WO2017033830A1

WO2017033830A1 - Liquid crystal display element

Info

Publication number: WO2017033830A1
Application number: PCT/JP2016/074097
Authority: WO
Inventors: 小川　真治; 芳典岩下; 長谷部　浩史; 士朗谷口
Original assignee: Dic株式会社
Priority date: 2015-08-21
Filing date: 2016-08-18
Publication date: 2017-03-02
Also published as: CN107924090A; KR20180042337A; TW201722996A; JPWO2017033830A1

Abstract

[Problem] The present invention addresses the problem of providing a liquid crystal display element that does not adversely affect the burn-in characteristics of a display element or liquid crystal display element characteristics such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, nematic phase stability at low temperatures, and γ₁. [Solution] A liquid crystal display element that is obtained by using a photoalignment film and a liquid crystal composition containing a compound represented by formula (i) and a compound represented by formula (J). The liquid crystal display element maintains the high-speed response properties of the liquid crystal composition and has excellent low-temperature stability.

Description

Liquid crystal display element

The present invention relates to a liquid crystal display element using a nematic liquid crystal composition that exhibits a positive dielectric anisotropy (Δε) useful as a liquid crystal display material.

Currently, as a liquid crystal display for smartphones, it has a high-quality and excellent visual characteristics, for example, an IPS mode liquid crystal display device or an FFS mode liquid crystal display device (Fringe Field Switching mode Liquid Display; FFS mode liquid crystal display device) ) Is widely used (see Patent Document 1 and Patent Document 2). The FFS mode is a method introduced to improve the low aperture ratio and transmittance of the IPS mode. At present, materials using p-type liquid crystal compositions having a positive dielectric anisotropy are widely used as liquid crystal compositions used in lateral alignment type liquid crystal display devices because they can easily reduce the voltage. Yes. In addition, since most of the applications of the FFS mode are portable terminals, there is a strong demand for further power saving, and liquid crystal element manufacturers are actively developing such as adopting an array using IGZO.

Also, as a liquid crystal molecule alignment method, a method called a rubbing method is often used. In this method, the surface of the alignment film is rubbed (rubbed) in a certain direction by rotating a roller wrapped with a cloth such as nylon while pressing it with a certain pressure on a thin film coated and baked with an alignment film material such as polyimide. ) To impart alignment regulating force to the liquid crystal molecules. The exact alignment mechanism of this method is not clear even now, rubbing the surface of the alignment film, causing streaky display unevenness, a part of the alignment film material falling off and mixing into the liquid crystal layer, and In the array substrate, there are problems such as a point that the TFT is broken by the generated static electricity, and a method of imparting orientation without rubbing has been studied. In particular, a photo-alignment film that imparts anisotropy to the alignment film using linearly polarized ultraviolet rays can be imparted in a non-contact manner, and therefore has been developed as a method for solving the problems of the rubbing method described above. The use of a photo-alignment film has also been sought for electric field type display elements (see Patent Document 3).

JP-A-11-202356 JP 2003-233083 A JP 2013-109366 A

However, due to the recent application of the liquid crystal display element and the expansion of the market, the use method and the manufacturing method have changed greatly, and the driving method of the liquid crystal display element (for example, TN type, STN type, VA type, IPS type, In addition to FFS type and the like, as the size of super-large size display elements of 50 type or more is put into practical use, the liquid crystal composition is injected from the conventional vacuum injection method to the liquid crystal composition liquid. A dropping injection method (ODF: One Drop Fill) method in which a droplet is dropped on one substrate surface and bonded to the other substrate is the mainstream of the injection method. Therefore, as described in Patent Documents 1 to 3, a laterally oriented electrode such as an IPS mode or an FFS mode has a plurality of strip-shaped electrodes formed on the substrate surface on one side arranged in parallel, and the substrate Since it has a structure in which the entire surface is covered with an alignment film, the surface of the substrate on one side has innumerable irregularities, so when the liquid crystal composition is dropped on the substrate surface, a drop mark is formed on the substrate. As a result, the problem that the drop marks cause deterioration in display quality has been brought to the surface. In addition to such problems, compatibility with the alignment film that is in direct contact with the liquid crystal composition also becomes a problem.

Furthermore, in the liquid crystal display element manufacturing process by the ODF method, it is necessary to drop an optimal liquid crystal injection amount according to the size of the liquid crystal display element. When the deviation of the injection amount increases from the optimum value, the balance between the refractive index and the driving electric field of the liquid crystal display element designed in advance is lost, and display defects such as spots and contrast defects occur. In particular, small liquid crystal display elements that are frequently used in smartphones that have become popular recently are difficult to control the deviation from the optimum value within a certain range because the optimum liquid crystal injection amount is small. Therefore, in order to keep the yield of the liquid crystal display element high, for example, there is little influence on the sudden pressure change and impact in the dropping device that occurs when dropping the liquid crystal, and the ability to keep dropping the liquid crystal stably for a long time Is also necessary.

In addition, when increasing the alignment regulating force of the photo-alignment film with respect to the liquid crystal molecules, there is a problem that it is necessary to increase irradiation energy or to irradiate for a long time.

Thus, in the liquid crystal composition used for the active matrix drive liquid crystal display element driven by a TFT element or the like, while maintaining the characteristics and performance required for a liquid crystal display element such as high-speed response performance, In addition to the characteristics of having a high specific resistance value or high voltage holding ratio, which are emphasized, and being stable against external stimuli such as light and heat, development in consideration of the manufacturing method of liquid crystal display elements has been required. ing.

Therefore, the problem of the present invention is to solve the above problems, dielectric anisotropy (Δε), viscosity (η), nematic phase-isotropic liquid transition temperature (TNI), nematic phase stability at low temperature, A p-type liquid crystal composition that is excellent in various characteristics as a liquid crystal display element such as rotational viscosity (γ1) and that can realize excellent display characteristics when used in a horizontal alignment type liquid crystal display element provided with a photo-alignment film was used. The object is to provide a liquid crystal display element.

Another object of the present invention is to use a p-type liquid crystal composition capable of realizing excellent display characteristics (contrast, etc.) when used in a horizontal alignment type liquid crystal display device having an alignment film with improved alignment control power. The object is to provide a liquid crystal display element.

The inventors of the present application have made extensive studies to solve the above-mentioned problems, and as a result of studying the configuration of the horizontal alignment type liquid crystal display element and the various configurations of various liquid crystal compositions and alignment films, the present invention has been completed. It came.

Since the liquid crystal display element according to the present invention undergoes very small changes in specific resistance and voltage holding ratio due to heat and light, the practicality of the product is high and high-speed response can be achieved.

The liquid crystal composition according to the present invention is very useful because it can stably exhibit performance in the manufacturing process of the liquid crystal display element used, and can be manufactured with high yield by suppressing display defects caused by the process.

The liquid crystal display element according to the present invention can use a liquid crystal composition excellent in low-temperature stability and high-speed response.

The present invention can provide a liquid crystal display element provided with a photo-alignment film in which the alignment regulating force of liquid crystal molecules is improved.

The liquid crystal display element according to the present invention can realize a high contrast excellent in alignment regulating force.

Since the liquid crystal display element according to the present invention uses a liquid crystal composition containing a polymerizable monomer, a very excellent high contrast can be realized.

It is a figure which shows typically an example of a structure of the liquid crystal display element of this invention. It is the top view to which the area | region enclosed by the II line | wire of the electrode layer 3 formed on the board | substrate 2 in FIG. 1 was expanded. FIG. 3 is a cross-sectional view of the liquid crystal display element shown in FIG. 1 cut along the line III-III in FIG. FIG. 3 is a modification of FIG. 2, and is an enlarged plan view of a region surrounded by II line of an electrode layer 3 formed on a substrate 2 in FIG. 1. FIG. 5 is a cross-sectional view of the liquid crystal display element shown in FIG. 1 taken along the line III-III in FIG. It is a top view which shows typically the electrode structure in the liquid crystal display element of this invention. It is a top view which shows typically the state before and behind superposition | polymerization of the liquid crystal layer in the area | region of the broken line part VII of FIG. FIG. 7 is a plan view schematically showing a driving state of a suitable liquid crystal layer used in the liquid crystal display element of the present invention in a region of a broken line part VII in FIG. 6.

The first of the present invention, the first substrate and the second substrate disposed opposite to each other,
A liquid crystal layer containing a liquid crystal composition filled between the first substrate and the second substrate;
Driven by the common electrode, a plurality of gate bus lines and data bus lines arranged in a matrix, a thin film transistor provided at an intersection of the gate bus line and the data bus line, and the thin film transistor on the first substrate. An electrode layer having a pixel electrode for each pixel that forms an electric field substantially parallel to the substrate with the common electrode;
A photo-alignment layer formed on at least one substrate between the liquid crystal layer and the first substrate and the liquid crystal layer and the second substrate;
The liquid crystal composition has a positive dielectric anisotropy, a nematic phase-isotropic liquid transition temperature of 60 ° C. or higher, and represented by the general formula (i):

(In the general formula (i), R ⁱ¹ and R ⁱ² are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or Represents an alkenyloxy group having 2 to 8 carbon atoms, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkoxy group or alkenyloxy group may be substituted with a fluorine atom. The methylene group in the group, alkoxy group or alkenyloxy group may be substituted with an oxygen atom unless the oxygen atom is continuously bonded, and may be substituted with a carbonyl group unless the carbonyl group is bonded continuously. ,
A ⁱ¹ is (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- .)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═) and (c) (C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) are each independently selected from the group consisting of cyano group, fluorine atom, chlorine atom, methyl group, trifluoromethyl group or trifluoro May be substituted with a methoxy group,
n ⁱ¹ represents 1, 2, 3 or 4, and when n ⁱ¹ is 2, 3 or 4, and there are a plurality of A ⁱ¹ , they may be the same or different, and n ⁱ¹ is When it is 2, 3 or 4 and a plurality of Z ⁱ¹ are present, they may be the same or different. ) And at least one compound selected from the group of compounds represented by formula (J):

(Wherein R ^J1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently —CH═CH—, — Optionally substituted by C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^J1 represents 0, 1, 2, 3 or 4;
A ^J1 , A ^J2 and A ^J3 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═) and (c) (C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) are each independently selected from the group consisting of cyano group, fluorine atom, chlorine atom, methyl group, trifluoromethyl group or trifluoro May be substituted with a methoxy group,
Z ^J1 and Z ^J2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents —COO—, —OCO— or —C≡C—,
When n ^J1 is 2, 3 or 4 and a plurality of A ^J2 are present, they may be the same or different, and n ^J1 is 2, 3 or 4 and a plurality of Z ^J1 is present. If they are the same or different,
X ^J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. It is a horizontal alignment type liquid crystal display element characterized by containing one or more of the compounds represented by formula (1).

The structure of the liquid crystal display element according to the present invention and the substrate and electrode layers which are constituent elements of the liquid crystal display element will be described with reference to FIGS. Next, the liquid crystal layer and the photo-alignment film layer will be described in detail with respect to the components of the liquid crystal display element.

Hereinafter, an embodiment of a liquid crystal display device according to the present invention will be described with reference to the drawings.

FIG. 1 is a diagram schematically showing a configuration of a liquid crystal display element. In FIG. 1, for convenience of explanation, each component is illustrated separately. As shown in FIG. 1, the configuration of the liquid crystal display element 10 according to the present invention is sandwiched between a first (transparent insulating) substrate 2 and a second (transparent insulating) substrate 7 that are arranged to face each other. A liquid crystal display element of a horizontal alignment mode having the liquid crystal composition (or liquid crystal layer 5), wherein the liquid crystal composition of the present invention is used as the liquid crystal composition. The first (transparent insulating) substrate 2 has an electrode layer 3 formed on the surface on the liquid crystal layer 5 side. Further, between the liquid crystal layer 5 and each of the first (transparent insulation) substrate 2 and the second (transparent insulation) substrate 7, the liquid crystal composition constituting the liquid crystal layer 5 is directly brought into contact to induce homogeneous alignment. The liquid crystal molecules in the liquid crystal composition are aligned so as to be substantially parallel to the substrates 2 and 7 when no voltage is applied. As shown in FIGS. 1 and 3, the second substrate 7 and the first substrate 2 may be sandwiched between a pair of

polarizing plates

1 and 8. Further, in FIG. 1, a color filter 6 is provided between the second substrate 7 and the alignment film 4. The liquid crystal display element according to the present invention may be a so-called color filter on array (COA), or may be provided with a color filter between an electrode layer including a thin film transistor and a liquid crystal layer, or the thin film transistor. A color filter may be provided between the electrode layer containing and the second substrate.

1 to 8, for the sake of explanation, as a preferred embodiment of the liquid crystal display element of the present invention, between the liquid crystal layer 5 and the first substrate 2 and between the liquid crystal layer 5 and the second substrate 7. Although the example in which the photo-alignment film 4 is formed on each of the first substrate and the second substrate is described, the liquid crystal display element of the present invention is on the first substrate 2 or the second substrate 7. The photo-alignment film 4 should just be formed in at least one.

For example, when the photo-alignment film 4 is formed between the liquid crystal layer 5 and the first substrate 2 so as to contact the liquid crystal layer 5 on the first substrate 2, the other liquid crystal layer 5 and the second substrate 2 It is preferable to form a photo-alignment film or a rubbing alignment film without providing an alignment film between the substrate 7 and more preferably to form a photo-alignment film.

That is, the liquid crystal display element 10 according to the present invention includes a first polarizing plate 1, a first substrate 2, an electrode layer 3 including a thin film transistor, a (first) alignment film 4, and a liquid crystal composition. It is preferable that the liquid crystal layer 5, the (second) alignment film 4, the color filter 6, the second substrate 7, and the second polarizing plate 8 are sequentially stacked.

The first substrate 2 and the second substrate 7 can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. The two substrates 2 and 7 are bonded together by a sealing material and a sealing material such as an epoxy thermosetting composition disposed in the peripheral region, and in order to maintain the distance between the substrates, for example, Spacer columns made of resin formed by granular spacers such as glass particles, plastic particles, alumina particles, or the photolithography method may be arranged. The substrate according to the present invention preferably contains a transparent conductive material.

FIG. 2 is an enlarged plan view of a region surrounded by the II line of the electrode layer 3 formed on the substrate 2 in FIG. FIG. 3 is a cross-sectional view of the liquid crystal display element shown in FIG. 1 cut along the line III-III in FIG. 2 and 3 describe an example of the FFS mode as an example of a horizontal alignment type liquid crystal display element according to the present invention. On the other hand, FIG. 4 and FIG. 5 described later describe an example of the IPS mode as an example of the horizontal alignment type liquid crystal display element according to the present invention. As shown in FIG. 2, the electrode layer 3 including thin film transistors formed on the surface of the first substrate 2 includes a plurality of gate bus lines 26 for supplying scanning signals and a plurality of gate bus lines 26 for supplying display signals. Data bus lines 25 are arranged in a matrix so as to cross each other. In FIG. 2, only a pair of gate bus lines 26 and a pair of data bus lines 25 are shown.

A unit pixel of the liquid crystal display device is formed by a region surrounded by the plurality of gate bus lines 26 and the plurality of data bus lines 25, and a pixel electrode 21 and a common electrode 22 are formed in the unit pixel. . A thin film transistor including a source electrode 27, a drain electrode 24, and a gate electrode 28 is provided in the vicinity of an intersection where the gate bus line 26 and the data bus line 25 intersect each other. The thin film transistor is connected to the pixel electrode 21 as a switch element that supplies a display signal to the pixel electrode 21. A common line 29 is provided in parallel with the gate bus line 26. The common line 29 is connected to the common electrode 22 in order to supply a common signal to the common electrode 22.

A preferred embodiment of the structure of the thin film transistor is provided, for example, as shown in FIG. 3 so as to cover the gate electrode 11 formed on the surface of the substrate 2 and the gate electrode 11 and cover the substantially entire surface of the substrate 2. A gate insulating layer 12, a semiconductor layer 13 formed on the surface of the gate insulating layer 12 so as to face the gate electrode 11, and a protective layer provided to cover a part of the surface of the semiconductor layer 13 14, a drain electrode 16 provided so as to cover one side end of the protective layer 14 and the semiconductor layer 13 and to be in contact with the gate insulating layer 12 formed on the surface of the substrate 2, and the protection A source electrode 17 which covers the other side edge of the layer 14 and the semiconductor layer 13 and is in contact with the gate insulating layer 12 formed on the surface of the substrate 2; and the drain Has an insulating protective layer 18 provided to cover the electrode 16 and the source electrode 17, a. An anodic oxide film (not shown) may be formed on the surface of the gate electrode 11 for reasons such as eliminating a step with the gate electrode.

Amorphous silicon, polycrystalline polysilicon, or the like can be used for the semiconductor layer 13, but when a transparent semiconductor film such as ZnO, IGZO (In—Ga—Zn—O), ITO, or the like is used, it results from light absorption. It is also preferable from the viewpoint of suppressing the adverse effect of optical carriers and increasing the aperture ratio of the element.

Furthermore, ohmic contact layers 15 may be provided between the semiconductor layer 13 and the drain electrode 16 or the source electrode 17 for the purpose of reducing the width and height of the Schottky barrier. For the ohmic contact layer, a material in which an impurity such as phosphorus such as n-type amorphous silicon or n-type polycrystalline polysilicon is added at a high concentration can be used.

The gate bus line 26, the data bus line 25, and the common line 29 are preferably metal films, more preferably Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni, or an alloy thereof, Al or Cu The case of using the alloy wiring is particularly preferable. The insulating protective layer 18 is a layer having an insulating function, and is formed of silicon nitride, silicon dioxide, silicon oxynitride film, or the like.

In the embodiment shown in FIGS. 2 and 3, the common electrode 22 is a flat electrode formed on almost the entire surface of the gate insulating layer 12, while the pixel electrode 21 is an insulating protective layer 18 covering the common electrode 22. It is a comb-shaped electrode formed on the top. That is, the common electrode 22 is disposed at a position closer to the first substrate 2 than the pixel electrode 21, and these electrodes are disposed so as to overlap each other via the insulating protective layer 18. The pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), IZTO (Indium Zinc Tin Oxide), and the like. Since the pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material, the area opened by the unit pixel area increases, and the aperture ratio and transmittance increase.

In addition, the pixel electrode 21 and the common electrode 22 have an interelectrode distance (also referred to as a minimum separation distance): R between the pixel electrode 21 and the common electrode 22 in order to form a fringe electric field between the electrodes. The distance between the first substrate 2 and the second substrate 7 is smaller than G. Here, the distance between electrodes: R represents the distance in the horizontal direction on the substrate between the electrodes. FIG. 3 shows an example in which the plate-shaped common electrode 22 and the comb-shaped pixel electrode 21 overlap with each other, and therefore, an interelectrode distance: R = 0 is shown, and the minimum separation distance: R is the first substrate. Since the distance between the substrate 2 and the second substrate 7 (that is, the cell gap) G becomes smaller, a fringe electric field E is formed. Therefore, the FFS type liquid crystal display element can use a horizontal electric field formed in a direction perpendicular to a line forming the comb shape of the pixel electrode 21 and a parabolic electric field. The electrode width of the comb-shaped portion of the pixel electrode 21: l and the width of the gap of the comb-shaped portion of the pixel electrode 21: m are such that all the liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. It is preferable to form.

The liquid crystal display element according to the present invention is preferably an FFS liquid crystal display element using a fringe electric field, and an interelectrode distance R (common electrode 22) between the common electrode 22 and the pixel electrode 21 adjacent to the common electrode 22 is used. And the pixel electrode 21 adjacent to the common electrode 22 is preferably shorter than the shortest separation distance G between the alignment layers 4 (inter-substrate distance). In the case of the FFS mode liquid crystal display element as in the preferred embodiment of the present invention, when a voltage is applied to the liquid crystal molecules arranged so that the long axis direction is parallel to the alignment direction of the alignment layer, it is common with the pixel electrode 21. An equipotential line of a parabolic electric field is formed between the electrode 22 and the upper part of the pixel electrode 21 and the common electrode 22 and is arranged along the electric field in which the major axis of the liquid crystal molecules in the liquid crystal layer 5 is formed. In particular, since the liquid crystal composition according to the present invention uses liquid crystal molecules having positive dielectric anisotropy, the major axis direction of the liquid crystal molecules is aligned along the generated electric field direction.

In the liquid crystal display element according to the present invention, the common electrode and the pixel electrode are preferably formed on the same substrate. For example, it is preferable that the common electrode and the pixel electrode are formed on the first substrate as shown in FIGS.

The color filter 6 preferably forms 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.

On the electrode layer 3 and the color filter 6, a pair of photo-alignment films 4 that are in direct contact with the liquid crystal composition constituting the liquid crystal layer 5 and induce homogeneous alignment are provided.

By using an alignment film as a photo-alignment film, we can reduce the problem of the alignment restriction on liquid crystal molecules due to uneven rubbing and dust generated during rubbing, and provide an FFS liquid crystal display element with excellent transmittance characteristics. can do.

In addition, the polarizing plate 1 and the polarizing plate 8 can be adjusted so that the viewing angle and the contrast are good by adjusting the polarizing axis of each polarizing plate, and the transmission axes thereof operate in the normally black mode. In addition, it is preferable to have transmission axes perpendicular to each other. In particular, any one of the polarizing plate 1 and the polarizing plate 8 is preferably arranged so as to have a transmission axis parallel to the alignment direction of the liquid crystal molecules. Further, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. Furthermore, a retardation film for widening the viewing angle can also be used.

Furthermore, in one embodiment of the liquid crystal display element according to the present invention, it is preferable that the common electrode is formed on substantially the entire surface of the first substrate and arranged on the first substrate side from the pixel electrode. That is, a preferred embodiment of the liquid crystal display element according to the present invention is filled between the first substrate and the second substrate that are disposed opposite to each other, and between the first substrate and the second substrate. A liquid crystal layer containing a liquid crystal composition, a common electrode including a transparent conductive material on the first substrate, a plurality of gate bus lines and data bus lines arranged in a matrix, and the gate bus lines and data A pixel electrode including a thin film transistor and a transparent conductive material provided at an intersection with a bus line, and a pixel electrode that is driven by the thin film transistor to form a fringe electric field with the common electrode; A photo-alignment film layer for inducing homogeneous alignment formed between the liquid crystal layer and the first substrate and the second substrate, respectively, and the pixel electrode and the common electrode The horizontal component R of the inter-electrode distance is smaller than the distance G between the first substrate and the second substrate, the common electrode is formed almost on the entire surface of the first substrate, and the first component is higher than the pixel electrode. Arranged on the substrate side. Note that FIGS. 2 to 3 which are one mode of the present invention show a mode in which the common electrode is formed on almost the entire surface of the first substrate and is arranged closer to the first substrate than the pixel electrode.

The FFS type liquid crystal display element described with reference to FIGS. 2 to 3 is an example, and can be implemented in various other forms without departing from the technical idea of the present invention.

Other embodiments of the liquid crystal display element according to the present invention will be described below with reference to FIGS. The liquid crystal display elements shown in FIGS. 4 and 5 are IPS liquid crystal display elements. For example, FIG. 4 is another embodiment of the plan view in which the region surrounded by the II line of the electrode layer 3 formed on the substrate 2 in FIG. 1 is enlarged. As shown in FIG. 4, the pixel electrode 21 may have a slit. Further, the slit pattern may be formed to have an inclination angle with respect to the gate bus line 26 or the data bus line 25.

The pixel electrode 21 shown in FIG. 4 has a shape in which a substantially rectangular flat plate electrode is cut out by a notch portion having a substantially rectangular frame shape. In addition, a comb-like common electrode 22 is formed on one surface of the back surface of the pixel electrode 21 via an insulating layer 18 (not shown). The (shortest) separation distance R between the adjacent common electrode and the pixel electrode is longer than the shortest separation distance G between the alignment layers (or substrates). The surface of the pixel electrode is preferably covered with a protective insulating film and an alignment film layer. A storage capacitor (not shown) for storing a display signal supplied through the data wiring 24 may be provided in an area surrounded by the plurality of gate bus lines 25 and the plurality of data bus lines 26. . The shape of the notch is not particularly limited, and is not limited to the substantially rectangular shape shown in FIG. 4, 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. With the arrangement of the notches as shown in FIG. 4, since the directions of the notches are provided line-symmetrically, multi-domain orientation control can be performed.

5 is a cross-sectional view of a liquid crystal display element according to an embodiment different from that of FIG. 3. FIG. 5 is another cross-sectional view of the liquid crystal display element shown in FIG. 1 taken along the line III-III in FIG. It is an example. The first substrate 2 on which the alignment layer 4 and the electrode layer 3 including the thin film transistor are formed on the surface, and the second substrate 8 on which the alignment layer 4 is formed on the surface are separated so that the alignment layers face each other at a predetermined interval G. This space is filled with a liquid crystal layer 5 containing a liquid crystal composition. The gate insulating film 12, the common electrode 22, the insulating film 18, the pixel electrode 21, and the alignment layer 4 are stacked in this order on part of the surface of the first substrate 2.

Further, in the example shown in FIG. 5, the common electrode 22 having a comb shape or a slit is used, and the inter-electrode distance R between the pixel electrode 21 and the common electrode 22 is not zero. Further, FIG. 3 shows an example in which the common electrode 22 is formed on the gate insulating film 12. However, as shown in FIG. 5, the common electrode 22 is formed on the first substrate 2. The pixel electrode 21 may be provided via the gate insulating film 12. The electrode width of the pixel electrode 21: l, the electrode width of the common electrode 22: n, and the interelectrode distance: R are appropriately adjusted to such a width that all liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. It is preferable. In a preferred embodiment of the liquid crystal display element according to the present invention, the interelectrode distance R is preferably longer than the shortest separation distance G between the substrates (that is, G <α). In FIG. 5, the pixel electrode 21 is provided on the liquid crystal layer side with respect to the common electrode 22, but the pixel electrode 21 and the common electrode 22 may be provided at the same height in the thickness direction, or the common electrode 22 is the pixel electrode. 21 may be provided on the liquid crystal layer side. As an embodiment in which the pixel electrode 21 and the common electrode 22 are provided at the same height in the thickness direction, as shown in FIG. 6A, the pixel electrode 21 and the common electrode 22 are loosely fitted on the same substrate. The structure to provide is mentioned. In this specification, when the horizontal component R of the interelectrode distance between the pixel electrode 21 and the common electrode 22 is longer than the inter-substrate distance G, an IPS mode liquid crystal display element is obtained, and when the R is shorter than the G, the FFS mode. It is called a liquid crystal display element.

For example, it is preferable that the common electrode and the pixel electrode are formed on the first substrate as shown in FIGS. When the common electrode and the pixel electrode are formed on the same substrate, an electric field substantially parallel to the substrate is generated between the electrodes.

The liquid crystal display element according to the present invention preferably has an IPS-type liquid crystal display composition using a horizontal electric field with respect to the substrate, and the substrate having a separation distance between the common electrode 22 and the pixel electrode 21 adjacent to the common electrode 22. If the horizontal component R is longer than the shortest separation distance D between the substrates (distance between the substrates), a horizontal electric field is formed between the common electrode and the pixel electrode, and the liquid crystal molecules are moved in the in-plane direction depending on the presence or absence of voltage. Switching is possible. In the case of the IPS mode liquid crystal display element as in the preferred embodiment of the present invention, when a voltage is applied to the liquid crystal molecules arranged so that the long axis direction is parallel to the alignment direction of the alignment layer, the pixel electrode 21 is shared. An equipotential line of a horizontal electric field is formed between the electrode 22 and the substrate, and is arranged along the electric field in which the major axis of the liquid crystal molecules in the liquid crystal layer 5 is formed. In particular, since the liquid crystal composition according to the present invention uses liquid crystal molecules having positive dielectric anisotropy, the major axis direction of the liquid crystal molecules is aligned along the generated electric field direction.

Since the IPS mode liquid crystal display element according to the present invention uses a specific liquid crystal composition and a specific photo-alignment film, it is possible to achieve both high-speed response and suppression of display defects.

In addition, when a liquid crystal layer 5 is injected between the first substrate 2 and the second substrate 7 in a horizontal alignment type liquid crystal display element such as an IPS mode or an FFS mode, for example, a vacuum injection method or a drop injection ( A method such as an ODF (One Drop Fill) method is performed, but in the present invention, in the ODF method, it is possible to suppress the occurrence of a drop mark when the liquid crystal composition is dropped onto a substrate. In addition, a dripping mark is defined as a phenomenon in which a mark on which a liquid crystal composition has been dropped floats white.

The occurrence of dripping marks is greatly affected by the liquid crystal material to be injected, but the influence is unavoidable depending on the configuration of the display element. In the horizontal alignment type liquid crystal display element, the thin film transistor formed in the display element, the pixel electrode 21 having a comb shape or a slit, and the like are only the thin alignment film 4 or the thin alignment film 4 and the thin insulating protective layer 18. Since there is no member that separates the liquid crystal composition, there is a high possibility that the ionic substance cannot be completely blocked, and it was impossible to avoid the formation of dripping marks due to the interaction between the metal material constituting the electrode and the liquid crystal composition. By using a combination of the liquid crystal composition of the present invention and the photo-alignment film in a horizontal alignment type liquid crystal display element, generation of dripping marks can be effectively suppressed.

Moreover, in the manufacturing process of the liquid crystal display element by the ODF method, it is necessary to drop an optimal liquid crystal injection amount according to the size of the liquid crystal display element. The liquid crystal display element can be kept at a high yield because liquid crystal can be stably dropped over a long period of time with little influence on abrupt pressure change or impact in the apparatus. In particular, small liquid crystal display elements that are frequently used in smartphones that have been popular recently are difficult to control the deviation from the optimal value within a certain range because the optimal liquid crystal injection amount is small. By using an object, a stable discharge amount of a liquid crystal material can be realized even in a small liquid crystal display element.

The liquid crystal layer and the photo-alignment film layer, which are other components of the liquid crystal display element according to the present invention, will be described in detail below.

(Liquid crystal layer)
The liquid crystal layer according to the present invention is a layer containing a liquid crystal composition, and is preferably composed of a liquid crystal composition. The liquid crystal composition is preferably applied to a liquid crystal display element of a horizontal alignment method, for example, an FFS mode and / or an IPS mode. A polymerizable monomer may be added to the liquid crystal composition according to the present invention. Therefore, the liquid crystal layer according to the present invention is preferably in a state in which the polymerizable monomer contained in the liquid crystal composition is polymerized. As will be described later, this can increase the alignment regulating force.

The liquid crystal composition in the present invention is one or more selected from the group consisting of a compound represented by the general formula (i) as the first component and a compound represented by the general formula (J) as the second component. A liquid crystal composition having a positive dielectric anisotropy value containing a compound of formula (i) and represented by formula (J) as a second component of one or more compounds represented by formula (i) It is preferable that 1 type or 2 types or more are included.

The lower limit of the preferable content of the compound represented by the general formula (i) and the compound represented by the general formula (J) with respect to the total amount of the composition of the present invention is 10% and 15%. 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70% 75% and 80%. The upper limit of the preferable content is 97%, 95%, 85%, 75%, 65%, 55%, 45%, 35%, 30% 25% and 20%.

Preferred physical property values of the liquid crystal composition according to the present invention are preferably that Δε is 1.5 to 12, and Δn is 0.08 to 0.20.

Hereinafter, each component (first component, second component, and other optional components) contained in the liquid crystal composition according to the present invention will be described.

In the general formula (i), when n ⁱ¹ is an integer of 2 to 4, the rings A ⁱ¹ may be the same or different. Ring A ⁱ¹ is preferably aromatic when it is required to increase Δn, and is preferably aliphatic for improving the response speed. Each ring A ⁱ¹ is independently Trans-1,4-cyclohexylene group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl 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, Represents a piperidine-1,4-diyl group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Like More preferably represents the following structure:

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

In the general formula (i), Z ⁱ¹ is more preferably a single bond. N ⁱ¹ is preferably 2, 3 or 4. In the case of preferable conditions, since there are a plurality of Z ^Mi1 , they may be the same or different.

When importance is attached to reliability, both R ⁱ¹ and R ⁱ² are preferably alkyl groups, and when importance is placed on reducing the volatility of the compound, it is preferably an alkoxy group, and importance is placed on lowering viscosity. In this case, at least one is preferably an alkenyl group.

R ⁱ¹ and R ⁱ² are each a straight-chain alkyl group having 1 to 5 carbon atoms or a straight-chain carbon atom having 1 to 4 carbon atoms when the ring structure to which R ⁱ¹ is bonded is a phenyl group (aromatic). When the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, a straight-chain alkyl group having 1 to 5 carbon atoms, A linear alkoxy group having 1 to 4 carbon atoms and a straight chain alkenyl group having 2 to 5 carbon atoms are preferred. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

In addition, the alkyl group, alkenyl group and alkoxy group according to the present invention are all preferably linear or branched. A more preferable alkenyl group according to the present invention is preferably selected from groups represented by any one of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

It is represented by

In the liquid crystal composition of the present invention, the content of the compound represented by the general formula (i) includes solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, process suitability, and drop marks. Therefore, it is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

When the total amount of the compound represented by the general formula (i) of the first component in the liquid crystal composition according to the present invention is large, it is high speed because it sufficiently includes a component having low polarity, that is, a high viscosity reducing effect. Responsiveness can be ensured. Moreover, the lower limit of the preferable content of the compound represented by the formula (i) with respect to the total amount of the composition of the present invention is 1%, 10%, 15%, and 20%. , 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75% 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 30%, 25% It is.

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

It is preferable that one or more compounds represented by the general formula (i) are contained and contained in an amount 5 to 20 times the compound represented by the general formula (M) of the second component. The compound represented by the general formula (i) as the first component has effects such as high-speed response.

The liquid crystal composition according to the present invention can also contain one or more compounds represented by the general formula (i). There are no particular limitations on the types of compounds that can be combined, but they are used in appropriate combinations according to desired performance such as solubility at low temperatures, viscosity, transition temperature, electrical reliability, and refractive index anisotropy. However, it is preferable that the compound represented by the general formula (i) includes a compound having a viscosity reducing action. Moreover, the kind of compound used as a compound represented with general formula (i) which is a 1st component is one kind as one embodiment of this invention, for example. Or in another embodiment of the present invention, there are two types. In another embodiment of the present invention, there are three types. Furthermore, in another embodiment of this invention, they are four types. Furthermore, in another embodiment of this invention, they are five types. Furthermore, in another embodiment of the present invention, there are six types. Furthermore, in another embodiment of the present invention, there are seven types. Furthermore, in another embodiment of this invention, they are eight types. Furthermore, in another embodiment of the present invention, there are nine types. Furthermore, in another embodiment of this invention, it is ten or more types.

The compound represented by the general formula (i) according to the present invention preferably has no chlorine atom in the molecule when chemical stability of the liquid crystal composition is required.

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

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

(In the formula, R ⁱ¹¹ and R ⁱ¹² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in the general formula (i).)
R ⁱ¹¹ and R ⁱ¹² are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

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

The lower limit of the preferable content is 1%, 2%, 3%, 5%, 7%, 10%, and 15% with respect to the total amount of the composition of the present invention. %, 20%, 25%, 30%, 35%, 40%, 45%, 50%, and 55%. The upper limit of the preferable content is 95%, 93%, 90%, 87%, 85%, 82%, and 80% with respect to the total amount of the composition of the present invention. %, 77%, 75%, 73%, 70%, 67%, 65%, 63%, 60%, 57%, 55% %, 52%, 50%, 47%, 45%, 43%, 40%, 35%, 30%, 25%.

When the viscosity of the composition of the present invention is kept low and a composition having a high response speed is required, the above lower limit value is preferably high and the upper limit value is preferably high. Furthermore, when the composition of the present invention requires a high Tni and a composition having good temperature stability, it is preferable that the lower limit value is moderate and the upper limit value is moderate. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the lower limit value is low and the upper limit value is low.

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

( ^Wherein R ⁱ¹² represents the same meaning as in general formula (i-1).)
The compound represented by the general formula (i-1-1) is a compound selected from the group of compounds represented by the formula (i-1-1.1) to the formula (i-1-1.3). And is preferably a compound represented by formula (i-1-1.2) or formula (i-1-1.3), and particularly represented by formula (i-1-1.3). It is preferable that it is a compound.

The lower limit of the preferable content of the compound represented by the formula (i-1-1.3) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, 7%, and 10%. The upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7%, and 6% with respect to the total amount of the composition of the present invention. %, 5%, 3%.

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

( ^Wherein R ⁱ¹² represents the same meaning as in general formula (i-1).)
The lower limit of the preferable content of the compound represented by the formula (i-1-2) with respect to the total amount of the composition of the present invention is 1%, 5%, 10%, 15% 17%, 20%, 23%, 25%, 27%, 30%, 35%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, 42%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 33%, and 30%.

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

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

The lower limit of the preferable total content of the compound represented by formula (i-1-1.3) and the compound represented by formula (i-1-2.2) relative to the total amount of the composition of the present invention The values are 10%, 15%, 20%, 25%, 27%, 30%, 35% and 40%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, 43%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, and 22%.

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

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

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

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

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

(In the formula, R ⁱ¹⁵ and R ⁱ¹⁶ each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ⁱ¹⁵ and R ⁱ¹⁶ are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

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

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

Furthermore, the compounds represented by the general formulas (i-1-4) and (i-1-5) are represented by the formulas (i-1-4.1) to (i-1-5.3). Are preferably selected from the group of compounds represented by formula (i-1-4.2) or (i-1-5.2).

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

Formula (i-1-1.3), Formula (i-1-2.2), Formula (i-1-3.1), Formula (i-1-3.3), Formula (i-1- 3.4), it is preferable to combine two or more compounds selected from the compounds represented by formula (i-1-3.11) and formula (i-1-3.12). -1.3), formula (i-1-2.2), formula (i-1-3.1), formula (i-1-3.3), formula (i-1-3.4) and It is preferable to combine two or more compounds selected from the compounds represented by formula (i-1-4.2), and the lower limit of the preferable content of the total content of these compounds is the composition of the present invention. 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18% of the total amount 20% and 23% 25%, 27%, 30%, 33%, 35%, and the upper limit is 80% and 70% with respect to the total amount of the composition of the present invention, 60%, 50%, 45%, 40%, 37%, 35%, 33%, 30%, 28%, 25%, 23% and 20%. When emphasizing the reliability of the composition, compounds represented by formula (i-1-3.1), formula (i-1-3.3) and formula (i-1-3.4)) It is preferable to combine two or more compounds selected from the group consisting of formulas (i-1-1.3) and (i-1-2.2) when the response speed of the composition is important. It is preferable to combine two or more compounds selected from the following compounds.

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

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

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

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

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

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

(In the formula, R ⁱ³¹ and R ⁱ³² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in the general formula (i).)
R ⁱ³¹ and R ⁱ³² are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

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

The lower limit of the preferred content of the compound represented by formula (i-3) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5% 7% and 10%. The upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7%, and 6% with respect to the total amount of the composition of the present invention. %, 5%, 3%.

When obtaining a high refractive index anisotropy, the effect is high when the content is set to be large, and conversely, when high Tni is emphasized, the effect is high when the content is set low. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

Further, the compound represented by the general formula (i-3) is preferably a compound selected from the group of compounds represented by the formulas (i-3.1) to (i-3.4) A compound represented by formula (i-3.2) to formula (i-3.7) is preferable.

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

(In the formula, R ⁱ⁴¹ and R ⁱ⁴² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in formula (i)).
R ⁱ⁴¹ is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ⁱ⁴² is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable. )
The compound represented by the general formula (i-4) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required performance such as low-temperature solubility, transition temperature, electrical reliability, and refractive index anisotropy. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

In the composition of the present invention, the content of the compound represented by the general formula (i-4) is the solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, process suitability, dropping. It is necessary to adjust appropriately according to the required performance such as marks, image sticking, and dielectric anisotropy.

The lower limit of the preferred content of the compound represented by formula (i-4) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5% 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40% . The upper limit of the preferable content of the compound represented by the formula (i-4) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, 30%. 20%, 15%, 10%, 5%.

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

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

When both the compound represented by formula (i-4.1) and the compound represented by formula (i-4.2) are contained, the amount of both compounds relative to the total amount of the composition of the present invention is The lower limit of the preferred content is 15%, 19%, 24%, and 30%, and the preferred upper limit is 45, 40%, 35%, and 30%. Yes, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the general formula (i-4) is preferably, for example, a compound represented by the formula (i-4.4) to the formula (i-4.6). It is preferable that it is a compound represented by this.

Depending on required performance such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, etc., even if it contains a compound represented by formula (i-4.4), Even if the compound represented by (i-4.5) is contained, both the compound represented by formula (i-4.4) and the compound represented by formula (i-4.5) You may contain.

The lower limit of the preferable content of the compound represented by formula (i-4.4) or formula (i-4.5) with respect to the total amount of the composition of the present invention is 3%, Yes, 7%, 9%, 11%, 12%, 13%, 18%, 21%. Preferred upper limit values are 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13% %, 10%, and 8%.

When both the compound represented by formula (i-4.4) and the compound represented by formula (i-4.5) are contained, the amount of both compounds relative to the total amount of the composition of the present invention The lower limit of the preferred content is 15%, 19%, 24%, and 30%, and the preferred upper limit is 45, 40%, 35%, and 30%. Yes, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the general formula (i-4) is preferably a compound represented by the formula (i-4.7) to the formula (i-4.10), and particularly the formula (i-4. The compound represented by 9) is preferred.

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

(In the formula, R ⁱ⁵¹ and R ⁱ⁵² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in formula (i)).
R ⁱ⁵¹ is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ⁱ⁵² is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable.

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

In the composition of the present invention, the content of the compound represented by the general formula (i-5) is such that solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, process suitability, dropping It is necessary to adjust appropriately according to the required performance such as marks, image sticking, and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (i-5) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5% 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40% . The upper limit of the preferable content of the compound represented by the formula (i-5) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, 30%. , 20%, 15%, 10%, 5% The compound represented by the general formula (i-5) is represented by the formula (i-5.1) or the formula (i-5.2). The compound represented by formula (i-5.1) is particularly desirable.

The lower limit of the preferable content of these compounds with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, and 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 (i-5) is preferably a compound represented by the formula (i-5.3) or the formula (i-5.4).

The compound represented by the general formula (i-5) is preferably a compound selected from the group of compounds represented by the formulas (i-5.5) to (i-5.7). The compound represented by i-5.7) is preferable.

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

( ^Wherein , R ⁱ⁶¹ and R ⁱ⁶² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in formula (i), and X ⁱ⁶¹ and X ⁱ⁶² each independently represent a hydrogen atom or a fluorine atom). )
R ⁱ⁶¹ and R ⁱ⁶² are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and one of X ⁱ⁶¹ and X ⁱ⁶² is a fluorine atom and the other is a hydrogen atom. Is preferred.

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

The lower limit of the preferable content of the compound represented by the formula (i-6) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5% 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40% . The upper limit of the preferable content of the compound represented by the formula (i-6) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, 30%. 20%, 15%, 10%, 5%. When emphasizing to increase Δn, it is preferable to increase the content, and when emphasizing the precipitation at low temperature, it is preferable to decrease the content.

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

There are no particular restrictions on the types of compounds that can be combined, but 1 to 3 types of these compounds are preferably contained, more preferably 1 to 4 types. Further, since the wide molecular weight distribution of the selected compound is also effective for the solubility, for example, one type of the compound represented by the formula (i-6.1) or (i-6.2), the formula (i- 6.4) or one type from the compound represented by (i-6.5), one type from the compound represented by formula (i-6.6) or formula (i-6.7), formula (i It is preferable to select one compound from the compounds represented by -6.8) or (i-6.9) and combine them appropriately. Among them, represented by formula (i-6.1), formula (i-6.3), formula (i-6.4), formula (i-6.6) and formula (i-6.9). It is preferable to include a compound.

Further, the compound represented by the general formula (i-6) is preferably, for example, a compound represented by the formula (i-6.10) to the formula (i-6.17). The compound represented by i-6.11) is preferable.

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

(In the formula, R ⁱ⁷¹ and R ⁱ⁷² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in formula (i), and A ⁱ⁷¹ and A ⁱ⁷² each independently represent A ⁱ² and in formula (i)). A 1 represents the same meaning as A ⁱ³ , but the hydrogen atoms on A ⁱ⁷¹ and A ⁱ⁷² may each independently be substituted with a fluorine atom, Z ⁱ⁷¹ represents the same meaning as Z ⁱ² in formula (i), X ⁱ⁷¹ and X ⁱ⁷² each independently represent a fluorine atom or a hydrogen atom.)
In the formula, R ⁱ⁷¹ and R ⁱ⁷² are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and A ⁱ⁷¹ and A ⁱ⁷² ^Are each independently preferably a 1,4-cyclohexylene group or a 1,4-phenylene group, the hydrogen atoms on A ⁱ⁷¹ and A ⁱ⁷² may be each independently substituted with a fluorine atom, and Q ⁱ⁷¹ is a single group. A bond or COO- is preferable, a single bond is preferable, and X ⁱ⁷¹ and X ⁱ⁷² are preferably a hydrogen atom.

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

In the composition of the present invention, the content of the compound represented by the general formula (i-7) includes solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, process suitability, dropping. It is necessary to adjust appropriately according to the required performance such as marks, image sticking, and dielectric anisotropy.

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

When an embodiment with high Tni is desired for the composition of the present invention, the content of the compound represented by formula (i-7) is preferably increased, and when an embodiment with low viscosity is desired, the content is It is preferable to reduce the amount.

Furthermore, the compound represented by the general formula (i-7) is preferably a compound represented by the formula (i-7.1) to the formula (i-7.4), and the formula (i-7. It is preferable that it is a compound represented by 2).

Furthermore, the compound represented by the general formula (i-7) is preferably a compound represented by the formula (i-7.11) to the formula (i-7.13), and the formula (i-7. It is preferable that it is a compound represented by 11).

Furthermore, the compound represented by the general formula (i-7) is a compound represented by the formula (i-7.21) to the formula (i-7.23). A compound represented by the formula (i-7.21) is preferable.

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

Furthermore, the compound represented by the general formula (i-7) is preferably a compound represented by the formula (i-7.41) to the formula (i-7.44), and the formula (i-7. 41) or / and a compound represented by formula (i-7.42).

The compound represented by the general formula (i) is preferably selected from the group represented by the following general formula (i-8).

( ^Wherein R ⁱ⁸¹ and R ⁱ⁸² each independently represents 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.)
The lower limit of the preferable content of the compound represented by formula (i-8) with respect to the total amount of the liquid crystal composition of the present invention is 1%, 2%, 4%, 5% 7%, 9%, 10%, 12%, 15%, and 17%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

The liquid crystal compound having an allyl ether group at the terminal has good characteristics as a component of the liquid crystal composition, but has a problem in reliability. However, the compound represented by the general formula (i-8) is remarkably improved in reliability by difluorinating a specific position of the benzene ring having an allyl ether group without impairing the original excellent characteristics of the skeleton. Improve, further improve compatibility, reduce viscosity. Furthermore, the dielectric anisotropy may have a slight positive dielectric anisotropy (5 or less) depending on the type of the side chain group. It is classified as.

In addition, in R ⁱ⁸² in the general formula (i-8), when an alkyl group or alkenyl group substituted with a fluorine atom is selected, a positive dielectric anisotropy can be imparted. It is. For example, the compound represented by formula (i-8) alone exhibits a liquid crystal phase in the range of 40 to 110 ° C., Δn is about 0.26, flow viscosity is as low as about 25 mPa · s, and dielectric constant Anisotropy is about +4 to 5, and it has very good compatibility when used as a component of a liquid crystal composition.

Furthermore, the compounds represented by the general formula (i-8) used in the liquid crystal composition of the present invention are specifically represented by the formulas (i-8.1) to (i-8.24). The compounds represented by formula (i-8.5), formula (i-8.6), formula (i-8.13) and formula (i-8.14) are particularly preferable. It is preferable to contain.

The lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention is 1%, 2%, 4%, 5%, 6%, 7% 8%, 9%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

In addition, the compound represented by the general formula (i-9) as the first component preferably contains at least one kind or two or more kinds of compounds represented by the following general formula (i-9.1). .

(In the above general formula (i-9), R ^L72 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an alkoxy having 1 to 10 carbon atoms. One group selected from the group consisting of groups.)
From the viewpoint of improving the light resistance, heat resistance or image sticking of the liquid crystal composition, it is preferable to include a compound represented by the general formula (i-9).

Further, the compound represented by the general formula (i-9) is particularly preferably a compound represented by the formula (i-9.1) to the formula (i-9.5).

The liquid crystal composition according to the present invention preferably contains one or more compounds represented by formula (J) as the second component (these compounds are dielectrically positive compounds (Δε is greater than 2). The general formula (J) as the second component is represented by the following chemical structure.

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

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

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

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

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

It is more preferable to represent the following structure.

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

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

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

There are no particular restrictions on the types of compounds that can be combined, but they are used in combination according to desired performance such as solubility at low temperatures, transition temperature, electrical reliability, and refractive index anisotropy. For example, in one embodiment of the present invention, there are one kind, two kinds, and three kinds of compounds to be used. Furthermore, in another embodiment of the present invention, there are four types, five types, six types, and seven or more types.

In the composition of the present invention, the content of the compound represented by the general formula (J) includes solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, process suitability, dripping marks, It is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the general formula (J) with respect to the total amount of the composition of the present invention is 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferable content is, for example, 95%, 85%, 75%, 65%, and 55% with respect to the total amount of the composition of the present invention. Yes, 45%, 35%, 25%.

When the composition of the present invention keeps the viscosity low and a composition having a high response speed is required, it is preferable to lower the lower limit and lower the upper limit. Furthermore, when the composition of the present invention keeps Tni high and a composition having good temperature stability is required, it is preferable to lower the lower limit and lower the upper limit. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable to increase the upper limit value while increasing the lower limit value.

The compound represented by the general formula (J) is preferably one or more selected from the group consisting of the compound represented by the general formula (M) and the compound represented by the general formula (K).

General formula (M) according to the present invention is

(In the general formula (M), R ^M1 represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. Represents an oxy group, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkoxy group or alkenyloxy group may be substituted with a fluorine atom, the alkyl group, alkenyl group, alkoxy group or alkenyloxy group And one or more non-adjacent two or more —CH ₂ — are each independently replaced by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—. May have been
PM represents 0, 1, 2, 3 or 4;
C ^M1 and C ^M2 are each independently
(D) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- And (e) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═).
Represents a group selected from the group consisting of the above-mentioned groups (d) and (e) each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
K ^M1 and K ^M2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents —COO—, —OCO— or —C≡C—,
When PM is 2, 3 or 4 and there are a plurality of K ^M1 , they may be the same or different, and when PM is 2, 3 or 4 and there are a plurality of C ^M2 They may be the same or different,
X ^M1 and X ^M3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,
X ^M2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. However, the compound represented by general formula (i) is excluded. ).

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

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

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

A ^M1 and A ^M2 are preferably aromatic when it is required to independently increase Δn, and are preferably aliphatic for improving the response speed, and trans-1,4 -Cyclohexylene group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro -1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2 2.2] Octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group, preferably the following structure:

It is more preferable to represent the following structure.

In formula ^{(M), Z M1} and ^{Z M2} _-CH 2 each _{independently} _{O -, - CF 2 O -} , - CH 2 CH 2 -, - CF 2 CF 2 - or may represent a single bond Preferably, —CF ₂ O—, —CH ₂ CH ₂ — or a single bond is more preferable, and —CF ₂ O— or a single bond is particularly preferable. X ^M1 is preferably a fluorine atom.

R ^M1 represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxy group having 1 to 4 carbon atoms when the ring structure to which R ^M1 is bonded is a phenyl group (aromatic). And an alkenyl group having 4 to 5 carbon atoms, and when the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, A straight-chain alkoxy group having 1 to 4 carbon atoms and a straight-chain alkenyl group having 2 to 5 carbon atoms are preferred. R ^M1 is preferably an alkyl group when emphasizing reliability, and is preferably an alkenyl group when emphasizing a decrease in viscosity.

The compound represented by the general formula (M) according to the present invention preferably does not have a chlorine atom in the molecule when chemical stability of the liquid crystal composition is required. Further, the compound having a chlorine atom in the liquid crystal composition is preferably 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, It is preferable not to contain substantially. “Substantially not contained” means that the compound produced as an impurity during the production of the compound is not intended and only a compound containing a chlorine atom is mixed in the liquid crystal composition.

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

The lower limit of the preferable content of the compound represented by the formula (M) with respect to the total amount of the composition of the present invention is 1%, 10%, 15%, 20%, 25 %, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% %. The upper limit of the preferable content is, for example, 95%, 85%, 75%, 65%, and 55% with respect to the total amount of the composition of the present invention. Yes, 45%, 35%, 30%, 25%.

The compound represented by the general formula (M) according to the present invention is preferably, for example, a compound selected from the group of compounds represented by the general formula (M-1).

(Wherein R ^M11 represents 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 X ^M11 to X ^M15 each independently represents hydrogen. represents an atom or a fluorine ^{atom, Y M11} represents a fluorine atom or OCF _3.)
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performances, such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (M-1) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8% 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by the general formula (M-1) is specifically preferably a compound represented by the formula (M-1.1) to the formula (M-1.4). A compound represented by M-1.1) or formula (M-1.2) is preferred, and a compound represented by formula (M-1.2) is more preferred. It is also preferred to use the compounds represented by formula (M-1.1) or formula (M-1.2) at the same time.

The lower limit of the preferable content of the compound represented by the formula (M-1.1) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 6% It is. The upper limit of the preferable content is 15%, 13%, 10%, 8%, and 5%.

The lower limit of the preferable content of the compound represented by the formula (M-1.2) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 6% It is. The upper limit of the preferable content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% It is.

The lower limit of the preferable total content of the compounds represented by the formulas (M-1.1) and (M-1.2) with respect to the total amount of the composition of the present invention is 1%, %, 5% and 6%. The upper limit of the preferable content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% It is.

Furthermore, the compound represented by the general formula (M) is preferably a compound selected from the group of compounds represented by the general formula (M-2), for example.

(Wherein R ^M21 represents 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 X ^M21 and X ^M22 each independently represent hydrogen represents an atom or a fluorine ^{atom, Y M21} represents a fluorine atom, a chlorine atom or OCF _3.)
The lower limit of the preferable content of the compound represented by the formula (M-1) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8% 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

When the composition of the present invention keeps the viscosity low and a composition having a high response speed is required, it is preferable to lower the lower limit and lower the upper limit. Furthermore, when the composition of the present invention is required to maintain a high Tni and hardly burn-in, it is preferable to lower the lower limit and lower the upper limit. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable to increase the upper limit value while increasing the lower limit value.

Further, the compound represented by the general formula (M-2) is preferably a compound represented by the formula (M-2.1) to the formula (M-2.5). 3) or / and a compound represented by the formula (M-2.5) is preferable.

The lower limit of the preferable content of the compound represented by the formula (M-2.2) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 6% It is. The upper limit of the preferable content is 15%, 13%, 10%, 8%, and 5%.

The lower limit of the preferable content of the compound represented by the formula (M-2.3) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 6% It is. The upper limit of the preferable content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% It is.

The lower limit of the preferable content of the compound represented by the formula (M-2.5) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 6% It is. The upper limit of the preferable content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% It is.

Lower limit value of the preferable total content of the compounds represented by formulas (M-2.2), (M-2.3) and formula (M-2.5) with respect to the total amount of the composition of the present invention Is 1%, 2%, 5%, 6%. The upper limit of the preferable content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% It is.

The content is preferably 1% or more with respect to the total amount of the composition of the present invention, more preferably 5% or more, further preferably 8% or more, further preferably 10% or more, and more preferably 14% or more. 16% or more is particularly preferable. In consideration of solubility at low temperature, transition temperature, electrical reliability, etc., the maximum ratio is preferably limited to 30% or less, more preferably 25% or less, more preferably 22% or less, and more preferably 20%. Less than is particularly preferred.

The compound represented by the general formula (M) used in the composition of the present invention is preferably a compound represented by the general formula (M-3).

(Wherein R ^M31 represents 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 X ^M31 to X ^M36 are each independently hydrogen. represents an atom or a fluorine ^{atom, Y M31} represents a fluorine atom, a chlorine atom or OCF _3.)
There are no particular limitations on the compounds that can be combined, but it is preferable to combine one or more compounds in consideration of solubility at low temperatures, transition temperature, electrical reliability, refractive index anisotropy, and the like.

The content of the compound represented by the general formula (M-3) is an upper limit for each embodiment in consideration of properties such as solubility at low temperatures, transition temperature, electrical reliability, and refractive index anisotropy. There is a lower limit.

The lower limit of the preferable content of the compound represented by the formula (M-3) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% 8%, 10%, 13%, 15%, 18%, and 20%. The upper limit of the preferable content is 20%, 18%, 15%, 13%, 10%, 8%, and 5%.

Furthermore, the compound represented by the general formula (M-3) used in the composition of the present invention is specifically represented by the formula (M-3.1) to the formula (M-3.4). A compound is preferable, and among them, a compound represented by Formula (M-3.1) and / or Formula (M-3.2) is preferably contained.

The lower limit of the preferable content of the compound represented by the formula (M-3.1) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferable content is 20%, 18%, 15%, 13%, 10%, 8%, and 5%.

The lower limit of the preferable content of the compound represented by the formula (M-3.2) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferable content is 20%, 18%, 15%, 13%, 10%, 8%, and 5%.

The lower limit of the preferable total content of the compounds represented by the formulas (M-3.1) and (M-3.2) with respect to the total amount of the composition of the present invention is 1%, %, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferable content is 20%, 18%, 15%, 13%, 10%, 8%, and 5%.

Furthermore, the compound represented by the general formula (M) is preferably a compound selected from the group represented by the general formula (M-4).

(Wherein R ^M41 represents 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 X ^M41 to X ^M48 are each independently fluorine. Represents an atom or a hydrogen atom, and Y ^M41 represents a fluorine atom, a chlorine atom or OCF _3. )
There are no particular restrictions on the compounds that can be combined, but it is preferable to combine one, two, or three or more in consideration of solubility at low temperatures, transition temperature, electrical reliability, refractive index anisotropy, and the like. .

The content of the compound represented by the general formula (M-4) is an upper limit for each embodiment in consideration of properties such as solubility at low temperatures, transition temperature, electrical reliability, and refractive index anisotropy. There is a lower limit.

The lower limit of the preferable content of the compound represented by the formula (M-4) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% 8%, 10%, 13%, 15%, 18%, and 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

When the composition of the present invention is used for a liquid crystal display device having a small cell gap, it is suitable to increase the content of the compound represented by the general formula (M-4). When used for a liquid crystal display element having a low driving voltage, it is suitable to increase the content of the compound represented by the general formula (M-4). Further, when used for a liquid crystal display element used in a low temperature environment, it is suitable to reduce the content of the compound represented by the general formula (M-4). In the case of a composition used for a liquid crystal display device having a high response speed, it is suitable to reduce the content of the compound represented by the general formula (M-4).

Furthermore, the compound represented by the general formula (M-4) used in the composition of the present invention is specifically represented by the formula (M-4.1) to the formula (M-4.4). Preferably, it is a compound, and among them, it is preferable to contain a compound represented by the formula (M-4.2) to the formula (M-4.4), and a compound represented by the formula (M-4.2) It is more preferable to contain.

Furthermore, the compound represented by the general formula (M) is preferably a compound represented by the general formula (M-5).

(Wherein R ^M51 represents 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 X ^M51 and X ^M52 are each independently hydrogen. represents an atom or a fluorine ^{atom, Y M51} represents a fluorine atom, a chlorine atom or OCF _3.)
Although there is no restriction | limiting in the kind of compound which can be combined, Considering solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, etc., it uses combining suitably for every embodiment. For example, one embodiment of the present invention has one type, another embodiment has two types, yet another embodiment has three types, yet another embodiment has four types, and yet another embodiment has five types, In still another embodiment, six or more types are combined.

The lower limit of the preferable content of the compound represented by the formula (M-5) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8% 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%. The upper limit of the preferable content is 50%, 45%, 40%, 35%, 33%, 30%, 28%, 25%, 23% 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by the general formula (M-5) is preferably a compound represented by the formula (M-5.1) to the formula (M-5.4), and the formula (M-5. A compound represented by formula (M-5.4) is preferable.

The lower limit of the preferred content of these compounds with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8%, 10%, 13% Yes, 15%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by the general formula (M-5) is preferably a compound represented by the formula (M-5.11) to the formula (M-5.17), and the formula (M-5. 11), a compound represented by formula (M-5.13) and formula (M-5.17) is preferable.

Further, the compound represented by the general formula (M-5) is preferably a compound represented by the formula (M-5.21) to the formula (M-5.28), and the formula (M-5. 21), a compound represented by formula (M-5.22), formula (M-5.23) and formula (M-5.25).

The lower limit of the preferred content of these compounds with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8%, 10%, 13% Yes, 15%, 18%, 20%, 22%, 25%, 30%. The upper limit of the preferable content is 40%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18% 15% 13% 10% 8% 5%

Furthermore, the compound represented by the general formula (M) is preferably a compound represented by the general formula (M-6).

(Wherein R ^M61 represents 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 X ^M61 to X ^M64 are each independently fluorine. Represents an atom or a hydrogen atom, and Y ^M61 represents a fluorine atom, a chlorine atom or OCF ₃ )
Although there is no restriction | limiting in the kind of compound which can be combined, It combines suitably for every embodiment in consideration of solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, etc.

The lower limit of the preferable content of the compound represented by the formula (M-6) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% 8%, 10%, 13%, 15%, 18%, and 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

When the composition of the present invention is used for a liquid crystal display device having a low driving voltage, it is suitable to increase the content of the compound represented by the general formula (M-6). In the case of a composition used for a liquid crystal display device having a high response speed, it is suitable to reduce the content of the compound represented by the general formula (M-6).

Further, the compound represented by the general formula (M-6) is specifically preferably a compound represented by the formula (M-6.1) to the formula (M-6.4). It is preferable to contain a compound represented by M-6.2) and formula (M-6.4).

The lower limit of the preferred content of these compounds relative to the total amount of the composition of the present invention is 1%, 2%, 4%, 5%, 8%, 10% Yes, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by the general formula (M-6) is specifically preferably a compound represented by the formula (M-6.11) to the formula (M-6.14). It is preferable to contain a compound represented by M-6.12) and formula (M-6.14).

Further, the compound represented by the general formula (M-6) is specifically preferably a compound represented by the formula (M-6.21) to the formula (M-6.24). It is preferable to contain a compound represented by formula (M-6.21), formula (M-6.22) and formula (M-6.24).

Furthermore, the compound represented by the general formula (M-6) is specifically preferably a compound represented by the formula (M-6.31) to the formula (M-6.34). Among them, it is preferable to contain a compound represented by the formula (M-6.31) and the formula (M-6.32).

Further, the compound represented by the general formula (M-6) is specifically preferably a compound represented by the formula (M-6.41) to the formula (M-6.44). It is preferable to contain a compound represented by M-6.42).

Furthermore, the compound represented by the general formula (M) is preferably a compound selected from the group of compounds represented by the general formula (M-7).

(Wherein, X ^M71 to X ^M76 each independently represents a fluorine atom or a hydrogen atom, and R ^M71 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 4 represents an alkoxy group, and Y ^M71 represents a fluorine atom or OCF _3. )
There are no particular restrictions on the types of compounds that can be combined, but one to two of these compounds are preferably contained, more preferably one to three, and more preferably one to four. More preferably.

The content of the compound represented by the general formula (M-7) is an upper limit for each embodiment in consideration of properties such as solubility at low temperatures, transition temperature, electrical reliability, and refractive index anisotropy. There is a lower limit.

The lower limit of the preferable content of the compound represented by the formula (M-7) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

When the composition of the present invention is used for a liquid crystal display device having a small cell gap, it is suitable to increase the content of the compound represented by the general formula (M-7). When used for a liquid crystal display element with a low driving voltage, it is suitable to increase the content of the compound represented by the general formula (M-7). In addition, when used for a liquid crystal display element used in a low temperature environment, it is suitable to reduce the content of the compound represented by the general formula (M-7). In the case of a composition used for a liquid crystal display device having a high response speed, it is suitable to reduce the content of the compound represented by the general formula (M-7).

Further, the compound represented by the general formula (M-7) is preferably a compound represented by the formula (M-7.1) to the formula (M-7.4), and the formula (M-7. It is preferable that it is a compound represented by 2).

Furthermore, the compound represented by the general formula (M-7) is preferably a compound represented by the formula (M-7.11) to the formula (M-7.14), and the formula (M-7. 11) and a compound represented by the formula (M-7.12) are preferable.

Further, the compound represented by the general formula (M-7) is preferably a compound represented by the formula (M-7.21) to the formula (M-7.24). 21) and a compound represented by the formula (M-7.22) are preferable.

Furthermore, the compound represented by the general formula (M) is preferably a compound represented by the general formula (M-8).

( ^Wherein , X ^M81 to X ^M84 each independently represents a fluorine atom or a hydrogen atom, Y ^M81 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M81 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and A ^M81 and A ^M82 are each independently 1,4-cyclohexylene group, 1,4-phenylene group or

However, the hydrogen atom on the 1,4-phenylene group may be substituted with a fluorine atom. )
The lower limit of the preferable content of the compound represented by formula (M-8) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

When the composition of the present invention keeps the viscosity low and a composition having a high response speed is required, it is preferable to lower the lower limit and lower the upper limit. Furthermore, when a composition that does not easily cause seizure is required, it is preferable to lower the lower limit and lower the upper limit. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable to increase the upper limit value while increasing the lower limit value.

Furthermore, the compound represented by the general formula (M-8) used in the composition of the present invention is specifically represented by the formula (M-8.1) to the formula (M-8.4). Preferably, it is a compound, and among them, it is preferable to contain a compound represented by formula (M-8.1) or formula (M-8.2).

Furthermore, the compound represented by the general formula (M-8) used in the composition of the present invention is specifically represented by the formula (M-8.11) to the formula (M-8.14). A compound is preferable, and among them, a compound represented by the formula (M-8.12) is preferably included.

Furthermore, the compound represented by the general formula (M-8) used in the composition of the present invention is specifically represented by the formula (M-8.21) to the formula (M-8.24). A compound is preferable, and among them, a compound represented by the formula (M-8.22) is preferably contained.

Furthermore, the compound represented by the general formula (M-8) used in the composition of the present invention is specifically represented by the formula (M-8.31) to the formula (M-8.34). A compound is preferable, and among them, a compound represented by the formula (M-8.32) is preferably contained.

Furthermore, the compound represented by formula (M-8) used in the composition of the present invention is specifically represented by formula (M-8.41) to formula (M-8.44). A compound is preferable, and among them, a compound represented by the formula (M-8.42) is preferably included.

Furthermore, the compound represented by the general formula (M-8) used in the composition of the present invention is specifically represented by the formula (M-8.51) to the formula (M-8.54). A compound is preferable, and among them, a compound represented by the formula (M-8.52) is preferably included.

Furthermore, the compound represented by the general formula (M) may have the following partial structure in its structure.

(The black spot in the formula represents a carbon atom in the ring structure to which the partial structure is bonded.)
The compound having the partial structure is preferably a compound represented by general formulas (M-10) to (M-18).

The compound represented by the general formula (M-10) is as follows.

( ^Wherein , X ^M101 and X ^M102 each independently represent a fluorine atom or a hydrogen atom, Y ^M101 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M101 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M101 and W ^M102 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by the general formula (M-10) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by formula (M-10) used in the composition of the present invention is specifically represented by formula (M-10.1) to formula (M-10.12). A compound is preferable, and among them, a compound represented by formula (M-10. 5) to formula (M-10.12) is preferably contained.

The compound represented by the general formula (M-11) is as follows.

( ^Wherein , X ^M111 to X ^M114 each independently represents a fluorine atom or a hydrogen atom, Y ^M111 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M111 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.)
The lower limit of the preferable content of the compound represented by the general formula (M-11) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Furthermore, the compound represented by the general formula (M-11) used in the composition of the present invention is specifically represented by the formula (M-11.1) to the formula (M-11.8). A compound is preferable, and among them, a compound represented by formula (M-11.1) to formula (M-11.4) is preferably contained.

The compound represented by the general formula (M-12) is as follows.

( ^Wherein , X ^M121 and X ^M122 each independently represent a fluorine atom or a hydrogen atom, Y ^M121 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M121 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M121 and W ^M122 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by formula (M-12) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Furthermore, the compound represented by the general formula (M-12) used in the composition of the present invention is specifically represented by the formula (M-12.1) to the formula (M-12.12). A compound is preferable, and among them, a compound represented by formula (M-12.5) to formula (M-12.8) is preferably contained.

The compound represented by the general formula (M-13) is as follows.

( ^Wherein , X ^M131 to X ^M134 each independently represents a fluorine atom or a hydrogen atom, Y ^M131 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M131 represents an alkyl group having 1 to 5 carbon atoms, ^Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M131 and W ^M132 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by formula (M-13) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Furthermore, the compound represented by the general formula (M-13) used in the composition of the present invention is specifically represented by the formula (M-13.1) to the formula (M-13.28). It is preferable that the compound is a compound, and among them, from the formulas (M-13.1) to (M-13.4), (M-13.11) to (M-13.14), (M-13.25) to ( It is preferable to contain a compound represented by M-13.28).

The compound represented by the general formula (M-14) is as follows.

( ^Wherein X ^M141 to X ^M144 each independently represents a fluorine atom or a hydrogen atom, Y ^M141 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M141 represents an alkyl group having 1 to 5 carbon atoms, ^Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M141 and W ^M142 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by the general formula (M-14) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Furthermore, the compound represented by the general formula (M-14) used in the composition of the present invention is specifically represented by the formula (M-14.1) to the formula (M-14.8). A compound is preferable, and among them, a compound represented by formula (M-14.5) and formula (M-14.8) is preferably contained.

The compound represented by the general formula (M-15) is as follows.

( ^Wherein X ^M151 and X ^M152 each independently represent a fluorine atom or a hydrogen atom, Y ^M151 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M151 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M151 and W ^M152 each independently represent —CH ₂ — or —O—.
The lower limit of the preferred content of the compound represented by formula (M-15) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Furthermore, the compound represented by the general formula (M-15) used in the composition of the present invention is specifically represented by the formulas (M-15.1) to (M-15.14). Preferably, the compound contains a compound represented by formula (M-15.5) to formula (M-15.8) or formula (M-15.11) to formula (M-15.14). It is preferable to do.

The compound represented by the general formula (M-16) is as follows.

( ^Wherein X ^M161 to X ^M164 each independently represents a fluorine atom or a hydrogen atom, Y ^M161 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M161 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.)
The lower limit of the preferable content of the compound represented by formula (M-16) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Furthermore, the compound represented by the general formula (M-16) used in the composition of the present invention is specifically represented by the formula (M-16.1) to the formula (M-16.8). A compound is preferable, and among them, it is preferable to include a compound represented by Formula (M-16.1) to Formula (M-16.4).

The compound represented by the general formula (M-17) is as follows.

^(Wherein, ^X M171 ^~ X ^M174 are each independently a fluorine atom or a hydrogen ^{atom, Y M171} fluorine atom, a chlorine atom or -OCF ^{_3, R M171} is an alkyl group having 1 to 5 carbon atoms, ^Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M171 and W ^M172 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by formula (M-17) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by the general formula (M-17) used in the composition of the present invention is specifically represented by the formula (M-17.1) to the formula (M-17.52). Preferably, the compound is a compound (M-17.9) to (M-17.12), (M-17.21) to (M-17.28), (M-17. 45) to a compound represented by the formula (M-17.48) is preferably contained.

The compound represented by the general formula (M-18) is as follows.

( ^Wherein X ^M181 to X ^M186 each independently represents a fluorine atom or a hydrogen atom, Y ^M181 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M181 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.)
The lower limit of the preferred content of the compound represented by formula (M-18) with respect to the total amount of the composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Furthermore, the compound represented by the general formula (M-18) used in the composition of the present invention is specifically represented by the formula (M-18.1) to the formula (M-18.12). A compound is preferable, and among them, it is preferable to include a compound represented by Formula (M-18.5) to Formula (M-18.8).

The composition of the present invention preferably contains one or more compounds represented by the general formula (K). These compounds correspond to dielectrically positive compounds (Δε is greater than 2).

(Wherein R ^K1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently —CH═CH—, — Optionally substituted by C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^K1 represents 0, 1, 2, 3 or 4;
A ^K1 and A ^K2 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- And (b) a 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═).
A hydrogen atom on the group (a) and the group (b) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^K1 and Z ^K2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents —COO—, —OCO— or —C≡C—,
When n ^K1 is 2, 3 or 4 and a plurality of A ^K2 are present, they may be the same or different, and n ^K1 is 2, 3 or 4 and a plurality of Z ^K1 is present If they are the same or different,
X ^K1 and X ^K3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,
X ^K2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. )
In general formula (K), R ^K1 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or alkenyloxy having 2 to 8 carbon atoms. A group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferable. An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms. (Propenyl group) is particularly preferred.

^RK1 is preferably an alkyl group when importance is placed on reliability, and an alkenyl group is preferred when importance is placed on lowering viscosity.

A ^K1 and A ^K2 are preferably aromatic when it is required to independently increase Δn, and are preferably aliphatic for improving the response speed, and trans-1,4 -Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2, 3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It preferably represents a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents the following structure:

It is more preferable to represent the following structure.

Z ^K1 and ^{Z K2} are each _{independently} _{-CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CF 2 O-, —CH ₂ CH ₂ — or a single bond is more preferable, and —CF ₂ O— or a single bond is particularly preferable.

n ^K1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when emphasizing the improvement of Δε, and preferably 1 or 2 when emphasizing Tni. .

In the composition of the present invention, the content of the compound represented by the general formula (K) is low-temperature solubility, transition temperature, electrical reliability, refractive index anisotropy, process suitability, dripping marks, It is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (K) with respect to the total amount of the composition of the present invention is 1%, 10%, 20%, 30%, 40% %, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferable content is, for example, 95%, 85%, 75%, 65%, and 55% with respect to the total amount of the composition of the present invention. Yes, 45%, 35%, 25%.

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

(Wherein R ^K11 represents 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 X ^K11 to X ^K14 are each independently hydrogen. represents an atom or a fluorine ^{atom, Y K11} represents a fluorine atom or OCF _3.)
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performances, such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-1) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8% 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by the general formula (K-1) is specifically preferably a compound represented by the formula (K-1.1) to the formula (K-1.4). A compound represented by formula (K-1.2) is preferred, and a compound represented by formula (K-1.2) is more preferred. It is also preferred to use the compounds represented by formula (K-1.1) or formula (K-1.2) at the same time.

The compound represented by General Formula (K) is preferably a compound selected from the group of compounds represented by General Formula (K-2), for example.

(Wherein R ^K21 represents 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 X ^K21 to X ^K24 are each independently hydrogen. represents an atom or a fluorine ^{atom, Y K21} represents a fluorine atom or OCF _3.)
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performances, such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-2) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8% 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by the general formula (K-2) is specifically preferably a compound represented by the formula (K-2.1) to the formula (K-2.6). A compound represented by formula (K-2.5) or formula (K-2.6) is preferred, and a compound represented by formula (K-2.6) is more preferred. It is also preferred to use the compounds represented by formula (K-2.5) or formula (K-2.6) at the same time.

The compound represented by General Formula (K) is preferably a compound selected from the group of compounds represented by General Formula (K-3), for example.

(Wherein R ^K31 represents 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 X ^K31 to X ^K36 are each independently hydrogen. Represents an atom or a fluorine atom, and Y ^K31 represents a fluorine atom or OCF _3. )
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performances, such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-3) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8% 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by the general formula (K-3) is preferably a compound represented by the formula (K-3.1) to the formula (K-3.4). A compound represented by K-3.1) or formula (K-3.2) is more preferable. It is also preferred to use the compounds represented by formula (K-3.1) and formula (K-3.2) at the same time.

The compound represented by the general formula (K) is preferably, for example, a compound selected from the group of compounds represented by the general formula (K-4).

(Wherein R ^K41 represents 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 X ^K41 to X ^K46 are each independently hydrogen. An atom or a fluorine atom, Y ^K41 represents a fluorine atom or OCF ₃ , and Z ^K41 represents —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, or —CF ₂ O—.
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performances, such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-4) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8% 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by the general formula (K-4) is preferably a compound represented by the formula (K-4.1) to the formula (K-4.18). More preferred are compounds represented by (K-4.1), formula (K-4.2), formula (K-4.11), and (K-4.12). It is also preferred to use compounds represented by formula (K-4.1), formula (K-4.2), formula (K-4.11), and (K-4.12) at the same time.

The compound represented by the general formula (K) is preferably a compound selected from, for example, a compound group represented by the general formula (K-5).

(Wherein R ^K51 represents 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 X ^K51 to X ^K56 are each independently hydrogen. An atom or a fluorine atom, Y ^K51 represents a fluorine atom or OCF ₃ , and Z ^K51 represents —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, or —CF ₂ O—.
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performances, such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-5) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8% 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by the general formula (K-5) is preferably a compound represented by the formula (K-5.1) to the formula (K-5.18). A compound represented by the formula (K-5.14) to the compound represented by the formula (K-5.14) is preferable, and a compound represented by the formula (K-5.12) is more preferable.

The compound represented by General Formula (K) is preferably a compound selected from the group of compounds represented by General Formula (K-6), for example.

( ^Wherein R ^K61 represents 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 X ^K61 to X ^K68 are each independently hydrogen. represents an atom or a fluorine ^{atom, Y K61} represents a fluorine atom or OCF ^{_3, Z K61} is _{_{-OCH 2 -, - CH 2 O}} -, - OCF 2 - or an _-CF 2 O-).
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performances, such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-6) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 8% 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.

Further, the compound represented by the general formula (K-6) is preferably a compound represented by the formula (K-6.1) to the formula (K-6.18). Compounds represented by formula (K-6.18) to formula (K-6.18) are preferred, and compounds represented by formula (K-6.16) and formula (K-6.17) are more preferred. It is also preferred to use the compounds represented by formula (K-6.16) and formula (K-6.17) at the same time.

In a preferred embodiment of the liquid crystal composition according to the present invention, as a first component, the following general formula (Ia) and general formula (Ib):

(In the above general formulas (Ia) and (Ib), R ^1a and R ^2a represent the same meaning as R ^{i1 in the} general formula (i), respectively, and R ^1b and R ^2b represent the general formula (i), respectively. represents the same meaning as ^{R i2} ^{in, n 1b} represents 1 or ^{2, a 1b} are each independently trans-1,4-cyclohexylene group, 1,3-dioxane-2,5-diyl group, Represents a tetrahydropyran-2,5-diyl group, a 1,4-phenylene group, a 1,4-cyclohexenylene group or a naphthalene-2,6-diyl group, and one hydrogen atom in the group is substituted with a fluorine atom It is preferable that at least one or two types are selected from the group of compounds represented by :), more preferably three types are selected.

Further, at least two compounds selected from the compound group represented by the general formula (Ia) and the general formula (Ib) are contained in an amount of 25 to 99% by mass in the entire liquid crystal composition. The content is preferably 30 to 80% by mass, more preferably 35 to 60% by mass, and still more preferably 40 to 55% by mass.

When the combination of the general formula (Ia) and the general formula (Ib) occupies 20 to 70% of the entire liquid crystal composition, an effect of high-speed response is obtained. When used in combination, compatibility is improved from the viewpoint of chemical structure or specificity, and storage stability is improved, so that the problem of precipitation of the liquid crystal compound can be suppressed / prevented.

More preferred embodiments of the liquid crystal composition according to the present invention include the general formula (II-a) and the general formula (II-b) as the second component.

(In the above general formulas (II-a) and (II-b), R ^3a and R ^3b represent the same meaning as R ⁱ¹ in the general formula (i), respectively, X ^1a and X ^1b represent a fluorine atom, —OCF ₃ or —CF ₃ , wherein A ^2a and A ^2b are each independently a trans-1,4-cyclohexylene group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5- Represents a diyl group, a 1,4-phenylene group, a 1,4-cyclohexenylene group or a naphthalene-2,6-diyl group, and one hydrogen atom in the group may be substituted with a fluorine atom. ^2a and Z ^2b each independently represents a single bond, —CF ₂ O—, OCF ₂ —, CH ₂ O— or —OCH ₂ —, and m ^2a and m ^2b represent 1 or 2. m ^2a and ^{m 2b} When the 2, may be identical or different each A ^2a and A ^2b, at least from the Z ^2a and Z ^2b may each be the same or different.) And a compound represented by 1 It is preferred that a species or two types of compounds are selected.

When the combination of the general formula (II-a) and the general formula (II-b) occupies 5 to 35% of the entire liquid crystal composition, an effect of ensuring an improvement of Δn and a driveable Δε is obtained. Furthermore, when it is used in combination with a suitable combination of the first component and the total amount of the first component is greater than the amount of the second component, high-speed response can be maintained. Further, the combination of the general formula (II-a) or the general formula (II-b) and the general formula (Ia) or the general formula (Ib) is a phase between the compounds of the components of the liquid crystal composition. In order to improve the solubility, the storage stability of the liquid crystal composition is improved, whereby the problem of precipitation of the liquid crystal compound can be suppressed / prevented.

That is, in the liquid crystal composition according to the present invention, as the first component, at least one compound or two or more compounds are selected from the compound group represented by the general formula (Ia) and the general formula (Ia). In addition, when at least two kinds are selected as the second component from the compound group represented by the general formula (IIa) and the general formula (IIb), not only the problem regarding the low temperature stability that the liquid crystal compound is precipitated, but also the dropwise addition All of the problems of scars and the effect of maintaining high-speed response can be achieved.

The lower limit value of the total content of the compounds represented by the general formula (i) and the general formula (J) with respect to the total amount of the composition of the present invention is 80%, 85%, 88% 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100% It is. The upper limit of the preferable content is 100%, 99%, 98%, and 95%.

The lower limit of the preferable total content of the compounds represented by the general formula (i), general formula (M) and (K) with respect to the total amount of the composition of the present invention is 80% and 85%. Yes, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% Yes, 100%. The upper limit of the preferable content is 100%, 99%, 98%, and 95%.

The formula (i), the general formula (M-1) to the general formula (M-18), and the general formula (K-1) to the general formula (K-6) with respect to the total amount of the composition of the present invention. The lower limit of the preferable total content of the compounds to be obtained is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95% %, 96%, 97%, 98%, 99%, 100%. The upper limit of the preferable content is 100%, 99%, 98%, and 95%.

The composition of the present invention preferably does not contain a compound having a structure in which oxygen atoms such as a peracid (—CO—OO—) structure are bonded in the molecule.

When emphasizing the reliability and long-term stability of the composition, the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less with respect to the total mass of the composition. Preferably, it is more preferably 1% or less, and most preferably not substantially contained.

When importance is attached to the stability by UV irradiation, 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, preferably 5% or less, more preferably 3% or less, and still more preferably substantially not contained.

It is preferable to increase the content of a compound in which all the ring structures in the molecule are 6-membered rings, and the content of the compound in which all the ring structures in the molecule are 6-membered rings is 80% relative to the total mass of the composition. % Or more, more preferably 90% or more, still more preferably 95% or more, and the composition is composed only of a compound in which all of the ring structures in the molecule are all 6-membered rings. Most preferably.

In order to suppress deterioration due to oxidation of the composition, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group as 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 still more preferably not contained.

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

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

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

The liquid crystal layer and / or liquid crystal composition according to the present invention may contain a polymerizable monomer and / or a cured product of the polymerizable monomer (that is, a polymer derived from the polymerizable monomer). Preferably exhibits liquid crystallinity. That is, the liquid crystal layer according to the present invention is preferably a polymerized polymerizable monomer contained in the liquid crystal composition. The specific content of the polymerizable monomer in the polymerizable monomer-containing liquid crystal composition according to the present invention is preferably 5% or less, more preferably 2% or less, still more preferably 1.5% or less, and further preferably 1% or less. Is particularly preferable, and 0.5% or less is most preferable. Generation | occurrence | production of dripping marks can be reduced as it is 5% or less. Further, the lower limit of the content of the polymerizable monomer in the liquid crystal composition is preferably 1000 ppm, more preferably 3000 ppm, and more preferably 5000 ppm.

When the liquid crystal composition contains a polymerizable monomer and / or a cured product of the polymerizable monomer, the alignment regulation amount is improved by curing the polymerizable monomer. Moreover, since the polymer derived from the polymerizable monomer traps an ionic component in the liquid crystal composition, there is an effect that the voltage holding ratio does not decrease.

The polymerizable monomer according to the present invention includes the general formula (P-1) and the general formula (P-2):

(In the above general formulas (P-1) to (P-2), R ^p11 , R ^p12 , R ^p21 and R ^p22 are each independently represented by the following formulas ( ^RI ) to (R-IX): ):

In the formulas (RI) to (R-IX), R ² to R ⁶ are independently of each other a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the number of carbon atoms. 1 to 5 halogenated alkyl groups, W is a single bond, —O— or a methylene group, T is a single bond or —COO—, and p, t and q are each independently 0, Represents 1 or 2,
A ^p11 , A ^p12 and A ^p22 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl Or a 1,3-dioxane-2,5-diyl group, which is unsubstituted or is a halogen atom, a cyano group, a nitro group, R ^p11 , an alkyl group having 1 to 12 carbon atoms (the alkyl group) One or two or more non-adjacent —CH ₂ — therein may be each independently substituted by —C≡C—, —O—, —CO—, —COO— or —OCO—. In the group Pieces or two or more hydrogen atoms of the non-adjacent each independently represents a fluorine may be substituted with atoms),
A ^p21 and A ^p23 each independently represent a divalent to tetravalent aromatic group or a divalent to tetravalent alicyclic group,
L ^p11 , L ^p12 , L ^p21 and L ^p22 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 ) _z— C (═O) —O—, — (CH ₂ ) _z —O— (C═O) —, —O— (C═O) — (CH ₂ ) _z —, — (C═O ) —O— (CH ₂ ) _z —, —O— (CH ₂ ) _z —O—, —OCF ₂ —, —CH═CHCOO—, —CH═CHOCO—, —COOCH═CH—, —OCOCH═CH -Represents C≡C-, z in the above formula represents an integer of 1 to 4,
m ^p11 , m ^p12 and m ^p22 each independently represent an integer of 0 to 3, and m ^p11 + m ^p12 represents an integer of 2 or more,
m ^p21 and m ^p23 each independently represents an integer of 1 to 4, and m ^p21 + m ^p23 ≧ 3;
When m ^p11 is 2 or more, a plurality of A ^p11 and L ^p11 may be the same or different, and when m ^p12 is 2 or more, a plurality of A ^p12 and L ^p12 are They may be the same or different,
when m ^p22 is 2 or more, a plurality of A ^p22 and L ^p21 may be the same or different from each other;
When m ^p21 is 2 or more, a plurality of R ^p21 and Sp ^p21 may be the same or different, and when m ^p23 is 2 or more, a plurality of R ^p22 and Sp ^p22 are They may be the same or different. It is preferable that it is 1 type, or 2 or more types selected from the group which consists of a compound represented by this.

In the general formula (P-1) and the general formula (P-2), Sp ^p11 , Sp ^p12 , Sp ^p21 and Sp ^p22 are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O—. (CH ₂ ) _s — (wherein _s represents an integer of 2 to 7 and the oxygen atom is bonded to the aromatic ring) is preferable.

In general formula (P-1) and general formula (P-2), A ^p11 , A ^p12 , and A ^p22 each independently represent 1,4-phenylene group, anthracene-2,6-diyl group, phenanthrene- More preferably, it represents a 2,7-diyl group or a naphthalene-2,6-diyl group, which is unsubstituted or an alkyl group having 1 to 5 carbon atoms, a halogen having 1 to 5 carbon atoms. An alkyl group, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, fluorine, and a cyano group.

In general formula (P-1) and general formula (P-2), L ^p11 , L ^p12 , L ^p21 and L ^p22 are each independently 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 -, - CF ₂ O—, — (CH ₂ ) _z —C (═O) —O—, — (CH ₂ ) _z —O— (C═O) —, —O— (C═O) — (CH ₂ ) _z— , — (C═O) —O— (CH ₂ ) _z —, —O— (CH ₂ ) _z —O—, —OCF ₂ —, —CH═CHCOO—, —CH═CHOCO—, —COOCH ═CH—, —OCOCH═CH— or —C≡C— is preferred, and z in the above formula preferably represents 4. When the linking group is the above group, the polymerizable monomer can take a linear structure.

In the compound represented by the general formula (P-1), it is more preferable that m ^p11 and m ^p12 each independently represent 0, 1 or 2. Further, m ^p11 + m ^p12 is more preferably 2 to 5, and m ^p11 + m ^p12 is further preferably 2 to 4.

In the compound represented by the general formula (P-2), it is preferable that ^mp21 and ^mp23 each independently represent 1, 2 or 3, and ^mp22 preferably represents 1 or 2. Further, it is more preferable that m ^p21 + m ^p23 = 3 to 6.

In the general formula (P-2), the divalent to tetravalent aromatic group is a divalent to tetravalent organic group including an aromatic ring, and all of the 2 to 4 bonding sites are derived from the aromatic ring. Specifically, a phenyl skeleton, a tetrahydronaphthalene skeleton, a phenanthrene skeleton, an anthracene skeleton, a naphthalene skeleton, and the like can be given.

In the general formula (P-2), the divalent to tetravalent alicyclic group is a divalent to tetravalent organic group including an alicyclic structure, and all of the 2 to 4 bonding sites are from the ring. In particular, a cyclohexylene skeleton, a cyclohexenylene skeleton, and the like can be given.

In the general formula (P-2), the divalent aromatic group includes 1,4-phenylene group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, pyridine-2,5-diyl. Group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or 1,3 -Represents a dioxane-2,5-diyl group but is unsubstituted or an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms It is preferably substituted with a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, a nitro group or R ^p11 .

In the general formula (P-2), the divalent to tetravalent aromatic group is any of the following formulas (bi) to (b-ix), and the aromatic group is unsubstituted or substituted with carbon. Alkyl group having 1 to 12 atoms, halogenated alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, halogenated alkoxy group having 1 to 12 carbon atoms, halogen atom, cyano group, nitro ^Optionally substituted with a group or R ^p11 .

(In the formula, Sp ^p21 or Sp ^p22 binds with *, and L ^p21 or L ^p22 binds with **.)
Further, the specific content of the polymerizable monomer represented by the general formula (P-1) or (P-2) in the entire liquid crystal composition is preferably 5% or less, more preferably 3% or less, It is more preferably 2% or less, particularly preferably 1% or less, and most preferably 0.8% or less. Further, the lower limit of the content of the polymerizable monomer in the liquid crystal composition is preferably 1000 ppm, more preferably 3000 ppm, and even more preferably 5000 ppm.

Hereinafter, preferred structures of the compounds represented by the general formula (P-1) to the general formula (P-2) according to the present invention will be exemplified.

In the compound represented by the general formula (P-1), 4 ≧ m ^p11 + m ^p12 ≧ 2, and L ^p11 or L ^p12 is —COO—, —OCO—, —COOC ₂ H ₄ —, —OCOC Selected from the group consisting of ₂ H ₄ —, —C ₂ H ₄ OCO—, —C ₂ H ₄ COO—, —CH═CHCOO—, —CH═CHOCO—, —COOCH═CH— and —OCOCH═CH—. A polymerizable monomer representing one of them is preferred. The polymerizable monomer having such a structure has the same linearity as that of the liquid crystal molecules and has a certain degree of freedom, and therefore has excellent compatibility with the liquid crystal compound.

Preferred examples of the compound represented by the general formula (P-1) according to the present invention include polymerizable compounds represented by the following formulas (Pa-1) to (Pa-33).

In the compound represented by the general formula (P-1), m ^p11 + m ^p12 = 2; A ^p11 and A ^p12 are 1,4-phenylene groups; and L ^p11 and L ^p12 are single bonds Is preferred. A polymerizable monomer having such a structure has a biphenyl structure, and a polymerizable compound containing these skeletons is optimal in alignment regulation after polymerization for a PSA type liquid crystal display element, and a good alignment state can be obtained. , Display unevenness is suppressed or does not occur at all.

Preferred examples of the compound represented by the general formula (P-1) according to the present invention include polymerizable compounds represented by the following formulas (Pb-1) to (Pb-34).

In the compound represented by the general formula (P-1), a polymerizable monomer in which m ^p11 + m ^p12 = 1 and A ^p11 or A ^p12 is a phenanthrene-2,7-diyl group is preferable. The polymerizable monomer having such a structure is considered to have a large photosensitive effect on the entire composition.
Preferable examples of the compound represented by the general formula (P-1) according to the present invention include polymerizable compounds represented by the following formulas (Pc-1) to (Pc-52).

In the general formula (P-2), ^mp22 represents an integer of 1 to 3, at least one of L ^{p21 and} L ^p22 is a single bond, and A ^p21 and A ^p23 are each independently an unsubstituted or carbon An alkyl group having 1 to 5 atoms (one or two or more non-adjacent —CH ₂ — in the alkyl group each independently represents —C≡C—, —O—, —CO—, —COO; -Or -OCO-, and one or two or more non-adjacent hydrogen atoms in the alkyl group may be each independently substituted with a fluorine atom), a fluorine atom, It is preferable to represent the following formulas (bi) to (b-ix) substituted with a cyano group or a nitro group.

(In the formula, Sp ^p21 or Sp ^p22 binds with *, and L ^p21 or L ^p22 binds with **.)
Preferable examples of the compound represented by the general formula (P-2) according to the present invention include polymerizable compounds represented by the following formulas (Pd-1) to (Pd-57).

The liquid crystal layer and / or liquid crystal composition in the liquid crystal display device according to the present invention preferably contains a polymerizable monomer in the liquid crystal layer and / or liquid crystal composition, and the polymerizable monomer is polymerized. Thereby, the alignment control force of the liquid crystal molecules of the photo-alignment film is improved. This will be described in more detail with reference to FIGS. FIG. 6A is a plan view of an IPS mode liquid crystal display element, in which the pixel electrode and the common electrode are formed in a comb shape, and they are separated from each other by a certain distance so as to be loosely fitted to each other on the same substrate. Is formed. In FIG. 6, (B) and (C) in FIG. 7 are enlarged views of the region of VII in the broken line portion. 7B and 7C and FIG. 8 are plan views in which the pixel electrode is on the upper side and the common electrode is on the lower side for the sake of convenience, the present invention is not limited to this. FIG. 7B shows that the liquid crystal composition of the present invention containing the liquid crystal compound 1a and the polymerizable monomer 1b is in a specific direction (along the alignment direction of the photo-alignment film) on the photo-alignment film. The arrangement is shown. FIG. 7C shows a state in which the liquid crystal compound 1a and the polymerizable monomer 1b are arranged in a specific direction (along the alignment direction of the photo-alignment film) on the photo-alignment film (that is, (B) In a state where a polymerizable monomer is polymerized. Due to the presence of the polymerized polymer 1c, an alignment regulating force in a specific direction is generated for the liquid crystal molecules. That is, when the polymerizable monomer is polymerized in the (B) state (no voltage applied), the polymerizable monomers are connected in a state of being oriented in the specific orientation direction ((C) state). For this reason, an interaction acts between the polymer 1c in which polymerizable monomers are linked to each other and the liquid crystal molecules 1b, so that it is considered that the pretilt angle is stabilized and the alignment regulating force of the alignment film on the liquid crystal molecules is improved. 7 and 8, a multi-domain is provided to solve problems such as viewing angle dependency.

FIG. 8 schematically shows the state of alignment of liquid crystal molecules when the voltage is turned on or off with respect to the state of FIG. 7C. When a voltage is applied, the liquid crystal molecules 1a are aligned along the direction of the electric field, and when the voltage is turned off, the liquid crystal molecules 1a have a polymer 1c in which polymerizable monomers are connected to each other in the liquid crystal layer, so that the initial alignment direction is maintained. It becomes easy to return to a specific orientation direction.

Therefore, in the liquid crystal display element, when the liquid crystal composition includes a polymerizable monomer and a liquid crystal compound and is provided with a liquid crystal layer obtained by polymerizing the polymerizable monomer, the polymerizable monomer can be used even when the voltage ON-OFF state is repeated. The interaction between the polymer 1c and the liquid crystal molecules 1b linked to each other is considered to improve the alignment regulating force on the liquid crystal molecules, which has been a problem in the past, and which decreases with time. Thereby, since a liquid crystal molecule can maintain the specific alignment direction given to the photo-alignment film, it is considered that the substantial alignment regulating force is improved. In particular, when alignment division is performed, since the alignment directions in the divided regions in the pixel are different from each other, the alignment regulating force with respect to the alignment direction in each alignment divided region can be improved.

In the case of adding a polymerizable monomer to the liquid crystal composition according to the present invention, the polymerization proceeds even in the absence of a polymerization initiator, but may contain a polymerization initiator in order to accelerate the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.

The liquid crystal composition according to the present invention can further contain a compound represented by the general formula (Q) as an antioxidant.

In the general formula (Q), R ^Q represents an alkyl group or an alkoxy group having 1 to 22 carbon atoms, one or more CH ₂ groups in the alkyl groups, so that oxygen atoms are not directly adjacent, - O -, - CH = CH - , - CO -, - OCO -, - COO -, - C≡C -, - CF 2 O -, - OCF 2 - may be replaced by, ^{M Q} is trans-1, It represents a 4-cyclohexylene group, a 1,4-phenylene group, or a single bond.

In the general formula (Q), ^RQ is preferably an alkyl group having 1 to 22 carbon atoms or an alkoxy group, and the alkyl group (including the alkyl group in the alkoxy group) is linear or branched It may be a chain. The ^RQ represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched alkoxy group, and one or more of the alkyl groups (including the alkyl group in the alkoxy group). The CH ₂ group is —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O—, —OCF so that the oxygen atom is not directly adjacent. _It may be substituted with 2-. ^{R Q} in the general formula (Q) is a number of 1 to 20 carbon atoms, a straight-chain alkyl groups, linear alkoxy groups, one CH ₂ group has been replaced -OCO- or -COO- in Preferably, the alkyl group is at least one selected from the group consisting of a linear alkyl group, a branched alkyl group, a branched alkoxy group and a branched alkyl group in which one CH ₂ group is substituted with —OCO— or —COO—. A linear alkyl group having 1 to 10 carbon atoms, a linear alkyl group in which one CH ₂ group is substituted by —OCO— or —COO—, a branched alkyl group, a branched alkoxy group, and one CH ₂ group More preferred is at least one selected from the group consisting of a branched alkyl group substituted with —OCO— or —COO—.

^MQ represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a single bond, and a trans-1,4-cyclohexylene group or a 1,4-phenylene group is preferred.

The compound represented by the general formula (Q) is preferably at least one compound selected from the group of compounds represented by the following general formulas (Qa) to (Qd): The compound represented by the general formula (Qa) and / or (Qc) is more preferable.

In the general formulas (Qa) to (Qd), R ^Q1 is preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group, and R ^Q2 is a straight chain having 1 to 20 carbon atoms. A chain alkyl group or a branched chain alkyl group is preferable, and R ^Q3 is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched chain alkyl group, a linear alkoxy group or a branched chain alkoxy group, and L ^Q is 1 carbon atom. A linear alkylene group or a branched alkylene group of 8 to 8 is preferred. Among these, the compound represented by the general formula (Q) is more preferably a compound represented by the following formula (Qa-1) and / or (Qc-1).

In the liquid crystal composition of the present invention, the compound represented by the general formula (Q) preferably contains one or two compounds, more preferably contains one to five compounds, and the content is It is preferably 0.001 to 1% by mass, preferably 0.001 to 0.1% by mass, and 0.001 to 0.05% by mass with respect to the total mass of the liquid crystal composition of the present invention. It is preferable that

(Orientation layer)
The photo-alignment layer according to the present invention is provided on at least one of the first substrate and the second substrate, and is preferably provided on both sides of the first substrate and the second substrate.

The alignment layer according to the present invention is preferably a photo-alignment film containing a photoresponsive polymer whose chemical structure changes in response to light.

Thereby, in the liquid crystal display element of the horizontal alignment direction method (IPS or FFS) using the p-type material, rubbing unevenness due to surface irregularities and dripping marks of the liquid crystal composition can be reduced by strip-shaped electrodes or the like. .

In the liquid crystal display device of the horizontal alignment direction method (IPS or FFS) using the photo-alignment film and the p-type material, the high-contrast advantage of the photo-alignment film is exhibited by using a liquid crystal composition containing a polymerizable monomer. In addition, the orientation regulating force can be improved.

In general, there are various types of photo-alignment films, for example, photoisomerization by light irradiation of an azo group (for example, azobenzene compound), a Schiff base, and a compound having an unsaturated bond site such as a carbon-carbon double bond. Those utilizing photodimerization such as cinnamic acid derivatives, those utilizing photo-cleavage (photolysis) of σ bond of coumarin, chalcone, or the polymer itself (for example, photodegradable polyimide) It is done.

More specifically, the photoresponsive polymer is at least one selected from the group consisting of a photoresponsive decomposition polymer, a photoresponsive dimerization polymer, and a photoresponsive isomerization polymer. The photoresponsive decomposition polymer is particularly preferable.

As the photoresponsive decomposable polymer according to the present invention, those utilizing photocleavage (photolysis) of σ bond of the polymer itself are preferable. More specifically, in any case, those having polysiloxane, polyimide, and polyamic acid derivative structures as the main chain are preferred, and polyimide and polyamic acid derivative structures are more preferred. The polyamic acid derivative is preferably an alkyl ester having 1 to 5 carbon atoms or an alkyl ammonium salt having 1 to 18 carbon atoms.

The photoresponsive decomposition type polymer according to the present invention contains at least one polymer selected from the group consisting of polyamic acid and polyimide obtained by reacting tetracarboxylic dianhydride with a diamine compound. Is preferred.

Examples of the tetracarboxylic dianhydride used as a raw material for polyimide and polyamic acid derivatives include the following.

(In the above formula, Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a fluorine atom, —NR ₂ , —SR, —OH. , —CH ₂ COOR, —CH ₂ CH ₂ COOR, —COR, —NO ₂ , —CN, wherein at least one of Z ¹ , Z ² , Z ³ , and Z ⁴ is a hydrogen atom or a methyl group R represents an alkyl group having 1 to 5 carbon atoms, and T represents a single bond, —CH ₂ —, —O—, —S—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) _2. Represents-, -CO-, or -SO-)

(In the above formula, T represents a single bond, —CH ₂ —, —O—, —S—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —CO—, —SO—).
Among the compounds as described above, the formula (TCA-1), formula (TCA-2), formula (TCA-3), formula (TCA-4), formula (TCA-5), formula (TCA-8) and Formula (TCA-10) is preferred, and formula (TCA-1) and formula (TCA-8) are particularly preferred.

Examples of the diamine compound used as a raw material for polyimide and polyamic acid derivatives include the following.

Among such compounds, the formula (DA-1), the formula (DA-25), the formula (DA-31), the formula (DA-32), and the formula (DA-49) are preferable, and the formula (DA-1) Formula (DA-25) and Formula (DA-49) are particularly preferable.

In the case where a type utilizing photoisomerization is employed in the photo-alignment film according to the present invention, at least one of a tetracarboxylic acid anhydride or a diamine compound includes the following formula (TCA-38) and formula (DA-50): It preferably contains at least one selected from the group consisting of formula (DA-56).

For example, in addition to (or instead of) the compounds of the formula (TCA-1) to the formula (TCA-37) exemplified as the tetracarboxylic acid anhydride, the following formula (TCA-38):

It is preferable to use the compound represented by these. Alternatively, in addition to (or instead of) the compounds of the formulas (DA-1) to (DA-49), the diamine compounds may be represented by the following formulas (DA-50) to (DA-56):

It is preferable to use the compound represented by these.

In addition, in the photo-alignment film according to the present invention, when a type utilizing photodimerization is adopted, at least one of hydrogen atoms in the diamine compound represented by the formulas (DA-1) to (DA-49) is used. It preferably has the following formula (V), and more preferably contains at least one selected from the group consisting of formula (DA-50) to formula (DA-53).

That is, in addition to (or instead of) the compounds of the formulas (DA-1) to (DA-49), as a diamine compound, the hydrogen atom in the compounds of (DA-1) to (DA-49) (V):

(In the formula, broken lines represent bonds to the atoms to which the hydrogen atoms of (DA-1) to (DA-49) were bonded, and G ¹ , G ² , G ³ , G ⁴ , and G ⁵ are independent of each other. A single bond, an alkylene group having 2 to 12 carbon atoms (one —CH ₂ — group or two or more non-adjacent —CH 2 groups are —O—, —CO—, —COO—, —OCO— , —NR—, —NRCO—, —CONR—, —NRCOO—, —OCONR—, —NRCONR—, —CH═CH—, —CC—, —OCOO——, where R is a hydrogen atom. Or an alkyl group having 1 to 20 carbon atoms), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O— , —OCF ₂ —, —CF ₂ CF ₂ —, —CC—, —CH═CHCOO—, —OCOCH═ CH—, wherein any one or more of G ¹ , G ² , G ³ , G ⁴ , G ⁵ represents —CH═CHCOO—, —OCOCH═CH—.
n ⁵ , n ⁶ , n ⁷ , n ^{8 each} represents 0 or 1, and E ¹ , E ² , E ³ , E ⁴ , E ⁵ are each independently trans-1,4-cyclohexylene, trans-1 , 4-dioxane-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, 2,5-thiophenylene group, 2 , 5-furanylene group or 1,4-phenylene group, which are unsubstituted or one or more hydrogen atoms may be substituted by fluorine atom, chlorine atom, methyl group or methoxy group, Z is A hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms (one —CH ₂ — group or two or more non-adjacent —CH ₂ — groups are —O—, —CO—, —COO—, — OCO-, -NR-, -NRCO-, -CO R—, —NRCOO—, —OCONR—, —NRCONR—, —CH═CH—, —CC— or —OCOO— may be substituted, and R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ), Which represents a cyano group, a nitro group, a hydroxyl group or a carboxyl group) is preferably used.

Specific examples of such a diamine compound include, for example, the following formulas (DA-57) to (DA-60).

As the photodecomposition type photo-alignment film according to the present invention, tetracarboxylic acid anhydride is represented by the formula (TCA-1), formula (TCA-2), formula (TCA- 3), formula (TCA-4), formula (TCA-5), formula (TCA-33) (in the formula (TCA-33), T is particularly preferably —CO—) and TCA-34 (formula ( In TCA-34), T is preferably —CO—, and is more preferably formula (TCA-1), formula (TCA-2), formula (TCA-3), formula (TCA-4) and formula (TCA- 5) is particularly preferred. In addition, as the photodecomposition type photo-alignment film according to the present invention, the diamine compound is represented by the formula (DA-1), the formula (DA-25), the formula (DA-49) from the viewpoint that a good liquid crystal orientation can be expressed. Is particularly preferred.

The tetracarboxylic anhydrides and diamine compounds listed above can be used singly or in combination of two or more depending on the required properties.

In the preferred polyamic acid of the photoresponsive decomposition type polymer according to the present invention, the mixing ratio of the above-mentioned tetracarboxylic dianhydride and the above-mentioned diamine compound is as follows. The proportion of the anhydride acid anhydride group is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents.

Further, in the photo-alignment film according to the present invention, it is preferable that the polyamic acid synthesis reaction by the condensation of the tetracarboxylic acid anhydride and the diamine compound is performed in an organic solvent. The reaction temperature is preferably −20 ° C. to 150 ° C., more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent include alcohols, ketones, esters, ethers, aprotic polar solvents, phenols and derivatives thereof, halogenated hydrocarbon solvents, hydrocarbon solvents, and the like.

As the alcohol, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether and the like are preferable.

Preferred examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, and diethyl malonate.

Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate. , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran and the like.

Specific examples of the aprotic polar solvent include, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphoryl Amides and the like are preferred.

As the phenol and derivatives thereof, for example, m-cresol, xylenol, halogenated phenol and the like are preferable.

Examples of the halogenated hydrocarbon solvent include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, and the like.

Examples of the hydrocarbon solvent include hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, and diisopentyl ether.

The total amount of tetracarboxylic dianhydride and diamine compound with respect to the organic solvent is preferably 0.1 to 50% by weight based on the total amount of the reaction solution.

When the tetracarboxylic dianhydride and the diamine compound are reacted under the above conditions, a reaction solution containing a polyamic acid is obtained. The obtained reaction solution may be used for the preparation of the alignment film as it is, or may be used for the preparation of the alignment film after isolating the polyamic acid contained in the reaction solution. May be used for the preparation of the alignment film.

Further, when the obtained polyamic acid is subjected to dehydration ring closure to obtain a polyimide, the reaction solution may be subjected to a dehydration ring closure reaction as it is, and the polyamic acid contained in the reaction solution is isolated and then subjected to dehydration ring closure. It may be subjected to a reaction, or may be subjected to a dehydration ring closure reaction after purifying the isolated polyamic acid. Isolation and purification of the polyamic acid can be performed according to known methods.

As a method of imidizing the polyamic acid obtained by the above reaction to obtain a polyimide, it can be obtained by dehydrating and ring-closing the polyamic acid to imidize. Specifically, it is carried out by a method of heating a polyamic acid or a method of dissolving a polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating as necessary.

Examples of the organic solvent used in the dehydration ring closure reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid, and are omitted here.

The polyimide as the alignment film according to the present invention may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure of the precursor polyamic acid, and only a part of the amic acid structure may be dehydrated. It may be a partially imidized product that is ring-closed and has an amic acid structure and an imide ring structure. The imidation ratio of the polyimide according to the present invention is preferably 30% or more, more preferably 40 to 99%, and still more preferably 45 to 98%. The said imidation rate represents the ratio which the number of the imide ring structure accounts with respect to the sum total of the number of the amic acid structures of polyimide, and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

In the present invention, the method for measuring the imidization ratio of polyimide is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and the peak integrated value of this proton is around 9.5 to 10.0 ppm. It is calculated using the proton peak integrated value derived from the NH group of the amic acid that appears.

In the present invention, the temperature when polyamic acid is thermally imidized in a solution is preferably 100 ° C. to 400 ° C., more preferably 120 ° C. to 250 ° C. In this case, a method is preferably performed while removing water generated by the imidization reaction from the system.

In the present invention, when the polyamic acid is imidized with a catalyst, a basic catalyst and an acid anhydride are added to the polyamic acid solution obtained above, preferably −20 to 250 ° C., more preferably 0 to It is obtained by stirring at 180 ° C. In this case, the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times of the amic acid group, preferably Is 3 to 30 mole times.

Examples of the basic catalyst include pyridine, collidine, lutidine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.

In addition, the imidation rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

In the present invention, when recovering the produced polyamic acid or polyimide from the reaction solution of polyamic acid or polyimide, the reaction solution may be poured into a poor solvent and precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.

When the concentration of the polyamic acid and polyimide according to the present invention is 10% by weight, the solution preferably has a solution viscosity of 10 to 800 mPa · s, and preferably has a solution viscosity of 15 to 500 mPa · s. More preferably. The solution viscosity (mPa · s) of these polymers is 10% by weight of a polymer solution prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). Is a value measured at 25 ° C. using an E-type viscometer.

As the photoresponsive dimerization polymer according to the present invention, the following general formula (1A) or general formula (1B):

(In the general formula (1), Sp is a single bond, — (CH ₂ ) _u — (wherein u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, —COO— , —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ —, and —C≡C—. In these substituents, at least one of the non-adjacent CH ₂ groups independently represents —O—, —CO—, —CO—O—, —O—CO—, — Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, — NR—CO—NR—, —CH═CH—, —C≡C— or —O—CO—O— (wherein R represents hydrogen or an alkyl group having 1 to 5 carbon atoms). )
A ¹ and A ² are each independently
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) a 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) a 1,4-cyclohexenylene group 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo (2.2.2) octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, deca Represents a group selected from the group consisting of a hydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, the group (a), group (b) or group (C) is each unsubstituted or one or more hydrogen atoms may be substituted by fluorine atom, chlorine atom, cyano group, methyl group or methoxy group,
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u — (wherein u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ —, or —C≡C—, but these substitutions One or more of the non-adjacent CH ₂ groups in the group are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH— , —C≡C— or —O—CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms),
X is —O—, a single bond, —NR— or a phenylene group,
R ^b is a polymerizable group, an alkoxy group, a cyano group, or a fluorinated alkyl group having 1 to 12 carbon atoms,
m is 0, 1, or 2;
M _b and M _d may be the same or different from each other and each represents a monomer unit of the following general formulas (U-1) to (U-13);

(In the above general formulas (U-1) to (U-10), the broken line represents a bond to Sp, and R ^a is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, a halogen atom. Any hydrogen atom in each structure may be substituted by a fluorine atom, a chlorine atom, a methyl group, a phenyl group, a methoxy group,
In the above general formulas (U-11) to (U-13), the broken line represents a bond to Sp, R ¹ is a tetravalent ring structure, R ² is a trivalent organic group, R ³ is a hydrogen atom, a hydroxyl group Represents an alkyl group having 1 to 15 carbon atoms and an alkoxy group having 1 to 15 carbon atoms. )
y and w represent the molar fraction of the copolymer, 0 <y ≦ 1 and 0 ≦ w <1, n represents 4 to 100,000, and the monomer units of M _b and M _d are each independently One type or two or more types of different units may be used. )
It is preferable that it is a photoresponsive dimerization type | mold polymer | macromolecule represented by these, its hydrolyzate, or the condensate of a hydrolyzate.

Moreover, as a preferable form of the photoresponsive polymer represented by the general formula (1) according to the present invention, a photoresponsive dimerization polymer in which Z ² is a single bond is preferable.

Other photoresponsive dimerization polymer according to the present invention is represented by the following general formula (2):

(In the above general formula (2), M ¹ and M ² are each independently of each other acrylate, methacrylate, 2-chloroacrylate, 2-phenyl acrylate, acrylamide, methacryl which may be N-substituted with a lower alkyl group. At least one repeating unit selected from the group consisting of amide, 2-chloroacrylamide, 2-phenylacrylamide, vinyl ether, vinyl ester, styrene derivative and siloxanes;
M ³ is acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, vinyl ether, vinyl ester, acrylic which may be N-substituted with lower alkyl. Linear or branched alkyl ester of acid or methacrylic acid, allyl ester of acrylic acid or methacrylic acid, alkyl vinyl ether or ester, phenoxynialkyl acrylate or phenoxyalkyl methacrylate or hydroxyalkyl acrylate or hydroxyalkyl methacrylate, phenylalkyl acrylate Or phenylalkyl methacrylate, acrylonitrile, methacrylonitrile, At least one repeating unit selected from the group consisting of tylene, 4-methylstyrene and siloxanes,
A ¹ , B ¹ , C ¹ , A ² , B ² and C ² are each independently of each other,
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) a 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) a 1,4-cyclohexenylene group 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo (2.2.2) octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, deca Represents a group selected from the group consisting of a hydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, the group (a), group (b) or group (C) is each unsubstituted or one or more hydrogen atoms may be substituted by fluorine atom, chlorine atom, cyano group, methyl group or methoxy group,
S ¹ and S ² are each independently a linear or branched alkylene group (— (CH ₂ ) _r —) or — (CH ₂ ) _r substituted with one or more fluorine atom, chlorine atom or cyano group —L— (CH ₂ ) _s — (wherein L is a single bond or —O—, —COO—, —OOC—, —NR ¹ —, —NR ¹ —CO—, —CO—NR ¹ —, —NR ¹ —COO—, —OCO—NR ¹ —, —NR ¹ —CO—NR ¹ —, —CH═CH— or —C≡C—, wherein R ¹ is a hydrogen atom or lower alkyl And r and s are integers from 1 to 20 under the condition r + s ≦ 24, and
D ¹ and D ² each independently represent —O—, —NR ² —, or the following formulas (d) to (f):
(D) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups not adjacent to each other are replaced with —O—, —NH— or —S—) May be)
(E) a 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (f) a 1,4-cyclohexenylene group 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo (2.2.2) octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, deca A group selected from the group consisting of a hydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (d), group (e) or group (F) means that each is unsubstituted or one or more hydrogen atoms may be substituted by a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group, wherein R ² is hydrogen An atom or a lower alkyl group,
X ¹ , X ² , Y ¹ and Y ² are each independently of one another substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or optionally a fluorine atom, and a CH ₂ group or a plurality of non-adjacent CH ₂ groups Means an alkyl group having 1 to 12 carbon atoms which may be optionally replaced by —O—, —COO—, —OOC— and / or —CH═CH—,
Z ^1a , Z ^1b , Z ^2a and Z ^2b are each independently a single bond, — (CH ₂ ) t—, —O—, —CO—, —CO—O—, —O—OC—, — NR ⁴ —, —CO—NR ⁴ —, —NR ⁴ —CO—, — (CH ₂ ) _u —O—, —O— (CH ₂ ) _u —, — (CH ₂ ) _u —NR ⁴ — or — NR ⁴ — (CH ₂ ) _u —, wherein R ⁴ represents a hydrogen atom or a lower alkyl group; t represents an integer of 1 to 4; u represents an integer of 1 to 3;
p ¹ , p ² , q ¹ and q ² are each independently 0 or 1,
R ^1a and R ^2a are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkyl- COO—, alkyl-CO—NR ³ or alkyl-OCO group, wherein R ³ represents a hydrogen atom or a lower alkyl group, and one or more hydrogen atoms of the alkyl group or the alkoxy group are fluorine May be substituted with an atom, a chlorine atom, a cyano group or a nitro group, and the CH ₂ group or a plurality of non-adjacent CH ₂ groups of the alkyl group or the alkoxy group may be —O—, —CH═CH— or —C≡. May be substituted with C-
n ¹ , n ² and n ³ are mole fractions of comonomer where 0 <n ¹ ≦ 1, 0 ≦ n ² <1 and 0 ≦ n ³ ≦ 0.5)
It is preferable that it is a photoresponsive dimerization type | mold polymer represented by these.

Hereinafter, a method for producing the liquid crystal display element of the present invention will be described. The liquid crystal display element of the present invention is preferably produced, for example, by the following steps (1) to (3).

In the method for producing a liquid crystal display element according to the present invention, it is preferable to form a coating film on the substrate by applying the photo-alignment film precursor solution according to the present invention on the substrate and then heating the coated surface ( Step (1)). More specifically, for example, the photo-alignment film precursor of the present invention is formed on the conductive film forming surface of the substrate provided with the transparent conductive film patterned in a comb-teeth shape and on one surface of the counter substrate provided with no conductive film. Each of the body solutions is applied, and each coated surface is heated to form a coating film.

The photo-alignment film precursor solution according to the present invention is preferably a solution containing the above-described photo-responsive decomposition type polymer. Further, the photoresponsive decomposition type polymer includes at least one polymer selected from the group consisting of polyamic acid and polyimide obtained by reacting tetracarboxylic dianhydride and a diamine compound, and the organic solvent. It is preferable to contain.

The photo-alignment film precursor solution of the present invention is preferably applied by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or poly (alicyclic olefin) can be used. As the transparent conductive film provided on one surface of the (first) substrate, a NESA film made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), or the like is used. Also good. Furthermore, in order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, or a mask having a desired pattern when forming a transparent conductive film is used. It can be employed in methods. In applying the photo-alignment film precursor solution, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the substrate surface is a known method such as a functional silane compound or a functional titanium compound. The surface treatment may be performed in advance.

After applying the photo-alignment film precursor solution, pre-baking may be performed as necessary. In this case, the pre-baking temperature is preferably 30 to 200 ° C. The prebake time is preferably 0.25 to 10 minutes. Then, it is preferable to perform a baking process for the purpose of removing a solvent completely and heat imidizing the amic acid structure which exists in a polymer as needed. The firing temperature at this time is preferably 80 to 300 ° C. The firing time is preferably 5 to 200 minutes. The film thickness thus formed is preferably 0.001 to 1 μm.

Moreover, when the polymer contained in the photo-alignment film precursor solution of the present invention is a polyamic acid or an imidized polymer having an imide ring structure and an amic acid structure, the film is further heated after the coating is formed. It is good also as a more imidized coating film by making a dehydration ring-closing reaction proceed.

In the method for producing a liquid crystal display element according to the present invention, it is preferable to irradiate a coating film containing polyamic acid or polyimide formed on the substrate (step (2)). Moreover, you may perform the said process (2) after the below-mentioned process (3). As the light applied to the coating film, ultraviolet rays or visible rays containing light having a wavelength of 150 to 800 nm can be used, and ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable.

As a light source for the irradiation light, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating. The amount of light irradiation is preferably 1,000 J / m ² or more and 100,000 J / m ² or less.

In the method for producing a liquid crystal display device according to the present invention, a pair of substrates on which a photo-alignment film or a coating film is formed face each other with a gap (cell gap) therebetween, and the liquid crystal composition according to the present invention is placed in the gap. It is preferable to fill (step (3)).

In addition, when a polymerizable monomer is mixed in the liquid crystal composition, the method may further include a step (4) of polymerizing the polymerizable monomer by a predetermined method without applying a voltage after filling the liquid crystal composition. .

As a method for filling the liquid crystal composition, (1) vacuum injection method (for a pair of substrates on which a photo-alignment film or a coating film is formed, a gap is formed so that the alignment directions of the two substrates are orthogonal to each other. (Cell gap) are placed facing each other, the periphery of the two substrates are bonded together using a sealant, liquid crystal is injected and filled into the cell gap defined by the substrate surface and the sealant, and the injection hole is sealed. And a method of forming a liquid crystal cell by stopping) or (2) ODF method. In the method of introducing the liquid crystal composition by the vacuum injection method, although no drop mark is generated, there is a problem in manufacturing time, cost, etc. as the substrate size increases. However, in this invention, it can be used conveniently by the display element manufactured using the ODF method from the combination of a photo-alignment film and a liquid-crystal composition.

Further, in the horizontal alignment method as in the present invention, an electrode layer 3 such as a TFT (a surface covered with a photo-alignment film) is formed on the surface of the same substrate (for example, the first substrate in FIGS. 3 and 5). Therefore, there are many irregularities on the surface, and it is easy to promote the generation of dripping marks, but this problem is thought to be mitigated by the combination of the photo-alignment film and the liquid crystal composition. It is done.

Further, the liquid crystal composition containing the polymerizable monomer according to the present invention is provided with liquid crystal alignment ability by polymerization of the polymerizable monomer contained therein by irradiation with ultraviolet rays, and light utilizing the birefringence of the liquid crystal composition. The liquid crystal display element is preferably used for controlling the amount of transmitted light. As a liquid crystal display element, it is useful for VA-IPS-LCD, FFS-LCD, AM-LCD (active matrix liquid crystal display element) and IPS-LCD (in-plane switching liquid crystal display element), but particularly useful for AM-LCD. Yes, it can be used for a transmissive or reflective liquid crystal display element.

The two substrates of the liquid crystal cell used in the liquid crystal display element can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

The color filter can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be manufactured. In addition, a pixel electrode provided with an active element such as a TFT or a thin film diode may be provided on the substrate.

The substrate is opposed so that the transparent electrode layer is on the inside. In that case, you may adjust the space | interval of a board | substrate through a spacer. In this case, it is preferable to adjust so that the thickness of the light control layer (liquid crystal layer) to be obtained is 1 to 100 μm. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness G so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

As a method of sandwiching the liquid crystal composition (containing a polymerizable monomer as necessary) between the two substrates, a normal vacuum injection method or an ODF method can be used. However, in the vacuum injection method, there is a problem that an injection mark remains instead of a drop mark. In this invention, it can use more suitably for the display element manufactured using ODF method. In the ODF liquid crystal display device manufacturing process, a sealant such as epoxy photothermal curing is drawn on a backplane or frontplane substrate using a dispenser in a closed-loop bank shape, and then removed. A liquid crystal display element can be manufactured by bonding a front plane and a back plane after dropping a predetermined amount of the liquid crystal composition in the air. The liquid crystal composition of the present invention can be preferably used because the liquid crystal composition can be stably dropped in the ODF process.

As a method for polymerizing the polymerizable monomer, an appropriate polymerization rate is desirable in order to obtain good alignment performance of the liquid crystal. Therefore, active energy rays such as ultraviolet rays or electron beams are irradiated singly or in combination or sequentially. The method of polymerizing by is preferred. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. In addition, when the polymerization is performed in a state where the polymerizable monomer-containing liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. I must. Moreover, 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 an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. In particular, when ultraviolet exposure is performed, it is preferable that the polymerizable monomer-containing liquid crystal composition is exposed to ultraviolet light without applying a voltage. In a horizontal electric field type MVA mode liquid crystal display element, it is preferable to control the pretilt angle (angle formed between the major axis of the liquid crystal molecules and the substrate surface) to about 0 ° from the viewpoint of alignment stability and contrast.

The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-rays to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed. Intensity of ultraviolet irradiation is ^preferably from 0.1mW / cm 2 ~ 100W / cm 2, 2mW / cm 2 ~ 50W / cm 2 is more preferable. The amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² . The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiating ultraviolet rays, but when using a metal halide lamp, high pressure mercury lamp or ultra high pressure mercury lamp, it is preferably 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds, and fluorescence. In the case of using a lamp, 60 seconds to 18000 seconds are preferable, and 600 seconds to 10800 seconds are preferable.

The first substrate or the second substrate is not particularly limited as long as it is substantially transparent, and glass, ceramics, plastics, or the like can be used. Plastic substrates include cellulose derivatives such as cellulose, triacetyl cellulose, diacetyl cellulose, polycycloolefin derivatives, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, polyethylene, etc. Polyolefin, polycarbonate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyamide, polyimide, polyimide amide, polystyrene, polyacrylate, polymethyl methacrylate, polyethersulfone, polyarylate, and glass fiber-epoxy resin Inorganic-organic composite materials such as glass fiber-acrylic resin can be used.

When using a plastic substrate, it is preferable to provide a barrier film. The function of the barrier film is to reduce the moisture permeability of the plastic substrate and to improve the reliability of the electrical characteristics of the liquid crystal display element. The barrier film is not particularly limited as long as it has high transparency and low water vapor permeability. Generally, vapor deposition, sputtering, chemical vapor deposition method (CVD method) using an inorganic material such as silicon oxide is used. ) Is used.

In the present invention, the same material or different materials may be used as the first substrate or the second substrate, and there is no particular limitation. Use of a glass substrate is preferable because a liquid crystal display element having excellent heat resistance and dimensional stability can be manufactured. In addition, a plastic substrate is preferable because it is suitable for a manufacturing method using a roll-to-roll method and is suitable for weight reduction or flexibility. For the purpose of imparting flatness and heat resistance, good results can be obtained by combining a plastic substrate and a glass substrate.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “mass%”.

In the examples, the measured characteristics are as follows.

Tni: Nematic phase-isotropic liquid phase transition temperature (° C)
Δn: Refractive index anisotropy at 295K (also known as birefringence)
Δε: Dielectric anisotropy at 295K η: Viscosity at 295K (mPa · s)
γ1: rotational viscosity at 295 K (mPa · s)
VHR: Voltage holding ratio (%) at 313K under conditions of frequency 60Hz and applied voltage 5V
Burn-in:
The burn-in evaluation of the liquid crystal display element is based on the following four-step evaluation of the afterimage level of the fixed pattern when the predetermined fixed pattern is displayed in the display area for 1440 hours and then the entire screen is displayed uniformly. went.

◎ No afterimages ○ Although there are only afterimages, acceptable level △ Without afterimages, unacceptable level × Without afterimages, quite poor Volatile / contamination of manufacturing equipment:
Evaluation of the volatility of the liquid crystal material was performed by observing the operating state of the vacuum stirring and defoaming mixer with a stroboscope and visually observing foaming of the liquid crystal material. Specifically, put 0.8kg of the liquid crystal composition in a dedicated container vacuum agitation defoaming mixer having a volume 2.0L, under degassing of 4 kPa, the revolution speed ^{15S -1,} vacuum stirring at rotation speed 7.5S ^-1 The defoaming mixer was operated, and the following four-step evaluation was performed according to the time until foaming started.

◎ More than 3 minutes to foam. The possibility of equipment contamination due to volatilization is low.

○ 1 minute or more and less than 3 minutes until foaming. There is concern about minor equipment contamination due to volatilization.

△ 30 seconds or more and less than 1 minute until foaming. Equipment contamination due to volatilization occurs.

X Within 30 seconds until foaming. There is concern about serious equipment contamination due to volatilization.

Process suitability:
The process suitability is that the liquid crystal is dropped 40 pL at a time by using a constant volume metering pump 100000 times in the ODF process, and the following “0 to 200 times, 201 to 400 times, 401 to 600 times, ..., 99801 to 100,000 times ”, the change in the amount of liquid crystal dropped 200 times was evaluated in the following four stages.

◎ Extremely small change (Stable liquid crystal display device can be manufactured)
○ Allowable level with slight change △ Level with change and unacceptable level (Yield deteriorated due to spots)
× There is a change and it is quite inferior (liquid crystal leakage and vacuum bubbles are generated)
Solubility at low temperature:
In order to evaluate the solubility at a low temperature, after preparing the liquid crystal composition, 0.5 g of the liquid crystal composition was weighed in a 1 mL sample bottle, and the next was “−20 ° C. (−20 ° C.)” in a temperature-controlled test tank. 1 hour hold) → temperature rise (0.2 ° C./min)→0° C. (1 hour hold) → temperature rise (0.2 ° C./min)→20° C. (1 hour hold) → temperature drop (−0. 2 ° C / min) → 0 ° C (hold for 1 hour) → temperature drop (−0.2 ° C / min) → −20 ° C. The following four-level evaluation was performed.

◎ No precipitate was observed for 600 hours or more.

○ No precipitate was observed for 300 hours or more.

△ Precipitates were observed within 150 hours.

X Precipitates were observed within 75 hours.

In the examples, the following abbreviations are used for the description of the compounds used in the liquid crystal composition.
(Side chain)
-F -F fluorine atom F- -F fluorine atom -n -C _n H _{2n + 1} linear alkyl group with n carbon atoms n- C _n H _{2n + 1} -linear alkyl group with n carbon atoms -On —OC _n H _{2n + 1} linear alkoxyl group having n carbon atoms nO—C _n H _{2n + 1} O— linear alkoxyl group having n carbon atoms —V ₂ —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 ₃ = CH-CH ₂ -CH _2-
-2V1 -CH ₂ -CH ₂ -CH = CH-CH ₃
1V2- CH ₃ —CH═CH—CH ₂ —CH ₂
OCF3 -O-CF ₃
(Linking group)
—CF ₂ O— (or —CFFO—) —CF ₂ —O—
-OCF2- (or -OCFF-) -O-CF _2-
-1O- -CH ₂ -O-
-O1- -O-CH _2-
-COO- -COO-
(Ring structure)
(Ring structure)

(Preparation Examples 1 to 16 (Liquid Crystal Compositions 1 to 16))
Liquid crystal compositions (Preparation Examples 1 to 16) having the following compositions were prepared, and their physical properties were measured. The results are shown in Tables 1 and 2 below.

Further, with respect to 99.7 parts by mass of the nematic liquid crystal composition shown in Preparation Examples 1, 2, 6, and 13, the formula (P.1):

The polymerizable monomer-containing liquid crystal composition 1, the polymerizable monomer-containing liquid crystal composition 2, the polymerizable monomer-containing liquid crystal composition 6, and the polymerizable property Monomer-containing liquid crystal composition 13 was prepared.

The physical properties of the polymerizable monomer-containing

liquid crystal compositions

1, 2, 6, and 13 were almost the same as the physical properties of the respective nematic liquid crystal compositions shown in Preparation Examples 1, 2, 6, and 13.

Further, for the nematic liquid crystal composition 99.7% shown in Preparation Examples 9, 12, and 16, the formula (P.2):

A polymerizable monomer-containing liquid crystal composition 9, a polymerizable monomer-containing liquid crystal composition 12, and a polymerizable monomer-containing liquid crystal composition 16 were prepared by adding 0.3% of each of the polymerizable monomers represented by formula (1) and uniformly dissolving them. . The physical properties of the polymerizable monomer-containing

liquid crystal compositions

9, 12, and 16 were almost the same as those of the respective nematic liquid crystal compositions shown in Preparation Examples 9, 12, and 16.

Using the liquid crystal composition of the present invention and the polymerizable monomer-containing liquid crystal composition, an FFS mode / IPS mode liquid crystal display element having a cell thickness of 3.0 μm, which is commonly used for TV, was prepared. It produced by the method like this.

<Photolytic photo-alignment film>
"Photo-alignment film 1"
After dissolving 1.0 mol% of p-phenylenediamine in N-methyl-2-pyrrolidone, 1 mol% of cyclobutanetetracarboxylic dianhydride was added thereto and reacted at 20 ° C. for 12 hours to obtain standard polystyrene. A polyamic acid varnish having a converted weight average molecular weight of about 100,000 and a weight average molecular weight / number average molecular weight (Mv / Mn) of about 1.6 was obtained. Next, after diluting the polyamic acid varnish to a concentration of 6% and adding γ-aminopropyltriethoxysilane in a solid content of 0.3% by weight, the first thin film laminate and the second thin film laminate It was printed on and heated at 210 ° C. for 30 minutes to form a photolytic insulating film (polyimide film).

Thereafter, the photodecomposition type polyimide film was subjected to an alignment treatment for irradiating light (ultraviolet rays) from a polarized UV lamp having a bright line in a wavelength range of 240 nm to 400 nm, for example. This alignment treatment is performed, for example, by irradiating ultraviolet light from a high-pressure mercury lamp with linear irradiation with a polarization ratio of about 20: 1 using a pile polarizer laminated with a quartz substrate and with an irradiation energy of about 4 J / cm ^2. It was.

"Photo-alignment film 2"
(Synthesis of polyamic acid A)
4, 4′-diaminodiphenyl ether 1.0 mol%, dissolved in N-methyl-2-pyrrolidone, 1 mol% of cyclobutanetetracarboxylic dianhydride was added thereto and reacted at 20 ° C. for 12 hours. A polyamic acid A solution having a weight average molecular weight of about 50,000 in terms of standard polystyrene and a weight average molecular weight / number average molecular weight (Mv / Mn) of about 1.6 was obtained.
(Synthesis of polyamic acid B)
4, 4′-diaminodiphenylamine 1.0 mol%, dissolved in N-methyl-2-pyrrolidone, 1 mol% of cyclobutanetetracarboxylic dianhydride was added thereto and reacted at 20 ° C. for 6 hours. A polyamic acid B solution having a standard polystyrene equivalent weight average molecular weight of about 55,000 and a weight average molecular weight / number average molecular weight (Mv / Mn) of about 1.9 was obtained.

(Adjusting the mixture)
The polyamic acid A solution and the polyamic acid B solution are mixed so that the mass ratio of the solid content is 1: 1, and further diluted with a mixed solvent having a mass ratio of N-methyl-2-pyrrolidone and 2-butoxyethanol of 1: 1. As a result, a polyamic acid solution was obtained.

This was printed on the first thin film laminate and the second thin film laminate, and heated at 230 ° C. for 30 minutes to form a photolytic insulating film (polyimide film). Thereafter, light (ultraviolet rays) from the high-pressure ultraviolet lamp is converted into linearly polarized light having an extinction ratio of about 100: 1 using a wire grid polarizer and irradiated with an irradiation energy of 0.5 J / cm ^{2 on} the photolytic polyimide film. I went there.

"Photo-alignment film 3"
(Preparation of solution for photo-alignment film)
32.40 g of N-methyl-2-pyrrolidone was added to 3.24 g of 1,4-phenylenediamine, and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 7.81 g of cyclobutanetetracarboxylic dianhydride was added, and 78.03 g of N-methyl-2-pyrrolidone was added, and the mixture was allowed to react by stirring at 30 ° C. for 18 hours in a nitrogen atmosphere. It was. Further, 62.68 g of a mixed solvent having a mass ratio of N-methyl-2-pyrrolidone and 2-butoxyethanol of 1: 1 was added at room temperature, and the mixture was diluted and stirred to obtain a solution for a photoalignment film.

(Formation of liquid crystal alignment film)
(Formation of photodegradable resin film)
On the comb-shaped transparent electrode formed on the first substrate, the photo-alignment film solution was formed by spin coating to form a resin film having a dry thickness of 0.1 μm. An alignment film was similarly formed on the second substrate. The substrate on which the resin film was formed was reacted at 230 ° C. for 30 minutes to form a photolytic resin film (polyimide film).

(Orientation treatment)
A 256 nm ultraviolet ray is extracted from the high-pressure mercury lamp using a bandpass filter, and is converted into linearly polarized light having an extinction ratio of about 100: 1 using a wire grid polarizer, and 1.0 J / cm ² is applied to the photodecomposable resin film. Photo-alignment treatment was performed by irradiation with irradiation energy. Thereafter, in order to remove the impurities generated by decomposition, after baking at 230 ° C. for 30 minutes, the polyimide film was washed with pure water and dried to obtain a glass substrate on which a photolytic alignment film was formed.

<Photodimerization type photo-alignment film>
"Photo-alignment film 4"
(Synthesis Example 1)
(Synthesis of polymer (PA-1))
In the following reaction route, 10 parts of monomer (I-1-1) synthesized via an intermediate of compounds 1 to 6 is dissolved in 45 parts of tetrahydrofuran (THF), and 0.03 part of azobisisobutyronitrile (AIBN) is dissolved. The solution to which was added was heated to reflux for 8 hours under a nitrogen atmosphere.

Next, the solution after the reaction was dropped and stirred in 600 parts of methanol, and the precipitate was collected and dissolved in 50 parts of THF, and then dropped and stirred in 1200 parts of ice-cooled hexane, and the precipitated solid was collected. The obtained solid was dissolved in 50 parts of THF and stirred dropwise into 1200 parts of ice-cooled methanol. The precipitated solid was collected, dissolved in THF, and then vacuum dried to obtain polymer (PA-1). It was. The obtained polymer (PA-1) had a weight average molecular weight (Mw) of 383,000 and a molecular weight distribution (Mw / Mn) of 2.75.

The molecular weight of the polymer was adjusted by adjusting the heating and reflux time in the nitrogen atmosphere and measuring the weight average molecular weight (Mw).

(Measurement of molecular weight)
Mw and Mn were measured by GPC (gel permeation chromatography) under the following measurement conditions.

Tosoh GPC equipment HLC-8220GPC is used as the measuring device, TSKgel には GMHXL × 2, TSKgel G2000XL × 1 and TSKgel G1000XL × 1 in series for the analytical column, and differential refractive index for the detector. As a standard sample for preparing (RI) detector and calibration curve, polystyrene standard sample STANDARDＡＲSM-105 (molecular weight range 1,300 to 3,800,000) manufactured by Showa Denko was used. The obtained polymer was dissolved in THF so as to have a concentration of 1 μg / mL, and the mobile phase was measured with THF, the liquid feed rate was 1 mL / min, the column temperature was 40 ° C., and the sample injection amount was 300 μL.

(Measurement of glass transition temperature)
The glass transition temperature was measured with a differential scanning calorimeter (DSC). As a measuring apparatus, a DSC apparatus DSC6220 manufactured by Seiko Instruments Inc. was used. When a polymer sample of about 4 mg was sealed in an aluminum pan and heated from −20 ° C. to 180 ° C. at a rate of 10 ° C./min, a baseline shift accompanying a glass transition was observed. The transition start point was read from the intersection of the tangent lines, and used as the glass transition temperature (Tg).

(Formation of liquid crystal alignment film)
(Preparation of photo-dimerization type resin film)
A mixture of 5 parts of the polymer (PA-1), 47.5 parts of N-methylpyrrolidone, and 47.5 parts of 2-butoxyethanol was stirred at room temperature for 10 minutes to be uniformly dissolved. Next, the solution was applied onto a glass substrate using a spin coater, and dried at 100 ° C. for 3 minutes to form a film on the glass substrate. When the formed film was visually observed, it was confirmed that a smooth film was formed.

(Photo-alignment treatment)
Next, a film in which linearly polarized light (illuminance: 10 mW / cm 2) of ultraviolet light (wavelength: 313 nm) is formed using a polarized light irradiation device including an ultra-high pressure mercury lamp, a wavelength cut filter, a band pass filter, and a polarizing filter On the other hand, the photo-alignment film was obtained by performing irradiation for 10 seconds from the vertical direction (irradiation light quantity: 100 mJ / cm 2). A baking process and a washing process were unnecessary. The dry thickness of the resin film was 0.1 μm.

<Photoisomerization type photo-alignment film>
"Photo-alignment film 5"
(Synthesis Example 1) Synthesis of Dichroic Compound (a) To 8.6 g (25 mmol) of 2,2′-benzidine disulfonic acid was added 230 ml of 2% hydrochloric acid, and while maintaining the temperature at 0 to 5 ° C., 3.5 g of sodium nitrite ( 51 mmol) was added dropwise little by little and reacted for 2 hours to prepare a diazonium salt. Next, 6.9 g (50 mmol) of salicylic acid was dissolved in 300 ml of 5% aqueous sodium carbonate solution, and the diazonium salt mixture was gradually added dropwise thereto. After reacting for 1 hour, 20% saline was added to obtain a precipitate. This precipitate was recrystallized with a mixed solvent of ethanol and water to obtain 4.8 g of an azo compound represented by the formula (a).

(Preparation of composition for photo-alignment film (1) for example)
2 parts of the compound represented by the formula (a) were dissolved in 98 parts of N-methyl-2-pyrrolidone (NMP) (solution A). Methylated melamine Sumimar M-100C (hereinafter referred to as M-100C) (manufactured by Changchun Artificial Resin. Hexamethoxymethylated melamine monomer, molecular weight = 390, average polymerization degree is 1.3 to 1.7) 2 parts 98 parts of 2-butoxyethanol (BC) was added to obtain a homogeneous solution (Solution B). 100 parts of solution A, 23 parts of solution B and 77 parts of BC were mixed to prepare a solution having a solid content ratio of 1.0%. The obtained solution was filtered with a 0.45 μm membrane filter to obtain a composition (1) for a photo-alignment film.

(Formation of liquid crystal alignment film)
(Preparation of photoisomerization type resin film)
The composition for photo-alignment film (1) was applied onto a glass substrate with a spin coater and dried at 100 ° C. for 1 minute.

(Photo-alignment treatment)
On the surface of the obtained coating film, ultraviolet light having a wavelength of around 365 nm (irradiation intensity: 10 mW / cm ² ) and parallel light are converted into glass through an ultrahigh pressure mercury lamp through a wavelength cut filter and a polarizing filter. Light irradiation was performed at an irradiation energy of 100 mJ / cm ² from the direction perpendicular to the substrate to obtain a photoalignment film. A baking process and a washing process were unnecessary. The dry thickness of the resin film was 0.1 μm.

<Rubbing type alignment film>
(Rubbing type alignment film)
(Formation of rubbing type polyimide liquid crystal alignment film)
(Preparation of alignment film solution)
59.72 g of N-methyl-2-pyrrolidone was added to 5.98 g of 4,4′-diaminodiphenylamine, and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 6.54 g of pyromellitic dianhydride was added, and 65.30 g of N-methyl-2-pyrrolidone was further added, and the mixture was stirred and reacted at 30 ° C. for 18 hours in a nitrogen atmosphere. Further, 71.06 g of a mixed solvent having a mass ratio of N-methyl-2-pyrrolidone and 2-butoxyethanol of 1: 1 was added at room temperature, and the mixture was diluted and stirred to obtain a polyamic acid solution.

(Formation of liquid crystal alignment film)
(Production of resin film)
The alignment film solution was applied onto the first substrate and the second substrate with a spin coater and reacted by heating at 230 ° C. for 30 minutes to form a polyimide insulating film.

(Orientation treatment)
An alignment treatment was performed by rotating a roller wrapped with a buff cloth in a direction opposite to the substrate transport direction and rubbing the surface of the alignment film formed on the substrate in one direction. The number of rotations of the roller was 600 rpm, the conveyance speed of the substrate was 5 mm / second, and the indentation depth of the buff cloth with respect to the substrate surface was 0.3 mm. Thereafter, the polyimide film was washed with pure water and dried in order to remove the alignment film debris scraped by rubbing and the fiber pieces of the buff cloth.

(Evaluation of display quality)
By using the alignment film as a photo-alignment film, it is possible to provide an FFS liquid crystal display element having excellent transmittance characteristics and capable of reducing a decrease in alignment with liquid crystal molecules due to rubbing unevenness. Since the liquid crystal alignment was evaluated by various photo-alignment films, the evaluation method will be described below.

A thin film transistor and a transparent electrode layer are formed on the first substrate, and an alignment film is formed thereon. When an alignment treatment is performed using a rubbing method which is a contact method, random scratches are formed on the alignment film surface by rubbing. In particular, in the first substrate on which the thin film transistor and the transparent electrode layer pattern are formed, deeper scratches due to the steps due to the thin film transistor and the transparent electrode layer pattern and the diameter (tens of μm) of the fiber of the buffing cloth of the rubbing roller , Easy to be formed along the step. Since the liquid crystal molecules cannot be aligned in a certain direction when the electric field is turned off at the portion where the scratch is formed, light leakage occurs in the liquid crystal panel during black display. As a result, it becomes difficult to obtain a contrast of a certain value or more.

Furthermore, in a resolution mode called 4K, which has been put into practical use in recent years, a one-pixel size is 0.23 mm in a calculation example in a 40-inch panel. In a resolution mode called 8K, which will be put to practical use later, in a calculation example in a 40-inch panel, the size of one pixel becomes as fine as 0.11 mm. That is, since the size of one pixel approaches the diameter of the buff cloth fiber of the rubbing roller, when the electric field is turned off in units of pixels or in units of intermittent pixel rows due to scratches formed when the alignment treatment is performed by the rubbing method. There are places where the liquid crystal molecules cannot be aligned in a certain direction, which may cause a significant decrease in contrast and a large number of display defects due to a large amount of light leakage during black display.

Therefore, by performing non-contact alignment processing by the photo-alignment method, scratches are not generated on the surface of the alignment film, so that high contrast and clear black display without light leakage can be realized.

An alignment film solution was formed on the comb-shaped transparent electrode formed on the first substrate by a spin coating method to form an alignment film having a dry thickness of 0.1 μm. An alignment film was similarly formed on the second substrate.

(Production of liquid crystal cell)
A liquid crystal cell was produced using the glass substrate provided with the liquid crystal alignment film. More specifically, the first substrate and the second substrate on which the alignment films are respectively formed, the liquid crystal alignment films face each other, and the direction in which the linearly polarized light is irradiated or rubbed is the antiparallel direction (180 °). The peripheral part was pasted with a sealing agent in a state where a constant gap (4 μm) was maintained between the two substrates. Next, the liquid crystal composition (Preparation Examples 1 to 12) and the polymerizable monomer-containing

liquid crystal compositions

1, 2, 6, 9 and 12 in the above table are placed in the cell gap defined by the surface of the liquid crystal alignment film and the sealant. Each liquid crystal cell was produced by filling at a temperature just above the clearing point by a dropping method and then cooling to room temperature.

In the case of polymerizable monomer-containing

liquid crystal compositions

1, 2, 6, 9 and 12, after preparing a liquid crystal cell in the same manner as described above, after measuring the pretilt angle (crystal rotation method) of this liquid crystal cell, the frequency was 1 kHz. While applying a 1.8 V rectangular wave, the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp (FL15UV34A (NP805) manufactured by Toshiba Lighting & Technology Corp.) through a filter that cuts ultraviolet rays of 320 nm or less. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm ² and irradiated for 700 seconds to obtain a horizontal alignment liquid crystal display element in which the polymerizable monomer in the polymerizable monomer-containing liquid crystal composition was polymerized.

Tables 3 to 8 below show examples of combinations of the alignment films used in the produced liquid crystal cells (liquid crystal display elements) and the liquid crystal compositions or polymerizable monomer-containing liquid crystal compositions used (Examples 1 to 24 and Comparative Examples). 1-2), the static contrast (CRS) evaluation results of the prepared liquid crystal cell, and the results of VHR measurement are shown in Tables 3 to 8 below.

The measurement method of static contrast (CRS) is shown below.

Polarizer-analyzer of optical measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.) equipped with white light source, spectroscope, polarizer (incident side polarizing plate), analyzer (exit side polarizing plate), detector In the meantime, the optical film to be measured was placed. Here, in a state where the rotation angle between the polarizer and the analyzer is 0 degree (the polarization direction of the polarizer and the analyzer is the parallel position [parallel Nicol]), the transmitted light is transmitted by the detector while rotating the optical film. The amount of transmitted light (on-time light amount) at the rotational position of the optical film (the polarization direction of the polarizer and the molecular long axis direction of the polymerizable liquid crystal are parallel) where the detected light amount becomes the largest is Yon. It was. In addition, with the position of the polarizer and the optical film fixed, the rotation angle of the analyzer with respect to the polarizer is 90 degrees (the polarization direction of the polarizer and the analyzer is the orthogonal position [cross Nicol]). The amount of light (light amount when off) was set to Yoff. Contrast CRS was calculated | required by following Formula (Formula 1).

CRS = Yon / Yoff ... (Formula 1)
The larger the numerical value of the static contrast CRS in (Expression 1), the smaller the off-time light amount Yoff, that is, the smaller the amount of light leakage, and the better the black display.

As a result, the FFSI / IPS mode display elements (Examples 1 to 24) manufactured by forming the photo-alignment film are the FFS mode display elements (Comparative Examples 1 and 2) manufactured by forming the rubbing alignment film. ), The contrast was excellent. More specifically, when Examples 1 to 24 are compared with Comparative Examples 1 and 2, it is confirmed that the contrast ratio and VHR are improved when the photo-alignment film is used. In addition, when a monomer is added to the liquid crystal composition, VHR is unlikely to decrease, so it is considered that the polymer obtained by polymerizing the monomer traps ions in the liquid crystal composition. In particular, in the rubbing alignment film, it is considered that there are more ionic components, impurities, and the like derived from the rubbing process than in the photo-alignment film.

Further, the liquid crystal display elements of Examples 1 to 24 were subjected to the following alignment regulating force (anchoring) measurement.

Using the above-mentioned liquid crystal display element, the azimuth anchoring energy at the interface between the liquid crystal alignment film surface and the liquid crystal layer is expressed by the following method called the torque balance method (Proc. The method reported on pages 251 to 252).

As a result, it was confirmed that the liquid crystal display elements of Examples 1 to 24 had an alignment regulating force necessary for aligning the liquid crystal compounds. In particular, the liquid crystal display elements of Examples 17 to 24 were As a result of polymerization of the polymerizable monomer, it was confirmed that the alignment regulating power of the photo-alignment film with respect to the liquid crystal compound was very good. It was confirmed that the horizontal alignment liquid crystal display device has excellent optical characteristics and high-speed response.

DESCRIPTION OF SYMBOLS 1a Liquid crystal molecule 1b Polymerizable monomer 1c Polymer which polymerized polymerizable monomer 100 1st board | substrate 102 TFT layer 103 Pixel electrode 104 Passivation film 105 1st alignment film 200 2nd board | substrate 201 Planarization film (overcoat layer)
202 Black matrix 203 Color filter 204 Transparent electrode 205 Second alignment film 301 Seal material 302 Projection (columnar spacer)
303 Liquid crystal layer 304 Protrusion (columnar spacer)
401 mask pattern 402 resin

layer L light

1,8 polarizing plate 2 first substrate 3 electrode layer 4 alignment film 5 liquid crystal layer 6 color filter 6G color filter green 6R color filter red 6B color filter blue 7 second substrate 11 gate electrode DESCRIPTION OF SYMBOLS 12 Gate insulating film 13 Semiconductor layer 14 Insulating layer 15 Ohmic contact layer 16 Drain electrode 17 Source electrode 18 Insulating protective layer 21 Pixel electrode 22 Common electrode 23 Storage capacitor 24 Drain electrode 25 Data wiring 27 Source wiring 29 Common line 30 Buffer layer

Claims

A first substrate and a second substrate disposed opposite to each other;
A liquid crystal layer containing a liquid crystal composition filled between the first substrate and the second substrate;
Driven by the common electrode, a plurality of gate bus lines and data bus lines arranged in a matrix, a thin film transistor provided at an intersection of the gate bus line and the data bus line, and the thin film transistor on the first substrate. An electrode layer having a pixel electrode for each pixel that forms an electric field substantially parallel to the substrate with the common electrode;
A photo-alignment layer formed on at least one substrate between the liquid crystal layer and the first substrate and the liquid crystal layer and the second substrate;
The liquid crystal composition has a positive dielectric anisotropy, a nematic phase-isotropic liquid transition temperature of 60 ° C. or higher, and represented by the general formula (i):

(In the general formula (i), R i1 and R i2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or Represents an alkenyloxy group having 2 to 8 carbon atoms, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkoxy group or alkenyloxy group may be substituted with a fluorine atom. The methylene group in the group, alkoxy group or alkenyloxy group may be substituted with an oxygen atom unless the oxygen atom is continuously bonded, and may be substituted with a carbonyl group unless the carbonyl group is continuously bonded. ,
A i1 is, (a) 1,4-cyclohexylene group (the one present in the group -CH 2 - or nonadjacent two or more -CH 2 - may be replaced by -O- Good.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═) and (c) (C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) are each independently selected from the group consisting of cyano group, fluorine atom, chlorine atom, methyl group, trifluoromethyl group or trifluoro May be substituted with a methoxy group,
n i1 represents 1, 2, 3 or 4, and when n i1 is 2, 3 or 4, and there are a plurality of A i1 , they may be the same or different, and n i1 is When it is 2, 3 or 4 and a plurality of Z i1 are present, they may be the same or different. ) Or one or more compounds selected from the compounds represented by the formula (J)

(Wherein R J1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH 2 — in the alkyl group are each independently —CH═CH—, — Optionally substituted by C≡C—, —O—, —CO—, —COO— or —OCO—,
n J1 represents 0, 1, 2, 3 or 4;
A J1 , A J2 and A J3 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 - may be replaced by -O-.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═) and (c) (C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) are each independently selected from the group consisting of cyano group, fluorine atom, chlorine atom, methyl group, trifluoromethyl group or trifluoro May be substituted with a methoxy group,
Z J1 and Z J2 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, Represents —COO—, —OCO— or —C≡C—,
When n J1 is 2, 3 or 4 and a plurality of A J2 are present, they may be the same or different, and n J1 is 2, 3 or 4 and a plurality of Z J1 is present. If they are the same or different,
X J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. A horizontal alignment type liquid crystal display element comprising one or more selected from compounds represented by the formula:
The liquid crystal display element according to claim 1, wherein the pixel electrode has a comb shape or a slit.
The liquid crystal display element according to claim 1, wherein an interelectrode distance R between the pixel electrode and the common electrode is smaller than a distance G between the first substrate and the second substrate.
The liquid crystal display element according to claim 1, wherein an interelectrode distance R between the pixel electrode and the common electrode is longer than a distance G between the first substrate and the second substrate.
The liquid crystal display element according to claim 1, wherein the photo-alignment layer is of a photolytic type.
6. The liquid crystal display device according to claim 1, wherein the liquid crystal layer contains a cured product of a polymerizable monomer in the liquid crystal composition.
4. The liquid crystal display according to claim 3, wherein the inter-electrode distance (R) is 0, and the common electrode is disposed on a substantially entire surface of the first substrate at a position closer to the first substrate than the pixel electrode. element.