TW201632609A - Liquid crystal display element and method of manufacturing the same - Google Patents

Abstract

A liquid crystal display element, and a method of manufacturing the same, is provided which is not prone to the occurrence of drip marks during manufacturing and does not lead to a worsening of burn-in characteristics of the liquid crystal element, or of various liquid crystal display element characteristics such as dielectric anisotropy, viscosity, nematic phase maximum temperature, rotational viscosity ([gamma]1), etc. Further, this invention makes it possible to manufacture a liquid crystal display element which has excellent high-speed responsiveness as a liquid crystal display element, stable orientation and pre-tilt angle of the liquid crystal molecules, minimal occurrence of burn-in, and minimal occurrence of drip marks during manufacturing. The liquid crystal display element manufactured according to this invention can be used effectively as a display element in liquid crystal televisions, monitors, etc.

Description

Liquid crystal display element and method of manufacturing same

The present invention relates to a liquid crystal display element useful as a constituent member of a liquid crystal TV or the like and a method of manufacturing the same.

The liquid crystal display element is started with a clock and a calculator, and is used for various measuring machines, automobile panels, word processors, electronic notebooks, printers, computers, televisions, clocks, advertisement display boards, and the like. Typical examples of the liquid crystal display method include a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, and a vertical orientation using a TFT (Thin Film Transistor). Vertical Aligned (VA) or IPS (In-Plane Switching) type. The liquid crystal composition used in these liquid crystal display elements is required to be stable to external factors such as moisture, air, heat, light, etc., and exhibits a liquid crystal phase in a temperature range as wide as possible around a room temperature, and has low viscosity. And the driving voltage is low. Further, in order to optimize the dielectric conductivity (Δε), the refractive index anisotropy (Δn), and the like for each liquid crystal display element, a liquid crystal composition is composed of several to several tens of compounds.

In the VA type display, a liquid crystal composition having a negative Δ ε is used, and is widely used for a liquid crystal TV or the like. On the other hand, in all driving methods, low voltage driving, high speed response, and a wide operating temperature range are required. That is, the absolute value of Δε is required to be large, the viscosity (η) is small, and the nematic phase-isotropic liquid phase transition temperature (T _ni ) is high. Further, it is necessary to adjust the Δn of the liquid crystal composition to an appropriate range in accordance with the cell gap based on the setting of Δn × d which is the product of Δn and the cell gap (d). In addition, when a liquid crystal display element is applied to a television or the like, a liquid crystal composition having a small rotational viscosity (γ ₁ ) is required because of high speed responsiveness.

On the other hand, in order to improve the viewing angle characteristics of a VA type display, a MVA (Multi-domain Vertical Alignment) type liquid crystal display element is widely used, which is provided by providing a protruding structure on a substrate. The orientation direction of the liquid crystal molecules is divided into a plurality. Although the MVA liquid crystal display element is excellent in viewing angle characteristics, the response speed of the liquid crystal molecules is different in the vicinity of the protruding structure on the substrate and in the portion far from the substrate, and the response speed is far from the protruding structure. The influence of the liquid crystal molecules has a problem that the overall response speed is insufficient, and there is a problem that the transmittance is lowered by the protruding structure. In order to solve this problem, a PSA liquid crystal display element has been developed as a method of providing a uniform pretilt angle in a divided pixel without providing a non-transmissive protruding structure in a cell, unlike a conventional MVA liquid crystal display device. Polymer sustained alignment, the polymer maintains orientation; includes PS liquid crystal display elements (polymer stabilised). In the PSA liquid crystal display device, a small amount of a reactive monomer is added to the liquid crystal composition, and the liquid crystal composition is introduced into the liquid crystal cell, and then a liquid crystal composition is applied by irradiation with an active energy ray while applying a voltage between the electrodes. The reactive monomer is polymerized and produced. Therefore, an appropriate pretilt angle can be imparted to the divided pixels, and as a result, an improvement in contrast obtained by increasing the transmittance and a high-speed response obtained by imparting a uniform pretilt angle can be achieved (for example, refer to Patent Document 1). However, in the PSA liquid crystal display device, it is necessary to add a reactive monomer to the liquid crystal composition, and in an active matrix liquid crystal display device requiring a high voltage holding ratio, there are many problems, and display defects such as afterimages are generated. problem.

As a method for improving the PSA liquid crystal display device, a method of imparting a uniform pretilt angle to liquid crystal molecules without mixing impurities other than the liquid crystal material in the liquid crystal composition has been developed, in which a reactive monomer is mixed into the alignment film material, and liquid crystal is incorporated. After the composition is introduced into the liquid crystal cell, the reactive monomer in the alignment film is polymerized by irradiation with an active energy ray while applying a voltage between the electrodes (see, for example, Patent Documents 2, 3, and 4).

On the other hand, with the large screen of the liquid crystal display element, the manufacturing method of the liquid crystal display element has also largely changed. That is, in the case of manufacturing a large panel, since the manufacturing process of the prior vacuum injection method requires a large amount of time, in the manufacture of a large panel, a manufacturing method using an ODF (one-drop-fill) method has gradually become mainstream (for example, Refer to Patent Document 5). Since this method can shorten the injection time as compared with the vacuum injection method, it is becoming the mainstream of the manufacturing method of the liquid crystal display element. However, the phenomenon in which the dropping of the liquid crystal composition is dropped after the liquid crystal display element is formed and remains in the liquid crystal display element in the form of dropping is a new problem. Further, the so-called drop mark is defined as a phenomenon in which a trace of a liquid crystal composition is dropped in a white form when black is displayed. In particular, in the above-described manner of adding a reactive monomer to the alignment film material to impart a pretilt angle to the liquid crystal molecules, since the liquid crystal composition is dropped onto the substrate, the reactive monomer as an impurity exists in the orientation. In the film, the problem of dropping marks is likely to occur. Moreover, the occurrence of traces is usually caused by the selection of liquid crystal materials, and the reason is not clear.

As a method for suppressing the addition of the traces, there is disclosed a method of polymerizing a polymerizable compound mixed in a liquid crystal composition to form a polymer layer in the liquid crystal composition layer, thereby suppressing the relationship with the orientation control film. The mark is dropped (for example, refer to Patent Document 6). However, according to this method, there is a problem that the residual image displayed by the reactive monomer added to the liquid crystal composition is similar to the PSA method or the like, and the effect of suppressing the dropping is not sufficient. , The industry has sought to develop a liquid crystal display element which maintains the basic characteristics of a liquid crystal display element and which is less likely to cause residual images or dripping marks. Further, since the liquid crystal display element is exposed to UV light at the time of its manufacture and use, it is important that deterioration or the like does not occur due to such UV irradiation, or that it does not affect the display even if it is generated.

In the Japanese Patent No. 05299595 (Patent Document 12) and the like, a liquid crystal display element is proposed in which a liquid crystal composition is introduced into a liquid crystal cell after a liquid crystal composition is introduced into a vertical alignment film. A specific liquid crystal composition is combined in a mode in which a reactive monomer in the alignment film is polymerized by irradiation of an active energy ray while applying a voltage between the electrodes. With the liquid crystal display element, it is possible to provide various characteristics of the liquid crystal display element and the afterimage characteristics of the liquid crystal display element without changing the dielectric conductivity, the viscosity, the nematic phase upper limit temperature, the rotational viscosity (γ ₁ ), and the like. In the case of a poor liquid crystal display element which is less likely to cause dripping at the time of manufacture, and a method of manufacturing the same. However, as the demand for liquid crystal display elements has become higher, the industry has demanded the development of liquid crystal compositions and liquid crystal display elements which have further improved various characteristics of liquid crystal display elements, in particular, high stability of pretilt angles formed.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-357830

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-107536

[Patent Document 3] US Patent Application Publication No. 2011/261295

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-227284

[Patent Document 5] Japanese Laid-Open Patent Publication No. Hei 6-235925

[Patent Document 6] Japanese Laid-Open Patent Publication No. 2006-58755

[Patent Document 7] Japanese Laid-Open Patent Publication No. 2011-95696

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2011-95697

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2009-139455

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2010-32860

[Patent Document 11] Japanese Patent Laid-Open Publication No. 2010-107537

[Patent Document 12] Japanese Patent No. 05299595

The present invention has been made in view of the above circumstances, and an object thereof is to prevent various dielectric properties, viscosity, nematic phase upper limit temperature, rotational viscosity (γ ₁ ), and the like as various characteristics of a liquid crystal display element and a liquid crystal display element. When the afterimage characteristics are deteriorated, a liquid crystal display element which is less likely to cause dripping marks during production, has high characteristics as a liquid crystal display element, and has high stability of a pretilt angle formed, and a method for producing the same are provided.

In order to solve the above problems, the inventors of the present invention have studied various liquid crystal compositions, and as a result, have found that the above problems can be solved by including a specific liquid crystal compound, and the present invention has been completed.

That is, the present invention is a liquid crystal display device comprising: a group substrate having a first substrate and a second substrate; and a liquid crystal composition layer sandwiched between the substrates; and the first substrate and the second substrate At least one of the first substrate and the second substrate has an alignment film containing the polymerizable group by polymerizing a polymerizable group to control the liquid crystal composition. The polymer in the orientation direction of the liquid crystal molecules in the layer, the liquid crystal composition constituting the liquid crystal composition layer is contained in the compound group represented by the following general formula (i), the general formula (ii), and the general formula (iii) One or two or more compounds selected from the group consisting of one or two or more compounds selected from the group consisting of the compounds represented by the formula (IV),

(wherein R ⁱ¹ , R ⁱ² , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱⁱ¹ and R ⁱⁱⁱ² each independently represent an alkyl group having 1 to 10 carbon atoms, and one of the alkyl groups or two or more adjacent ^thereto - CH ₂ - may be independently substituted with -CH=CH-, -C≡C-, ^-O- , ^-CO- , -COO- or -OCO-, A ⁱ¹ , A ⁱ² , A ⁱⁱ¹ , A ⁱⁱ² , A ⁱⁱⁱ¹ and A ⁱⁱⁱ² are respectively independently selected from

(a) 1,4-cyclohexylene (one present in the group -CH ₂ - or two or more non-contiguous -CH ₂ - may be substituted with -O-), (b) 1,4- a 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= can be replaced by -N=)

The group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, respectively, Z ⁱ¹ , Z ⁱ² , Z ⁱⁱ¹ , Z ⁱⁱ² , Z ⁱⁱⁱ¹ and Z ⁱⁱⁱ² each independently represent a single bond, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -, at least one Z ⁱ¹ represents -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -, and Z ⁱⁱⁱ³ represents -CH ₂ - or an oxygen atom, X ⁱⁱ¹ represents a hydrogen atom or a fluorine atom, and m ⁱ¹ , m ⁱ² , m ⁱⁱ¹ , m ⁱⁱ² , m ⁱⁱⁱ¹ and m ⁱⁱⁱ² each independently represent an integer of 0 to 3, and m ⁱ¹ +m ⁱ² is 0, 1, 2 or 3, m ⁱⁱ¹ +m ⁱⁱ² and m ⁱⁱⁱ¹ +m ⁱⁱⁱ² are 1, 2 or 3, respectively, and when there are a plurality of A ⁱ¹ ~A ⁱⁱⁱ² , Z ⁱ¹ ~Z ⁱⁱⁱ² , the same or different)

(wherein R ⁴⁴ and R ⁴⁵ each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more of the groups -CH ₂ - 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- or -OCF ₂ -, one or more hydrogen atoms in the group may Each of them is independently substituted with a fluorine atom or a chlorine atom, and A ⁴¹ to A ⁴³ are each independently selected from

(a) 1,4-cyclohexylene (one present in the group -CH ₂ - or two or more non-contiguous -CH ₂ - may be substituted with -O-), (b) 1,4- a 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= can be replaced by -N=)

The group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, and Z ⁴¹ and Z ⁴² each independently represent a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-,m ⁴¹ denotes an integer of 0 to 2, which may be the same or different when there are a plurality of A ⁴¹ and Z ⁴¹ .

Moreover, the present invention is a method of fabricating a liquid crystal display device by forming at least one of the first substrate and the second substrate by applying an alignment material and heating to form an alignment film material. The liquid crystal composition is sandwiched between the first substrate and the second substrate, and the active energy ray is irradiated to the electrode under application of a voltage, whereby the polymerizable group of the polymerizable group contained in the alignment film material is made. And an alignment film having a direction of controlling the alignment direction of the liquid crystal molecules in the liquid crystal composition layer, wherein the liquid crystal composition contains a compound represented by the following formula (i), formula (ii), and formula (iii) One or two or more compounds selected from the group, and one or more selected from the group consisting of compounds represented by the formula (IV),

(wherein R ⁱ¹ , R ⁱ² , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱⁱ¹ and R ⁱⁱⁱ² each independently represent an alkyl group having 1 to 10 carbon atoms, and one of the alkyl groups or two or more adjacent ^thereto - CH ₂ - may be independently substituted with -CH=CH-, -C≡C-, ^-O- , ^-CO- , -COO- or -OCO-, A ⁱ¹ , A ⁱ² , A ⁱⁱ¹ , A ⁱⁱ² , A ⁱⁱⁱ¹ and A ⁱⁱⁱ² are respectively independently selected from

(a) 1,4-cyclohexylene (one present in the group -CH ₂ - or two or more non-contiguous -CH ₂ - may be substituted with -O-), (b) 1,4- a 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= can be replaced by -N=)

The group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, respectively, Z ⁱ¹ , Z ⁱ² , Z ⁱⁱ¹ , Z ⁱⁱ² , Z ⁱⁱⁱ¹ and Z ⁱⁱⁱ² independently represent a single bond, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -, respectively. One Z ⁱ¹ represents -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -, Z ⁱⁱⁱ³ represents -CH ₂ - or an oxygen atom , X ⁱⁱ¹ represents a hydrogen atom or a fluorine atom, and m ⁱ¹ , m ⁱ² , m ⁱⁱ¹ , m ⁱⁱ² , m ⁱⁱⁱ¹ and m ⁱⁱⁱ² each independently represent an integer of 0 to 3, and m ⁱ¹ +m ⁱ² is 0, 1, 2 or 3, respectively. , m ⁱⁱ¹ +m ⁱⁱ² and m ⁱⁱⁱ¹ +m ⁱⁱⁱ² are 1, 2 or 3, respectively, and when there are a plurality of A ⁱ¹ ~A ⁱⁱⁱ² , Z ⁱ¹ ~Z ⁱⁱⁱ² , the same or different)

(wherein R ⁴⁴ and R ⁴⁵ each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more of the groups -CH ₂ - 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- or -OCF ₂ -, one or more hydrogen atoms in the group may Each of them is independently substituted with a fluorine atom or a chlorine atom, and A ⁴¹ to A ⁴³ are each independently selected from

(a) 1,4-cyclohexylene (one present in the group -CH ₂ - or two or more non-contiguous -CH ₂ - may be substituted with -O-), (b) 1,4- a 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= can be replaced by -N=)

The group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, and Z ⁴¹ and Z ⁴² each independently represent a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-,m ⁴¹ denotes an integer of 0 to 2, which may be the same or different when there are a plurality of A ⁴¹ and Z ⁴¹ .

According to the present invention, since the liquid crystal display element is excellent in high-speed responsiveness, the generation of residual images is small, and the occurrence of dripping marks during production is small, and the characteristics of the liquid crystal display element are excellent, and the pretilt angle formed is also formed. Since it has high stability, it can be effectively used as a display element of a liquid crystal TV, a monitor, or the like.

Moreover, according to the present invention, it is possible to manufacture an efficient liquid crystal display element which is less likely to cause dripping marks.

10‧‧‧Liquid display components

11‧‧‧First substrate

12‧‧‧second substrate

13‧‧‧Liquid composition layer

14‧‧‧Common electrode

15‧‧‧pixel electrode

16‧‧‧Vertical alignment film

17‧‧‧Vertical alignment film

18‧‧‧Color filters

19‧‧‧ liquid crystal molecules

20‧‧‧ polymer layer

21‧‧‧ polymer layer

Fig. 1 is a schematic perspective view showing an embodiment of a liquid crystal display element of the present invention.

Fig. 2 is a schematic plan view showing an example of a slit electrode (comb electrode) used in the liquid crystal display device of the present invention.

Fig. 3 is a view showing the definition of the pretilt angle in the liquid crystal display element of the present invention.

Embodiments of the liquid crystal display device of the present invention and a method of manufacturing the same will be described.

Furthermore, this embodiment is specifically designed to better understand the gist of the invention. The present invention is not limited to the invention unless otherwise specified.

[Liquid Crystal Display Element]

The liquid crystal display device of the present invention has a liquid crystal composition layer sandwiched between a pair of substrates, which is based on the application of a voltage to the liquid crystal composition layer to cause liquid crystal molecules in the liquid crystal composition layer to occur in Friedrich. Freedericksz is transformed to function as a function of an optical switch, and a well-known conventional technique can be used in this respect.

In a conventional vertical alignment liquid crystal display device in which two substrates have electrodes for causing a Friedrichs transition of liquid crystal molecules, a method of applying a charge perpendicularly between two substrates is generally employed. In this case, one electrode becomes a common electrode and the other electrode becomes a pixel electrode. The most typical embodiment of this mode is shown below.

Fig. 1 is a schematic perspective view showing an embodiment of a liquid crystal display element of the present invention.

The liquid crystal display element 10 of the present embodiment is configured by a first substrate 11 and a second substrate 12, and a liquid crystal composition layer 13 sandwiched between the first substrate 11 and the second substrate 12, and is provided in the first a common electrode 14 on the surface of the substrate 11 facing the liquid crystal composition layer 13 , a pixel electrode 15 provided on the surface of the second substrate 12 facing the liquid crystal composition layer 13 , and a liquid crystal provided on the common electrode 14 The vertical alignment film 16 on the surface of the composition layer 13 opposite thereto, the vertical alignment film 17 disposed on the surface of the pixel electrode 15 opposite to the liquid crystal composition layer 13, and the polymerization formed on the vertical alignment film 16 as needed The material layer 20, the polymer layer 21 formed on the vertical alignment film 17, and the color filter 18 disposed between the first substrate 11 and the common electrode 14.

As the first substrate 11 and the second substrate 12, a glass substrate or a plastic base can be used. board.

As the plastic substrate, a substrate made of a resin such as an acrylic resin, a methacrylic resin, polyethylene terephthalate, polycarbonate, or a cyclic olefin resin can be used.

The common electrode 14 is usually made of a material having transparency such as indium tin oxide (ITO).

The pixel electrode 15 is usually made of a material having transparency such as indium tin oxide (ITO).

The pixel electrodes 15 are arranged in a matrix on the second substrate 12. The pixel electrode 15 is controlled by a drain electrode of an active device typified by a TFT switching element having a gate line as an address signal line and a source line as a data line in a matrix. Furthermore, the configuration of the TFT switching elements is not shown here.

When the pixel is divided into a plurality of regions by dividing the oblique direction of the liquid crystal molecules in the pixel in order to improve the viewing angle characteristics, a slit having a stripe-like or V-shaped pattern may be provided in each pixel (the electrode is not formed). Part of the pixel electrode.

2 is a schematic plan view showing a typical form of a slit electrode (comb electrode) when the inside of the pixel is divided into four regions. The slit electrode has a slit in a comb shape in four directions from the center of the pixel, and the liquid crystal molecules in the respective pixels which are substantially perpendicularly oriented with respect to the substrate when no voltage is applied, the liquid crystal molecules are applied The directors are gradually approaching the horizontal orientation towards 4 different directions. As a result, since the directional orientation of the liquid crystal in the pixel can be divided into a plurality of directions, it has an extremely wide viewing angle characteristic.

As a method for performing pixel division, in addition to the above method of providing a slit to a pixel electrode, a method for providing a structure such as a linear protrusion in a pixel, and setting a pixel can be provided. A method of an electrode or an electrode other than the common electrode. The alignment direction of the liquid crystal molecules can also be divided by these methods, but in terms of transmittance and ease of fabrication, it is preferable to use a slit electrode. Since the pixel electrode provided with the slit does not have a driving force for the liquid crystal molecules when no voltage is applied, it is impossible to impart a pretilt angle to the liquid crystal molecules. However, the pretilt angle can be imparted by using the alignment film material used in the present invention in combination, and by combining with the pixel-divided slit electrode, a wide viewing angle formed by pixel division can be achieved.

In the present invention, the pretilt angle means that the director of the liquid crystal molecules is perpendicular to the substrate surface (the surface of the first substrate 11 and the second substrate 12 adjacent to the liquid crystal composition layer 13) in a state where no voltage is applied. The direction is slightly different.

(orientation film)

Since the liquid crystal display element of the present invention is a vertical alignment (VA) type liquid crystal display element, the director of the liquid crystal molecules is oriented substantially vertically with respect to the substrate surface when no voltage is applied. In order to orient the liquid crystal molecules vertically, a (vertical) oriented film is usually used.

In the present invention, an oriented film containing a polymer which controls the orientation direction of liquid crystal molecules in the liquid crystal composition layer by polymerizing a polymerizable group of a compound having a polymerizable group is used. That is, in the present invention, an oriented film containing a polymer obtained by polymerizing a polymerizable group of a compound having a polymerizable group having a function of controlling the orientation direction of liquid crystal molecules in the composition is used.

As the material for forming the vertical alignment film (vertical alignment film material), a polyimide, a polyamide, a polyoxyalkylene, a cured product of a polymerizable liquid crystal compound, or the like can be used.

In the case where polyimine is used as the alignment film material for forming the vertical alignment film, it is preferred to use a mixture of tetracarboxylic dianhydride and diisocyanate, poly-proline, polyphthalamide. The polyimine solution in which the amine is dissolved or dispersed in a solvent, and in this case, the content of the polyimine in the polyimide reaction solution is preferably 1% by mass or more and 10% by mass or less, more preferably 3 mass% or more and 5% by mass or less, and more preferably 10 mass% or less.

Further, in the case where a polyoxyalkylene-based material is used as the alignment film material for forming the vertical alignment film, a ruthenium compound, an alcohol derivative, and an oxalic acid derivative having an alkoxy group by mixing at a specific ratio can be used. A polyoxane solution obtained by dissolving polysiloxane produced by heating.

In the liquid crystal display device of the present invention, the vertical alignment films 16 and 17 formed of polyimide or the like contain a polymer formed by polymerization of a polymerizable compound having a reactive group. The polymerizable compound imparts a function of fixing the pretilt angle of the liquid crystal molecules. In other words, by using a slit electrode or the like, the director of the liquid crystal molecules in the pixel can be tilted in different directions when a voltage is applied. However, even in the configuration using the slit electrode, when no voltage is applied, the liquid crystal molecules are oriented almost perpendicularly with respect to the substrate surface, and no pretilt angle is generated, and a voltage is applied between the electrodes to slightly tilt the liquid crystal molecules. Next, the reactive monomer in the liquid crystal composition is polymerized by irradiation of ultraviolet rays or the like to give a suitable pretilt angle.

In addition, the polymerizable compound can be cured while the voltage is applied to the liquid crystal composition, and the polymerizable compound can be cured while applying a voltage, and the polymer layer 20 can be separated while the polymerizable compound is separated. 21 is formed on the surface of the above-mentioned vertical alignment films 16, 17 in the form of a polymer.

The orientation of the liquid crystal molecules is improved by the polymer contained in the vertical alignment films 16, 17 and the polymer layers 20, 21 formed on the surfaces of the vertically oriented films 16, 17 formed as needed. The production of high and residual images is less, and the production of drops and marks is more Less.

In the present invention, the term "substantially perpendicular" means that the director of the vertically oriented liquid crystal molecules is slightly inclined from the vertical direction to give a pretilt angle. If the case of the full vertical orientation is set to a pretilt angle of 90° and a horizontal orientation (oriented horizontally with the substrate surface) is set to a pretilt angle of 0°, the so-called substantially vertical is preferably 89.5 to 85°, more preferably It is 89.5~87°.

The vertical alignment films 16, 17 containing a polymer having a reactive group-containing polymerizable compound are formed by the effect of a polymerizable compound mixed in a vertically oriented film material. Therefore, it is presumed that the vertically oriented film is intricately crosslinked with the polymerizable compound to form a polymer alloy, but the exact structure cannot be shown.

Further, the polymerizable layers 20 and 21 which are formed as needed in the liquid crystal composition are formed on the surface of the vertical alignment films 16 and 17 while being separated from the liquid crystal composition during polymerization. Whether or not it is uniformly formed on the entire surface of the vertically oriented film, whether or not the island structure is formed in a non-uniform manner differs depending on the conditions of manufacture, and the accurate structure cannot be shown. Figure 1 shows the case of uniform formation.

The alignment film used in the present invention must have a vertical alignment function for orienting liquid crystal molecules in the liquid crystal composition layer in a direction perpendicular to the substrate surface, and further has an orientation control function for controlling the orientation direction of the liquid crystal molecules. As a method of obtaining an oriented film having two functions of the above-described vertical alignment function and orientation control function, there is a method of generally preparing a polymerizable compound having a reactive group in an alignment film material, and using a side chain moiety to have crosslinkability A method of using a polymer of a polymerizable compound of a functional group as a method of orienting a film material, and using a cured product of a polymerizable liquid crystal compound as an oriented film material. Hereinafter, each method will be described.

(Parts in which a polymerizable compound having a reactive group is formulated in an oriented film material) law)

As a method of formulating a polymerizable compound having a reactive group in the alignment film material, a method of formulating a polymerizable compound having a reactive group in the alignment film material described above can be exemplified.

The polymerizable compound having a reactive group contained in the alignment film material may contain a liquid crystal primordial moiety or may not contain a liquid crystal primordial moiety. Further, from the viewpoint of durability, the polymer of the polymerizable compound having a reactive group preferably has a crosslinked structure, and the polymerizable compound having a reactive group is preferably difunctional from the viewpoint of durability. Or a trifunctional functional polymerizable compound having two or more reactive groups.

In the polymerizable compound having a reactive group, the reactive group is preferably a substituent having a polymerizability using light. In particular, when a vertical alignment film is formed by thermal polymerization, since the reaction of the polymerizable compound having a reactive group can be suppressed at the time of thermal polymerization of the vertically oriented film material, the reactive group is preferably a polymerizable property using light. Substituent.

As the polymerizable compound having a reactive group, specifically, the following formula (V) is preferred.

(wherein, X ⁷ and X ⁸ each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH ₂ ) _s - (where s represents an integer from 2 to 7, X represents O, OCOO, OCO, or COO, X is bonded to an aromatic ring present in U), and U represents a linear chain of 2 to 20 carbon atoms. Or a branched polyalkylene group, a linear or branched polyalkylene group having 3 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms; an alkyl group or a plurality of stretches in a polyalkylene group The alkenyl group in the alkenyl group may be substituted with -O-, -CO-, -CF ₂ - in the range in which the oxygen atoms are not adjacent, and may be substituted with an alkyl group having 5 to 20 carbon atoms. The alkylene group may be a polymerizable compound represented by an alkyl group which may be substituted with an oxygen atom in a range in which the oxygen atoms are not adjacent, or a cyclic substituent, and k represents an integer of 0 to 5.

In the above formula (V), X ⁷ and X ⁸ each independently represent a hydrogen atom or a methyl group, and when a reaction rate is important, a hydrogen atom is preferred, and when it is important to reduce the residual amount of the reaction, it is preferred. Is a methyl group.

In the above formula (V), Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH ₂ ) _s - (wherein s represents 2 to 7). An integer, X represents O, OCOO, or COO, and X bonds to an aromatic ring present in U), preferably the carbon chain is not too long, and is preferably a single bond or a carbon number of 1 to 5 The alkyl group is more preferably a single bond or an alkylene group having 1 to 3 carbon atoms. Further, when Sp ¹ and Sp ² represent -X-(CH ₂ ) _s -, s is also preferably 1 to 5, more preferably 1 to 3, and more preferably at least one of Sp ¹ and Sp ² The one is a single button, and the best one is a single button.

In the above formula (V), k represents an integer of 0 to 5, and in the case of paying attention to the controllability of the orientation direction of the liquid crystal molecules in the liquid crystal composition layer, k is preferably an integer of 1 to 5, more preferably k is an integer from 1 to 3, and further preferably k is 1.

In the above formula (V), U represents a linear or branched polyalkylene group having 2 to 20 carbon atoms, a linear or branched polyalkylene group having 3 to 20 carbon atoms or a carbon number of 5~. a polyvalent cyclic substituent of 30, wherein the alkylene group in the polyalkylene group may be substituted with -O-, -CO-, -CF ₂ - in the range in which the oxygen atoms are not adjacent, or may be substituted into a carbon atom. The alkyl group of 5 to 20 (the alkylene group in the group may be substituted with an oxygen atom in the range in which the oxygen atoms are not adjacent) or the cyclic substituent is preferably substituted with two or more cyclic substituents.

In the above formula (V), specifically, U preferably represents the following formula (Va-1) to formula (Va-5), more preferably represents formula (Va-1), formula (Va-2) ), the formula (Va-5), and more preferably represents the formula (Va-1).

(wherein, both ends are bonded to Sp ¹ or Sp ² (in the case of k = 1 above), and when k is an integer of 2 to 5, the number of linkages is correspondingly increased; Z ¹ , Z ² And Z ³ independently represent -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - , -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ - , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO- or a single bond, Any hydrogen atom in all aromatic rings in the formula may be substituted with a fluorine atom)

In the above U, Z ¹ , Z ² and Z ³ are each independently, preferably -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, - CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, more preferably -COO-, -OCO- or a single bond, particularly preferably a single bond.

In the case where U has the above ring structure, it is preferred that at least one of Sp ¹ and Sp ² represents a single bond, and it is preferable that both of them are single bonds.

In the above formula (V), k represents an integer of 0 to 5, preferably a difunctional compound in which k is 1, or a trifunctional compound in which k is 2, and more preferably a difunctional compound.

Specifically, the compound represented by the above formula (V) is preferably a compound represented by the following formula (Va-1-1) to (Va-5-3).

Further, among the compounds represented by the above formula (Va-1-1) to formula (Va-5-3), preferred are compounds represented by formula (Va-1-1) to formula (Va-2-11). More preferably, it is a compound represented by the formula (Va-1-1) to the formula (Va-1-13).

The content of the above-mentioned polymerizable compound having a reactive group, particularly the compound represented by the above formula (V), in the oriented film material forming the alignment film is preferably from 0.1 to 6% by mass, more preferably from 0.5 to 4% by mass. Further, it is preferably 1 to 2% by mass.

(Method of using a polymer having a polymerizable compound having a crosslinkable functional group in a side chain portion as an oriented film material)

The polymerizable compound having a crosslinkable functional group as a side chain moiety is not particularly limited as long as the side chain moiety has a crosslinkable functional group (polymerizable group), and it is preferred to use the above-mentioned one. The compound having a quinone imine skeleton or a siloxane skeleton as a main chain moiety is more preferably a compound having a polyimine skeleton in the main chain portion.

The polymerizable compound having a polyimine skeleton in the main chain portion and having a crosslinkable functional group as a side chain, and a repeating unit (main chain portion) constituting the polyimine structure has a crosslinkable functional group as a side chain. Compound. Further, the crosslinkable functional group becomes a polymerization initiation point, and a polymerizable compound having a polymerizable group which is formulated in the alignment film material undergoes a radical reaction to form a side chain, thereby having a control liquid crystal composition layer Orientation control function of the orientation direction of liquid crystal molecules. The crosslinkable functional group may have any structure as long as it can undergo a radical reaction, and is preferably a group represented by (V2-1) to (V2-7) shown below, and more preferably (V2- The group represented by 1) to (V2-3) is further preferably a group represented by (V2-1) or (V2-2).

(R ₁ represents an alkyl group having 1 to 5 carbon atoms)

The crosslinkable functional group may be bonded to the main chain moiety via a covalent bond, or may be directly bonded to the main chain moiety, or may be bonded to the main chain moiety via a linking group, and is preferably used as a linking group. -OC ₆ H ₄ - or -OC ₆ H ₄ -(R ² O) _r - (R ² represents an alkylene group having 1 to 20 carbon atoms, and r represents an integer of 1 or more).

The polymerizable compound having a polyethylenimine skeleton as a main chain and having a crosslinkable functional group as a side chain, for example, a compound represented by the following formula (V2) can be exemplified.

(In the formula (V2), R ³ represents any one of the groups represented by the following (V2-A) to (V2-F), and R ⁴ and R ⁵ each independently represent a stretch of 1 to 20 carbon atoms. The alkyl group, R ⁶ and R ⁷ each independently represent any one of the groups represented by the above (V2-1) to (V2-7), n represents an integer of 1 or more, and m1 and m2 represent 0 or 1, respectively, m3 And m4 respectively represent an integer of 0 or more, m5 and m6 respectively represent 0 or 1, but at least one of m5 and m6 represents 1)

The polymerizable compound having a polymerizable group which is blended in the alignment film material together with the polymerizable compound having a polyfluorene imine skeleton in the main chain portion and having a crosslinkable functional group as a side chain may be exemplified by the above formula ( The compounds represented by V) are the same.

Further, in the case where a polymer of a polymerizable compound having a crosslinkable functional group in a side chain portion is used as the material of the alignment film, a known polyamidene-based material as described above may be used in combination.

(Method of using a cured product of a polymerizable liquid crystal compound as an oriented film)

In the case where a cured product of a polymerizable liquid crystal compound is used as the oriented film, an oriented film composed of a polyimide-based material or a polyoxyalkylene-based material as described above may be used as the undercoat alignment film.

Specifically, the polymerizable liquid crystal compound which forms the alignment film preferably contains one or two or more kinds of polymerizable liquid crystal compounds represented by the following formula (V3).

(wherein X ¹ represents a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s - (wherein, s Indicates an integer from 2 to 7, the oxygen atom is bonded to the aromatic ring), and Z ¹ represents -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ - , -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO- CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CY ¹ =CY ² - (Y ¹ and Y ² each independently represent a hydrogen atom, a fluorine atom), -C≡C- or a single bond, and Y represents a carbon number of 1 An alkyl group of ~8, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, a hydrogen atom, a fluorine atom or a cyano group, or the following structure,

(wherein, X ² represents a hydrogen atom or a methyl group), and the C ring represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and a 1,4-phenylene group in the C ring. Any hydrogen atom may be substituted with a fluorine atom).

In the above formula (V3), X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and when a reaction rate is important, a hydrogen atom is preferred, and when it is important to reduce the residual amount of the reaction, it is preferred. Is a methyl group.

In the above formula (V3), Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s - (wherein s represents 2 to 7) An integer, the oxygen atom is bonded to the aromatic ring, preferably the carbon chain is not too long, and is preferably a single bond or an alkylene group having 1 to 5 carbon atoms, more preferably a single bond or a carbon atom. A number of 1-3 alkyl groups. Further, in the case where Sp ¹ and Sp ² represent -O-(CH ₂ ) _s -, s is also preferably from 1 to 5, more preferably from 1 to 3, and still more preferably at least one of Sp ¹ and Sp ² . The one is a single button, and the best one is a single button.

In the above formula (V3), Z ¹ represents -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, - CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO- CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO -, -CY ¹ = CY ² -, -C≡C- or a single bond, preferably -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, more preferably -COO-, -OCO- or a single bond, particularly preferably a single bond.

In the above formula (V3), C represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond in which any hydrogen atom may be substituted with a fluorine atom, preferably 1,4-stretch. Phenyl or single bond.

In the case where C represents a ring structure other than a single bond, Z ^{1 is} also preferably a linking group other than a single bond. When C is a single bond, Z ^{1 is} preferably a single bond.

Y 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, an alkenyloxy group having 2 to 8 carbon atoms, a hydrogen atom, a fluorine atom or The cyano compound is a monofunctional polymerizable liquid crystal compound, and Y does not have a polymerizable skeleton. On the other hand, a compound in which Y represents a polymerizable skeleton as described above is a difunctional polymerizable liquid crystal compound. In the present invention, any of a monofunctional polymerizable liquid crystal compound or a difunctional polymerizable liquid crystal compound can be used. From the viewpoint of heat resistance, a difunctional polymerizable liquid crystal compound is preferable, and these may be used at the same time. Both.

In the above aspect, as a polymerizable liquid crystal compound having a ring structure, The compound represented by the following general formulae (V3-1) to (V3-6) is particularly preferably a compound represented by the general formulae (V3-1) to (V3-4), and the most preferable one is a general formula (V3). -2) The compound represented.

When a cured product of a polymerizable liquid crystal compound is used as the alignment film, after heating the polymerizable liquid crystal compound in the alignment film forming material to form an isotropic liquid, it is necessary to lower the temperature and set the orientation of the polymerizable liquid crystal compound to Vertical orientation. Thereafter, a pretilt angle is applied in a state where a magnetic field inclined at a specific angle from the substrate surface is applied, and in this state, the polymerizable liquid crystal compound is cured by irradiation with ultraviolet rays to form an alignment film.

Further, the alignment film may have a horizontal alignment film as a base layer of the alignment film. Specifically, it may have a horizontal alignment film by applying a horizontal alignment film material to a substrate by spin coating using a polyimide-based horizontal alignment film material or the like, and removing the solvent by heating or the like. Thereafter, firing is performed to form a base layer, and rubbing treatment is performed to impart horizontal orientation. (Polymerizable compound contained in the liquid crystal composition for forming a polymer layer on the surface of the alignment film)

In the liquid crystal display device of the present invention, the vertical alignment film contains a polymer formed by polymerization of a polymerizable compound having a reactive group, by which a suitable pretilt angle can be imparted, and further, if necessary, liquid crystal The composition contains a polymerizable compound, and after the liquid crystal composition is sandwiched between the substrates, the polymerizable compound is cured while applying a voltage, whereby the polymerizable compound is formed as a polymer layer while being phase-separated. Further, the surface of the vertically oriented film can further obtain a liquid crystal display element in which the directivity of the liquid crystal molecules or the stability of the pretilt angle is high, the generation of residual images is small, and the occurrence of dripping marks at the time of manufacture is small.

The polymerizable compound which forms the above-mentioned polymerizable layer may, for example, be a monofunctional polymerizable compound having one reactive group, or a polyfunctional polymerizable compound having two or more reactive groups such as a difunctional or trifunctional group, and the like. It is a polyfunctional polymerizable compound having two or more reactive groups such as a difunctional or trifunctional group. The polymerizable compound to be used may be one type or two or more types. The polymerizable compound having a reactive group preferably contains a liquid crystal prime site.

As the polymerizable compound forming the polymer layer, the formula (V1) similar to the above formula (V) is preferred.

(wherein, X ⁷ and X ⁸ each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH ₂ ) _s - (where s represents an integer from 2 to 7, X represents O, OCOO, OCO, or COO, X is bonded to an aromatic ring present in U), and U represents a linear chain of 2 to 20 carbon atoms or a branched polyalkylene group, a linear or branched polyalkylene group having 3 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms; an alkylene group or a polyalkylene group in a polyalkylene group The alkenyl group in the group may be substituted with -O-, -CO-, -CF ₂ - in the range in which the oxygen atoms are not adjacent, and may be substituted with an alkyl group having 5 to 20 carbon atoms. A polymerizable compound represented by an alkyl group which may be substituted with an oxygen atom in a range in which oxygen atoms are not adjacent to each other or a cyclic substituent, and k represents an integer of 1 to 5.

In the above formula (V1), X ⁷ and X ⁸ each independently represent a hydrogen atom or a methyl group, and when a reaction rate is important, a hydrogen atom is preferred, and when it is important to reduce the residual amount of the reaction, it is preferred. Is a methyl group.

In the above formula (V1), Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH ₂ ) _s - (wherein s represents 2 to 7). An integer, X represents O, OCOO, or COO, and X is bonded to an aromatic ring present in U), preferably the carbon chain is not too long, and is preferably a single bond or a carbon number of 1 to 5 The alkyl group is more preferably a single bond or an alkyl group having 1 to 3 carbon atoms. Further, when Sp ¹ and Sp ² represent -X-(CH ₂ ) _s -, s is also preferably 1 to 5, more preferably 1 to 3, and more preferably at least one of Sp ¹ and Sp ² The one is a single button, and the best one is a single button.

In the above formula (V1), k represents an integer of 0 to 5, and in the case of paying attention to the controllability of the orientation direction of the liquid crystal molecules in the liquid crystal composition layer, k is preferably an integer of 1 to 5, more preferably k is an integer from 1 to 3, and further preferably k is 1.

In the above formula (V1), U represents a linear or branched polyalkylene group having 2 to 20 carbon atoms, a linear or branched polyalkylene group having 3 to 20 carbon atoms or a carbon number of 5~ a polyvalent cyclic substituent of 30, wherein the alkylene group in the polyalkylene group may be substituted with -O-, -CO-, -CF ₂ - in the range in which the oxygen atoms are not adjacent, or may be substituted into a carbon atom. The alkyl group of 5 to 20 (the alkylene group in the group may be substituted with an oxygen atom in a range in which the oxygen atoms are not adjacent) or the cyclic substituent is preferably substituted with two or more cyclic substituents. Specifically, U preferably represents the following formula (V1a-1) to formula (V1a-5), and more preferably represents formula (V1a-1), formula (V1a-2), and formula (V1a-5). It is especially preferable to express the formula (V1a-1).

(wherein, both ends are bonded to Sp ¹ or Sp ² (in the case of k = 1 above), and when k is an integer of 2 to 5, the number of linkages is correspondingly increased; Z ¹ , Z ² And Z ³ independently represent -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - , -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ - , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO- or a single bond, Any hydrogen atom in all aromatic rings in the formula may be substituted with a fluorine atom)

In the above U, Z ¹ , Z ² and Z ³ are each independently, preferably -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, - CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, more preferably -COO-, -OCO- or a single bond, particularly preferably a single bond.

In the case where U has the above ring structure, it is preferred that at least one of Sp ¹ and Sp ² represents a single bond, and it is preferable that both of them are single bonds.

The compound represented by the above formula (V1) is preferably a compound represented by the following formula (V1b).

(wherein X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ^1b and Sp ^2b each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s - (wherein, s represents an integer from 2 to 7, the oxygen atom is bonded to the aromatic ring), and Z ⁴ represents -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O -, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH= CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CY ¹ =CY ² -, -C≡C- or a single bond, and the C ring represents a 1,4-phenylene group or a single bond. Any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom)

In the above formula (V1b), X ¹ and X ² each independently represent a hydrogen atom or a methyl group, preferably a diacrylate derivative each representing a hydrogen atom, or a dimethacrylate derivative derived from a methyl group. The substance is also preferably a compound in which one represents a hydrogen atom and the other represents a methyl group. Regarding the polymerization rate of the compounds, the diacrylate derivative is the fastest, the dimethacrylate derivative is slow, and the asymmetric compound is in the middle thereof, and a preferred aspect can be used depending on the use thereof.

In the above formula (V1b), Sp ^1b and Sp ^2b each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s -, preferably at least one of which is a single A bond, and preferably a compound which each represents a single bond or one of which is a single bond, and the other represents an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s -. In this case, an alkylene group having 1 to 4 carbon atoms is preferred, and s is preferably 1 to 4.

In the above formula (V1b), Z ⁴ represents -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, - CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO- CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO -, -CY ¹ = CY ² -, -C≡C- or a single bond, preferably -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, more preferably -COO-, -OCO- or a single bond, particularly preferably a single bond.

In the case where C represents a ring structure other than a single bond, Z ^{4 is} also preferably a linking group other than a single bond. When C is a single bond, Z ^{4 is} preferably a single bond.

In the above formula (V1b), it is preferred that C represents a single bond and a ring structure is formed of two rings, and as a polymerizable compound having a ring structure, specifically, the following is preferred. The compound represented by the formula (V1b-1) to (V1b-6) is particularly preferably a compound represented by the formula (V1b-1) to (V1b-4), and is preferably represented by the formula (V1b-2). Compound.

(Sp ^1b and Sp ^2b respectively have the same meanings as Sp ¹ and Sp ² described in the general formula (V1b))

Specifically, the compound represented by the above formula (V1) is also preferably a compound represented by the following formula (V1c).

(wherein, X ¹ , X ² and X ³ each independently represent a hydrogen atom or a methyl group, and Sp ^1c , Sp ^2c and Sp ^3c each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O -(CH ₂ ) _s - (wherein, s represents an integer from 2 to 7, the oxygen atom is bonded to the aromatic ring), and Z ¹¹ represents -OCH ₂ -, -CH ₂ O-, -COO-, -OCO -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH- , -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CY ¹ =CY ² -, -C≡C- or a single bond, J represents 1,4-phenylene, Or a single bond, wherein any hydrogen atom in the 1,4-phenylene group in the formula may be substituted with a fluorine atom)

The total content of the polymerizable compound used for forming the polymer layer on the surface of the vertically oriented film in the liquid crystal composition is preferably from 0 to 1% by mass, more preferably from 0.03 to 0.8% by mass, still more preferably from 0.05 to 0.6. quality%.

(liquid crystal composition)

The liquid crystal composition of the present invention contains one or two or more compounds represented by the formula (i), the formula (ii), and the formula (iii).

The compound represented by the formula (i), the formula (ii) and the formula (iii) is preferably A compound in which each dielectric (Δε) is negative and its absolute value is greater than 3.

In the general formula (i), the general formula (ii) and the general formula (iii), R ⁱ¹ , R ⁱⁱ¹ and R ⁱⁱⁱ¹ are each independently, preferably an alkyl group having 1 to 8 carbon atoms and a carbon number of 1 to 8. Alkoxy group, alkenyl group having 2 to 8 carbon atoms or alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or carbon The alkenyl group having 2 to 5 atoms or the alkenyloxy group having 2 to 5 carbon atoms is further preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably a carbon atom. The alkyl group having 2 to 5 or the alkenyl group having 2 to 3 carbon atoms is particularly preferably an alkenyl group having 3 carbon atoms (acryloyl group). R ⁱ² , R ⁱⁱ² and R ⁱⁱⁱ² are each independently, 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 2 to 2 carbon atoms. The alkenyloxy group of 8 is more 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 alkenyl group having 2 to 5 carbon atoms. Further, it is preferably an alkoxy group having 1 to 4 carbon atoms. In the case where the improvement of the response speed of the display element is emphasized, the alkenyl group is preferred, and when the reliability of the voltage holding ratio or the like is emphasized, the alkyl group is preferred.

Further, when the ring structure to which R ⁱ¹ , R ⁱ² , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱⁱ¹ and R ⁱⁱⁱ² are bonded is a phenyl group (aromatic), it is preferably a linear one having 1 to 5 carbon atoms. An alkyl group, a linear alkoxy group having 1 to 4 carbon atoms and an alkenyl group having 4 to 5 carbon atoms bonded to R ⁱ¹ , R ⁱ² , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱⁱ¹ and R ⁱⁱⁱ² The ring structure 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.

When R ⁱ¹ , R ⁱ² , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱⁱ¹ and R ⁱⁱⁱ² are alkenyl groups, it is preferably selected from the group represented by any one of formula (R1) to formula (R5). (* in each formula indicates the bonding site on the ring structure)

In the general formula (i), the general formula (ii) and the general formula (iii), A ⁱ¹ , A ⁱ² , A ⁱⁱ¹ , A ⁱⁱ² , A ⁱⁱⁱ¹ and A ⁱⁱⁱ² are independent, respectively, and when the Δn is increased, Preferably, it is aromatic, and in order to improve the response speed, it is preferably aliphatic, and A ²¹ preferably represents trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-benzene , 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 1,4-extension Hexenyl, 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 represents the following structure,

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

Z ⁱ¹ , Z ⁱ² , Z ⁱⁱ¹ , Z ⁱⁱ² , Z ⁱⁱⁱ¹ and Z ⁱⁱⁱ² each independently represent a single bond, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH _2- or -CF ₂ CF ₂ -, preferably -CH ₂ O-, -CF ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, and more preferably -CH ₂ O-, -CH ₂ CH ₂ - or a single bond, particularly preferably -CH ₂ O- or a single bond.

Further, at least one of Z ⁱ¹ represents -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -, preferably -CH ₂ O-, -CF ₂ O-, -CH ₂ CH ₂ -, or -CF ₂ CF ₂ , further preferably -CH ₂ O-, or -CH ₂ CH ₂ -, more preferably -CH ₂ O- .

Z ⁱⁱⁱ³ represents -CH ₂ - or an oxygen atom, preferably an oxygen atom.

m ⁱ¹ , m ⁱ² , m ⁱⁱ¹ , m ⁱⁱ² , m ⁱⁱⁱ¹ and m ⁱⁱⁱ² each independently represent an integer of 0 to 3, m ⁱ¹ +m ⁱ² is 0, 1, 2 or 3, m ⁱⁱ¹ +m ⁱⁱ² and m ⁱⁱⁱ¹ + m ⁱⁱⁱ² is 1, 2 or 3, respectively, preferably m ⁱ¹ + m ⁱ² , m ⁱⁱ¹ + m ⁱⁱ² and m ⁱⁱⁱ¹ + m ⁱⁱⁱ² are 1 or 2, respectively.

The compound represented by the formula (i) preferably contains one or two or more compounds represented by the formula (i-1).

(wherein A ⁱ¹¹ , A ⁱ¹² and A ⁱ¹³ each independently represent a 1,4-cyclohexylene group or a 1,4-phenylene group, and one of the 1,4-cyclohexylene groups is present as -CH ₂ - or not Two or more adjacent -CH ₂ - may be substituted with -O- or -S-, and one hydrogen atom present in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom, respectively. ^I11 and m ⁱ¹² respectively represent 0 or 1, and R ⁱ¹ , R ⁱ² , Z ⁱ¹ and Z ⁱ² respectively represent the same meanings as R ⁱ¹ , R ⁱ² , Z ⁱ¹ and Z ⁱ² in the general formula (i))

The compound represented by the formula (i-1) is preferably a compound represented by the formula (i-1A), the formula (i-1B) or the formula (i-1C).

(wherein R ⁱ¹ , R ⁱ² , A ⁱ¹¹ and Z ⁱ¹ each independently represent the same meaning as R ⁱ¹ , R ⁱ² , A ⁱ¹¹ and Z ⁱ¹ in the general formula (i-1))

(wherein R ⁱ¹ , R ⁱ² , A ⁱ¹¹ , A ⁱ¹² and Z ⁱ¹ each independently represent the same meaning as R ⁱ¹ , R ⁱ² , A ⁱ¹¹ , A ⁱ¹² and Z ⁱ¹ in the general formula (i-1))

(wherein, ^{i i13} represents 1 or 2, and R ⁱ¹ , R ⁱ² , A ⁱ¹¹ , A ⁱ¹² , A ⁱ¹³ , Z ⁱ¹ , Z ⁱ² and m ⁱ¹¹ respectively represent R ⁱ¹ in the general formula (i-1) , R ⁱ² , A ⁱ¹¹ , A ⁱ¹² , A ⁱ¹³ , Z ⁱ¹ , Z ⁱ² and m ^{i11 have the} same meaning)

The compound represented by the formula (i-1A) is preferably a compound represented by the following formula (i-1A-1) to (i-1A-4), more preferably a formula (i-). The compound represented by 1A-1) and the compound represented by the formula (i-1A-4) are more preferably a compound represented by the formula (i-1A-1).

(wherein R ⁱ¹ and R ⁱ² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in the formula (i-1))

The compound represented by the formula (i-1B) is preferably a compound represented by the following formula (i-1B-1) to (i-1B-6), more preferably a formula (i-). 1B-1), a compound represented by the formula (i-1B-3), and a compound represented by the formula (i-1B-6), and more preferably represented by the formula (i-1B-1) a compound and a compound represented by the formula (i-1B-3).

(wherein R ⁱ¹ and R ⁱ² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in the formula (i-1))

The compound represented by the formula (i-1C) is preferably a compound represented by the following formula (i-1C-1) to (i-1C-4), more preferably a formula (i-). 1C-1), and a compound represented by the formula (i-1C-2).

(wherein R ⁱ¹ and R ⁱ² each independently represent the same meaning as R ⁱ¹ and R ⁱ² in the formula (i-1))

Further, the compound represented by the formula (i-1) is preferably a compound represented by the formula (i-1D).

(wherein R ⁱ¹ and R ⁱ² each independently represent the same meaning as R ⁱ¹ , R ⁱ² , A ⁱ¹¹ and Z ⁱ¹ in the general formula (i-1))

The compound represented by the formula (i-1D) is preferably a compound represented by the following formula (i-1D-1) to (i-1D-14).

The compound represented by the formula (ii) is preferably a compound represented by the formula (ii-1A), the formula (ii-1B) or the formula (ii-1C).

(wherein R ⁱⁱ¹ , R ⁱⁱ² , Z ⁱⁱ¹ and X ⁱⁱ¹ each independently represent the same meaning as R ⁱⁱ¹ , R ⁱⁱ² , Z ⁱⁱ¹ and X ⁱⁱ¹ in the formula (ii), and A ^ii1c and A ^ii1d are independently represents 1,4-cyclohexylene or 1,4-phenylene group, a -CH ₂ present in the 1,4-cyclohexylene group of - or abutment of two or more of -CH ₂ - may be substituted with - O- or -S-, one of the hydrogen atoms present in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom, and Z ^ii1c and Z ^ii1d each independently represent a single bond, -OCH ₂ - , -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -)

In the compound represented by the formula (ii-1A) or the formula (ii-1B), Z ⁱⁱ¹ preferably represents a single bond, -OCH ₂ -, -CH ₂ O- or -CH ₂ CH ₂ .

The compound represented by the formula (ii-1C) is preferably a compound represented by the following formula (ii-1C-1) to (ii-1C-6).

(wherein R ⁱⁱ¹ and R ⁱⁱ² each independently represent the same meaning as R ⁱⁱ¹ and R ⁱⁱ² in the formula (ii))

The compound represented by the formula (iii) is preferably a compound represented by the formula (iii-1A), the formula (iii-1B) or the formula (iii-1C).

(wherein R ⁱⁱⁱ¹ , R ⁱⁱⁱ² and Z ⁱⁱⁱ¹ each independently represent the same meaning as R ⁱⁱⁱ¹ , R ⁱⁱⁱ² and Z ⁱⁱⁱ¹ in the formula (iii), and A ^iii1c and A ^iii1d each independently represent 1,4-extension cyclohexyl or 1,4-phenylene, 1,4-cyclohexylene present in the a group -CH ₂ - or two or more of the adjacent -CH ₂ - may be substituted with -O- or -S- One of the hydrogen atoms present in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom, and Z ^iii1c and Z ^iii1d each independently represent a single bond, -OCH ₂ -, -CH ₂ O- , -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -)

In the compound represented by the formula (iii-1A) or the formula (iii-1B), Z ⁱⁱⁱ¹ preferably represents a single bond, -OCH ₂ -, -CH ₂ O- or -CH ₂ CH ₂ .

The compound represented by the formula (iii-1C) is preferably a compound represented by the following formula (iii-1C-1) to (ii-1C-4).

(wherein R ⁱⁱⁱ¹ and R ⁱⁱⁱ² each independently represent the same meaning as R ⁱⁱⁱ¹ and R ⁱⁱⁱ² in the formula (iii))

In the liquid crystal composition of the present invention, when two or more compounds represented by the general formulae (i) to (iii) are contained, two or more kinds may be contained only from the general formula (i) to (iii). The compound of any one of the compounds represented by the formula may further contain two or more compounds selected from two or more formulae selected from the compounds represented by the general formulae (i) to (iii).

The liquid crystal composition of the present invention preferably contains one or two or more compounds represented by the formula (i), more preferably one or two or more of the formula (i-1A) and the formula (i-1B). Or a compound represented by the formula (i-1C), and further preferably contains two to ten kinds.

More specifically, the general formula (i-1A), the general formula (i-1B), and the general formula (i-1C) preferably each have one or two or more selected from the formula (i-1A-). 1) a compound in the compound group represented by the formula (i-1B-1) and the formula (i-1C-1), more preferably a compound represented by the formula (i-1A-1) and a formula A combination of compounds represented by (i-1B-1).

The total amount of the compound represented by the formula (i), the formula (ii), and the formula (iii) is preferably from 10 to 90% by mass, and more preferably 15%, based on the liquid crystal composition of the present invention. ~90% by mass, further preferably 20 to 90% by mass, further preferably 20 to 80% by mass, further preferably 30 to 80% by mass, further preferably 45 to 80% by mass, particularly preferably 45 to 5% by mass 75 mass%.

More specifically, the total amount of the compounds represented by the general formula (i), the general formula (ii), and the general formula (iii) is preferably 0.1% by mass in the composition. The % of the following composition means % by mass or more, preferably 5% or more, preferably 10% or more, preferably 13% or more, preferably 15% or more, preferably 18%. The above content is preferably 20% or more, preferably 23% or more, preferably 25% or more, preferably 28% or more, preferably 30% or more, and more preferably 33% or more. It is preferably contained in an amount of 35% or more, preferably 38% or more, and more preferably 40% or more. Further, the upper limit is preferably 95% or less, preferably 90% or less, more preferably 88% or less, more preferably 85% or less, still more preferably 83% or less, and more preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 73% or less, preferably 70% or less, preferably 68% or less, preferably 65 or more. % or less is preferably 63% or less, preferably 60% or less, preferably 55% or less, preferably 50% or less, and more preferably 40% or less.

In addition to the general formula (i), the general formula (ii), and the general formula of the liquid crystal composition of the present invention (iii) In addition to the compound represented by the formula, one or two or more compounds represented by the formula (iv) each having a negative dielectric (Δε) and an absolute value of more than 3 may be used.

(wherein R ³ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms, and B is 1,4- Phenyl or trans-1,4-cyclohexylene, m represents 0, 1 or 2, when m is 2, two B may be the same or different)

Specifically, the compound represented by the above formula (iv) is preferably a compound represented by the following formula (iv-1) to formula (iv-6).

(wherein R ^3a represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^4a represents an alkyl group having 1 to 5 carbon atoms)

The liquid crystal composition of the present invention may contain one or two or more compounds represented by the formula (iv), and the total amount of the compound represented by the formula (iv) is in the liquid crystal composition of the present invention as an upper limit. The value is preferably 55% or less, preferably 50% or less, preferably 45% or less, preferably 40% or less, preferably 35% or less, and more preferably 30% or less. It is preferably contained in an amount of 25% or less, preferably 20% or less, preferably 15% or less, and more preferably 10% or less.

The liquid crystal composition of the present invention contains one or two or more compounds represented by the formula (IV).

(wherein R ⁴⁴ and R ⁴⁵ each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more of the groups -CH ₂ - 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- or -OCF ₂ -, one or more hydrogen atoms in the group may Each of them is independently substituted with a fluorine atom or a chlorine atom, and A ⁴¹ to A ⁴³ are each independently selected from (a) 1,4-cyclohexylene (one present in the group -CH ₂ - or not adjacent) More than -CH ₂ - may be substituted with -O-), (b) 1,4-phenylene (one present in the group -CH= or two or more adjacent to -CH= may be Substituted as -N=), and (c) naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl ( One of the naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl-CH= or two or more non-contiguous-CH= can be substituted -N=)

The group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, and Z ⁴¹ and Z ⁴² each independently represent a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-,m ⁴¹ denotes an integer of 0 to 2, and when there are a plurality of A ⁴¹ and Z ⁴¹ , the same may be the same or different)

In the formula (IV), R ⁴⁴ and R ⁴⁵ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or The alkenyloxy group having 2 to 8 carbon atoms is preferably a linear chain. In the case where the improvement of the response speed of the display element is emphasized, the alkenyl group is preferred, and when the reliability of the voltage holding ratio or the like is emphasized, the alkyl group is preferred. In the case where R ⁴⁴ and R ⁴⁵ are an alkenyl group, it is preferably selected from the group represented by any one of the formulae (R1) to (R5).

(The black dots in each formula indicate the point of connection with the ring)

The combination of R ⁴⁴ and R ⁴⁵ is not particularly limited, and it is preferred that both represent an alkyl group; either one represents an alkyl group and the other represents an alkenyl group; or either one represents an alkyl group and the other represents an alkyl group. Alkoxy; or either means an alkyl group and the other represents an oxy group. In the case where reliability is important, it is preferred that both R ⁴⁴ and R ⁴⁵ are alkyl groups. When it is important to reduce the volatility of the compound, it is preferably an alkoxy group, and when the viscosity is lowered, Preferably, at least one of them is an alkenyl group.

A ⁴¹ to A ⁴³ are preferably aromatic in the case of increasing Δn, and are preferably aliphatic in order to improve the response speed, and are each independently independent, preferably representing a trans-1,4-cyclohexylene group. , 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 3, 5-difluoro-1,4-phenylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-two Alkane-2,5-diyl, 1,4-bicyclo[2.2.2]exenyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4 - tetrahydronaphthalene-2,6-diyl, more preferably any of the following structures

Further preferably

Z ⁴¹ and Z ⁴² each independently represent a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-, and further preferably a single _{bond, -CH 2 CH 2 -, -} OCF 2 - or -CF ₂ O-, attention to the circumstances at the time of the response speed, and particularly preferably a single bond.

m ^{41 is} preferably an integer representing 1 or 2. In the case where a plurality of A ⁴¹ and Z ⁴¹ are present, the same may be the same or different.

The compounds represented by the formula (IV) may be used singly or in combination. The type of the compound that can be combined is not particularly limited, and is based on solubility at low temperature, transfer temperature, The properties required for electrical reliability, birefringence, and the like are appropriately combined and used. The type of the compound to be used is, for example, one embodiment of the present invention. Or in another embodiment of the present invention, there are two, three, four, five, six, seven, eight, nine, ten or more.

In the composition of the present invention, the content of the compound represented by the formula (IV) must be based on solubility at low temperature, transfer temperature, electrical reliability, birefringence, process compatibility, dropping marks, afterimage The performance required for dielectric guidance, etc., is appropriately adjusted.

The content of the compound represented by the formula (IV) is preferably from 1% by mass to 80% by mass, preferably from 1% by mass to 70% by mass, preferably from 1% by mass to 60% by mass, preferably from 10% by mass. ~50% by mass, preferably 10% by mass to 40% by mass, preferably 15% by mass to 40% by mass.

More specifically, the content of the compound represented by the formula (IV) is preferably 0.5% by mass or more (% by mass in the following composition) of the composition, and preferably contains the content of the compound. 1% or more, preferably 3% or more, preferably 5% or more, preferably 8% or more, preferably 10% or more, preferably 13% or more, preferably 15% The above content is preferably 18% or more, and preferably 20% or more. Further, the upper limit is preferably 80% or less, preferably 70% or less, more preferably 65% or less, more preferably 60% or less, still more preferably 55% or less, and more preferably 50% or less, preferably 45% or less, preferably 40% or less, preferably 38% or less, preferably 35% or less, preferably 33% or less, preferably 30%. % or less is preferably 28% or less, preferably 25% or less.

The compound represented by the formula (IV) preferably contains one or two or more compounds represented by the formula (IV-1).

(wherein R ⁴¹¹ and R ⁴¹² 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 2 to 8 carbon atoms; Alkenyloxy, A ⁴¹¹ represents 1,4-phenylene or trans-1,4-cyclohexylene, k represents 1 or 2, and in the case where k is 2, two A's may be the same or different)

The total content of the compound represented by the formula (IV-1) is preferably from 1% by mass to 80% by mass, preferably from 1% by mass to 70% by mass, preferably from 1% by mass to 60% by mass, preferably from 1% by mass to 60% by mass. 10% by mass to 50% by mass, preferably 10% by mass to 40% by mass, preferably 15% by mass to 40% by mass.

More specifically, the content of the compound represented by the formula (IV-1) is preferably 0.5% by mass or less (% by mass in the following composition) or more, preferably as a lower limit of the composition. It is contained in an amount of 1% or more, preferably 3% or more, preferably 5% or more, preferably 8% or more, preferably 10% or more, preferably 13% or more, preferably contains 15% or more, preferably 18% or more, preferably 20% or more. Further, the upper limit is preferably 80% or less, preferably 70% or less, more preferably 65% or less, more preferably 60% or less, still more preferably 55% or less, and more preferably 50% or less, preferably 45% or less, preferably 40% or less, preferably 38% or less, preferably 35% or less, preferably 33% or less, preferably 30%. % or less is preferably 28% or less, preferably 25% or less.

As the compound represented by the formula (IV-1), specifically, for example, it can be listed The compound represented by the group of compounds represented by the following formula (IV-1a) to formula (IV-1f) is given.

(wherein R ⁴¹¹ and R ⁴¹² each independently represent the same meaning as R ⁴¹¹ and R ⁴¹² in the formula (IV-1))

R ⁴¹¹ and R ⁴¹² are each independently, preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkoxy group having 2 to 8 carbon atoms, more preferably a carbon atom number. An alkyl group of 1 to 5, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 2 to 5 carbon atoms. Further, R ⁴¹¹ and R ⁴¹² may be the same or different, and preferably represent different substituents.

The compound selected from the group consisting of the compounds represented by the general formulae (IV-1a) to (IV-1f) preferably contains one to ten kinds, more preferably one to eight kinds, and particularly preferably one type to five. It is also preferred to contain two or more compounds. It is preferred to contain a compound represented by the formula (IV-1a). In the case of the compound represented by the formula (IV-1a), when R ⁴¹¹ represents an alkenyl group, it is preferably contained, for example, from the formula (IV-1a1).

(wherein R ⁴¹³ represents a hydrogen atom or a methyl group, and R ⁴¹⁴ 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) At least one compound of the group of compounds.

More specifically, the compound represented by the formula (IV-1a1) is preferably a compound described below.

When the compound represented by the formula (IV-1a1) is contained, the content of the compound represented by the formula (IV-1a1) in the liquid crystal composition is preferably 1% by mass, and is preferably 1% by mass. It is preferably 5% by mass, more preferably 15% by mass, still more preferably 20% by mass, particularly preferably 23% by mass, most preferably 25% by mass, and as the upper limit, preferably 70% by mass, more preferably It is 60% by mass, more preferably 55% by mass, particularly preferably 52% by mass, and most preferably 50% by mass. More specifically, when the response speed is emphasized, the lower limit value is preferably 20% by mass. It is more preferably 30% by mass, further preferably 35% by mass, particularly preferably 38% by mass, most preferably 35% by mass, and as an upper limit, preferably 70% by mass, more preferably 60% by mass, and further Preferably, it is 55 mass%, particularly preferably 52 mass%, and most preferably 50 mass%. When the driving voltage is more important, the lower limit value is preferably 5% by mass, more preferably 15% by mass, and further It is preferably 20% by mass, particularly preferably 23% by mass, most preferably 25% by mass, and as the upper limit, preferably 60% by mass, more preferably 50% by mass, still more preferably 45% by mass, particularly preferably 42% by mass, most preferably 40% by mass. The ratio of the compound represented by the formula (IV-1a1) to the total content of the compound represented by the formula (IV) in the liquid crystal composition, and the content of the compound represented by the formula (IV-1a1), The limit value is preferably 60% by mass, more preferably 70% by mass, still more preferably 75% by mass, still more preferably 78% by mass, most preferably 80% by mass, and as the upper limit, preferably 90% by mass. More preferably, it is 95% by mass, further preferably 97% by mass, particularly preferably 99% by mass, and most preferably 100% by mass.

Further, the compound represented by the formula (IV-1a) to the formula (IV-1e) other than the compound represented by the formula (IV-1a1) is more preferably a compound described below.

Among these, the formula (IV-1a1-2), the formula (IV-1a1-4), the formula (IV-1a1-6), the formula (IV-1a2) to the formula (IV-1a7), and the formula (IV) are preferred. IV-1b2), formula (IV-1b6), formula (IV-1d1), formula (IV-1d2), formula (IV-1d3), formula (IV-1e2), formula (IV-1e3) and formula (IV) -1e4) The compound represented.

Further, the compound represented by the formula (IV) is preferably a compound represented by the following formula (IV-2) to formula (IV-7).

(wherein R ⁴¹⁵ and R ⁴¹⁶ 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 2 to 8 carbon atoms; Alkenyloxy)

Further, as the compound represented by the formula (IV), it is preferred to contain one or two or more of the formula (IV-8), the formula (IV-9) or the formula (VI-10). Compound.

(wherein R ⁴¹⁵ and R ⁴¹⁶ 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 2 to 8 carbon atoms; The alkenyloxy group, X ⁴¹ and X ⁴² each independently represent a fluorine atom or a hydrogen atom, and any of X ⁴¹ and X ⁴² is a fluorine atom and the other is a hydrogen atom)

Further, the compound represented by the formula (IV) may contain one or two or more compounds represented by the formula (IV-11-1) to the formula (IV-11-3).

The additive (antioxidant, UV absorber, etc.) in the liquid crystal composition of the present invention is preferably from 100 ppm to 1% by mass.

The liquid crystal composition of the present invention can use a nematic phase-isotropic liquid phase transfer temperature (T _ni ) in a wide range, but the nematic phase-isotropic liquid phase transition temperature (T _ni ) is relatively Preferably, it is 60 to 120 ° C, more preferably 70 to 100 ° C, and particularly preferably 70 to 85 ° C.

The dielectric conductivity Δ ε of the liquid crystal composition of the present invention is preferably -2.0 to -6.0 at 25 ° C, more preferably -2.5 to -5.0, and particularly preferably -2.5 to -3.5.

The refractive index anisotropy Δn of the liquid crystal composition in the present invention is preferably from 0.08 to 0.13, more preferably from 0.09 to 0.12 at 25 °C. In more detail, the refractive index anisotropy of the liquid crystal composition of the present invention is preferably 0.10 to 0.12 at 25 ° C in the case of dealing with a thin cell gap, and in further detail, In the case of a thin cell gap (cell gap of 3.4 μm or less), it is preferably about 0.9 to about 0.12, and in the case of dealing with a thick cell gap (cell gap of 3.5 μm or more), it is preferably about 0.08 to about 0.1 or so.

The upper limit of the rotational viscosity (γ ₁ ) of the liquid crystal composition of the present invention is preferably 150 (mPa ‧ s) or less, more preferably 130 (mPa ‧ s) or less, and particularly preferably 120 (mPa ‧ s) or less. On the other hand, the lower limit of the rotational viscosity (γ ₁ ) is preferably 20 (mPa ‧ s) or more, more preferably 30 (mPa ‧ s) or more, still more preferably 40 (mPa ‧ s) or more, and more preferably Further, it is preferably 50 (mPa ‧ s) or more, more preferably 60 (mPa ‧ s) or more, and still more preferably 70 (mPa ‧ s) or more.

In the liquid crystal composition of the present invention, the function Z of the rotational viscosity and the refractive index anisotropy preferably represents a specific value.

(In the above formula, γ ₁ represents rotational viscosity, and Δn represents refractive index anisotropy)

Z is preferably 13,000 or less, more preferably 12,000 or less, and still more preferably 11,000 or less.

When the liquid crystal composition of the present invention is used for an active matrix display device, it is required to have a specific resistance of 10 ¹¹ (Ω‧ m) or more, preferably 10 ¹² (Ω·m), more preferably 10 ¹³ (Ω‧ m) above.

The liquid crystal composition of the present invention can use a nematic phase-isotropic liquid phase transition temperature (T _N1 ) in a wide range, but the phase transition temperature (T _N1 ) is preferably 60 to 120 ° C, more Good is 70~110°C, especially preferably 75~100°C.

[Method of Manufacturing Liquid Crystal Display Element]

Next, a method of manufacturing a liquid crystal display element of the present invention will be described with reference to Fig. 1 .

Applying an oriented film containing a polymerizable compound having a reactive group to a surface of the first substrate 11 on which the common electrode 14 is formed and a surface of the second substrate 12 on which the pixel electrode 15 is formed The material or the polymerizable liquid crystal compound is heated and heated, whereby the vertical alignment films 16, 17 are formed. Further, in the case where a polymerizable liquid crystal compound is used as the alignment film, a usual alignment film may be used as the substrate alignment film.

Here, first, a polymer compound containing a polymer compound precursor which is a first polymer compound and/or a compound represented by the above formula (V2) and a compound represented by the above formula (V), or a polymerizable compound or the like An alignment film material of a photopolymerizable or photocrosslinkable compound or an alignment film material composed of a polymerizable liquid crystal compound.

In the case where the first polymer compound is a polyimine, the polymer compound precursor may, for example, be a mixture of tetracarboxylic dianhydride and diisocyanate, or polylysine, or dissolve the polyimine. Or a polyimine solution or the like dispersed in a solvent. The content of the polyimine in the polyimine solution is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 5% by mass or less.

In the case where the first polymer compound is a polyoxymethane, examples of the polymer compound precursor include a fluorene compound having an alkoxy group, a hydrazine compound having a halogenated alkoxy group, an alcohol, and oxalic acid. A polyoxane solution obtained by mixing and heating at a specific blending ratio to obtain a polyoxyalkylene oxide and dissolving it in a solvent.

Further, a compound having photocrosslinkability, a photopolymerization initiator, a solvent, or the like may be added to the alignment film material as needed.

After the alignment film material is prepared, the alignment film material is applied or printed on the first substrate 11 and the second substrate 12 so as to cover the common electrode 14 and the pixel electrode 15 and the slit portion (not shown). Heat and other treatments. Thereby, the polymer compound precursor contained in the coated or printed alignment film material and/or the compound represented by the above formula (V2), or The polymerizable liquid crystal compound is polymerized and cured to form a polymer compound, and the vertical alignment films 16 and 17 in which the polymer compound and the polymerizable compound or the polymerizable liquid crystal compound are semi-cured are formed.

Here, in the case of performing heat treatment, the temperature thereof is preferably 80 ° C or higher, more preferably 150 to 200 ° C.

Further, at this stage, a vertical alignment function of orienting the liquid crystal molecules in the liquid crystal composition layer in the vertical direction with respect to the substrate surface is formed. Thereafter, treatment such as friction may be performed as needed.

Then, the first substrate 11 and the second substrate 12 are overlapped, and the liquid crystal composition layer 13 containing liquid crystal molecules is sealed between them.

Specifically, the surface of the first substrate 11 and the second substrate 12 on which the vertical alignment films 16 and 17 are formed is dispersed to ensure a gap between the cell gaps, for example, plastic beads, etc., and by, for example, In the screen printing method, a sealing portion such as an epoxy adhesive is used.

Thereafter, the first substrate 11 and the second substrate 12 are bonded to each other via the spacer protrusions and the sealing portion so that the vertical alignment films 16 and 17 face each other, and liquid crystal containing liquid crystal molecules and, if necessary, a polymerizable compound is injected. Composition.

Thereafter, the sealing portion is cured by heating or the like, whereby the liquid crystal composition is sealed between the first substrate 11 and the second substrate 12.

Then, a voltage is applied between the common electrode 14 and the pixel electrode 15 by using a voltage application means. The voltage is applied, for example, in a size of 5 to 30 (V). The above application also has a case where charges are applied substantially perpendicularly to the first substrate and the second substrate. Thereby, a surface adjacent to the liquid crystal composition layer 13 in the first substrate 11 (surface facing the liquid crystal composition layer 13) and a surface adjacent to the liquid crystal composition layer 13 of the second substrate 12 are generated ( Opposite to the liquid crystal composition layer 13 The electric field in the direction of the specific angle, the liquid crystal molecules 19 are oriented obliquely from the normal direction of the first substrate 11 and the second substrate 12 in a specific direction. At this time, the tilt angle of the liquid crystal molecules 19 is substantially equal to the pretilt angle θ imparted to the liquid crystal molecules 19 by the steps described below. Therefore, by appropriately adjusting the magnitude of the voltage, the magnitude of the pretilt angle θ of the liquid crystal molecules 19 can be controlled (refer to Fig. 3).

Further, in a state where a voltage is applied, for example, the liquid crystal composition layer 13 is irradiated with ultraviolet light UV from the outer side of the first substrate 11, whereby the polymerizable compound or the polymerizable liquid crystal compound and the liquid crystal in the vertical alignment films 16 and 17 are formed. The polymerizable compound in the composition is polymerized to form a polymer.

In this case, the intensity of the ultraviolet light UV to be irradiated may be fixed or unfixed, and the irradiation time at each intensity when the irradiation intensity is changed is also arbitrary, and in the case of using the irradiation step of two or more stages, it is preferable. The intensity of the irradiation intensity after the second stage is selected to be weaker than the intensity of the first stage, and it is preferable that the total irradiation time after the second stage is longer than the irradiation time of the first stage and the total irradiation energy is large. Further, in the case of discontinuously changing the irradiation intensity, it is preferable that the average irradiation light intensity in the first half of the entire irradiation step time is stronger than the average irradiation intensity in the second half portion, and more preferably the intensity after the first irradiation is the strongest, and thus As the irradiation time passes, the illumination intensity continues to decrease to a certain value. In this case, the ultraviolet light intensity is preferably 2 mW/cm ^-2 to 100 mW/cm ^-2 , more preferably the first stage in the case of multi-stage irradiation, or the entire irradiation step in the case of discontinuously changing the irradiation intensity. the maximum illumination intensity of ^{10mW / cm -2 ~ 100mW / cm} -2, the second stage of the case 2 and the multi-stage irradiation, or discontinuously changing the minimum intensity of the irradiation intensity of the irradiation case 2mW / cm ^{- 2} ~ 50mW / cm ^-2 . Further, the total irradiation energy is preferably 10 J to 300 J, more preferably 50 J to 250 J, and further preferably 100 J to 250 J.

In this case, the applied voltage may be alternating current or direct current.

As a result, the orientation control function (not shown) including the vertical alignment film material fixed to the orientation control portions of the vertical alignment films 16 and 17 is provided, and further, the polymer layers 20 and 21 are formed on the surface thereof as needed. The orientation control portion has a function of imparting a pretilt angle θ to the liquid crystal molecules 19 located in the vicinity of the interface with the polymer layers 20, 21 (vertical alignment films 16, 17) in the non-driving state. control function). In addition, ultraviolet light UV is irradiated from the outer side of the first substrate 11 , but ultraviolet light UV may be irradiated from the outer side of the second substrate 12 , or two substrates of the first substrate 11 and the second substrate 12 may be used. The outside is irradiated with UV light UV.

As described above, in the liquid crystal display device of the present invention, the liquid crystal molecules 19 in the liquid crystal composition layer 13 have a specific pretilt angle θ. As a result, the response speed to the driving voltage can be greatly improved as compared with the liquid crystal display device in which the pretilt treatment is not performed and the liquid crystal display device including the liquid crystal display device.

In the liquid crystal display device of the present invention, as the polymer compound precursor constituting the vertical alignment films 16, 17, a non-photosensitive polyimide precursor is preferable.

[Examples]

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

In the following examples and comparative examples, T _ni , Δn, Δε, η, and γ ₁ were defined as follows.

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

T _cn : solid phase-nematic phase transfer temperature (°C)

△n: refractive index anisotropy at 20 ° C

△ ε: dielectric conductivity of 20 ° C

γ ₁ : 20 ° C rotational viscosity (mPa ‧ s)

K ₃₃ : elastic constant (pN) of bending at 20 ° C

In the following examples and comparative examples, the afterimage, the dropping marks, and the pretilt angle of the liquid crystal display element were evaluated by the following methods.

(afterimage)

The afterimage evaluation of the liquid crystal display element was performed by displaying the specific fixed pattern in the display area for 1,000 hours, and then visually evaluating the level of the residual image of the fixed pattern when the entire screen was uniformly displayed based on the following four levels.

◎: no residual image

○: There is very little afterimage and it is a tolerable level

△: There is a residual image, which is an unacceptable level.

×: There is a residual image, very bad

(drops)

The evaluation of the dropping marks of the liquid crystal display device was carried out by visual observation, and the white marks which appeared in the case where the entire surface was displayed in black were evaluated according to the following four levels.

◎: no residual image

○: There is very little afterimage and it is a tolerable level

△: There is a residual image, which is an unacceptable level.

×: There is a residual image, very bad

(pretilt angle)

Five parts were randomly measured in the plane of the liquid crystal display element, and the average value was used as the pretilt angle. Further, in the case of evaluating the stability of the pretilt angle, the change in the pretilt angle before and after the stress is compared. The stress was applied by placing the liquid crystal display device in an oven maintained at 70 ° C and applying a rectangular wave of 1 kHz and 30 V for 168 hours.

Pretilt angle of change (°): pretilt angle after stress - pretilt angle before stress

Further, in the examples, the description of the compounds is as follows. Furthermore, n represents a natural number.

(side chain)

(link base)

-n- -C _n H _2n -

(ring structure)

(Example 1)

Making a first substrate (common electrode substrate) having a transparent portion made of a transparent common electrode And an electrode layer and a color filter layer; and a second substrate (pixel electrode substrate) including a pixel electrode layer having a transparent pixel electrode driven by the active device.

In the pixel electrode substrate, as the respective pixel electrodes, in order to divide the alignment of the liquid crystal molecules, the ITO is etched so that the pixel electrodes have slits having no electrodes.

The vertical alignment film material containing the polyimide precursor and the polymerizable compound having a polymerizable group is applied to the common electrode substrate and the pixel electrode substrate by a spin coating method, and the coating film is heated at 200 ° C. Thereby, the polyimide precursor in the vertical alignment film material is hardened, and a vertical alignment film of 100 nm ± 20 nm is formed on the surface of each substrate. At this stage, the polymerizable compound having a polymerizable group in the vertically oriented film is not hardened.

As a material for the vertical alignment film formation, a polyimine solution (trade name: JALS2131-R6, manufactured by JSR Corporation) containing 3% of a polyimide precursor is contained in a formula of 3% or less (Va-1- 1) A solution of a polymerizable compound having a reactive group.

The liquid crystal composition (LC-A) containing the compound represented by the chemical formula shown below is sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film is formed, and then the sealing material is cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.0 μm using a spacer having a thickness of 3.0 μm.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. Using the UIS-S2511RZ manufactured by Ushio Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, the liquid crystal display element was irradiated with ultraviolet rays for 600 seconds at 20 mW, and the liquid crystal display of Example 1 was obtained. element. By this step, a vertical alignment film of a polymer containing a polymerizable compound having a reactive group is formed, and a liquid crystal molecule in the liquid crystal composition layer is given a pretilt angle.

Here, the pretilt angle is defined in the manner as shown in FIG. In the case of performing a completely vertical orientation, the pretilt angle (θ) becomes 90°, and when the pretilt angle is given, the pretilt angle (θ) becomes less than 90°.

The liquid crystal display element of the first embodiment has a pretilt angle in different directions in the four blocks along the slit of the pixel electrode as shown in FIG. 2, and after the hardening of the polymerizable compound, even in the state of cutting off the alternating electric field The pretilt angle is also maintained. The pretilt angle maintained was 87.1°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 1 are shown in Table 2. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Example 1 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Comparative Example 1)

A liquid crystal display device of Comparative Example 1 was obtained under the same conditions as in Example 1 except that the liquid crystal composition (LC-B) containing the compound shown in the following Table was used.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the polymerizable compound having a reactive group in the alignment film is cured. The liquid crystal display element of Comparative Example 1 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Comparative Example 1 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 87.8°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Comparative Example 1 are shown in Table 4. As a result, the liquid crystal composition used in the liquid crystal display element of Comparative Example 1 produced a small amount of dropping marks and caused an afterimage. Further, the pretilt angle formed is not stable and is applied After the stress, the value before the stress is applied changes greatly in the negative direction. As a result, it is presumed that the liquid crystal composition used in the liquid crystal display device of Comparative Example 1 does not contain the compound represented by the general formula (i), and the interaction with the alignment film is small, so that the pretilt angle formed cannot be due to stress. Maintenance, the result is the cause of the afterimage.

(Example 2)

A liquid crystal composition (LC-A2) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. Further, as a material for vertically oriented film formation, a polyimine solution (trade name: JALS2131-R6, manufactured by JSR Corporation) containing 3% of a polyimide precursor is contained in a formula of 3% or less (Va- 1-3) A solution of a polymerizable compound having a reactive group. The other conditions were the same as in Example 1, and the liquid crystal display element of Example 2 was obtained.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 2 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Embodiment 2 is the same as Embodiment 1. The sample has a pretilt angle, and after the curing of the polymerizable compound, the pretilt angle is maintained even in the state where the alternating electric field is cut. The pretilt angle maintained was 86.5°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 2 are shown in Table 6. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Example 2 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Comparative Example 2)

A liquid crystal display device of Comparative Example 2 was obtained under the same conditions as in Example 2 except that the liquid crystal composition (LC-B2) containing the compound shown in the following Table was prepared and the liquid crystal composition was used.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the polymerizable compound having a reactive group in the alignment film is cured. The liquid crystal display element of Comparative Example 2 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Comparative Example 2 had a pretilt angle similarly to that of Example 1 and Example 2. After the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 86.9°.

The drip mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of the comparative example 2 are shown in Table 8. As a result, the liquid crystal composition used in the liquid crystal display element of Comparative Example 2 produced a small amount of dropping marks and caused an afterimage. Further, the pretilt angle formed is not stable and is applied After the stress, the value before the stress is applied changes greatly in the negative direction. As a result, it is presumed that the liquid crystal composition used in the liquid crystal display device of Comparative Example 2 does not contain the compound represented by the general formula (i), and the interaction with the alignment film is small, so that the pretilt angle formed cannot be due to stress. Maintenance, the result is the cause of the afterimage.

(Example 3)

A liquid crystal composition (LC-A3) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 1, and the liquid crystal display element of Example 3 was obtained.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 3 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 3 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 86.6°.

The evaluation of the drop mark, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 3 are shown in Table 10. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Example 3 did not cause dropping marks and did not cause an afterimage. And then form a suitable pretilt angle, even if The pretilt angle is also maintained after the stress is applied.

(Example 4)

A liquid crystal composition (LC-A4) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. Further, as a material for vertically oriented film formation, a polyimine solution (trade name: JALS2131-R6, manufactured by JSR Corporation) containing 3% of a polyimide precursor is contained in a formula of 3% or less (Va- 1-14) A solution of a polymerizable compound having a reactive group. The other conditions were the same as in Example 1, and the liquid crystal display element of Example 4 was obtained.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 4 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 4 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 87.5°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 4 are shown in Table 12. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Example 4 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Example 5)

A liquid crystal composition (LC-A5) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The conditions other than this were set to be the same as in Example 1, and the liquid of Example 5 was obtained. Crystal display element.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 5 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 5 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 87.0°.

Droplet evaluation, afterimage evaluation and pretilt of the liquid crystal display element of Example 5 The results of the angular evaluation are shown in Table 14. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Example 5 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Example 6)

A liquid crystal composition (LC-A6) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 1, and the liquid crystal display element of Example 6 was obtained.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 6 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 6 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 87.3°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 6 are shown in Table 16. As a result, it was found that the liquid crystal composition used in the liquid crystal display element of Example 6 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Example 7)

Manufacturing a first substrate (common electrode substrate) including a transparent electrode layer and a color filter layer formed of a transparent common electrode; and a second substrate (pixel electrode substrate) having a transparent pixel driven by an active device The pixel electrode layer of the electrode.

In the pixel electrode substrate, as the respective pixel electrodes, in order to divide the alignment of the liquid crystal molecules, the ITO is etched so that the pixel electrodes have slits having no electrodes.

The vertical alignment film material containing the polyimide precursor and the polymerizable compound having a reactive group is applied to the common electrode substrate and the pixel electrode substrate by a spin coating method, and the coating film is heated at 200 ° C. Thereby, the polyimide precursor in the vertical alignment film material is hardened, and a vertical alignment film of 100 nm is formed on the surface of each substrate. At this stage, the polymerizable compound having a reactive group in the vertically oriented film is not hardened.

As the material for the vertical alignment film formation, a polymerizable compound having a reactive group represented by a formula of 3% or less and a polymerizable group represented by a formula (Va-1-1) of 3% or less is used. N-methyl-2-pyrrolidone solution.

The liquid crystal composition (LC-A) containing the compound represented by the chemical formula shown below is sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film is formed, and then the sealing material is cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.0 μm using a spacer having a thickness of 3.0 μm.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 7 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. By this step, a vertical alignment film containing a polymer having a polyfluorene imine skeleton as a main chain and a polymerizable compound having a crosslinkable functional group as a side chain is formed, and liquid crystal molecules in the liquid crystal composition layer are given inclination.

The liquid crystal display element of the seventh embodiment has a pretilt angle in different directions in the four blocks along the slit of the pixel electrode as shown in FIG. 2, and after the hardening of the polymerizable compound, The pretilt angle is also maintained in a state where it is easy to cut off the alternating electric field. The pretilt angle maintained was 87.0°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 7 are shown in Table 18. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Example 7 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Comparative Example 3)

A liquid crystal display device of Comparative Example 3 was obtained under the same conditions as in Example 7 except that the liquid crystal composition (LC-B) containing the compound shown in the following Table was prepared and the liquid crystal composition was used.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Comparative Example 3 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. By this step, a vertical alignment film containing a polymer having a polyfluorene imine skeleton as a main chain and a polymerizable compound having a crosslinkable functional group as a side chain is formed, and liquid crystal molecules in the liquid crystal composition layer are given inclination.

The liquid crystal display element of Comparative Example 3 has a pretilt angle in different directions in four blocks along the slit of the pixel electrode as shown in FIG. 2, and after the hardening of the polymerizable compound, even in the state of cutting off the alternating electric field The pretilt angle is also maintained. The pretilt angle maintained was 88.0°.

The evaluation of the drop mark, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Comparative Example 3 are shown in Table 20. As a result, the liquid crystal composition used in the liquid crystal display element of Comparative Example 3 produced a small amount of dropping marks and caused an afterimage. Further, the formed pretilt angle is not stable, and after the stress is applied, the value before the stress is applied largely changes in the negative direction. As a result, it is presumed that the liquid crystal composition used in the liquid crystal display device of Comparative Example 3 does not contain the compound represented by the general formula (i), and the interaction with the alignment film is small, so that the pretilt angle formed cannot be due to stress. Maintenance, the result is the cause of the afterimage.

(Example 8)

A liquid crystal composition (LC-A3) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. Further, as the material for the vertical alignment film formation, a polymerizable group having a reactive group represented by a polyimine derivative represented by a formula of 3% or less and a formula (Va-1-3) of 3% or less is used. A solution of the compound in N-methyl-2-pyrrolidone. The other conditions were the same as in Example 7, and the liquid crystal display element of Example 8 was obtained.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 8 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 8 had a pretilt angle similarly to Example 7, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 86.7°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 8 are shown in Table 22. As a result, it was found that the liquid crystal composition used in the liquid crystal display element of Example 8 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Example 9)

A liquid crystal composition (LC-A6) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 7, and the liquid crystal display element of Example 9 was obtained.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 9 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 9 had a pretilt angle similarly to Example 7, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 86.9°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 9 are shown in Table 24. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Example 9 did not cause dropping marks and did not cause an afterimage. And then form a suitable pretilt angle, even if The pretilt angle is also maintained after the stress is applied.

(Embodiment 10)

Manufacturing a first substrate (common electrode substrate) including a transparent electrode layer and a color filter layer formed of a transparent common electrode; and a second substrate (pixel electrode substrate) having a transparent pixel driven by an active device The pixel electrode layer of the electrode.

A vertical alignment film material containing a polymerizable liquid crystal compound and a polymerization initiator was applied to the common electrode substrate and the pixel electrode substrate by a spin coating method to form a vertical alignment film precursor layer having a thickness of 200 nm. As the material for vertically oriented film formation, UCL-011-K1 (manufactured by DIC Corporation) was used.

Each substrate coated with the vertically oriented film forming material was heated by a thermostat at 70 ° C for 15 minutes, whereby the polymerizable liquid crystal compound in the applied vertical alignment film forming material was made into an isotropic liquid.

Thereafter, the temperature was lowered to room temperature at a rate of 10 ° C/min, and the orientation of the polymerizable liquid crystal compound was set to a vertical orientation.

A magnetic field inclined by 70° from the substrate surface is applied to each of the pixel electrode substrate and the common electrode substrate to impart a pretilt angle to the polymerizable liquid crystal compound. In this state, the ultraviolet ray is irradiated to cure the polymerizable liquid crystal compound to form a vertical alignment film.

The liquid crystal composition (LC-A) containing the compound represented by the chemical formula shown below is sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film is formed, and then the sealing material is cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.0 μm using a spacer having a thickness of 3.0 μm.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the polymerizable liquid crystal compound. The liquid crystal display element of Example 10 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. By this step, a polymer containing a polymerizable liquid crystal compound is formed The vertical alignment film imparts a pretilt angle to the liquid crystal molecules in the liquid crystal composition layer.

The liquid crystal display element of the embodiment 10 has a pretilt angle in different directions in the four blocks along the slit of the pixel electrode as shown in FIG. 2, and after the hardening of the polymerizable compound, even in the state of cutting off the alternating electric field The pretilt angle is also maintained. The pretilt angle maintained was 87.4°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 10 are shown in Table 26. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Example 10 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Comparative Example 4)

A liquid crystal display device of Comparative Example 4 was obtained under the same conditions as in Example 10 except that the liquid crystal composition (LC-B) of the compound shown in the following Table was prepared and the liquid crystal composition was used.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the polymerizable liquid crystal compound. The liquid crystal display element of Comparative Example 4 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. By this step, a vertical alignment film of a polymer containing a polymerizable liquid crystal compound is formed, and a liquid crystal molecule in the liquid crystal composition layer is given a pretilt angle.

The liquid crystal display element of Comparative Example 4 has a pretilt angle in different directions in four blocks along the slit of the pixel electrode as shown in FIG. 2, and after the hardening of the above polymerizable compound, even in the state of cutting off the alternating electric field The pretilt angle is also maintained. The pretilt angle maintained was 87.8°.

Droplet evaluation, afterimage evaluation, and pretilt of the liquid crystal display element of Comparative Example 4 The results of the angular evaluation are shown in Table 28. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Comparative Example 4 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Example 11)

A liquid crystal display device of Example 11 was obtained under the same conditions as those in Example 10 except that the liquid crystal composition (LC-A3) containing the compound shown in the following Table was prepared and the liquid crystal composition was used.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the polymerizable liquid crystal compound. The liquid crystal display element of Example 11 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 11 had a pretilt angle similarly to that of Example 10. After the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 87.0°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 11 are shown in Table 30. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Example 11 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Embodiment 12)

A liquid crystal display device of Example 12 was obtained under the same conditions as those in Example 10 except that the liquid crystal composition (LC-A6) containing the compound shown in the following Table was prepared and the liquid crystal composition was used.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the polymerizable liquid crystal compound. The liquid crystal display element of Example 12 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 12 had a pretilt angle similarly to that of Example 10. After the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 87.6°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 12 are shown in Table 32. As a result, it was found that the liquid crystal composition used in the liquid crystal display element of Example 12 did not cause dropping marks and did not cause an afterimage. Forming a suitable pretilt angle, even The pretilt angle is also maintained after the stress is applied.

(Example 13)

A liquid crystal composition (LC-A7) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 2, and the liquid crystal display element of Example 13 was obtained.

Photographing the obtained liquid crystal display element in a state where a rectangular alternating electric field is applied Ultraviolet rays are emitted to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 13 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 13 had a pretilt angle similarly to Example 2, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 87.5°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 13 are shown in Table 34. As a result, it was found that the liquid crystal composition used in the liquid crystal display device of Example 13 did not cause dropping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

(Example 14)

A liquid crystal composition (LC-A8) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 2, and the liquid crystal display element of Example 14 was obtained.

The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 14 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 14 had a pretilt angle similarly to Example 2, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut. The pretilt angle maintained was 87.0°.

The drop mark evaluation, the afterimage evaluation, and the pretilt angle evaluation result of the liquid crystal display element of Example 13 are shown in Table 36. As a result, it is understood that the liquid crystal display element of Example 13 is used. The liquid crystal composition did not cause dripping marks and did not cause an afterimage. Further, a suitable pretilt angle is formed, which is maintained even after stress is applied.

10‧‧‧Liquid display components

11‧‧‧First substrate

12‧‧‧second substrate

13‧‧‧Liquid composition layer

14‧‧‧Common electrode

15‧‧‧pixel electrode

16‧‧‧Vertical alignment film

17‧‧‧Vertical alignment film

18‧‧‧Color filters

19‧‧‧ liquid crystal molecules

20‧‧‧ polymer layer

21‧‧‧ polymer layer

Claims (12)

A liquid crystal display device comprising: a group substrate having a first substrate and a second substrate; and a liquid crystal composition layer sandwiched between the substrates; and at least one of the first substrate and the second substrate has an electrode And an alignment film having at least one of the first substrate and the second substrate, wherein the alignment film contains liquid crystal molecules in the liquid crystal composition layer by polymerizing a polymerizable group of a compound having a polymerizable group The polymer in the orientation direction, the liquid crystal composition constituting the liquid crystal composition layer contains one or both selected from the group consisting of compounds represented by the following general formula (i), general formula (ii), and general formula (iii) a compound selected from the group consisting of one or more selected from the group consisting of compounds represented by the formula (IV), (wherein R ⁱ¹ , R ⁱ² , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱⁱ¹ and R ⁱⁱⁱ² each independently represent an alkyl group having 1 to 10 carbon atoms, and one of the alkyl groups or two or more adjacent ^thereto - CH ₂ - may be independently substituted with -CH=CH-, -C≡C-, ^-O- , ^-CO- , -COO- or -OCO-, A ⁱ¹ , A ⁱ² , A ⁱⁱ¹ , A ⁱⁱ² , A ⁱⁱⁱ¹ and A ⁱⁱⁱ² each independently represent a group selected from (a) 1,4-cyclohexylene (one of -CH ₂ - present in the group or two or more -CH ₂ - which may not be adjacent to - may be substituted - O-), (b) 1,4-phenylene (one present in the group -CH= or two or more non-contiguous -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 a group of 2,3,4-tetrahydronaphthalene-2,6-diyl-CH= or two or more non-contiguous -CH= can be substituted with -N=) The above group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, respectively, Z ⁱ¹ , Z ⁱ² , Z ⁱⁱ¹ , Z ⁱⁱ² , Z ⁱⁱⁱ¹ and Z ⁱⁱⁱ² , respectively, independently Represents a single bond, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -, at least one Z ⁱ¹ represents -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -, Z ⁱⁱⁱ³ represents -CH ₂ - or an oxygen atom, X ⁱⁱ¹ represents a hydrogen atom or a fluorine atom, and m ⁱ¹ , m ⁱ² , m ⁱⁱ¹ , m ⁱⁱ² , m ⁱⁱⁱ¹ and m ⁱⁱⁱ² each independently represent an integer of 0 to 3, and m ⁱ¹ + m ⁱ² is 0, 1, 2 or 3, m ⁱⁱ¹ + m ⁱⁱ² and m ⁱⁱⁱ¹ + m ⁱⁱⁱ² are 1, 2 or 3 respectively, and when there are a plurality of A ⁱ¹ ~ A ⁱⁱⁱ² , Z ⁱ¹ ~ Z ⁱⁱⁱ² , the same may be the same, Can be different); (wherein R ⁴⁴ and R ⁴⁵ each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more of the groups -CH ₂ - 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 - or -OCF ₂ -, one or more hydrogen atoms in the group may Each of them is independently substituted with a fluorine atom or a chlorine atom, and A ⁴¹ to A ⁴³ are each independently selected from (a) 1,4-cyclohexylene (one present in the group -CH ₂ - or not adjacent) More than one -CH ₂ - may be substituted with -O-), (b) 1,4-phenylene (one present in the group -CH= or two or more adjacent to -CH= may be Substituted as -N=), and (c) naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl ( One of the naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl-CH= or two or more non-contiguous-CH= can be substituted -N=) a group in the group, the above-mentioned group (a), group (b) and group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, respectively, and Z ⁴¹ and Z ⁴² are independently Represents a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OC H ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-, m ⁴¹ represents an integer of 0 to 2, and in the case where a plurality of A ⁴¹ and Z ⁴¹ are present, the same may be used. different). A liquid crystal display element according to claim 1, which has a plurality of pixels having two or more regions having different pretilt angles. The liquid crystal display device of claim 1 or 2, wherein the first substrate has a common electrode and the second substrate has a pixel electrode. The liquid crystal display device of claim 3, wherein the alignment film is provided between the common electrode and the pixel electrode, and the alignment film applies an electric charge substantially perpendicularly to the first substrate and the second substrate to control the liquid crystal. The liquid crystal molecules in the composition layer. The liquid crystal display element according to any one of claims 1 to 4, wherein The film contains a polymer which controls the orientation direction of the liquid crystal molecules in the liquid crystal composition layer, or is formed of a cured product of a polymerizable liquid crystal compound. A liquid crystal display element according to claim 5, which comprises a polymer having a compound having a reactive group or a polymerizable compound having a polyfluorene imine skeleton as a main chain and having a crosslinkable functional group as a side chain. The polymer serves as a polymer for controlling the orientation direction of the liquid crystal molecules in the liquid crystal composition layer. The liquid crystal display element according to any one of the first to sixth aspects of the invention, further comprising a polymer of one or two or more polymerizable compounds which control the orientation of the liquid crystal molecules and stabilize the surface of the alignment film. A method for manufacturing a liquid crystal display device, wherein the first substrate having the electrode and the above is formed by forming at least one of the first substrate and the second substrate by applying an alignment material and heating to form an alignment film material The liquid crystal composition is sandwiched between the second substrate, and the active energy ray is irradiated to the electrode while applying a voltage, thereby polymerizing the polymerizable group of the polymerizable group contained in the alignment film material to control the above. An alignment film of an alignment direction of liquid crystal molecules in a liquid crystal composition layer, wherein the liquid crystal composition contains one selected from the group consisting of compounds represented by the following general formula (i), general formula (ii), and general formula (iii); Or two or more compounds, and one or more compounds selected from the group consisting of compounds represented by the formula (IV), (wherein R ⁱ¹ , R ⁱ² , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱⁱ¹ and R ⁱⁱⁱ² each independently represent an alkyl group having 1 to 10 carbon atoms, and one of the alkyl groups or two or more adjacent ^thereto - CH ₂ - may be independently substituted with -CH=CH-, -C≡C-, ^-O- , ^-CO- , -COO- or -OCO-, A ⁱ¹ , A ⁱ² , A ⁱⁱ¹ , A ⁱⁱ² , A ⁱⁱⁱ¹ and A ⁱⁱⁱ² each independently represent a group selected from (a) 1,4-cyclohexylene (one of -CH ₂ - present in the group or two or more -CH ₂ - which may not be adjacent to - may be substituted - O-), (b) 1,4-phenylene (one present in the group -CH= or two or more non-contiguous -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 a group of 2,3,4-tetrahydronaphthalene-2,6-diyl-CH= or two or more non-contiguous -CH= can be substituted with -N=) The above group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, respectively, Z ⁱ¹ , Z ⁱ² , Z ⁱⁱ¹ , Z ⁱⁱ² , Z ⁱⁱⁱ¹ and Z ⁱⁱⁱ² , respectively, independently Represents a single bond, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -, at least one Z ⁱ¹ represents -OCH ₂ -, -CH ₂ O-, -OCF ₂ -, -CF ₂ O-, -CH ₂ CH ₂ - or -CF ₂ CF ₂ -, Z ⁱⁱⁱ³ represents -CH ₂ - or an oxygen atom, X ⁱⁱ¹ represents a hydrogen atom or a fluorine atom, and m ⁱ¹ , m ⁱ² , m ⁱⁱ¹ , m ⁱⁱ² , m ⁱⁱⁱ¹ and m ⁱⁱⁱ² each independently represent an integer of 0 to 3, and m ⁱ¹ + m ⁱ² is 0, 1, 2 or 3, m ⁱⁱ¹ + m ⁱⁱ² and m ⁱⁱⁱ¹ + m ⁱⁱⁱ² are 1, 2 or 3 respectively, and when there are a plurality of A ⁱ¹ ~ A ⁱⁱⁱ² , Z ⁱ¹ ~ Z ⁱⁱⁱ² , the same may be the same, Can be different); (wherein R ⁴⁴ and R ⁴⁵ each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more of the groups -CH ₂ - 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- or -OCF ₂ -, one or more hydrogen atoms in the group may Each of them is independently substituted with a fluorine atom or a chlorine atom, and A ⁴¹ to A ⁴³ are each independently selected from (a) 1,4-cyclohexylene (one present in the group -CH ₂ - or not adjacent) More than one -CH ₂ - may be substituted with -O-), (b) 1,4-phenylene (one present in the group -CH= or two or more adjacent to -CH= may be Substituted as -N=), and (c) naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl ( One of the naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl-CH= or two or more non-contiguous-CH= can be substituted -N=) a group in the group, the above-mentioned group (a), group (b) and group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, respectively, and Z ⁴¹ and Z ⁴² are independently Represents a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-, m ⁴¹ represents an integer of 0 to 2, and in the case where a plurality of A ⁴¹ and Z ⁴¹ are present, the same may be the same or different ). The method for producing a liquid crystal display device according to claim 8, wherein the alignment film material contains a polymer which controls an orientation direction of liquid crystal molecules in the liquid crystal composition layer, or is formed of a cured product of a polymerizable liquid crystal compound. The method for producing a liquid crystal display element according to claim 9, wherein the liquid crystal display element contains a polymer having a compound having a reactive group or a polyetherimine skeleton as a main chain and has a crosslinkable functional group. A polymer which is a side chain polymerizable compound is used as a polymer which controls the orientation direction of the liquid crystal molecules in the liquid crystal composition layer. The method for producing a liquid crystal display device according to the ninth or tenth aspect, wherein the liquid crystal display device further has one or two or more polymerizable compounds which control the orientation of the liquid crystal molecules and stabilize the surface of the alignment film. The polymer. The method for producing a liquid crystal display device according to any one of claims 9 to 11, wherein the active energy ray is ultraviolet ray, the intensity is 2 mW/cm ^-2 to 100 mW/cm ^-2 , and the total irradiation energy is 10 J~300 J.