TW201723538A - Liquid crystal display element - Google Patents

Abstract

The present invention addresses the problem of providing a liquid crystal display element that is provided with a photoalignment film and that does not adversely affect the burn-in characteristics of the 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 [gamma]1. 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 (M). The liquid crystal display element comprises a photoalignement film, 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 having a positive dielectric (Δε) positive value as a liquid crystal display material.

At present, as a liquid crystal display for smart phones, a liquid crystal display element of an IPS mode or an FFS mode liquid crystal display element (Fringe Field Switching mode Liquid Crystal Display element) having high quality and excellent visual characteristics is widely used (refer to Patent Document 1 and Patent Document 2). The FFS mode is introduced in order to improve the aperture ratio and the transmittance of the IPS mode. As a liquid crystal composition to be used, it is easy to reduce the voltage. A material of a liquid crystal composition. In addition, since most of the applications of the FFS mode are portable terminals, the industry is strongly demanding further power saving, and liquid crystal component manufacturers are continuing to actively develop and use arrays using IGZO.

Further, as a method of aligning liquid crystal molecules, a method called a rubbing method is often used. This method is a film obtained by coating an oriented film material such as polyimide and firing it, and pressing it while pressing a roll of a cloth such as nylon under a constant pressure, thereby wiping in a certain direction (friction) Orienting the surface of the film, thereby imparting an orientation limiting force to the liquid crystal molecules. The tight orientation mechanism of this method is not clear now, and there is a streaky appearance due to wiping the surface of the oriented film. In the case where unevenness is observed, one of the alignment film materials is partially removed, and the liquid crystal layer is mixed into the liquid crystal layer, and the TFT is broken due to static electricity generated on the array substrate, and the orientation imparting method without using friction is studied. In particular, the use of linearly polarized ultraviolet light to impart anisotropic light-oriented film to the orientation can be imparted without contact, and thus development as a method for solving the above-mentioned friction method is progressing even if The use of a light directing film has also been gradually explored in a lateral electric field type display element (see Patent Document 3).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-202356

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-233083

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-109366

However, due to the expansion of the use or market of liquid crystal display elements in recent years, the methods of use and manufacturing methods have also seen significant changes, not only the driving methods of liquid crystal display elements (for example, TN type, STN type, VA type, IPS type, FFS type, etc., and a display element of an ultra-large size having a size of 50 or more is put into practical use. Accordingly, the method of injecting the liquid crystal composition into the substrate is also changed into a droplet of the liquid crystal composition by a conventional vacuum injection method. The drop drop injection method (ODF, One Drop Fill) which is added to one substrate surface and bonded to another substrate becomes the mainstream of the injection method. Further, if a vertical electric field type such as a VA mode (for example, VA-IPS) is compared with a horizontal electric field type such as an IPS mode or an FFS mode, the orientation change of the liquid crystal molecules is regarded as an essential optical characteristic. The difference is not the same.

Therefore, as described in the above Patent Documents 1 to 3, the electrodes of the IPS mode or the FFS mode are arranged in parallel with a plurality of short strip electrodes provided on the surface of the substrate on one side, and the alignment film is coated on the entire surface of the substrate surface. Therefore, there are innumerable concavities and convexities on the surface of the substrate on the one side, and the structure causes a dripping mark to be formed on the substrate when the liquid crystal composition is dropped onto the surface of the substrate, and the problem of the display quality is lowered due to the dropping of the liquid crystal. It has to be superficial.

Further, not only the vertical electric field type, but also the manufacturing steps of the horizontal electric field type liquid crystal display element such as the IPS mode or the FFS mode, it is necessary to drop the optimum liquid crystal injection amount according to the size of the liquid crystal display element by the ODF method. Therefore, when the injection amount is deviated from the optimum value, the balance between the refractive index of the liquid crystal display element designed in advance or the driving electric field is collapsed, and display defects such as unevenness or poor contrast are generated. In particular, small liquid crystal display elements which are mostly used in recently popular smart phones have a relatively small amount of liquid crystal injection, and it is difficult to control the deviation from the optimum value within a certain range. Therefore, in order to keep the yield of the liquid crystal display element high, for example, it is necessary to add a small amount of influence to the severe pressure change or impact in the dropping device when the liquid crystal is dropped, and it is possible to stably continue to drip for a long time. Add liquid crystal performance. In addition to such problems, compatibility with an alignment film that is in direct contact with the liquid crystal composition is also a problem.

Therefore, in the liquid crystal composition used for driving the liquid crystal display element by the active matrix driven by the TFT element or the like, in addition to maintaining high-speed response performance or the like as a characteristic or performance required for the liquid crystal display element, it has been emphasized from the past. In addition to the higher specific resistance value or higher voltage holding ratio, or the stability to external stimuli such as light or heat, development of a manufacturing method of a liquid crystal display element is required. Moreover, in the case of a vertical orientation type such as the VA-IPS mode, the problem of viewing angle dependence is caused, but the conventional friction method is The cloth on the roll wipes the entire process of the substrate, and there is a problem that it is difficult to achieve the orientation division. Further, since the light directing film is always irradiated with the backlight, there is a problem that the contrast is degraded over time due to deterioration or the like.

Accordingly, an object of the present invention is to solve the above problems and to provide a dielectric transition (Δε), a viscosity (η), a nematic phase-isotropic liquid transition temperature (Tni), and a nematic phase stability at a low temperature. The p-type liquid crystal composition which exhibits excellent display characteristics (contrast, etc.) by a liquid crystal display element which has a photo-alignment film is excellent in the characteristic of a liquid crystal display element, and is used. Vertically oriented liquid crystal display element.

In order to solve the above problems, the inventors of the present invention have studied the composition of the liquid crystal display element and the composition of various liquid crystal compositions or photo-alignment films which are optimal for the liquid crystal display element, and as a result, completed the present invention.

Since the liquid crystal display element of the present invention has a small change in specific resistance or voltage holding ratio due to heat or light, the product has high practicability and can achieve high-speed response. The liquid crystal display device of the present invention is excellent in reliability and high-speed response.

Since the liquid crystal composition of the present invention can stably exhibit performance in the production steps of the liquid crystal display element to be used, it is very useful because the display defects caused by the steps are suppressed and can be produced at a high yield.

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

The invention can provide a light setting with improved directional restriction force of liquid crystal molecules Liquid crystal display element to the film.

The liquid crystal display element of the present invention can achieve a high contrast excellent in orientation limiting force.

The liquid crystal display element of the present invention can maintain high contrast for a long period of time.

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

100‧‧‧1st substrate

102‧‧‧TFT layer

103‧‧‧pixel electrode

104‧‧‧passivation film

105‧‧‧1st oriented film

200‧‧‧2nd substrate

201‧‧‧Flating film (protective layer)

202‧‧‧Black matrix

203‧‧‧Color filters

204‧‧‧Transparent electrode

205‧‧‧2nd oriented film

301‧‧‧ sealing material

302‧‧‧protrusions (columnar spacers)

303‧‧‧Liquid layer

304‧‧‧protrusion (columnar spacer)

401‧‧‧ mask pattern

402‧‧‧ resin layer

L‧‧‧Light

1, 8‧‧‧ polarizing plate

2‧‧‧First substrate

3‧‧‧electrode layer

4‧‧‧ Orientation film

5‧‧‧Liquid layer

6‧‧‧Color filters

6G‧‧‧Color Filter Green

6R‧‧‧Color Filter Red

7‧‧‧second substrate

11‧‧‧ gate electrode

12‧‧‧Gate insulation film

13‧‧‧Semiconductor layer

14‧‧‧Insulation

15‧‧‧Ohm contact layer

16‧‧‧汲electrode

17‧‧‧Source electrode

18‧‧‧Insulating protective layer

21‧‧‧pixel electrode

22‧‧‧Common electrode

23‧‧‧Storage capacitor

24‧‧‧汲electrode

25‧‧‧Data wiring

27‧‧‧Source wiring

29‧‧‧Shared line

30‧‧‧buffer layer

Fig. 1 is a view schematically showing an example of the configuration of a liquid crystal display element of the present invention.

Fig. 2 is a plan view showing an enlarged region of the electrode layer 3 formed on the substrate 2 in Fig. 1 surrounded by a line II.

Fig. 3 is a cross-sectional view showing the liquid crystal display element shown in Fig. 1 taken along the line III-III in Fig. 2;

Fig. 4 is a plan view showing a modification of Fig. 2 in which a region surrounded by an II line of the electrode layer 3 formed on the substrate 2 in Fig. 1 is enlarged.

Fig. 5 is a cross-sectional view showing the liquid crystal display element of Fig. 1 taken along the line III-III in Fig. 4;

Fig. 6 is a cross-sectional view schematically showing the state before and after polymerization of the liquid crystal display element of the present invention.

Figure 7 is a cross-sectional view schematically showing the vicinity of the interface between the light-aligning film and the liquid crystal layer of the liquid crystal display element of the present invention.

The first aspect of the present invention is a vertical alignment type liquid crystal display device having: a first substrate and a second substrate disposed opposite to each other; and a liquid crystal layer including a liquid crystal filled between the first substrate and the second substrate The electrode layer has a plurality of gate bus lines and data bus lines arranged in a matrix on each of the pixels on the first substrate, and is disposed at the intersection of the gate bus line and the data bus line. a thin film transistor and a pixel electrode driven by the thin film transistor; a common electrode formed on the first substrate or the second substrate; and a light alignment layer formed on the liquid crystal layer and the first substrate And at least one of the liquid crystal layer and the second substrate, wherein the liquid crystal composition has positive dielectric conductivity, and the transition temperature of the nematic phase-isotropic liquid is 60° C. or higher, and is selected from the group consisting of Formula (i)

(In the above formula (i), R ⁱ¹ and R ⁱ² each independently represent 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 carbon. One or more alkenyloxy groups having 2 to 8 atoms, and one or more hydrogen atoms of the alkyl group, alkenyl group, alkoxy group or alkenyloxy group may be substituted with a fluorine atom, the alkyl group, an alkenyl group, an alkoxy group or The methylene group in the alkenyloxy group may be substituted with an oxygen atom as long as the oxygen atom is discontinuously bonded, and may be substituted into a carbonyl group as long as the carbonyl group is discontinuously bonded, and A ⁱ¹ is selected from (a) 1,4-extension. a cyclohexyl group (one -CH ₂ - or two or more -CH ₂ - which are not adjacent to the group may be substituted with -O-) (b) 1,4-phenylene group (present in the group) One of -CH= or two or more adjacent -CH= can be substituted with -N=) and (c)naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene -2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl) One -CH= or two or more non-contiguous -CH= can be replaced by -N=)

The group in the group formed, the above-mentioned group (a), group (b) and group (c) may independently pass through a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group. Substituent, Z ⁱ¹ represents a single bond, -OCH ₂ -, -OCF ₂ -, -CH ₂ O- or CF ₂ O-, n ⁱ¹ represents 1, ₂ , 3 or 4, and n ⁱ¹ is 2, 3 or 4 In the case where there are a plurality of A ⁱ¹ , the same may be different, and when n ⁱ¹ is 2, 3 or 4 and there are multiple Z ⁱ¹ , the compounds may be the same or different) One or more compounds, and a formula (J) selected from the group consisting of

(wherein, R ^J1 represents an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent -CH ₂ - may be independently substituted with -CH=CH-, - C≡C-, -O-, -CO-, -COO- or -OCO-, n ^J1 represents 0, 1, 2, 3 or 4, and A ^J1 , A ^J2 and A ^J3 are independently represented by (a) ) 1,4-cyclohexylene group (in the presence of a group -CH ₂ - not adjacent two or more of the -CH ₂ - may be substituted with -O -) (b) 1,4- extending benzene a group (one present in the group -CH= or two or more adjacent to -CH= may be substituted with -N=) and (c) naphthalene-2,6-diyl, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2, One of the 6-diyl groups -CH= or two or more non-contiguous -CH= can be replaced by -N=)

The group in the group formed, the above-mentioned group (a), group (b) and group (c) may independently pass through a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group. Substituting, Z ^J1 and Z ^J2 each independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O -, -COO-, -OCO- or -C≡C-, when n ^J1 is 2, 3 or 4 and there are multiple A ^J2 , the same or different, and n ^J1 is 2, 3 Or 4, in the case where a plurality of Z ^J1 are present, the same may be different, and X ^J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group. One or more of the compounds represented by trifluoromethoxy or 2,2,2-trifluoroethyl).

The structure of the liquid crystal display element of the present invention will be described with reference to Figs. 1 to 5, and a substrate and an electrode layer which are constituent elements of the liquid crystal display element will be described. Next, the constituent elements of the liquid crystal display element will be described in detail with respect to the liquid crystal layer and the photo-alignment film layer.

Hereinafter, an embodiment of the liquid crystal display element of the present invention will be described based on the drawings.

Fig. 1 is a view schematically showing the configuration of a liquid crystal display element. In Figure 1, it is For the sake of explanation, each component is described separately. The liquid crystal display device 10 of the present invention has a configuration as shown in FIG. 1, and is characterized in that it has a liquid crystal sandwiched between a first (transparent insulating) substrate 2 and a second (transparent insulating) substrate 7 which are disposed opposite each other. A VA-IPS and/or VA-FFS mode liquid crystal display element of the composition (or the liquid crystal layer 5), and the liquid crystal composition of the present invention described above is used as the liquid crystal composition. The electrode layer 3 is formed on the surface of the first transparent insulating substrate 2 on the liquid crystal layer 5 side. Further, between the liquid crystal layer 5 and the first transparent insulating substrate 2 and the second transparent insulating substrate 7, there is a direct contact with the liquid crystal composition constituting the liquid crystal layer 5 to cause a vertical alignment of the light alignment film (or Referring to the light-aligning layer 4, the liquid crystal molecules in the liquid crystal composition are oriented substantially parallel to the substrates 2, 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 by a pair of polarizing plates 1 and 8. Further, in FIGS. 1 and 3, a color filter 6 is provided between the second substrate 7 and the alignment film 4. Further, as a form of the liquid crystal display element of the present invention, a so-called integrated color filter (COA) may be used, or a color filter may be provided between the electrode layer including the thin film transistor and the liquid crystal layer, or A color filter is disposed between the electrode layer containing the thin film transistor and the second substrate.

Further, in FIGS. 1 to 5, a preferred embodiment of the liquid crystal display device of the present invention is described between the liquid crystal layer 5 and the first substrate 2 and between the liquid crystal layer 5 and the second substrate 7. An example in which the light directing film 4 is formed on the first substrate and the second substrate, respectively, but the liquid crystal display element of the present invention may be formed with the light directing film 4 on at least one of the first substrate 2 and the second substrate 7. .

For example, when the light directing film 4 is formed on the first substrate 2 in contact with the liquid crystal layer 5 between the liquid crystal layer 5 and the first substrate 2, the liquid crystal layer 5 and the second substrate 7 are not An orientation film is separately provided, preferably a light alignment film or a rubbing alignment film is formed, and more preferably A light directing film is formed.

That is, the liquid crystal display element 10 of the present invention preferably sequentially laminates the first polarizing plate 1, the first substrate 2, the electrode layer 3 including the thin film transistor, the alignment film 4, the liquid crystal layer 5 containing the liquid crystal composition, and the alignment film. 4. The color filter 6, the second substrate 7, and the second polarizing plate 8 are formed. In the case where the electrode layer 3 is used as the pixel electrode, a new electrode layer may be separately disposed between the electrode layer 3 and the substrate 2, and the new electrode layer may be used as a common electrode, or the electrode layer 3 may also represent a pixel electrode and a common electrode. Both. Representative examples of the former are shown in Figs. 2 to 5, for example. As an example of the latter, for example, a configuration may be adopted in which a pair of comb-shaped electrodes are arranged to be spaced apart from each other, and one of the electrodes is used as a pixel electrode, the other electrode is used as a common electrode, and the cross section is a pixel electrode. Alternate with the common electrode.

The first substrate 2 and the second substrate 7 may be made of glass or a transparent material such as plastic, or one of them may be an opaque material such as tantalum. The two substrates 2 and 7 are bonded together by a sealing material such as an epoxy thermosetting composition disposed in a peripheral region, and a sealing material. For example, glass particles, plastic particles, and alumina may be disposed therebetween. A granular spacer such as a particle or a spacer formed of a resin formed by photolithography. The substrate of the present invention preferably contains a transparent conductive material.

Fig. 2 is a plan view showing an enlarged region of the electrode layer 3 formed on the substrate 2 in Fig. 1 surrounded by a line II. Fig. 3 is a cross-sectional view showing the liquid crystal display element shown in Fig. 1 taken along the line III-III in Fig. 2; As shown in FIG. 2, the electrode layer 3 including the thin film transistor formed on the surface of the first substrate 2 is used to supply a plurality of gate bus bars 26 for scanning signals and a plurality of data bus bars for supplying display signals. The lines 25 are arranged in a matrix shape so as to intersect each other. Furthermore, only a pair of gate bus bars 26 and a pair of data bus bars 25 are shown in FIG.

A unit pixel of the liquid crystal display device is formed by a region surrounded by a plurality of gate bus bars 26 and a plurality of data bus bars 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 portion where the gate bus bar 26 and the data bus bar 25 cross each other. The thin film transistor is connected to the pixel electrode 21 as a switching element that supplies a display signal to the pixel electrode 21. Further, a common line 29 is provided in parallel with the gate bus bar 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 has, for example, a gate electrode 11 formed on the surface of the substrate 2, and is provided so as to cover the gate electrode 11 and cover substantially the entire surface of the substrate 2. a gate insulating layer 12; a semiconductor layer 13 formed on a surface of the gate insulating layer 12 opposite to the gate electrode 11; and a protective layer 14 provided to cover a portion of a surface of the semiconductor layer 13. a drain electrode 16 disposed to cover a side end portion of one of the protective layer 14 and the semiconductor layer 13 and in contact with the gate insulating layer 12 formed on the surface of the substrate 2 to cover the protective layer And a source electrode 17 disposed to be in contact with the gate insulating layer 12 formed on the surface of the substrate 2; and covering the gate electrode 16 and the source An insulating protective layer 18 is provided in the form of a pole electrode 17. An anodic oxide film (not shown) may be formed on the surface of the gate electrode 11 for reasons such as eliminating the step difference from the gate electrode.

As the semiconductor layer 13, amorphous germanium, polycrystalline germanium or the like can be used. When a transparent semiconductor film such as ZnO, IGZO (In-Ga-Zn-O) or ITO is used, the disadvantages of the optical carrier caused by light absorption can be suppressed, and the thickness is increased. It is also preferable from the viewpoint of the aperture ratio of the element.

Furthermore, in order to reduce the width or height of the Schottky barrier, it is also possible to An ohmic contact layer 15 is provided between the drain electrode 16 and the source electrode 17 respectively. As the ohmic contact layer, a material in which an impurity such as phosphorus is added at a high concentration such as an n-type amorphous germanium or an n-type polycrystalline germanium can be used.

The gate bus bar 26 or the data bus bar 25 and the common line 29 are preferably metal films, more preferably Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or alloys thereof. It is especially preferable to use wiring of Al or its alloy. Further, the insulating protective layer 18 is a layer having an insulating function and is formed of tantalum nitride, hafnium oxide, hafnium oxynitride film or the like.

In the embodiment shown in FIG. 2 and FIG. 3, the common electrode 22 is a flat electrode formed on substantially the entire surface of the gate insulating layer 12. On the other hand, the pixel electrode 21 covers the common electrode 22. A comb-shaped electrode formed on the insulating protective layer 18. That is, the common electrode 22 is disposed closer to the first substrate 2 than the pixel electrode 21, and the electrodes are disposed so as to overlap each other with the edge protection layer 18. The pixel electrode 21 and the common electrode 22 are formed of, for example, a transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), or IZTO (Indium Zinc Tin Oxide). Since the pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material, the area of the opening in the unit pixel area is increased, and the aperture ratio and the transmittance are increased.

Moreover, in FIG. 3, the pixel electrode 21 and the common electrode 22 form a lateral fringe electric field between the electrodes, and the electrode spacing (also referred to as a minimum separation distance) between the pixel electrode 21 and the common electrode 22 is short. The distance between the first substrate 2 and the second substrate 7 is: G. Here, the electrode pitch: R indicates the distance in the horizontal direction with respect to the substrate between the electrodes. Further, in FIG. 3, since the flat-shaped common electrode 22 and the comb-shaped pixel electrode 21 overlap each other, in order to show an electrode pitch: R=0, since the minimum separation distance: R is smaller than the first substrate 2 and the The distance between the two substrates 7 (i.e., cell gap): G, thus forming a lateral fringe electric field E. Therefore, the liquid crystal display element can be made to be perpendicular to the line of the comb shape with respect to the pixel electrode 21 formed. An electric field in the horizontal direction and a parabolic electric field. The electrode width of the comb portion of the pixel electrode 21: 1, and the width of the gap of the comb portion of the pixel electrode 21: m is preferably such that the liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. The width is formed.

The liquid crystal display device of the present invention preferably has a liquid crystal display composition of the VA-IPS mode. If the shortest separation distance R between the adjacent electrodes of the common electrode 22 and the pixel electrode 21 is shorter than the shortest separation distance G between the alignment layers 4 (substrate pitch), then A lateral fringe electric field can be formed between the common electrode and the pixel electrode, and the orientation of the liquid crystal molecules in the horizontal direction and the vertical direction can be utilized efficiently. In a VA-IPS (or VA-FFS) type liquid crystal display device which is a preferred embodiment of the present invention, in a state where no external electric field exists, the long axis direction of the liquid crystal molecules is (substantially) perpendicular to the substrate. Way orientation. When a voltage is applied to the liquid crystal molecules, an equipotential line of a parabolic electric field between the pixel electrode 21 and the common electrode 22 is formed to the upper portion of the pixel electrode 21 and the common electrode 22, and the long axis of the liquid crystal molecules in the liquid crystal layer 5 The resulting electric field is aligned. In particular, since the liquid crystal composition of the present invention uses liquid crystal molecules having positive dielectric conductivity, the long axis directions of the liquid crystal molecules are aligned in the direction of the generated electric field. In the case of such a VA-IPS (or VA-FFS) method, since the long-axis direction of the liquid crystal molecules is aligned in a direction perpendicular to the substrate without applying a voltage, if a voltage is applied, the liquid crystal molecules are opposite to each other. Since the substrates are arranged in a substantially parallel direction, they are not arranged in a state of being parallel to the substrate as in the conventional IPS method. Therefore, in the case of the VA-IPS (or VA-FFS) method, if the voltage is not applied, the liquid crystal molecules are likely to return to a substantially vertical state with respect to the substrate without being substantially parallel to the substrate. The problem of the state. However, in the case where the liquid crystal composition containing a polymerizable compound and polymerizing the polymerizable compound described below is provided (FIG. 7 and FIG. 8), the alignment film is easily formed. The liquid crystal molecules are vertically induced to be immobilized, so that the restraining force with respect to the vertical direction of the substrate is increased. As a result, the problem that the liquid crystal molecules do not return to the original state is also improved.

From the viewpoint of preventing light leakage, the color filter 6 preferably forms a black matrix (not shown) corresponding to a portion corresponding to the thin film transistor and the storage capacitor 23.

The electrode layer 3 and the color filter 6 are directly in contact with the liquid crystal composition constituting the liquid crystal layer 5, and one of the induced vertical alignments is provided to the light directing film 4.

By setting the alignment film as the light-aligning film, it is possible to reduce the decrease in the alignment regulating force against the liquid crystal molecules caused by the unevenness in friction, and to provide a liquid crystal display element of the VA-IPS type having excellent transmittance characteristics.

Further, the polarizing plate 1 and the polarizing plate 8 can be adjusted so that the polarization axes of the respective polarizing plates are adjusted to improve the viewing angle or the contrast, and it is preferable that the transmission axes have a mutual movement in the normally black mode. Orthogonal penetration axis. It is particularly preferable that either of the polarizing plate 1 and the polarizing plate 8 is disposed so as to have a transmission axis parallel to the orientation 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. Further, a retardation film for expanding the viewing angle may also be used.

Further, in the liquid crystal display device of the present invention, it is preferable that the common electrode is formed on substantially the entire surface of the first substrate and disposed closer to the first substrate than the pixel electrode. That is, a preferred embodiment of the liquid crystal display device of the present invention includes: a first substrate and a second substrate disposed opposite to each other; and a liquid crystal layer including a liquid crystal composition filled between the first substrate and the second substrate; The electrode layer has a common electrode including a transparent conductive material, a plurality of gate bus lines arranged in a matrix, and a data bus line on each of the pixels on the first substrate, and is disposed on the gate bus line and a thin film transistor at the intersection of the data bus and a transparent conductive material a pixel electrode driven by the thin film transistor to form a lateral fringe electric field between the common electrode; and a light directing layer respectively formed between the liquid crystal layer and the first substrate and the second substrate and induced to be vertically oriented And an electrode spacing R between the pixel electrode and the common electrode is smaller than a distance G between the first substrate and the second substrate, wherein the common electrode is formed on substantially the entire surface of the first substrate, and is disposed closer to the pixel electrode One substrate side. Further, in FIGS. 1 to 3 which are one embodiment of the present invention, the common electrode is formed on substantially the entire surface of the first substrate, and is disposed closer to the first substrate than the pixel electrode.

The VA-IPS type liquid crystal display element described with reference to FIGS. 1 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 device of the present invention will be described below with reference to Figs. 4 and 5 . For example, FIG. 4 is a plan view showing an area surrounded by the line II of the electrode layer 3 formed on the substrate 2 in FIG. 1, and is an embodiment of another liquid crystal display element. As shown in FIG. 4, the pixel electrode 21 may also have a slit. Further, the pattern of the slits may be formed so as to have an inclination angle with respect to the gate bus bar 26 or the data bus bar 25.

The pixel electrode 21 shown in FIG. 4 has a shape in which a substantially rectangular frame-shaped cutout portion is punched through an electrode of a substantially rectangular plate body. Further, a common electrode 22 having a comb shape is formed by interposing the edge layer 18 (not shown) over the entire back surface of the pixel electrode 21. Further, 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 (in FIG. 4, for convenience, R seems to be shorter than G, and actually R is longer than G). Further, it is preferable that the surface of the pixel electrode is covered with a protective insulating film and an alignment film layer. Furthermore, a storage capacitor (not shown) for storing the supplied display signal may be disposed in a region surrounded by the plurality of gate bus bars 25 and the plurality of data bus bars 26 via the data bus bar 26 . . Furthermore, The shape of the cutout portion is not particularly limited, and not only a substantially rectangular shape as shown in FIG. 4 but also a cutout portion of a known shape such as an ellipse, a circle, a rectangle, a diamond, a triangle, or a parallelogram may be used.

Fig. 5 is a cross-sectional view showing a modification of Fig. 3, in which the liquid crystal display element is cut along the line III-III of the same position as Fig. 2 in Fig. 4. The first substrate 2 having the alignment layer 4 and the electrode layer 3 including the thin film transistor 20 and the second substrate 8 having the alignment layer 4 formed on the surface thereof are spaced apart from each other at a specific interval G so that the alignment layers face each other. This space is filled with a liquid crystal layer 5 containing a liquid crystal composition. A gate insulating film 12, a common electrode 22, an insulating film 18, a pixel electrode 21, and an alignment layer 4 are sequentially laminated on one surface of the first substrate 2. Further, as shown in FIG. 4, the pixel electrode 21 has a shape in which a central portion and both end portions of the flat plate are pierced by a triangular cutout portion, and the remaining portion is penetrated by a rectangular cutout portion, and is shared. The electrode 22 has a structure in which the common electrode of the comb-tooth shape is disposed closer to the first substrate than the pixel electrode so as to be substantially parallel to the substantially rectangular cutout portion of the pixel electrode 21.

Further, in FIGS. 4 and 5, a comb-shaped or slit-shaped common electrode 22 is used, and the electrode pitch of the pixel electrode 21 and the common electrode 22 is a condition that the electrode pitch R is not zero. Further, although the example in which the common electrode 22 is formed on the gate insulating film 12 is shown in FIG. 3, as shown in FIG. 5, the common electrode 22 may be formed on the first substrate 2, and the gate insulating film 12 is interposed. The pixel electrode 21 is provided. The electrode width of the pixel electrode 21: 1, the electrode width of the common electrode 22: n, and the electrode pitch: R are preferably adjusted so as to be wide enough to drive all the liquid crystal molecules in the liquid crystal layer 5 by the generated electric field.

Further, in FIG. 5, the pixel electrode 21 is disposed closer to the liquid crystal layer than the common electrode 22, but may be the same height in the thickness direction of the pixel electrode 21 and the common electrode 22. Alternatively, the common electrode 22 may be disposed closer to the liquid crystal layer side than the pixel electrode 21. As an embodiment in which the pixel electrode 21 and the common electrode 22 are disposed at the same height in the thickness direction, as described above, FIG. 6 as described below is configured such that the pixel electrode and the common electrode are alternated in cross section. The structure in which the pixel electrode and the common electrode are provided on the same substrate by movable fitting is exemplified.

For example, as shown in FIGS. 1, 4 and 5, the common electrode and the pixel electrode are preferably formed on the first substrate. 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.

In the case of the VA-IPS method which does not utilize such a lateral fringe electric field, as shown in FIG. 7(C), the liquid crystal molecules in the vicinity of the surface of the alignment film have little change in the orientation of the liquid crystal molecules even under the application of a voltage. In the normal IPS mode, the state is parallel with respect to the substrate without changing the orientation. Therefore, when the voltage is not applied, the liquid crystal molecules are not likely to return to the substrate relative to the substrate in a state parallel to the substrate. The problem of the direction of the vertical. Such a problem can be alleviated by adding a polymerizable monomer to the liquid crystal composition and polymerizing the polymerizable monomer as described in FIGS. 6 to 7.

Further, when a liquid crystal layer 5 is injected between the first substrate 2 and the second substrate 7 in a vertical alignment type liquid crystal display device such as a VA-IPS mode, for example, a vacuum injection method or an ODF (One Drop Fill) method is performed. In the method of the present invention, it is possible to suppress the occurrence of dripping marks when the liquid crystal composition is dropped onto the substrate in the ODF method. Further, the so-called drop mark is defined as a phenomenon in which a trace formed by dropping a liquid crystal composition is whitened and appears.

The occurrence of the drop marks is greatly affected by the liquid crystal material to be injected, and further, the influence of the constitution of the display elements is unavoidable. In a liquid crystal display element, in a display element The formed thin film transistor, and the comb-shaped or slit-shaped pixel electrode 21 and the like are separated from the liquid crystal composition by only the thinner alignment film 4, or the thinner alignment film 4 and the thinner insulating protective layer 18 and the like. Therefore, there is a high possibility that the ionic substance cannot be completely blocked, and the occurrence of the drop mark caused by the interaction between the metal material constituting the electrode and the liquid crystal composition cannot be avoided, and in the lateral electric field type liquid crystal display element, When the liquid crystal composition and the light directing film of the present invention are used in combination, the occurrence of dripping marks can be effectively suppressed.

Further, in the manufacturing step of the liquid crystal display element by the ODF method, it is necessary to drip the optimum liquid crystal injection amount according to the size of the liquid crystal display element, and the liquid crystal composition of the present invention is, for example, a dropping device which is generated when the liquid crystal is dropped. The influence of the pressure change or the impact of the impatience is small, and the liquid crystal can be continuously dripped continuously for a long period of time, so that the yield of the liquid crystal display element can be kept high. In particular, the small liquid crystal display elements which are mostly used in the recently popular smart phones have a small amount of liquid crystal injection, so it is difficult to control the deviation from the optimum value within a certain range, but by using the invention of the present invention. The liquid crystal composition can achieve a stable discharge amount of the liquid crystal material even in a small liquid crystal display element.

Hereinafter, the liquid crystal layer and the photo-alignment film layer which are other constituent elements of the liquid crystal display element of the present invention will be described in detail.

(liquid crystal layer)

Hereinafter, an embodiment of the liquid crystal composition of the present invention will be described. The liquid crystal composition of the present invention is preferably used in a liquid crystal display element of a vertical alignment mode (e.g., VA-IPS). Further, the liquid crystal layer of the present invention is a layer containing a liquid crystal composition. A polymerizable compound can be added to the liquid crystal composition of the present invention. Therefore, the liquid crystal layer of the present invention is preferably in a state in which the polymerizable compound contained in the liquid crystal composition is polymerized. The following will be said to improve the directional restraint Bright.

The liquid crystal composition of the present invention contains at least one selected from the group consisting of one or more compounds represented by the formula (i) as the first component and one or more compounds represented by the formula (J) as the second component. The liquid crystal composition having a positive dielectric value of each of the above compounds is preferably one or more compounds represented by the formula (i) and one or more compounds represented by the formula (J) as the second component.

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

The preferred physical properties of the liquid crystal composition of the present invention are preferably Δε of 1.5 to 12 and Δn of 0.08 to 0.20.

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

In the above formula (i), when n ⁱ¹ is an integer of 2 to 4, the rings A ⁱ¹ may be the same or different. Further, the ring A ⁱ¹ is preferably aromatic when it is required to increase Δn, and is preferably aliphatic in order to improve the response speed, and the ring A ⁱ¹ preferably independently represents a trans-1,4-extension ring. Hexyl, 1,3-two Alkano-2,5-diyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-stretch Phenyl, 3,5-difluoro-1,4-phenylene, 1,4-cyclohexenyl, 1,4-bicyclo[2.2.2]exenyl, piperidine-1,4-di a base, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, more preferably represented by the structure described below,

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

In the above formula (i), Z ^{i1 is more} preferably a single bond. Also, n ^{i1 is} preferably 2, 3 or 4. In the case where n ⁱ¹ is an integer of 2, 3 or 4, since there are a plurality of Z ⁱ¹ , the same may be the same or different.

In the case where reliability is important, it is preferred that both R ⁱ¹ and R ⁱ² are alkyl groups. When it is important to reduce the volatility of the compound, at least one of them is preferably an alkoxy group, and the viscosity is lowered. In the case, it is preferred that at least one is an alkenyl group.

When R ⁱ¹ and R ^{i2 are} in the case where the ring structure to which the bond is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms and a linear carbon number of 1 to 1 are preferable. The alkoxy group of 4 or the alkenyl group having 4 to 5 carbon atoms preferably has a linear carbon number of 1 to 5 when the ring structure to which the ring structure is a saturated ring structure such as cyclohexane. The alkyl group, the linear alkoxy group having 1 to 4 carbon atoms, and the linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, it is preferred that the total number of carbon atoms and oxygen atoms in the case of being present is 5 or less, and is preferably linear.

Further, the alkyl group, the alkenyl group and the alkoxy group of the present invention are each preferably a linear or branched chain, more preferably a linear alkyl group, an alkenyl group or an alkoxy group. In the present specification, examples of the alkyl group are common, and are appropriately selected from the above examples in accordance with the number of carbon atoms of each alkyl group.

Further, as a more preferred alkenyl group of the present invention, it is preferred to be from the formula (R1) to the formula (R5). One of the bases indicated by either. (black dots in various formulas represent carbon atoms in the ring structure)

In the liquid crystal composition of the present invention, the content of the compound represented by the formula (i) is determined according to solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy, process compatibility, and trace addition. The performance required for the afterimage, the dielectric image, and the like are appropriately adjusted.

The lower limit of the preferred content of the compound represented by the formula (i) relative 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 preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 30%, 25%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred that the lower limit value is higher and the upper limit value is higher. Further, in the case where the composition of the present invention has a Tni which is high and requires a composition having good temperature stability, it is preferred that the lower limit value is higher and the upper limit value is higher. Further, in order to increase the dielectric specificity 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 liquid crystal composition of the present invention contains one or two or more compounds represented by the formula (i). The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, viscosity, transfer temperature, electrical reliability, and refractive index anisotropy. Among them, the compound represented by the formula (i) preferably contains a compound which exhibits a viscosity reducing effect. Further, the type of the compound used as the compound represented by the formula (i) as the first component is, for example, one embodiment of the present invention. Or in another embodiment of the invention, there are two types. Further, in another embodiment of the present invention, there are three types. Further, in another embodiment of the present invention, there are four types. Further, in another embodiment of the present invention, there are five types. Further, in another embodiment of the present invention, there are six types. Further, in another embodiment of the present invention, there are seven types. Further, in another embodiment of the present invention, there are eight types. Further, in another embodiment of the present invention, there are nine types. Further, in another embodiment of the present invention, there are ten or more types.

In the liquid crystal composition of the present invention, the content of the compound represented by the formula (i) is determined according to solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy, process compatibility, and trace addition. The performance required for the afterimage, the dielectric image, and the like are appropriately adjusted.

When the compound represented by the formula (i) of the present invention requires chemical stability of the liquid crystal composition, it is preferred that the compound does not have a chlorine atom in the molecule.

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

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

(wherein R ⁱ¹¹ and R ⁱ¹² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in the 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 formula (i-1) may be used singly or in combination of two or more. The type of the compound that can be combined is not particularly limited, and is appropriately combined according to the properties required for solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy, and the like. use. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

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

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred that the lower limit value is higher and the upper limit value is higher. Further, in the case where the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, the lower limit is preferably centered, and the upper limit is intermediate. Further, in order to increase the dielectric specificity 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 formula (i-1) is preferably a compound selected from the group consisting of compounds represented by the formula (i-1-1).

(wherein R ⁱ¹² represents the same meaning as in the formula (i-1))

The compound represented by the formula (i-1-1) is preferably a compound selected from the group consisting of the compounds represented by the formula (i-1-1.1) to the formula (i-1-1.3), preferably a formula (i) -1-1.2) or a compound represented by the formula (i-1-1.3), particularly preferably a compound represented by the formula (i-1-1.3).

The lower limit of the preferred 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 preferred content is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3% with respect to the total amount of the composition of the present invention.

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

(wherein R ⁱ¹² represents the same meaning as in the formula (i-1))

The lower limit of the preferred 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 preferred content is 60%, 55%, 50%, 45%, 42%, 40%, 38%, 35%, 33%, 30% with respect to the total amount of the composition of the present invention.

Further, the compound represented by the formula (i-1-2) is preferably a compound selected from the group consisting of compounds represented by the formula (i-1-2.1) to the formula (i-1-2.4), preferably a formula (i-1-2.2) to a compound represented by the formula (i-1-2.4). In order to particularly improve the response speed of the composition of the present invention, a compound represented by the formula (i-1-2.2) is particularly preferred. Further, when Tni is required to be higher than the response speed, it is preferable to use the expression represented by the formula (i-1-2.3) or the formula (i-1-2.4). Compound. In order to improve the solubility at a low temperature, it is not preferable to set the content of the compound represented by the formula (i-1-2.3) and the formula (i-1-2.4) to 30% or more.

The lower limit of the preferred 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%, 40%. The upper limit of the preferred content is 60%, 55%, 50%, 45%, 43%, 40%, 38%, 35%, 32%, 30%, 27 with respect to the total amount of the composition of the present invention. %, 25%, 22%.

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

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

(wherein R ⁱ¹³ and R ⁱ¹⁴ each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms)

R ⁱ¹³ and R ^{i14 are} preferably 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 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 preferred content is 60%, 55%, 50%, 45%, 40%, 37%, 35%, 33%, 30%, 27%, 25 with respect to the total amount of the composition of the present invention. %, 23%, 20%, 17%, 15%, 13%, 10%.

Further, the compound represented by the formula (i-1-3) is preferably a compound selected from the group consisting of compounds represented by the formula (i-1-3.1) to the formula (i-1-3.12), preferably a formula (i-1-3.1), a compound represented by the formula (i-1-3.3) or the formula (i-1-3.4). In order to particularly improve the response speed of the composition of the present invention, a compound represented by the formula (i-1-3.1) is particularly preferred. Further, when Tni is required to be higher than the response speed, it is preferred to use the formula (i-1-3.3), the formula (i-1-3.4), the formula (i-1-3.11), and the formula (i-1-3.12). ) the compound represented. In order to make the solubility at a low temperature good, it is not preferable to formulate the compound represented by the formula (i-1-3.3), the formula (i-1-3.4), the formula (i-1-3.11), and the formula (i-1-3.12). The total content is set to 20% or more.

The lower limit of the preferred content of the compound represented by the 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 preferred content is 20%, 17%, 15%, 13%, 10%, 8%, 7%, 6% with respect to the total amount of the composition of the present invention.

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

(wherein R ⁱ¹⁵ and R ⁱ¹⁶ each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms)

R ⁱ¹⁵ and R ^{i16 are} preferably 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 the 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%. More The upper limit of the content is 25%, 23%, 20%, 17%, 15%, 13%, 10% with respect to the total amount of the composition of the present invention.

The lower limit of the preferred 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 preferred content is 25%, 23%, 20%, 17%, 15%, 13%, 10% with respect to the total amount of the composition of the present invention.

Further, the compounds represented by the formulae (i-1-4) and (i-1-5) are preferably selected from the group consisting of the compounds represented by the formula (i-1-4.1) to the formula (i-1-5.3). The compound represented by the formula (i-1-4.2) or the formula (i-1-5.2).

The lower limit of the preferred 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 preferred content is 20%, 17%, 15%, 13%, 10%, 8%, 7%, 6% with respect to the total amount of the composition of the present invention.

Preferably, the combination is selected from the group consisting of formula (i-1-1.3), formula (i-1-2.2), and formula (i-1) -3.1), two or more compounds of the formula (i-1-3.3), formula (i-1-3.4), formula (i-1-3.11), and formula (i-1-3.12) Preferably, the combination is selected from the group consisting of 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) And a compound of two or more of the compounds represented by the formula (i-1-4.2), and a lower limit of the total content of the total content of the compounds is 1 with respect to the total amount of the composition of the present invention. %, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, upper limit 80%, 70%, 60%, 50%, 45%, 40%, 37%, 35%, 33%, 30%, 28%, 25%, 23% with respect to the total amount of the composition of the present invention 20%. When the reliability of the composition is emphasized, it is preferred to combine two of the compounds represented by the formula (i-1-3.1), the formula (i-1-3.3), and the formula (i-1-3.4). When the above compound is used as the response speed of the composition, it is preferred to combine two or more compounds selected from the compounds represented by the formula (i-1-1.3) and the formula (i-1-2.2). .

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

(wherein R ⁱ²¹ and R ⁱ²² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in the 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 ^{2 is} preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms or An alkoxy group having 1 to 4 carbon atoms.

The compound represented by the formula (i-1) may be used singly or in combination of two or more. The types of compounds that can be combined are not particularly limited, and are dissolved according to low temperature. The properties required for solvability, transfer temperature, electrical reliability, refractive index anisotropy, and the like are appropriately combined and used. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

When the solubility in low temperature is emphasized, if the content is set to be large, the effect is high. Conversely, when the response speed is emphasized, if the content is set to be small, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content to be centered.

The lower limit of the preferred 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 preferred content is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3% with respect to the total amount of the composition of the present invention.

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

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

(wherein R ⁱ³¹ and R ⁱ³² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in the formula (i))

R ⁱ³¹ and R ⁱ³² are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

The compound represented by the formula (i-3) may be used singly or in combination of two or more. The kind of the compound which can be combined is not particularly limited, and it is used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

The lower limit of the preferred content of the compound represented by the 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 preferred content is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3% with respect to the total amount of the composition of the present invention.

In the case of obtaining a higher refractive index anisotropy, if the content is set to be larger, the effect is higher. Conversely, when the higher Tni is emphasized, if the content is set to be less, the effect is obtained. Higher. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content to be centered.

Further, the compound represented by the formula (i-3) is preferably a compound selected from the group consisting of compounds represented by the formula (i-3.1) to the formula (i-3.4), preferably the formula (i-3.2) to Formula (i -3.7) Compounds indicated.

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

(wherein R ⁱ⁴¹ and R ⁱ⁴² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in the 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} preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms or An alkoxy group having 1 to 4 carbon atoms.

The compound represented by the formula (i-4) may be used singly or in combination of two or more. The kind of the compound which can be combined is not particularly limited, and it is used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

In the composition of the present invention, the content of the compound represented by the formula (i-4) is determined according to solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy, process compatibility, and dropwise addition. The performance required for traces, afterimages, and dielectrics is appropriately adjusted.

The lower limit of the preferred content of the compound represented by the 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 preferred 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 formula (i-4) is preferably a compound represented by the formula (i-4.1) to the formula (i-4.3), for example.

The compound represented by the formula (i-4.1) may be contained according to the properties required for solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy, etc., and the formula (i-4.2) The compound, the compound represented by the formula (i-4.1) and the compound represented by the formula (i-4.2) may further contain all the compounds represented by the formula (i-4.1) to the formula (i-4.3). The lower limit of the preferred content of the compound represented by the formula (i-4.1) or the formula (i-4.2) with respect to the total amount of the composition of the present invention is 3%, 5%, 7%, 9%, 11 %, 12%, 13%, 18%, 21%, preferably upper limit is 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

In the case where both the compound represented by the formula (i-4.1) and the compound represented by the formula (i-4.2) are contained, the lower limit of the preferable content of the two compounds with respect to the total amount of the composition of the present invention The values are 15%, 19%, 24%, 30%, and preferably the upper limits are 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the formula (i-4) is preferably a compound represented by the formula (i-4.4) to the formula (i-4.6), and preferably a compound represented by the formula (i-4.4).

The compound represented by the formula (i-4.4) may be contained according to the properties required for solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy, etc., and is represented by the formula (i-4.5). The compound may further contain both a compound represented by the formula (i-4.4) and a compound represented by the formula (i-4.5).

The lower limit of the preferred content of the compound represented by the formula (i-4.4) or the formula (i-4.5) with respect to the total amount of the composition of the present invention is 3%, 5%, 7%, 9%, 11 %, 12%, 13%, 18%, 21%. Preferably, the upper limit is 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

In the case where both the compound represented by the formula (i-4.4) and the compound represented by the formula (i-4.5) are contained, the lower limit of the preferable content of the two compounds with respect to the total amount of the composition of the present invention The values are 15%, 19%, 24%, 30%, preferably the upper limit is 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the formula (i-4) is preferably a compound represented by the formula (i-4.7) to the formula (i-4.10), and more preferably a compound represented by the formula (i-4.9).

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

^(Wherein, R i51 and ^R i52 and each independently represents the same meaning as R ⁱ² of the general formula (R i) in the ⁱ¹⁾

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} preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms or An alkoxy group having 1 to 4 carbon atoms.

The compound represented by the formula (i-5) may be used singly or in combination of two or more. The kind of the compound which can be combined is not particularly limited, and it is used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

In the composition of the present invention, the content of the compound represented by the formula (i-5) is determined according to solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy, process compatibility, and dropwise addition. The performance required for traces, afterimages, and dielectrics is appropriately adjusted.

The lower limit of the preferred 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 preferred 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 formula (i-5) is preferably a compound represented by the formula (i-5.1) or the formula (i-5.2), and more preferably a compound represented by the formula (i-5.1).

The lower limit of the preferred content of the compounds relative to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, 7%. The preferred upper limits of the compounds are 20%, 15%, 13%, 10%, 9%.

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

The lower limit of the preferred content of the compounds relative to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, 7%. The preferred upper limits of the compounds are 20%, 15%, 13%, 10%, 9%.

The compound represented by the formula (i-5) is preferably a compound selected from the group consisting of compounds represented by the formula (i-5.5) to the formula (i-5.7), and more preferably represented by the formula (i-5.7). Compound.

The lower limit of the preferred content of the compounds relative to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, 7%. The preferred upper limits of the compounds are 20%, 15%, 13%, 10%, 9%.

The compound represented by the 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 the 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 an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and X ⁱ⁶¹ and X ^{i62 are} preferably one of fluorine atoms and the other is A hydrogen atom.

The compound represented by the formula (i-6) may be used singly or in combination of two or more. The types of compounds that can be combined are not particularly limited, and are dissolved according to low temperature. The properties required for solvability, transfer temperature, electrical reliability, refractive index anisotropy, and the like are appropriately combined and used. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

The lower limit of the preferred 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 preferred 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 the focus is on increasing the Δn, it is preferable to increase the content, and when the emphasis is on the precipitation at a low temperature, the content is preferably small.

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

The type of the compound which can be combined is not particularly limited, and it is preferred to contain one to three kinds selected from the compounds, and more preferably one to four. Further, since the selected compound has a broad molecular weight distribution and is effective for solubility, it is preferably selected, for example, from a compound selected from the group consisting of compounds represented by formula (i-6.1) or (i-6.2). a compound represented by (i-6.4) or (i-6.5), a compound selected from the group consisting of a compound represented by the formula (i-6.6) or the formula (i-6.7), selected from the formula (i- One of the compounds represented by 6.8) or (i-6.9) is appropriately combined. Among them, preferred are compounds represented by the formula (i-6.1), the formula (i-6.3), the formula (i-6.4), the formula (i-6.6), and the formula (i-6.9).

Further, the compound represented by the formula (i-6) is preferably a compound represented by the formula (i-6.10) to the formula (i-6.17), and among them, a compound represented by the formula (i-6.11) is preferred. .

The lower limit of the preferred content of the compounds relative to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, 7%. The preferred upper limits of the compounds are 20%, 15%, 13%, 10%, 9%.

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

(wherein R ⁱ⁷¹ and R ⁱ⁷² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in the formula (i), and A ⁱ⁷¹ and A ⁱ⁷² independently represent A ⁱ² in the formula (i) and A ^{i3 has the} same meaning, the hydrogen atoms on A ⁱ⁷¹ and A ⁱ⁷² can be independently substituted into fluorine atoms, and Z ⁱ⁷¹ represents the same meaning as Z ⁱ² in the general formula (i), and X ⁱ⁷¹ and X ⁱ⁷² are respectively independently Represents a fluorine atom or a hydrogen atom)

In the formula, R ⁱ⁷¹ and R ⁱ⁷² are each independently 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, A ⁱ⁷¹ and A ^i72. Preferably, each is independently a 1,4-cyclohexylene group or a 1,4-phenylene group, and the hydrogen atoms on A ⁱ⁷¹ and A ⁱ⁷² may be independently substituted with a fluorine atom, and Q ^{i71 is} preferably a single bond or COO. Preferably, it is a single bond, and X ⁱ⁷¹ and X ^{i72 are} preferably a hydrogen atom.

The type of the compound which can be combined is not particularly limited, and is combined according to the properties required at the low temperature such as solubility, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two, three, or four as one embodiment of the present invention.

In the composition of the present invention, the content of the compound represented by the formula (i-7) is determined according to solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy, process compatibility, and dropwise addition. The performance required for traces, afterimages, and dielectrics is appropriately adjusted.

The lower limit of the preferred 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 preferred 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%, 20%, 18%, 15%, 10%. 5%.

In the case where the composition of the present invention is expected to be a higher Tni embodiment, it is preferred to increase the content of the compound represented by the formula (i-7), and in the case of an embodiment in which a low viscosity is desired, it is preferably Reduce its content.

Further, the compound represented by the formula (i-7) is preferably a compound represented by the formula (i-7.1) to the formula (i-7.4), and preferably a compound represented by the formula (i-7.2).

Further, the compound represented by the formula (i-7) is preferably a compound represented by the formula (i-7.11) to the formula (i-7.13), and preferably a compound represented by the formula (i-7.11).

Further, the compound represented by the formula (i-7) is a compound represented by the formula (i-7.21) to the formula (i-7.23). Preferred is a compound represented by the formula (i-7.21).

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

Further, the compound represented by the formula (i-7) is preferably a compound represented by the formula (i-7.41) to the formula (i-7.44), preferably a formula (i-7.41) or/and a formula (i- 7.42) Compounds indicated.

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

(wherein R ⁱ⁸¹ and R ⁱ⁸² each independently represent 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 preferred content of the compound represented by the 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%, 17%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

The liquid crystal compound having an allyl ether group at the terminal has good characteristics as a constituent component of the liquid crystal composition, but there is a problem in reliability. However, the compound represented by the formula (i-8) is difluorinated by a specific position of the benzene ring having an allyl ether group, and the reliability is remarkably improved without impairing the original characteristics of the skeleton. Improve compatibility and reduce stickiness. Further, as the dielectric conductivity, there are a number of positive dielectric directions depending on the type of the side chain. In the case of conductivity (5 or less), it is classified as a constituent component of a neutral liquid crystal compound in the present specification.

Further, when R ⁱ⁸² in the formula (i-8) is an alkyl group or an alkenyl group (for example, a vinyl group) substituted with a fluorine atom, the positive dielectric conductivity can be imparted. For example, the compound represented by the formula (i-8) exhibits a liquid crystal phase in the form of a single component in the range of 40 to 110 ° C, Δn is about 0.26, and the flow viscosity is as low as about 25 mPa ‧ s. It is about +4 to 5, and further has excellent compatibility when used as a component of a liquid crystal composition.

Further, the compound represented by the formula (i-8) used in the liquid crystal composition of the present invention is specifically preferably a compound represented by the formula (i-8.1) to the formula (i-8.24), of which The compound represented by the formula (i-8.5), the formula (i-8.6), the formula (i-8.13), and the formula (i-8.14) is contained.

The lower limit of the preferred content of the compounds relative 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%, 5%.

In addition, the compound represented by the formula (i-9) which is the first component preferably contains at least one or two or more compounds represented by the formula (i-9.1).

(In the above formula (i-9), R ^{L72 is} independently an alkyl group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. One of the groups consisting of

From the viewpoint of improving the reliability of the liquid crystal composition such as light resistance, heat resistance or afterimage, it is preferred to contain a compound represented by the formula (i-9).

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

The liquid crystal composition of the present invention preferably contains one or two or more compounds represented by the formula (J) as a second component (these compounds correspond to a compound having a positive dielectric property (Δε 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 of the alkyl groups or two or more non-adjacent -CH ₂ - may be independently substituted with -CH=CH-, - C≡C-, -O-, -CO-, -COO- or -OCO-, n ^J1 represents 0, 1, 2, 3 or 4, and A ^J1 , A ^J2 and A ^J3 are independently represented by (a) ) 1,4-cyclohexylene group (in the presence of a group -CH ₂ - not adjacent two or more of the -CH ₂ - may be substituted with -O -) (b) 1,4- extending benzene a group (one present in the group -CH= or two or more adjacent to -CH= may be substituted with -N=) and (c) naphthalene-2,6-diyl, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2, One of the 6-diyl groups -CH= or two or more non-contiguous -CH= can be replaced by -N=)

The group in the group formed, the above-mentioned group (a), group (b) and group (c) may independently pass through a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group. Substituting, Z ^J1 and Z ^J2 each independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O -, -COO-, -OCO- or -C≡C-, when n ^J1 is 2, 3 or 4 and there are multiple A ^J2 , the same or different, and n ^J1 is 2, 3 Or 4, in the case where a plurality of Z ^J1 are present, the same may be different, and X ^J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group. , trifluoromethoxy or 2,2,2-trifluoroethyl)

In the formula (J), R ^{J1 is} preferably 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 a carbon number of 2 to 8. The alkenyloxy group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. It is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, particularly preferably An alkenyl group (propylene group) having 3 carbon atoms.

In the case where reliability is important, R ^{J1 is} preferably an alkyl group, and when a viscosity is lowered, an alkenyl group is preferred.

Further, in the case where the ring structure to which the bond is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms and a linear alkyl group having 1 to 4 carbon atoms are preferable. An oxy group and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure to which the bond is bonded is cyclohexane, pyran and In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear carbon atom number 2 are preferred. ~5 alkenyl. In order to stabilize the nematic phase, it is preferred that the total number of carbon atoms and oxygen atoms in the case of being present is 5 or less, and is preferably linear.

The alkenyl group is preferably selected from the group represented by any one of the formulae (R1) to (R5). (The black dots in the formulas represent the carbon atoms in the ring structure to which the alkenyl group is bonded)

A ^J1 , A ^J2 and A ^J3 are each independent. When it is required to increase Δn, it is preferably aromatic. In order to improve the response speed, it is preferably aliphatic, preferably trans-1,4-extension. Cyclohexyl, 1,4-phenylene, 1,4-cyclohexenyl, 1,4-bicyclo[2.2.2]exenyl, piperidin-1,4-diyl, naphthalene-2,6 -diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, which may be substituted with a fluorine atom, more preferably represented by the following structure,

More preferably, it shows the following structure.

Z ^J1 and Z ^J2 are each independently, preferably -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, and more preferably -OCH ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or a single bond, particularly preferably -OCH ₂ -, -CF ₂ O- or a single bond.

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

n ^{J1 is} preferably 0, 1, 2 or 3, preferably 0, 1 or 2, and is preferably 0 or 1 when the emphasis is on improving Δ ε, and preferably 1 when Tni is emphasized. Or 2.

The type of the compound which can be combined is not particularly limited, and it is used in accordance with a desired combination of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two or three kinds of embodiments of the present invention. Further, in another embodiment of the present invention, there are four, five, six, and seven or more.

In the composition of the present invention, the content of the compound represented by the formula (J) is determined according to solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy, process compatibility, dropping marks, The performance required for the afterimage, dielectric guidance, etc. is appropriately adjusted.

The lower limit of the preferred content of the compound represented by the 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 preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25% in the form of one aspect of the present invention, relative to the total amount of the composition of the present invention. .

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, when the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

In the case where reliability is important, R ^{J1 is} preferably an alkyl group, and when a viscosity is lowered, an alkenyl group is preferred.

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

The general formula (M) of the present invention is

(In the above 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 a carbon number of 2 to 8; The alkenyloxy group, one or more hydrogen atoms of the alkyl group, alkenyl group, alkoxy group or alkenyloxy group may be substituted with a fluorine atom, and one of the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group Two or more non-contiguous -CH ₂ - may be independently substituted with -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, PM represents 0, 1, 2, 3 or 4, C ^M1 and C ^M2 each independently represent a selected from (d) 1,4-cyclohexylene (one -CH ₂ - present in the group or 2 adjacent to each other) The above -CH ₂ - may be substituted with -O- or -S-) and (e) 1,4-phenylene (one present in the group -CH= or two or more adjacent thereto - CH= can be replaced by -N=)

In the group formed, the above-mentioned groups (d) and (e) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, and K ^M1 and K ^M2 each independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -COO-, -OCO- or -C≡C-, at PM 2, 3 or 4, when there are multiple K ^M1 cases, the same may or may not be the same. When the PM is 2, 3 or 4 and there are multiple C ^M2 , the same or different, X ^M1 and X ^M3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom, and X ^M2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, or a trifluoro group. Methoxy or 2,2,2-trifluoroethyl. Wherein, except for the compound represented by the formula (i)).

In the above formula (M), A ^M1 and A ^M2 are each independently, and when it is required to increase Δn, it is preferably aromatic, and in order to improve the response speed, it is preferably aliphatic, preferably trans. -1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1, 4-phenylene, 2,3-difluoro-1,4-phenylene, 1,4-cyclohexenyl, 1,4-bicyclo[2.2.2]exenyl, piperidine-1, 4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, more preferably represented by the following Structure,

More preferably, it shows the following structure.

K ^M1 and K ^M2 are each independently, preferably -CH ₂ O-, -CF ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, and more preferably -CF ₂ O- , -CH ₂ CH ₂ - or a single bond, particularly preferably -CF ₂ O- or a single bond.

X ^M1 and X ^M3 are each independently a hydrogen atom or a fluorine atom, and X ^{M2 is} preferably a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group.

In the formula (M), R ^{M1 is} preferably 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 a carbon number of 2 to 8. The alkenyloxy group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. It is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, particularly preferably An alkenyl group (propylene group) having 3 carbon atoms.

In the case where reliability is important, R ^{M1 is} preferably an alkyl group, and when a viscosity is lowered, an alkenyl group is preferred.

Further, in the case where the ring structure to which the bond is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms and a linear alkyl group having 1 to 4 carbon atoms are preferable. An oxy group and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure to which the bond is bonded is cyclohexane, pyran and In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear carbon atom number 2 are preferred. ~5 alkenyl. In order to stabilize the nematic phase, it is preferred that the total number of carbon atoms and oxygen atoms in the case of being present is 5 or less, and is preferably linear.

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

In the liquid crystal composition of the present invention, the compound represented by the formula (M) is contained The amount needs to be appropriately adjusted according to the properties required at the low temperature such as solubility, transfer temperature, electrical reliability, refractive index anisotropy, process compatibility, dropping marks, afterimage, dielectric orientation, and the like.

The lower limit of the preferred 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 preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 30%, for example, in one embodiment of the present invention, relative to the total amount of the composition of the present invention. 25%.

In the case where the viscosity of the liquid crystal composition of the present invention is kept low and a liquid crystal composition having a fast response speed is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, when the Tni of the liquid crystal composition of the present invention is kept high and a liquid crystal composition having good temperature stability is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

The type of the compound which can be combined is not particularly limited, and it is used in accordance with a desired combination of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two or three kinds of embodiments of the present invention. Further, in another embodiment of the present invention, there are four, five, six, and seven or more.

When the compound represented by the formula (M) of the present invention requires chemical stability of the liquid crystal composition, it is preferred that the compound does not have a chlorine atom in the molecule. Further, in the liquid crystal composition, the compound having a chlorine atom is preferably 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, and preferably substantially not contained. The term "substantially does not contain a compound containing a chlorine atom in a compound or the like which is formed only as an impurity in the production of a compound" Into the liquid crystal composition.

The compound represented by the formula (M) of the present invention is preferably, for example, a compound selected from the group consisting of compounds represented by the 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 represent a hydrogen atom or Fluorine atom, Y ^M11 represents fluorine atom or OCF ₃ )

The type of the compound which can be combined is not particularly limited, and it is used in accordance with a desired combination of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two or three or more of the embodiments of the present invention.

The lower limit of the preferred 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, when the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

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

The lower limit of the preferred 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%. The upper limit of the preferred content is 15%, 13%, 10%, 8%, 5%.

The lower limit of the preferred 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%. The upper limit of the preferred content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

The lower limit of the preferred content of the total of the compounds represented by the formula (M-1.1) and the formula (M-1.2) with respect to the total amount of the composition of the present invention is 1%, 2%, 5%, 6%. . The upper limit of the preferred content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

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

(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 a hydrogen atom or Fluorine atom, Y ^M21 represents fluorine atom, chlorine atom or OCF ₃ )

The lower limit of the preferred 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where the Tni of the composition of the present invention is kept high and a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-2) is preferably a compound represented by the formula (M-2.1) to the formula (M-2.5), preferably a formula (M-2.3) or/and a formula (M-). 2.5) Compounds indicated.

The lower limit of the preferred 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%. The upper limit of the preferred content is 15%, 13%, 10%, 8%, 5%.

The lower limit of the preferred 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%. The upper limit of the preferred content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

The lower limit of the preferred 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%. The upper limit of the preferred content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

The lower limit of the preferred content of the total of the compounds represented by the formula (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 preferred content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

The content is preferably 1% or more, more preferably 5% or more, still more preferably 8% or more, still more preferably 10% or more, and still more preferably 14% or more, based on the total amount of the composition of the present invention. More than 16%. Further, in consideration of solubility at low temperature, transfer temperature, electrical reliability, and the like, it is preferable to limit the maximum ratio to 30% or less, more preferably 25% or less, still more preferably 22% or less, and particularly preferably no. Up to 20%.

The compound represented by the formula (M) used in the composition of the present invention is preferably a compound represented by the 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 each independently represent a hydrogen atom or Fluorine atom, Y ^M31 represents fluorine atom, chlorine atom or OCF ₃ )

The compound which can be combined is not particularly limited, and it is preferred to combine one or two or more kinds in consideration of solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy and the like.

The content of the compound represented by the formula (M-3) has upper limit and lower limit in each embodiment in consideration of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. .

The lower limit of the preferred 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%, 20%. The upper limit of the preferred content is 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by the formula (M-3) used in the composition of the present invention is preferably a compound represented by the formula (M-3.1) to the formula (M-3.4), and preferably contains a compound. A compound represented by the formula (M-3.1) and/or the formula (M-3.2).

The lower limit of the preferred 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 preferred content is 20%, 18%, 15%, 13%, 10%, 8%, 5%.

The lower limit of the preferred 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 preferred content is 20%, 18%, 15%, 13%, 10%, 8%, 5%.

The lower limit of the preferred content of the total of the compounds represented by the formula (M-3.1) and 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 preferred content is 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by the formula (M) is preferably a compound selected from the group represented by the 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 each independently represent a fluorine atom or a hydrogen atom, Y ^M41 represents a fluorine atom, a chlorine atom or OCF ₃ )

The compound which can be combined is not particularly limited, and one, two or more kinds are preferably combined in consideration of solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy and the like.

The content of the compound represented by the formula (M-4) has upper limit and lower limit in each embodiment in consideration of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. .

The lower limit of the preferred 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%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

When the composition of the present invention is used for a liquid crystal display element having a small cell gap, the content of the compound represented by the general formula (M-4) is suitably increased. In the case of driving a liquid crystal display element having a small voltage, it is preferable to increase the content of the compound represented by the general formula (M-4). Moreover, in the case of a liquid crystal display element used in a low temperature environment, it is desirable to reduce the general formula. The content of the compound represented by (M-4). When it is used in the case of a composition of a liquid crystal display element which is fast in response, it is preferable to reduce the content of the compound represented by the formula (M-4).

Further, the compound represented by the formula (M-4) used in the composition of the present invention is preferably a compound represented by the formula (M-4.1) to the formula (M-4.4), and preferably contains a compound. The compound represented by the formula (M-4.2) to the formula (M-4.4) preferably contains the compound represented by the formula (M-4.2).

Further, the compound represented by the formula (M) is preferably a compound represented by the 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 each independently represent a hydrogen atom or Fluorine atom, Y ^M51 represents fluorine atom, chlorine atom or OCF ₃ )

The type of the compound which can be combined is not limited, and is appropriately combined and used in each embodiment in consideration of solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy and the like. For example, in one embodiment of the present invention, one type is combined, and in another embodiment, two types are combined, and in still another embodiment, three types are combined, and in still another embodiment, four types are combined, and yet another embodiment Five types are combined, and in still another embodiment, six or more types are combined.

The lower limit of the preferred 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 preferred content is 50%, 45%, 40%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where the Tni of the composition of the present invention is kept high and a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-5) is preferably a compound represented by the formula (M-5.1) to the formula (M-5.4), preferably a formula (M-5.1) to a formula (M-5.4). The compound represented.

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

Further, the compound represented by the formula (M-5) is preferably a compound represented by the formula (M-5.11) to the formula (M-5.17), preferably a formula (M-5.11) or a formula (M-5.13). And a compound represented by the formula (M-5.17).

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

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

The lower limit of the preferred content of the compounds relative 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 40%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by the formula (M) is preferably a compound represented by the 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 each independently represent a fluorine atom or a hydrogen atom, Y ^M61 represents a fluorine atom, a chlorine atom or OCF ₃ )

The type of the compound which can be combined is not limited, and is appropriately combined in each embodiment in consideration of solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy and the like.

The lower limit of the preferred 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%, 20%. The upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

When the composition of the present invention is used for driving a liquid crystal display element having a small voltage, it is preferable to increase the content of the compound represented by the general formula (M-6). Further, in the case of a composition for a liquid crystal display element having a fast response speed, the content of the compound represented by the general formula (M-6) is suitably reduced.

Further, the compound represented by the formula (M-6) is specifically preferably a compound represented by the formula (M-6.1) to the formula (M-6.4), and it is preferred to contain the formula (M-6.2) and the formula. (M-6.4) The compound represented.

The lower limit of the preferred content of the compounds relative 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%, 5%.

Further, the compound represented by the formula (M-6) is specifically preferably a compound represented by the formula (M-6.11) to the formula (M-6.14), and preferably contains the formula (M-6.12) and the formula. (M-6.14) The compound represented.

The lower limit of the preferred content of the compounds relative 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%, 5%.

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

The lower limit of the preferred content of the compounds relative 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%, 5%.

Further, the compound represented by the 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 formula (M-6.31) And a compound represented by the formula (M-6.32).

The lower limit of the preferred content of the compounds relative 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%, 5%.

Further, the compound represented by the formula (M-6) is specifically preferably a compound represented by the formula (M-6.41) to the formula (M-6.44), and preferably contains a compound represented by the formula (M-6.42). Compound.

The lower limit of the preferred content of the compounds relative 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%, 5%.

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

(wherein, X ^M71 to X ^M76 each independently represent 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 an alkane having 1 to 4 carbon atoms; ^Oxy group, Y ^M71 represents a fluorine atom or OCF ₃ )

The type of the compound which can be combined is not particularly limited, and it is preferably one or two kinds selected from the group consisting of one or three kinds of the compounds, more preferably one type or three types, and further preferably one type. Four.

The content of the compound represented by the formula (M-7) has upper limit and lower limit in each embodiment in consideration of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. .

The lower limit of the preferred 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%, 5%.

In the case where the composition of the present invention is used for a liquid crystal display element having a small cell gap, the content of the compound represented by the general formula (M-7) is suitably increased. In the case of driving a liquid crystal display element having a small voltage, it is preferable to increase the content of the compound represented by the general formula (M-7). Further, in the case of a liquid crystal display element used in a low-temperature environment, the content of the compound represented by the formula (M-7) is suitably reduced. When it is used in the case of a composition of a liquid crystal display element which is fast in response, it is preferable to reduce the content of the compound represented by the general formula (M-7).

Further, the compound represented by the formula (M-7) is preferably a compound represented by the formula (M-7.1) to the formula (M-7.4), and is preferably a compound represented by the formula (M-7.2).

The lower limit of the preferred content of the compounds relative 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%, 5%.

Further, the compound represented by the formula (M-7) is preferably a compound represented by the formula (M-7.11) to the formula (M-7.14), preferably a formula (M-7.11) and a formula (M-7.12). The compound represented.

The lower limit of the preferred content of the compounds relative 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%, 5%.

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

The lower limit of the preferred content of the compounds relative 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%, 5%.

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

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

a hydrogen atom on a 1,4-phenylene group may be substituted with a fluorine atom)

The lower limit of the preferred content of the compound represented by the formula (M-8) 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-8) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-8.1) to the formula (M-8.4), and preferably contains A compound represented by the formula (M-8.1) and the formula (M-8.2).

The lower limit of the preferred content of the compounds relative 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%, 5%.

Further, the compound represented by the formula (M-8) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-8.11) to the formula (M-8.14), preferably containing A compound represented by the formula (M-8.12).

The lower limit of the preferred content of the compounds relative 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%, 5%.

Further, the compound represented by the formula (M-8) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-8.21) to the formula (M-8.24), preferably containing A compound represented by the formula (M-8.22).

The lower limit of the preferred content of the compounds relative 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%, 5%.

Further, the compound represented by the formula (M-8) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-8.31) to the formula (M-8.34). It is preferred to contain a compound represented by the formula (M-8.32).

The lower limit of the preferred content of the compounds relative 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%, 5%.

Further, the compound represented by the formula (M-8) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-8.41) to the formula (M-8.44), preferably containing A compound represented by the formula (M-8.42).

The lower limit of the preferred content of the compounds relative 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%, 5%.

Further, the compound represented by the formula (M-8) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-8.51) to the formula (M-8.54), preferably containing A compound represented by the formula (M-8.52).

The lower limit of the preferred content of the compounds relative 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%, 5%.

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

(The black dots in the formula represent the carbon atoms in the ring structure to which the above partial structure is bonded)

As the compound having the above partial structure, a compound represented by the formula (M-10) to (M-18) is preferred.

The compound represented by the formula (M-10) is as described below.

(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 , and R ^M101 represents an alkyl group having 1 to 5 carbon atoms, and 2 to 2 carbon atoms; 5 alkenyl or alkoxy having 1 to 4 carbon atoms, W ^M101 and W ^M102 independently represent -CH ₂ - or -O-)

The lower limit of the preferred content of the compound represented by the formula (M-10) 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-10) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-10.1) to the formula (M-10.12), preferably containing A compound represented by the formula (M-10.5) to the formula (M-10.12).

The lower limit of the preferred content of the compounds relative 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%, 5%.

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

(wherein, X ^M111 to X ^M114 each independently represent a fluorine atom or a hydrogen atom, Y ^M111 represents a fluorine atom, a chlorine atom or -OCF ₃ , and R ^M111 represents an alkyl group having 1 to 5 carbon atoms, and 2 to 2 carbon atoms; 5 alkenyl or alkoxy having 1 to 4 carbon atoms)

The lower limit of the preferred content of the compound represented by the formula (M-11) 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-11) used in the composition of the present invention is preferably a compound represented by the formula (M-11.1) to the formula (M-11.8), and preferably contains a compound. A compound represented by the formula (M-11.1) to the formula (M-11.4).

The lower limit of the preferred content of the compounds relative 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%, 5%.

The compound represented by the formula (M-12) is as described below.

(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 , and R ^M121 represents an alkyl group having 1 to 5 carbon atoms, and 2 to 2 carbon atoms; 5 alkenyl or alkoxy having 1 to 4 carbon atoms, W ^M121 and W ^M122 each independently represent -CH ₂ - or -O-)

The lower limit of the preferred content of the compound represented by the formula (M-12) 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-12) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-12.1) to the formula (M-12.12), preferably containing A compound represented by the formula (M-12.5) to the formula (M-12.8).

The lower limit of the preferred content of the compounds relative 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%, 5%.

The compound represented by the formula (M-13) is as described below.

(wherein, X ^M131 to X ^M134 each independently represent a fluorine atom or a hydrogen atom, Y ^M131 represents a fluorine atom, a chlorine atom or -OCF ₃ , and R ^M131 represents an alkyl group having 1 to 5 carbon atoms, and 2 to 2 carbon atoms; alkenyl or 5 carbon atoms of the alkoxy group having 1 to 4, W ^M131 W ^M132 and each independently represents -CH ₂ - or -O-)

The expression expressed by the general formula (M-13) with respect to the total amount of the composition of the present invention The lower limit of the preferred content of the compound 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-13) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-13.1) to the formula (M-13.28), preferably containing A compound represented by the formulae (M-13.1) to (M-13.4), (M-13.11) to (M-13.14), (M-13.25) to (M-13.28).

The lower limit of the preferred content of the compounds relative 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%, 5%.

The compound represented by the formula (M-14) is as described below.

(wherein, X ^M141 to X ^M144 each independently represent a fluorine atom or a hydrogen atom, Y ^M141 represents a fluorine atom, a chlorine atom or -OCF ₃ , and R ^M141 represents an alkyl group having 1 to 5 carbon atoms, and 2 to 2 carbon atoms; 5 alkenyl or alkoxy having 1 to 4 carbon atoms, W ^M141 and W ^M142 independently representing -CH ₂ - or -O-)

The lower limit of the preferred content of the compound represented by the formula (M-14) 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-14) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-14.1) to the formula (M-14.8), and preferably contains A compound represented by the formula (M-14.5) and the formula (M-14.8).

The lower limit of the preferred content of the compounds relative 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%, 5%.

The compound represented by the formula (M-15) is as described below.

(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 , and R ^M151 represents an alkyl group having 1 to 5 carbon atoms, and 2 to 2 carbon atoms; An alkenyl group of 5 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 the formula (M-15) 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-15) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-15.1) to the formula (M-15.14), preferably containing A compound represented by the formula (M-15.5) to the formula (M-15.8), the formula (M-15.11) to the formula (M-15.14).

The lower limit of the preferred content of the compounds relative 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%, 5%.

The compound represented by the formula (M-16) is as described below.

(wherein, X ^M161 to X ^M164 each independently represent a fluorine atom or a hydrogen atom, Y ^M161 represents a fluorine atom, a chlorine atom or -OCF ₃ , and R ^M161 represents an alkyl group having 1 to 5 carbon atoms, and 2 to 2 carbon atoms; 5 alkenyl or alkoxy having 1 to 4 carbon atoms)

The lower limit of the preferred content of the compound represented by the formula (M-16) 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-16) used in the composition of the present invention is preferably a compound represented by the formula (M-16.1) to the formula (M-16.8), and preferably contains a compound. A compound represented by the formula (M-16.1) to the formula (M-16.4).

The lower limit of the preferred content of the compounds relative 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%, 5%.

The compound represented by the formula (M-17) is as described below.

(wherein, X ^M171 to X ^M174 each independently represent a fluorine atom or a hydrogen atom, Y ^M171 represents a fluorine atom, a chlorine atom or -OCF ₃ , and R ^M171 represents an alkyl group having 1 to 5 carbon atoms, and 2 to 2 carbon atoms; 5 alkenyl or alkoxy having 1 to 4 carbon atoms, and W ^M171 and W ^M172 independently represent -CH ₂ - or -O-)

The lower limit of the preferred content of the compound represented by the formula (M-17) 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-17) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-17.1) to the formula (M-17.52), preferably containing A compound represented by the formula (M-17.9) to the formula (M-17.12), the formula (M-17.21) to the formula (M-17.28), and the formula (M-17.45) to the formula (M-17.48).

The lower limit of the preferred content of the compounds relative 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%, 5%.

The compound represented by the formula (M-18) is as described below.

(wherein, X ^M181 to X ^M186 each independently represent a fluorine atom or a hydrogen atom, Y ^M181 represents a fluorine atom, a chlorine atom or -OCF ₃ , and R ^M181 represents an alkyl group having 1 to 5 carbon atoms, and 2 to 2 carbon atoms; 5 alkenyl or alkoxy having 1 to 4 carbon atoms)

The lower limit of the preferred content of the compound represented by the formula (M-18) 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, in the case where a composition which is less likely to cause an afterimage is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (M-18) used in the composition of the present invention is specifically preferably a compound represented by the formula (M-18.1) to the formula (M-18.12), preferably containing A compound represented by the formula (M-18.5) to the formula (M-18.8).

The lower limit of the preferred content of the compounds relative 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%, 5%.

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

(wherein, R ^K1 represents an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent -CH ₂ - may be independently substituted with -CH=CH-, - C≡C-, -O-, -CO-, -COO- or -OCO-, n ^K1 represents 0, 1, 2, 3 or 4, and A ^K1 and A ^K2 are independently represented by (a) 1, respectively. 4- cyclohexylene (in the presence of a group -CH ₂ - or not adjacent two or more of the -CH ₂ - may be substituted with -O- or -S-), and (b) 1,4- Stretching phenyl (one present in the group -CH= or more than two adjacent -CH= can be substituted for -N=)

In the group formed, the hydrogen atoms on the above-mentioned groups (a) and (b) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, and Z ^K1 and Z ^K2 each independently represent a single bond. , -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -COO-, -OCO- or -C≡C - in the case where n ^K1 is 2, 3 or 4 and there are a plurality of A ^K2 , the same may be different, and when n ^K1 is 2, 3 or 4 and there are a plurality of Z ^K1 , such X ^K1 and X ^K3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom, and X ^K2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, or a second group. Fluoromethoxy, trifluoromethoxy or 2,2,2-trifluoroethyl)

In the general formula (K), R ^{K1 is} preferably 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 a carbon number of 2 to 8. The alkenyloxy group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. It is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, particularly preferably An alkenyl group (propylene group) having 3 carbon atoms.

In the case where reliability is important, R ^{K1 is} preferably an alkyl group, and when a viscosity is lowered, an alkenyl group is preferred.

Further, in the case where the ring structure to which the bond is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms and a linear alkyl group having 1 to 4 carbon atoms are preferable. An oxy group and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure to which the bond is bonded is cyclohexane, pyran and In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear carbon atom number 2 are preferred. ~5 alkenyl. In order to stabilize the nematic phase, it is preferred that the total number of carbon atoms and oxygen atoms in the case of being present is 5 or less, and is preferably linear.

The alkenyl group is preferably selected from the group represented by any one of the formulae (R1) to (R5). (The black dots in the formulas represent the carbon atoms in the ring structure to which the alkenyl group is bonded)

A ^K1 and A ^K2 are each independently, and when it is required to increase Δn, it is preferably aromatic, and in order to improve the response speed, it is preferably aliphatic, preferably trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,3 -difluoro-1,4-phenylene, 1,4-cyclohexenyl, 1,4-bicyclo[2.2.2]exenyl, piperidin-1,4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, more preferably represented by the structure described below,

More preferably, it shows the following structure.

Z ^K1 and Z ^K2 are each independently, preferably -CH ₂ O-, -CF ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, and more preferably -CF ₂ O- , -CH ₂ CH ₂ - or a single bond, particularly preferably -CF ₂ O- or a single bond.

n ^{K1 is} preferably 0, 1, 2 or 3, preferably 0, 1 or 2, and is preferably 0 or 1 when the emphasis is on improving Δ ε, and preferably 1 when Tni is emphasized. Or 2.

The type of the compound which can be combined is not particularly limited, and it is used in accordance with a desired combination of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two or three kinds of embodiments of the present invention. Further, in another embodiment of the present invention, there are four, five, six, and seven or more.

In the composition of the present invention, the content of the compound represented by the formula (K) is determined according to solubility at low temperature, transfer temperature, electrical reliability, refractive index anisotropy, process compatibility, dropping marks, The performance required for the afterimage, dielectric guidance, etc. is appropriately adjusted.

The lower limit of the preferred 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 preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25% in the form of one aspect of the present invention, relative to the total amount of the composition of the present invention. .

Keeping the viscosity of the composition of the present invention low and requiring a faster response In the case of the composition, it is preferable to lower the above lower limit value and lower the upper limit value. Further, when the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

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

(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 each independently represent a hydrogen atom or Fluorine atom, Y ^K11 represents fluorine atom or OCF ₃ )

The type of the compound which can be combined is not particularly limited, and it is used in accordance with a desired combination of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two or three or more of the embodiments of the present invention.

The lower limit of the preferred 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%, 5%.

Keeping the viscosity of the composition of the present invention low and requiring a faster response In the case of the composition, it is preferable to lower the above lower limit value and lower the upper limit value. Further, when the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (K-1) is specifically preferably a compound represented by the formula (K-1.1) to the formula (K-1.4), preferably a formula (K-1.1) or a formula (K). The compound represented by the formula -1.2) is further preferably a compound represented by the formula (K-1.2). Further, it is also preferred to use a compound represented by the formula (K-1.1) or the formula (K-1.2) at the same time.

The lower limit of the preferred content of the compounds relative 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%, 5%.

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

(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 each independently represent a hydrogen atom or Fluorine atom, Y ^K21 represents fluorine atom or OCF ₃ )

The type of the compound which can be combined is not particularly limited, and it is used in accordance with a desired combination of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two or three or more of the embodiments of the present invention.

The lower limit of the preferred 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, when the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

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

The lower limit of the preferred content of the compounds relative 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%, 5%.

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

(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 each independently represents a hydrogen atom or Fluorine atom, Y ^K31 represents fluorine atom or OCF ₃ )

The type of the compound which can be combined is not particularly limited, and it is used in accordance with a desired combination of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two or three or more of the embodiments of the present invention.

The lower limit of the preferred 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, when the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the above lower limit value and lower the upper limit value. Also, in order to maintain the driving voltage When it is lower and it is desired to increase the dielectric specificity, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (K-3) is specifically preferably a compound represented by the formula (K-3.1) to the formula (K-3.4), more preferably a formula (K-3.1) or a formula (K). -3.2) The compound represented. Further, it is also preferred to use a compound represented by the formula (K-3.1) and the formula (K-3.2) at the same time.

The lower limit of the preferred content of the compounds relative 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%, 5%.

The compound represented by the formula (K) is preferably, for example, a compound selected from the group consisting of compounds represented by the 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 each independently represent a hydrogen 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-)

The type of the compound which can be combined is not particularly limited, and it is used in accordance with a desired combination of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two or three or more of the embodiments of the present invention.

The lower limit of the preferred 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, when the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (K-4) is specifically preferably a compound represented by the formula (K-4.1) to the formula (K-4.18), more preferably a formula (K-4.1) or a formula (K). -4.2), a compound represented by the formula (K-4.11), (K-4.12). Also, it is preferable to use the simultaneous use (K) -4.1), a compound represented by the formula (K-4.2), the formula (K-4.11), and (K-4.12).

The lower limit of the preferred content of the compounds relative 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%, 5%.

The compound represented by the formula (K) is preferably, for example, a compound selected from the group of compounds represented by the 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 each independently represent a hydrogen atom or 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-)

The type of the compound which can be combined is not particularly limited, and it is used in accordance with a desired combination of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two or three or more of the embodiments of the present invention.

The lower limit of the preferred 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, when the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (K-5) is specifically preferably a compound represented by the formula (K-5.1) to the formula (K-5.18), preferably a formula (K-5.11) to a formula (K). - 5.14) The compound represented by the formula (K-5.12) is further preferably a compound represented by the formula (K-5.12).

The lower limit of the preferred content of the compounds relative 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%, 5%.

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

(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 each independently represent a hydrogen atom or Fluorine atom, Y ^K61 represents a fluorine atom or OCF ₃ , and Z ^K61 represents -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-)

The type of the compound which can be combined is not particularly limited, and it is used in accordance with a desired combination of properties such as solubility at low temperature, transfer temperature, electrical reliability, and refractive index anisotropy. The types of the compounds to be used are, for example, one, two or three or more of the embodiments of the present invention.

The lower limit of the preferred 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%, 5%.

In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred to lower the above lower limit value and lower the upper limit value. Further, when the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the above lower limit value and lower the upper limit value. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and increase the upper limit value.

Further, the compound represented by the formula (K-6) is specifically preferably a compound represented by the formula (K-6.1) to the formula (K-6.18), preferably a formula (K-6.15) to a formula (K). - 6.18) The compound represented by the formula (K-6.16) and the compound represented by the formula (K-6.17). Further, it is also preferred to use a compound represented by the formula (K-6.16) and the formula (K-6.17) at the same time.

The lower limit of the preferred content of the compounds relative 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%, 5%.

A preferred embodiment of the liquid crystal composition of the present invention is preferably the first component from the following formula (Ia) and formula (Ib):

(In the above formulae (Ia) and (Ib), R ^1a and R ^2a each have the same meaning as R ⁱ¹ in the formula (i), and R ^1b and R ^2b respectively represent R in the formula (i) ^{I2 has the} same meaning, n ^1b represents 1 or 2, and A ^1b independently represents trans-1,4-cyclohexylene, 1,3-di Alkano-2,5-diyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-cyclohexenylene or naphthalene-2,6-diyl, this group At least one or two of the compound groups represented by one of the hydrogen atoms may be substituted with a fluorine atom, and more preferably three.

In addition, when at least one or two or more selected from the group consisting of the compounds represented by the formula (Ia) and the formula (Ib), it is preferred to contain 15 to 80% by mass, more preferably, the entire liquid crystal composition. It is contained in an amount of 20 to 70% by mass, more preferably 25 to 60% by mass, still more preferably 30 to 55% by mass.

When the combination of the general formula (Ia) and the general formula (Ib) accounts for 20 to 70% of the entire liquid crystal composition, the effect of high-speed responsiveness is exerted, and if it is used in combination with the second component described below, From the viewpoint of chemical structure or specificity, compatibility is improved and storage stability is improved, so that the problem of precipitation of a liquid crystal compound can be suppressed and prevented.

A more preferred embodiment of the liquid crystal composition of the present invention is preferably a formula (II-a) and a formula (II-b) as a second component.

(In the above formulae (II-a) and (II-b), R ^3a and R ^3b each have the same meaning as R ⁱ¹ in the formula (i), and X ^1a and X ^1b represent a fluorine atom, -OCF ₃ Or -CF ₃ , A ^2a and A ^2b independently represent trans-1,4-cyclohexylene, 1,3-di Alkano-2,5-diyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-cyclohexenylene or naphthalene-2,6-diyl, this group One of the hydrogen atoms may be substituted with a fluorine atom. Z ^2a and Z ^2b each independently represent a single bond, -CF ₂ O-, OCF ₂ -, CH ₂ O- or -OCH ₂ -, and m ^2a and m ^2b represent 1 or 2. Further, when m ^2a and m ^2b are 2, A ^2a and A ^2b may be the same or different, and Z ^2a and Z ^2b may be the same or different, and at least one or two compounds are selected from the group of compounds represented. .

When the combination of the formula (II-a) and the formula (II-b) accounts for 5 to 35% of the entire liquid crystal composition, the effect of ensuring the improvement of Δn and the driveable Δ ε is exhibited, and further, When the preferred combination of the first components is used in combination, and the total amount of the first component is more than the amount of the second component, high-speed responsiveness can be maintained. Further, since the combination of the formula (II-a) or the formula (II-b) and the formula (Ia) or the formula (Ib) specifically enhances the compatibility of the compounds of the components of the liquid crystal composition, The storage stability of the liquid crystal composition is improved, and the problem of precipitation of the liquid crystal compound can be suppressed and prevented.

In the liquid crystal composition of the present invention, at least one or two or more compounds are selected from the group of compounds represented by the general formula (I-a) and the general formula (I-a) as the first formation. And selecting at least two of the compound groups represented by the general formula (IIa) and the general formula (IIb) as the second component can solve not only the problems associated with the precipitation of the liquid crystal compound and the low temperature stability, but also all of them can be achieved. The problem of dropping marks and maintaining high-speed responsiveness.

The lower limit of the preferred content of the total 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%. The upper limit of the preferred content is 100%, 99%, 98%, 95%.

The lower limit of the preferred content of the total of the compounds represented by the general formula (i), the general formula (M) and the (K) 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%. The upper limit of the preferred content is 100%, 99%, 98%, 95%.

It is represented by the general 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 preferred content of the total of the compounds is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100. %. The upper limit of the preferred content is 100%, 99%, 98%, 95%.

The composition of the invention of the present invention is preferably a compound which does not contain a structure in which an oxygen atom such as a peroxy (-CO-OO-) structure is bonded to each other.

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

In the case of emphasizing the stability under UV irradiation, it is preferred to replace the chlorine The content of the compound is 15% or less, preferably 10% or less, more preferably 8% or less, still more preferably 5% or less, more preferably 5% or less, based on the total mass of the above composition. It is set to 3% or less, and further preferably does not substantially contain.

Preferably, the content of the compound having a ring structure of all 6 in the molecule is set to be large, and it is preferred that the content of the compound having a ring structure of all 6 in the molecule is set as the total amount of the above composition. The mass is 80% or more, more preferably 90% or more, further preferably 95% or more, and most preferably a composition consisting essentially of a compound having a ring structure of all 6 in the molecule.

In order to suppress deterioration caused by oxidation of the composition, it is preferred to set the content of the compound having a cyclohexene group as a ring structure to be small, and it is preferred to set the content of the compound having a cyclohexene group as a relative The total mass of the above composition is 10% or less, preferably 8% or less, more preferably 5% or less, more preferably 3% or less, and further preferably substantially not contained.

When attention is paid to the improvement of viscosity and the improvement of Tni, it is preferred to set the content of a compound having a 2-methylbenzene-1,4-diyl group in which a hydrogen atom can be substituted into a halogen in the molecule. The content of the compound having the above 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less, more preferably 8% or less, more preferably 8% or less, based on the total mass of the above composition. It is preferably 5% or less, preferably 3% or less, and more preferably substantially not contained.

In the present case, the term "substantially not contained" means that it is not contained except for those that are not intentionally contained.

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

The liquid crystal layer and/or the liquid crystal composition of 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), the polymerizable monomer It is preferred to exhibit liquid crystallinity. That is, the liquid crystal layer of the present invention preferably polymerizes the polymerizable monomer contained in the liquid crystal composition. The specific content of the polymerizable monomer in the liquid crystal composition of the polymerizable monomer of the present invention is preferably 5% or less, more preferably 2% or less, still more preferably 1.5% or less, and particularly preferably 1 Below %, the best is below 0.5%. If it is 5% or less, the occurrence of dripping marks can be reduced. Further, the lower limit of the content of the polymerizable monomer in the liquid crystal composition is preferably 1000 ppm, preferably 3,000 ppm, more preferably 5,000 ppm.

The polymerizable monomer of the present invention is preferably selected from the group consisting of the formula (P-1) and the formula (P-2):

(In the above formula (P-1) to formula (P-2), R ^p11 , R ^p12 , R ^p21 and R ^p22 each independently represent the following formula (RI) to formula (R-IX):

In any one of the above formulae (RI) to (R-IX), R ² to R ^{6 are} each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Halogenated alkyl group, W is a single bond, -O- or methylene group, T is a single bond or -COO-, and p, t and q each independently represent 0, 1 or 2, A ^p11 , A ^p12 , and A ^p22 Respectively represent 1,4-phenylene, 1,4-cyclohexylene, indole-2,6-diyl, phenanthrene-2,7-diyl, pyridine-2,5-diyl, pyrimidine-2 , 5-diyl, naphthalene-2,6-diyl, indane-2,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or 1,3-di An alkane-2,5-diyl group which is unsubstituted or represents a halogen atom, a cyano group, a nitro group, a R ^p11 group or an alkyl group having 1 to 12 carbon atoms (one of the above alkyl groups or two or more non-adjacent groups) -CH ₂ - may be independently substituted with -C≡C-, -O-, -CO-, -COO- or -OCO-, one of the groups or two or more non-adjacent hydrogen atoms may be ^{Each of} them is independently substituted with a fluorine atom), and A ^p21 and A ^p23 independently represent a divalent to tetravalent aromatic group or a divalent to tetravalent alicyclic group, L ^p11 , L ^p12 , L ^p21 and L ^P22 independently represents 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- or -C≡C-, in the above formula z 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, and m ^p21 and m ^p23 independently represent 1 to 4, respectively. It The number, and represents m ^p21 + m ^p23 ≧ 3, m ^p11 is 2 or more in the case, a plurality of A ^p11 on the existence and L ^p11, respectively, these may be the same or different, is 2 or more in the m ^p12 In the case of the plurality of A ^p12 and L ^{p12 present} , the same may be the same or different. When m ^p22 is 2 or more, regarding the plurality of A ^p22 and L ^p21 existing, the respective The same or different, when m ^p21 is 2 or more, the plurality of R ^p21 and Sp ^p21 may be the same or different, and when m ^p23 is 2 or more, One or more of a plurality of groups of compounds represented by the plurality of R ^p22 and Sp ^p22 , which may be the same or different.

In the general formula (P-1) and the general formula (P-2), it is preferred that 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 an oxygen atom is bonded to an aromatic ring).

In the general formula (P-1) and the general formula (P-2), it is more preferred that A ^p11 , A ^p12 and A ^p22 each independently represent a 1,4-phenylene group, a fluorene-2,6-diyl group. , phenanthrene-2,7-diyl or naphthalene-2,6-diyl, the group may be unsubstituted or substituted by an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a carbon atom The alkoxy group of 1 to 5, the alkyl ester group having 1 to 5 carbon atoms, the halogenated alkoxy group having 1 to 5 carbon atoms, fluorine or cyano group.

In the formula (P-1) and the formula (P-2), it is preferred that 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-, and preferably z in the above formula represents 4. When the linking group is the above group, the polymerizable monomer may have a linear structure.

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

In the compound represented by the formula (P-2), m ^p21 and m ^p23 each independently represent 1, 2 or 3, and preferably m ^p22 represents 1 or 2. Further, it is more preferably 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 containing an aromatic ring, and preferably 2 to 4 bonding sites are derived from an aromatic ring. Examples thereof include a phenyl skeleton, a tetrahydronaphthalene skeleton, a phenanthrene skeleton, an anthracene skeleton, and a naphthalene skeleton.

In the formula (P-2), the divalent to tetravalent alicyclic group is a divalent to tetravalent organic group having an alicyclic structure, and preferably 2 to 4 bonding sites are derived from Specific examples of the ring include a cyclohexyl skeleton, a cyclohexene skeleton, and the like.

In the formula (P-2), as a divalent aromatic group, it represents 1,4-phenylene, anthracene-2,6-diyl, phenanthrene-2,7-diyl, pyridine-2,5. -diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, indane-2,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl Or 1,3-two An alkane-2,5-diyl group, preferably an unsubstituted or alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, carbon A halogenated alkoxy group having 1 to 12 atoms, a halogen atom, a cyano group, a nitro group or R ^{p11 is} substituted.

In the formula (P-2), the divalent to tetravalent aromatic group is any one of the following formulas (bi) to (b-ix), and the aromatic group is unsubstituted or can be subjected to An alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, Nitro or R ^p11 substituted.

(wherein, by * bonding with Sp ^p21 or Sp ^p22 , by ** bonding with L ^p21 or L ¹²² )

In addition, the specific content of the polymerizable monomer represented by the above formula (P-1) or (P-2) in the entire liquid crystal composition is preferably 5% or less, more preferably 3% or less, and further It is preferably 2% or less, more 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, preferably 3,000 ppm, more preferably 5,000 ppm.

Hereinafter, preferred structures of the compounds represented by the general formulae (P-1) to (P-2) of the present invention are exemplified.

In the compound represented by the above formula (P-1), preferably 4≧m ^p11 +m ^p12 ≧2 and L ^p11 or L ^p12 represents a group selected from -COO-, -OCO-, -COOC ₂ H ₄ - , -OCOC 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 of one of the groups. Since the polymerizable monomer having such a structure has the same linearity as the liquid crystal molecules and has a certain degree of freedom, it is excellent in compatibility with a liquid crystal compound.

A preferred example of the compound represented by the formula (P-1) of the present invention is a polymerizable compound represented by the following formula (P-a-1) to (P-a-33).

In the compound represented by the above formula (P-1), it is preferred that m ^p11 + m ^p12 = 2, A ^p11 and A ^p12 are 1,4-phenylene groups and L ^p11 and L ^p12 are single bonds. Sexual monomer. Since the polymerizable monomer having such a structure has a biphenyl structure, the orientation restricting power after polymerization of the polymerizable compound containing the skeleton is most suitable for the PSA type liquid crystal display element, and a good orientation state can be obtained, so that display unevenness can be suppressed. Or no display unevenness at all.

A preferred example of the compound represented by the formula (P-1) of the present invention is a polymerizable compound represented by the following formula (P-b-1) to (P-b-34).

Among the compounds represented by the above formula (P-1), m ^p11 + m ^p12 =1 and A ^p11 or A ^p12 are a polymerizable monomer of a phenanthrene-2,7-diyl group. It is considered that the composition of the polymerizable monomer of this structure is largely photosensitive.

A preferred example of the compound represented by the formula (P-1) of the present invention is a polymerizable compound represented by the following formula (P-c-1) to (P-c-52).

In the formula (P-2), m ^p22 preferably represents an integer of 1 or more and 3 or less, at least one of L ^p21 or L ^p22 is a single bond, and A ^p21 and A ^p23 each independently represent an unsubstituted group. Or an alkyl group having 1 to 5 carbon atoms (one of the above alkyl groups or two or more non-adjacent -CH ₂ - may be independently substituted with -C≡C-, -O-, -CO -, -COO- or -OCO-, one of the above alkyl groups or two or more non-adjacent hydrogen atoms may be independently substituted with a fluorine atom), a fluorine atom, a cyano group or a nitro group substituted Formula (bi)~(b-ix).

(wherein, by * bonding with Sp ^p21 or Sp ^p22 , by ** bonding with L ^p21 or L ^p22 ) as a preferred example of the compound represented by the formula (P-2) of the present invention, The polymerizable compound represented by the following formula (Pd-1) to formula (Pd-57) is listed.

The liquid crystal layer in the liquid crystal display device of the present invention is preferably contained in the liquid crystal composition. There is a polymerizable compound, and the polymerizable compound is polymerized. Thereby, the orientation restricting force of the liquid crystal molecules of the photo-alignment film is improved. More specifically, description will be made using FIGS. 6 to 7. Fig. 6 is a schematic cross-sectional view showing a light alignment film and a liquid crystal layer in a liquid crystal display device. Fig. 6(A) shows a state in which liquid crystal compositions containing liquid crystal molecules 1a and polymerizable monomers 1b are aligned on a light-oriented film in a specific direction (in the direction in which the light-aligning film is oriented). Further, in Fig. 6(A), since the vertical alignment type light directing film is used, the liquid crystal molecules are arranged in a direction substantially perpendicular to the substrate. Therefore, the polymerizable monomer 1b preferably exhibits liquid crystallinity. Further, (B) of FIG. 6 is a state in which the liquid crystal molecules 1a and the polymerizable monomer 1b are aligned on the light-aligning film in a direction substantially perpendicular to the substrate in the state of FIG. 6(A). The state in which the body is polymerized. Although the polymer obtained by polymerizing a polymerizable monomer is not shown in FIG. 6(B), it is considered to exist in a large amount at the interface between the light-aligning film and the liquid crystal layer. In (B) of Fig. 6, an enlarged view of the IV region is shown in Fig. 7(D). 7 is an enlarged schematic view of the vicinity of the interface between the liquid crystal layer and the photo-alignment layer, and it is considered that the orientation restriction force is improved by the interaction of the polymer with the liquid crystal molecules or the vertical orientation to induce the interaction of the component with the polymer.

Fig. 7 is a schematic cross-sectional view showing a liquid crystal display device, which is a schematic cross-sectional view of a light alignment film and a liquid crystal layer in a liquid crystal display device. More specifically, FIG. 7 is a view showing a change in switching of liquid crystal molecules due to the presence or absence of a voltage after polymerization of a polymerizable monomer. (B) of FIG. 7 is the same as the state of (B) of FIG. 6 described above, and shows a state in which no voltage is applied. Further, in FIGS. 6 and 7, in order to solve problems such as viewing angle dependency, directional division and pretilt angle are provided. When a voltage is applied, the liquid crystal molecules 1a are oriented in the direction of the electric field (Fig. 7(C)), and if the voltage is turned OFF, the liquid crystal molecules 1a are restored to a vertical orientation having a specific pretilt angle (Fig. 7(B)). As described above, in the case where the polymerizable monomer is polymerized without applying a voltage, it is considered that the interaction is due to the interaction. (Wan Vale, etc.) The polymer 1c and the liquid crystal molecule 1a which are connected to each other by a polymerizable monomer function, and the pretilt angle is stabilized. Further, as shown in Fig. 7(C), it is also considered that the interaction between the polymer obtained by polymerizing the polymerizable monomer and the vertical orientation inducing component increases the orientation regulating force of the liquid crystal molecules in the substantially vertical direction.

Therefore, when a liquid crystal layer containing a polymerizable compound and a liquid crystal compound and polymerizing the polymerizable monomer is provided in the liquid crystal display device, it is considered that even if the voltage is turned ON-OFF, the interaction is Since the polymer 1c in which the polymerizable monomers are bonded to each other and the liquid crystal molecules 1a function, it is possible to improve the pretilt angle which is reduced in the temporality of the problem from the previous time. Thereby, it is considered that the liquid crystal molecules can maintain a specific orientation direction applied to the light directing film, and thus the substantial orientation restricting force is improved.

In the case where a polymerizable compound is added to the liquid crystal composition of the present invention, when a polymerization initiator is contained in order to promote polymerization, benzoin ethers, benzophenones, acetophenones, and benzophenes may be mentioned. Ketone ketones, sulfhydryl phosphine oxides, and the like. However, it is preferred not to use a polymerization initiator.

The liquid crystal composition of the present invention may further contain a compound represented by the formula (Q) as an antioxidant.

In the above formula (Q), R ^Q represents an alkyl group or an alkoxy group having 1 to 22 carbon atoms, and one or more CH ₂ groups in the alkyl group may be substituted with -O in a manner in which the oxygen atoms are not directly adjacent to each other. -, -CH=CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O-, -OCF ₂ -, M ^Q represents trans-1,4-cyclohexylene , 1,4-phenylene, or a single bond.

In the above formula (Q), R ^{Q is} preferably an alkyl group or alkoxy group having 1 to 22 carbon atoms, and the alkyl group (including the alkyl group in the above alkoxy group) may be linear or branched. shape. Further, R ^Q 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 an alkyl group in the above alkoxy group) The CH ₂ group may be substituted with -O-, -CH=CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O-, -OCF in such a manner that the oxygen atoms are not directly adjacent to each other. ₂ -. In the above formula (Q), R ^{Q is} preferably a carbon number of 1 to 20 and is selected from a linear alkyl group, a linear alkoxy group, and a CH ₂ group to be substituted with -OCO- or COO-. Preferably, at least one of the linear alkyl group, the branched alkyl group, the branched alkoxy group, and the one CH ₂ group is substituted with a branched alkyl group of -OCO- or COO-, more preferably Selecting a linear alkyl group having 1 to 10 carbon atoms, a CH ₂ group substituted with a linear alkyl group of -OCO- or COO-, a branched alkyl group, a branched alkoxy group, and a CH ₂ group At least one of the group consisting of a branched alkyl group substituted with -OCO- or COO-.

M ^Q represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a single bond, preferably a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

The compound represented by the above formula (Q) is preferably at least one compound selected from the group consisting of compounds represented by the following formulae (Qa) to (Qd), more preferably a formula (Qa) and/or Or a compound represented by (Qc).

In the above formula (Qa) to formula (Qd), R ^{Q1 is} preferably a linear alkyl group or a branched alkyl group having 1 to 10 carbon atoms, and R ^{Q2 is} preferably a linear alkyl group having 1 to 20 carbon atoms. Or a branched alkyl group, R ^{Q3 is} preferably a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group, a linear alkoxy group or a branched alkoxy group, and L ^{Q is} preferably a carbon atom number 1 ~8 linear alkyl or branched alkyl. In the above, the compound represented by the 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, it is preferred to contain one or two kinds of compounds represented by the above formula (Q), and further preferably one to five kinds, and the content thereof is relative to the liquid crystal composition of the present invention. The total mass is preferably 0.001 to 1% by mass, preferably 0.001 to 0.1% by mass, preferably 0.001 to 0.05% by mass.

(orientation layer)

The light directing layer of the present invention is disposed on at least one of the first substrate and the second substrate, and is preferably disposed on both sides of the first substrate and the second substrate.

The alignment layer of the present invention is preferably a photo-alignment film (or also referred to as a photo-alignment layer) containing a photoresponsive polymer which responds to light and whose chemical structure changes. Further, the light directing layer of the present invention is preferably a vertically oriented type of oriented layer. The so-called vertical alignment type is preferably such that the long-axis direction of the liquid crystal molecules having positive dielectric properties is oriented substantially perpendicular to the substrate.

Thereby, in the liquid crystal display element using the p-type material, the unevenness of the rubbing caused by the unevenness of the surface or the dripping of the liquid crystal composition can be reduced by the (common or pixel) electrode structure or the like.

Generally, the photo-alignment film has various means, and examples thereof include an unsaturated bond having an azo group (for example, an azobenzene compound), a Schiff base, and a carbon-carbon double bond. Photoisomerization by light irradiation of a compound such as a moiety; photodimerization using a cinnamic acid derivative; light cracking (photolysis) using coumarin, chalcone, or the sigma bond of the polymer itself (for example, photodegradable polyimine, etc.) or the like.

More specifically, the photoresponsive polymer is preferably at least selected from the group consisting of a photoresponsive decomposition polymer, a photoresponsive dimerization polymer, and a photoresponsive isomerization polymer. One is, in particular, a photoresponsive decomposition polymer.

Further, it is preferred that the light-aligning film of the present invention contains a vertical orientation inducing component for vertically aligning liquid crystal molecules. In this case, the vertical alignment inducing component may be contained as a repeating unit of copolymerization in the photoresponsive polymer, or may be a substituent of a side chain or a main chain of the photoresponsive polymer, or may be used as a substituent of the side chain or the main chain of the photoresponsive polymer. It is contained in a photo-alignment film in a mixture different from the photoresponsive polymer.

The photoresponsive decomposition type polymer of the present invention is preferably a light crack (photodecomposition) by a σ bond of the polymer itself. More specifically, it is preferred to have a structure of a polysiloxane, a polyimine, and a polyphthalic acid derivative as a main chain, and more preferably a polyimine or a polyamine derivative structure. The polyproline derivative is preferably an alkyl ester having 1 to 5 carbon atoms or an alkylammonium salt having 1 to 18 carbon atoms.

The photoresponsive decomposition polymer of the present invention preferably contains at least one polymer selected from the group consisting of polylysine and polyimine obtained by reacting a tetracarboxylic dianhydride with a diamine compound.

The above tetracarboxylic dianhydride which is a raw material of a polyimine and a poly phthalic acid derivative is mentioned below.

(In the above formula, Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent 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, but at least one of Z ¹ , Z ² , Z ³ , Z ⁴ is not a hydrogen atom or a methyl group, and R represents a carbon atom. a number of 1 to 5 alkyl groups, T represents a single bond, -CH ₂ -, -O-, -S-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CO-, -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 above compounds, preferred are formula (TCA-1), formula (TCA-2), formula (TCA-3), formula (TCA-4), formula (TCA-5), formula (TCA-8). And (TCA-10), especially the formula (TCA-1), formula (TCA-8).

The following diamine compound which is a raw material of a polyimine and a poly phthalic acid derivative is mentioned below.

Among such compounds, preferred are the formula (DA-1), the formula (DA-25), the formula (DA-31), the formula (DA-32), the formula (DA-49), and more preferably the formula (DA- 1), formula (DA-25), formula (DA-49).

Further, in the case where a photoisomerization type is used in the photo-alignment film of the present invention, it is preferred that at least one of the tetracarboxylic anhydride or the diamine compound is selected from the following formula (TCA-38). At least one of the group consisting of (DA-50) and (DA-56).

For example, in addition to (or instead of) the compound of the above formula (TCA-1) to the above formula (TCA-37) exemplified as the above tetracarboxylic anhydride, the following formula (TCA-38) is preferably used:

The compound represented. Alternatively, in addition to (or instead of) the compound of the formula (DA-1) to the formula (DA-49), as the diamine compound, the following formula (DA-50) to formula (DA-56) is preferably used:

The compound represented.

Further, when a photodimerization type is used in the photo-alignment film of the present invention, hydrogen in the diamine compound represented by the above formula (DA-1) to (DA-49) is preferred. At least one of the atoms 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 compound of the above formula (DA-1) to (DA-49), it is preferred to use a hydrogen atom in the compound of (DA-1) to (DA-49) as the diamine compound. Substituted as general formula (V):

(In the formula, the dotted line indicates the bonding bond of the atom bonded to the hydrogen atom of (DA-1) to (DA-49), and G ¹ , G ² , G ³ , G ⁴ , and G ⁵ each independently represent a single bond. A bond, an alkylene group having 2 to 12 carbon atoms (1 -CH ₂ - group or 2 or more non-contiguous -CH ₂ - groups may be substituted with -O-, -CO-, -COO-, - OCO-, -NR-, -NRCO-, -CONR-, -NRCOO-, -OCONR-, -NRCONR-, -CH=CH-, -C≡C-, -OCOO-. R represents a hydrogen atom or a carbon atom Alkyl groups 1 to 20), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF ₂ O-, -OCF ₂ - -CF ₂ CF ₂ -, -C≡C-, -CH=CHCOO-, -OCOCH=CH-, wherein any one of G ¹ , G ² , G ³ , G ⁴ , G ⁵ or more represents - CH=CHCOO-, -OCOCH=CH-.

n ⁵ , n ⁶ , n ⁷ , n ⁸ represent 0 or 1, and E ¹ , E ² , E ³ , E ⁴ , and E ⁵ each independently represent trans-1,4-cyclohexylene, trans-1, 4-two Alkano-2,5-diyl, 1,4-strandyl, 2,6-anthranyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 2,5-thienylene , 2,5-furanyl or 1,4-phenylene, such unsubstituted or more than one hydrogen atom may be substituted with a fluorine atom, a chlorine atom, a methyl group or a methoxy group, and Z represents a hydrogen atom, A fluorine atom or an alkyl group having 1 to 12 carbon atoms (1 -CH ₂ - group or 2 or more non-contiguous -CH ₂ - groups may be substituted with -O-, -CO-, -COO-, - OCO-, -NR-, -NRCO-, -CONR-, -NRCOO-, -OCONR-, -NRCONR-, -CH=CH-, -C≡C- or -OCOO-. R is a hydrogen atom or a carbon atom Those having a number of 1 to 20 alkyl groups, cyano groups, nitro groups, hydroxyl groups or carboxyl groups).

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

As a photo-degradable light-aligning film of the present invention, tetracarboxylic anhydride is more preferably a formula (TCA-1), a formula (TCA-2) or a formula (TCA-) from the viewpoint of exhibiting good liquid crystal orientation. 3), formula (TCA-4), formula (TCA-5), formula (TCA-33) (in the above formula (TCA-33), T is preferably -CO-) and TCA-34 (the above formula (TCA) In -34), T is preferably -CO-), and more preferably is TCA-1, TCA-2, TCA-3, TCA-4. And (TCA-5). Further, as the photo-degradable photo-alignment film of the present invention, the diamine compound is preferably a formula (DA-1), a formula (DA-25), or a formula (see a viewpoint of exhibiting good liquid crystal orientation). DA-49).

The tetracarboxylic anhydride or the diamine compound exemplified above may be used alone or in combination of two or more kinds depending on the desired properties.

In the preferred polylysine for the photoresponsive decomposition polymer of the present invention, the mixing ratio of the above tetracarboxylic dianhydride to the above diamine compound is preferably 1 equivalent to the amine group of the diamine, and The acid anhydride group of the carboxylic acid dianhydride has a ratio of 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents.

Further, in the photo-alignment film of the present invention, the synthesis reaction of the poly-proline is carried out by condensation of a tetracarboxylic anhydride with a diamine compound, preferably in an organic solvent. The reaction temperature is preferably from -20 ° C to 150 ° C, more preferably from 0 to 100 ° C. Further, the reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

Examples of the organic solvent include alcohols, ketones, esters, ethers, aprotic polar solvents, phenol and its derivative-based solvents, halogenated hydrocarbon-based solvents, and hydrocarbon-based solvents.

The above-mentioned alcohol is preferably, for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol or ethylene glycol monomethyl ether.

As the ketone, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or the like is preferable.

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

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

Specific examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl. Kea, γ-butyrolactone, tetramethylurea, and hexamethylphosphonium triamine.

As the phenol and a derivative thereof, for example, m-cresol, xylenol, halogenated phenol or the like is preferable.

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

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

The total amount of the tetracarboxylic dianhydride and the diamine compound relative to the organic solvent is preferably from 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 polyamic acid can be obtained. The obtained reaction solution may be directly supplied to the preparation of the oriented film, or the polylysine contained in the reaction solution may be isolated and supplied to the preparation of the oriented film, or may be obtained by isolation. The polyamic acid is refined and then supplied to the preparation of the oriented film.

Further, when the polylysine obtained above is dehydrated and closed to form a polyimine, the reaction solution may be directly supplied to the dehydration ring closure reaction, or may be contained in the reaction solution. The polylysine is subjected to a dehydration ring-closing reaction after being separated, or the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. The isolation and purification of polylysine can be carried out in accordance with a known method.

As a method of producing a polyimine by imidization of a polyphosphonium amide obtained by the above reaction, it can be obtained by dehydrating a poly-proline and ringing it and performing imidization. Specifically, it can be carried out by a method of heating polyglycolic acid or dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed.

The organic solvent used for the dehydration ring-closure reaction is exemplified as the organic solvent exemplified as the user of the synthesis of the polyamic acid, and thus is omitted here.

The polyimine which is the oriented film of the present invention may be a fully ruthenium imide formed by dehydration ring closure of all of the proline structures of the precursor, polyglycolic acid, or may be only a proline. One part of the structure is subjected to a dehydration ring closure and a partial ruthenium imide of the proline structure and the quinone ring structure. The polyimine of the present invention preferably has a sulfhydrylation ratio of 30% or more, more preferably 40 to 99%, still more preferably 45 to 98%. The ruthenium iodization ratio is expressed as a percentage of the total number of quinone imine ring structures in the total number of decylamine structures and the number of quinone imine ring structures. Here, one part of the quinone ring may also be an isoindole ring.

Further, in the present invention, the method for measuring the imidization ratio of polyimine is to determine a proton derived from a structure which does not change before and after imidization as a reference proton, and the peak value and the origin of the proton are used. The cumulative value of the proton peak of the NH group of proline which appeared near 9.5 to 10.0 ppm was calculated.

In the present invention, the temperature at which the polyamic acid is thermally imidized in a solution is preferably from 100 ° C to 400 ° C, more preferably from 120 ° C to 250 ° C. In this case, it is preferred to carry out the method in which the water produced by the hydrazine imidization reaction is discharged to the outside of the system.

In the present invention, when the polyphosphonium amide is imidized by a catalyst, a basic catalyst and an acid anhydride may be added to the solution of the polyamic acid obtained above, and preferably -20~ It is obtained by stirring at 250 ° C, more preferably 0 to 180 ° C. Further, in this case, the amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the proline group, and the amount of the anhydride is 1 to 50 moles of the amidate group. Times, preferably 3 to 30 moles.

Examples of the basic catalyst include pyridine, trimethylpyridine, dimethylpyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride.

Further, the imidization ratio obtained by imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

In the present invention, in the case where the produced polyamic acid or polyimine is recovered from the reaction solution of polyphosphoric acid or polyimine, the reaction solution is poured into a poor solvent to precipitate. . Examples of the poor solvent used for the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer which has been introduced into a poor solvent and precipitated is recovered by filtration, and then dried under normal pressure or reduced pressure at normal temperature or under heating.

When the concentration of the polyglycine and the polyimine of the present invention is 10% by weight, it is preferably a solution viscosity of 10 to 800 mPa·s, more preferably a solution viscosity of 15 to 500 mPa·s. By. Furthermore, the solution viscosity (mPa‧s) of the polymers is a concentration of 10 weights prepared for a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer. The % polymer solution was measured at 25 ° C using an E-type rotational viscometer.

The light-responsive polymer of the present invention is preferably the following general formula (1A) or general formula (1B) in addition to the above:

(In the above formula (1), Sp is selected from a single bond, -(CH ₂ ) _u - (wherein, u represents 1 to 20), -OCH ₂ -, -CH ₂ O-, -COO-, - At least one divalent linking group of the group consisting of OCO-, -CH=CH-, -CF=CF-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, and -C≡C- One or more of the non-adjacent CH ₂ groups in the substituents may be independently substituted with -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), and A ¹ and A ² each independently represent (a) trans-1,4-cyclohexylene (one methylene group present in the group or two or more methylene groups not adjacent to each other may be substituted with -O-, -NH- or S- ), (b) 1,4-phenylene (one or two or more present in the group -CH= may be substituted with -N=), and (c) 1,4-cyclohexene Base, 2,5-thenylene, 2,5-furanyl, 1,4-bicyclo (2.2.2) octyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, Decalin-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl

The group in the group formed, the above-mentioned group (a), the group (b) or the group (c) are respectively unsubstituted, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group or a methyl group. Or methoxy, Z ¹ , Z ² and Z ³ each independently represent 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-, which are non-contiguous One or more of the CH ₂ groups may be independently substituted with -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 phenyl group, R ^b It is a polymerizable group, an alkoxy group, a cyano group or a fluorinated alkyl group having 1 to 12 carbon atoms, and m is 0, 1, or 2, and M _b and M _d are each independently and may be the same or different, and represent the following Any one of the monomer units of the formula (U-1) to (U-13),

(In the above general formulae (U-1) to (U-10), a broken line indicates a bond with Sp, and R ^a independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen atom. Any hydrogen atom in each structure may be substituted with a fluorine atom, a chlorine atom, a methyl group, a phenyl group, a methoxy group, and in the above formula (U-11) to (U-13), a broken line indicates a bond with Sp. a bond, R ¹ represents a tetravalent ring structure, R ² represents a trivalent organic group, and R ³ represents a hydrogen atom, a hydroxyl group, 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 may be independently composed of one unit or two The above different units constitute)

A condensate of a photoresponsive dimerization type polymer, a hydrolyzate or a hydrolyzate thereof.

Further, as a preferred embodiment of the photoresponsive polymer represented by the above formula (1) of the present invention, a photoresponsive dimerization polymer having a single bond of Z ² is preferred.

The other photoresponsive dimerization type polymer of the present invention is preferably the following formula (2):

(In the above formula (2), M ¹ and M ² are each independently selected from the group consisting of acrylate, methacrylate, 2-chloroacrylate, 2-phenyl acrylate, and N- via a lower alkyl group. At least one selected from the group consisting of acrylamide, methacrylamide, 2-chloropropenylamine, 2-phenylpropenylamine, vinyl ether, vinyl ester, styrene derivative, and oxoxane The repeating unit, M ³ is selected from the group consisting of acrylate, methacrylate, 2-chloro acrylate, 2-phenyl acrylate, propylene amide, which can be N-substituted via a lower alkyl group, methacrylamide, 2 - a chloropropenylamine, a 2-phenylpropenylamine, a vinyl ether, a vinyl ester, a linear alkyl or acrylic alkyl acrylate or a methacrylate, an allyl acrylate or methacrylate, An alkyl vinyl ether or alkyl vinyl ester, a phenoxyalkyl acrylate or a phenoxyalkyl methacrylate, a hydroxyalkyl acrylate or a transalkylalkyl methacrylate, a phenylalkyl acrylate or Phenylalkyl methacrylate, acrylonitrile, methacrylonitrile, styrene, 4-methylstyrene and oxime Group of the class consisting of at least one repeating ^{unit, A 1, B 1, C} 1, A 2, B 2 and C ² each, independently selected from the group consisting of (a) trans-1,4-cyclohexylene group ( One methylene group present in the group or two or more methylene groups not adjacent thereto may be substituted with -O-, -NH- or S-), (b) 1,4-phenylene group (existing One or more of the groups -CH= may be substituted with -N=), and (c) 1,4-cyclohexenylene, 2,5-threthiophenyl, 2,5- Furanyl, 1,4-bicyclo (2.2.2) octyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl

The group in the group formed, the above-mentioned group (a), the group (b) or the group (c) are respectively unsubstituted, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group or a methyl group. Or a methoxy group, S ¹ and S ² are each independently a linear or branched alkyl group (-(CH ₂ ) _r -) or - (substituted by a fluorine atom, a chlorine atom or a cyano group 1 or more). CH ₂ ) _r -L-(CH ₂ ) _s - (wherein L means 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-, in which case R ¹ means a hydrogen atom or a lower stage The alkyl group, r and s are integers of 1 to 20 based on the condition of r+s≦24), and D ¹ and D ² are each independently -O-, -NR ² - or contain a compound selected from the following formula ( d)~(f): (d) trans-1,4-cyclohexylene (one methylene group present in the group or two or more methylene groups not adjacent to each other may be substituted with -O- , -NH- or S-), (e) 1,4-phenylene (one or two or more present in the group -CH= may be substituted with -N=), and (f)1 , 4-cyclohexenylene, 2,5-thenylene, 2,5-extended furyl, 1,4-bicyclo (2.2.2) octyl, naphthalene-1,4-diyl, naphthalene- 2, 6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl

The group in the group formed, the above-mentioned group (d), group (e) or group (f) are respectively unsubstituted, or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group Or a methoxy group, in which case R ² is a hydrogen atom or a lower alkyl group, and X ¹ , X ² , Y ¹ and Y ² are each independently and mean a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, and optionally a fluorine. The atom-substituted and CH ₂ group or a plurality of non-contiguous CH ₂ groups may be substituted with an alkyl group having 1 to 12 carbon atoms, such as -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 -, where R ⁴ means a hydrogen atom or a lower alkyl group; t means an integer from 1 to 4; u is an integer from 1 to 3, and p ¹ , p ² , q ¹ and q ² are respectively Independent of each other, 0 or 1, R ^1a and R ^2a are each independently and mean a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, or a linear or branched chain having 1 to 20 carbon atoms. Alkyl, alkoxy, alkyl-COO-, alkane a group of -CO-NR ³ or an alkyl-OCO group, wherein R ³ means a hydrogen atom or a lower alkyl group, and at least one hydrogen atom of the above alkyl group or the above alkoxy group may be substituted with a fluorine atom or a chlorine atom. Or a cyano group or a nitro group, the above alkyl group or a CH ₂ group of the above alkoxy group or a plurality of non-contiguous CH ₂ groups may be substituted with -O-, -CH=CH- or -C≡C-, n ¹ , n ² and n ³ are 0 < n ¹ ≦ 1, 0 ≦ n ² < 1 and 0 ≦ n ³ ≦ 0.5 of the molar fraction of the copolymerized monomer)

The photoresponsive dimerization polymer represented.

The vertical orientation inducing component of the present invention can be contained as a repeating unit of a photoresponsive polymer, or can be used as a substituent of a side chain and/or a main chain of a photoresponsive polymer, and can be used as a light responsiveness. The mixture of molecules is contained in the photo-alignment film.

The vertical orientation inducing component of the present invention preferably contains an alkyl group having 3 or more and 30 or less carbon atoms, an alkoxy group having 3 or more and 30 or less carbon atoms, and the following formula (H) and the following formula (J). -1) and the following formula (J-2).

The above formula (H) is preferably

(In the above chemical formula (H), the dotted line means a bond to a carbon atom or a nitrogen atom, and R ^1H and R ^2H each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and L ^1H represents -O-, -OCO- or -COO-, r represents an integer of 1 or more and 10 or less).

The alkyl group is more preferably an alkyl group having 5 or more and 25 or less carbon atoms, further preferably an alkyl group having 8 or more and 20 or less carbon atoms, more preferably an alkyl group having 10 or more and 25 or less carbon atoms. Further, it is preferably an alkyl group having 8 or more and 20 or less carbon atoms. Further, one or more CH ₂ of the alkyl group in the vertical orientation inducing component may be substituted with an oxygen atom. Further, the alkyl group includes a linear chain, a branched chain or a cyclic chain, and more preferably a linear chain or a branched chain.

When the vertical alignment inducing component of the present invention is contained in the photoresponsive polymer as a repeating unit of copolymerization, it is preferred to contain the formula (RI) to the formula (R-IX):

(In the above formula (RI) to (R-IX), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ^{61 are} each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a carbon atom. a number of 1 to 5 halogenated alkyl groups, and V is a vertical orientation inducing component, and is an alkyl group having 3 or more and 20 or less carbon atoms, an alkoxy group having 3 or more carbon atoms and 20 or less or a general formula (H):

(In the above chemical formula (H), the dotted line means a bond to a carbon atom or a nitrogen atom, and R ^1H and R ^2H each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and L ^1H represents -O-, -OCO- or -COO-, r represents an integer of 1 or more and 10 or less), wherein W is a single bond, -O- or methylene, and T is a single bond or -COO-, p, t and q is a repeating unit derived from a polymerizable compound represented by any one of 0, 1, or 2), and is derived from the group consisting of the above formula (1A), formula (1B), and formula (2) A polymer of repeating units of at least one compound of the group consisting of compounds.

When the vertical orientation inducing component of the present invention is contained in a photo-alignment film as a mixture different from the photoresponsive polymer, it is preferred to polymerize the compound containing the above formula (RI) to formula (R-IX). The polymer obtained by polymerization is mixed with the above photoresponsive polymer.

When the vertical orientation inducing component of the present invention is used as a substituent of a side chain and/or a main chain of a photoresponsive polymer, the above diamine compound (formula (DA1) to (DA60)), tetracarboxylic acid may be used. The hydrogen atom substitution of the acid dianhydride (formula (TCA1) to formula (TCA38)), the compound represented by the formula (1A), the formula (1B), and the formula (2) is the above-described vertical orientation inducing component (for example, the above Formula (RI) to V in the formula (R-IX).

The above formula (J-1) is preferably

(In the above formula (J-1), Xc1 to Xc3 are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

The above formula (J-2) is preferably

(In the above formula (J-2), Xc1 to Xc3 are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

A preferred example of the photoresponsive polymer of the present invention is preferably a polyimine or a polyphthalic acid derivative, and more preferably a tetracarboxylic dianhydride (formula (TCA1) to (TCA38)) A polymer of a repeating unit obtained by polymerization with the following diamine compound (formula (K)).

(In the above formula (K), Spm represents -O- or -COO-, and Rm is selected from the group consisting of the general formula (H), the general formula (J-1), and the general formula (J-2). At least one orientation-inducing component)

Hereinafter, a method of manufacturing the liquid crystal display element of the present invention will be described. The liquid crystal display element of the present invention is preferably produced by, for example, the following steps.

In the method for producing a liquid crystal display device of the present invention, after the photo-alignment film precursor solution of the present invention is applied onto a substrate, a coating film is formed on the substrate by heating the coated surface. More specifically, for example, the light-aligning film precursor solution of the present invention is coated on one surface of a conductive film forming surface on which a substrate patterned into a comb-shaped transparent conductive film is provided, and one surface of a facing substrate on which a conductive film is not provided, Each coated surface is then heated to form a coating film.

Preferably, the photo-alignment film precursor solution of the present invention is applied by an offset printing method, a spin coating method, a roll coating method or an inkjet printing method, respectively. Here, as the substrate, for example, glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly (aliphatic ring) can be used. A transparent substrate made of plastic such as olefin). 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 can be used. Further, in order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, or a method of using a mask having a desired pattern when forming a transparent conductive film may be employed. Wait. When the photo-alignment film precursor solution is applied, the substrate surface and the adhesion between the transparent conductive film and the coating film are further improved, and the substrate can be preliminarily coated by a known method such as a functional decane compound or a functional titanium compound. The surface is surface treated.

After coating the above photo-alignment film precursor solution, pre-baking may be performed as needed, and in this case, the pre-baking temperature is preferably 30 to 200 °C. Moreover, the pre-bake time is preferably 0.25 to 10 minutes. Thereafter, in order to completely remove the solvent and, if necessary, to thermally imidize the proline structure present in the polymer, it is preferred to carry out the calcination step. The firing temperature at this time is preferably 80 to 300 °C. The firing time is preferably from 5 to 200 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 μm.

As the light to be applied to the coating film, ultraviolet rays or visible rays containing light having a wavelength of 150 to 800 nm, preferably ultraviolet rays having a wavelength of 300 to 400 nm can be used.

As the light source of the above-mentioned irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. Further, the ultraviolet light in the above preferred wavelength region can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, or the like. The amount of irradiation of light 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 of the present invention, it is preferable that one of the photo-alignment film or the coating film is formed to face the substrate gap (cell gap), and the liquid crystal composition of the present invention is filled in the gap.

As a method of filling the liquid crystal composition, (1) a vacuum injection method (the method is such that, for a substrate on which a light alignment film or a coating film is formed, the orientation direction of the film of the two substrates becomes orthogonal) The gap (cell gap) is arranged in the opposite direction, and the peripheral portions of the two substrates are bonded together using a sealant, and the filling liquid crystal is injected into the cell gap defined by the surface of the substrate and the sealant, and the injection hole is sealed to form a liquid crystal cell. Or (2) ODF method. The method of introducing the liquid crystal composition by the vacuum injection method does not cause dropping marks, but as the size of the substrate is increased, there is a problem in manufacturing time, cost, and the like. However, in the invention of the present invention, it can be more preferably used for a display element produced by a combination of a photo-alignment film and a liquid crystal composition using an ODF method.

Further, in the liquid crystal display device of the VA-IPS type which is a preferred embodiment of the present invention, an electrode layer 3 such as a TFT is formed on the surface of the same substrate (the first substrate in FIG. 3) (the surface covered by the light alignment film) Therefore, there is a large amount of irregularities on the surface, which is an environment in which the occurrence of the dropping marks is easily promoted. However, it is considered that this problem is alleviated by the combination of the light-aligning film and the liquid crystal composition.

Further, the liquid crystal composition containing the polymerizable compound of the present invention is preferably used for imparting liquid crystal alignment ability by polymerizing a polymerizable compound contained therein by ultraviolet irradiation, and is controlled by birefringence of the liquid crystal composition. A liquid crystal display element that transmits light in light. As a liquid crystal display element, for ECB-LCD, VA-LCD, VA-IPS-LCD, FFS-LCD, AM-LCD (Active Matrix Liquid Crystal Display Element), TN (Nematic Liquid Crystal Display Element), STN- LCD (super-twisted nematic liquid crystal display element), OCB-LCD and IPS-LCD (coplanar switching liquid crystal display element) are useful, especially useful for AM-LCD, and can be used for transmissive or reflective liquid crystal display elements.

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

The color filter can be produced, for example, by a pigment dispersion method, a printing method, a plating method, a dyeing method, or the like. When a method of producing a color filter by a pigment dispersion method is described as an example, a curable coloring composition for a color filter is applied onto the transparent substrate, patterned, and then heated. Or light irradiation to harden it. This step is performed in three colors of red, green, and blue, whereby the pixel portion for the color filter can be produced. In addition to this, 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 to each other such that the transparent electrode layer is inside. At this time, the interval between the substrates can also be adjusted via the spacer. In this case, it is preferable to adjust so that the thickness of the obtained light control layer (liquid crystal layer) becomes 1 to 100 μm. Further, it is preferably 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. Further, in the case where two polarizing plates are present, the polarizing axes of the respective polarizing plates can be adjusted to adjust the viewing angle or contrast. Further, a retardation film for expanding the viewing angle may also be used. Examples of the separator include a columnar spacer composed 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 in the form of a liquid crystal injection port. On the substrate, the substrates are bonded to each other and heated to thermally cure the sealant.

A method of sandwiching a liquid crystal composition (containing a polymerizable compound as needed) between two substrates can be carried out by a usual vacuum injection method, ODF method, or the like. However, although the vacuum injection method does not cause a drop mark, there is a problem of residual injection marks. In the invention of the present invention, it can be more preferably used for a display element manufactured by the ODF method. In the manufacturing process of the liquid crystal display element of the ODF method, the epoxy-based photothermal heat is applied to the substrate of either the bottom plate or the front plate in a closed-loop bank using a sealant such as curable material, and is degassed downward. After a specific amount of the liquid crystal composition is dropped, the front plate and the bottom plate are joined, whereby a liquid crystal display element can be manufactured. The liquid crystal composition of the present invention can be preferably used because it can stably carry out the dropwise addition of the liquid crystal composition in the ODF step.

As a method of polymerizing the polymerizable compound, in order to obtain good orientation properties of the liquid crystal, it is preferred to employ a moderate polymerization rate, and therefore it is preferred to irradiate a single ultraviolet light or an electron beam or the like, or to use them in combination or sequentially. A method of irradiating an active energy ray such as an ultraviolet ray or an electron beam to polymerize it. For the case of using ultraviolet rays, a polarized light source or a non-polarized light source may be used. In the case where the liquid crystal composition containing the polymerizable compound is polymerized in a state of being sandwiched between the two substrates, it is necessary to impart appropriate transparency to the active energy ray to the substrate on the irradiation surface side. Further, a method of using a mask to irradiate only a specific portion after light irradiation, and changing the orientation state of the unpolymerized portion by changing conditions such as an electric field, a magnetic field, or a temperature, and further irradiating the active energy ray may be used. And make it aggregate. In particular, when ultraviolet exposure is performed, it is preferred to perform ultraviolet exposure without applying a voltage to the liquid crystal composition containing the polymerizable monomer. In the liquid crystal display element of the vertical alignment type VA mode, it is preferable to control the pretilt angle to be 85 to 89.9 degrees from the viewpoint of orientation stability and contrast.

The temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. It is preferred to polymerize at a temperature close to room temperature, i.e., typically 15 to 35 °C. As the lamp for generating ultraviolet rays, a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, or the like can be used. Further, as the wavelength of the ultraviolet ray to be irradiated, it is preferred to irradiate ultraviolet rays in a wavelength region which is not an absorption wavelength region of the liquid crystal composition, and it is preferred to use ultraviolet rays as needed. The intensity of the ultraviolet ray to be irradiated is preferably from 0.1 mW/cm ² to 100 W/cm ² , more preferably from 2 mW/cm ² to 50 W/cm ² . The energy of the ultraviolet ray to be irradiated can be appropriately adjusted, preferably from 10 mJ/cm ² to 500 J/cm ² , more preferably from 100 mJ/cm ² to 200 J/cm ² . The intensity can also be changed when ultraviolet rays are irradiated. The time for irradiating the ultraviolet ray may be appropriately selected depending on the intensity of the ultraviolet ray to be irradiated, and in the case of using a metal halide lamp, a high pressure mercury lamp or an ultrahigh pressure mercury lamp, it is preferably from 10 seconds to 3600 seconds, more preferably from 10 seconds to 600 seconds. In the case of using a fluorescent lamp, it is preferably from 60 seconds to 18,000 seconds, preferably from 600 seconds to 10800 seconds.

The material of the first substrate or the second substrate is not particularly limited as long as it is substantially transparent, and glass, ceramics, plastic, or the like can be used. As the plastic substrate, cellulose derivatives such as cellulose, triacetyl cellulose, and diethyl phthalocyanine; polycycloolefin derivatives, polyethylene terephthalate, polyethylene naphthalate, etc. can be used. Polyester; polyolefin such as polypropylene, polyethylene; polycarbonate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyamide, polyimine, polyamidamine, polystyrene, Polyacrylate, polymethyl methacrylate, polyether oxime, polyarylate; and inorganic-organic composite materials such as glass fiber-epoxy resin, glass fiber-acrylic resin, and the like can be used.

Further, when a plastic substrate is used, 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 improve the reliability of the electrical characteristics of the liquid crystal display element. As the barrier film, as long as the transparency is high and the water vapor permeability is small, there is no In particular, a film formed by using an inorganic material such as cerium oxide and formed by vapor deposition or sputtering or chemical vapor deposition (CVD) is usually used.

In the present invention, the first substrate or the second substrate may be the same material or different materials, and is not particularly limited. When a glass substrate is used, a liquid crystal display element excellent in heat resistance and dimensional stability can be produced, which is preferable. Moreover, if it is a plastic substrate, it is suitable for the manufacturing method by the roll-to-roll method, and is suitable for weight reduction or flexibility, and it is preferable. Moreover, if the objective is to provide flatness and heat resistance, a plastic substrate and a glass substrate can be combined, and good results can be obtained.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. Further, "%" in the compositions of the following examples and comparative examples means "% by mass".

In the examples, the measured characteristics are as follows.

Tni: nematic phase-isotropic liquid phase transfer temperature (°C)

△n: refractive index anisotropy of 295K (alias: birefringence)

△ ε: 295K dielectric dielectrics

η: viscosity of 295K (mPa‧s)

Γ1: 295K rotational viscosity (mPa‧s)

VHR: Voltage holding ratio (%) at 313K under the condition of frequency 60Hz and applied voltage of 5V

Afterimage:

In the afterimage evaluation of the liquid crystal display device, after the specific fixed pattern was displayed in the display area for 1440 hours, the level of the residual image of the fixed pattern when the entire screen was uniformly displayed was evaluated by visual observation based on the following four levels.

◎ no residual image

○ There are very few afterimages and are tolerable

△ There is residual image, which is an unacceptable level

×There is a residual image, very poor

Volatile/manufacturing device contamination:

The evaluation of the volatility of the liquid crystal material was carried out while observing the operation state of the vacuum stirring defoaming mixer by means of a flash lamp, and visually observing the foaming of the liquid crystal material, thereby evaluating. Specifically, a liquid crystal composition of 0.8 kg was placed in a special container of a vacuum stirring and defoaming mixer having a capacity of 2.0 L, and a vacuum stirring was performed at a revolution speed of 15 S ^-1 and a rotation speed of 7.5 S ^-1 at a degassing rate of 4 kPa. The bubble mixer was evaluated based on the following four grades based on the time until foaming started.

◎ It is 3 minutes or more until foaming. The possibility of contamination of the device due to volatilization is low.

○ It is 1 minute or more until foaming, and it is less than 3 minutes. There are concerns about slight contamination of the device due to volatilization.

△ It is 30 seconds or more until foaming, and it is less than 1 minute. Contamination of the device due to volatilization.

× is less than 30 seconds until foaming. There are concerns about serious contamination of the device due to volatilization.

Process compatibility:

The process compatibility is in the ODF process. The liquid crystal is dripped in a 40pL manner using a constant volume metering pump. The operation is performed 100,000 times, and the following four levels are followed by "0~200 times, 201~ The change in the amount of liquid crystal added 200 times each of 400 times, 401 to 600 times, ... 99801 to 100000 times was evaluated.

◎ Very small change (can stably manufacture liquid crystal display elements)

○ There are a few changes and are tolerable

△ There is a change, which is an unacceptable level (the yield is deteriorated due to unevenness)

×Changes, very poor (liquid crystal leakage or vacuum bubbles)

Solubility at low temperatures:

Evaluation of Solubility at Low Temperature After preparing a liquid crystal composition, 0.5 g of the liquid crystal composition was weighed and placed in a 1 mL sample vial in a temperature-controlled test cell at "-20 ° C (for 1 hour) → temperature increase (0.2 °C/min)→0°C (for 1 hour)→temperature (0.2°C/min)→20°C (for 1 hour)→cooling (-0.2°C/min)→0°C (for 1 hour)→cooling (-0.2 ° C / min) → -20 ° C" The temperature change was continuously applied as one cycle, and the occurrence of precipitates from the liquid crystal composition was visually observed, and the following four grades were evaluated.

◎ No precipitate was observed for 600 hours or more.

○ No precipitate was observed for 300 hours or more.

A precipitate was observed within Δ150 hours.

The precipitate was observed within ×75 hours.

In the examples, the description of the compounds uses the following abbreviations.

(side chain)

-F -F fluorine atom

F--F fluorine atom

-n -C _n H _{2n+1 a} linear alkyl group having n carbon atoms

N- C _n H _2n+1 - a linear alkyl group having n carbon atoms

-On -OC _n H _{2n+1 a} linear alkoxy group having n carbon atoms

nO- C _n H _2n+1 O- linear alkoxy group having n carbon atoms

-V -CH=CH ₂

V- CH ₂ =CH-

-V1 -CH=CH-CH ₃

1V- CH ₃ -CH=CH-

-2V -CH ₂ -CH ₂ -CH=CH ₃

V2-CH 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

(link base)

-CF2O-(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 compositions shown below were prepared, and their physical property values 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 14, the formula (P.1) was added:

0.3 parts by mass of the polymerizable monomer represented, and uniformly dissolved, thereby preparing a liquid crystal composition containing a polymerizable monomer, a liquid crystal composition containing a polymerizable monomer, and a liquid crystal containing a polymerizable monomer Compositions 1, 2, 6, and 14.

The physical properties of the liquid crystal compositions 1, 2, 6, and 14 containing the polymerizable monomer and the physical properties of the nematic liquid crystal compositions shown in Preparation Examples 1, 2, 6, and 14 were hardly different.

Further, with respect to 99.7 parts by mass of the nematic liquid crystal compositions shown in Preparation Examples 9, 12, and 16, the formula (P.2) was added:

0.3 parts by mass of the polymerizable monomer shown was uniformly dissolved, whereby liquid crystal compositions 9, 12, and 16 containing a polymerizable monomer were prepared. The physical properties of the liquid crystal compositions 9 and 12 containing the polymerizable monomer were hardly different from those of the nematic liquid crystal compositions shown in Preparation Examples 9, 12 and 16.

Using the liquid crystal composition of the present invention and a liquid crystal composition containing a polymerizable monomer, a liquid crystal display element of a VA-IPS (including FFS mode) mode generally having a cell thickness of 3.0 μm for TV is used, and the oriented film is as follows The method of making.

<Photodegradable light-oriented film>

"Light Orientation Film 1"

The molar ratio of the diamine compound of the following formula (J.1) is 1.0%

After dissolving in N-methyl-2-pyrrolidone, 1 mol% of cyclobutanetetracarboxylic dianhydride was added thereto, and the mixture was reacted at 20 ° C for 12 hours to obtain a weight average molecular weight in terms of standard polystyrene. A polyamic acid varnish having a weight average molecular weight/number average molecular weight (Mv/Mn) of about 1.6. Then, the polyamic acid varnish was diluted to a concentration of 6%, and 0.3% by weight of γ-aminopropyltriethoxysilane was added as a solid component, and then printed on the first thin film laminate and the second thin film laminate. The film was heated at 210 ° C for 30 minutes to form the following photo-decomposable insulating film (polyimine film).

Thereafter, the photodegradable polyimine film was irradiated with polarized UV light having a wavelength of 254 nm at 1000 mJ/cm ² to carry out orientation treatment.

"Light Orientation Film 2"

0.1% by mole of the diamine compound of the following formula (J.2),

After the above-mentioned (J.1) diamine compound 0.05 mol% and p-phenylenediamine 0.85 mol% are dissolved in N-methyl-2-pyrrolidone, cyclobutane tetracarboxylic dianhydride is added thereto. A 1% molar solution was reacted at 60 ° C for 5 hours to prepare a polyaminic acid solution. Thereafter, N-methyl-2-pyrrolidone was added, and the total amount was prepared to be 500 g, pyridine and acetic anhydride were added, and dehydration and ring opening was carried out at 115 ° C for 4.5 hours, and N-methyl-2-pyrrolidone was carried out. The solvent was replaced, and pyridine and acetic anhydride were distilled off. Adding butyl cellosolve to a polyimine solution (solid content: 20% by mass) having an imidization ratio of about 53%, diluting to a solid content of 6%, and printing on the first thin film laminate and the second thin film layer The film was heated at 210 ° C for 30 minutes to form the following photo-decomposable insulating film (polyimine film).

Thereafter, the photodegradable polyimine film was irradiated with polarized UV light having a wavelength of 254 nm at 1000 mJ/cm ² to carry out orientation treatment.

"Light Orientation Film 3"

(Preparation of solution for photo-alignment film)

To 3.24 g of 1,4-phenylenediamine, 32.40 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while supplying nitrogen gas. While stirring the diamine solution, 7.81 g of cyclobutanetetracarboxylic dianhydride was added, and 78.03 g of N-methyl-2-pyrrolidone was further added thereto, and the mixture was stirred under a nitrogen atmosphere at 30 ° C for 18 hours to cause a reaction. Further, 62.68 g of a mixed solvent of N-methyl-2-pyrrolidone and 2-butoxyethanol in a mass ratio of 1:1 was added thereto at room temperature, followed by dilution and stirring to obtain a solution for a photo-alignment film.

(Formation of liquid crystal alignment film)

(Formation of photo-decomposable resin film)

The photo-alignment film solution was formed on the comb-shaped transparent electrode formed on the first substrate by a spin coating method to form a resin film having a dry thickness of 0.1 μm. In the same manner, an alignment film is also formed on the second substrate. The substrate on which the resin film was formed was heated at 230 ° C for 30 minutes to react, thereby forming a photo-decomposable resin film (polyimine film).

(directed processing)

A 650 nm ultraviolet light is extracted from a high pressure mercury lamp using a band pass filter, and a linear polarization of an extinction ratio of about 100:1 is formed using a wire grid polarizing element, and the photodecomposition type resin film is irradiated with an irradiation energy of 1.0 J/cm ² . Perform light directional processing. Thereafter, in order to remove impurities formed by decomposition, the film was baked at 230 ° C for 30 minutes, and then the polyimide film was washed with pure water and dried to obtain a glass substrate on which a photo-decomposable alignment film was formed.

<Photodimerization type photo-alignment film>

"Light Orientation Film 4"

(vertical orientation inducer)

Stearic acid acrylate (V-2) (manufactured by Tokyo Chemical Industry Co., Ltd.) was purchased and used.

(Synthesis of polymer (PAV-1))

10 parts of the monomer (I-1-1) and 0.5 parts of the monomer (V-1) were dissolved in 45 parts of tetrahydrofuran (THF), and 0.03 part of azobisisobutyronitrile (AIBN) was added under a nitrogen atmosphere. The thus obtained solution was heated under reflux for 8 hours to cause a reaction. Then, the solution after the reaction was added dropwise to 600 parts of methanol and stirred, and the precipitate was collected and dissolved in 50 parts of THF, and then added dropwise to 1200 parts of hexane cooled in an ice bath and stirred to precipitate. The solid is recovered. The obtained solid was dissolved in 50 parts of THF, added dropwise to 1200 parts of methanol cooled in an ice bath, and stirred, and the precipitated solid was recovered, dissolved in THF, and dried in vacuo to obtain a polymer. (PAV-1).

Further, the adjustment of the molecular weight of the polymer was carried out by adjusting the heating reflux time in the above nitrogen atmosphere and measuring the weight average molecular weight (Mw).

(Measurement of molecular weight)

Mw and Mn were measured by GPC (Gel Permeation Chromatography) based on the following measurement conditions.

The measuring device used the GPC device HLC-8220GPC manufactured by Tosoh Corporation, and the analytical column used TSKgel GMHXL×2, TSKgel G2000XL×1, TSKgel G1000XL × 1 total of 4 series in series, the detector uses a differential refractive index (RI) detector, the standard sample used to make the calibration curve uses the polystyrene standard sample STANDARD SM-105 manufactured by Showa Denko (molecular weight range 1,300 ~3,800,000). The obtained polymer was dissolved in THF so as to have a concentration of 1 μg/mL, the mobile phase was set to THF, the liquid supply rate was set to 1 mL/min, the column temperature was set to 40 ° C, and the sample was injected. The measurement was performed by setting the amount to 300 μL.

(Formation of liquid crystal alignment film)

(Production of photodimerization type resin film)

A mixture of 5 parts of a polymer (PAV-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. Then, this 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 above glass substrate. It was confirmed by visual observation of the formed film that a smooth film was formed.

(light directional processing)

Then, using a polarized light irradiation device including an ultrahigh pressure mercury lamp, a wavelength cut filter, a band pass filter, and a polarizing filter, the formed film is irradiated with ultraviolet light for 10 seconds (irradiation amount of 100 mJ/cm ² ) from the vertical direction ( A linearly polarized light (illuminance: 10 mW/cm ² ) of a wavelength of 313 nm) was thereby obtained as a light directing film. Further, the dried thickness of the resin film was 0.1 μm.

<Friction type oriented film>

(friction type oriented film)

(Formation of friction type polyimine liquid crystal alignment film)

(Preparation of oriented film solution)

Adding 59.72g of N-methyl-2-pyrrolidone to 5.98g of 4,4'-diaminodiphenylamine, The mixture was stirred and dissolved while supplying nitrogen gas. While stirring the diamine solution, 6.54 g of pyromellitic dianhydride was added, and 65.30 g of N-methyl-2-pyrrolidone was further added thereto, and the mixture was stirred under a nitrogen atmosphere at 30 ° C for 18 hours to cause a reaction. 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 thereto at room temperature to carry out dilution and stirring to obtain a polyaminic 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 by a spin coater, and heated at 230 ° C for 30 minutes to react to form an insulating film of polyimide.

(directed processing)

The roller on which the polishing cloth is wound is rotated in a direction opposite to the direction in which the substrate is conveyed, and the surface of the alignment film formed on the substrate is wiped in each direction, whereby the alignment treatment is performed. The rotation speed of the rolls was 600 rpm, the conveyance speed of the substrate was 5 mm/sec, and the penetration depth of the polishing cloth with respect to the substrate surface was 0.3 mm. Thereafter, in order to remove the fiber sheet of the oriented film by rubbing or the fiber sheet of the polishing cloth, the polyimide film is washed with pure water and dried to obtain a rubbed polyimide film oriented film. glass substrate.

(evaluation of display quality)

By setting the alignment film as a light alignment film, the decrease in the directivity of the liquid crystal molecules caused by the unevenness in friction can be reduced, and the VA-IPS (or VA-FFS) method which provides excellent transmittance characteristics can be provided. Liquid crystal display element. The liquid crystal directionality of the various (light) alignment films produced above has been evaluated, and the evaluation method will be described below.

Forming a thin film transistor and a transparent electrode layer on the first substrate, and forming thereon Oriented film. If the orientation treatment is performed using the rubbing method as the contact method, random scratches are formed on the surface of the orientation film due to friction. In particular, in the first substrate on which the thin film transistor or the transparent electrode layer pattern is formed, it is easy to be caused by the step formed by the pattern of the thin film transistor or the transparent electrode layer and the diameter (tens of μm) of the fiber of the polishing cloth of the rubbing roller. A deeper bruise is 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, the liquid crystal panel generates light leakage during black display. As a result, it becomes difficult to obtain a contrast of a certain value or more. Moreover, the rubbed alignment film is difficult to perform orientation division.

Further, in the resolution model called 4K which has been put into practical use in recent years, in the calculation example of the 40-inch panel, the 1-pixel size is 0.23 mm. Further, in the resolution mode called 8K, which has been put into practical use, in the calculation example of the 40-inch panel, the 1-pixel size is even fine to 0.11 mm. That is, the 1 pixel size is close to the diameter of the fiber of the polishing cloth of the rubbing roller, so the scratch formed by the orientation treatment by the rubbing method causes the liquid crystal molecules to be generated when the electric field is turned off in the pixel unit or the intermittent pixel column unit. It is impossible to arrange the parts in a certain direction, and there is a possibility that the contrast caused by a large amount of light leakage due to black display is greatly reduced, or a large number of display defects are caused.

Therefore, by performing the alignment treatment by the photo-alignment method in a non-contact manner, scratches are not generated on the surface of the alignment film, so that a high contrast without contrast and a sharp black display can be realized.

The 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. In the same manner, an alignment film is also formed on the second substrate.

(Production of liquid crystal cell)

A liquid crystal cell was produced using a glass substrate having the above various liquid crystal alignment films. More specific In the liquid crystal alignment film, the first substrate and the second substrate on which the alignment film is formed are disposed so that the direction in which the linear polarization or the rubbing direction is reversed (180°), and the substrate is held constant between the two substrates. In the state of the gap (4 μm), the peripheral portion was bonded by a sealant. Then, at a temperature of +15 ° C at a transparent point, the liquid crystal composition of the above table (Preparation Examples 1 to 16) and the polymerizable monomer are filled in a cell gap partitioned by the surface of the liquid crystal alignment film and the sealant by a dropping method. The liquid crystal compositions 1, 2, 6, 9, 12, 14 and 16 were then cooled to room temperature to prepare liquid crystal cells, respectively.

In the case of the liquid crystal compositions 1, 2, 6, 9, 12, 14 and 16 containing a polymerizable monomer, the liquid crystal cell is produced in the same manner as described above, and the pretilt angle of the liquid crystal cell is measured (crystal rotation method). Then, a rectangular wave of 1.8 V was applied at a frequency of 1 kHz, and a liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp (FL15UV34A (NP805) manufactured by Toshiba Lighting & Technology Co., Ltd.) through a filter that cuts off ultraviolet rays of 320 nm or less. The horizontally oriented liquid crystal display element in which the polymerizable monomer in the liquid crystal composition containing the polymerizable monomer was polymerized was adjusted by irradiating for 700 seconds so that the irradiation intensity of the unit surface became 10 mW/cm ² .

a combination example of the alignment film used in the produced liquid crystal cell (liquid crystal display device) and the liquid crystal composition or the liquid crystal composition containing the polymerizable monomer (Examples 1 to 24 and Comparative Examples 1 and 2) The evaluation results of the static contrast (CRS) of the liquid crystal cell produced are shown in Tables 4 to 10 below. Further, the static contrast (CRS) was measured by the following method.

Polarizing element for optical measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.) equipped with a white light source, a spectroscope, a polarizing element (incident-side polarizing plate), a light-emitting element (emission-side polarizing plate), and a detector The above-mentioned light to be measured is disposed between the optical elements Learn film. Here, in a state where the rotation angle of the polarizing element and the light-emitting element is 0 degrees (the polarization direction of the polarizing element and the light-emitting element is parallel (parallel polarization)), the optical film is rotated while being detected by the detector. The amount of light that penetrates the light, and the amount of light passing through the light (the amount of light when the polarization direction of the polarizing element is parallel to the long axis direction of the molecular axis of the polymerizable liquid crystal) is the maximum amount of light to be detected. Yon. Further, in a state where the position of the polarizing element and the optical film are fixed, the rotation angle of the deposition element with respect to the polarizing element is set to 90 degrees (the polarization direction of the polarizing element and the light-emitting element is an orthogonal position [orthogonal polarization] The amount of light that passes through the light (the amount of light when it is turned off) is set to Yoff. The contrast CRS is obtained by the following formula (Formula 1).

CRS=Yon/Yoff (Formula 1)

The larger the value of the static contrast CRS of (Formula 1), the smaller the amount of off-time Yoff, that is, the less light leakage, and therefore the more excellent black display.

As a result, the display elements of the VA-IPS and VA-FFS modes (Examples 1 to 24) produced by the photo-alignment film and the VA-IPS mode display elements produced by the rub-orientation film were formed (Comparative Examples 1 and 2). In comparison, the contrast shows excellent characteristics.

In particular, in the liquid crystal display device (Examples 1 to 24) using the photo-alignment film, since the light amount Yoff (the darkest luminance) is small at the time of turning off, the contrast tends to be high. Therefore, it is considered that the embodiment using the light directing film can exhibit a black display element having a depth as compared with the comparative example.

Further, it was confirmed that when a polymerizable monomer was added, the step (aging) of 5 V and 60 Hz short-wave waves applied at 60 ° C for 10 hours was not easily lowered (Examples 17 to 24). Therefore, it is considered that since the polymer derived from the polymerizable monomer assists the action of the alignment film which restricts the orientation of the liquid crystal molecules, it is less likely to cause orientation disorder.

Further, the following directional restraining force (fixed anchor) measurement was performed on the liquid crystal display elements of Examples 1 to 24.

Using the above liquid crystal display element, the interface between the surface of the liquid crystal alignment film and the liquid crystal layer is determined by the following strong electric field method (method reported on pages 402 to 403 of the Japanese Liquid Crystal Society Symposium (1998)). Anchor energy.

As a result, it was confirmed that the liquid crystal display elements of Examples 1 to 24 produced an orientation restricting force to a sufficient extent. In addition, it was confirmed that the orientation restricting force in the liquid crystal display elements of Examples 17 to 24 was improved as compared with Examples 1 to 16, and thus the photo-alignment film was produced by polymerization of a polymerizable monomer. Directional restraint. It was confirmed that the horizontally-oriented liquid crystal display element has excellent optical characteristics and high-speed responsiveness.

1, 8‧‧‧ polarizing plate

2‧‧‧First substrate

3‧‧‧electrode layer

4‧‧‧ Orientation film

5‧‧‧Liquid layer

6‧‧‧Color filters

7‧‧‧second substrate

10‧‧‧Liquid display components

Claims (7)

A vertically oriented liquid crystal display device having a first substrate and a second substrate disposed opposite to each other; a liquid crystal layer comprising a liquid crystal composition filled between the first substrate and the second substrate; and an electrode layer Each of the pixels on the first substrate has a plurality of gate bus lines and data bus lines arranged in a matrix, and a thin film transistor disposed at an intersection of the gate bus line and the data bus line. a pixel electrode driven by the thin film transistor; a common electrode formed on the first substrate or the second substrate; and a photo alignment layer formed on the liquid crystal layer and the first substrate and the liquid crystal layer and the first At least one of the substrates between the two substrates, the liquid crystal composition has positive dielectric conductivity, and the transition temperature of the nematic phase-isotropic liquid is 60 ° C or higher, and is selected from the formula (i) (In the above formula (i), R ⁱ¹ and R ⁱ² each independently represent 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 carbon. One or more alkenyloxy groups having 2 to 8 atoms, and one or more hydrogen atoms of the alkyl group, alkenyl group, alkoxy group or alkenyloxy group may be substituted with a fluorine atom, the alkyl group, an alkenyl group, an alkoxy group or The methylene group in the alkenyloxy group may be substituted with an oxygen atom as long as the oxygen atom is discontinuously bonded, and may be substituted into a carbonyl group as long as the carbonyl group is discontinuously bonded, and A ⁱ¹ is selected from (a) 1,4-extension ring. a hexyl group (one -CH ₂ - or two or more -CH ₂ - which are not adjacent to the group may be substituted with -O-), (b) 1,4-phenylene group (present in the group) One of -CH= or two or more adjacent -CH= can be substituted with -N=), and (c)naphthalene-2,6-diyl, 1,2,3,4-tetrahydrogen Naphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl) One of -CH= or two or more non-contiguous -CH= can be substituted with -N=), the above-mentioned group (a), base (b) and base (c) Independently via cyano, fluorine, chlorine, methyl, trifluoromethyl or tri Methoxy group, Z ⁱ¹ represents a single bond, -COO -, - OCO -, - OCH 2 -, - OCF 2 -, - CH 2 O- or CF ₂ O-, n ⁱ¹ represents 2, 3 or 4 In the case where n ⁱ¹ is 2, 3 or 4 and there are a plurality of A ⁱ¹ , the same may be different, and when n ⁱ¹ is 2, 3 or 4 and there are multiple Z ⁱ¹ , the One or two or more compounds of the compounds represented by the same or different formulas, and a formula (J) selected from the group consisting of (wherein, R ^J1 represents an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent -CH ₂ - may be independently substituted with -CH=CH-, - C≡C-, -O-, -CO-, -COO- or -OCO-, n ^J1 represents 0, 1, 2, 3 or 4, and A ^J1 , A ^J2 and A ^J3 are independently represented by (a) ) 1,4-cyclohexylene group (in the presence of a group -CH ₂ - not adjacent two or more of the -CH ₂ - may be substituted with -O -), (b) 1,4- extending Phenyl group (one present in the group -CH=or two or more adjacent to -CH= may be substituted with -N=), and (c)naphthalene-2,6-diyl, 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene- One of the 2,6-diyl groups -CH= or two or more non-contiguous -CH=substitutable groups substituted with -N=), the above-mentioned group (a), group (b) And the group (c) may be independently substituted by a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group, and Z ^J1 and Z ^J2 each independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -COO-, -OCO- or -C≡C-, at n ^J1 is 2, 3 or 4 and there are multiple When the case A ^J2, these may be the same or different, when n ^J1 to 2, 3 or 4 in the case of the presence of a plurality of Z ^J1, these may be identical or different, X ^J1 is a hydrogen atom, a fluorine atom, One or more of the compounds represented by a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group) . The liquid crystal display device of claim 1, wherein the pixel electrode has a comb shape or a slit. The liquid crystal display device of claim 1 or 2, wherein the common electrode layer containing the transparent conductive material is disposed on the first substrate, and the electrode pitch R is shorter than the substrate The distance G. The liquid crystal display device of claim 1 or 2, wherein the common electrode including the transparent conductive material is provided on the first substrate, and the electrode pitch R is longer than the distance G between the substrates. The liquid crystal display element according to any one of claims 1 to 4, wherein the photo-alignment layer has a vertical alignment inducing component for vertically aligning liquid crystal molecules, and contains a photoresponsive polymer. The liquid crystal display device of claim 5, wherein the photoresponsive polymer is selected from the group consisting of a photoresponsive decomposition polymer, the photoresponsive dimerization polymer, and a photoresponsive isomerization type. At least one of the group of molecules. The liquid crystal display device according to any one of claims 1 to 6, wherein the liquid crystal layer contains a cured product of a polymerizable compound in the liquid crystal composition.