrate 7 And the second polarizing plate 8 are sequentially laminated.

FIG. 15 is an enlarged plan view of a part of the region surrounded by the II line of the electrode layer 3 formed on the first substrate 2 of FIG. 1 in the IPS liquid crystal display unit. As shown in FIG. 15, in a region surrounded by a plurality of gate bus lines 26 for supplying scanning signals and a plurality of source bus lines 25 for supplying display signals (in a unit pixel), a comb-tooth shape is formed. The first electrode (for example, pixel electrode) 21 and the comb-shaped second electrode (for example, common electrode) 22 are loosely engaged with each other (the two electrodes are spaced apart and meshed with each other while maintaining a certain distance). Is 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 each other. The thin film transistor is connected to the first electrode 21 as a switch element that supplies a display signal to the first electrode 21. Further, a common line (V _com ) 29 is provided in parallel with the gate bus line 26. The common line 29 is connected to the second electrode 22 in order to supply a common signal to the second electrode 22.

FIG. 17 is a cross-sectional view of the IPS liquid crystal panel cut in the direction of the line III-III in FIG. On the first substrate 2, a gate insulating layer 32 is provided so as to cover the gate bus line 26 (not shown) and to cover substantially the entire surface of the first substrate 2, and on the surface of the gate insulating layer 32. The formed insulating protective layer 31 is provided, and on the insulating protective film 31, a first electrode (pixel electrode) 21 and a second electrode (common electrode) 22 are provided separately. The insulating protective layer 31 is a layer having an insulating function, and is formed of silicon nitride, silicon dioxide, silicon oxynitride film, or the like.

In the embodiment as shown in FIG. 15 and FIG. 17, the first electrode 21 and the second electrode 22 are comb-shaped electrodes formed on the insulating protective layer 31, that is, on the same layer. It is provided in a state of being separated and meshed. In the IPS liquid crystal display unit, the interelectrode 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 distance between electrodes: G represents the shortest distance in the horizontal direction on the substrate between the first electrode 21 and the second electrode 22. In the example shown in FIGS. 15 and 17, the first electrode 21 is used. And a distance in the horizontal direction with respect to the line formed by alternately fitting the second electrode 22 and the second electrode 22. 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 The distance (namely, cell gap) between the alignment layers 4 (outermost surfaces) provided on each of the substrate 2 and the second substrate 7 and the thickness of the liquid crystal layer are represented.

On the other hand, in the aforementioned FFS type liquid crystal display unit, 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 equal to or more than the shortest distance in the horizontal direction with respect to the substrate. The distance between the two electrodes 22 is less than the shortest distance in the horizontal direction on 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 liquid crystal display element drives liquid crystal molecules by using an electric field in a horizontal direction with respect to a 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 such that all the liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field.

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

The configuration of the liquid crystal panel 10 in the liquid crystal display element according to the present invention includes a second electrode having a transparent electrode (layer) 3 ′ (also referred to as a common electrode 3 ′) made of a transparent conductive material, as shown in FIG. A first substrate 2 including a pixel electrode and an electrode layer 3 on which a thin film transistor for controlling the pixel electrode included in each pixel is formed; and between the first substrate 2 and the second substrate 7 A liquid crystal display element having a liquid crystal composition (or a liquid crystal layer 5) sandwiched between the substrates, wherein 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. 19, the first substrate 2 and the second substrate 7 may be sandwiched between a pair of

polarizing plates

1 and 8. Further, in FIG. 19, 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 surfaces of the transparent electrodes (layers) 3 and 3 ′ so as to be in direct contact with the liquid crystal composition constituting the liquid crystal layer 5 adjacent to the liquid crystal layer 5 according to the present invention. Also good.

FIG. 18 is a diagram illustrating an inverted L-shaped pixel electrode as an example of the shape of the pixel electrode 21, and an area surrounded by the II line of the electrode layer 3 formed on the substrate 2 in FIG. 3 is enlarged. It is a top view. 13, 14 and 15, the pixel electrode 21 is formed in an inverted L shape over substantially the entire area surrounded by the gate bus line 26 and the source bus line 25. The shape is not limited.

Unlike the IPS type and FFS type, the liquid crystal display part of the vertical alignment type liquid crystal display element is formed with a common electrode 22 (not shown) facing and separating from the pixel electrode 21. In other words, the pixel electrode 21 and the common electrode 22 are formed on different substrates. On the other hand, in the aforementioned FFS or IPS type liquid crystal display element, the pixel electrode 21 and the common electrode 22 are formed on the same substrate.

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 from the viewpoint of preventing light leakage.

FIG. 19 is a cross-sectional view of the liquid crystal display element shown in FIG. 2 taken 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 has a first polarizing plate 1, a first substrate 2, an electrode layer (also referred to as a thin film transistor layer) 3 including a thin film transistor, and a liquid crystal vertically aligned. 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. It is a configuration.

The vertical alignment type liquid crystal display element described in detail above is preferably one in which a pixel is divided and aligned having a multi-domain in which the pixel is divided into two to eight in order to improve the viewing angle dependency. Such divisional alignment may be produced by mask rubbing the alignment film 4,
1) means for forming ribs on both the first substrate 2 side and the second substrate 7;
2) means for forming ribs on the second substrate 7 using electrode slits in the first pixel electrode 21;
3) Means for forming a rib on the second substrate 7 using a fine slit electrode for the first pixel electrode 21;
4) Means using slit electrodes for the first pixel electrode 21 and the second common electrode 22;
5) Means for using a fine slit electrode for the first pixel electrode 21 and forming a pretilt in the liquid crystal with a polymer,
6) It is a multi-domain type VA device in which the alignment orientation of the liquid crystal is defined by means using a so-called photo-alignment film capable of imparting a uniform alignment orientation to the liquid crystal by irradiation with linearly polarized ultraviolet rays as the alignment film. Is preferable because it is easy. Among these, in particular, it is easy to form a polymer network of the liquid crystal layer 5, 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). It is easy to control the alignment easy axis directions to the same or substantially the same direction. Therefore, it was obtained by means of 5) means for forming a pretilt in liquid crystal with a polymer, or means for using 6) a photo-alignment film. A liquid crystal display element is preferable.

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. 24 is preferable from the viewpoint of stability of the orientation direction. The fishbone type electrode will be described in detail with reference to FIG. 24. The electrode is made of a transparent electrode such as ITO, and is provided with a slit portion 512c from which a part of the electrode material (ITO) is removed. A slit portion 512c having a cross shape connecting the midpoints of the opposing sides of the rectangular cell and having a width of about 3 to 5 μm functions as an alignment regulating structure, and extends from the slit portion 512c in an oblique 45 ° direction and has a width of 5 μm. A plurality of 512c are formed with a pitch of 8 μm, and these function as an auxiliary orientation control factor that suppresses disturbance in the azimuth direction during tilting. The width of the display pixel electrode is 3 μm, for example. In FIG. 24, the pixel trunk electrode 512a and the pixel branch electrode 512b have an angle of 45 degrees, and have a structure in which the branch electrodes extend in four directions that differ by 90 degrees with respect to the center of the pixel. Yes. The liquid crystal molecules are tilted when a voltage is applied, but tilted so that the orientation of the tilted alignment coincides with these four directions. Therefore, a four-divided domain is formed in one pixel to increase the display viewing angle. Can be wide.

The liquid crystal display element according to the present invention may have a local dimming technique for improving the contrast by controlling the brightness of the backlight unit 100 for each of a plurality of sections smaller than the number of pixels of the liquid crystal.

As a local dimming method, it is possible to use a plurality of light emitting elements L as light sources in a specific area on the liquid crystal panel and control each light emitting element L according to the luminance of the display area. In this case, the plurality of light emitting elements L may be arranged in a planar shape, or may be arranged in a line on one side of the liquid crystal panel 10.

In the case of a structure having the light guide portion 102 of the backlight unit 100 and the liquid crystal panel 10 as the local dimming method, the light guide plate (and / or the light diffusing plate) and the substrate on the light source side of the liquid crystal panel In the meantime, the light guide unit 102 may include a control layer that controls the amount of light of the backlight for each specific region smaller than the number of pixels of the liquid crystal.

As a method for controlling the amount of light of the backlight, a liquid crystal element having fewer than the number of pixels of the liquid crystal may be further included, and various existing methods can be used as the liquid crystal element. An LCD layer containing is preferable in terms of transmittance. The layer containing the (nematic) liquid crystal in which the polymer network is formed (if necessary, the layer containing the (nematic) liquid crystal in which the polymer network is sandwiched between a pair of transparent electrodes) scatters light when the voltage is OFF, In order to transmit light when the voltage is turned on, an LCD layer including a liquid crystal formed with a polymer network partitioned so as to divide the entire display screen into a plurality of partitions, a light guide plate (and / or a light diffusion plate) and a liquid crystal panel Local dimming can be realized by providing it between the substrate on the light source side.

The liquid crystal display element 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. Among these, VA, IPS, FFS, VA-TN, TN, and ECB are particularly preferable. The liquid crystal display element of the present invention can be distinguished from a PSA (Polymer Sustained Alignment) type liquid crystal display element having a polymer or copolymer on the alignment film in that a polymer network is formed in the liquid crystal layer.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the examples, the following abbreviations are used for describing the compounds. N represents a natural number.

"N-type compounds"
(Side chain)
-N -C _n H _{2n + 1} linear alkyl group with n carbon atoms n- C _n H _{2n + 1} -linear alkyl group with n carbon atoms -On -OC _n H _{2n + 1} linear chain with n carbon atoms -Like alkoxyl group nO- C _n H _{2n + 1} O- linear alkoxyl group having n carbon atoms -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-
-2V1 -CH ₂ -CH ₂ -CH = CH-CH ₃
1V2- CH ₃ —CH═CH—CH ₂ —CH ₂
(Linking group)
-N- -C _n H _2n-
—NO— —C _n H _2n —O—
—On— —O—C _n H _2n —
—COO— —C (═O) —O—
-OCO- -OC (= O)-
—CF ₂ O——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 each example is Irgacure 651.

The characteristics 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. η: Viscosity at 25 ° C. (mPa · s)
γ ₁ : rotational viscosity at 25 ° C. (mPa · s)
VHR measurement (voltage holding ratio (%) at 333K under conditions of frequency 60Hz and applied voltage 1V)
LED light resistance test with main emission peak at 450 nm:
The VHR before and after the visible light LED light source having a main emission peak at 450 nm of 20,000 cd / m ² was exposed to the liquid crystal panel for 1 week was measured.

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

(Adjustment of polymerizable liquid crystal composition)
Liquid crystal compositions were prepared as N-type liquid crystal compositions according to the formulations shown in Tables 1 to 15 below, then heated to 60 ° C., and polymerizable monomers [(P2-1M), (P2- 2M) or (P4-4M)] was mixed and dissolved. It was confirmed with a polarizing microscope that each polymerizable liquid crystal composition was uniformly dissolved at room temperature to show a nematic liquid crystal phase. A polymerizable photoinitiator (Irgacure 651) was mixed with this solution to prepare a polymerizable liquid crystal composition.

[Liquid Crystal Panel, Backlight Unit, and Liquid Crystal Display Element Manufacturing Method]
(1) Production of liquid crystal panel (Manufacture of light conversion layer or color filter)
(A) Preparation of red light-emitting nanocrystal-containing composition, green light-emitting nanocrystal-containing composition, and blue (light-emitting nanocrystal-containing) composition (A) Red light-emitting nanocrystal-containing composition, green light-emitting nanocrystal Preparation of containing composition and blue (containing nanocrystal for light emission) composition [containing nanocrystal for red light emission]
30 parts by mass of red light emitting nanocrystals, 30 parts by mass of dipentaerystol hexaacrylate (KAYARAD (trade name) DPHA, manufactured by Nippon Kayaku Co., Ltd.) and a polymerization initiator (Irgacure-907 (trade name)) BASF 5 parts by mass) and 30 parts by mass of a polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.) are mixed, and propylene glycol monomethyl ether acetate is mixed so that the solid content becomes 20% by mass. The mixture was stirred with a dispersion stirrer and filtered through a filter having a pore size of 1.0 μm to obtain a nanocrystal-containing composition for red light emission.

[Red coloring composition]
10 parts of a red pigment (CI Pigment Red 254 having a water content of 0.3% and a specific electric conductivity of 30 μS / cm) are placed in a plastic bottle, 55 parts of propylene glycol monomethyl ether acetate, Dispersic LPN21116 (manufactured by Big Chemie Co., Ltd.) 7 0.0 parts, 0.3-0.4 mmφ Sepul beads were added, and dispersed for 4 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.), followed by filtration with a 5 μm filter to obtain a pigment dispersion. 75.00 parts of this pigment dispersion, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerystol hexaacrylate (KAYARAD (trade name) DPHA, Nippon Kayaku) 5.00 parts of Yakuhin Co., Ltd., 1.00 parts of benzophenone (KAYACURE (trade name) BP-100, Nippon Kayaku Co., Ltd.) and 13.5 parts of Euker Ester EEP are stirred with a dispersion stirrer. Filtration through a 0 μm filter gave a red pigment coloring composition 1.

The water content of the pigment is based on JIS K5101-16-1 (Pigment test method-Part 16: Water content-Section 1: Boiling extraction method).

In particular,
1. Weigh 5.00 g of pigment correctly in a 500 mL hard beaker, add 200 mL of ion-exchanged water (conductivity 5 μS / cm or less, pH = 7.0 ± 1.0) in small portions, and add 5 mL of reagent primary methanol. After wetting well, add the whole amount and boil for 5 minutes.
2. This was cooled to room temperature, transferred to a 250 mL graduated cylinder, further added with the above ion-exchanged water to 250 mL, and stirred well to make a filter paper No. 1 manufactured by Advantech. Filter at 5C.
3. Discard the first approximately 50 mL of the filtrate, and weigh out 100 mL from the remainder with a graduated cylinder and transfer to an evaporating dish of known mass. Rinse the filtrate adhering to the graduated cylinder into the evaporating dish with a small amount of ion exchange water.
4). The evaporating dish is evaporated to dryness on a water bath, dried in a drier kept at 105 to 110 ° C. for 2 hours, placed in a desiccator, allowed to cool, and weighed to determine the remaining evaporation.
5). The water content is calculated by the following formula.

Water content of pigment (%) = remaining evaporation (g) × 2.5 / mass of pigment (g) × 100
The specific conductivity of the pigment was measured using a conductivity meter (such as CM-30V manufactured by Toa DKK Corporation) after measuring the specific conductivity of ion-exchanged water, and 100 mL was measured with a graduated cylinder in 3 above. The filtrate obtained is measured using the same conductivity meter, and the measured value is corrected by the following formula.

Specific conductivity of pigment = specific conductivity of filtrate-specific conductivity of ion-exchanged water used

[Nanocrystal-containing composition for green light emission]
Instead of the red light emitting nanocrystal of the red light emitting nanocrystal-containing composition, a green light emitting nanocrystal-containing composition was obtained in the same manner as described above using a green light emitting nanocrystal.

[Green coloring composition]
Instead of 10 parts of the red pigment 1 of the red

pigment coloring composition

1, 6 parts of green pigment 1 (CI Pigment Green 36 having a water content of 0.3% and a specific conductivity of 40 μS / cm) and a yellow pigment 2 (water solution) Using a pigment (water content: 0.4%, specific conductivity: 50 μS / cm) mixed with 4 parts of CI Pigment Yellow 150 (0.6% min, specific conductivity: 70 μS / cm) in the same manner as above. Thus, a green coloring composition was obtained.

[Blue (containing nanocrystals for light emission) composition]
The blue light-emitting nanocrystal-containing composition is replaced with the blue light-emitting nanocrystal instead of the red light-emitting nanocrystal of the red light-emitting nanocrystal-containing composition 1. A crystal-containing composition was obtained.

[Blue Coloring Composition 1]
The blue coloring composition was prepared by mixing propylene glycol monomethyl ether acetate, Dispersic LPN21116 (manufactured by Big Chemie Co., Ltd.), 0.3-0.4 mmφ zirconia beads “ER-120S” manufactured by Saint-Gobain, and paint conditioner (Toyo After dispersion for 4 hours by Seiki Co., Ltd., a 1 μm filter was used to prepare a dispersion. Next, 75 parts by mass of the dispersion, 5.5 parts by mass of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerystol hexaacrylate (KAYARAD (trade name) DPHA, Japan) 5 parts by mass of Kayaku Co., Ltd.), 1 part by mass of benzophenone (KAYACURE ™ BP-100, Nippon Kayaku Co., Ltd.) and 13.5 parts by mass of Euker Ester EEP are stirred with a dispersion stirrer. Filtration through a 0 μm filter gave a blue colored composition 1.

[Blue Coloring Composition 2]
In the blue coloring composition, blue dye 1 (CI Solvent Blue 7) is put in a polybin, propylene glycol monomethyl ether acetate, Dispersic LPN21116 (manufactured by Big Chemie Co., Ltd.), 0.3-0. 4 mmφ zirconia beads “ER-120S” was added and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, followed by filtration with a 1 μm filter to obtain a pigment dispersion.

75 parts by mass of this pigment dispersion, 5.5 parts by mass of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerystol hexaacrylate (KAYARAD (trade name) DPHA, Nippon Kayaku) 5 parts by mass of Yakuhin Co., Ltd., 1.00 parts of benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Euker Ester EEP are stirred with a dispersion stirrer, and the pore size is 1.0 μm. The blue colored composition 2 was obtained by filtering with a filter.

[Nanocrystal-containing composition for yellow light emission]
The yellow light-emitting nanocrystal-containing composition was replaced with the red light-emitting nanocrystal, and a yellow light-emitting nanocrystal was used in the same manner as described above to obtain a yellow light-emitting nanocrystal-containing composition.

[Yellow coloring composition]
Instead of the red pigment of the red pigment composition, yellow pigment (CI Pigment Yellow 150 having a water content of 0.6% and a specific conductivity of 70 μS / cm) was used in the same manner as above for yellow coloring. A composition was obtained.

(B) Manufacture of light conversion layer The nanocrystal containing composition for red light emission was apply | coated to the glass substrate in which the black matrix was previously formed so that it might become a film thickness of 2 micrometers by spin coating. After drying at 70 ° C. for 20 minutes, striped pattern exposure was performed using a photomask with ultraviolet rays using an exposure machine equipped with an ultrahigh pressure mercury lamp. Spray development with an alkali developer for 90 seconds, washing with ion exchange water, and air drying. Further, post-baking was performed at 180 ° C. for 30 minutes in a clean oven to form red pixels, which are striped colored layers, on a transparent substrate.

Next, the nanocrystal-containing composition for green light emission is similarly applied by spin coating so that the film thickness becomes 2 μm. After drying, the striped colored layer was exposed and developed at a place different from the above-mentioned red pixel by an exposure machine, thereby forming a green pixel adjacent to the above-mentioned red pixel.

Hereinafter, the light conversion layer 1 having stripe-like pixels of three colors of red, green, and blue, using the light emitting nanocrystal-containing composition or the coloring composition so as to have the configuration shown in Table 1 below. A light conversion layer 2 having stripe-like pixels of 3, 5 or four colors of red, green, blue, and yellow was obtained.

Further, a light conversion layer 4 in which a blue layer is formed on the entire surface of the stripe-shaped pixels of three colors of red, green, and blue by applying the blue coloring composition 2 on the entire surface of the light conversion layer 1 and irradiating with ultraviolet rays. Got.

(Method of manufacturing an electrode substrate having an in-cell polarizing layer)
On the light conversion layer 1, an aqueous solution of “Poval 103” manufactured by Kuraray Co., Ltd. (solid content concentration: 4% by mass) was applied and dried, followed by rubbing treatment.

Next, on the rubbing surface, 0.03 parts by mass of Megafac F-554 (manufactured by DIC Corporation), 1 part by mass of an azo dye of the following formula (az-1), and an azo dye of the following formula (az-2) 1 part by mass,

98 parts by mass of chloroform, 2 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), 2 parts by mass of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), Irgacure A substrate having a polarizing layer and a light conversion layer is prepared by applying and drying a polarizing layer coating solution consisting of 0.06 parts by mass of 907 (manufactured by Ciba Specialty Chemicals) and Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.). Created. Thereafter, ITO was deposited by sputtering to produce a counter substrate (= second (electrode) substrate).

(VA type liquid crystal panel 1)
After forming a polyimide-based vertical alignment layer on ITO of the second (electrode) substrate and a transparent electrode of the first substrate, respectively, the first substrate on which the transparent electrode and the polyimide-based vertical alignment layer are formed, The second (electrode) substrate on which the polyimide-based vertical alignment layer is formed is disposed so that the alignment layers face each other and the alignment direction of the alignment layer is an antiparallel direction (180 °). The peripheral part was bonded with a sealing agent in a state where a constant gap (4 μm) was maintained between the substrates. Next, the polymerizable liquid crystal compositions of Examples 1 to 27 described below are filled into the cell gap defined by the alignment layer surface and the sealing agent by vacuum injection, and a polarizing plate is attached to the first substrate. By combining them, a VA type liquid crystal panel 1 was produced. The liquid crystal panel thus fabricated was used as an evaluation element, and VHR measurement and display quality evaluation for UV were performed.

The results are shown in Tables 2 to 16 below.

While applying a rectangular wave voltage of 2.43 V at a frequency of 1 kHz to this liquid crystal panel, irradiation with ultraviolet light having an irradiation intensity of 15 mW / cm ² for 12 seconds was performed using a light source of an ultraviolet LED with a wavelength of 365 nm, and then ultraviolet irradiation was continued. In this state, the voltage was set to 0V to return to the vertical alignment, and ultraviolet rays were irradiated for 68 seconds from the time when the voltage was returned to 0V. The liquid crystal panel thus fabricated was used as an evaluation element, and VHR measurement and display quality evaluation for UV were performed.

The results are shown in the following table.

In Tables 2 to 16 above, the decrease rate is “the initial (= 1 W before the light resistance test) VHR value / 1 W (= 1 week) after the light resistance test”. Therefore, the closer the reduction rate is to 1, the more stable it is to light having a main emission peak at 450 nm or light having a main emission peak at 385 nm, so that the light resistance is excellent, and visible light or ultraviolet light having a short wavelength is excellent. It is considered that it is difficult to deteriorate even for such high energy rays.

From the above experimental data, it is confirmed that composition example 2 has the lowest decrease rate when irradiated with light having a main emission peak at 450 nm for one week. In addition, when the light having the main emission peak at 385 nm was irradiated for 60 seconds, it was confirmed that Examples 2, 11 and 20 had the lowest reduction rate. On the other hand, when γ1 related to the high-speed response of the liquid crystal display element was observed, it was confirmed that Examples 3, 12, and 21 were the highest. The cause of the former is considered to be related to the fact that it contains two or more liquid crystal compounds including a condensed ring (naphthalene) and thus easily absorbs light. In addition, the latter is considered to be due to the increase in viscosity because the liquid crystal compound contains two or more rings including a chroman ring.

Next, the polymerizable liquid crystal composition described in Examples 1, 10, and 19 was applied to the VA liquid crystal panel 2 in which the gap (4 μm) of the VA liquid crystal panel 1 was changed to the gap (3.5 μm), and the VA liquid crystal. The transmittance was simulated using the VA liquid crystal panel 3 in which the gap (4 μm) of the panel 1 was changed to the gap (2.8 μm) (using LCD Master manufactured by Shintech Co., Ltd.). The results are shown below.

From the above results, it was confirmed that when the retardation was changed from 325 nm to 260 nm, the transmittance was improved by about 20%.

Retardation (Re) is expressed by the following formula (1).

(In the above formula (1), Δn represents the refractive index anisotropy at 589 nm, and d represents the cell thickness (μm) of the liquid crystal layer of the liquid crystal display element.)
Similarly, it is confirmed that the transmittance is improved in Examples 2 to 9, 11 to 18, and 20 to 27. Therefore, it is considered that the transmittance is improved in the range of 220 to 300 nm.

In Examples 8, 17, and 26, the initial VHR is lower than that of the other composition examples. Therefore, the antioxidant of the following formula (III-22) is used with respect to 100 parts by mass of the liquid crystal composition of Composition Example 8. Was added in an amount of 0.03 parts by mass.

As a result, the initial VHR was 98% or more, and the LED light resistance test having the main emission peak at 450 nm and the LED light resistance test having the main emission peak at 385 nm were confirmed. The rate of decrease is shown in Table 4 above. The result was almost the same as the value.

(Manufacture of VA type liquid crystal panel 4)
The first substrate on which the transparent electrode is formed and the second transparent electrode substrate on which the light conversion layer 1 having the in-cell polarizing layer on the surface is disposed so that the respective electrodes face each other. The peripheral part was bonded with a sealant in a state where a constant gap (4 μm) was maintained between the substrates. Next, in the cell gap defined by the alignment layer surface and the sealing agent, the spontaneous alignment agent (the following formula (al-1)) 2 with respect to the polymerizable liquid crystal composition of Example 1 (100 parts by mass) 2 Parts by mass

The added liquid crystal composition was filled by a vacuum injection method, and a polarizing plate was bonded onto the first substrate, whereby a VA liquid crystal panel 4 was produced.

(Manufacture of VA type liquid crystal panel 5)
The first substrate on which the transparent electrode is formed and the second transparent electrode substrate on which the light conversion layer 1 having the surface of the in-cell polarizing layer is formed are arranged so that the respective electrodes face each other. The peripheral part was bonded with a sealing agent in a state where a constant gap (4 μm) was maintained between the substrates. Next, in the cell gap defined by the alignment layer surface and the sealing agent, the spontaneous alignment agent (formula (P-1-2) below) is used with respect to the polymerizable liquid crystal composition of Example 1 (100 parts by mass). 2 parts by mass

The added liquid crystal composition was filled by a vacuum injection method, and a polarizing plate was bonded to the first substrate, whereby a VA liquid crystal panel 5 was produced.

(Manufacture of VA liquid crystal panel 6)
On the transparent electrode formed on the first substrate, a vertical alignment layer solution including the vertical alignment layer solution used in Example 22 of International Publication No. 2013/002260 pamphlet is formed by spin coating, and then dried. An alignment layer having a thickness of 0.1 μm was formed. Similarly, an alignment layer was formed on the surface of the second transparent electrode substrate on which the light conversion layer 1 having the polarizing layer on the surface was formed. The first substrate on which the transparent electrode and the alignment layer are formed and the second (electrode) substrate, which is the counter substrate on which the light conversion layer 1 is formed, are opposed to each other, and the alignment direction of the alignment layer is The peripheral portions were bonded together with a sealant in a state of being arranged in an antiparallel direction (180 °) and maintaining a constant gap (4 μm) between the two substrates. Next, the polymerizable liquid crystal composition of Example 1 below is filled into the cell gap defined by the alignment layer surface and the sealing agent by vacuum injection, and the polarizing plate is bonded onto the first substrate. Thus, a VA type liquid crystal panel 6 was produced.

(IPS liquid crystal panel)
An alignment layer solution was formed on the pair of comb-shaped electrodes formed on the first substrate by a spin coating method to form an alignment layer. A first substrate on which a comb-shaped transparent electrode and an alignment layer are formed; and an alignment layer, the in-cell polarizing layer, the light conversion layer 1, and a second substrate on which a planarizing film is formed on the light conversion layer 1. The alignment layers face each other and are arranged so that the direction of linearly polarized light irradiation or rubbing in the horizontal direction is the anti-parallel direction (180 °), and a constant gap (4 μm) is provided between the two substrates. In the state kept, the peripheral part was pasted together with a sealant. Next, the polymerizable liquid crystal composition of Example 6 (liquid crystal composition 6) is filled into the cell gap defined by the alignment layer surface and the sealing agent by a vacuum injection method, and then the pair of polarizing plates is first bonded. An IPS type liquid crystal panel was bonded to the substrate and the second substrate.

(FFS type liquid crystal panel)
After forming a flat common electrode on the first transparent substrate, an insulating layer film is formed, a transparent comb electrode is further formed on the insulating layer film, and an alignment layer solution is then applied on the transparent comb electrode. A first electrode substrate was formed by spin coating. The alignment layer was formed in the same manner on the second substrate on which the alignment layer, the in-cell polarizing layer, the light conversion layer 1 and the planarizing film were formed. Next, the first substrate on which the comb-shaped transparent electrode and the alignment layer are formed, and the alignment layer, the polarizing layer, the light conversion layer 1, and the second substrate on which the planarizing film is formed on the light conversion layer 1, Are arranged in such a way that the direction where the linearly polarized light is radiated or rubbed is in the anti-parallel direction (180 °) and a constant gap (4 μm) is maintained between the two substrates. Were pasted together with a sealant. Next, the polymerizable liquid crystal composition of Example 9 was filled into the cell gap partitioned by the alignment layer surface and the sealing agent by a dropping method, to produce an FFS type liquid crystal panel.

(2) Production of backlight unit (Production of backlight unit 1)
A blue LED light source was installed at the end of one side of the light guide plate, the portion excluding the irradiated surface was covered with a reflective sheet, and a diffusion sheet was placed on the irradiation side of the light guide plate to produce a backlight unit 1.

(Preparation of backlight unit 2)
A blue LED is arranged in a lattice pattern on the lower reflection plate that scatters and reflects light, a diffusion plate is arranged immediately above the irradiation side, and a diffusion sheet is further arranged on the irradiation side to produce a backlight unit 2. .

(3) Production of liquid crystal display element and measurement of color reproduction region The above-obtained

backlight units

1 and 2 are attached to the obtained VA type liquid crystal panel 1 and VA type liquid crystal panel 2, and the color reproduction region is set. It was measured. As a result, it was confirmed that the color reproduction region was expanded in the former in both the liquid crystal display element having the light conversion unit and the conventional liquid crystal display element not having the light conversion unit.

Similarly, the

backlight units

1 and 2 prepared above were attached to the IPS liquid crystal panel (on-cell) and IPS liquid crystal panel (in-cell) obtained above, and the color reproduction region was measured. As a result, it was confirmed that the color reproducible region was expanded in the former in both the liquid crystal display element having the light conversion unit and the conventional liquid crystal display element not having the light conversion unit.

The backlight units 1 to 4 prepared above were attached to the obtained FFS type liquid crystal panel (on-cell) and FFS type liquid crystal panel (in-cell), and the color reproduction area was measured. As a result, it was confirmed that the color reproducible region was expanded in the former in both the liquid crystal display element having the light conversion unit and the conventional liquid crystal display element not having the light conversion unit.

1000: Liquid crystal display element 100: Backlight unit (101: light source unit, 102: light guide unit, 103: light conversion unit)
101: light source part (L: light emitting element (105: light emitting diode, 110: light source substrate), 112a, b: fixing member)
102: Light guide section (106: diffusion plate, 104: light guide plate)
103: light conversion unit 110: light source substrate 111: transparent filling container 112a, b: fixing member 113: recessed container SUB1: (transparent) electrode substrate SUB2: (transparent) substrate (including a case where electrodes are provided)
SUB3: (Transparent) substrate NC: Nanocrystal for light emission (compound semiconductor)
DESCRIPTION OF SYMBOLS 1, 8: Polarizing layer 2, 7: Transparent substrate 3: 1st electrode layer 3 ': 2nd electrode layer 4: Alignment film 5: Liquid crystal layer 6: Color filter (The case where the pigment | dye is contained in resin is also included. )
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

Claims

A pair of substrates provided so that the first substrate and the second substrate are opposed to 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 light source unit including a light emitting element;
It has three primary color pixels of red (R), green (G), and blue (B), and red (R), green (G), and blue (B) by light from the light source unit incident on at least one of the three primary colors. A light conversion layer containing a light-emitting nanocrystal having an emission spectrum,
The liquid crystal layer comprises a polymer network (A) and a 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 an alkyl group having 2 to 8 carbon atoms. A alkenyloxy group, A represents a 1,4-phenylene group or trans-1,4-cyclohexylene group, and n represents 0 or 1). A liquid crystal display element comprising the composition (B).
The light conversion layer has a black matrix and contains a first light emitting nanocrystal that absorbs blue light and emits red light and a second light emitting nanocrystal that absorbs blue light and emits green light. The liquid crystal display element according to claim 1, wherein the light emitting element has an emission spectrum in a blue region.
The display element according to claim 2, wherein light emitted from the light source unit is blue light, and a blue pixel region forming a blue pixel in the light conversion layer transmits the blue light.
The light conversion layer has a black matrix, absorbs ultraviolet light and emits red light, a third light emitting nanocrystal, absorbs ultraviolet light and emits green light, and emits green light and ultraviolet light. The liquid crystal display element according to claim 1, comprising a fifth light-emitting nanocrystal that absorbs light and emits blue light, and the light-emitting element has an emission spectrum in an ultraviolet region.
5. The liquid crystal display element according to claim 1, wherein the light conversion layer is provided on a substrate side facing the substrate on the light source unit side.
The display element according to any one of claims 1 to 5, wherein at least one polarizing plate is sandwiched between the first substrate and the second substrate.
The liquid crystal display element according to any one of claims 1 to 6, wherein a half-value width of at least one emission spectrum in a red (R), green (G), and blue (B) region is 20 to 50 nm.
The nanocrystal for light emission has a core including at least one or more first semiconductor materials, and a shell that covers the core and includes a second semiconductor material that is the same as or different from the core. Item 8. The liquid crystal display device according to any one of items 1 to 7.
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 Or the liquid crystal display element of Claim 8 which is 2 or more types.
2. The liquid crystal display according to claim 1, wherein in the liquid crystal layer, the optical axis direction or the easy axis direction of the polymer network (A) is the same as the easy axis direction of the liquid crystal composition (B). element.
The liquid crystal display according to claim 1 or 10, wherein the liquid crystal layer is formed by polymerizing a polymerizable liquid crystal composition containing the polymerizable monomer component (a) and the liquid crystal composition (B) as essential components. element.
12. The liquid crystal layer is obtained by polymerizing a polymerizable liquid crystal composition having 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 element as described.
The liquid crystal display element according to claim 11, 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.
The liquid crystal according to claim 1, wherein the liquid crystal molecules constituting the liquid crystal material (B) with respect to the transparent substrate are formed so as to form a pretilt angle of 0.1 to 30 ° with respect to the normal direction of the substrate. Display element.
The liquid crystal display element according to claim 1 or 10, 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) is represented by the following general formula (P1)

(In the formula, 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 with a halogen atom, or a hydrogen atom in which a hydrogen atom is substituted with a halogen atom) A suitable 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 with a halogen atom, or 1 to carbon atoms in which a hydrogen atom may be substituted with a halogen atom 15 alkenyloxy groups or -Sp p12 -R p12 ,
R p11 and R p12 are each independently the following formulas (RP11-1) to (RP11-8)

(Wherein, * represents a bonding point), and in the formulas (RP11-1) to (RP11-8), R P111 to R P112 are independently of each other 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 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 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) 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 each independently represents a hydrogen atom or 1 to 4 in which tm12 represents an integer of 1 to 4).
M p11 , M p12 and M p13 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, 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, A halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, a nitro group or —Sp p11 —R p11 may be substituted with the same meaning, mp12 represents 1 or 2, and mp13 to mp14 each independently represent 0, 1, 2 or 3, mp11 and mp15 represents an 1, 2 or 3 independently, they when Z pi 1 there are a plurality of independently identical or different And 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. And 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 are present. In some cases, they may be the same or different. When a plurality of Mp13 are present, they may be the same or different. The liquid crystal display element according to claim 11, which is represented by:
In addition to the compound represented by the general formula (i), the liquid crystal composition (B) includes the following general formulas (N-1), (N-2), (N-3) and (N-4)

(In the formula, 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 a group having 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. A structural portion having a chemical structure substituted by —, an alkyl group having 1 to 8 carbon atoms, or one or non-adjacent two or more —CH 2 — in an alkyl chain having 2 to 8 carbon atoms. A structural moiety having a chemical structure each independently 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) a 1,4-cyclohexylene group,
(B) a divalent organic group having a structure in which one —CH 2 — existing in a 1,4-cyclohexylene structure or two or more non-adjacent —CH 2 — is replaced by —O— 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 A structure in which one —CH═ present in a 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure or two or more non-adjacent —CH═ are replaced by —N═ And (g) a group selected from the group consisting of 1,4-cyclohexenylene group,
The group (a), group (b), group (c), group (d), group (e), group (f), and group (g) are each independently a cyano group, a fluorine atom or chlorine. May be substituted with atoms,
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-
XN21 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,
n N11 + n N12 , n N21 + n N22 and n N31 + n N32 are each independently 1, 2 or 3, and A N11 , A N12 , A N21 , A N22 , A N31 , A N32 , Z N11 , Z N12 , Z N21 , Z N22 , Z N31 , and Z N32 , they 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 41 and A N42 , Z N41 and Z N42 , they may be the same or different. )
The liquid crystal display element according to claim 1, wherein the liquid crystal display element comprises one or more compounds selected from the group consisting of the compounds represented by formula (1) and a negative dielectric anisotropy.
In addition to the compound represented by the general formula (i), the liquid crystal composition (B) has the following general formula (J)

(Wherein R J1 represents an alkyl group having 1 to 8 carbon atoms, or one or two or more non-adjacent —CH 2 — in an alkyl chain having 2 to 8 carbon atoms, each independently — A 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 the specified chemical structure,
(C) 1,4-phenylene group (d) Chemical structure in which one —CH═ existing in the 1,4-phenylene structure or two or more non-adjacent —CH═ 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 A structure in which one —CH═ present in a 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure or two or more non-adjacent —CH═ are replaced by —N═ Represents a group selected from the group consisting of divalent organic groups having the above-mentioned groups (a), (b), (c), (d), (e), and (f): Each independently may be 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 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, Represents —COO—, —OCO— or —C≡C—,
When n J1 is 2, 3 or 4 and a plurality of A J2 are present, 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 the same 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 comprises at least one compound having a positive dielectric anisotropy.
The liquid crystal display element according to claim 1, wherein Δn of the liquid crystal composition in the liquid crystal layer is 0.05 to 0.15.