JP6797361B2 - Liquid crystal display element - Google Patents

Description

The present invention relates to a liquid crystal display element.

Due to its excellent display quality, active matrix liquid crystal display devices are on the market for mobile terminals, liquid crystal televisions, projectors, computers and the like. As the active matrix display method, TFT (thin film transistor) or MIM (metal insulator metal) or the like is used for each pixel, and in combination with a liquid crystal composition having a high voltage retention rate, a TN type (twisted nematic) is used. It is widely used as a general liquid crystal display element. Further, in order to obtain a wider viewing angle characteristic, VA (vertical alignment: vertical alignment), IPS (In Plane Switching: in-plane switching), FFS (Fringe Field Switching: fringe field switching) which is an improved version of IPS, etc. are used. In order to support such display elements, new liquid crystal compounds or liquid crystal compositions are still being proposed.

On the other hand, since the liquid crystal display element is not a self-luminous type, a light source for emitting light is indispensable, and a white light source having an emission spectrum in a color reproduction region required for a display is used. As a light source, a cold cathode tube, a white LED (light emitting diode), or the like is used, but from the viewpoint of luminous efficiency, the white LED is currently the mainstream. Currently, one element cannot cover the entire visible light region from 380 nm to 750 nm, and several types are known for obtaining white light.
1) Combination of blue LED and yellow phosphor 2) Combination of each of the three primary colors (red, green, blue) 3) Combination of near-ultraviolet or purple LED and red, green, blue phosphor Among these three methods, From the viewpoint of obtaining the optimum white light as the light source of the liquid crystal display element, 3) is the best, and in the order of 2) and 1), 1) is the best from the viewpoint of luminous efficiency.

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

Although this method is excellent in luminous efficiency, it is inferior in characteristics as a white light source such as lack of red light, and has a problem in color reproducibility. In particular, since the liquid crystal display element uses a color filter together with the liquid crystal element to realize color display, it is difficult to improve the color reproducibility even if the light source unit is improved. Therefore, in order to improve the color reproducibility. It was necessary to increase the color purity by increasing the pigment concentration in the color filter or by increasing the coloring film thickness. However, in this case, there is a problem that the transmittance is lowered, the amount of light must be increased, and the power consumption is increased.

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

Further, in the development of a liquid crystal display element, there is also a method of controlling an initial orientation state by a spontaneous orientation compound without using the alignment film itself. In the liquid crystal display element, a polymerizable liquid crystal composition containing a polymerizable compound in the liquid crystal composition is dropped onto a substrate, and while another substrate is sandwiched, ultraviolet rays are irradiated to polymerize the polymerizable compound. However, it solves problems such as insufficient initial orientation and changes over time, and liquid crystal display while satisfying display in a wide temperature range, high-speed response, and low-voltage driveability. It was necessary to reduce the number of display defects when using the element.

Special Table 2001-523758 International Publication No. 2004/07473 Pamphlet U.S. Pat. No. 8,648,524

SID 2012 DIGEST, p895-896

As described above, when quantum dots, which are an example of nanocrystals for light emission as in Patent Documents 2 and 3 and Non-Patent Document 1, are used in a liquid crystal display element, a short wavelength or a short wavelength is used as a light source to cause excitation of the quantum dots. Since a visible light source of ultraviolet light is required, the light transmitted through the liquid crystal layer is mainly in a short wavelength region, unlike the case where conventional white light is used.

More specifically, short-wavelength visible light and ultraviolet light used as a light source for emitting light-emitting nanocrystals are high-energy rays, and the liquid crystal layer that functions as an optical switch is the length of these high-energy light. It is required to be able to withstand time exposure. In particular, in the case of a liquid crystal display element that does not use the alignment film itself, problems such as decomposition of the liquid crystal material itself when the liquid crystal layer is exposed to high-energy light such as short-wavelength visible light or ultraviolet light have been further confirmed.

Therefore, the problem to be solved by the present invention is the irradiation of high-energy light rays while achieving both high luminous efficiency and color reproducibility when an optical conversion layer containing nanocrystals for light emission is used instead of a color filter. It is an object of the present invention to provide a liquid crystal display element which does not use an alignment film on at least one of between the first substrate and the second substrate and the liquid crystal layer, which can suppress or prevent deterioration of the liquid crystal layer due to the above.

As a result of diligent studies to solve the above problems, the present inventors have used a liquid crystal layer containing a specific liquid crystal compound for a liquid crystal display element using luminescent nanocrystals such as quantum dots as a color filter. Then, it was found that the above-mentioned problems could be solved, and the invention of the present application was completed.

The liquid crystal display element of the present invention is less likely to deteriorate even with high-energy light such as short-wavelength visible light and ultraviolet light, and maintains a color reproduction region for a long period of time.

The liquid crystal display element of the present invention has excellent transmittance and maintains a color reproduction region for a long period of time.

It is a perspective view which shows the embodiment of the liquid crystal display element of this invention. It is a perspective view which shows the other embodiment of the liquid crystal display element of this invention. It is a schematic diagram of the cross section which cut the liquid crystal display element in the direction of line I-I of FIGS. It is a schematic diagram of the cross section which cut the liquid crystal display element in the direction of line I-I of FIGS. 1 and 2, and is the schematic diagram which shows another example of the light conversion layer in the liquid crystal display element of this invention. It is a schematic diagram of the cross section which cut the liquid crystal display element in the direction of line I-I of FIGS. It is a schematic diagram of the cross section which cut the liquid crystal display element in the direction of line I-I of FIGS. 1 and 2, and is the schematic diagram which shows another example of the light conversion layer in the liquid crystal display element of this invention. It is a schematic diagram of the cross section which cut the liquid crystal display element in the direction of line I-I of FIGS. 1 and 2, and is the schematic diagram which shows another example of the light conversion layer in the liquid crystal display element of this invention. It is a schematic diagram of the cross section which cut the liquid crystal display element in the direction of line I-I of FIGS. It is a schematic diagram of the cross section which cut the liquid crystal display element in the direction of line I-I of FIGS. 1 and 2, and is the schematic diagram which shows another example of the light conversion layer in the liquid crystal display element of this invention. It is a schematic diagram which showed the pixel part of the liquid crystal display element of this invention by the equivalent circuit. It is a schematic diagram which shows an example of the shape of the pixel electrode of this invention. It is a schematic diagram which shows an example of the shape of the pixel electrode of this invention. It is a schematic diagram which shows the electrode structure of the IPS type liquid crystal display element of this invention. FIG. 14 is a schematic view showing an example of the optical conversion layer 6. FIG. 15 is a schematic view showing an example of the optical conversion layer 6. FIG. 16 is a schematic view showing an example of the optical conversion layer 6. It is a figure which shows the emission spectrum of a quantum dot.

The first aspect of the present invention is a pair of substrates on which the first substrate and the second substrate are provided facing each other.
A liquid crystal layer sandwiched between the first substrate and the second substrate,
With the pixel electrodes provided on at least one of the first substrate or the second substrate,
With a common electrode provided on at least one of the first substrate or the second substrate,
A light source unit equipped with a light emitting element and
It is provided with three primary color pixels of red (R), green (G), and blue (B), and is red (R), green (G), and blue (B) due to 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 in any of the above is provided.
Between the first substrate and the second substrate and the liquid crystal layer, there is no alignment film and an orientation control layer formed of a polymerizable compound.
The liquid crystal layer has the general formulas (N-1), (N-2) and (N-3).

(In the formula, ^RN11 , ^RN12 , ^RN21 , ^RN22 , ^RN31 and ^RN32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two non-adjacent ones. More than one −CH ₂₋ may be independently substituted by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are independently (a) 1,4-cyclohexylene groups (one -CH _2- or adjacent to each other in this group). No two or more -CH _2- may be replaced by -O-) and (b) 1,4-phenylene group (one -CH = or non-adjacent 2 present in this group) More than one -CH = may be replaced with -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 = existing in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. )
(D) Represents a group selected from the group consisting of 1,4-cyclohexenylene groups, and the above groups (a), group (b), group (c) and group (d) are independently fluorine atoms. May be replaced,
^{Z N11, Z N12, Z N21} , Z N22, Z N31 and ^{Z N32} 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-
X ^N21 represents a hydrogen atom or a fluorine atom.
^TN31 represents −CH _2- or oxygen atom,
Although n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 each independently represent an integer of 0 to 3, n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are independent of each other. When it is 1, 2 or 3, and there are a plurality of A ^{N11 to} A ^N32 and Z ^{N11 to} Z ^N32 , they may be the same or different. ) Is contained in one or more compounds selected from the compounds represented by) and one or more polymerizable compounds, and a liquid crystal composition having a negative dielectric anisotropy (Δε) is used. It is a liquid crystal display element.

In the present invention, the first highly reliable liquid crystal layer is provided with a liquid crystal layer capable of withstanding long-term exposure to high-energy rays such as short-wavelength visible light and ultraviolet light used as a light source by configuring the liquid crystal layer as a characteristic. A liquid crystal display element having no alignment film on at least one of the substrate and the second substrate and the liquid crystal layer can be provided.

Further, the light emitting element is preferably a light emitting element that emits ultraviolet or visible light.

A suitable 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 entire example of the liquid crystal display element used in the present embodiment, and each component is described separately for convenience for explanation.

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 that acts as a light guide plate (not shown) or a light diffusing 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 arranged 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 placed not only on one side surface side 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. A light source unit 101 including a plurality of light emitting elements L surrounds three side surfaces of the light guide unit 102 or the entire circumference of the light guide unit 102 so as to surround the light guide unit 102. As described above, it may be provided on four side surfaces. The light guide unit 102 may be provided with a light diffusing plate (not shown) instead of the light guide plate, if 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. Further, a second (transparent insulating) substrate 7 is arranged so as to face the first substrate 2 with the liquid crystal layer 5 interposed therebetween, and an optical conversion layer (so-called chromosphere) 6 and polarized light are provided 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 at least one of the three primary colors has a pixel from the light source unit. It contains luminescent nanocrystals having an emission spectrum in any of red (R), green (G), and blue (B) depending on the 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, not shown) is shown. In FIGS. 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.

Further, in FIG. 1, a light conversion layer 6 is provided between the second substrate 7 and the liquid crystal layer 5, but other embodiments of the liquid crystal display element according to the present invention include FIGS. It may be a so-called color filter-on array (COA) as shown in 11. In this case, a light conversion layer 6 may be provided between the electrode layer 3 and the liquid crystal layer 5, or the electrode layer 3 and the first may be provided. An optical conversion layer 6 may be provided between the substrate 2 and the substrate 2. Further, if necessary, an overcoat layer (not shown) may be provided so as to cover the light conversion layer 6 to prevent substances contained in the light conversion layer from flowing out to the liquid crystal layer.

In FIG. 1, the light emitted from the light emitting element L passes through the light guide unit 102 (for example, via a light guide plate or a light diffusing plate) and is incident on 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 orientation direction of the liquid crystal molecules in the liquid crystal layer 5 can be controlled by driving the electrode layer 3. The light whose polarization direction is changed by the liquid crystal layer 5 that serves as an optical shutter is blocked by the second polarizing layer 8 or polarized in a specific direction, and then enters the light conversion layer 6. In the light conversion layer 6, the light entering the light conversion layer 6 is absorbed by the light emitting nanocrystals and converted into an emission spectrum into any of red (R), green (G), and blue (B). As a result, 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 body having a side surface in which the thickness gradually decreases from the side surface on which the light emitted from the light emitting element L is incident to the facing surface (side surface surface). (A tapered form or a wedge-shaped quadrangular plate) and a line light can be converted into surface light, which makes it easier for light to enter the liquid crystal panel 10 (described later as an embodiment).

FIG. 2 shows an entire example of a liquid crystal display element having a so-called direct-type backlight structure in which a plurality of light emitting elements L are arranged in a plane with respect to a flat light guide portion 102 in the backlight unit 100. It is a perspective view. For convenience, each component is described separately.

In the direct type backlight structure, since the light from the light emitting element L is surface light, the shape of the light guide portion 102 does not need to be tapered unlike that in FIG.

The liquid crystal panel 10 in FIG. 2 has 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, and a second substrate 2. A second substrate 7 provided with the electrode layer 3'(for example, a common electrode) and a liquid crystal layer 5 sandwiched between the first substrate 2 and the second substrate 7 are provided. Further, 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 second electrode layer 3'on the light conversion layer 6 is provided. The polarizing layer 8 of the above is provided.

That is, in the embodiment of FIG. 3, the liquid crystal display element 1000 is also referred to as an electrode layer (or a thin film transistor layer or a pixel electrode) including a backlight unit 100, a first polarizing plate 1, a first substrate 2, and a thin film transistor. ) 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.

In FIG. 2, the light emitted from the light emitting element L passes through the light guide unit 102 (via the light diffusing plate or the light diffusing plate) and is incident on 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 polarized in the liquid crystal layer 5 by driving the first electrode layer 3 and the second electrode layer 3'. The light whose direction has been changed is blocked by the second polarizing layer 8 or polarized in a specific direction, and then enters the light conversion layer 6. In the light conversion layer 6, the light entering the light conversion layer 6 is absorbed by the light emitting nanocrystals and converted into an emission spectrum into any of red (R), green (G), and blue (B). Therefore, any one of red (R), green (G), and blue (B) can be displayed.

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

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

3 to 9 are schematic cross-sectional views of a liquid crystal panel 10 portion of the liquid crystal display element cut out in order to show the configuration of the liquid crystal panel used in the present embodiment, and are a polarizing layer and an optical conversion layer in the liquid crystal panel 10. It is the schematic which shows the stacking mode of the liquid crystal layer. Further, in FIGS. 3 to 9, for convenience of explaining the positional relationship between 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 like shown in FIGS. 1 and 2 are shown. Is omitted and shown schematically.

Further, in FIGS. 3 to 9, with respect to the liquid crystal layer 5, the substrate on the backlight unit (light source) side and the laminate laminated on the substrate are referred to as an array substrate (A-SUB), and the array substrate and the liquid crystal layer 5 are provided. A substrate facing each other and a laminate laminated on the substrate are referred to as a facing substrate (O-SUB). The configurations and preferred embodiments of the array substrate (A-SUB) and the opposed substrate (O-SUB) will be described in detail in the description of the electrode structure in FIGS. 12 to 19 described later. Although FIGS. 3 to 9 show an example in which the TFT is formed on the array substrate side, the array substrate and the facing substrate may be interchanged.

In the embodiment of FIG. 3, the optical conversion layer 6 is provided on a facing substrate (O-SUB), and the optical conversion layer 6 and the second polarizing layer 8 are a pair of substrates (first substrate 2 and It is a form including a so-called in-cell polarizing layer provided between the second substrates 7).

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

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

That is, when the light conversion layer 6 uses light having a main peak in the vicinity of 450 nm such as a blue LED as a light source, the blue light emitted by the blue LED can be used as blue. Therefore, when the light from the light source unit is blue light, the light conversion pixel layer (NC-Blue) among the light conversion pixel layers (NC-Red, NC-Green, NC-Blue) of each color is omitted. However, for blue, the backlight light may be used as it is. In this case, the color layer displaying blue can be formed of a transparent resin, a color material layer containing a blue color material (so-called blue color filter), or the like. Therefore, in FIGS. 3 and 16, since the blue light emitting nanocrystals can be an arbitrary component, the blue light emitting nanocrystals are indicated by a dashed line.

Further, as a particularly preferable embodiment, the red color layer in the light conversion layer 6 contains a red light emitting nanocrystal NC that absorbs light (for example, blue light) emitted by a light source unit and emits red light, and has a green color. An example is described in which the layer contains nanocrystal NC for green light emission that absorbs light (for example, blue light) emitted by a light source unit and emits green light, but the present invention is not limited thereto.

The light emitting nanocrystal NC according to the present invention absorbs light emitted by a light source unit (for example, blue light) and emits blue light, and absorbs light emitted by a light source unit (for example, blue light). It is represented by at least one selected from the group consisting of nanocrystal NC for green light emission that emits green light and nanocrystal NC for red light emission that absorbs light (for example, blue light) emitted by the light source and emits red light. Is preferable, nanocrystal NC for blue light emission that absorbs light emitted by the light source unit (for example, blue light) and emits blue light, and nano for green light emission that absorbs light emitted by the light source unit (for example, blue light) and emits green light. It is more preferable to be represented by two types of light emitting nanocrystal NC selected from the group consisting of the crystal NC and the red light emitting nanocrystal NC that absorbs the light (for example, blue light) emitted by the light source unit and emits red light. .. It is particularly preferable that the light conversion layer according to the present invention includes a layer containing nanocrystals for red light emission (NC-Red) and a layer containing nanocrystals for green light emission (NC-Green).

In the liquid crystal display element of the present invention shown in FIG. 3, a black matrix may be provided for the purpose of preventing color mixing between the color layers. Further, in FIG. 3, a color layer containing a blue color material (so-called “blue”) is provided between the light conversion layer 6 and the second polarizing layer 8 depending on the type of light source used (blue LED as a light emitting element). It is preferable to provide a "color filter") on one surface between them from the viewpoint of preventing unnecessary light from entering from the outside and suppressing deterioration of image quality. The structure in which such a blue color filter is arranged is shown in FIG.

When the embodiment shown in FIG. 3 is applied to a VA type liquid crystal display element, between the liquid crystal 5 and the second polarizing layer 8 or between the second polarizing layer 8 and the optical conversion layer on the opposite substrate side O-SUB. It is preferable that the electrode layer 3'(common electrode) is provided between the electrode layer 3 and the electrode layer 3 (pixel electrode), and the electrode layer 3 (pixel electrode) is formed on the first substrate 2. Further, when the liquid crystal display element in FIG. 3 is an FFS type or an IPS type, it is preferable that the pixel electrode and the common electrode are formed on the first group 2.

Next, in the embodiment of FIG. 4, the optical conversion layer 6 is provided on the facing substrate (O-SUB), and the optical conversion layer 6 is a pair of substrates (first substrate 2 and second substrate 7). ) Is provided on the 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. 4, the red (R) pixel portion (red color layer portion) is a light conversion pixel layer (NC-Red) containing nanocrystals for red light emission, as in the embodiment of FIG. The green (R) pixel portion (green color layer portion) includes a light conversion pixel layer (NC-Green) containing nanocrystals for green light emission, and the blue (R) pixel portion (blue color). The layer portion) includes an optical conversion pixel layer (NC-Blue) containing nanocrystals for emitting blue light, if necessary. Further, the preferred embodiments of the red (R) pixel portion, the green (G) pixel portion, and the blue (B) pixel portion in the optical conversion layer 8 in FIG. 4 are the same as those in the embodiment shown in FIG. It is omitted here.

When the embodiment shown in FIG. 4 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 polarizing layer 8 on the opposite substrate side O-SUB, and the electrode layer 3'(common electrode) is provided. It is preferable that the electrode layer 3 (pixel electrode) is formed on the first substrate 2. Further, when the liquid crystal display element in FIG. 4 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. 5, the optical conversion layer 6 is provided on the facing substrate side O-SUB, and the optical conversion layer 6 and the second polarizing layer 8 are paired substrates (first substrate 2 and second). In each of the red and green color layer portions constituting the light conversion layer 6, the red color layer portion is a nano for red light emission, which is provided with an in-cell polarizing plate provided between the substrates 7). It has a two-layer structure in which a light conversion pixel layer (NC-Red) containing crystals and a color material layer containing a red color material (so-called red color filter) (CF-Red) are laminated, and has a green color. In the layer portion, 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 are laminated. It has a two-layer structure.

That is, the two-layer structure of such a color layer transmits the remaining excitation light when all 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) and a color material layer of each color are laminated for the purpose of absorbing light.

According to FIG. 5, 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 backlit. It is provided on the substrate side O-SUB facing the substrate A-SUB on the unit (light source) side. Further, in FIG. 5, the second polarizing layer 8 is provided with an in-cell polarizing plate provided between a pair of substrates (first substrate 2 and second substrate 7). The embodiment in FIG. 5 is a form in which the light conversion layer 6 of FIG. 3 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. It is configured as a two-layer structure consisting of a light conversion pixel layer (NC-Red) containing nanocrystals for light emission and a color material layer (CF-Red) containing a red color material. The green (R) pixel portion (green color layer portion) consists of a light conversion pixel layer (NC-Green) containing nanocrystals for green light emission and a color material layer (CF-Green) containing a green color material. It is configured as a layered structure. In this case, in FIG. 5, the green color layer portion includes a light conversion pixel layer (NC-Green) containing nanocrystals for green light emission 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) containing nanocrystals for emitting blue light, if necessary.

A light conversion pixel layer (NC-Red) containing nanocrystals for red light emission, a light conversion pixel layer (NC-Green) containing nanocrystals for green light emission, and nanocrystals for blue light emission in the light conversion layer 6 in FIG. 5 are required. The preferred form of the including color layer (NC-Blue) is the same as that of the embodiment shown in FIG. 3, and is therefore omitted here. Also in FIG. 5, the red color layer portion, the green color layer portion, and the blue color layer portion are shown to be in contact with each other, but in order to prevent color mixing, as a light-shielding layer between them. A black matrix may be placed.

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) is provided between the light conversion layer 6 and the second polarizing layer 8 in FIG. Is preferable because it is possible to prevent unnecessary light from entering from the outside and suppress deterioration of image quality. Examples of the layer structure in which the two-layer structure optical conversion layer 6 and the blue color filter are essential components include the structure shown in FIG.

When the embodiment shown in FIG. 5 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 polarizing layer 8 on the opposite substrate side O-SUB. Moreover, it is preferable that the electrode layer 3 (pixel electrode) is formed on the first substrate 2. Further, when the liquid crystal display element in FIG. 5 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, the embodiment of FIG. 6 is a form in which the second polarizing layer 8 is provided with an in-cell polarizing plate provided between a pair of substrates (first substrate 2, second substrate 7), and emits light. It has a two-layer optical conversion layer 6 in which a layer containing nanocrystals for use and a color filter are laminated. Specifically, in the light conversion layer 6, the red (R) pixel portion (red color layer portion) is composed of a layer ( NC ) containing nanocrystals for light emission and a color material layer containing 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 nanocrystals for light emission and a color material layer containing a green color material. In addition, the blue (R) pixel portion (blue color layer portion) is composed of a two-layer structure of a layer (NC) containing light-emitting nanocrystals and a color material layer containing a blue color material.

In this case, the light emitting nanocrystal in the layer containing the light emitting nanocrystal NC is a blue light emitting nanocrystal that absorbs incident light (light from a light source, preferably blue light) and emits blue light, and incident light (from a light source). (Preferably blue light) and emits green light. It consists of a green light emitting nanocrystal and a red light emitting nanocrystal that absorbs incident light (light from a light source, preferably blue light) and emits red light. It preferably comprises one or two selected from the group. In this embodiment as well, a black matrix may be provided for the purpose of preventing color mixing between the color layers.

Further, in the embodiment of FIG. 6, it is preferable to provide a blue or yellow color filter on one surface so as to be adjacent to the liquid crystal layer side of the light conversion layer 6 from the viewpoint of preventing unnecessary light from entering and suppressing deterioration of image quality. The structure in which such a blue or yellow color filter is arranged can be shown in FIG.

When the embodiment shown in FIG. 6 or 7 is applied to the VA type 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. It is preferable that the electrode layer 3 (pixel electrode) is provided and is formed on the first display substrate SUB1. Further, when the liquid crystal display element in FIG. 6 is an FFS type or an IPS type, it is preferable that the pixel electrode and the common electrode are formed on the first display substrate SUB1.

In the embodiments shown in FIGS. 3 to 7 described in detail above, light using a light source of high-energy light such as short-wavelength visible light or ultraviolet light is converted into light via a liquid crystal layer and a polarizing layer that function as an optical switch. The light emitting nanocrystals contained in the layer absorb the absorbed light, and the absorbed light is converted into light having a specific wavelength by the light emitting nanocrystals to emit light, thereby displaying the color.

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

When the embodiment shown in FIG. 8 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. It is preferable that the electrode layer 3 (pixel electrode) is formed on the first substrate 2.

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

Further, when the liquid crystal display element in FIG. 8 is an FFS type or an IPS type, the pixel electrode and the common electrode are placed on the first substrate 2, for example, between the first substrate 2 and the optical conversion layer 6. It is preferably formed between one polarizing layer 1 and the light conversion layer 6 or between the first polarizing layer 1 and the liquid crystal layer 5. Further, it is preferable to provide a blue color filter on one surface between the optical conversion layer 6 and the first substrate 2 from the viewpoint of preventing unnecessary light from entering and suppressing deterioration of image quality. When the incident light is blue light, the color layer displaying blue does not have to use blue light emitting nanocrystals. In this case, a color layer containing a transparent resin or a blue color material (so-called blue color filter). ) Etc. can be configured.

In the embodiment shown in FIG. 9, 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 paired. It is a form provided on the outside between the substrates (first substrate 2, second substrate 7). Therefore, the support substrate 9 that supports the first polarizing layer 1 and the light conversion layer 6 is provided on the light source portion (backlight unit) side of the first substrate 2.

When the embodiment shown in FIG. 9 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. It is preferable that the electrode layer 3 (pixel electrode) is formed on the first substrate 2. For example, it is preferable that the common electrode 3'is formed between the first substrate 2 and the liquid crystal layer 5. Further, when the liquid crystal display element in FIG. 9 is an FFS type or an IPS type, the pixel electrode and the common electrode are on the first substrate 2, for example, between the first substrate 2 and the liquid crystal layer 5. And it is preferable that a common electrode is formed. Further, it is preferable to provide a blue color filter on one surface between the optical conversion layer 6 and the support substrate 9 from the viewpoint of preventing unnecessary light from entering and suppressing deterioration of image quality. Further, when the incident light is blue light, the color layer displaying blue does not have to use blue light emitting nanocrystals. In this case, a color material layer containing a transparent resin or a blue color material (so-called blue color). It can be configured by a filter) or the like.

As described in detail above, in the embodiments shown in FIGS. 8 to 9, among the light using the light source of high energy light such as short wavelength visible light and ultraviolet light, the light is absorbed by the light emitting nanocrystal contained in the light conversion layer. The light that did not exist, particularly the light that passed through the blue color layer portion, displays the color through the liquid crystal layer that functions as an optical switch.

Among the above embodiments of FIGS. 3 to 9, in particular, the optical conversion layer 6 shown in FIGS. 3 to 7 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 from the viewpoint that the effect of the present invention that the deterioration of the liquid crystal layer due to the irradiation of high-energy light can be suppressed or prevented is remarkably exhibited.

As described above, the positional relationship between the polarizing layer, the light conversion layer, and the liquid crystal layer in the preferable liquid crystal display element (particularly the liquid crystal panel) of the present invention has been described with reference to the schematic views of FIGS. 3 to 9.

"Optical conversion layer"
Next, to further describe the optical conversion layer in the present invention, the component of the pixel portion contains nanocrystals for light emission as an essential component, and has an affinity for a resin component and other necessary nanocrystals for light emission. It may contain a certain molecule, a known additive, or other coloring material. Further, as described above, it is preferable to have a black matrix at the boundary portion of each pixel layer from the viewpoint of contrast.

(Nanocrystals for light emission)
The photoconversion layer according to the present invention contains nanocrystals for light emission. As used herein, the term "nanocrystal" preferably refers to particles 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 nanocrystals include an elongated shape, a rod shape, a circular shape (spherical shape), an elliptical shape, a pyramid shape, a disc shape, a branch shape, a net shape, or an arbitrary irregular shape. In some embodiments, the nanocrystals are preferably quantum dots or quantum rods.

The light emitting nanocrystals preferably have a core containing at least one first semiconductor material and a shell covering the core and containing a second semiconductor material that is the same as or different from the core.

Therefore, the light-emitting nanocrystal comprises at least a core containing the first semiconductor material and a shell containing the second semiconductor material, and the first semiconductor material and the second semiconductor material may be the same or different. Further, both the core and / or the shell may contain a third semiconductor material other than the first semiconductor and / or the second semiconductor. The term "covering the core" as used herein means that at least a part of the core may be covered.

Further, the luminescent nanocrystals require a core containing at least one first semiconductor material and a first shell covering the core and containing a second semiconductor material that is the same as or different from the core. It is preferable to have a second shell that covers the first shell and contains a third semiconductor material that is the same as or different from the first shell.

Therefore, the luminescent nanocrystal according to the present invention has a form having a core containing the first semiconductor material and a shell containing the core and the same second semiconductor material as the core, that is, one type or two. A mode composed of more than one type of semiconductor material (= core-only structure (also referred to as core structure)), a core containing the first semiconductor material, and a second semiconductor material that covers the core and is different from the core. A form having a shell containing the above, that is, a core / shell structure, a core containing the first semiconductor material, and a first shell covering the core and containing a second semiconductor material different from the core, said. At least one of three structures, that is, a core / shell / shell structure, which covers the first shell and has a second shell containing a third semiconductor material different from the first shell. It is preferable to have.

Further, as described above, the luminescent nanocrystal according to the present invention preferably contains three forms of a core structure, a core / shell structure, and a core / shell / shell structure. In this case, the core is two or more types of semiconductors. It may be a mixed crystal containing a material (for example, CdSe + CdS, CIS + ZnS, etc.). Furthermore, the shell may also be a mixed crystal containing two or more kinds of 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 affinity molecule is a small molecule and a polymer having a functional group having an affinity for a nanocrystal for light emission, and the functional group having an affinity is not particularly limited, but nitrogen. , Oxygen, sulfur and phosphorus are preferably groups containing one element selected from the group. For example, an organic sulfur group, an organic phosphate group, a pyrrolidone group, a pyridine group, an amino group, an amide group, an isocyanate group, a carbonyl group, a hydroxyl group and the like can be mentioned.

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

Specifically, the semiconductor material according to the present invention includes CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSte, ZnSeS, ZnSeTe, ZnSte, HgSeS, and HgSe. , CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSte, CdHgSeS , AlSb, InN, InP, InAs, InSb, PLAPP, PLGAs, VMwareSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlPSb, GaAlNAs, GaAlNAs , GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb; , SnPbSSe, SnPbSeTe, SnPbSTe; Si, Ge, SiC, SiGe, AgInSe2, CuGaSe2, CuInS2, CuGaS2, CuInSe2, AgInS2, AgGaSe2, AgGaS2, C, Si and Ge. These compound semiconductors may be used alone or in admixture of two or more of them, 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 and Cu ₂ Selected from the group consisting of ZnSnS ₄ It is more preferable that at least one of these compound semiconductors is selected, and these compound semiconductors may be used alone or in combination of two or more.

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

In the present invention, the upper limit of the wavelength peak of the fluorescence spectrum of the nanocrystal for red emission that emits red light is 665 nm, 663 nm, 660 nm, 658 nm, 655 nm, 653 nm, 651 nm, 650 nm, 647 nm, 645 nm, 643 nm, 640 nm, 637 nm, 635 nm. , 632 nm or 630 nm, and the lower limit of the wavelength peak is preferably 628 nm, 625 nm, 623 nm, 620 nm, 615 nm, 610 nm, 607 nm or 605 nm.

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

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

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

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

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

The upper limit of the particle size (primary particles) of the red light emitting nanocrystals according to the present invention is preferably 50 nm or less, 40 nm or less, 30 nm or less, and 20 nm or less in this order.

The upper limit of the peak wavelength of the nanocrystal for red light emission according to the present invention is 665 nm, and the lower limit is 605 nm, and the compound and its particle size are selected so as to match this peak wavelength. Similarly, the upper limit of the peak wavelength of the nanocrystal for green light emission is 560 nm, the lower limit is 500 nm, the upper limit of the peak wavelength of the nanocrystal for blue light emission is 420 nm, and the lower limit is 480 nm, respectively, so as to match this peak wavelength. 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 luminescent nanocrystals, CdSe rod-shaped luminescent nanocrystals, and rod-shaped luminescent nanocrystals having a core-shell structure). It is a nanocrystal, the shell portion is CdS and the inner core portion is CdSe, and the rod-shaped light emitting nanocrystal having a core shell structure is provided. The shell portion is CdS and the inner core portion is ZnSe and core shell. It is a luminescent nanocrystal having a structure, the shell portion is CdS and the inner core portion is CdSe, and the luminescent nanocrystal having a core-shell structure is CdS and the inner core portion. Is ZnSe, nanocrystals for light emission of mixed crystals of CdSe and ZnS, nanocrystals for light emission of mixed crystals of CdSe and ZnS, nanocrystals for light emission of InP, nanocrystals for light emission of InP, rod-like light emission of InP. Nanocrystals for light emission, mixed crystal luminescence nanocrystals of CdSe and CdS, rod-shaped luminescent nanocrystals of mixed crystals of CdSe and CdS, luminescent nanocrystals of mixed crystals of ZnSe and CdS, ZnSe and CdS Mixed crystal rod-shaped luminescence nanocrystals, etc.), green (CdSe luminescence nanocrystals, CdSe rod-shaped luminescence nanocrystals, mixed crystal luminescence nanocrystals of CdSe and ZnS, mixed crystals of CdSe and ZnS It has rod-shaped luminescence nanocrystals of crystals) and blue (ZnSe luminescence nanocrystals, ZnSe rod-shaped luminescence nanocrystals, ZnS luminescence nanocrystals, ZnS rod-shaped luminescence nanocrystals, and core-shell structure. It is a nanocrystal for light emission, the shell part is ZnSe and the inner core part is ZnS, and the rod-shaped nanocrystal for light emission having a core-shell structure is the shell part is ZnSe and the inner core part is ZnS. , CdS luminescent nanocrystals, CdS rod-shaped luminescent nanocrystals). Other colors (for example, yellow) may be contained in the optical conversion layer, if necessary, and different colors of 4 or more pixels in close proximity may be used.

The average particle size (primary particles) of the luminescent nanocrystals 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 directly observing particles with an electron microscope to measure the average particle size. Since nanocrystals for light emission are easily deteriorated by moisture and the like, in the present invention, any plurality of crystals are directly observed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM), and the length and shortness of the projected two-dimensional image are used. A method of calculating each particle size from the diameter ratio and obtaining the average thereof is preferable. Therefore, in the present invention, the average particle size is calculated by applying the above method. The primary particles of luminescent nanocrystals are single crystals having a size of several to several tens of nm or crystallites close to them, and the size and shape of the primary particles of luminescent nanocrystals are the primary particles. It is considered that it depends on the chemical composition, structure, manufacturing method and manufacturing conditions of.

In the photoconversion layer according to the present invention, it is preferable that the nanocrystals for light emission have an organic ligand on the surface thereof from the viewpoint of dispersion stability. The organic ligand may be coordinate-bonded to the surface of the luminescent nanocrystal, for example. In other words, the surface of the luminescent nanocrystals may be passivated by an organic ligand. Further, the luminescent nanocrystals may have a polymer dispersant on the surface thereof. In one embodiment, for example, the organic ligand is removed from the luminescent nanocrystal having the above-mentioned organic ligand, and the polymer dispersant is bound to the surface of the luminescent nanocrystal by exchanging the organic ligand with the polymer dispersant. You may let me. However, from the viewpoint of dispersion stability when the ink is used as an inkjet ink, it is preferable that the polymer dispersant is blended with the luminescent nanocrystals in which the organic ligand is coordinated.

The organic ligand is a small molecule or a polymer having a functional group having an affinity for the nanocrystal particles for light emission, and the functional group having an affinity is not particularly limited, but nitrogen, oxygen, and the like. It is preferably a group containing one element selected from the group consisting of sulfur and phosphorus. For example, an organic sulfur group, an organic phosphate group, a pyrrolidone group, a pyridine group, an amino group, an amide group, an isocyanate group, a carbonyl group, a hydroxyl group and the like can be mentioned. For example, TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), oleic acid, oleylamine, octylamine, trioctylamine, hexadecylamine, octanethiol, dodecanethiol, hexylphosphonic acid (HPA), tetradecyl. Phosphonate (TDPA) and octylphosphinic acid (OPA) can be mentioned.

The other organic ligand has an aliphatic hydrocarbon having an ethylene oxide chain and / or a propylene oxide chain as an affinity group from the viewpoint of further improving the dispersibility and luminescence intensity of the luminescent nanocrystal particles. Is preferable.

The preferred organic ligand may be, for example, an organic ligand represented by the following general formula (1).

[In equation (1), p represents an integer from 0 to 50, and q represents an integer from 0 to 50. ]
In the organic ligand represented by the general formula (1), at least one of p and q is preferably 1 or more, and both p and q are more preferably 1 or more.

As the luminescent nanocrystals, those dispersed in a colloidal form in an organic solvent can be used. The surface of the luminescent nanocrystals dispersed in an organic solvent is preferably passivated by the above-mentioned organic ligand. Examples of the organic solvent include cyclohexane, hexane, heptane, chloroform, toluene, octane, chlorobenzene, tetralin, diphenyl ether, propylene glycol monomethyl ether acetate, butyl carbitol acetate, or a mixture thereof.

The light conversion layer (or the ink composition for preparing the light conversion layer) according to the present invention preferably contains a polymer dispersant. The polymer dispersant can uniformly disperse the light-scattering particles in the ink.

The photoconversion layer in the present invention preferably contains, in addition to the nanocrystal particles for light emission shown above, a polymer dispersant that appropriately disperses and stabilizes the nanocrystal particles for light emission.

In the present invention, the polymer dispersant is a polymer compound having a weight average molecular weight of 750 or more and having a functional group having an affinity for light-scattering particles, and has a function of dispersing light-scattering particles. Has. In the polymer dispersant, the polymer dispersant is adsorbed on the light scattering particles via a functional group having an affinity for the light scattering particles, and the polymer dispersants undergo electrostatic repulsion and / or steric repulsion between the polymer dispersants. Light scattering particles are dispersed in the ink composition. The polymer dispersant is preferably bonded to the surface of the light-scattering particles and adsorbed on the light-scattering particles, but it may be bonded to the surface of the light-emitting nanocrystals and adsorbed on the light-emitting nanoparticles. It may be free in the ink composition.

Examples of the functional group having an affinity for the light scattering particles include an acidic functional group, a basic functional group and a nonionic functional group. The acidic functional group has a dissociative proton and may be neutralized with a base such as an amine or a hydroxide ion, and the basic functional group is neutralized with an acid such as an organic acid or an inorganic acid. You may.

The acidic functional group, a carboxyl group (-COOH), a sulfo group _(-SO 3 H), sulfuric acid group (-OSO ₃ H), a phosphonic acid group (-PO _{(OH) 3),} phosphoric acid group (-OPO ( OH) ₃ ), phosphinic acid group (-PO (OH)-), mercapto group (-SH), and the like.

Examples of the basic functional group include primary, secondary and tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole, and triazole.

The nonionic functional group, hydroxy group, an ether group, a thioether group, a sulfinyl group (-SO-), a sulfonyl group _(-SO 2 -), a carbonyl group, a formyl group, an ester group, carbonic ester group, an amide group, Examples thereof include a carbamoyl group, a ureido group, a thioamide group, a thioureide group, a sulfamoyl group, a cyano group, an alkenyl group, an alkynyl group, a phosphine oxide group and a phosphine sulfide group.

Acidic functional groups from the viewpoint of dispersion stability of light-scattering particles, from the viewpoint of less likely to cause the side effect of precipitation of light-emitting nanocrystals, from the viewpoint of ease of synthesis of polymer dispersants, and from the viewpoint of functional group stability. A carboxyl group, a sulfo group, a phosphonic acid group and a phosphoric acid group are preferably used as the basic functional group, and an amino group is preferably used as the basic functional group. Among these, a carboxyl group, a phosphonic acid group and an amino group are more preferably used, and most preferably an amino group is used.

A polymer dispersant having an acidic functional group has an acid value. The acid value of the polymer dispersant having an acidic functional group is preferably 1 to 150 mgKOH / g in terms of solid content. When the acid value is 1 or more, sufficient dispersibility of the light-scattering particles can be easily obtained, and when the acid value is 150 or less, the storage stability of the pixel portion (cured product of the ink composition) is unlikely to decrease. ..

Further, the polymer dispersant having a basic functional group has an amine value. The amine value of the polymer dispersant having a basic functional group is preferably 1 to 200 mgKOH / g in terms of solid content. When the amine value is 1 or more, sufficient dispersibility of the light-scattering particles can be easily obtained, and when the amine value is 200 or less, the storage stability of the pixel portion (cured product of the ink composition) is unlikely to decrease. ..

The polymer dispersant may be a polymer of a single monomer (homopolymer) or a copolymer of a plurality of types of monomers (copolymer). Further, the polymer dispersant may be any of a random copolymer, a block copolymer or a graft copolymer. When the polymer dispersant is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer. The polymer dispersant may be, for example, acrylic resin, polyester resin, polyurethane resin, polyamide resin, polyether, phenol resin, silicone resin, polyurea resin, amino resin, polyamine such as polyethyleneimine and polyallylamine, epoxy resin, polyimide and the like. It may be there.

Commercially available products can also be used as the polymer dispersant, and the commercially available products include Ajinomoto Fine-Techno Co., Ltd.'s Ajispar PB series, BYK's DISPERBYK series, BYK-series, and BASF's Efka series. Etc. can be used.

The light conversion layer (or the ink composition for preparing the light conversion layer) according to the present invention preferably contains a resin component that functions as a binder in the cured product. The resin component according to the present invention is preferably a curable resin, and the curable resin is preferably a thermosetting resin or a UV curable resin.

The thermosetting resin has a curable group, and examples of the curable group include an epoxy group, an oxetane group, an isocyanate group, an amino group, a carboxyl group, a methylol group, and the like, and the cured product of the ink composition. An epoxy group is preferable from the viewpoint of excellent heat resistance and storage stability, and excellent adhesion to a light-shielding portion (for example, black matrix) and a substrate. The thermosetting resin may have one kind of curable group or may have two or more kinds of curable groups.

The thermosetting resin may be a polymer (homopolymer) of a single monomer, or may be a copolymer (copolymer) of a plurality of types of monomers. Further, the thermosetting resin may be any of a random copolymer, a block copolymer, and a graft copolymer.

As the thermosetting resin, a compound having two or more thermosetting functional groups in one molecule is used, and it is usually used in combination with a curing agent. When a thermosetting resin is used, a catalyst (curing accelerator) capable of accelerating the thermosetting reaction may be further added. In other words, the ink composition may contain a thermosetting component containing a thermosetting resin (as well as a curing agent and a curing accelerator used as needed). In addition to these, a polymer that does not have a polymerization reactivity by itself may be further used.

As a compound having two or more thermosetting functional groups in one molecule, for example, an epoxy resin having two or more epoxy groups in one molecule (hereinafter, also referred to as “polyfunctional epoxy resin”) may be used. The "epoxy resin" includes both a monomeric epoxy resin and a polymeric epoxy resin. The number of epoxy groups contained in one molecule of the polyfunctional epoxy resin is preferably 2 to 50, more preferably 2 to 20. The epoxy group may have a structure having an oxylan ring structure, and may be, for example, a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, or the like. Examples of the epoxy resin include known polyvalent epoxy resins that can be cured by a carboxylic acid. Such epoxy resins are widely disclosed in, for example, "Epoxy Resin Handbook" edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (1987), and these can be used.

When a polyfunctional epoxy resin having a relatively small molecular weight is used as the thermosetting resin, epoxy groups are replenished in the ink composition (inkjet ink), the reaction point concentration of the epoxy becomes high, and the crosslink density can be increased. it can.

As the curing agent and curing accelerator used for curing the thermosetting resin, any known and commonly used one that can be dissolved or dispersed in the above-mentioned organic solvent can be used.

The thermosetting resin may be alkali-insoluble from the viewpoint that a color filter pixel portion having excellent reliability can be easily obtained. When the thermosetting resin is alkali-insoluble, the amount of the thermosetting resin dissolved in 1% by mass of a potassium hydroxide aqueous solution at 25 ° C. is 30% by mass or less based on the total mass of the thermosetting resin. Means that. The dissolved amount of the thermosetting resin is preferably 10% by mass or less, and more preferably 3% by mass or less.

The weight average molecular weight of the thermosetting resin is from the viewpoint that an appropriate viscosity can be easily obtained as an inkjet ink, from the viewpoint of improving the curability of the ink composition, and the solvent resistance of the pixel portion (cured product of the ink composition). And from the viewpoint of improving the wear resistance, it may be 750 or more, 1000 or more, or 2000 or more. From the viewpoint of obtaining an appropriate viscosity as an inkjet ink, it may be 500,000 or less, 300,000 or less, or 200,000 or less. However, this does not apply to the molecular weight after cross-linking.

The content of the thermosetting resin includes the viewpoint that an appropriate viscosity can be easily obtained as an inkjet ink, the viewpoint that the curability of the ink composition is good, and the solvent resistance of the pixel portion (cured product of the ink composition). From the viewpoint of improving the wear resistance, it may be 10% by mass or more, 15% by mass or more, or 20% by mass or more based on the mass of the non-volatile content of the ink composition. The content of the thermosetting resin may be 90% by mass or less based on the mass of the non-volatile content of the ink composition from the viewpoint that the thickness of the pixel portion does not become too thick for the light conversion function, and is 80. It may be 0% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.

The UV curable resin is preferably a resin obtained by polymerizing a photoradical polymerizable compound or a photocationic polymerizable compound that is polymerized by irradiation with light, and may be a photopolymerizable monomer or oligomer. These are used with photopolymerization initiators. The photoradical polymerizable compound is preferably used together with the photoradical polymerization initiator, and the photocationic polymerizable compound is preferably used together with the photocationic polymerization initiator. In other words, the ink composition for the photoconversion layer according to the present invention may contain a photopolymerizable component containing a photopolymerizable compound and a photopolymerization initiator, and the photoradical polymerizable compound and the photoradical polymerization initiator. It may contain a photoradical polymerizable component containing, or may contain a photocationic polymerizable component containing a photocationic polymerizable compound and a photocationic polymerization initiator. A photoradical polymerizable compound and a photocationic polymerizable compound may be used in combination, or a compound having photoradical polymerizable property and photocationic polymerizable property may be used, and a photoradical polymerization initiator and a photocationic polymerization initiator May be used together. One type of photopolymerizable compound may be used alone, or two or more types may be used in combination.

Examples of the photoradical polymerizable compound include (meth) acrylate compounds. The (meth) acrylate compound may be a monofunctional (meth) acrylate having one (meth) acryloyl group, or may be a polyfunctional (meth) acrylate having a plurality of (meth) acryloyl groups. It is preferable to use a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate in combination from the viewpoint of suppressing a decrease in smoothness due to curing shrinkage during the production of a color filter. In addition, in this specification, (meth) acrylate means "acrylate" and the corresponding "methacrylate". The same applies to the expression "(meth) acryloyl".

Examples of the photocationically polymerizable compound include epoxy compounds, oxetane compounds, vinyl ether compounds and the like.

Further, as the photopolymerizable compound in the present embodiment, the photopolymerizable compounds described in paragraphs 0042 to 0049 of JP2013-182215A can also be used.

In the ink composition for a photoconversion layer according to the present invention, when the curable component is composed of only a photopolymerizable compound or a main component thereof, the photopolymerizable compound as described above has a polymerizable functional property. It is more preferable to use a bifunctional or higher polyfunctional photopolymerizable compound having two or more groups in one molecule as an essential component because the durability (strength, heat resistance, etc.) of the cured product can be further enhanced.

The photopolymerizable compound may be alkali-insoluble from the viewpoint that a color filter pixel portion having excellent reliability can be easily obtained. In the present specification, the fact that the photopolymerizable compound is alkali-insoluble means that the amount of the photopolymerizable compound dissolved in 1% by mass of an aqueous potassium hydroxide solution at 25 ° C. is 30 based on the total mass of the photopolymerizable compound. It means that it is mass% or less. The dissolved amount of the photopolymerizable compound is preferably 10% by mass or less, and more preferably 3% by mass or less.

The content of the photopolymerizable compound is determined from the viewpoint of improving the curability of the ink composition and improving the solvent resistance and abrasion resistance of the pixel portion (cured product of the ink composition). Based on the mass of the non-volatile component, it may be 10% by mass or more, 15% by mass or more, or 20% by mass or more. The content of the photopolymerizable compound may be 90% by mass or less, and 80% by mass or less, based on the mass of the non-volatile content of the ink composition, from the viewpoint of obtaining more excellent optical characteristics (leakage light). It may be 70% by mass or less, 60% by mass or less, or 50% by mass or less.

The photopolymerizable compound has a crosslinkable group from the viewpoint of excellent stability of the pixel portion (cured product of the ink composition) (for example, deterioration over time can be suppressed, and high temperature storage stability and wet heat storage stability are excellent). You may be doing it. The crosslinkable group is a functional group that reacts with another crosslinkable group by heat or active energy rays (for example, ultraviolet rays), for example, an epoxy group, an oxetane group, a vinyl group, an acryloyl group, an acryloyloxy group, a vinyl ether group, or the like. Can be mentioned.

As the photoradical polymerization initiator, a molecular cleavage type or hydrogen abstraction type photoradical polymerization initiator is suitable.

The content of the photopolymerization initiator may be 0.1 part by mass or more and 0.5 part by mass or more with respect to 100 parts by mass of the photopolymerizable compound from the viewpoint of curability of the ink composition. It may be 1 part by mass or more. The content of the photopolymerization initiator may be 40 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the photopolymerizable compound, from the viewpoint of the temporal stability of the pixel portion (cured product of the ink composition). It may be less than or equal to 20 parts by mass or less.

In addition, some thermoplastic resins may be used in combination with these UV curable resins, and the thermoplastic resins include, for example, urethane-based resin, acrylic-based resin, polyamide-based resin, polyimide-based resin, and styrene maleic acid-based resin. Examples thereof include resins and maleic anhydride-based resins.

Further, a known organic solvent may be used in the ink composition for preparing the photoconversion layer according to the present invention, for example, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether. , Diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, alldiacetate at 1,4-butane, glyceryl triacetate and the like.

Further, in the light conversion layer (or the ink composition for preparing the light conversion layer) according to the present invention, in addition to the curable resin, the polymer dispersant, and the nanocrystal particles for light emission, light scattering particles are used. It may contain known additives.

When a color filter pixel portion (hereinafter, also simply referred to as “pixel portion”) is formed by an ink composition using luminescent nanocrystals, the light from the light source is not absorbed by the luminescent nanocrystals and leaks from the pixel portion. Sometimes. Such leaked light lowers the color reproducibility of the pixel portion. Therefore, when the pixel portion is used as the light conversion layer, it is preferable to reduce the leaked light as much as possible. The light scattering particles are preferably used in order to prevent light leakage from the pixel portion. The light-scattering particles are, for example, optically inactive inorganic fine particles. The light scattering particles can scatter the light from the light source irradiated to the color filter pixel portion.

Examples of the material constituting the photoscattering particles include simple metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum and gold; silica, barium sulfate, barium carbonate, calcium carbonate, etc. Metal oxides such as talc, titanium oxide, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, alumina white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconium oxide, zinc oxide; magnesium carbonate, Metal carbonates such as barium carbonate, bismuth subcarbonate, calcium carbonate; metal hydroxides such as aluminum hydroxide; composite oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate, strontium titanate, etc. Examples thereof include metal salts such as bismuth subnitrate. The light-scattering particles preferably contain at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate and silica from the viewpoint of being more excellent in reducing leakage light. It is more preferable to contain at least one selected from the group consisting of titanium oxide, barium sulfate and calcium carbonate.

The shape of the light-scattering particles may be spherical, filamentous, indefinite, or the like. However, as the light-scattering particles, it is possible to use particles having less directional particle shape (for example, spherical or tetrahedral particles) to improve the uniformity, fluidity and light scattering property of the ink composition. It is preferable in that it can be enhanced.

The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 0.05 μm or more, or 0.2 μm or more, from the viewpoint of being more excellent in the effect of reducing leaked light. It may be 0.3 μm or more. The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 1.0 μm or less, 0.6 μm or less, or 0, from the viewpoint of excellent ejection stability. It may be 4 μm or less. The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition is 0.05 to 1.0 μm, 0.05 to 0.6 μm, 0.05 to 0.4 μm, 0.2 to 1. It may be 0.0 μm, 0.2 to 0.6 μm, 0.2 to 0.4 μm, 0.3 to 1.0 μm, 0.3 to 0.6 μm, or 0.3 to 0.4 μm. From the viewpoint that such an average particle diameter (volume average diameter) can be easily obtained, the average particle diameter (volume average diameter) of the light-scattering particles used may be 50 nm or more, and may be 1000 nm or less. The mean particle diameter (volume mean diameter) of the light-scattering particles is obtained by measuring with a dynamic light-scattering nanotrack particle size distribution meter and calculating the volume mean diameter. The average particle diameter (volume average diameter) of the light-scattering particles used can be obtained by measuring the particle diameter of each particle with, for example, a transmission electron microscope or a scanning electron microscope, and calculating the volume average diameter.

The content of the light scattering particles may be 0.1% by mass or more, or 1% by mass or more, based on the mass of the non-volatile content of the ink composition from the viewpoint of being more excellent in the effect of reducing leakage light. It may be 5% by mass or more, 7% by mass or more, 10% by mass or more, or 12% by mass or more. The content of the light-scattering particles may be 60% by mass or less, 50% by mass or less, based on the mass of the non-volatile content of the ink composition from the viewpoint of being excellent in the effect of reducing leakage light and being excellent in ejection stability. It may be less than or equal to, 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, and 15% by mass. It may be as follows. In the present embodiment, since the ink composition contains a polymer dispersant, the light-scattering particles can be well dispersed even when the content of the light-scattering particles is within the above range.

The mass ratio of the content of light-scattering particles to the content of light-emitting nanocrystals (light-scattering particles / light-emitting nanocrystals) is 0.1 to 5.0. The mass ratio (light scattering particles / nanocrystals for light emission) may be 0.2 or more, or 0.5 or more, from the viewpoint of being more excellent in reducing light leakage. The mass ratio (light scattering particles / nanocrystals for light emission) may be 2.0 or less, or 1.5 or less, from the viewpoint of being more excellent in reducing light leakage. The mass ratio (light scattering particles / nanocrystals for light emission) is 0.1 to 2.0, 0.1 to 1.5, 0.2 to 5.0, 0.2 to 2.0, 0.2. It may be ~ 1.5, 0.5 ~ 5.0, 0.5 ~ 2.0, or 0.5 ~ 1.5. It is considered that the reduction of leakage light by the light scattering particles is due to the following mechanism. That is, in the absence of light-scattering particles, the backlight light only travels almost straight through the pixel portion and is considered to have little chance of being absorbed by the light-emitting nanocrystals. On the other hand, if the light-scattering particles are present in the same pixel portion as the light-emitting nanocrystal, the backlight light is scattered in all directions in the pixel portion, and the light-emitting nanocrystal can receive the light, which is the same. It is considered that the amount of light absorption in the pixel portion increases even if the backlight of the above is used. As a result, it is considered that such a mechanism makes it possible to prevent leakage of light.

The photoconversion layer in the present invention preferably contains, in addition to the luminescence nanocrystals shown above, a resin component that appropriately disperses and stabilizes the luminescence nanocrystals according to the manufacturing process.

From the viewpoint of producing the photoconversion layer by a photolithography method, such a resin component is preferably a polymer of a photopolymerizable compound and can be alkaline-developed. Specifically, for example, , 1,6-Hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate and the like bifunctional monomers Polymers: Polyfunctional with relatively small molecular weight such as trimethylroll propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. Examples thereof include polymer of monomer, polymer of polyfunctional monomer having a relatively large molecular weight such as polyester acrylate, polyurethane acrylate, polyether acrylate and the like.

Further, a part of the thermoplastic resin may be used in combination with these polymers, and the thermoplastic resin includes, for example, a urethane resin, an acrylic resin, a polyamide resin, a polyimide resin, and a styrene maleic acid resin. , Styrene anhydride-based maleic acid resin and the like.

Further, in the photoconversion layer according to the present invention, if necessary, in addition to the transparent resin and the nanocrystals for light emission, a polymerization initiator, a catalyst, alumina, silica, titanium oxide beads, a scattering agent such as zeolite or zirconia, etc. It may contain known additives.

(Color material)
The optical conversion layer according to the present invention includes a three-color pixel portion of red (R), green (G), and blue (B), and may contain a color material if necessary. The color material is known as a color material. Can be used, for example, diketopyrrolopyrrole pigment and / or anionic red organic dye in the red (R) pixel portion, and copper halide phthalosinian pigment, phthalocyanine-based in the green (G) pixel portion. At least one selected from the group consisting of a mixture of a green dye, a phthalocyanine-based blue dye and an azo-based yellow organic dye contains an ε-type copper phthalosinian pigment and / or a cationic blue organic dye in the blue (B) pixel portion. It is preferable to do so.

The preferred coloring material optionally added together with the luminescent nanocrystals into 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 is preferable, and one or more selected from Red 254, 255, 264 and 272. Is more preferable, and C.I. I. Pigment Red 254 is particularly preferred. 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 preferable, and C.I. I. Solvent Red 124 is particularly preferred.

In the red color layer according to the present invention, as a coloring material, 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 selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, and 162.

The preferred coloring material optionally added together with the luminescent nanocrystals in the green color layer according to the present invention is from a metal halide phthalocyanine pigment, a phthalocyanine green dye, and a mixture of a phthalocyanine blue dye and an azo yellow organic dye. It is preferable to contain at least one selected from the group. Examples of the metal halide phthalocyanine pigment include the following two groups of metal halide phthalocyanine pigments.

(Group 1)
Phthalocyanine 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. It is a metal halide 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 has one halogen atom and a hydroxyl group. or any sulfonic acid group (-SO 3 _H) is bonded, if the central metal is tetravalent metals, one oxygen atom or two halogens may also be different in the same at the center of the metal A metal halide phthalocyanine pigment to which any of an atom, a hydroxyl group or a sulfonic acid group is bonded.

(Group 2)
2 of phthalocyanine metal halide in which a trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In is used as a central metal and 8 to 16 halogen atoms are bonded to the benzene ring of the phthalocyanine molecule per phthalocyanine molecule. A halogen in which a molecule is a constituent unit and each central metal of these constituent units is bonded via a divalent atomic group selected from the group consisting of an oxygen atom, a sulfur atom, a sulfinyl (-SO-) and a sulfonyl (-SO _2- ). A pigment consisting of a metal phthalocyanine dimer.

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

Here, the metal halide 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 has a bright green color and is ideal for use in the green pixel area of a color filter. The metal halide phthalocyanine pigment used in the present invention is insoluble or sparingly soluble in water or an organic solvent. The metal halide phthalocyanine pigment used in the present invention includes both pigments that have not been finished (also referred to as crude pigments), which will be described later, and pigments that have been finished.

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

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

In the general formula (PIG-1), X _{1 to} X ₁₆ represent 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 the X _{1 to} X ₁₆ bonded to the four benzene rings, 8 to 16 are chlorine, bromine or iodine atoms. M represents the central metal. In later-described Y and halogenated metal phthalocyanine pigment range of number m that it is the same, 16 chlorine atoms of X ₁ to X _16, pigment sum is less than 8 bromine atom and an iodine atom is blue Similarly 16 chlorine atoms of X ₁ to X _16, yellowness becomes stronger as the sum of the bromine atom and an iodine atom is larger the sum by 8 or more pigments. Y bonded to the central metal M is a monovalent atomic group selected from the group consisting of a halogen atom 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. It represents the number of Y to be used, and is an integer of 0 to 2.

The value of m is determined by the valence of the central metal M. When the central metal M has a valence of trivalent such as 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 binds to the central metal. When the central metal M has a valence of tetravalence such as Si, Ti, V, Ge, Zr, and Sn, m = 2, and one of the oxygens is bonded to the central metal, or fluorine, chlorine, Two groups selected from the group consisting of bromine, iodine, hydroxyl groups and sulfonic acid groups bind to the central metal. When the central metal M has a valence of divalent such as Mg, Fe, Co, Ni, Zn, Zr, Sn, and Pb, Y does not exist.

Further, the metal halide phthalocyanine pigment belonging to the second group is as follows in the above general formula (PIG-1).

In the general formula (PIG-1), X _{1 to} X ₁₆ have the same meaning as the above definition, 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 next atomic group.

In the chemical structure of the atomic group Y, the central metal M has the same meaning as the above definition, and X _{17 to} X _{32 have the same} meaning as the above definition of 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 a sulfonyl (-SO _2- ). M in the general formula (PIG-1) and M of the atomic group Y represent that they are bonded via the divalent atomic group A.

That is, the metal halide phthalocyanine pigment belonging to the second group is a metal halide phthalocyanine dimer in which two molecules of metal halide phthalocyanine are constituent 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 pigments, halogenated nickel phthalocyanine pigments and halogenated zinc phthalocyanine pigments. A metal halide phthalocyanine pigment having as a metal and having 8 to 16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule. Among these, the chlorinated brominated zinc phthalocyanine pigment is C.I. I. Pigment Green 58, which is particularly preferable.

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

(3) The central metal is a tetravalent metal selected from the group consisting of Si, Ti, V, Ge, Zr and Sn, such as oxytitanium phthalocyanine halide and oxyvanadium phthalocyanine halide. It has one oxygen atom or two halogen atoms which may be the same or different, a hydroxyl group or a sulfonic acid group, and 8 to 16 halogen atoms are bonded to 4 benzene rings per phthalocyanine molecule. Metal halide 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 two molecules of the halogenated metal phthalocyanine in which 8 to 16 halogen atoms are bonded to 4 benzene rings per phthalocyanine molecule are the constituent units, and each central metal of these constituent units is an oxygen atom. A pigment consisting of a metal halide phthalocyanine dimer bonded via a divalent atomic group selected from the group consisting of a sulfur atom, sulfinyl and sulfonyl.

Other colorants include C.I. in the green chromosphere. I. Solvent Blue 67 and C.I. I. Mixture with Solvent Yellow 162, or C.I. I. It is preferable to optionally contain Pigment Green 7 and / or 36.

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

The preferred coloring material optionally added together with the luminescent nanocrystals into the blue color layer according to the present invention preferably contains an epsilon-type copper phthalocinine pigment and / or a cationic blue organic dye. The epsilon-type copper phthalosinian 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, 5, 6, 7, 23, 43, 72, 124, C.I. I. Basic Blue 7 and 26 are preferable, and C.I. I. Solvent Blue 7 and Basic Blue 7 are more preferable, and C.I. I. Solvent Blue 7 is particularly preferred.

In the blue color layer according to the present invention, as a coloring material, 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 preferably contains at least one organic dye selected from the group consisting of Direct Blue 86.

Further, when the light conversion layer according to the present invention contains a yellow (Y) pixel portion (yellow color layer), as a color material, in the yellow color layer, C.I. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. It is also preferable to contain at least one yellow organic dye selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, and 162.

In the photoconversion layer of 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, and 50 parts by mass with respect to 100 parts by mass of the transparent resin. The lower limit of the content of the nanocrystals for light emission is preferably 1.0 part by mass, 3.0 parts by mass, 5.0 parts by mass, and 10.0 parts by mass with respect to 100 parts by mass of the transparent resin. When the light conversion layer contains a plurality of types of nanocrystals for light emission, the above-mentioned content represents the total amount.

(Color filter)
The optical conversion layer according to the present invention is preferably a laminated body in which a layer (NC) containing nanocrystals for light emission and a color filter (CF) are laminated (for example, FIG. 19). More specifically, the light conversion layer preferably has a red color layer R, a green color layer G, and a blue color layer B. In this case, the red (R) pixel portion R (red color layer portion R) is composed of a layer (NC) containing nanocrystals for red light emission and a color material layer (CF-Red) containing a red color material. It is preferable to be done. The green (R) pixel portion (green color layer portion G) includes a layer (NC) containing nanocrystals for green light emission and a color material layer (CF-Green) containing a green color material or a yellow color material. It is preferably composed of a color material layer (yellow color layer). The blue (R) pixel portion (blue color layer portion B) includes a color material layer containing a blue color material (CF-Blue layer containing a blue color material) and / or a transparent resin layer, and if necessary, blue light emission. It is preferably composed of a layer (NC) containing nanocrystals for use. In the present invention, the color material layer (CF-Green, CF, Red) laminated on the optical conversion pixel layer in FIG. 7, the color filter (CFL) in FIG. 8 or 9, and the blue color filter (CF-Blue) in FIG. ), A color filter containing a coloring material can be appropriately used.

The color filter is preferably formed by using the above coloring material. For example, a diketopyrrolopyrrole pigment and / or an anionic red organic dye in a red (R) color filter, a copper halide phthalosinian pigment, a phthalocyanine green dye, and a phthalocyanine blue dye in a green (G) color filter. It is preferable that at least one selected from the group consisting of a mixture of the azo-based yellow organic dye and the azo-based yellow organic dye contains an ε-type copper phthalosine pigment and / or a cationic blue organic dye in the blue (B) color filter.

Further, the color filter may contain the above-mentioned transparent resin, the above-mentioned photocurable compound, the dispersant and the like, if necessary, and the color filter can be produced by a known photolithography method or the like.

(Manufacturing method of optical conversion layer)
The light conversion layer can be formed by a conventionally known method. A typical method for forming the pixel portion is a photolithography method, in which a photocurable composition containing nanocrystals for light emission, which will be described later, is provided with a black matrix of a transparent substrate for a conventional color filter. After applying and heat-drying (pre-baking) on the side surface, pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photocurable compound at the portion corresponding to the pixel portion, and then unexposed. This is a method in which a portion is developed with a developing solution, a non-pixel portion is removed, and the pixel portion is fixed to a transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition containing nanocrystals for light emission is formed on a transparent substrate.

A photocurable composition described later is prepared for each pixel of another color such as a red (R) pixel, a green (G) pixel, a blue (B) pixel, and a yellow (Y) pixel if necessary. By repeating the above operations, it is possible to manufacture an optical conversion layer having colored pixel portions of red (R) pixels, green (G) pixels, blue (B) pixels, and yellow (Y) pixels at predetermined positions.

Examples of the method of applying the nanocrystal-containing photocurable composition for light emission described later 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 photocurable composition containing nanocrystals for light emission applied to the transparent substrate vary depending on the type of each component, the mixing ratio, etc., but are usually at 50 to 150 ° C. for about 1 to 15 minutes. is there. Further, as the light used for photocuring the nanocrystal-containing photocurable composition for light emission, it is preferable to use ultraviolet rays in the wavelength range of 200 to 500 nm or visible light. 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, a spray method and the like. After the exposure and development of the photocurable composition, the transparent substrate on which the pixel portions of the required colors are formed is washed with water and dried. The color filter thus obtained is heat-treated (post-baked) at 90 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven to remove volatile components in the colored coating film and at the same time emit light. The unreacted photocurable compound remaining in the cured colored film of the photocurable composition containing the nanocrystals for use is thermoset to complete the photoconversion layer.

When the color material and resin for the light conversion layer of the present invention are used with the nanocrystals for light emission of the present invention, the voltage retention rate (VHR) of the liquid crystal layer is lowered, deterioration due to blue light or ultraviolet light, and ion density (ID). It is possible to provide a liquid crystal display device that can prevent the increase in display defects and solve problems of display defects such as white spots, uneven orientation, and printing.

As a method for producing the above-mentioned photocurable composition containing nanocrystals for light emission, nanocrystals for light emission and an organic solvent are mixed, and if necessary, a molecule, a dispersant, a coloring material (= dye and) having an affinity are used. / Or pigment composition) and the like, and the mixture is stirred and dispersed so as to be uniform. First, a dispersion liquid for forming the pixel portion of the photoconversion layer is prepared, and then the photocurable compound is added thereto. A general method is to add a thermoplastic resin, a photopolymerization initiator, or the like as necessary to obtain a light-emitting nanocrystal-containing photocurable composition containing light-emitting nanocrystals.

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

Examples of the dispersant used here include Disparbic 130, Disparbic 161 and Disparbic 162, Disparbic 163, Disparbic 170, Disparbic 171 and Disparbic 174, Disparbic 180 and Disparbic 182 of Big Chemie. Disparbic 183, Disparbic 184, Disparbic 185, Disparbic 2000, Disparbic 2001, Disparbic 2020, Disparbic 2050, Disparbic 2070, Disparbic 2096, Disparbic 2150, Disparbic LPN21116, Disparbic LPN6919 EFKA 46, EFKA 47, EFKA 452, EFKA LP4008, EFKA 4009, EFKA LP4010, EFKA LP4050, LP4055, EFKA 400, EFKA 401, EFKA 402, EFKA 403, EFKA 450, EFKA 451, EFKA 453, EFKA 4540, EFKA 4550, EFKA LP4560, EFKA 120, EFKA 150, EFKA 1501, EFKA 1502, EFKA 1503, Lubrizole Solspers 3000, Solspers 9000, Solspers 13240, Solspers 13650, Solspers 13940, Solspers 17000, 18000, Solspers 20000, Solspers 21000, Solspers 20000 , Solspurs 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 36000, Solsperse 37000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajinomoto Co., Ltd. Dispersants such as hydrangea PB821, hydrangea PB822, hydrangea PB814, hydrangea PN411, hydrangea PA111, natural rosins such as acrylic resin, urethane resin, alkyd resin, wood rosin, gum rosin, tall oil rosin, polymerized rosin, disproportionate Modified rosins such as rosin, hydrogenated rosin, oxidized rosin, maleated rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin derivatives such as rosin modified phenol, etc. A synthetic resin that is liquid and water-insoluble at room temperature can be contained. The addition of these dispersants and resins also contributes to the reduction of flocculation, the improvement of the dispersion stability of the pigment, and the improvement of the viscosity characteristics of the dispersion.

Further, as the dispersion aid, organic pigment derivatives such as phthalimide methyl derivative, sulfonic acid derivative, N- (dialkylamino) methyl derivative, N- (dialkylaminoalkyl) sulfonic acid amide derivative and the like are also contained. You can also do it. Of course, two or more different types of these derivatives can be used in combination.

Examples of the thermoplastic resin used for preparing the nanocrystal-containing photocurable composition for light emission include urethane resin, acrylic resin, polyamide resin, polyimide resin, styrene maleic acid resin, and styrene maleic anhydride type. Examples include resin.

Examples of the nanocrystal-containing photocurable compound for light emission include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, and 3. -Bifunctional monomers such as methylpentanediol diacrylate, trimethylroll propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol penta Examples thereof include polyfunctional monomers having a relatively small molecular weight such as acrylate, and polyfunctional monomers having a relatively large molecular weight such as polyester acrylate, polyurethane acrylate, and polyether acrylate.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4'-azidobenzal) -2-propane, and 1,3-bis (4'). -Azidobenzal) -2-Propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like can be mentioned. Examples of commercially available photopolymerization initiators include BASF's "Irgacure (trade name) -184", "Irgacure (trade name) -369", "DaroCure (trade name) -1173", and BASF's "Lucillin-". "TPO", "Kayacure (trade name) DETX" manufactured by Nippon Kayaku Co., Ltd., "Kayacure (trade name) OA", "BiCure 10", "BiCure 55" manufactured by Stoffer, "Trigonal PI" manufactured by Akzo, Sand Company There are "Sandley 1000" manufactured by "Sandley 1000", "Dap" manufactured by Upjon, and "Biimidazole" manufactured by Kurokin Kasei.

Further, 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, and 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% with respect to the compound having a photopolymerizable or photocurable functional group on a mass basis. If it is less than 0.1%, the photosensitivity during photocuring tends to decrease, and if it exceeds 30%, crystals of the photopolymerization initiator are precipitated and applied when the coating film of the pigment-dispersed resist is dried. It may cause deterioration of film properties.

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 are used per 100 parts of the luminescent nanocrystals of the present invention. The dyeing pigment solution can be obtained by stirring and dispersing so as to be uniform. Next, the total amount of the thermoplastic resin and the photocurable compound was 0.125 to 2500 parts per 100 parts of this pigment dispersion, and 0.05 to 10 parts of the photopolymerization initiator per part of the photocurable compound, and if necessary. Further, an organic solvent is further added, and the photocurable composition containing nanocrystals for light emission for forming pixel portions by stirring and dispersing so as to be uniform can be obtained.

As the developing solution, 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 is alkaline-soluble, washing with an alkaline aqueous solution is a color filter. It is effective in forming the pixel portion.

Here, the method for manufacturing the colored pixel portions of R pixel, G pixel, B pixel, and Y pixel by the photolithography method has been described in detail, but the pixel portion prepared by using the nanocrystal-containing composition for light emission of the present invention. To produce an optical conversion layer by forming each color pixel portion by other methods such as electrodeposition method, transfer method, micelle electrolysis method, PVED (Photolithography) method, inkjet method, reverse printing method, and heat curing method. May be good.

A method for producing an ink composition for an optical conversion layer according to the present invention will be described. The method for producing the ink composition includes, for example, a first step of preparing a dispersion of light-scattering particles containing a light-scattering particle and a polymer dispersant, and a dispersion of light-scattering particles and a luminescent nano. It comprises a second step of mixing the crystal particles. In this method, the dispersion of the light-scattering particles may further contain a thermosetting resin, and the thermosetting resin may be further mixed in the second step. According to this method, the light scattering particles can be sufficiently dispersed. Therefore, an ink composition capable of reducing leakage light in the pixel portion can be easily obtained.

In the step of preparing a dispersion of light-scattering particles, a dispersion of light-scattering particles is obtained by mixing the light-scattering particles, a polymer dispersant, and, in some cases, a thermosetting resin, and performing a dispersion treatment. May be prepared. The mixing and dispersion treatment may be carried out using a dispersion device such as a bead mill, a paint conditioner, or a planetary stirrer. It is preferable to use a bead mill or a paint conditioner from the viewpoint that the dispersibility of the light-scattering particles is good and the average particle size of the light-scattering particles can be easily adjusted to a desired range.

Even if the method for producing an ink composition further includes a step of preparing a dispersion of luminescent nanocrystal particles containing the luminescent nanocrystal particles and a thermosetting resin before the second step. Good. In this case, in the second step, the dispersion of the light-scattering particles and the dispersion of the luminescent nanocrystal particles are mixed. According to this method, the luminescent nanocrystal particles can be sufficiently dispersed. Therefore, an ink composition capable of reducing leakage light in the pixel portion can be easily obtained. In the step of preparing the dispersion of the luminescent nanocrystal particles, the luminescent nanocrystal particles and the thermosetting resin are mixed and dispersed using the same dispersion device as in the step of preparing the dispersion of the light scattering particles. Processing may be performed.

When the ink composition of the present embodiment is used as an ink composition for an inkjet method, it is preferably applied to a piezojet type inkjet recording device using a mechanical ejection mechanism using a piezoelectric element. In the piezo jet method, the ink composition is not instantaneously exposed to a high temperature at the time of ejection, deterioration of luminescent nanocrystal particles is unlikely to occur, and the color filter pixel portion (light conversion layer) also has the expected light emitting characteristics. Is easier to obtain.

In the light conversion layer according to the present invention, for example, after forming a black matrix which is a light-shielding portion on a base material in a pattern, the pixel portion forming region partitioned by the light-shielding portion on the base material is formed by the above-described embodiment. It can be produced by a method in which an ink composition (injection ink) is selectively adhered by an inkjet method and the ink composition is cured by irradiation or heating with active energy rays.

The method of forming the light-shielding portion is to form a metal thin film such as chromium or a thin film of a resin composition containing light-shielding particles in a region serving as a boundary between a plurality of pixel portions on one surface side of the base material. Examples thereof include a method of patterning this thin film. The metal thin film can be formed by, for example, a sputtering method, a vacuum vapor deposition method, or the like, and the thin film of the resin composition containing the light-shielding particles can be formed, for example, by a method such as coating or printing. Examples of the method for patterning include a photolithography method and the like.

Examples of the inkjet method include a bubble jet (registered trademark) method using an electrothermal converter as an energy generating element, a piezojet method using a piezoelectric element, and the like.

When the ink composition is cured by irradiation with active energy rays (for example, ultraviolet rays), for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED or the like may be used. The wavelength of the light to be irradiated may be, for example, 200 nm or more and 440 nm or less. The exposure amount may be, for example, 10 mJ / cm ² or more, and may be 4000 mJ / cm ² or less.

When the ink composition is cured by heating, the heating temperature may be, for example, 110 ° C. or higher and 250 ° C. or lower. The heating time may be, for example, 10 minutes or more and 120 minutes or less.

Further, in the present specification, materials such as compounds and resins used in the inkjet method may be used in the photolithography method, and conversely, materials such as compounds and resins used in the photolithography method are used in the inkjet method. It goes without saying that it may be used in law.

Although the color filter, the optical conversion layer, and one embodiment of these manufacturing methods have been described above, the present invention is not limited to the above embodiment.

"LCD panel"
Next, the structure of the liquid crystal panel in the liquid crystal display element according to the present invention will be described.

A preferred embodiment of the liquid crystal panel 10 will be described with reference to FIGS. 10-13 and 14-16. FIG. 10 shows a schematic diagram of the structural diagram of the electrode layer 3 of the liquid crystal display unit, and is a schematic diagram showing the electrode portion of the liquid crystal panel 10 with an equivalent circuit, and FIGS. 111 and 12 show an example of the shape of the pixel electrode. It is a schematic diagram, and is the schematic diagram which shows the electrode structure of the FFS type liquid crystal display element as an example of this embodiment. FIG. 13 is a schematic view showing an electrode structure of an IPS type liquid crystal display element as an example of the present embodiment. As shown in FIGS. 1 and 2, the liquid crystal panel 10 is driven as a liquid crystal display element by providing a backlight unit as a lighting means for illuminating the liquid crystal panel 10 from the side surface side or the back surface side.

In FIGS. 1 to 2 and 10, the electrode layers 3 and 3'according to the present invention include one or more common electrodes and / or one or more pixel electrodes. For example, in the FFS type liquid crystal display element, the pixel electrodes are arranged on the common electrode via an insulating layer (for example, silicon nitride (SiN)), and in the VA type liquid crystal display element, they are common to the pixel electrodes. The electrodes are arranged so as to face each other via the liquid crystal layer 5.

Pixel electrodes are arranged for each display pixel, and a slit-shaped opening is formed. The common electrode and the pixel electrode are transparent electrodes formed by, for example, ITO (Indium Tin Oxide), and the electrode layer 3 is a gate bus line GBL (in the display unit) extending along a line in which a plurality of display pixels are arranged. GBL1, GBL2 ... GBLm), the source bus line SBL (SBL1, SBL2 ... SBLm) extending along a row in which a plurality of display pixels are arranged, and the vicinity of the position where the gate bus line and the source bus line intersect. It is equipped with a thin film transistor as a pixel switch. Further, 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 a liquid crystal display unit. Further, a plurality of gate bus lines are electrically connected to the output terminal of the gate driver, and a 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 a plurality of gate bus lines to supply the on-voltage to the gate electrodes of the thin film transistor electrically connected to the selected gate bus line. Conduction occurs between the source and drain electrodes of the thin film transistor to which the on-voltage is supplied to the gate electrode. The source driver supplies output signals corresponding to each of the plurality of source bus lines. The signal supplied to the source bus line is applied to the corresponding pixel electrodes via the thin film transistor in which the source and drain electrodes are conducted. The operation of the gate driver and the source driver is controlled by a display processing unit (also referred to as a control circuit) arranged outside the liquid crystal display element.

The display processing unit according to the present invention may have a low frequency drive function and an intermittent drive function in order to reduce the drive power in addition to the normal drive, and is an LSI for driving the gate bus line of the TFT liquid crystal panel. It controls 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. In addition, a common voltage _VCOM is supplied to the common electrode to control the operation of the backlight unit. For example, the display processing unit according to the present invention has a local dimming means for dividing the entire display screen into a plurality of sections and adjusting the light intensity of the backlight according to the brightness of the image projected on each section. May be good.

An example of an FFS type liquid crystal panel in the liquid crystal display element according to the present invention will be described with reference to FIGS. 11 and 12.

FIG. 11 is a diagram showing 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 a line II of the electrode layer 3 formed on the substrate 2 in FIGS. 1 and 2. Is. As shown in FIG. 11, the electrode layer 3 including the thin film transistor formed on the surface of the first substrate 2 has a plurality of gate bus lines 26 for supplying scanning signals and a plurality of gate bus lines 26 for supplying display signals. The source bus lines 25 are arranged so as to intersect each other in a matrix. A unit pixel of the liquid crystal display device is formed by the 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 with each other. This thin film transistor is connected to the pixel electrode 21 as a switch element that supplies a display signal to the pixel electrode 21. Further, 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 via an insulating layer 18 (not shown). The horizontal component of the shortest separation path between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance (cell gap) between the alignment layers (or between the substrates). The surface of the pixel electrode is preferably covered with a protective insulating film and an alignment layer. The "horizontal component of the shortest separation path" referred to here is the decomposition of the shortest separation path connecting the adjacent common electrode and the pixel electrode into the horizontal direction with respect to the substrate and the vertical direction (= thickness direction) with respect to the substrate. Of the components, the components in the horizontal direction with respect to the substrate. A storage capacitor (not shown) for storing the display signal supplied via the source bus line 25 may be provided in the area surrounded by the plurality of gate bus lines 26 and the plurality of source bus lines 25. Good.

Further, FIG. 12 is a modification of FIG. 11, and is a diagram showing a slit-shaped pixel electrode as an example of the shape of the pixel electrode. In the pixel electrode 21 shown in FIG. 12, the electrode of a substantially rectangular flat plate body is hollowed out with a triangular notch at the center and both ends of the flat plate body, and the other portions are notched in a substantially rectangular frame shape. The shape is hollowed out in 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.

Note that only a pair of gate bus lines 26 and a pair of source bus lines 25 in one pixel are shown in FIGS. 11 and 12.
The optical conversion layer 6 will be described below with reference to FIGS. 14 to 16.

FIG. 14 shows an example of an enlarged schematic diagram of the optical conversion layer 6 according to the present invention. The light conversion layer 6 has a red color layer R, a green color layer G, and a blue color layer B. The red (R) pixel portion R (red color layer R) is a light conversion pixel layer (NC-Red) containing nanocrystals for red light emission and a color material layer containing a blue or yellow color material (so-called yellow color filter). Or it is composed of a blue color filter). The green (G) pixel portion G (green color layer G) is a light conversion pixel layer (NC-Green) containing nanocrystals for green light emission and a color material layer containing a blue or yellow color material (so-called yellow color filter). Or it is composed of a blue color filter). The blue (B) pixel portion B (blue color layer B) is a light conversion pixel layer (or transparent resin layer) containing nanocrystals for emitting blue light, and a color material layer containing a blue or yellow color material (so-called). It is composed of a yellow color filter or a blue color filter). Therefore, in the light conversion layer 6, a color layer (so-called color filter) CFL containing a color material is laminated on the light source side with respect to the nanocrystal layer NCL containing a red color layer, a green color layer, and a blue color layer. Layers are provided. Further, a black matrix BM is provided as a light-shielding layer between the red color layer, the green color layer, and the blue color layer in order to prevent color mixing. Further, by providing the yellow color filter on one surface, it is possible to cut blue light that is not absorbed by the nanocrystals for light emission.

In FIG. 14, as one of the preferred modes of the light conversion layer, a nanocrystal layer NCL and a color material layer (so-called color filter) CFL containing a color material are laminated. Since all the light from the light source (excitation light, for example, blue light) cannot be converted by the optical conversion layer, it is necessary that the remaining excitation light is absorbed without passing through the optical conversion layer. Therefore, the light conversion layer does not visually recognize the remaining excitation light (blue light) by laminating a layer (NC) containing nanocrystals for light emission and a color layer (so-called color filter) CFL containing a coloring material. It is suppressed. However, if necessary, the color layer (so-called color filter) CFL containing the color material may be eliminated. In that case, as another preferred mode of the optical conversion layer, it is composed of a nanocrystal layer NCL as shown in FIG. 16 and the like.

Further, in FIG. 14, as the color filter layer CFL, a color layer containing a blue color material is provided as a light source assuming light having a main emission peak in a wavelength region of 420 nm or more and 480 nm or less (for example, light such as a blue LED). However, the type of the color layer is appropriately changed depending on the type of the light source used.

Further, the red color layer R, the green color layer G, and the blue color layer B may contain a color material as appropriate, if necessary. Further, the layer (NCL) containing the nanocrystal NC for light emission may contain a coloring material corresponding to each color.

FIG. 15 schematically shows another one of the preferred modes of the light conversion layer. The light conversion layer 6 has a red color layer R, a green color layer G, and a blue color layer B. The red (R) pixel portion R (red color layer R) is a light conversion pixel layer (NC) containing a color material layer (so-called red color filter) CF-Red containing a red color material and nanocrystals for red light emission. It is composed of a color material layer CFL (blue or yellow color filter CF-BLue · Yellow) containing a blue color material. The green (G) pixel portion (green color layer G) includes a color material layer containing a green color material (so-called green color filter) CF-Green and an optical conversion pixel layer (NC) containing nanocrystals for green light emission. It is composed of a color material layer CFL (blue or yellow color filter CF-Blue / Yellow) containing a blue color material. The blue (R) pixel portion (blue color layer B) is a color layer CFL (so-called blue or yellow color filter) containing a transparent resin layer and / or a blue or yellow color material, and nanocrystals for light emission included as necessary. It is composed of a layer containing (NC) and a color layer CFL (blue or yellow color filter) containing a blue color material. Further, a black matrix is arranged as a light-shielding layer between each of the red color layer, the green color layer, and the blue color layer. By providing the yellow color filter on one surface, it is possible to cut blue light that is not absorbed by the nanocrystals for light emission.

Therefore, the light conversion layer 6 includes a color filter layer CFL (blue or yellow), a layer (NCL) containing nanocrystal NC for light emission, and three primary color pixels of red (R), green (G), and blue (B). The red (R), green (G), and blue (B) color filters provided with the above are laminated in this order, and have a three-layered laminated body. However, the color filter layer CFL may be eliminated if necessary. Instead of the color material layer containing a green color material (so-called green color filter) CF-Green, a color material layer containing a yellow color material (so-called yellow color filter) may be used for color adjustment.

Further, the red color layer R, the green color layer G, and the blue color layer B may contain a color material as appropriate, if necessary. Further, the layer (NCL) containing the nanocrystal NC for light emission may contain a coloring material corresponding to each color.

With the above configuration, among the light from the light source (excitation light, for example, blue light), the light that is not absorbed by the light emitting nanocrystals is absorbed by the color filter of each color or the blue color filter layer CFL provided on one surface. Therefore, it is possible to reduce or suppress the remaining excitation light from passing through the light conversion layer. Further, also in FIG. 15, a blue color filter layer is provided as the color filter layer CFL assuming a blue LED as a light source, but the color type of the color filter layer is appropriately changed depending on the type of the light source used.

FIG. 16 shows another example of an enlarged schematic diagram of the optical conversion layer 6 according to the present invention. The light conversion layer 6 has a red color layer R, a green color layer G, and a blue color layer B. The red (R) pixel portion R (red color layer R) is composed of a light conversion pixel layer (NC-Red) containing nanocrystals for red light emission. The green (G) pixel portion G (green color layer G) is composed of a light conversion pixel layer (NC-Green) containing nanocrystals for green light emission. The blue (B) pixel portion B (blue color layer portion B) is composed of a (light conversion pixel) layer (or a transparent resin layer) containing nanocrystals for emitting blue light, if necessary. Therefore, the light conversion layer 6 is composed of one layer of the nanocrystal layer NCL including the red color layer R, the green color layer G, and the blue color layer B. Further, a black matrix BM is provided as a light-shielding layer between the red color layer R, the green color layer G, and the blue color layer B in order to prevent color mixing.

Further, the red color layer R, the green color layer G, and the blue color layer B may contain a color material as appropriate, if necessary. Further, the layer (NCL) containing the nanocrystal NC for light emission may contain a coloring material corresponding to each color.

In the embodiment of the FFS type liquid crystal display element as shown in FIGS. 1, 12, and 12, the common electrode 22 is a flat electrode formed on almost the entire surface of the gate insulating layer 12, while the common electrode 22 is a flat electrode. The pixel electrode 21 is a comb-shaped electrode formed on the insulating protective layer 18 that covers the common electrode 22. That is, the common electrode 22 is arranged at a position closer to the first substrate 2 than the pixel electrode 21, and these electrodes are arranged so as to overlap each other via the insulating protective layer 18. The pixel electrode 21 and the common electrode 22 are formed of, for example, a transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and IZTO (Indium Zinc Tin Oxide). Since the pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material, the area opened in a unit pixel area becomes large, and the opening ratio and the transmittance increase.

Further, in order to form a fringe electric field between the pixel electrode 21 and the common electrode 22, the horizontal component of the inter-electrode path between the pixel electrode 21 and the common electrode 22 (also the horizontal component of the minimum separation path). R is formed so as 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 horizontal component R of the path between the electrodes represents the distance in the horizontal direction to the substrate between the electrodes. The FFS type liquid crystal display element can utilize a horizontal electric field formed in a direction perpendicular to the comb-shaped line 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. Further, the horizontal component R of the minimum separation path between the pixel electrode and the common electrode can be adjusted by adjusting the (average) film thickness of the insulating film or the like.

An example of an IPS type liquid crystal panel, which is a modification of the FFS type liquid crystal panel in the liquid crystal display element according to the present invention, will be described with reference to FIG. The configuration of the liquid crystal panel 10 in 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 a substrate on one side as in the FFS type shown in FIG. The first polarizing layer 1, the first substrate 2, the electrode layer 3, the liquid crystal layer 5 containing the liquid crystal composition, the second polarizing layer 8, the light conversion layer 6, and the second substrate 7. , Are sequentially laminated.

FIG. 13 is an enlarged plan view of a part of the region surrounded by the line II of the electrode layer 3 formed on the first substrate 2 of FIG. 1 in the IPS type liquid crystal display unit. As shown in FIG. 13, in a region (within a unit pixel) 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, a comb-toothed shape. The first electrode (for example, a pixel electrode) 21 and the comb-shaped second electrode (for example, a common electrode) 22 are loosely fitted to each other (both electrodes are separated and mesh with each other while maintaining a certain distance). It is provided in the same state). 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 the intersection where the gate bus line 26 and the source bus line 25 intersect with each other. This 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.

In the embodiment as shown in FIG. 13, 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, and are separated from each other. It is provided in a meshed state. In the IPS type liquid crystal display unit, the distance G between the electrodes 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 of G ≧ H. Distance between electrodes: G represents the shortest distance between the first electrode 21 and the second electrode 22 in the horizontal direction on the substrate, and in the example shown in FIG. 13, the first electrode 21 and the second electrode 22 Indicates a distance in the horizontal direction with respect to a line formed alternately with the electrodes 22 of the above. Distance between the first substrate 2 and the second substrate 7: H represents the thickness of the liquid crystal layer between the first substrate 2 and the second substrate 7, and specifically, the first substrate 2. It represents the distance between the outermost surfaces (that is, the cell gap) provided on each of the substrate 2 and the second substrate 7, and the thickness of the liquid crystal layer.

On the other hand, in the above-mentioned FFS type liquid crystal panel, the thickness of the liquid crystal layer between the first substrate 2 and the second substrate 7 is the substrate between the first electrode 21 and the second electrode 22. In the IPS type liquid crystal display unit, the thickness of the liquid crystal layer between the first substrate 2 and the second substrate 7 is the thickness of the first electrode 21 and the second electrode. It is less than the shortest horizontal distance to the substrate between 22 and 22.

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

Another preferred embodiment of the liquid crystal panel of the present invention is a vertically oriented liquid crystal panel (VA type liquid crystal display).

As shown in FIG. 2, the configuration of the liquid crystal panel 10 in the liquid crystal display element according to the present invention includes a (transparent) electrode layer 3'(also referred to as a common electrode 3'), a second polarizing layer 8, and optical conversion. A second substrate 7 provided with a layer 6, a first substrate 2 including an electrode layer 3 formed with a pixel electrode and a thin film transistor for controlling the pixel electrode provided on each pixel, and the first substrate 2 and a second substrate. It has a liquid crystal layer 5 (composed of a liquid crystal composition) sandwiched between the two substrates 7, and the orientation of the liquid crystal molecules in the liquid crystal composition when no voltage is applied to the substrates 2 and 7. It is a liquid crystal display element that is substantially perpendicular to the liquid crystal display element, and one of its features is that a specific liquid crystal composition is used as the liquid crystal layer. Further, it is preferable that the electrode layer 3'is made of a transparent conductive material like other liquid crystal display elements.

Unlike the above-mentioned IPS type and FFS type, the liquid crystal panel portion of the vertically oriented liquid crystal display element has a common electrode 3'(not shown) separated from the pixel electrode 21 and placed on a substrate facing the TFT. It is formed. In other words, the pixel electrode 21 and the common electrode 22 are formed on a different substrate. On the other hand, in the above-mentioned FFS or IPS type liquid crystal display element, the pixel electrode 21 and the common electrode 22 are formed on the same substrate.

Further, the optical conversion layer 6 may form a black matrix (not shown) in a portion corresponding to the thin film transistor and the storage capacitor 23 from the viewpoint of preventing light leakage.

The liquid crystal display element according to the present invention may have a local dimming method 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 region on the liquid crystal panel and control each light emitting element L according to the brightness of the display region. In this case, the plurality of light emitting elements L may be arranged in a plane, or may be arranged in a row on one side surface side of the liquid crystal panel 10.

In the case where the structure has 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 are used. In between, the light guide unit 102 may have a control layer that controls the amount of light from the backlight for each specific region that is 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 a smaller number of pixels than the liquid crystal may be further provided, and various existing methods can be used as the liquid crystal element, but the liquid crystal on which the polymer network is formed. The LCD layer containing the above is preferable in terms of transmittance. The layer containing the (nematic) liquid crystal on which the polymer network is formed (the layer containing the (nematic) liquid crystal on which the polymer network formed by the pair of transparent electrodes is formed if necessary) scatters light when the voltage is off. Since light is transmitted when the voltage is turned on, the LCD layer including the liquid crystal in which the polymer network is divided so as to divide the entire display screen into a plurality of sections is formed as a light guide plate (and / or a light diffuser) and a liquid crystal panel. Local dimming can be realized by providing it between the substrate on the light source side of.

Further, in the liquid crystal display element according to the present invention, when a light source unit having a main emission peak at 450 nm is used, the retardation (Re) (25 ° C.) defined by the following mathematical formula (1) is Re = Δn × d. It is represented by.

(In the above mathematical 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.

A normal liquid crystal display element that switches the transmission of conventional white light including wavelengths in the entire visible light range, and blue visible light (so-called short wavelength region light) or ultraviolet light transmission of about 500 nm or less that causes excitation of the quantum dots. Since the transmitted light and the optical properties of the transmitted light are different from those of the switching liquid crystal display element, the characteristics required for each element are also different. In the prior art, the difference between a light source used in a liquid crystal display element that uses luminescent nanocrystals such as quantum dots as a light emitting element and a light source used in a normal liquid crystal display element that does not contain luminescent nanocrystals such as quantum dots. The optical characteristics of the liquid crystal material have not been optimized due to the above, and it has been confirmed that the optical characteristics of the display element using nanocrystals for light emission such as quantum dots cannot be fully utilized. However, the transmittance of the liquid crystal display element can be improved by the above retardation conditions. Therefore, another problem to be solved by the invention is to suppress or prevent a decrease in the transmittance of the liquid crystal display element.

Hereinafter, a light source unit, a polarizing layer, a liquid crystal layer, and an orientation layer which may be provided as needed, which are the main constituent elements of the liquid crystal display element according to the present invention, will be described.

(Light source)
The light source unit according to the present invention has a light emitting element that emits ultraviolet or visible light. The light emitting device is not particularly limited in the wavelength region, but preferably has a main emission peak in the blue region. For example, the light emitting device (or light emitting diode) according to the present invention having a main emission peak in a wavelength region of 420 nm or more and 480 nm or less is not particularly limited in the wavelength region, but has a main emission peak in a blue region. Is preferable. For example, a light emitting diode having a main emission peak in a wavelength region of 430 nm or more and 500 nm or less (420 nm or more and 480 nm or less) can be preferably used. As the light emitting diode having the main light emitting peak in the blue region, a known light emitting diode can be used. Examples of the light emitting diode having a main light emitting peak in the blue region include a seed layer made of AlN formed on a sapphire substrate, a base layer formed on the seed layer, and a laminated semiconductor layer mainly composed of GaN. An example is one that has at least. In addition, examples of the laminated semiconductor layer include those formed by laminating 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 low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, electrodeless lamps, metal halide lamps, xenon arc lamps, LEDs, and the like. As L, an LED that generates ultraviolet light is preferable in addition to the LED having a main emission peak in the wavelength region of 420 nm or more and 480 nm or less.

In the present specification, light having an emission center wavelength in the wavelength band of 420 to 480 nm is referred to as blue light, and light having an emission center wavelength in the wavelength band of 500 to 560 nm is referred to as green light, and has a wavelength of 605 to 665 nm. Light having a emission center wavelength in the band is called red light. Further, the ultraviolet light in the present specification means light having a emission center wavelength in a wavelength band of 300 nm or more and less than 420 nm. Further, in the present specification, the "full width at half maximum" means the width of the peak at the peak height of 1/2.

(Polarizing layer)
The polarizing layer according to the present invention is not particularly limited, and a known polarizing plate (polarizing layer) can be used. For example, a dichroic organic dye polarizer, a coating type polarizing layer, a wire grid type polarizer, a cholesteric liquid crystal type polarizer, and the like can be mentioned. For example, a wire grid type polarizer is formed on a first substrate, a second substrate, and a color filter, and is formed by any one of nanoimprint method, block copolymer method, E-beam lithography method, and glancing angle deposition method. Is preferable. Further, when forming a coating type polarizing layer, an orientation layer described below in this specification may be further provided. Therefore, when the polarizing layer according to the present invention is a coating type polarizing layer, it is preferable to have a coating type polarizing layer and an orientation layer.

Hereinafter, a liquid crystal layer, an alignment layer which may be provided if necessary, and the like, which are constituent elements of the liquid crystal panel portion of the liquid crystal display element according to the present invention, will be described.

The liquid crystal composition used for the liquid crystal layer of the liquid crystal display element according to the present invention has a negative dielectric anisotropy, the transition temperature of the nematic phase-isotropic liquid is 60 ° C. or higher, and the dielectric anisotropy. The absolute value of is 1.5 or more, and contains one or more compounds selected from the group of compounds represented by the following general formulas (N-1), (N-2) and (N-3). ..

(In the formula, ^RN11 , ^RN12 , ^RN21 , ^RN22 , ^RN31 and ^RN32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two non-adjacent ones. More than one −CH ₂₋ may be independently substituted by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are independently (a) 1,4-cyclohexylene groups (one -CH _2- or adjacent to each other in this group). No two or more -CH _2- may be replaced by -O-) and (b) 1,4-phenylene group (one -CH = or non-adjacent 2 present in this group) More than one -CH = may be replaced with -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 = existing in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. )
(D) Represents a group selected from the group consisting of 1,4-cyclohexenylene groups, and the above groups (a), group (b), group (c) and group (d) are independently fluorine atoms. May be replaced,
^{Z N11, Z N12, Z N21} , Z N22, Z N31 and ^{Z N32} 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-
X ^N21 represents a hydrogen atom or a fluorine atom.
^TN31 represents −CH _2- or oxygen atom,
Although n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 each independently represent an integer of 0 to 3, n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are independent of each other. When it is 1, 2 or 3, and there are a plurality of A ^{N11 to} A ^N32 and Z ^{N11 to} Z ^N32 , they may be the same or different. )
The compounds represented by the general formulas (N-1), (N-2) and (N-3) correspond to dielectrically negative compounds (the sign of Δε is negative and its absolute value is larger than 2). To do.

The compounds represented by the general formulas (N-1), (N-2) and (N-3) are preferably compounds having a negative Δε and an absolute value greater than 3.

In the general formulas (N-1), (N-2) and (N-3), ^RN11 , ^RN12 , ^RN21 , ^RN22 , ^RN31 and ^RN32 are independent of each other and have 1 to 8 carbon atoms. Alkyl group, alkoxy group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms or alkenyloxy group having 2 to 8 carbon atoms is preferable, and the alkyl group having 1 to 5 carbon atoms and the number of carbon atoms are preferable. An alkoxy group having 1 to 5 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 further preferable, and an alkenyl group (propenyl group) having 3 carbon atoms is particularly preferable.

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

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

A ^N11 , ^AN12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are preferably aromatics when it is required to increase Δn independently, and fats are used to improve the response rate. It is preferably a group, and is preferably a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 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, which are preferably represented as follows. It is more preferable to represent the structure of

It is more preferable to represent 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.

Fluorine atom is preferable for X ^N21 .

Oxygen atom is preferable for ^TN31 .

n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are preferably 1 or 2, n ^N11 is 1 and n ^N12 is 0, n ^N11 is 2 and n ^N12 is 0, n ^{The combination of N11} being 1 and ^nN12 being 1, the combination of ^nN11 being 2 and ^nN12 being 1, the combination of ^nN21 being 1 and ^nN22 being 0, ^nN21 being 2 and ^nN22 being A combination of 0, a combination of n ^N31 of 1 and n ^N32 of 0, and a combination of n ^N31 of 2 and n ^N32 of 0 are preferred.

In the present application,% means mass% unless otherwise specified.

The lower limit of the preferable content of the compound represented by the formula (N-1) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1% and 10%. 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%. Is.

The lower limit of the preferable content of the compound represented by the formula (N-2) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1% and 10%. 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%. Is.

The lower limit of the preferable content of the compound represented by the formula (N-3) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1% and 10%. 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%. Is.

When a composition having a low viscosity and a high response speed is required for the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention, it is preferable that the lower limit value and the upper limit value are low. Further, when a composition having a high Tni of the composition of the present invention and good temperature stability is required, it is preferable that the above lower limit value is low and the upper limit value is low. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is high and the upper limit value is high.

Examples of the compound represented by the general formula (N-1) include a group of compounds represented by the following general formulas (N-1a) to (N-1g).

^{(Wherein, R N11} and ^{R N12} are as defined ^{R N11} and ^{R N12} in the general formula ^{(N-1), n Na11} represents 0 or ^{1, n NB11} is 1 or ^{2, n NC11} is ^Represents 0 or 1, n ^Nd11 represents 1 or 2, n ^Ne11 represents 1 or 2, n ^Nf12 represents 1 or 2, n ^{Ng 11} represents 1 or 2, and A ^{Ne 11} represents trans-1,4. ^{-Represents a} cyclohexylene group or a 1,4-phenylene group, and A ^Ng11 represents a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group, but at least one. ^{Represents a} 1,4-cyclohexenylene group, Z ^Ne11 represents a single bond or ethylene, but at least one present in the molecule represents ethylene, and multiple A ^Ne11 , Z ^Ne11 , and / or present in the molecule. A ^{Ng 11} may be the same or different.)
More specifically, the compound represented by the general formula (N-1) may be a compound selected from the compound group represented by the general formulas (N-1-1) to (N-1-21). preferable.

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

^{(Wherein, R N111} and ^{R N112} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a propyl group, a pentyl group or a vinyl group. ^RN112 is 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, and preferably an ethoxy group or a butoxy group.

The compound represented by the general formula (N-1-1) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set low. Further, when improving the dripping marks and the seizure 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 (N-1-1) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35% is there. The preferred upper limit of the content is 50%, 40%, 38%, 35%, 33%, 30%, 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6 %, 5%, and 3%.

Further, the compound represented by the general formula (N-1-1) is a compound selected from the compound group represented by the formulas (N-1-1.1) to (N1-1.23). It is preferable that the compound is represented by the formulas (N-1-1.1) to (N-1-1.4), and the formulas (N-1-1.1) and the formula (N-1-1.4) are preferable. The compound represented by -1-1.3) is preferable.

The compounds represented by the formulas (N-1-1.1) to (N1-1.22) can be used alone or in combination, but the composition of the present invention can be used. The lower limit of the preferred content of the single or these compounds relative to the total amount is 5%, 10%, 13%, 15%, 17%, 20%, 23%. , 25%, 27%, 30%, 33%, 35%. The preferred upper limit of the content is 50%, 40%, 38%, 35%, 33%, 30%, 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6 %, 5%, and 3%.

The compound represented by the general formula (N-1-2) is the following compound.

^{(Wherein, R N121} and ^{R N122} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, a butyl group or a pentyl group. The ^RN122 is 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, and a methyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group. preferable.

The compound represented by the general formula (N-1-2) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set low, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-1-2) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 7%. Yes, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33% Yes, 35%, 37%, 40%, 42%. The preferred upper limit of the content is 50%, 48%, 45%, 43%, 40%, 38%, 35% with respect to the total amount of the composition of the present invention. %, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10 %, 8%, 7%, 6%, 5%.

Further, the compound represented by the general formula (N-1-2) is a compound selected from the compound group represented by the formulas (N-1-2.1) to (N-1-2.22). It is preferable that there are formulas (N-1-2.3) to formulas (N-1-2.7), formulas (N1-2.10), formulas (N-1-2.11), and formulas. It is preferably a compound represented by (N-1-2.13) and the formula (N-1-2.20), and when the improvement of Δε is emphasized, the formula (N-1-2.3) is used. is preferably a compound represented by the formula (N-1-2.7) _from when emphasizing improvements in _{T NI} formula (N-1-2.10), formula (N-1-2.11) And the compound represented by the formula (N-1-2.13) is preferable, and the compound represented by the formula (N-1-2.20) is used when the improvement of the response speed is emphasized. Is preferable.

The compounds represented by the formulas (N-1-2.1) to (N-1-2.22) can be used alone or in combination, but the composition of the present invention can be used. The lower limit of the preferred content of these compounds alone or of these compounds relative to the total amount of is 5%, 10%, 13%, 15%, 17%, 20%, 23. %, 25%, 27%, 30%, 33%, 35%. The preferred upper limit of the content is 50%, 40%, 38%, 35%, 33%, 30%, 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6 %, 5%, and 3%.

The compound represented by the general formula (N-1-3) is the following compound.

^{(Wherein, R N131} and ^{R N132} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably a 1-propenyl group, an ethoxy group, a propoxy group or a butoxy group. ..

The compound represented by the general formula (N-1-3) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-1-3) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

Further, the compound represented by the general formula (N-1--3) is a compound selected from the compound group represented by the formulas (N-1-3.21) to (N-1-3.21). It is preferable that the compound is represented by the formulas (N-1-3.1) to (N-1-3.7) and (N-1-3.21), and is preferably the compound represented by the formula (N-1-3.21). -1-3.1), Eq. (N-1-3.2), Eq. (N-1-3.3), Eq. (N-1-3.4) and Eq. (N-1-3.6) ) Is preferable.

The compounds represented by the formulas (N-1-3.1) to (N-1-3.4), the formula (N-1-3.6) and the formula (N-1-3.21) are independent. It can be used in the above or in combination, but it is a combination of the formulas (N-1-3.1) and (N-1-3.2) and the formula (N-1-3.3). ), Formula (N-1-3.4) and formula (N-1-3.6), 2 or 3 combinations are preferred. The lower limit of the preferable content of a single compound or these compounds with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, 10%, 13%, and 15%. It is 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

The compound represented by the general formula (N-1-4) is the following compound.

^{(Wherein, R N141} and ^{R N142} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
Independently R ^N141 and ^{R N142} are each an alkyl group having 1 to 5 carbon atoms, preferably an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 4-5, methyl group, propyl group, ethoxy A group or a butoxy group is preferable.

The compound represented by the general formula (N-1-4) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set low. Further, when improving the dripping marks and the seizure 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 (N-1-4) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 3%, which is 5%. Yes, 7%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. , 20%, 18%, 15%, 13%, 11%, 10%, 8%.

Further, the compound represented by the general formula (N-1--4) is a compound selected from the compound group represented by the formulas (N-1-4.1) to (N-1-4.14). It is preferable that the compound is represented by the formulas (N-1-4.1) to (N-1-4.4), and the compounds are preferably of the formulas (N-1-4.1) and (N-1-4.4). The compounds represented by -1-4.2) and the formula (N-1-4.4) are preferable.

The compounds represented by the formulas (N-1-4.1) to (N-1-4.14) can be used alone or in combination, but the liquid crystal display according to the present invention. The lower limit of the preferable content of the composition alone or these compounds with respect to the total amount of the composition used for the liquid crystal layer of the device is 3%, 5%, 7%, 10%, and 13%. Yes, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. , 20%, 18%, 15%, 13%, 11%, 10%, 8%.

The compound represented by the general formula (N-1-5) is the following compound.

^{(Wherein, R N151} and ^{R N152} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
Each of ^RN151 and ^RN152 is independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, preferably an ethyl group, a propyl group, or a butyl group. Is preferable.

The compound represented by the general formula (N-1-5) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set low, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-1-5) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 8%. Yes, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 33%, 30%, 28%, and 25% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. , 23%, 20%, 18%, 15%, 13%.

Further, the compound represented by the general formula (N-1-5) is a compound selected from the compound group represented by the formulas (N-1-5.1) to (N-1-5.6). It is preferable that the compound is represented by the formula (N-1-5.1), the formula (N-1-5.2) and the formula (N-1-5.4).

The compounds represented by the formulas (N-1-5.1), (N-1-5.2) and (N-1-5.4) may be used alone or in combination. However, the lower limit of the preferable content of the composition alone or of these compounds with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, 8%, and 10%. %, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 33%, 30%, 28%, and 25% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. , 23%, 20%, 18%, 15%, 13%.

The compound represented by the general formula (N-1-10) is the following compound.

^{(Wherein, R N1101} and ^{R N1102} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, a butyl group, a vinyl group or a 1-propenyl group. ^RN1102 is 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, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-10) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set low. Further, when improving the dripping marks and the seizure 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 (N-1-10) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

Further, the compound represented by the general formula (N-1-10) is a compound selected from the compound group represented by the formulas (N-1-10.14) to (N-110.14). It is preferable that the compound is represented by the formulas (N-1-10.1) to (N-1-10.5), and the compounds are preferably represented by the formulas (N-1-10.1) to (N-1-10.5). The compound represented by 1-10.2) is preferable.

The compounds represented by the formulas (N-1-10.1) and (N-1-10.2) can be used alone or in combination, but the liquid crystal according to the present invention. The lower limit of the preferable content of the composition alone or these compounds with respect to the total amount of the composition used for the liquid crystal layer of the display element is 5%, 10%, 13%, 15%, and 17%. It is 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

The compound represented by the general formula (N-1-11) is the following compound.

^{(Wherein, R N1111} and ^{R N1112} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, a butyl group, a vinyl group or a 1-propenyl group. ^RN1112 is 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, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-11) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set low, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-1-11) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

Further, the compound represented by the general formula (N-1-11) is a compound selected from the compound group represented by the formulas (N-1-11.1) to (N-1-1.14). It is preferable that the compound is represented by the formulas (N-1-11.1) to (N-1-1.14), and the formulas (N-1-11.2 and N-) are preferable. The compound represented by 1-11.4) is preferable.

The compounds represented by the formulas (N-1-11.2) and (N-1-11.4) can be used alone or in combination, but the liquid crystal according to the present invention. The lower limit of the preferable content of the composition alone or these compounds with respect to the total amount of the composition used for the liquid crystal layer of the display element is 5%, 10%, 13%, 15%, and 17%. It is 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

The compound represented by the general formula (N-1-12) is the following compound.

^{(Wherein, R N1121} and ^{R N1122} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1122 is 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, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-12) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set low. Further, when improving the dripping marks and the seizure 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 (N-1-12) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%.

The compound represented by the general formula (N-1-13) is the following compound.

^{(Wherein, R N1131} and ^{R N1132} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1132 is 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, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-13) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-1-13) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

The compound represented by the general formula (N-1-14) is the following compound.

^{(Wherein, R N1141} and ^{R N1142} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1141 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1142 is 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, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-14) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set low. Further, when improving the dripping marks and the seizure 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 (N-1-14) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

The compound represented by the general formula (N-1-15) is the following compound.

^{(Wherein, R N1151} and ^{R N1152} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1151 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1152 is 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, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-15) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-1-15) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

The compound represented by the general formula (N-1-16) is the following compound.

^{(Wherein, R N1161} and ^{R N1162} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1162 is 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, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-16) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-1-16) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

The compound represented by the general formula (N-1-17) is the following compound.

^{(Wherein, R N1171} and ^{R N1172} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1171 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1172 is 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, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-17) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-1-17) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

The compound represented by the general formula (N-1-18) is the following compound.

^{(Wherein, R N1181} and ^{R N1182} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a methyl group, an ethyl group, a propyl group or a butyl group. ^RN1182 is 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, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-18) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-1-18) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

Further, the compound represented by the general formula (N-1-18) is a compound selected from the compound group represented by the formulas (N-1-18.1) to (N-1-18.5). It is preferable that the compound is represented by the formulas (N-1-18.1) to (N-1-11.3), and the compounds are preferably represented by the formulas (N-1-18.2) and (N-1-11.3). The compound represented by 1-18.3) is preferable.

The compound represented by the general formula (N-1-20) is the following compound.

^{(Wherein, R N1201} and ^{R N1202} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1201 and ^RN1202 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group.

The compound represented by the general formula (N-1-20) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-1-20) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

The compound represented by the general formula (N-1-21) is the following compound.

^{(Wherein, R N1211} and ^{R N1212} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1211 and ^RN1212 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group.

The compound represented by the general formula (N-1-21) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-2-1) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 5%, which is 10%. Yes, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 20%, it is 18%, it is 15%, and it is 13%.

The compound represented by the general formula (N-1-22) is the following compound.

^{(Wherein, R N1221} and ^{R N1222} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1221 and ^RN1222 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group.

The compound represented by the general formula (N-1-22) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-2-1) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, which is 5%. Yes, 10%, 13%, 15%, 17%, and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. , 20%, 18%, 15%, 13%, 10%, 5%.

Further, the compound represented by the general formula (N-1-22) is a compound selected from the compound group represented by the formulas (N-1-22.1) to (N-1-2.12.2). It is preferable that the compound is represented by the formulas (N-1-22.1) to (N-1-22.5), and the compounds are preferably represented by the formulas (N-1-22.1) to (N-). The compound represented by 1-22.4) is preferable.

The compound represented by the general formula (N-3) is preferably a compound selected from the compound group represented by the general formula (N-3-2).

^{(Wherein, R N321} and ^{R N322} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-3).)
^RN321 and ^RN322 are preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a propyl group or a pentyl group.

The compound represented by the general formula (N-3-2) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set high, and when the _TNI is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure 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 (N-3-2) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 3%, which is 5%. Yes, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33% Yes, it is 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, and 33% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. , 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%. It is 7%, it is 6%, and it is 5%.

Further, the compound represented by the general formula (N-3-2) is a compound selected from the compound group represented by the formulas (N-3-2.1) to (N-3-2.3). It is preferable to have.

Among the compounds represented by the general formulas (N-1), (N-2) and (N-3) contained in the liquid crystal composition, Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32. The total content of the compounds in which is a single bond is 5 to 50% by mass with respect to the total content of the compounds represented by the general formulas (N-1), (N-2) and (N-3). In the compound represented by the general formula (N-1) contained in the liquid crystal composition, the compound in which Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32 are single-bonded. The total content of the compounds is preferably 5 to 50% by mass with respect to the total content of the compounds represented by the general formulas (N-1), (N-2) and (N-3).

^Examples of the compound represented by the general formula (N-1) in which Z ^N11 and Z ^N12 are single bonds include the general formulas (N-1a), (N-1b), (N-1c) and (N-1g). The compound represented by (N-1a), (N-1b) and (N-1c) is preferable.

In addition, the general formulas (N-1-1), (N-1-2), (N-1-3), (N-1--4), (N-1-5) and (N-1-22) ) Is preferable.
Compounds represented by the general formulas (N-1-1), (N-1-2), (N-1-3), (N-1-4) and (N-1-5) are preferable.

The total content of the compounds represented by the general formulas (N-1), (N-2) and (N-3) in the total content of the compounds having a negative dielectric anisotropy is 80% or more. It is preferably 85% or more, 87% or more, 90% or more, 93% or more, 96% or more, and more preferably 96% or more. It is preferably 98% or more, and substantially 100% or more. Substantially means excluding compounds that are unintentionally contained, such as impurities during production.

Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32 in the compounds represented by the general formulas (N-1), (N-2) and (N-3) contained in the liquid crystal composition. The total content of the compounds that are single bonds is preferably 50 to 100% of the total content of the compounds represented by the general formulas (N-1), (N-2) and (N-3). , 60-100%, preferably 65-95%, preferably 70-90%.

The total content of the compounds in which Z ^N11 and Z ^N12 are single bonds in the compound represented by the general formula (N-1) contained in the liquid crystal composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is The total content of the compounds represented by the general formulas (N-1), (N-2) and (N-3) is preferably 50 to 100%, preferably 60 to 100%, and 65 to 95%. Is preferable, and 70 to 90% is preferable.

The compounds represented by the general formulas (N-1a), (N-1b), (N-1c) and (N-1g) contained in the liquid crystal composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. The total content is preferably 50 to 100%, preferably 60 to 100%, based on the total content of the compounds represented by the general formulas (N-1), (N-2) and (N-3). It is preferably 65 to 95%, preferably 70 to 90%.

The general formulas (N-1-1), (N-1-2), (N-1-3) and (N-1-) contained in the liquid crystal composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. The total content of the compounds represented by 4) is 50 to 100% of the total content of the compounds represented by the general formulas (N-1), (N-2) and (N-3). Is preferable, 60 to 100% is preferable, 65 to 95% is preferable, and 70 to 90% is preferable.

In the general formulas (N-1), (N-2) and (N-3) with respect to the total content of the compounds represented by the general formulas (N-1), (N-2) and (N-3). The content of the compound in which Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32 are single bonds in the represented compound, Z ^N11 and Z ^N12 in the compound represented by the general formula (N-1). The content of the compound in which is a single bond, the content of the compound represented by the general formulas (N-1a), (N-1b), (N-1c) and (N-1g), and the general formula (N-1). The preferable lower limit of the content of the compounds represented by -1), (N-1-2), (N-1-3) and (N-1--4) is 50% and 60%. , 65% and 70%. Similarly, the preferred upper limits are 100%, 98%, 95%, 93%, 91%, and 90%.

When a liquid crystal display element is produced using the liquid crystal composition having the adjusted content, the liquid crystal display element does not have an alignment film on at least one of the first substrate and the second substrate and the liquid crystal layer. However, when a light conversion layer containing nanocrystals for light emission is used instead of a color filter, deterioration of the liquid crystal layer due to irradiation with high-energy light rays is suppressed or prevented while achieving both high light emission efficiency and color reproducibility. can do.

The liquid crystal composition used for the liquid crystal layer of the liquid crystal display element according to the present invention preferably contains one or more compounds represented by the general formula (L). The compound represented by the general formula (L) corresponds to a dielectrically substantially neutral compound (the value of Δε is -2 to 2). Therefore, the number of polar groups such as halogens contained in the molecule is preferably 2 or less, preferably 1 or less, and preferably not present.

(Wherein, R ^L1 and R ^L2 represent each independently an alkyl group having 1 to 8 carbon atoms, one or non-adjacent two or more -CH 2 in the alkyl group _- is independently It may be replaced 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 (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - May be replaced with -O-) and (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = -N May be replaced with =)
(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 = existing in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. )
Representing a group selected from the group consisting of, the above group (a), group (b) and group (c) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, respectively.
Z ^L1 and ^{Z L2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
If n ^L1 is 2 or 3 and there are a plurality of A ^L2s , they may be the same or different, and if n ^L1 is 2 or 3 and there are a plurality of Z ^L3s , they may be the same or different. May be the same or different, except for the compounds represented by the general formulas (N-1), (N-2) and (N-3). )
The compound represented by the general formula (L) may be used alone, or may be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to desired performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The type of compound used is, for example, one type 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, and ten. More than a kind.

In the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention, the content of the compound represented by the general formula (L) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. It is necessary to make appropriate adjustments according to the required performance such as process compatibility, dripping marks, seizure, 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 composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, 10%, and 20%. , 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, and 25%.

When a composition having a low viscosity and a high response rate is required, it is preferable that the above lower limit value is high and the upper limit value is high. Further, when a composition having a high Tni of the composition of the present invention and good temperature stability is required, it is preferable that the above lower limit value is high and the upper limit value is high. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is low and the upper limit value is low.

Both ^RL1 and ^RL2 are preferably alkyl groups when reliability is important, and alkoxy groups are preferable when reducing the volatility of the compound is important, and reduction of viscosity is important. It is preferable that at least one of them is an alkenyl group.

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

^RL1 and ^RL2 are linear alkyl groups having 1 to 5 carbon atoms and linear carbon atoms 1 to 4 when the ring structure to which they are bonded is a phenyl group (aromatic). The alkoxy group and the alkenyl group having 4 to 5 carbon atoms are preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, the linear carbon atom number is 1 to 5. Alkyl groups, linear alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

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

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

Preferably A ^L1, A ^L2, and A ^L3 if it is required to increase the Δn is aromatic, preferably to improve the response speed is an aliphatic, 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 is preferable to represent a −diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably to represent the following structure.

It is more preferable to represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

Z ^L1 and Z ^L2 are preferably single-bonded when response speed is important.

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

The compound represented by the general formula (L) is preferably a compound selected from the compound group represented by the general formulas (L-1) to (L-7).

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

^{(Wherein, R L11} and ^{R L12} are each independently the same meaning as ^{R L1} and ^{R L2} in Formula (L).)
R ^L11 and ^RL12 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 (L-1) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

The lower limit of the preferable content is 1%, 2%, 3%, 5%, and 7% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%. Is. The preferred upper limit of the content is 95%, 90%, 85%, 80%, 75%, 70%, 65% with respect to the total amount of the composition of the present invention. %, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%.

When a composition having a low viscosity and a high response speed is required for the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention, it is preferable that the above lower limit value is high and the upper limit value is high. Further, when a composition having a high Tni of the composition of the present invention and good temperature stability is required, it is preferable that the above lower limit value is moderate and the upper limit value is moderate. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is low and the upper limit value is low.

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

(In the formula, ^RL12 has the same meaning as in the general formula (L-1).)
The compound represented by the general formula (L-1-1) shall be a compound selected from the compound group represented by the formulas (L-1-1.1) to (L-1-1.3). Is preferable, and it is preferable that the compound is represented by the formula (L-1-1.2) or the formula (L-1-1.3), and in particular, the compound is represented by the formula (L-1-1.3). It is preferably a compound.

The lower limit of the preferable content of the compound represented by the formula (L-1-1.3) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, which is 2%. %, 3%, 5%, 7%, 10%. The upper limit of the preferable content is 20%, 15%, 13%, 10%, and 8% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 7%, it is 6%, it is 5%, and it is 3%.

The compound represented by the general formula (L-1) is preferably a compound selected from the compound group represented by the general formula (L-1-2).

(In the formula, ^RL12 has the same meaning as in the general formula (L-1).)
The lower limit of the preferable content of the compound represented by the formula (L-1-2) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, which is 5%. Yes, 10%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 35%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, and 42% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 40%, 38%, 35%, 33%, and 30%.

Further, the compound represented by the general formula (L-1-2) is a compound selected from the compound group represented by the formulas (L-1-2.1) to (L-1-2.4). It is preferable that the compound is represented by the formulas (L-1-2.2) to (L-1-2.4). In particular, the compound represented by the formula (L-1-2.2) is preferable because it particularly improves the response rate of the composition of the present invention. Further, when obtaining Tni higher than the response speed, it is preferable to use a compound represented by the formula (L-1-2.3) or the formula (L-1-2.4). The content of the compounds represented by the formulas (L-1-2.3) and (L-1-2.4) is not preferably 30% or more in order to improve the solubility at a low temperature.

The lower limit of the preferable content of the compound represented by the formula (L-1-2.2) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 10%, which is 15 %, 18%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 38%, 40. %. The upper limit of the preferable content is 60%, 55%, 50%, 45%, and 43% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. , 40%, 38%, 35%, 32%, 30%, 27%, 25%, 22%.

The compound represented by the formula (L-1-1.3) and the compound represented by the formula (L-1-2.2) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. The lower limit of the preferred total content of the compounds is 10%, 15%, 20%, 25%, 27%, 30%, 35%, 40%. is there. The upper limit of the preferable content is 60%, 55%, 50%, 45%, and 43% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. , 40%, 38%, 35%, 32%, 30%, 27%, 25%, 22%.

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

(In the formula, ^RL13 and ^RL14 independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
^RL13 and ^RL14 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 (L-1-3) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, which is 5%. Yes, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 30%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, and 40% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. 37%, 35%, 33%, 30%, 27%, 25%, 23%, 20%, 17%, 15%. It is 13% and 10%.
Further, the compound represented by the general formula (L-1--3) is a compound selected from the compound group represented by the formulas (L-1-3.1) to (L-1-3.13). It is preferable that the compound is represented by the formula (L-1-3.1), the formula (L-1-3.3) or the formula (L-1-3.4). In particular, the compound represented by the formula (L-1-3.1) is preferable because it particularly improves the response rate of the composition of the present invention. Further, when obtaining Tni higher than the response speed, the formula (L-1-3.3), the formula (L-1-3.4), the formula (L-1-3.11) and the formula (L-) are obtained. It is preferable to use the compound represented by 1-3.12). Total of compounds represented by formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L-1-3.13) The content of is not preferably 20% or more in order to improve the solubility at low temperature.

The lower limit of the preferable content of the compound represented by the formula (L-1-3.1) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, which is 2%. %, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferable content is 20%, 17%, 15%, 13%, and 10% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 8%, it is 7%, and it is 6%.

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

(In the formula, ^RL15 and ^RL16 independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
^RL15 and ^RL16 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 (L-1-4) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, which is 5%. Yes, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 25%, 23%, 20%, 17%, and 15% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 13% and 10%.

The lower limit of the preferable content of the compound represented by the formula (L-1-5) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, which is 5%. Yes, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 25%, 23%, 20%, 17%, and 15% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 13% and 10%.

Further, the compounds represented by the general formulas (L-1-4) and (L-1-5) are represented by the formulas (L-1-5.3) from the formulas (L-1-4.1). It is preferable that the compound is selected from the above-mentioned compound group, and the compound represented by the formula (L-1-4.2) or the formula (L-1-5.2) is preferable.

The lower limit of the preferable content of the compound represented by the formula (L-1-4.2) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, which is 2%. %, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferable content is 20%, 17%, 15%, 13%, and 10% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 8%, it is 7%, and it is 6%.

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

(In the formula, ^RL17 and ^RL18 each independently represent a methyl group or a hydrogen atom.)
The lower limit of the preferable content of the compound represented by the formula (L-1-6) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, which is 5%. Yes, 10%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 35%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, and 42% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 40%, 38%, 35%, 33%, and 30%.

Further, the compound represented by the general formula (L-1-6) is a compound selected from the compound group represented by the formulas (L-1-6.1) to (L-1-6.3). It is preferable to have.

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

^{(Wherein, R L21} and ^{R L22} are each independently the same meaning as ^{R L1} and ^{R L2} in Formula (L).)
^RL21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and ^RL22 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or a carbon atom. Alkoxy groups of numbers 1 to 4 are preferred.

The compound represented by the general formula (L-2) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When the solubility at low temperature is emphasized, the effect is high when the content is set high, and conversely, when the response speed is emphasized, the effect is high when the content is set low. Further, when improving the dripping marks and the seizure 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 (L-2) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1% and 2%. It is 3%, 5%, 7%, and 10%. The upper limit of the preferable content is 20%, 15%, 13%, 10%, and 8% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 7%, it is 6%, it is 5%, and it is 3%.

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

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

^{(Wherein, R L31} and ^{R L32} are each independently the same meaning as ^{R L1} and ^{R L2} in Formula (L).)
Each of ^RL31 and ^RL32 is 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. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

The lower limit of the preferable content of the compound represented by the formula (L-3) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1% and 2%. It is 3%, 5%, 7%, and 10%. The upper limit of the preferable content is 20%, 15%, 13%, 10%, and 8% with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. It is 7%, it is 6%, it is 5%, and it is 3%.

When a high birefringence is obtained, the effect is high when the content is set high, and conversely, when high Tni is emphasized, the effect is high when the content is set low. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

Further, the compound represented by the general formula (L-3) is preferably a compound selected from the compound group represented by the formulas (L-3.1) to (L-3.7), preferably the formula. It is preferably a compound represented by the formula (L-3.5) from (L-3.2).

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

^{(Wherein, R L41} and ^{R L42} are each independently the same meaning as ^{R L1} and ^{R L2} in Formula (L).)
^RL41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and ^RL42 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or a carbon atom. Alkoxy groups of numbers 1 to 4 are preferred. )
The compound represented by the general formula (L-4) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

In the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention, the content of the compound represented by the general formula (L-4) includes solubility at low temperature, transition temperature, electrical reliability, and birefringence. It is necessary to make appropriate adjustments according to the required performance such as rate, process compatibility, dripping marks, seizure, 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 composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1% and 2%. 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, It is 35% and 40%. The upper limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 50% and 40%. 35%, 30%, 20%, 15%, 10%, 5%.

The compound represented by the general formula (L-4) is preferably a compound represented by the formulas (L-4.1) to (L-4.3), for example.

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., even if the compound represented by the formula (L-4.1) is contained, the formula (L) Even if it contains the compound represented by 4.2), it contains both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2). It may contain all the compounds represented by the formulas (L-4.1) to (L-4.3). The lower limit of the preferable content of the compound represented by the formula (L-4.1) or the formula (L-4.2) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 3, 5%, 7%, 9%, 11%, 12%, 13%, 18%, 21%, and the preferred upper limit is , 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, It is 10% and 8%.

When both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2) are contained, the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. The lower limit of the preferred content of both compounds with respect to the total amount of is 15%, 19%, 24%, 30%, and the preferred upper limit is 45, 40%. , 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the general formula (L-4) is preferably a compound represented by the formulas (L-4.4) to (L-4.6), for example, preferably the compound represented by the formula (L-4.4). ) Is preferable.

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., even if the compound represented by the formula (L-4.4) is contained, the formula (L) Even if it contains the compound represented by −4.5), it contains both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5). You may be.

The lower limit of the preferable content of the compound represented by the formula (L-4.4) or the formula (L-4.5) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is It is 3%, it is 5%, it is 7%, it is 9%, it is 11%, it is 12%, it is 13%, it is 18%, and it is 21%. Preferred upper limits are 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13 %, 10%, 8%.

When both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5) are contained, the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. The lower limit of the preferred content of both compounds with respect to the total amount of is 15%, 19%, 24%, 30%, and the preferred upper limit is 45, 40%. , 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the general formula (L-4) is preferably a compound represented by the formulas (L-4.7) to (L-4.10), and in particular, the compound represented by the formula (L-4. The compound represented by 9) is preferable.

The compound represented by the general formula (L-5) is the following compound.

^{(Wherein, R L51} and ^{R L52} are each independently the same meaning as ^{R L1} and ^{R L2} in Formula (L).)
^RL51 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and ^RL52 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or a carbon atom. Alkoxy groups of numbers 1 to 4 are preferred.

The compound represented by the general formula (L-5) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

In the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention, the content of the compound represented by the general formula (L-5) includes solubility at low temperature, transition temperature, electrical reliability, and birefringence. It is necessary to make appropriate adjustments according to the required performance such as rate, process compatibility, dripping marks, seizure, 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 composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1% and 2%. 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, It is 35% and 40%. The upper limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 50% and 40%. 35%, 30%, 20%, 15%, 10%, 5%.

The compound represented by the general formula (L-5) is preferably a compound represented by the formula (L-5.1) or the formula (L-5.2), and in particular, the compound represented by the formula (L-5. It is preferably a compound represented by 1).

The lower limit of the preferable content of these compounds with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, 2%, 3%, and 5%. , 7%. The upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.

The compound represented by the general formula (L-5) is preferably a compound represented by the formula (L-5.3) or the formula (L-5.4).

The lower limit of the preferable content of these compounds with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, 2%, 3%, and 5%. , 7%. The upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.

The compound represented by the general formula (L-5) is preferably a compound selected from the compound group represented by the formulas (L-5.5) to (L-5.7), and particularly the compound represented by the formula (L-5). It is preferably a compound represented by L-5.7).

The lower limit of the preferable content of these compounds with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, 2%, 3%, and 5%. , 7%. The upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.

The compound represented by the general formula (L-6) is the following compound.

^{(Wherein, R L61} and ^{R L62} each independently represent the same meaning as ^{R L1} and ^{R L2} in Formula ^{(L), X L61} and ^{X L62} each independently represents a hydrogen atom or a fluorine atom. )
R ^L61 and ^RL62 are preferably alkyl groups having 1 to 5 carbon atoms or alkenyl groups having 2 to 5 carbon atoms independently, and one of ^XL61 and ^XL62 is a fluorine atom and the other is a hydrogen atom. Is preferable.

The compound represented by the general formula (L-6) may be used alone, or may be used in combination of two or more compounds. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

The lower limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1% and 2%. 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, It is 35% and 40%. The upper limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 50% and 40%. 35%, 30%, 20%, 15%, 10%, 5%. When focusing on increasing Δn, it is preferable to increase the content, and when focusing on precipitation at a low temperature, it is preferable that the content is small.

The compound represented by the general formula (L-6) is preferably a compound represented by the formulas (L-6.1) to (L-6.9).

The types of compounds that can be combined are not particularly limited, but it is preferable to contain 1 to 3 types of these compounds, and even more preferably 1 to 4 types. Further, since the wide molecular weight distribution of the selected compound is also effective for solubility, for example, one kind from the compounds represented by the formula (L-6.1) or (L-6.2), the formula (L-). One type from the compound represented by 6.4) or (L-6.5), one type from the compound represented by the formula (L-6.6) or the formula (L-6.7), one type from the compound represented by the formula (L-6.7), the formula (L). It is preferable to select one kind of compound from the compounds represented by −6.8) or (L-6.9) and combine these appropriately. Among them, it is represented by the formula (L-6.1), the formula (L-6.3), the formula (L-6.4), the formula (L-6.6) and the formula (L-6.9). It preferably contains a compound.

Further, the compound represented by the general formula (L-6) is preferably a compound represented by the formulas (L-6.10) to (L-6.17), for example, and among them, the compound represented by the formula (L-6.17) is preferable. It is preferably a compound represented by L-6.11).

The lower limit of the preferable content of these compounds with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1%, 2%, 3%, and 5%. , 7%. The upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.

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 Although it has the same meaning as A ^L3 , the hydrogen atoms on A ^L71 and A ^L72 may be independently substituted with fluorine atoms, and Z ^L71 has the same meaning as Z ^L2 in the general formula (L). X ^L71 and X ^L72 independently represent a fluorine atom or a hydrogen atom.)
In the formula, ^RL71 and ^RL72 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 ^AL71 and ^AL72. Are each independently preferably a 1,4-cyclohexylene group or a 1,4-phenylene group, the hydrogen atoms on ^AL71 and ^AL72 may be independently substituted with fluorine atoms, and Z ^L71 is ^simply Bonds or COO− are preferred, single bonds are preferred, and ^XL71 and ^XL72 are preferably hydrogen atoms.

The types of compounds that can be combined are not particularly limited, but they are combined according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, and four types as one embodiment of the present invention.

In the composition of the present invention, the content of the compound represented by the general formula (L-7) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dropping marks, and the like. It is necessary to make appropriate adjustments according to the required performance such as seizure 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 composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 1% and 2%. It is 3%, 5%, 7%, 10%, 14%, 16%, and 20%. The upper limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is 30% and 25%. It is 23%, 20%, 18%, 15%, 10%, and 5%.

When an embodiment of Tni having a high composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is desired, it is preferable to increase the content of the compound represented by the formula (L-7), and the viscosity is low. If an embodiment is desired, the content is preferably reduced.

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formulas (L-7.1) to (L-7.4), and the compound represented by the formula (L-7. It is preferably a compound represented by 2).

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formulas (L-7.11) to (L-7.13), and the compound represented by the formula (L-7. It is preferably a compound represented by 11).

Further, the compound represented by the general formula (L-7) is a compound represented by the formulas (L-7.21) to (L-7.23). It is preferably a compound represented by the formula (L-7.21).

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formulas (L-7.31) to (L-7.34), and the compound represented by the formula (L-7. It is preferably a compound represented by 31) or / and the formula (L-7.32).

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formulas (L-7.41) to (L-7.44), and the compound represented by the formula (L-7. It is preferably a compound represented by 41) or / and the formula (L-7.42).

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formulas (L-7.51) to (L-7.53).

The total amount of the compounds represented by the general formulas (i), (ii), general formulas (L) and (N) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention is preferable. The lower limit of the content is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96%. Yes, 97%, 98%, 99%, 100%. The preferred upper limit of the content is 100%, 99%, 98% and 95%.

General formula (i), general formula (ii), general formulas (L-1) to (L-7) and (M-1) with respect to the total amount of the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention. ) To (M-8), the lower limit of the total preferable content of the compounds is 80%, 85%, 88%, 90%, 92%, 93%. , 94%, 95%, 96%, 97%, 98%, 99%, 100%. The preferred upper limit of the content is 100%, 99%, 98% and 95%.

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

When the reliability and long-term stability of the composition are emphasized, the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less, based on the total mass of the composition. It is preferably 1% or less, and most preferably not substantially contained.

When the stability by UV irradiation is emphasized, the content of the compound substituted with chlorine atoms is preferably 15% or less, preferably 10% or less, based on the total mass of the composition. % Or less, more preferably 5% or less, more preferably 3% or less, and even more preferably substantially no content.

It is preferable to increase the content of the compound having all 6-membered ring structures in the molecule, and the content of the compound having all 6-membered ring structures in the molecule is 80 with respect to the total mass of the composition. % Or more, more preferably 90% or more, further preferably 95% or more, and the composition is composed only of a compound in which substantially all the ring structures in the molecule are 6-membered rings. It is most preferable to do so.

In order to suppress deterioration of the composition due to oxidation, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group is added to the total mass of the composition. On the other hand, it is preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially not contained.

When the improvement of viscosity and the improvement of Tni are emphasized, the content of the compound having a 2-methylbenzene-1,4-diyl group in which the hydrogen atom may be substituted with halogen may be reduced. Preferably, the content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less, preferably 8% or less, based on the total mass of the composition. It is more preferably 5% or less, more preferably 3% or less, and further preferably substantially not contained.

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

When the compound contained in the composition of the first embodiment of the present invention has an alkenyl group as a side chain, and the alkenyl group is bonded to cyclohexane, the number of carbon atoms of the alkenyl group is 2 to 5. When the alkenyl group is bonded to benzene, the number of carbon atoms of the alkenyl group is preferably 4 to 5, and the unsaturated bond of the alkenyl group and benzene are directly bonded. It is preferable that there is no such thing.

The average elastic constant ( _KAVG ) of the liquid crystal composition used in the present invention is preferably 10 to 25, but the lower limit thereof is preferably 10 is preferable, 10.5 is preferable, 11 is preferable, and 11.5 is preferable. , 12 is preferred, 12.3 is preferred, 12.5 is preferred, 12.8 is preferred, 13 is preferred, 13.3 is preferred, 13.5 is preferred, 13.8 is preferred, 14 is preferred, 14 .3 is preferred, 14.5 is preferred, 14.8 is preferred, 15 is preferred, 15.3 is preferred, 15.5 is preferred, 15.8 is preferred, 16 is preferred, 16.3 is preferred, 16 .5 is preferable, 16.8 is preferable, 17, is preferable, 17.3 is preferable, 17.5 is preferable, 17.8 is preferable, 18 is preferable, and 25 is preferable and 24.5 is preferable as the upper limit value thereof. Is preferred, 24 is preferred, 23.5 is preferred, 23 is preferred, 22.8 is preferred, 22.5 is preferred, 22.3 is preferred, 22 is preferred, 21.8 is preferred, and 21.5 is preferred. , 21.3 is preferable, 21 is preferable, 20.8 is preferable, 20.5 is preferable, 20.3 is preferable, 20 is preferable, 19.8 is preferable, 19.5 is preferable, and 19.3 is preferable. , 19 is preferred, 18.8 is preferred, 18.5 is preferred, 18.3 is preferred, 18 is preferred, 17.8 is preferred, 17.5 is preferred, 17.3 is preferred, and 17 is preferred. When emphasizing power reduction, it is effective to suppress the amount of light of the backlight, it is preferred that the liquid crystal display device to improve the light transmittance, it To achieve this the set lower value of K _AVG preferable. When the improvement of the response speed is emphasized, it is preferable to set the _KAVG value higher.

As the polymerizable compound used in the liquid crystal layer of the liquid crystal display element according to the present invention, it is preferable to use one or more compounds represented by the following general formula (P).

(In the above general formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or -Sp ^p2- P ^p2 , and one or a non-alkyl group. Two or more adjacent −CH ₂ −s may be independently substituted by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−. One or more hydrogen atoms in the alkyl group may be independently substituted with a cyano group, a fluorine atom or a chlorine atom.
P ^p1 and P ^p2 are independent of each other, and the general formulas (P ^p1-1 ) to (P ^p1-9 ) are respectively.

(In the formula, R ^p11 and R ^p12 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and W ^p11 is a single bond, −O. Representing a −, −COO− or methylene group, t ^p11 represents 0, 1 or 2, but if there are multiple R ^p11 , R ^p12 , W ^p11 and / or t ^{p11 in} the molecule, they are the same. It may be different or different.)
Represents one of
Sp ^p1 and Sp ^p2 independently represent a single bond or a spacer group, respectively.
Z ^p1 and Z ^p2 are independent, single-bonded, -O-, -S-, -CH _2- , -OCH _2- , -CH ₂ O-, -CO-, -C ₂ H ₄ -,-, respectively. _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO-NR ZP1 -, - NR ZP1 -CO -, - SCH 2 -, - CH 2 S- ^{, -CH = CR ZP1 -COO -,} - CH = CR ZP1 -OCO -, - COO-CR ZP1 = CH -, - OCO-CR ZP1 = CH -, - COO-CR ZP1 = CH-COO -, - COO -CR ^ZP1 = CH- ^{OCO-, -OCO} -CR ^ZP1 = CH- ^{COO-, -OCO} -CR ^ZP1 = CH-OCO-,-(CH ₂ ) _z- COO-,-(CH ₂ ) _2- OCO- , -OCO- (CH ₂ ) ₂ -,-(C = O) -O- (CH ₂ ) _2- , -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 - or -C≡C- ^{(wherein, R ZP1} is Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but when a plurality of R ^ZP1s are present in the molecule, they may be the same or different.)
Represents
A ^p1 , A ^p2 and A ^p3 are independent of each other.
^(A p) 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 p) 1,4-phenylene group (the one present in the group -CH = or non-adjacent two or more -CH = may be replaced by -N =.) And (c ^p ) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, phenanthrene-2,7-diyl group or anthracene -2,6-diyl groups (one -CH = existing in these groups or two or more -CH = not adjacent to each other may be replaced with -N =, and hydrogen existing in this group. The atom may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 1 to 8 carbon atoms.)
Represents a group selected from the group consisting of the above group (a ^p), group (b ^p) and group (c ^p) are each independently hydrogen atoms present in this group may be substituted with a halogen atom, a carbon It may be substituted with an alkyl group having 1 to 8 atoms or an alkenyl group having 1 to 8 carbon atoms. It may be substituted with a cyano group, a fluorine atom, a chlorine atom or -Sp ^p2 -P ^p2 .
m ^p1 represents 0, 1, 2 or 3, and when a plurality of Z ^p1 , ^Ap2 , Sp ^p2 and / or P ^p2 are present in the molecule, they may be the same or different. A ^p3 represents a single bond when m ^p1 is 0 and A ^p1 is a phenanthrene-2,7-diyl group or an anthracene-2,6-diyl group. )
The compound represented by is preferable. Further, it is preferable that the polymerizable monomer is contained alone or in combination of two or more.

In the general formula (P), R ^p1 is preferably −Sp ^p2 −P ^p2 .

It is preferable that P ^p1 and P ^p2 are independently one of the formulas (P ^p1-1 ) to (P ^p1 -3), and it is preferably (P ^p1-1 ).

It is preferable that R ^p11 and R ^p12 are independently hydrogen atoms or methyl groups, respectively.

t ^p11 is preferably 0 or 1.

W ^p11 is preferably a single bond, a methylene group or an ethylene group.

m ^p1 is preferably 0, 1 or 2, preferably 0 or 1.

Z ^p1 and ^{Z p2} are each independently a single _{bond, -OCH 2 -, - CH 2} O -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - COOC 2 H 4 - _{, -OCOC 2 H 4 -, -} C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - CF 2 -, - CF 2 O -, - (CH 2) 2 -COO- ,-(CH ₂ ) _2- OCO-, -OCO- (CH ₂ ) _2- , -CH = CH-COO-, -COO-CH = CH-, -OCOCH = CH-, -COO- (CH ₂ ) ₂ -, - OCF ₂ - or -C≡C-, more preferably a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - COO -, - OCO -, - COOC 2 H 4 _{-, - OCOC 2 H 4 -} , - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - (CH 2) 2 -COO -, - (CH 2) 2 -OCO- , -OCO- (CH ₂ ) _2- , -CH = CH-COO-, -COO-CH = CH-, -OCOCH = CH-, -COO- (CH ₂ ) ₂ -or -C≡C- are preferred. , only one -OCH ₂ present in the molecule _{-, - CH 2 O -,} - C 2 H 4 -, - COO -, - OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, _{-C 2 H 4 OCO -, -} C 2 H 4 COO -, - CH = CH -, - (CH 2) 2 -COO -, - (CH 2) 2 -OCO -, - OCO- (CH 2) 2 -, -CH = CH-COO-, -COO-CH = CH-, -OCOCH = CH-, -COO- (CH ₂ ) _2- or -C≡C-, and all others are single-bonded. preferably, only one present in the _{molecule, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - COO- or a -OCO-, that other are all single bonds Preferably, all are single-bonded.

Also, only one of Z ^p1 and Z ^p2 present in the molecule is -CH = CH-COO-, -COO-CH = CH-,-(CH ₂ ) _2- COO-,-(CH ₂ ) _{2. -OCO -, - O-CO- (} CH 2) 2 -, - COO- (CH 2) 2 - is a linking group selected from the group consisting of, it is preferred the other is a single bond.

Sp ^p1 and Sp ^p2 independently represent a single bond or a spacer group, but the spacer group is preferably an alkylene group having 1 to 30 carbon atoms, and −CH ₂ − in the alkylene group contains oxygen atoms. As long as it is not directly linked, it may be substituted with −O−, −CO−, −COO−, −OCO−, −CH = CH− or −C≡C−, and the hydrogen atom in the alkylene group is a halogen atom. Although it may be substituted with, a linear alkylene group having 1 to 10 carbon atoms or a single bond is preferable.

A ^p1 , A ^p2 and A ^p3 are independently 1,4-phenylene group or 1,4-cyclohexylene group, preferably 1,4-phenylene group. The 1,4-phenylene group is preferably substituted with one fluorine atom, one methyl group or one methoxy group in order to improve the compatibility with the liquid crystal compound.

The total content of the compounds represented by the general formula (P) is preferably 0.05 to 10% with respect to the liquid crystal composition containing the compound represented by the general formula (P) of the present application. , 0.1 to 8% is preferably contained, 0.1 to 5% is preferably contained, 0.1 to 3% is preferably contained, and 0.2 to 2% is contained. Is preferable, 0.2 to 1.3% is preferably contained, 0.2 to 1% is preferably contained, and 0.2 to 0.56% is preferably contained.

The preferable lower limit of the total content of the compounds represented by the general formula (P) is 0.01% with respect to the liquid crystal composition containing the compound represented by the general formula (P) of the present application, which is 0. .03%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.03%. It is 3%.

The preferable upper limit of the total content of the compounds represented by the general formula (P) is 10% and 8% with respect to the liquid crystal composition containing the compound represented by the general formula (P) of the present application. Yes, 5%, 3%, 1.5%, 1.2%, 1%, 0.8%, 0.5%.

If the content is low, the effect of adding the compound represented by the general formula (P) is unlikely to appear, and problems such as weak orientation control force of the liquid crystal composition or weakening over time occur. Problems such as a large amount remaining afterwards, a long time for curing, and a decrease in the reliability of the liquid crystal occur. Therefore, the content is set in consideration of these balances.

Preferred examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulas (P-1-1) to (P-1-46).

(In the formula, P ^p11 , P ^p12 , Sp ^p11 and Sp ^p12 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-2-1) to (P-2-12).

(In the formula, P ^p21 , P ^p22 , Sp ^p21 and Sp ^p22 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-3-1) to (P-3-15).

(In the formula, P ^p31 , P ^p32 , Sp ^p31 and Sp ^p32 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-4-1) to (P-4-15).

(In the formula, P ^p41 , P ^p42 , Sp ^p41 and Sp ^p42 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)
When a polymerizable compound is added to the composition used for the liquid crystal layer of the liquid crystal display element according to the present invention, the polymerization proceeds even in the absence of the polymerization initiator, but the polymerization initiator is contained in order to promote the polymerization. You may be. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides and the like.

As described above, the liquid crystal display element of the present invention does not have an alignment film between the first substrate and the second substrate and the liquid crystal layer, and the orientation control formed from the polymerizable compound. It is characterized by having a layer. However, the other may have an alignment layer derived from an alignment film. As the alignment film, it is easy to manufacture a liquid crystal display element by using a solvent-soluble oriented polyimide or aligning the liquid crystal with a photoalignment film, particularly a non-polyimide-based photoalignment film. It is preferable from the point of view.

In order to form the orientation control layer formed from the above-mentioned polymerizable compound, a spontaneous orientation compound is provided in order to further impart vertical orientation to the composition used for forming the liquid crystal layer of the liquid crystal display element of the present invention. Is preferably contained. The spontaneous orientation compound is a compound that controls the orientation of the liquid crystal composition without using a conventional liquid crystal alignment film such as polyimide for one or both of the substrates.

The spontaneously oriented compound is mainly used by being added to a liquid crystal composition, and a member (electrode (for example, ITO), a substrate (for example, a glass substrate, an acrylic substrate, a transparent substrate) that directly contacts the liquid crystal layer containing the liquid crystal composition. , Flexible substrate, etc.), resin layer (for example, color filter, alignment film, overcoat layer, etc.), insulating film (for example, inorganic material film, SiNx, etc.), and homeo of liquid crystal molecules in the liquid crystal layer. It has a function of inducing a tropic sequence or a homogeneous orientation.

Spontaneous orientation compounds are polymerizable groups for polymerization, mesogen groups similar to liquid crystal molecules, adsorption groups that can interact with members that come into direct contact with the liquid crystal layer, and orientation-inducing groups that induce the orientation of liquid crystal molecules. It is preferable to have.

It is preferable that the adsorbent group and the orientation-inducing group are bonded to the mesogen group, and the polymerizable group is substituted with the mesogen group, the adsorption group and the orientation-inducing group directly or, if necessary, via a spacer group. It is preferable to replace it with a mesogen group as a polymerizable group in which a polymerizable group is incorporated.

Hereinafter, * at the left end and * at the right end in the chemical formula represent a bond.

"Orientation inducer"
The orientation-inducing group according to the present invention has a function of inducing the orientation of liquid crystal molecules, and the orientation-inducing group is preferably a group represented by the general formula (AK).

(Wherein, R ^AK1 represents a linear or branched alkyl group having 1 to 20 carbon atoms, one or two or more -CH 2 in the alkyl group _- is attached is an oxygen atom directly Independently, they may be independently substituted with −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−, and one of the alkyl groups. Alternatively, two or more hydrogen atoms may be independently substituted with a halogeno group.)
R ^AK1 preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and is linear. It is more preferable to represent an alkyl group having 1 to 8 carbon atoms. In addition, one or two or more -CH ₂ −s that are not adjacent to each other in the alkyl group are independently −CH = CH−, −C≡C−, −O−, −CO−, −. It may be replaced by COO- or -OCO-. The hydrogen atom in the alkyl group may be substituted with a fluorine atom or a chlorine atom, or may be substituted with a fluorine atom. )
From the viewpoint that the spontaneously oriented compound has so-called amphipathic properties with respect to the liquid crystal layer, the orientation-inducing group is preferably bonded to a mesogen group.

"Polymerizable group"
Polymerizable ^group, P ^{AP1 -Sp} AP1 - is preferably represented by.

P ^AP1 is preferably a group selected from the group represented by the following general formulas (AP-1) to (AP-9).

(In the formula, R ^AP1 and R ^AP2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 10 carbon atoms, and one of the alkyl groups or two or more -CH 2 _- may be replaced by -O- or -CO-, 1 or 2 or more hydrogen atoms in the alkyl group each independently substituted with a halogen atom or a hydroxyl group W ^AP1 represents a single bond, -O-, -COO- or -CH _2- , and t ^AP1 represents 0, 1 or 2).
P ^AP1 is preferably a group represented by the general formula (AP-1) to the general formula (AP-7), and is a group represented by the general formula (AP-1) or the general formula (AP-2). Is preferable, and the general formula (AP-1) is preferable.

Sp ^AP1 preferably represents a single-bonded or linear or branched alkylene group having 1 to 20 carbon atoms, and represents a single-bonded or linear alkylene group having 1 to 20 carbon atoms. Is more preferable, and it is more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms. Further, in Sp ^AP1 , one or two or more −CH ₂ ^−s in the alkylene group, which are not adjacent to each other, are independently −CH = CH−, −C≡C−, −O−, −CO. It may be replaced by −, −COO− or −OCO−.

In spontaneous orientation compounds according to the present invention, the polymerizable group ^{(P AP1 -Sp} AP1 -) number of, preferably 1 to 5 or less, more preferably 1 to 4, 2 to 4 Is even more preferable, 2 or 3 is even more preferable, and 2 is even more preferable.

P ^AP1 -Sp ^AP1 - hydrogen atoms in the polymerizable group, may be substituted with an adsorptive group and / or orientation-induced group.

In spontaneous orientation compounds according to the present invention, the polymerizable group (P ^{AP1 -Sp AP1 -),} the polymerizable group, mesogen group may be bonded to an adsorptive group and / or orientation-induced group.

Further, the spontaneous alignment compound according to the present invention, the polymerizable group (P ^{AP1 -Sp AP1 -)} is preferably binding to the mesogenic groups, the adsorption group or orientation-induced group, to mesogen groups or adsorptive groups It is more preferable to combine them.

When a plurality of P ^AP1 and / or Sp ^AP1 − are present in the molecule, they may be the same or different from each other.

"Mesogen group"
The mesogen group according to the present invention refers to a group having a rigid portion, for example, one having one or more cyclic groups, preferably having 2 to 4 cyclic groups, and a cyclic group. It is more preferable to have 3 to 4 of the cyclic groups, and if necessary, the cyclic groups may be linked by a linking group. The mesogen group preferably has a skeleton similar to that of the liquid crystal compound used for the liquid crystal layer.

In the present specification, the "cyclic group" refers to an atomic group in which constituent atoms are cyclically bonded, and is a carbocyclic ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a monocyclic or bicyclic structure, or a polycyclic ring. Includes formula structures, aromatics, non-aromatics, etc. Further, the cyclic group may contain at least one heteroatom, and may be further substituted with at least one substituent (halogeno group, polymerizable group, organic group (alkyl, alkoxy, aryl, etc.)). When the formula group is monocyclic, the mesogen group preferably contains two or more monocyclic rings.

The mesogen group is preferably represented by, for example, the general formula (AL).

(In the formula, Z ^AL1 is a single bond, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -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 an alkylene group having 1 to 20 carbon atoms, among the alkylene groups. one or not adjacent two or more -CH ₂ - is -O -, - COO- or -OCO- may be substituted with,
A ^AL1 and A ^AL2 each independently represent a divalent cyclic group.
One or more hydrogen atoms in Z ^AL and ^{A AL} is independently halogeno group, adsorptive ^group, P al ^{-Sp al} - may be substituted by or a monovalent organic group,
When a plurality of Z ^AL1 and A ^AL1 are present in the molecule, they may be the same or different from each other.
m ^AL1 represents an integer of 1-5. )
In the general formula (AL), Z ^AL1 is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, preferably a single bond or an alkylene group having 2 to 10 carbon atoms, and is a single bond, − (CH ₂ ) _2. − Or − (CH ₂ ) ₄ − is preferable. One or two or more non-adjacent −CH ₂ −s in the alkylene group may be substituted with −O−, −COO− or −OCO−. Further, when the purpose is the linearity of the rod-shaped molecule, a single bond in which the ring and the ring are directly connected or a form in which the number of atoms directly connecting the ring and the ring is an even number is preferable. For example, in the case of −CH ₂ −CH ₂ COO−, the number of atoms directly connecting the rings is four.

In the general formula (AL), A ^AL1 and A ^AL2 represent a divalent cyclic group, and the divalent cyclic group includes a 1,4-phenylene group, a 1,4-cyclohexylene group, and 1,4. -Cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, thiophene-2,5-diyl group, 1, 4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group , Thiophen-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydro Phenantren-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4 , 5-b'] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b'] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] One structure selected from the group consisting of a thiophene-2,7-diyl group, a [1] benzoselenopheno [3,2-b] serenophen-2,7-diyl group and a fluorene-2,7-diyl group. , And these structures may be unsubstituted or substituted, 1,4-phenylene group, 1,4-cyclohexylene group, 2,6-naphthylene group or phenanthrene-2,7-diyl group. Is more preferable, and a 1,4-phenylene group or a 1,4-cyclohexylene group is preferable. The substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be substituted with a fluorine atom or a hydroxyl group.

Also, one or more hydrogen atoms are halogeno groups in the cyclic group, adsorptive group, P ^{AL1 -Sp} AL1 ^- or which may be substituted with a monovalent organic group.

In the general formula (AL), a monovalent organic group is a group having a chemical structure formed by forming an organic compound in the form of a monovalent group, and is formed by removing one hydrogen atom from the organic compound. An atomic group, for example, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, an alkenyloxy group having 2 to 15 carbon atoms, and the like. Therefore, an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms is preferable. Alkyl groups of ~ 5 or alkoxy groups having 1 to 4 carbon atoms are preferable, alkyl groups having 1 to 3 carbon atoms or alkoxy groups having 1 to 2 carbon atoms are preferable, and alkyl groups having 1 or 2 carbon atoms or An alkoxy group having 1 carbon atom is preferable. Further, one or two or more -CH ₂ −s in the above alkyl group, alkenyl group, alkoxy group and alkenyloxy group may be substituted with −O−, −COO− or −OCO−. Furthermore, the monovalent organic group may have a role as an orientation-inducing group described later.

In the above general formula (AL), m ^AL1 is preferably an integer of 1 to 4, preferably an integer of 1 to 3, preferably 2 or 3.

Preferred forms of the mesogen group include the following formulas (me-1) to (me-44).

(The general formula (AL) is a structure in which two hydrogen atoms in these structures are eliminated.)
These formulas (me-1) ~ (me -44) in the cyclohexane ring, one of the hydrogen atoms of the benzene ring or a naphthalene ring or two or more independently halogeno ^group, P AP1 ^{-Sp AP1} -, It may be substituted with a monovalent organic group (for example, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorbing group or an orientation inducing group. )
The preferred forms of the mesogen groups are formulas (me-8) to (me-44), and more preferably the formulas (me-8) to (me-10) and formulas (me-12) to (me). -18), formulas (me-22) to (me-24), formulas (me-26) to (me-27) and formulas (me-29) to (me-44), more preferably formulas. (Me-12), (me-15) to (me-16), (me-22) to (me-24), (me-29), (me-34), (me-36) to (me) -37), (me-42) to (me-44).

A particularly preferable form of the mesogen group is represented by the following general formula (AL-1) or (AL-2), and the formula (AL-1) is more preferable.

(In the above formula, X ^{AL101 to} X ^AL118 and X ^{AL201 to} X ^AL214 independently represent a hydrogen atom, a halogeno group, ^PAPl −Sp ^APl −, an adsorbent group or an orientation inducing group, and ring A and ring B are Each independently represents a cyclohexane ring or a benzene ring,
Any one or more of X ^{AL101 to} X ^AL118 and X ^{AL201 to} X ^AL214 are substituted with the adsorbent group.
Any one or more of X ^{AL101 to} X ^AL118 and X ^{AL201 to} X ^AL214 are substituted with the orientation inducer.
Adsorptive group and orientation derivative groups ^P AP1 ^{-Sp AP1} - may be substituted with,
The general formula (AL-1) or the general formula (AL-2) has one or more P ^AP1l- Sp ^APl- in its molecule. )
In the general formula (AL-1), X ^AL101 is preferably an orientation inducer.

In the general formula (AL-1), at least one of X ^AL109 , X ^AL110 and X ^AL111 is preferably an adsorbent group, and both X ^AL109 and X ^AL110 are adsorbent groups or X ^AL110 is an adsorbent group. It is preferable that X ^AL110 is an adsorbent group.

In formula ^(AL-1), at least one of ^{X AL109,} X ^AL110 and ^{X AL111} is ^P AP1 ^{-Sp AP1} - or is, preferably has a polymerizable possible sites within the structure of the adsorptive group, X is preferably - both or one of the ^AL109 and ^{X AL111} is ^P AP1 ^{-Sp AP1.}

In the general formula (AL-1), one or two of X ^{AL104 to} X ^AL108 and X ^{AL112 to} X ^AL116 are independently an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms. Alternatively, it is preferably a halogeno group, preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom, and X ^AL105 , X ^AL106 or X ^AL107 is an alkyl group or a fluorine atom having 1 to 3 carbon atoms. It is preferable to have.

In the general formula (AL-2), X ^AL201 is preferably an orientation inducer.

In the general formula (AL-2), at least one of X ^AL207 , X ^AL208 and X ^AL209 is preferably an adsorbent group, and both X ^AL207 and X ^AL208 are adsorbent groups or X ^AL208 is an adsorbent group. It is preferable that X ^AL208 is an adsorbent group.

In formula ^(AL-2), at least one of ^{X AL207,} X ^AL208 and ^{X AL209} is ^P AP1 ^{-Sp AP1} - or is, preferably has a polymerizable possible sites within the structure of the adsorptive group, X is preferably - both or one of the ^AL207 and ^{X AL209} is ^P AP1 ^{-Sp AP1.}

In the general formula (AL-2), one or two of X ^{AL202 to} X ^AL206 and X ^{AL210 to} X ^AL214 are independently alkyl groups having 1 to 5 carbon atoms and alkoxy groups having 1 to 5 carbon atoms. Alternatively, it is preferably a halogeno group, preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom, and X ^AL204 , X ^AL205 or X ^AL206 is an alkyl group or a fluorine atom having 1 to 3 carbon atoms. It is preferable to have.

"Adsorption group"
The adsorbent group according to the present invention is a group having a role of adsorbing with an adsorption medium, which is a layer that comes into contact with a liquid crystal composition such as a substrate, a film, and an electrode. Adsorption is generally classified into chemical adsorption that forms a chemical bond (covalent bond, ionic bond or metal bond) and adsorbs between the adsorption medium and the adsorbent, or physical adsorption other than the chemical adsorption. The adsorption of the book may be either chemical adsorption or physical adsorption, but it is preferable to adsorb with the adsorption medium by physical adsorption. Therefore, the adsorbent group according to the present invention is preferably a group that can be physically adsorbed to the adsorption medium, and it is more preferable that the adsorbent group is bonded to the adsorption medium by an intermolecular force. Examples of the form of binding to the adsorption medium by the intermolecular force include binding to the adsorption medium by interaction such as permanent dipole, permanent quadrupole, dispersion force, charge transfer force or hydrogen bond. A preferred form of the adsorbent according to the present invention is a form capable of binding to an adsorption medium by hydrogen bonding. In this case, the adsorbent group according to the present invention may be a donor or acceptor of a proton intervening a hydrogen bond, or may be both.

The adsorbent group according to the present invention is a group containing a polar element having an atomic group in which a carbon atom and a hetero atom are linked. The polar element referred to in the present specification means an atomic group in which a carbon atom and a hetero atom are directly linked. The heteroatom is preferably at least one selected from the group consisting of N, O, S, P, B and Si, and at least one selected from the group consisting of N, O and S. It is preferable that it is at least one selected from the group consisting of N and O, and it is preferably O.

Further, in the spontaneously oriented compound according to the present invention, the valence of the polar elements according to the present invention is not particularly limited such as monovalent, divalent and trivalent, and the number of polar elements in the adsorbent group is also particularly limited. There is nothing.

The spontaneously oriented compound according to the present invention preferably has 1 to 8 adsorbent groups, more preferably 1 to 4 adsorbent groups, and even more preferably 1 to 3 adsorbent groups in one molecule.

Incidentally, the adsorption group according to the present invention, excluding the polymerizable group and the orientation induced group, a hydrogen atom is ^P AP1 ^-Sp in adsorptive group ^AP1 - substituted structures and ^P AP1 ^{-Sp AP1} - hydrogen atoms in The structure in which is substituted with -OH is an adsorbent group.

The adsorbent group according to the present invention contains one or more polar elements, and the adsorbent group is roughly classified into a cyclic group type and a chain type group type. A cyclic base type is a form in which a cyclic group having a cyclic structure containing a polar element is included in the structure, and a chain type is a form in which a cyclic group having a cyclic structure containing a polar element is included in the structure. There is no form. The chain type group has a form having a polar element in a linear or branched chain group, and may have a cyclic structure in which a polar element is not included in a part thereof.

The form in which the adsorbent group according to the present invention contains a cyclic group means a form in which at least one polar element is contained in a cyclic atomic arrangement. The cyclic group in the present specification is as described above. Therefore, when the adsorbent group according to the present invention has a form containing a cyclic group, it is sufficient that the adsorbent group contains a cyclic group including a polar element, and the adsorbent group as a whole may be branched or linear. ..

The form in which the adsorbent group according to the present invention is a chain type group means that there is no cyclic atomic arrangement containing polar elements in the molecule, and at least one polar element is in a linear atomic arrangement (which may be branched). Means the included form. The chain group in the present specification refers to an atomic group in which constituent atoms are linearly (may be branched) bonded without a cyclic atomic arrangement in the structural formula, and refers to an acyclic group. .. In other words, it refers to a linear or branched aliphatic group, which may contain either a saturated bond or an unsaturated bond, including, for example, alkyl, alkenyl, alkoxy, ester, ether or ketone, and at least one. It is a concept that may be substituted with a substituent (reactive functional group (vinyl group, acrylic group, methacryl group, etc.), chain organic group (alkyl, cyano, etc.). Further, the chain type group of the present invention is a direct group. It may be chain-shaped or branched.

When the adsorbing group according to the present invention is a cyclic group, a heteroaromatic group having 3 to 20 carbon atoms (including a fused ring) or a heteroaliphatic group having 3 to 20 carbon atoms (including a fused ring) ) Is more preferable, and a heteroaromatic group having 3 to 12 carbon atoms (including a fused ring) or a complex aliphatic group having 3 to 12 carbon atoms (including a fused ring) is further preferable, and a 5-membered ring complex is more preferable. It is more preferable to represent an aromatic group, a 5-membered ring heterolipid group, a 6-membered ring heteroaromatic group or a 6-membered ring heterolipid group, and the hydrogen atom in these ring structures is a halogeno group and the number of carbon atoms. It may be substituted with 1 to 5 linear or branched alkyl groups or alkyloxy groups.

When the adsorbent group according to the present invention is a chain type group, it is preferable that the hydrogen atom or −CH _{2− in the} linear or branched alkyl group having 1 to 20 carbon atoms is replaced with a polar element. , One or two or more non-adjacent -CH _2- in the alkyl group are -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- May be replaced by. When the adsorbent group according to the present invention is a chain type group, it is preferable that the end portion contains a polar element or contains two or more polar elements.

The hydrogen atom of the adsorbent according to the present invention may be substituted with a polymerizable group.

Specifically, the types of polar elements according to the present invention include polar elements containing oxygen atoms (hereinafter, oxygen-containing polar elements), polar elements containing nitrogen atoms (hereinafter, nitrogen-containing polar elements), and polarities containing phosphorus atoms. Element (hereinafter, phosphorus-containing polar element), polar element containing boron atom (hereinafter, boron-containing polar element), polar element containing silicon atom (hereinafter, silicon-containing polar element) or polar element containing sulfur atom (hereinafter, including) It is preferably a partial structure represented by (sulfur polar element), and from the viewpoint of adsorption ability, a nitrogen-containing polar element, a nitrogen-containing polar element or an oxygen-containing polar element is more preferable, and an oxygen-containing polar element is further preferable.

The oxygen-containing polar element includes at least one group selected from the group consisting of a hydroxyl group, an alkylol group, an alkoxy group, a formyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group and an ester group, or the group thereof. It is preferably a group linked to a carbon atom.

The nitrogen-containing polar element includes at least one group selected from the group consisting of a cyano group, a primary amino group, a secondary amino group, a tertiary amino group, a pyridyl group, a carbamoyl group and a ureido group, or the group thereof. It is preferably a group linked to a carbon atom.

The phosphorus-containing polar element is preferably at least one group selected from the group consisting of a phosphinyl group and a phosphoric acid group, or a group in which the group is linked to a carbon atom.

Therefore, in the adsorption group according to the present invention, the cyclic group is a group having an oxygen-containing polar element (hereinafter, oxygen-containing cyclic group), and the cyclic group is a group having a nitrogen atomic polar element (hereinafter, nitrogen-containing ring). (Formula group), a group whose chain type group has an oxygen-containing polar element (hereinafter, oxygen-containing chain type group) and a group whose chain type group has a nitrogen atom polar element (hereinafter, nitrogen-containing chain type group). It is preferable to contain one or more groups selected from the group or the group itself, and from the viewpoint of adsorption ability, an oxygen-containing cyclic group, a sulfur-containing cyclic group, an oxygen-containing chain type group and a nitrogen-containing chain type. It is more preferable to include one or more groups selected from the group consisting of groups.

The oxygen-containing cyclic group preferably has an ether group or a carbonyl group in the ring, and the ether group preferably contains the following groups.

Further, the carbonyl group, carbonate group and ester group preferably contain any of the following groups.

The nitrogen-containing cyclic group preferably contains any of the following groups.

The oxygen-containing chain type group preferably contains any of the following groups.

(In the above general formula, ^Rat1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the above general formula, Z ^at1 is a single bond, linear or branched with 1 to 15 carbon atoms. Jo alkylene group or 2 to 18 carbon atoms in a linear or branched alkenylene groups, -CH 2 of the alkylene group or the alkenylene group _- is such that oxygen atoms are not directly adjacent -O-, It may be substituted with −COO−, −C (= O) −, ^−OCO− , X ^at1 represents an alkyl group having 1 to 15 carbon atoms, and −CH _{2− of the} alkyl group has an oxygen atom. It may be replaced with -O-, -COO-, -C (= O)-, -OCO- so as not to be directly adjacent to each other.)
The nitrogen-containing chain type group preferably contains the following groups.

(In the general ^{formula, R at, R bt, R} ct and ^{R dt} independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
As the adsorbent group according to the present invention, a group represented by the following general formula (AT) is preferable.

(In the formula, Sp ^AT1 represents a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atom in the alkylene group is -OH, -CN, -W ^AT1- Z. ^AT1 or ^P AP1 ^{-Sp AP1} - may be substituted by, -CH ₂ in the alkylene group - the cyclic group such that oxygen atoms are not linked directly, -O -, - COO -, - C (= O )-, -OCO-, -CH = CH- may be substituted.
W ^AT1 represents a single bond or the formula (WAT1) or (WAT2),

(In the formula, Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atom in the alkylene group is -OH,-. ^CN, -Sp ^AT1 -W ^{AT1 -Z AT1} or ^P AP1 ^{-S AP1} - may be substituted by, -CH ₂ in the alkylene group - so does not bind the oxygen atom directly cyclic group, -O- , -COO-, -C (= O)-, -OCO-, -CH = CH- may be substituted.)
Z ^AT1 represents a monovalent group containing a polar ^component, a hydrogen atom in ^{Z AT1} is ^{-OH, -CN, -Sp AT1 -W AT1} -Z AT1 or ^P AP1 ^{-S AP1} - may be substituted by .. )
Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, preferably a single bond or a linear carbon atom. It is more preferable to represent 1 to 20 alkylene groups, and more preferably to represent a single bond or linear alkylene group having 2 to 10 carbon atoms. Further, in Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 , one in the alkylene group or two or more -CH ₂ − not adjacent to each other are independently bonded to each other so that oxygen atoms are not directly bonded to each other. It may be replaced by CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-.

The ^hydrogen atoms in ^{Sp AT1} and ^{Sp WAT1} each ^{independently,} -Sp ^AT1 -W ^{AT1 -Z AT1} or ^P AP1 ^{-S AP1} - may be substituted for.

Z ^AT1 represents a monovalent group containing a polar element, and is preferably a group represented by the general formula (ZAT1-1) or (ZAT1-2).

(In the formula, Sp ^ZAT11 and Sp ^ZAT12 each independently represent a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atom in the alkylene group is -OH, -CN, -. Sp ^AT1- W ^AT1- Z ^AT1 or P ^AP1- S ^AP1 -may be substituted, and -CH _2- in the alkylene group is a cyclic group, -O-, -COO so that oxygen atoms are not directly adjacent to each other. It may be replaced with −, −C (= O) −, −OCO−, −CH = CH−.
Z ^ZAT11 represents a group containing a polar element, the structure represented by the ring containing Z ^ZAT12 in the general formula (ZAT1-2) represents a 5- to 7-membered ring, and the hydrogen atoms of Z ^ZAT11 and ^ZZAT12 are ^{-OH, -CN, -Sp AT1 -W AT1} -Z AT1 or ^P AP1 ^{-S AP1} - it may be substituted by,
R ^ZAT11 and ^RZAT12 each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms, and the hydrogen atom in the alkyl group is -OH, -CN, -Sp ^AT1- W. ^AT1- Z ^AT1 or P ^AP1- S ^AP1 -may be substituted, and -CH _2- in the alkyl group is a cyclic group, -O-, -COO-, -C so that an oxygen atom is not directly bonded. It may be replaced with (= O) −, −OCO−, −CH = CH−. )
As the group represented by the general formula (ZAT1-1), the groups represented by the general formulas (ZAT1-1-1) to (ZAT1-1-30) are preferable.

(Wherein a hydrogen atom bound to a carbon ^{atom, -OH, -CN, -Sp AT1 -W} AT1 -Z AT1 or ^P AP1 ^{-S AP1} - it may be substituted by,
Sp ^ZAT11 represents a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atom in the alkylene group is -OH, -CN, -Sp ^AT1- W ^AT1- Z ^AT1 or P ^AP1. -S ^AP1 - may be substituted by, -CH ₂ in the alkylene group - the cyclic group such that oxygen atoms are not directly adjacent, -O -, - COO -, - C (= O) -, - It may be replaced with OCO−, −CH = CH−,
R ^ZAT11 represents a linear or branched alkyl group having 1 to 8 carbon atoms, and the hydrogen atom in the alkyl group is -OH, -CN, -Sp ^AT1- W ^AT1- Z ^AT1 or P ^AP1. -S ^AP1 - may be substituted by, -CH ₂ in the alkyl group - so does not bind the oxygen atom directly cyclic group, -O -, - COO -, - C (= O) -, - It may be replaced with OCO−, −CH = CH−. )
As the group represented by the general formula (ZAT1-2), the groups represented by the general formulas (ZAT1-2-1) to (ZAT1-2-9) are preferable.

(Wherein a hydrogen atom bound to a carbon atom, a halogen ^{atom, -OH, -CN, -Sp AT1 -W} AT1 -Z AT1 or ^P AP1 ^{-S AP1} - it may be substituted by,
Sp ^ZAT11 represents a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atom in the alkylene group is -OH, -CN, -Sp ^AT1- W ^AT1- Z ^AT1 or P ^AP1. -S ^AP1 - may be substituted by, -CH ₂ in the alkylene group - the cyclic group such that oxygen atoms are not directly adjacent, -O -, - COO -, - C (= O) -, - It may be replaced with OCO−, −CH = CH−. )
Examples of the group represented by the general formula (ZAT1-1) include the following groups.

(In the ^{formula, R tc} represents a hydrogen atom, a carbon atom number of 1 to 20 alkyl group or a polymerizable group ^P al ^{-Sp al} - represents, a hydrogen atom in the alkyl group -OH, -CN, - Sp ^AT1- W ^AT1- Z ^AT1 or P ^AP1- S ^AP1 -may be substituted, and -CH _2- in the alkyl group is a cyclic group, -O-, -COO so that oxygen atoms are not directly adjacent to each other. -, -C (= O)-, -OCO-, -CH = CH- may be substituted, and the hydrogen atom in the molecule may be substituted with the above-mentioned polymerizable group P ^al- Sp ^al- , *. Represents a bond.)
In the spontaneously oriented compound according to the present invention, a form in which the polar element contained in the adsorbent group or the polar element contained in the polymerizable group is localized is preferable. The adsorbent group is an important structure for vertically orienting the liquid crystal composition, and the adsorbent group and the polymerizable group are adjacent to each other, so that better orientation can be obtained and good orientation to the liquid crystal composition is obtained. Shows solubility. Specifically, a form having a polymerizable group and an adsorbing group on the same ring of the mesogen group is preferable. In this case, among the form in which one or more polymerizable groups and one or more adsorbent groups are bonded on the same ring, and at least one of one or more polymerizable groups or at least one of one or more adsorbent groups. It includes a form in which one is bonded to the other and has a polymerizable group and an adsorbing group on the same ring. Further, in this case, the hydrogen atom of the spacer group of the polymerizable group may be substituted with the adsorbent group, and further, the form in which the hydrogen atom of the molecule of the adsorbent group is bonded to the spacer group of the polymerizable group is also included.

The spontaneously oriented compound according to the present invention is preferably a compound represented by the following general formula (SAL).

(Wherein a hydrogen atom bound to a carbon atom, 1 to 25 carbon atoms or a straight-chain or branched alkyl ^{group, -OH, -CN, -Sp AT1 -W} AT1 -Z AT1 or ^{P AP1} - S ^AP1 - may be substituted by a hydrogen atom in the alkyl group ^{-OH, -CN, -Sp AT1 -W AT1} -Z AT1 or ^P AP1 ^{-S AP1} - may be substituted by said alkyl group -CH _{2-in the} inside may be replaced with a cyclic group, -O-, -COO-, -C (= O)-, -OCO-, -CH = CH- so that oxygen atoms are not directly bonded. ..
R ^AK1 represents the same meaning as ^{R AK1} in the general formula (AK),
A ^AL1 and A ^AL2 independently represent the same meanings as A ^AL1 and A ^AL2 in the general formula (AL).
Z ^AL1 represents the same meaning as ^{Z AL1} in the general formula (AL),
m ^AL1 denotes the same meaning as ^{m AL1} in the general formula (AL),
Sp ^AT1 represents the same meaning as ^{Sp AT1} in formula (AT),
W ^AT1 represents the same meaning as ^{W AT1} in formula (AT),
Z ^AT1 represents the same meaning as ^{Z AT1} in formula (AT),
The compounds in the molecule, at least one or more ^P AP1 ^{-S AP1} - having. )
As the compound represented by the general formula (SAL), the compounds represented by the following formulas (SAL-1.1) to (SAL-2.9) are preferable.

The lower limit of the content of the spontaneously oriented compound in the liquid crystal composition used in the present invention is preferably 0.02% by mass, preferably 0.03% by mass, preferably 0.04% by mass, and preferably 0.05% by mass. , 0.06% by mass, preferably 0.07% by mass, preferably 0.08% by mass, preferably 0.09% by mass, preferably 0.1% by mass, preferably 0.12% by mass, 0. .15% by mass is preferable, 0.17% by mass is preferable, 0.2% by mass is preferable, 0.22% by mass is preferable, 0.25% by mass is preferable, 0.27% by mass is preferable, and 0.3. By mass% is preferable, 0.32 mass% is preferable, 0.35 mass% is preferable, 0.37 mass% is preferable, 0.4 mass% is preferable, 0.42 mass% is preferable, and 0.45 mass% is preferable. Is preferable, 0.5% by mass is preferable, and 0.55% by mass is preferable.

The upper limit of the content of the spontaneously oriented compound in the liquid crystal composition used in the present invention is preferably 2.5% by mass, preferably 2.3% by mass, preferably 2.1% by mass, preferably 2% by mass, and 1 8.8% by mass is preferable, 1.6% by mass is preferable, 1.5% by mass is preferable, 1% by mass is preferable, 0.95% by mass is preferable, 0.9% by mass is preferable, and 0.85% by mass is preferable. Is preferable, 0.8% by mass is preferable, 0.75% by mass is preferable, 0.7% by mass is preferable, 0.65% by mass is preferable, 0.6% by mass is preferable, and 0.55% by mass is preferable. , 0.5% by mass, preferably 0.45% by mass, and preferably 0.4% by mass.

Further, the total content of the compounds represented by the general formula (SAL) in the liquid crystal composition used in the present invention is 0, with respect to the liquid crystal composition containing the compound represented by the general formula (SAL) of the present application. It preferably contains 05 to 10%, preferably 0.1 to 8%, preferably 0.1 to 5%, and preferably 0.1 to 3%. It preferably contains 0.2 to 2%, preferably 0.2 to 1.3%, preferably 0.2 to 1%, and contains 0.2 to 0.56%. It is preferable to be.

Further, the preferable lower limit of the total content of the compounds represented by the general formula (SAL) in the liquid crystal composition used in the present invention is the liquid crystal composition containing the compound represented by the general formula (SAL) of the present application. 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%. , 0.25% and 0.3%.

The preferable upper limit of the total content of the compounds represented by the general formula (SAL) in the liquid crystal composition used in the present invention is the liquid crystal composition containing the compound represented by the general formula (SAL) of the present application. 10%, 8%, 5%, 3%, 1.5%, 1.2%, 1%, 0.8%, 0.5% Is.

If the content is low, the effect of adding the compound represented by the general formula (SAL) is unlikely to appear, and problems such as weak orientation control of the liquid crystal composition or weakening over time occur. Problems such as a large amount remaining afterwards, a long time for curing, and a decrease in the reliability of the liquid crystal occur. Therefore, the content is set in consideration of these balances.

The composition used for forming the liquid crystal layer of the liquid crystal display element of the present invention can further contain a compound represented by the general formula (Q).

(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 linear 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, but the number of carbon atoms is 1 to 10. Linear alkyl group, linear alkoxy group, 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 -OCO- Alternatively, a branched chain alkyl group substituted with -COO- is preferable, a linear alkyl group having 1 to 20 carbon atoms, and a linear alkyl group in which one CH ₂ group is substituted with -OCO- or -COO-, or branched. A chain alkyl group, a branched alkoxy group, and a branched chain alkyl group in which one CH ₂ group is substituted with -OCO- or -COO- are further preferable. ^MQ represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a single bond, with a trans-1,4-cyclohexylene group or a 1,4-phenylene group being preferred.

More specifically, the compound represented by the general formula (Q) is preferably a compound represented by the following general formulas (Qa) to (Qd).

Wherein, R ^Q1 is preferably a linear alkyl group or branched alkyl group having 1 to 10 carbon atoms, R ^Q2 is preferably a linear alkyl group or branched alkyl group having 1 to 20 carbon atoms, R ^Q3 is linear alkyl group having a carbon number of 1 to 8, branched chain alkyl group, preferably a linear alkoxy group or a branched chain alkoxy group, L ^Q is preferably a linear alkylene group or branched alkylene group having 1 to 8 carbon atoms .. Among the compounds represented by the general formulas (Qa) to (Qd), the compounds represented by the general formulas (Qc) and the general formula (Qd) are more preferable.

The composition of the present invention preferably contains one or two compounds represented by the general formula (Q), more preferably one to five, and the content thereof is from 0.001. It is preferably 1% by mass, more preferably 0.001 to 0.1% by mass, and particularly preferably 0.001 to 0.05% by mass.

Further, as the antioxidant or the light stabilizer that can be used in the present invention, more specifically, the compounds represented by the following (III-1) to (III-38) are preferable.

(In the formula, n represents an integer from 0 to 20.)
In the composition used for forming the liquid crystal layer of the liquid crystal display element of the present invention, one or two compounds represented by the general formula (Q) or compounds selected from the general formulas (III-1) to (III-38) are used. It is preferable to contain more than one species, more preferably 1 to 5 species, and the content thereof is preferably 0.001 to 1% by mass, further preferably 0.001 to 0.1% by mass. 0.001 to 0.05% by mass is particularly preferable.

The composition containing a polymerizable compound used for forming the liquid crystal layer of the liquid crystal display element of the present invention is imparted with a liquid crystal orientation ability by polymerizing the polymerizable compound contained therein by irradiation with ultraviolet rays, and birefringence of the composition. It is used in a liquid crystal display element that controls the amount of transmitted light by utilizing.

When the liquid crystal composition used for forming the liquid crystal layer of the liquid crystal display element of the present invention contains a polymerizable compound, as a method for polymerizing the polymerizable compound, in order to obtain good orientation performance of the liquid crystal, appropriate polymerization is performed. Since the speed is desirable, a method of polymerizing by irradiating with active energy rays such as ultraviolet rays or electron beams alone, in combination, or in sequence is preferable. When ultraviolet rays are used, a polarized light source may be used, or a non-polarized light source may be used. Further, when the polymerization is carried out in a state where the polymerizable compound-containing composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency to the active energy rays. It doesn't become. In addition, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as electric field, magnetic field, or temperature, and further irradiation with active energy rays. You may use the means of polymerizing. In particular, when exposed to ultraviolet rays, it is preferable to expose the polymerable compound-containing composition to ultraviolet rays while applying an AC electric field. The AC electric field to be applied is preferably an AC having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 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 the horizontal electric field type MVA mode liquid crystal display element, it is preferable to control the pretilt angle from 80 degrees to 89.9 degrees from the viewpoint of orientation stability and contrast.

The temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the composition used for forming the liquid crystal layer of the liquid crystal display element of the present invention is maintained. It is preferable to polymerize at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As the lamp that generates ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Further, as the wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate the ultraviolet rays in a wavelength region other than the absorption wavelength region of the composition, and it is preferable to cut the ultraviolet rays before use, if 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 the ultraviolet rays to be irradiated can be appropriately adjusted, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² . The intensity may be changed when irradiating with ultraviolet rays. The time for irradiating the ultraviolet rays is appropriately selected depending on the intensity of the ultraviolet rays to be irradiated, but is preferably 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds.

As a method for polymerizing a polymerizable compound, an appropriate polymerization rate is desirable in order to obtain good orientation performance of the liquid crystal. Therefore, irradiation with active energy rays such as ultraviolet rays or electron beams alone, in combination, or in order. The method of polymerizing by is preferable. When ultraviolet rays are used, a polarized light source may be used, or a non-polarized light source may be used. Further, when the polymerization is carried out in a state where the polymerizable compound-containing composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency to the active energy rays. It doesn't become. In addition, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as electric field, magnetic field, or temperature, and further irradiation with active energy rays. You may use the means of polymerizing. In particular, when exposed to ultraviolet rays, it is preferable to expose the polymerable compound-containing composition to ultraviolet rays while applying an AC electric field. The AC electric field to be applied is preferably an AC having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 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 the horizontal electric field type MVA mode liquid crystal display element, it is preferable to control the pretilt angle from 80 degrees to 89.9 degrees from the viewpoint of orientation stability and contrast.

The temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the composition used for forming the liquid crystal layer of the liquid crystal display element of the present invention is maintained. It is preferable to polymerize at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As the lamp that generates ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Further, as the wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate the ultraviolet rays in a wavelength region other than the absorption wavelength region of the composition, and it is preferable to cut the ultraviolet rays before use, if 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 the ultraviolet rays to be irradiated can be appropriately adjusted, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm 2. The intensity may be changed when irradiating with ultraviolet rays. The time for irradiating the ultraviolet rays is appropriately selected depending on the intensity of the ultraviolet rays to be irradiated, but is preferably 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds.

"Orientation layer"
In the preferred liquid crystal display element of the present invention, as described above, since the liquid crystal molecules of the liquid crystal layer 5 are oriented on the surface between the first substrate and the second substrate in contact with the liquid crystal composition, if necessary. An alignment layer may be provided. In a liquid crystal display element that requires an alignment layer, it is arranged between the light conversion layer and the liquid crystal layer, but even if the alignment layer is thick, it is as thin as 100 nm or less, and it is for light emission that constitutes the light conversion layer. It does not completely block the interaction between dyes such as nanocrystals and pigments and the liquid crystal compounds constituting the liquid crystal layer.

The orientation layer that may be possessed in the present invention is preferably at least one selected from the group consisting of a rubbing alignment layer and a photo-alignment layer. In the case of the rubbing alignment layer, there is no particular limitation, and a known polyimide-based alignment layer can be preferably used.

As the rubbing orientation layer material, a transparent organic material such as polyimide, polyamide, BCB (penzocyclobutenepolymer), or polyvinyl alcohol can be used, and in particular, p-phenylenediamine and 4,4'-diaminodiphenyl. Aliphatic or alicyclic tetracarboxylic dianhydrides such as diamines and butanetetracarboxylic dianhydrides such as methane and aliphatic or alicyclic tetracarboxylic dianhydrides such as 2,3,5-tricarboxycyclopentylacetic acid anhydrides and pyromellitic acids. A polyimide oriented layer obtained by imidizing a polyamic acid synthesized from an aromatic tetracarboxylic dianhydride such as a dianhydride is preferable. When it is used for a vertically oriented layer or the like, it can be used without giving orientation.

(Light orientation)
When the alignment layer that may be possessed in the present invention is a photo-alignment layer, it may contain at least one photoresponsive molecule. The photoresponsive molecule is a photoresponsive dimerized molecule that forms a crosslinked structure by dimerization in response to light, and is photoresponsive that is isomerized in response to light and oriented substantially perpendicular or parallel to the polarization axis. At least one selected from the group consisting of an isomerized molecule and a photoresponsive decomposition type polymer in which a polymer chain is cleaved in response to light is preferable, and the photoresponsive isomerized molecule has sensitivity and orientation restricting power. It is particularly preferable from the viewpoint of.

In the photoresponsive isomerized polymer, the light used for isomerization in response to light and orientation substantially perpendicular to the polarization axis is preferably 200 to 500 nm, preferably 300 to 500 nm. More preferably, it is more preferably 300 to 400 nm.

The weight average molecular weight of the photoresponsive isomerized polymer according to the present invention is preferably 10,000 to 800,000, more preferably 1,000 to 400,000, further preferably 50,000 to 400,000, and even more preferably 50,000 to 300,000. Is particularly preferable.

The weight average molecular weight (Mw) is obtained as a result of GPC (Gel Permeation Chromatography) measurement.

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

(Side chain)
−N −C _n H _{2n + 1} Linear alkyl group with n _{+ 1} carbon atoms n − C _n H _{2n + 1} − Linear alkyl group with n carbon atoms −On −OC _n H _{2n + 1} Linear linear alkyl group with _n carbon atoms Jo alkoxyl group nO- C _n H _2n + 1 O- carbon atoms n linear alkoxyl group -V -CH = CH ₂
V-CH ₂ = CH-
−V1 −CH = CH-CH ₃
1V-CH _3- CH = CH-
_{-2V -CH 2 -CH 2 -CH = CH} 3
_{V2- CH 2 = CH-CH 2} -CH 2 -
_{-2V1 -CH 2 -CH 2 -CH = CH} -CH 3
1V2-CH ₃ -CH = CH-CH ₂ -CH ₂
(Connecting 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) −
-CF2O- -CF ₂ -O-
-OCF2--O-CF _2-
(Ring structure)

The characteristics measured in the examples are as follows.

T _NI : Nematic phase-isotropic liquid phase transition temperature (° C)
Δn: Refractive index anisotropy at 20 ° C Δε: Dielectric anisotropy at 20 ° C γ ₁ : Rotational viscosity at 20 ° C (mPa · s)
K ₁₁ : Elastic constant at 20 ° C K ₁₁ (pN)
K ₃₃ : Elastic constant at 20 ° C K ₃₃ (pN)
"VHR measurement"
(Voltage retention rate (%) at 333K under the conditions of frequency 60Hz and applied voltage 1V)
Blue LED light source with a main emission peak at 450 nm Light resistance test:
The VHR before and after irradiating the liquid crystal panel with 68 J at a wavelength of 450 nm for 14 hours with a blue monochromatic LED light source having a peak at 450 nm was measured.

LED light resistance test with main emission peak at 385 nm:
The VHR before and after irradiating the liquid crystal panel with 10 J of a monochromatic LED having a peak of 385 nm at a wavelength of 385 nm for 60 seconds was measured.

"Method of manufacturing liquid crystal panel, backlight unit and liquid crystal display element"
(1) Manufacturing of liquid crystal panel (manufacturing of optical conversion layer or color filter)
(A) "Preparation of luminescent nanocrystals"
The following operations for producing luminescent nanocrystals and ink were performed in a glove box filled with nitrogen or in a flask with the atmosphere blocked and under a nitrogen stream.
In addition, all the raw materials exemplified below were used by introducing nitrogen gas into the container and replacing it with nitrogen gas in advance. As for the liquid material, nitrogen gas was introduced into the liquid to replace the dissolved oxygen with nitrogen gas. Before use, titanium oxide was heated at 120 ° C. for 2 hours under a reduced pressure of 1 mmHg and allowed to cool in a nitrogen gas atmosphere.

The organic solvent and liquid material used below were dehydrated and dried for 48 hours or more by adding Kanto Chemical Co., Inc. Molecular Sieve 3A at a ratio of 1 g per 10 ml in a nitrogen atmosphere.

[Manufacturing of red luminescent nanocrystals]
17.48 g of indium acetate, 25.0 g of trioctylphosphine oxide, and 35.98 g of lauric acid were placed in a 1000 ml flask, and the mixture was stirred at 160 ° C. for 40 minutes while bubbling with nitrogen gas. After further stirring at 250 ° C. for 20 minutes, the mixture was heated to 300 ° C. and stirring was continued. 4.0 g of tris (trimethylsilyl) phosphine was dissolved in 15.0 g of trioctylphosphine in the glove box and then filled in a glass syringe. This was poured into the flask heated to 300 ° C. and reacted at 250 ° C. for 10 minutes. Further, 5 ml of a mixed solution prepared by dissolving 7.5 g of tris (trimethylsilyl) phosphine in 30.0 g of trioctylphosphine in the glove box was added dropwise to the above reaction solution in 12 minutes, and then 5 ml of each reaction solution was added at 15-minute intervals until it was used up. In addition to.

Indium acetate (5.595 g), trioctylphosphine oxide (10.0 g), and lauric acid (11.515 g) were charged in another three-necked flask, and the mixture was stirred at 160 ° C. for 40 minutes while bubbling with nitrogen gas. Further, the mixture was stirred at 250 ° C. for 20 minutes, heated to 300 ° C., and then a mixed solution cooled to 70 ° C. was added to the above reaction solution. In the glove box, 5 ml of a mixed solution prepared by dissolving 4.0 g of tris (trimethylsilyl) phosphine in 15.0 g of trioctylphosphine was added dropwise to the above reaction solution over 12 minutes, and then 5 ml was reacted at 15-minute intervals until it was used up. Added to solution. After maintaining stirring for 1 hour and cooling to room temperature, 100 ml of toluene and 400 ml of ethanol were added to aggregate the fine particles. After precipitating the fine particles using a centrifuge, the supernatant was discarded, and the precipitated fine particles were dissolved in trioctylphosphine to obtain a trioctylphosphine solution of indium phosphide (InP) red luminescent nanocrystals. ..

[Manufacture of green luminescent nanocrystals]
23.3 g of indium acetate, 40.0 g of trioctylphosphine oxide, and 48.0 g of lauric acid were placed in a 1000 ml flask, and the mixture was stirred at 160 ° C. for 40 minutes while bubbling with nitrogen gas. After further stirring at 250 ° C. for 20 minutes, the mixture was heated to 300 ° C. and stirring was continued. 10.0 g of tris (trimethylsilyl) phosphine was dissolved in 30.0 g of trioctylphosphine in the glove box and then filled in a glass syringe. This was poured into the flask heated to 300 ° C. and reacted at 250 ° C. for 5 minutes. The flask was cooled to room temperature, and 100 ml of toluene and 400 ml of ethanol were added to agglomerate the fine particles. After precipitating the fine particles using a centrifuge, the supernatant was discarded, and the precipitated fine particles were dissolved in trioctylphosphine to obtain a trioctylphosphine solution of indium phosphide (InP) green luminescent nanocrystals. ..

[Manufacture of InP / ZnS core-shell nanocrystals]
The trioctylphosphine solution of indium phosphide (InP) red luminescent nanocrystals synthesized above was adjusted to 3.6 g of InP and 90 g of trioctylphosphine, and then placed in a 1000 ml flask, and further 90 g of trioctylphosphine oxide and laurin. Add 30 g of acid. On the other hand, a stock solution was prepared by mixing 42.9 ml of a 1 M hexane solution of diethylzinc and 92.49 g of a trioctylphosphine 9.09 wt% solution of bistrimethylsilylsulfide in a glove box with 162 g of trioctylphosphine. After replacing the inside of the flask with a nitrogen atmosphere, the temperature of the flask was set to 180 ° C., and when the temperature reached 80 ° C., 15 ml of the above stock solution was added, and then 15 ml was continuously added every 10 minutes. (Flask temperature maintained at 180 ° C). After the final addition was completed, the reaction was terminated by maintaining the temperature for another 10 minutes. After completion of the reaction, the solution was cooled to room temperature, and 500 ml of toluene and 2000 ml of ethanol were added to aggregate the nanocrystals. After precipitating the nanocrystals using a centrifuge, discard the supernatant and dissolve the precipitate in chloroform again so that the nanocrystal concentration in the solution is 20% by mass. InP / ZnS core-shell nanocrystals A (red luminescent) chloroform solution (QD dispersion 1) was obtained.

Further, instead of the indium phosphide (InP) red luminescent nanocrystals, the above-mentioned indium phosphide (InP) green luminescent nanocrystals are used, and a chloroform solution (QD dispersion) of InP / ZnS core-shell nanocrystals (green luminescent) is used. Liquid 2) was obtained.

[Ligand exchange of luminescent nanocrystals]
Triethylene glycol monomethyl ether ester of 3-mercaptopropanoic acid (triethylene glycol monomethyl ether mercaptopropionate) (TEGMEMP) was synthesized with reference to JP-A-2002-121549 (public patent publication of Mitsubishi Chemical Corporation). It was dried under reduced pressure.

In a container filled with nitrogen gas, nanocrystal (quantum dot) dispersion 1 (including the above InP / ZnS core-shell nanocrystal (red luminescent)) and 80 g of a chloroform solution in which 8 g of TEGMEMP synthesized above is dissolved are mixed. The ligand was exchanged by stirring at 80 ° C. for 2 hours, and the mixture was cooled to room temperature.

Then, toluene / chloroform was evaporated with stirring at 40 ° C. under reduced pressure, and the mixture was concentrated until the liquid volume reached 100 ml. Four times the weight of n-hexane was added to this dispersion to aggregate the QD, and the supernatant was removed by centrifugation and decantation. 50 g of toluene was added to the precipitate and the mixture was redispersed by ultrasonic waves. This washing operation was performed a total of three times to remove the free ligand component remaining in the liquid. The precipitate after decantation was vacuum dried at room temperature for 2 hours to obtain 2 g of powder of QD (QD-TEGMEMP (red emission)) modified with TEGMEMP. A powder of QD (QD-TEGMEMP (green emission)) was obtained by the same method.

(B) Preparation of Coloring Composition, Nanocrystal-Containing Composition for Light Emission, and Ink Composition [Nanocrystal-Containing Composition for Red Light Emission 1]
30 parts by mass of the nanocrystal solid content (including ligand) for red light emission, 30 parts by mass of Zipentaeristol hexaacrylate (KAYARAD (trade name) DPHA, manufactured by Nippon Kayaku Co., Ltd.), and a polymerization initiator (Irgacare). -907 (trade name) manufactured by BASF, 5 parts by mass and 30 parts by mass of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.) are mixed to obtain a solid content of 20% by mass. The composition was diluted with propylene glycol monomethyl ether acetate, stirred with a dispersion stirrer, and filtered with a filter having a pore size of 1.0 μm to obtain a nanocrystal-containing composition 1 for red light emission.

[Composition for red coloring]
10 parts of red pigment (water content 0.3%, specific conductivity 30 μS / cm CI Pigment Red 254) was placed in a polybin, 55 parts of propylene glycol monomethyl ether acetate, and Disperbic LPN21116 (manufactured by Big Chemie Co., Ltd.) 7 0.0 parts, 0.3-0.4 mmφ Sepul beads were added, dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered with a 5 μm filter to obtain a pigment dispersion liquid. 75.00 parts of this pigment dispersion, 5.50 parts of polyester acrylate resin (Aronix (brand name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), Zipenta Eristol Hexaacrylate (KAYARAD (brand name) DPHA, Japan) 5.00 parts (manufactured by Yakuhin Co., Ltd.), benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 parts, and 13.5 parts of Eukerester EEP were stirred with a dispersion stirrer to obtain a pore size of 1. The mixture was filtered through a 0 μm filter to obtain a red pigment coloring composition 1.

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

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

Water content of pigment (%) = remaining amount of evaporation (g) x 2.5 / mass of pigment (g) x 100
The specific conductivity of the pigment is measured by measuring the specific conductivity of ion-exchanged water using a conductivity meter (CM-30V type manufactured by Toa DKK Co., Ltd.), and then measuring 100 mL with a measuring cylinder in 3 above. The collected filtrate is measured using the same conductivity meter, and the measured value is corrected by the following formula to calculate.

Specific conductivity of pigment = Specific conductivity of filtrate-Specific conductivity of ion-exchanged water used [Nanocrystal-containing composition for green light emission 1]
Instead of the red light emitting nanocrystals of the red light emitting nanocrystal-containing composition, the green light emitting nanocrystals were used to obtain a green light emitting nanocrystal-containing composition 1 in the same manner as described above.

[Composition for coloring green]
Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 6 parts of the green pigment 1 (water content 0.3%, specific conductivity 40 μS / cm CI Pigment Green 36) and yellow pigment 2 (water water) Using a pigment (water content 0.4%, specific conductivity 50 μS / cm) mixed with 4 parts of CI Pigment Yellow 150 with a specific conductivity of 0.6% and a specific conductivity of 70 μS / cm, the same procedure as above was performed. The green coloring composition 1 was obtained.

[Blue (containing nanocrystals for light emission) composition]
The blue (containing nanocrystals for light emission) composition uses nanocrystals for blue light emission instead of the nanocrystals for red light emission of the nanocrystal-containing composition 1 for red light emission, and nanocrystals for blue light emission are used in the same manner as described above. A crystal-containing composition was obtained.

[Blue coloring composition 1]
The composition for blue coloring is a mixture of propylene glycol monomethyl ether acetate, Disperbic LPN21116 (manufactured by BIC Chemie Co., Ltd.), and 0.3-0.4 mmφ zirconia beads "ER-120S" manufactured by Saint-Gobain, and a paint conditioner (Toyo). After dispersing for 4 hours with Seiki Co., Ltd., a dispersion was prepared by filtering with a 1 μm filter. Next, 75 parts by mass of the dispersion, 5.5 parts by mass of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), Zipenta Eristol Hexaacrylate (KAYARAD (trade name) DPHA, Japan). 5 parts by mass of benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts by mass of Eukerester EEP were stirred with a dispersion stirrer. The mixture was filtered through a 0 μm filter to obtain a blue colored composition 1.

[Blue coloring composition 2]
The blue coloring composition is prepared by putting blue dye 1 (CI Solvent Blue 7) in a polybin, propylene glycol monomethyl ether acetate, Disperbic LPN21116 (manufactured by Big Chemie Co., Ltd.), and 0.3-0 by Saint-Gobin. 4 mmφ zirconia beads “ER-120S” were added, dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered through a 1 μm filter to obtain a pigment dispersion.

75 parts by mass of this pigment dispersion, polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.) 5.5 parts by mass, Zipenta Eristol Hexaacrylate (KAYARAD (trade name) DPHA, Japan) 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 Eukerester EEP are stirred with a dispersion stirrer and have a pore size of 1.0 μm. Filtered with the filter of No. 2 to obtain a blue coloring composition 2.

[Nanocrystal-containing composition for yellow emission]
As the yellow-emitting nanocrystal-containing composition, instead of the above-mentioned red-emitting nanocrystals, yellow-colored emitting nanocrystals were used to obtain a yellow-emitting nanocrystal-containing composition in the same manner as described above.

[Yellow coloring composition]
Instead of the red pigment in the red pigment composition, 10 parts of a yellow pigment (CI Pigment Yellow 150 having a water content of 0.6% and a specific conductivity of 70 μS / cm) is used for yellow coloring in the same manner as above. The composition was obtained.

"Preparation of ink composition"
[Preparation of titanium oxide dispersion]
In a container filled with nitrogen gas, 6 g of titanium oxide, 1.01 g of a polymer dispersant, and 1,4-butanediol diacetate were mixed so as to have a non-volatile content of 40%. After adding zirconia beads (diameter: 1.25 mm) to the formulation in the container filled with nitrogen gas, the closed container filled with nitrogen gas is shaken for 2 hours using a paint conditioner to disperse the formulation. Was done. As a result, a light scattering particle dispersion 1 was obtained. For all the above materials, nitrogen gas was introduced to replace the dissolved oxygen with nitrogen gas.

[Preparation of Nanocrystal-Containing Ink Composition 1 for Red Light Emission]
After uniformly mixing the following (1), (2) and (3) in a container filled with nitrogen gas, the mixture is filtered through a filter having a pore size of 5 μm in a glove box, and nitrogen gas is further put into ink. It was introduced and the nitrogen gas was saturated. Then, the pressure was reduced to remove the nitrogen gas to obtain an ink composition. In this way, a deoxidized, substantially water-free, final ink composition 1 was obtained. The materials used are as follows.

[Light scattering particles]
-Titanium oxide: MPT141 (manufactured by Ishihara Sangyo Co., Ltd.)
[Thermosetting resin]
-Glysidyl group-containing solid acrylic resin: "Findick A-254"
(Made by DIC Corporation)
[Polymer dispersant]
-Polymer dispersant: BYK-2164
(The product name "DISPERBYK" manufactured by BYK is a registered trademark)
[Organic solvent]
・ 1,4-Butanediol diacetate (manufactured by Daicel Corporation)
(1) QD-TEGMEMP dispersion 1 (InP / ZnS described above) prepared above by mixing the organic solvent 1,4-butanediol diacetate with the QD (QD-TEGMEMP (red emission)) to obtain a non-volatile content of 30%. Includes core-shell nanocrystals (red luminescent): 22.5 g
(2) Thermosetting resin: "Findick A-254" (6.28 g) manufactured by DIC Co., Ltd. and curing agent: 1-methylcyclohexane-4,5-dicarboxylic acid anhydride (1.05 g). Accelerator: Dimethylbenzylamine (0.08 g) dissolved in an organic solvent: 1,4-butanediol diacetate so as to have a non-volatile content of 30%, a thermosetting resin solution: 12.5 g
(3) The light-scattering particle dispersion 1: 7.5 g
[Preparation of Nanocrystal-Containing Ink Composition 2 for Green Light Emission]
Instead of the QD-TEGMEMP dispersion 1 (including the InP / ZnS core-shell nanocrystals (red luminescent)), a dispersion of QD (QD-TEGMEMP (green luminescence)) (InP / ZnS core-shell nanocrystals) (Including (green luminescent)) was used to obtain an ink composition 2 in the same manner as the ink composition 1.

[Preparation of Ink Composition 3]
Y138 (manufactured by BASF Corporation) 0.50 parts by mass was ground together with 1.50 parts by mass of sodium chloride and 0.75 parts by mass of diethylene glycol. Then, this mixture was poured into 600 parts by mass of warm water and stirred for 1 hour. The water-insoluble matter was separated by filtration, washed well with warm water, and then air-dried at 90 ° C. for pigmentation. The particle system of the pigment was 100 nm or less, and the average length / width ratio of the particles was less than 3.00. The following dispersion test and color filter evaluation test were carried out using the obtained yellow pigment of the quinophthalone compound.

0.660 parts by mass of Y138 (manufactured by BASF Corporation) pigmented by the above method was placed in a glass bottle, and 6.42 parts by mass of propylene glycol monomethyl ether acetate, DISPERBYK (registered trademark) LPN-6919 (manufactured by BIC Chemie Co., Ltd.) 0. .467 parts by mass, DIC Corporation acrylic resin solution Unidic (registered trademark) ZL-295 0.700 parts by mass, 0.3-0.4 mmφ Sepul beads 22.0 parts by mass, paint conditioner (Toyo Seiki Co., Ltd.) (Manufactured) for 4 hours to obtain a pigment dispersion. Further, 2.00 parts by mass of the obtained pigment dispersion, 0.490 parts by mass of acrylic resin solution Unidic (registered trademark) ZL-295 manufactured by DIC Corporation, and 0.110 parts by mass of propylene glycol monomethyl ether acetate were placed in a glass bottle. , Ink composition 3 was prepared.

[Preparation of light-scattering ink composition ScB]
Instead of the above QD-TEGMEMP dispersion 1 (including the above InP / ZnS core-shell nanocrystals (red light emitting)), 1,4-butanediol diacetate was used as (1) in the same manner as in the ink composition 1. The light-scattering ink composition ScB was obtained.

(C) Manufacture of optical conversion layer (manufacture of optical conversion layers 1 to 5 by photolithography method)
A nanocrystal-containing composition for red light emission was applied to a glass substrate on which a black matrix was formed in advance by spin coating so as to have a film thickness of 2 μm. After drying at 70 ° C. for 20 minutes, ultraviolet rays were exposed to a striped pattern through a photomask with an exposure machine equipped with an ultra-high pressure mercury lamp. It was spray-developed with an alkaline developer for 90 seconds, washed with ion-exchanged water, and air-dried. 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 the transparent substrate.

Next, the nanocrystal-containing composition for green light emission was also applied by spin coating so that the film thickness was 2 μm. After drying, the striped colored layer was exposed to a place deviated from the above-mentioned red pixels by an exposure machine and developed to form green pixels adjacent to the above-mentioned red pixels.

Hereinafter, as shown in Table 1 below, a light conversion layer 1 having stripe-shaped pixels of three colors of red, green, and blue using a nanocrystal-containing composition for light emission or a composition for coloring of each color. An optical conversion layer 3 having stripe-shaped 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 striped 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

[Preparation of Optical Conversion Layer 6 by Inkjet Method]
Metallic chromium is sputtered on a glass substrate made of non-alkali glass (“OA-10G” manufactured by Nippon Electric Glass Co., Ltd.), and after pattern formation by a photolithography method, Photoresist SU-8 (manufactured by Nippon Electric Glass Co., Ltd.) ) Was applied, exposed, developed, and post-baked to form a SU-8 pattern on the chrome pattern.

The design of the partition wall pattern thus created was a pattern having an opening portion corresponding to a sub-pixel of 100 μm × 300 μm, the line width was 20 μm, and the thickness was 8 μm. This BM substrate was used to prepare the optical conversion layer 6.

A solid pattern was created by the same method, and the contact angle of the solvent (1,4-BDDA) used for the ink was measured. As a result, it was confirmed that the temperature was 45 ° and the solvent was liquid repellent.

Using an inkjet printer (manufactured by FUJIFILM Dimatix, trade name "DMP-2850"), the above ink compositions 1 and 2 and the nanocrystal-containing ink composition 1 for red light emission except that QD-TEGMEMP is not used. Similarly, a light-scattering ink composition ScB was prepared, and these ink compositions were ejected into the openings. 16 nozzles are formed in the head portion of the inkjet printer for ejecting ink, and the amount of the ink composition used per nozzle per ejection is 10 pL.

A black matrix (hereinafter, also referred to as BM) is placed on a platen (base material table) of DMP-2850, the black matrix pattern on the base material and the scanning direction of the head are matched, and alignment is performed to perform alignment of the BM. Ink was ejected to the opening portion at a speed of 6 m / sec.

The ink was ejected and formed until the thickness of the cured film of the ink was 80% or more of the thickness of the partition wall of the black matrix. The film thickness of the ink-cured film printed and cured in the opening of the BM was measured with a light interference type film thickness meter (Vert Scan).

The ink was dried and cured as follows.

When the ink is thermosetting, it contains a solvent, so it was dried under reduced pressure, heated in a nitrogen atmosphere in a glove box at 100 ° C. for 3 minutes, and then heated at 150 ° C. for 30 minutes to be cured.

When the ink was photopolymerizable, the printed substrate was placed in a closed container (purge box) having a light-transmitting window filled with nitrogen gas, and UV light was irradiated with an ultraviolet irradiation device to make the effect effective.

In this way, blue light is generated on the BM substrate by a pixel portion that converts blue light into red light, a pixel portion that converts blue light into green light, and a light scatterer-containing dispersion liquid that does not contain luminescent nanocrystals. A pixel portion to be transmitted (without color conversion) was formed.
By the above operation, a patterned optical conversion layer 6 having a plurality of types of pixel portions was obtained (configuration of FIG. 16).

[Preparation of Optical Conversion Layer 7 by Inkjet Method]
After the light conversion layer 1 is formed on the glass substrate by the same method as described above, the surface opposite to the glass substrate surface on which the light conversion layer 1 is formed, that is, the cured ink composition 1 which is a pixel portion. The ink composition 3 was applied onto ScB of the ink composition 2 and the cured ink composition by a spin coater, and then dried. Next, by heating at 180 ° C. for 1 hour, a yellow color filter layer is coated on one surface, and a pixel portion that converts blue light into red light, a pixel portion that converts blue light into green light, and a luminescent nano A pixel portion that transmits blue light (without color conversion) with a crystal-free light scatterer-containing dispersion and a light conversion layer 7 formed in the opening of the BM substrate were produced (configuration of FIG. 14). ..

[Manufacturing method of electrode substrate provided with in-cell polarizing layer]
An aqueous solution of "Poval 103" manufactured by Kuraray Co., Ltd. (solid content concentration: 4% by mass) on the light conversion layer 1 was applied and dried, and then a rubbing treatment was performed.

Next, on the rubbing surface, 0.03 part by mass of Megafuck F-554 (manufactured by DIC Corporation), 1 part by mass of the azo dye of the following formula (az-1), and the 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 provided with a polarizing layer and an optical conversion layer 1 by applying and drying a coating liquid for a polarizing layer consisting of 0.06 parts by mass of 907 (manufactured by Ciba Specialty Chemicals) and KayaCure DETX (manufactured by Nippon Kayaku). 1 was created. Then, ITO was deposited by a sputtering method to prepare a counter substrate 1 (= second (electrode) substrate).

Similarly, the opposing substrate 6 (= second (electrode) substrate) was produced by using the optical conversion layer 6 instead of the optical conversion layer 1.

Similarly, the opposing substrate 7 (= second (electrode) substrate) was produced by using the optical conversion layer 7 instead of the optical conversion layer 1.

(Example 1) (Spontaneous orientation type VA liquid crystal panel)
The first substrate on which the transparent electrode is formed and the opposing substrate 6 (the second transparent electrode substrate) on which the optical conversion layer 6 having the in-cell polarizing layer on the surface is formed are opposed to each other. The two substrates were arranged, and the peripheral portions were bonded with a sealing agent while maintaining a constant gap (4 μm) between the two substrates. Next, 0.5 parts by mass of the following polymerizable compound (spontaneous alignment agent) (following formula (SA-1)) and the following polymerizable compound (spontaneous alignment agent) in the surface of the alignment layer and the cell gap partitioned by the sealant XX-1) A liquid crystal composition obtained by mixing 0.5 parts by mass and 99.0 parts by mass of the following liquid crystal composition 1 is injected by a vacuum injection method into a liquid crystal panel containing a substrate with ITO without an alignment film with a cell gap of 4 μm. did.

Then, a high-pressure mercury lamp was used in a state where a voltage of 10 V was applied at a frequency of 100 Hz to a liquid crystal panel into which the liquid crystal composition containing the polymerizable compound was injected, and ultraviolet rays were irradiated through a filter that cuts ultraviolet rays of 325 nm or less. At this time, the illuminance measured under the condition of a central wavelength of 365 nm was adjusted to be 100 mW / cm ² , and ultraviolet rays having an integrated light intensity of 10 J / cm ² were irradiated. Then, using a fluorescent UV lamp, central wavelength illuminance measured under the conditions of 313nm is adjusted to 3 mW / cm ^2, further irradiated with ultraviolet light at an accumulated light intensity 10J / cm ^2, spontaneous alignment type VA liquid crystal panel 1 was obtained, and the light resistance test with blue light having a main emission peak at 450 nm and the light resistance test with light having a main emission peak at 385 nm were evaluated. The results are shown below.

(Examples 2 to 16, Comparative Example 1)
A spontaneously oriented VA liquid crystal panel was produced under the same conditions as in Example 1 except that the liquid crystal composition and the polymerizable compound used were changed to the following. Then, a light resistance test using blue light having a main emission peak at 450 nm and a light resistance test using light having a main emission peak at 385 nm were evaluated. The results are shown below.

In Tables 3 and 7 to 10 above, the rate of decrease at the main emission peak at 450 nm is "VHR value after 14-hour light resistance test / initial (= 14-hour light resistance test) VHR value", and the main emission peak at 385 nm. The rate of decrease in is "VHR value after 60 seconds light resistance test / initial (= before 60 seconds light resistance test) VHR value". Therefore, the closer the reduction rate is to 1, the more stable the light is with respect to blue light having a main emission peak at 450 nm or light having a main emission peak at 385 nm. According to the above experimental results, the liquid crystal display element of the present invention is superior in light resistance to the liquid crystal display element (Comparative Example 1) outside the range of the present invention, and the deterioration of nanocrystals for light emission and partial high-energy light rays It is considered that the deterioration of the liquid crystal layer due to the irradiation spot of the above can be suppressed or prevented.

(Manufacturing of liquid crystal display element and measurement of color reproduction area)
The backlight units 1 and 2 produced above were attached to the obtained spontaneously oriented VA liquid crystal panel, and the color reproduction region was measured. As a result, it was confirmed that the liquid crystal display elements provided with the optical conversion layer all had a wide color reproduction region.

1000: Liquid crystal display element 100: Backlight unit (101: light source unit, 102: light guide unit, 103: light conversion unit)
101: Light source unit (L: light emitting element (105: light emitting diode, 110: light source substrate), 112a, b: fixing member)
102: Light guide unit (106: diffusion plate, 104: light guide plate)
103: Light source / light guide unit 110: Light source substrate 111: Transparent filling container 112a, b: Fixing member NC: Nanocrystal for light emission (compound semiconductor)
1, 8: Polarizing layer 2, 7: Transparent substrate 3: First electrode layer 3': Second electrode layer 5: Liquid crystal layer 6: Color filter (including the case where the resin contains a dye)
9: Support substrate 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 electrodes 23, 25: Insulating layer

Claims (13)

A pair of substrates on which the first substrate and the second substrate are provided facing each other,
A liquid crystal layer sandwiched between the first substrate and the second substrate,
With the pixel electrodes provided on at least one of the first substrate or the second substrate,
With a common electrode provided on at least one of the first substrate or the second substrate,
A light source unit equipped with a light emitting element and
It is provided with three primary color pixels of red (R), green (G), and blue (B), and is red (R), green (G), and blue (B) due to 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 in any of the above is provided.
The light source unit, the liquid crystal layer, and the light conversion layer are arranged in this order.
At least one of the first substrate and the second substrate and the liquid crystal layer does not have an alignment film, but has an orientation control layer formed of a polymerizable compound.
The liquid crystal layer has the general formulas (N-1), (N-2) and (N-3).

(In the formula, ^RN11 , ^RN12 , ^RN21 , ^RN22 , ^RN31 and ^RN32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two non-adjacent ones. More than one −CH ₂₋ may be independently substituted by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are independently (a) 1,4-cyclohexylene groups (one -CH _2- or adjacent to each other in this group). No two or more -CH _2- may be replaced by -O-) and (b) 1,4-phenylene group (one -CH = or non-adjacent 2 present in this group) More than one -CH = may be replaced with -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 = existing in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. )
(D) Represents a group selected from the group consisting of 1,4-cyclohexenylene groups, and the above groups (a), group (b), group (c) and group (d) are independently fluorine atoms. May be replaced,
^{Z N11, Z N12, Z N21} , Z N22, Z N31 and ^{Z N32} 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-
X ^N21 represents a hydrogen atom or a fluorine atom.
^TN31 represents −CH _2- or oxygen atom,
Although n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 each independently represent an integer of 0 to 3, n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are independent of each other. When it is 1, 2 or 3, and there are a plurality of A ^{N11 to} A ^N32 and Z ^{N11 to} Z ^N32 , they may be the same or different. ) Is contained in one or more compounds selected from the compounds represented by) and one or more polymerizable compounds, and a liquid crystal composition having a negative dielectric anisotropy (Δε) is used. Liquid crystal display element. 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 the light emitted from the light source unit is blue light, and the blue pixel region forming the blue pixel in the light conversion layer transmits the blue light. The light conversion layer has a black matrix, a third light emitting nanocrystal that absorbs ultraviolet light and emits red light, a fourth light emitting nanocrystal that absorbs ultraviolet light and emits green light, and ultraviolet light. The liquid crystal display element according to claim 1, which contains 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. The liquid crystal display element according to any one of claims 1 to 4, wherein the light conversion layer is provided on a substrate side facing the substrate on the light source portion 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 device according to any one of claims 1 to 6, wherein the half width of at least one emission spectrum in the red (R), green (G), and blue (B) regions is 20 to 50 nm. The luminescent nanocrystals include a core containing at least one or two or more first semiconductor materials.
The liquid crystal display element according to any one of claims 1 to 7, which has a shell that covers the core and contains a second semiconductor material that is the same as or different from the core. The first semiconductor material is one selected from the group consisting of II-VI group semiconductors, III-V group semiconductors, I-III-VI group semiconductors, IV group semiconductors and I-II-IV-VI group semiconductors. The liquid crystal display element according to claim 8, which is two or more types. In the compounds represented by the general formulas (N-1), (N-2) and (N-3) contained in the liquid crystal composition, Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z. The total content of the compounds in which ^N32 is a single bond is 50 to 100% by mass with respect to the total content of the compounds represented by the general formulas (N-1), (N-2) and (N-3). The liquid crystal display element according to any one of claims 1 to 9, which is%. At least one of Z ^N11 and Z ^N12 in the compounds represented by the general formulas (N-1), (N-2) and (N-3) contained in the liquid crystal composition is a linking group other than a single bond. , Z ^N21 and Z ^N22 are non-single bond linking groups, and at least one of Z ^N31 and Z ^N32 is a non-single bond linking group. The total content of the compounds is the general formula (N-1). ), (N-2) and (N-3), the liquid crystal display according to any one of claims 1 to 9, which is 5 to 50% by mass with respect to the total content of the compounds. element. The liquid crystal display device according to any one of claims 1 to 11, which contains one or more compounds represented by the general formula (P) as the polymerizable compound contained in the liquid crystal composition.

(In the above general formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or -Sp ^p2- P ^p2 , and one or a non-alkyl group. Two or more adjacent −CH ₂ −s may be independently substituted by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−. One or more hydrogen atoms in the alkyl group may be independently substituted with a cyano group, a fluorine atom or a chlorine atom.
P ^p1 and P ^p2 are independent of each other, and the general formulas (P ^p1-1 ) to (P ^p1-9 ) are respectively.

(In the formula, R ^p11 and R ^p12 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and W ^p11 is a single bond, −O. Representing a −, −COO− or methylene group, t ^p11 represents 0, 1 or 2, but if there are multiple R ^p11 , R ^p12 , W ^p11 and / or t ^{p11 in} the molecule, they are the same. It may be different or different.)
Represents one of
Sp ^p1 and Sp ^p2 independently represent a single bond or a spacer group, respectively.
Z ^p1 and Z ^p2 are independent, single-bonded, -O-, -S-, -CH _2- , -OCH _2- , -CH ₂ O-, -CO-, -C ₂ H ₄ -,-, respectively. _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO-NR ZP1 -, - NR ZP1 -CO -, - SCH 2 -, - CH 2 S- ^{, -CH = CR ZP1 -COO -,} - CH = CR ZP1 -OCO -, - COO-CR ZP1 = CH -, - OCO-CR ZP1 = CH -, - COO-CR ZP1 = CH-COO -, - COO -CR ^ZP1 = CH- ^{OCO-, -OCO} -CR ^ZP1 = CH- ^{COO-, -OCO} -CR ^ZP1 = CH-OCO-,-(CH ₂ ) _z- COO-,-(CH ₂ ) _2- OCO- , -OCO- (CH ₂ ) ₂ -,-(C = O) -O- (CH ₂ ) _2- , -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 - or -C≡C- ^{(wherein, R ZP1} is Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but when a plurality of R ^ZP1s are present in the molecule, they may be the same or different.)
Represents
A ^p1 , A ^p2 and A ^p3 are independent of each other.
^(A p) 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 p) 1,4-phenylene group (the one present in the group -CH = or non-adjacent two or more -CH = may be replaced by -N =.) And (c ^p ) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, phenanthrene-2,7-diyl group or anthracene -2,6-diyl groups (one -CH = existing in these groups or two or more -CH = not adjacent to each other may be replaced with -N =, and hydrogen existing in this group. The atom may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms.)
Represents a group selected from the group consisting of the above group (a ^p), group (b ^p) and group (c ^p) are each independently hydrogen atoms present in this group may be substituted with a halogen atom, a carbon It may be substituted with an alkyl group having 1 to 8 atoms or an alkenyl group having 2 to 8 carbon atoms. It may be substituted with a cyano group, a fluorine atom, a chlorine atom or -Sp ^p2 -P ^p2 .
m ^p1 represents 0, 1, 2 or 3, and when a plurality of Z ^p1 , ^Ap2 , Sp ^p2 and / or P ^p2 are present in the molecule, they may be the same or different. A ^p3 represents a single bond when m ^p1 is 0 and A ^p1 is a phenanthrene-2,7-diyl group or an anthracene-2,6-diyl group. ) The liquid crystal display device according to any one of claims 1 to 12, which contains one or more compounds represented by the general formula (SAL) as the polymerizable compound contained in the liquid crystal composition.

(Wherein, R ^AK1 represents a linear or branched alkyl group having 1 to 20 carbon atoms, one or two or more -CH 2 in the alkyl group _- is attached is an oxygen atom directly Independently, they may be independently substituted with −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−, and one of the alkyl groups. Alternatively, two or more hydrogen atoms may be independently substituted with a halogeno group.
A ^AL1 and A ^AL2 each independently represent a divalent cyclic group.
Z ^AL1 is a single bond, -CH = CH -, - CF = CF -, - C≡C -, - COO -, - OCO -, - OCOO -, - 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 an alkylene group having 1 to 20 carbon atoms, one or adjacent to this alkylene group. No two or more -CH _2- may be replaced with -O-, -COO- or -OCO-
One or more hydrogen atoms in A ^AL1 , A ^AL2 and Z ^AL1 may be independently substituted with a halogeno group, an adsorbent group, P ^AP1 - Sp ^AP1- or a monovalent organic group, respectively. ..
m ^AL1 represents an integer of 1-5.
P ^AP1 is a general formula (AP-1) to a general formula (AP-9).

(In the formula, R ^AP1 and R ^AP2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 10 carbon atoms, and one of the alkyl groups or two or more -CH 2 _- may be replaced by -O- or -CO-, 1 or 2 or more hydrogen atoms in the alkyl group each independently substituted with a halogen atom or a hydroxyl group may ^{be, W AP1} represents a single bond, -O -, - COO- or -CH ₂ - ^{represents, t AP1} is a group selected from the group represented by represents) 0, 1 or 2. Yes,
Sp ^AP1 represents a single-bonded or linear or branched alkylene group having 1 to 20 carbon atoms.
Sp ^AT1 represents a single bond, linear or branched alkylene group having 1 to 25 carbon atoms.
Z ^AT1 represents a monovalent group containing a polar ^component, a hydrogen atom in ^{Z AT1} is ^{-OH, -CN, -Sp AT1 -W AT1} -Z AT1 or ^{P AP1} - ^Sp AP1 - may be substituted by ..
W ^AT1 represents a single bond or the formula (WAT1) or (WAT2),

(In the formula, Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atom in the alkylene group is -OH,-. CN, -Sp ^AT1- W ^AT1- Z ^AT1 or P ^AP1 - Sp ^AP1 -may be substituted, and -CH _2- in the alkylene group is a cyclic group, -O- so that oxygen atoms are not directly bonded. , -COO-, -C (= O)-, -OCO-, -CH = CH- may be substituted.)
The compound has at least one P ^AP1 - Sp ^AP1- in its molecule. )

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