WO2016093142A1

WO2016093142A1 - Liquid crystal display element and method of manufacturing the same

Info

Publication number: WO2016093142A1
Application number: PCT/JP2015/083979
Authority: WO
Inventors: 平田　真一; 長島　豊; 小川　真治; 芳典岩下
Original assignee: Dic株式会社
Priority date: 2014-12-12
Filing date: 2015-12-03
Publication date: 2016-06-16
Also published as: TW201632608A; KR20170094331A; JP6011904B1; CN107209421A; CN107209421B; KR102450332B1; JPWO2016093142A1

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 (γ₁), 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 manufacturing method thereof

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

Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type (vertical alignment; VA) using TFT (thin film transistor), and IPS. (In-plane switching) type. The liquid crystal composition used in these liquid crystal display elements is stable against external factors such as moisture, air, heat, and light, and exhibits a liquid crystal phase in the widest possible temperature range centering on room temperature. It is required to be viscous and have a low driving voltage. Furthermore, the liquid crystal composition is composed of several to several tens of kinds of compounds in order to optimize dielectric anisotropy (Δε), refractive index anisotropy (Δn), etc. for each liquid crystal display element. It is composed of

In the VA type display, a liquid crystal composition having a negative Δε is used, which is widely used for liquid crystal TVs and 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 large, the viscosity (η) is small, and a high nematic phase-isotropic liquid phase transition temperature (T _ni ) is required. Further, from the setting of Δn × d, which is the product of Δn and the cell gap (d), it is necessary to adjust Δn of the liquid crystal composition to an appropriate range according to the cell gap. In addition, when applying a liquid crystal display element to a television or the like, since high-speed response is important, a liquid crystal composition having a low rotational viscosity (γ ₁ ) is required.

On the other hand, in order to improve the viewing angle characteristics of a VA display, an MVA (multi-domain vertical alignment) type that divides the alignment direction of liquid crystal molecules in a pixel into a plurality of parts by providing a protrusion structure on the substrate. Liquid crystal display elements have been widely used. Although the MVA type liquid crystal display element is excellent in view angle characteristics, the response speed of liquid crystal molecules is different between the vicinity of the protrusion structure on the substrate and the part away from the protrusion structure, and the liquid crystal having a slow response speed away from the protrusion structure. There is a problem that the response speed as a whole is insufficient due to the influence of molecules, and there is a problem of a decrease in transmittance due to the protruding structure. In order to solve this problem, PSA is a method for providing a uniform pretilt angle in a divided pixel without providing a non-transparent protrusion structure in a cell, unlike a normal MVA liquid crystal display element. Liquid crystal display elements (including polymer sustained alignment: polymer sustaining alignment and PS liquid crystal display elements (polymer stabilized)) have been developed. A PSA liquid crystal display element is obtained by adding a small amount of a reactive monomer to a liquid crystal composition, introducing the liquid crystal composition into a liquid crystal cell, and then irradiating active energy rays while applying a voltage between the electrodes. It is produced by polymerizing the reactive monomer. Therefore, an appropriate pretilt angle can be given in the divided pixels, and as a result, high contrast can be achieved by improving the transmittance and high speed response by giving a uniform pretilt angle (see, for example, Patent Document 1). However, in a PSA liquid crystal display element, it is necessary to add a reactive monomer to the liquid crystal composition, and in an active matrix liquid crystal display element that requires a high voltage holding ratio, there are many problems and display defects such as burn-in are caused. There were also problems that occurred.

As a method of improving the drawbacks of PSA liquid crystal display elements and providing a uniform pretilt angle to liquid crystal molecules without introducing foreign substances other than the liquid crystal material into the liquid crystal composition, a reactive monomer is mixed into the alignment film material. Then, after introducing the liquid crystal composition into the liquid crystal cell, a method of polymerizing the reactive monomer in the alignment film by applying active energy rays while applying a voltage between the electrodes has been developed (for example, Patent Document 2, 3 and 4).

On the other hand, with the increase in the screen size of the liquid crystal display element, the manufacturing method of the liquid crystal display element has also undergone great changes. That is, in the conventional vacuum injection method, when a large panel is manufactured, the manufacturing process takes a lot of time. Therefore, in the manufacture of a large panel, a manufacturing method using an ODF (one-drop-fill) method is mainly used. (For example, see Patent Document 5). Since this method can shorten the injection time compared with the vacuum injection method, it has become the mainstream method for manufacturing liquid crystal display elements. However, a phenomenon in which a drop mark in which a liquid crystal composition is dropped remains in the liquid crystal display element in a dropped shape after the liquid crystal display element is produced has become a new problem. In addition, a dripping mark is defined as a phenomenon in which a mark in which a liquid crystal composition is dripped appears white when displaying black. In particular, in the method in which a reactive monomer is added to the alignment film material described above to give a pretilt angle to the liquid crystal molecules, the reactive monomer that is a foreign substance is present in the alignment film when the liquid crystal composition is dropped onto the substrate. Therefore, the problem of dripping marks is likely to occur. In general, the occurrence of dripping marks is often caused by the selection of a liquid crystal material, and the cause is not clear.

As a method for suppressing the drop mark, the polymerizable compound mixed in the liquid crystal composition is polymerized to form a polymer layer in the liquid crystal composition layer, thereby suppressing the drop mark generated in relation to the alignment control film. Is disclosed (see, for example, Patent Document 6). However, this method alone has a problem of display burn-in caused by the reactive monomer added to the liquid crystal composition, as in the PSA method and the like, and the effect on the suppression of dripping marks is insufficient. There has been a demand for the development of a liquid crystal display element that does not easily cause image sticking or dripping marks while maintaining basic characteristics as a display element. Furthermore, since the liquid crystal display element is exposed to UV light at the time of manufacture and use, it is important that the UV irradiation does not cause deterioration or the like even if it does not deteriorate.

Therefore, in Japanese Patent No. 05299595 (Patent Document 12) and the like, a reactive monomer is contained in the vertical alignment film, and after introducing the liquid crystal composition into the liquid crystal cell, the voltage is applied between the electrodes, The liquid crystal display element which combined the specific liquid crystal composition in the system which superposes | polymerizes the reactive monomer in alignment film by irradiation of an energy ray was proposed. With this liquid crystal display element, various characteristics as a liquid crystal display element such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity (γ ₁ ) and the image sticking characteristic of the liquid crystal display element are not deteriorated. It has become possible to provide a liquid crystal display element in which dripping marks do not easily occur and a method for manufacturing the same. However, with the increasing demand for liquid crystal display elements, further improvements in various characteristics as liquid crystal display elements, particularly development of liquid crystal compositions and liquid crystal display elements with higher reliability have been demanded.

JP 2002-357830 A JP 2010-107536 A US Patent Application Publication No. 2011/261295 JP 2011-227284 A JP-A-6-235925 JP 2006-58755 A JP 2011-95696 A Japanese Patent Application Laid-Open No. 2011-95697 JP 2009-139455 A JP 2010-32860 A JP 2010-107537 A Japanese Patent No. 05299595

The present invention has been made in view of the above circumstances, and has various characteristics as a liquid crystal display device such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity (γ ₁ ), and image sticking of the liquid crystal display device. It is an object of the present invention to provide a liquid crystal display element that does not easily cause dripping marks during manufacturing, does not deteriorate characteristics, has high characteristics as a liquid crystal display element, and has high reliability, and a method for manufacturing the same.

As a result of studying various liquid crystal compositions in order to solve the above problems, the present inventors have found that the above problems can be solved by including a specific polymerizable compound, and have completed the present invention. .

That is, the present invention includes a pair of substrates 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. Liquid crystal molecules in the liquid crystal composition layer having an electrode on at least one and polymerizing a polymerizable group of a compound having a polymerizable group on at least one of the first substrate and the second substrate A liquid crystal composition comprising an alignment film containing a polymer that controls the alignment direction of the liquid crystal composition layer is composed of the following general formula (N-1), general formula (N-2), and general formula (N-3)

(Wherein, R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or non-adjacent 2 in the alkyl group _Two or more —CH ₂ — may be each independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31, and A ^N32 are each independently (a) a 1,4-cyclohexylene group (one —CH ₂ — or adjacent to each other in this group). And two or more —CH ₂ — may be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or not adjacent 2 More than one -CH = may be replaced by -N =.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—. , —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—,
^XN21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents —CH ₂ — or an oxygen atom,
n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31, and n ^N32 each independently represent an integer of 0 to 3, but n ^N11 + n ^N12 , n ^N21 + n ^N22, and n ^N31 + n ^N32 are each independently When there are a plurality of A ^N11 to A ^N32 and Z ^N11 to Z ^N32 , they may be the same or different. ) Containing one or more compounds selected from the group of compounds represented by
The compound having a polymerizable group is represented by the general formula (I)

(Wherein X ¹⁰ and X ¹¹ each independently represent a hydrogen atom or a methyl group, and Sp ³ and Sp ⁴ each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —X— (CH ₂ ) _t — (wherein _t represents an integer of 2 to 7, X represents —O—, —OCOO—, —OCO—, or —COO—, and X represents a bond to the phenanthrene ring. It is a liquid crystal display device containing one or more compounds represented by.

In addition, after forming an alignment film material by applying an alignment material to at least one of the first substrate and the second substrate and heating, the first substrate and the second substrate having electrodes on at least one of them By sandwiching the liquid crystal composition between the substrates and irradiating the electrode with active energy rays in a state where a voltage is applied, the polymerizable group of the compound having a polymerizable group contained in the alignment film material is polymerized. The liquid crystal composition layer has an alignment film for controlling the alignment direction of liquid crystal molecules, and the liquid crystal composition has the following general formula (N-1), general formula (N-2), and general formula (N- 3)

(Wherein X ¹⁰ and X ¹¹ each independently represent a hydrogen atom or a methyl group, and Sp ³ and Sp ⁴ each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —X— (CH ₂ ) _t — (wherein _t represents an integer of 2 to 7, X represents —O—, —OCOO—, —OCO—, or —COO—, and X represents a bond to the phenanthrene ring. This is a method for producing a liquid crystal display device containing one or more compounds represented by the formula (1).

According to the present invention, the high-speed response as a liquid crystal display element is excellent, the occurrence of image sticking is small, the occurrence of dripping marks during the production thereof is small, the various characteristics as a liquid crystal display element are excellent, and the reliability is high. It can be effectively used as a display element for liquid crystal TVs, monitors and the like.

Further, according to the present invention, it is possible to manufacture an efficient liquid crystal display element in which dripping marks are hardly generated.

It is a schematic perspective view which shows one Embodiment of the liquid crystal display element of this invention. It is a schematic plan view which shows an example of the slit electrode (comb-shaped electrode) used for the liquid crystal display element of this invention. It is a figure which shows the definition of the pretilt angle in the liquid crystal display element of this invention.

Embodiments of the liquid crystal display element and the manufacturing method thereof according to the present invention will be described.

Note that this embodiment is specifically described in order to better understand the gist of the invention, and does not limit the present invention unless otherwise specified.
[Liquid crystal display element]
The liquid crystal display element of the present invention is a liquid crystal display element having a liquid crystal composition layer sandwiched between a pair of substrates, and a voltage is applied to the liquid crystal composition layer to displace the liquid crystal molecules in the liquid crystal composition layer. This is based on the principle of acting as an optical switch by transferring, and a well-known and conventional technique can be used in this respect.

In a normal vertical alignment liquid crystal display element in which two substrates have electrodes for causing Fredericks transition of liquid crystal molecules, a method of applying a charge vertically between the two substrates is generally employed. In this case, one electrode is a common electrode and the other electrode is a pixel electrode. The most typical embodiment of this scheme is shown below.

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

The liquid crystal display element 10 of this embodiment includes a first substrate 11, a second substrate 12, a liquid crystal composition layer 13 sandwiched between the first substrate 11 and the second substrate 12, and a first The common electrode 14 provided on the surface of the substrate 11 facing the liquid crystal composition layer 13, the pixel electrode 15 provided on the surface of the second substrate 12 facing the liquid crystal composition layer 13, and the common electrode 14, a vertical alignment film 16 provided on the surface facing the liquid crystal composition layer 13, a vertical alignment film 17 provided on the surface of the pixel electrode 15 facing the liquid crystal composition layer 13, and as necessary. A polymer layer 20 formed on the vertical alignment film 16, a polymer layer 21 formed on the vertical alignment film 17, and a color filter 18 provided between the first substrate 11 and the common electrode 14. It is roughly composed.

As the first substrate 11 and the second substrate 12, a glass substrate or a plastic substrate is used.

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

The common electrode 14 is usually made of a transparent material such as indium-added tin oxide (ITO).

The pixel electrode 15 is usually made of a transparent material such as indium-added 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 element typified by a TFT switching element, and the TFT switching element has a gate line as an address signal line and a source line as a data line in a matrix. Here, the configuration of the TFT switching element is not shown.

In order to improve viewing angle characteristics, when pixel division is performed to divide the direction in which the liquid crystal molecules in the pixel fall into several regions, slits having striped or V-shaped patterns (electrode formation) are formed in each pixel. A pixel electrode having a portion that is not provided) may be provided.

FIG. 2 is a schematic plan view showing a typical form of a slit electrode (comb electrode) when the inside of a pixel is divided into four regions. The slit electrode has comb-like slits in four directions from the center of the pixel, so that the liquid crystal molecules in each pixel that are substantially perpendicularly aligned with respect to the substrate when no voltage is applied are applied with voltage application. The liquid crystal molecules are directed in four different directions, approaching horizontal alignment. As a result, the orientation direction of the liquid crystal in the pixel can be divided into a plurality of parts, so that the viewing angle characteristic is extremely wide.

As a method for dividing the pixel, in addition to a method of providing a slit in the pixel electrode, a method of providing a structure such as a linear protrusion in the pixel, a method of providing an electrode other than the pixel electrode and the common electrode, and the like are used. . Although the alignment direction of the liquid crystal molecules can be divided by these methods, a configuration using a slit electrode is preferable from the viewpoint of transmittance and ease of production. Since the pixel electrode provided with the slit does not have a driving force for the liquid crystal molecules when no voltage is applied, the pretilt angle cannot be given to the liquid crystal molecules. However, when the alignment film material used in the present invention is used in combination, a pretilt angle can be given, and a wide viewing angle by pixel division can be achieved by combining with a slit electrode obtained by pixel division.

In the present invention, having a pretilt angle means that the liquid crystal molecules are perpendicular to the substrate surface (the surface adjacent to the liquid crystal composition layer 13 in the first substrate 11 and the second substrate 12) in the state where no voltage is applied. The director is slightly different.
(Alignment 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 aligned substantially perpendicular to the substrate surface when no voltage is applied. In order to align liquid crystal molecules vertically, a (vertical) alignment film is generally used.

In the present invention, an alignment film containing a polymer that controls the alignment 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 alignment film containing a polymer obtained by polymerizing a polymerizable group of a compound having a polymerizable group is used, and the polymer has an ability to control the alignment direction of liquid crystal molecules in the composition.

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

When using polyimide as the alignment film material for forming the vertical alignment film, it is preferable to use a mixture of tetracarboxylic dianhydride and diisocyanate, polyamic acid, or a polyimide solution in which polyimide is dissolved or dispersed in a solvent. The polyimide content in the polyimide 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, and still more preferably 10% by mass or less.

In addition, when a polysiloxane material is used as an alignment film material for forming a vertical alignment film, it is manufactured by mixing and heating a silicon compound having an alkoxy group, an alcohol derivative, and an oxalic acid derivative at a predetermined blending ratio. A polysiloxane solution in which the prepared polysiloxane is dissolved can be used.

In the liquid crystal display element of the present invention, the

vertical alignment films

16 and 17 formed of polyimide or the like include a polymer formed by polymerization of a polymerizable compound having a polymerizable group. This polymerizable compound imparts a function of fixing the pretilt angle of the liquid crystal molecules. That is, it is possible to tilt the director of the liquid crystal molecules in the pixel in different directions when a voltage is applied, using a slit electrode or the like. However, even in the configuration using the slit electrode, when no voltage is applied, the liquid crystal molecules are aligned almost perpendicularly to the substrate surface and no pretilt angle is generated, but a voltage is applied between the electrodes to slightly displace the liquid crystal molecules. In the tilted state, ultraviolet rays or the like are irradiated to polymerize the reactive monomer in the liquid crystal composition, thereby giving an appropriate pretilt angle.

Further, if necessary, the polymer layers 20 and 21 can be polymerized by sandwiching a polymerizable compound contained in a liquid crystal composition between substrates and then curing the polymerizable compound while applying a voltage. The compound can be formed as a polymer on the surfaces of the

vertical alignment films

16 and 17 while phase-separating.

The polymer contained in the

vertical alignment films

16 and 17 and the polymer layers 20 and 21 formed on the surfaces of the

vertical alignment films

16 and 17 that are formed as necessary provide the alignment of liquid crystal molecules. High, less occurrence of image sticking, and less generation of dripping marks during the production.

In the present invention, the term “substantially vertical” means a state in which the directors of vertically aligned liquid crystal molecules are slightly tilted from the vertical direction to give a pretilt angle. When the pretilt angle is 90 ° for complete vertical alignment and 0 ° for homogeneous alignment (aligned horizontally on the substrate surface), substantially vertical is preferably 89.5 to 85 °. More preferably, it is 5 to 87 °.

The

vertical alignment films

16 and 17 containing a polymer of a polymerizable compound having a polymerizable group are formed by the effect of the polymerizable compound mixed in the vertical alignment film material. Therefore, it is presumed that the vertical alignment film and the polymerizable compound are intertwined in a complicated manner to form a kind of polymer alloy, but the exact structure cannot be shown.

In addition, the polymer layers 20 and 21 that are formed as necessary are formed on the

vertical alignment films

16 and 17 while phase-separating from the liquid crystal composition when the polymerizable compound contained in the liquid crystal composition is polymerized. Although it is formed on the surface, whether it is formed uniformly on the entire surface of the vertical alignment film or nonuniform sea-island structure is considered to differ depending on the manufacturing conditions, and the exact structure is shown I can't. FIG. 1 shows the case where it is formed uniformly.

The alignment film used in the present invention needs to have a vertical alignment ability for aligning liquid crystal molecules in the liquid crystal composition layer in a direction perpendicular to the substrate surface and an alignment control ability for controlling the alignment direction of the liquid crystal molecules. . As a method for obtaining an alignment film having two functions of the vertical alignment ability and the alignment control ability, a method of blending a polymerizable compound having a polymerizable group in a commonly used alignment film material, and a side chain as an alignment film material There are a method using a polymer of a polymerizable compound having a crosslinkable functional group in a portion and a method using a cured product of a polymerizable liquid crystal compound. Hereinafter, each method will be described.
(Method of blending a polymerizable compound having a polymerizable group in the alignment film material)
Examples of the method of blending the polymerizable compound having a polymerizable group in the alignment film material include a method of blending the polymerizable compound having a polymerizable group into the aforementioned alignment film material.

The polymerizable compound having a polymerizable group contained in the alignment film material may or may not contain a mesogenic moiety, but the compound having a polymerizable group is represented by the general formula (I)

(Wherein X ¹⁰ and X ¹¹ each independently represent a hydrogen atom or a methyl group, and Sp ³ and Sp ⁴ each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —X— (CH ₂ ) _t — (wherein _t represents an integer of 2 to 7, X represents —O—, —OCOO—, —OCO—, or —COO—, and X represents a bond to the phenanthrene ring. It is important that the phenanthrene ring in the formula contains one or two or more compounds represented by any hydrogen atom may be substituted by a fluorine atom. Since the compound represented by the general formula (I) has a high reaction rate, the polymer formed in the alignment film reduces the amount of energy, that is, the irradiation amount of ultraviolet rays or the like, by containing the compound. It becomes possible.

In the general formula (I), X ¹⁰ and X ¹¹ each independently represent a hydrogen atom or a methyl group. However, when importance is attached to the reaction rate, a hydrogen atom is preferable, and importance is placed on reducing the amount of residual reaction. In this case, a methyl group is preferred.

In the general formula (I), Sp ³ and Sp ⁴ are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —X— (CH ₂ ) _t — (wherein t is 2 to 7 X represents —O—, —OCOO—, or —COO—, and X is assumed to be bonded to the phenanthrene ring. Alternatively, an alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or an alkylene group having 1 to 3 carbon atoms is more preferable. Also, when Sp ³ and Sp ⁴ represent —X— (CH ₂ ) _t —, t is preferably 1 to 5, more preferably 1 to 3, and at least one of Sp ³ and Sp ⁴ is a single bond. More preferably, it is particularly preferable that both are single bonds.

Specifically, the compound represented by the general formula (I) is preferably a compound represented by the following general formula (I-1) to (I-52).

The content of the compound represented by the general formula (I) in the polymer compound precursor forming the alignment film is preferably 0.1 to 6% by mass, and preferably 0.5 to 5% by mass. More preferably, the content is 1 to 4% by mass.

As a polymerizable compound having a polymerizable group contained in the alignment film material, in addition to the compound represented by the general formula (I), the following general formula (V)

(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 — (wherein _s represents an integer of 2 to 7, X represents O, OCOO, OCO, or COO, and X is bonded to an aromatic ring present in U.) U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms, a linear or branched polyvalent alkenylene group having 3 to 20 carbon atoms, or a polyvalent cyclic substituent having 5 to 30 carbon atoms. The alkylene group in the polyvalent alkylene group or the alkenylene group in the polyvalent alkenylene group may be substituted with —O—, —CO—, —CF ₂ — within the range in which the oxygen atom is not adjacent, An alkyl group of 5 to 20 (alkylene in the group) The oxygen group may be substituted with an oxygen atom in the range where the oxygen atoms are not adjacent to each other)), or may be substituted with a cyclic substituent, and k represents an integer of 0 to 5.) May contain a functional compound.

In the general formula (V), X ⁷ and X ⁸ each independently represent a hydrogen atom or a methyl group. However, when importance is attached to the reaction rate, a hydrogen atom is preferable, and importance is placed on reducing the residual amount of the reaction. In this case, a methyl group is preferred.

In the general formula (V), Sp ¹ and Sp ² are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —X— (CH ₂ ) _s — (wherein s is 2 to 7 X represents O, OCOO, or COO, and X is bonded to an aromatic ring present in U.), but the carbon chain is preferably not so long, and a single bond or An alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or an alkylene group having 1 to 3 carbon atoms is more preferable. In addition, when Sp ¹ and Sp ² represent —X— (CH ₂ ) _s —, s is preferably 1 to 5, more preferably 1 to 3, and at least one of Sp ¹ and Sp ² is a single bond. More preferably, it is particularly preferable that both are single bonds.

In the general formula (V), k represents an integer of 0 to 5. However, when emphasizing controllability of the alignment direction of liquid crystal molecules in the liquid crystal composition layer, k represents an integer of 1 to 5. More preferably, k represents an integer of 1 to 3, and k represents more preferably 1.

In the general formula (V), U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms, a linear or branched polyvalent alkenylene group having 3 to 20 carbon atoms, or a polyvalent having 5 to 30 carbon atoms. Represents a cyclic substituent, and the alkylene group in the polyvalent alkylene group may be substituted with —O—, —CO—, —CF ₂ — in the range in which the oxygen atom is not adjacent, and has 5 to 20 carbon atoms. An alkyl group (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent), or may be substituted with a cyclic substituent, and may be substituted with two or more cyclic substituents; It is preferable.

In the general formula (V), U specifically preferably represents the following formulas (Va-1) to (Va-5), and the formulas (Va-1) and (Va-2) It is more preferable to represent, and it is particularly preferable to represent the formula (Va-1).

(In the formula, both ends are bound to Sp ¹ or Sp ² (when k = 1), and when k is an integer of 2 to 5, the number of linking groups increases correspondingly. Z ¹ , Z ² and Z ³ are each independently —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 Represents a single bond, and all aromatic rings in the formula are replaced with any hydrogen atom by a fluorine atom. May be.)
In the above U, Z ¹ , Z ² and Z ³ are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond is preferable, —COO—, —OCO— or a single bond is more preferable, and a single bond is particularly preferable.

When U has the ring structure, at least one of Sp ¹ and Sp ² preferably represents a single bond, and it is also preferable that both are single bonds.

In the above general formula (V), k represents an integer of 0 to 5, but k is preferably a bifunctional compound of 1 or k is a trifunctional compound of 2, and k is a bifunctional compound of 1. It is more preferable.

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

Among the compounds represented by the above formulas (Va-1-1) to (Va-5-3), compounds represented by the formulas (Va-1-1) to (Va-2-11) Are preferred, and compounds represented by the formulas (Va-1-1) to (Va-1-13) are more preferred.

The content of the compound represented by the general formula (V) in the alignment film material forming the alignment film is preferably 0 to 6% by mass, more preferably 0.5 to 4% by mass. The content is preferably 1 to 2% by mass.

The content of the whole polymerizable compound having a polymerizable group in the polymer compound precursor forming the alignment film is preferably 0.1 to 6% by mass, and preferably 0.5 to 5% by mass. More preferably, it is 1 to 4% by mass.
(Method of using a polymer of a polymerizable compound having a crosslinkable functional group in the side chain portion as the alignment film material)
The polymerizable compound having a crosslinkable functional group in the side chain portion is not particularly limited as long as it has a crosslinkable functional group (polymerizable group) in the side chain portion. It is preferable to use a compound having an imide skeleton or a siloxane skeleton, and it is more preferable to use a compound having a polyimide skeleton in the main chain portion. Examples of the polymerizable compound having a polyimide skeleton in the main chain portion and a crosslinkable functional group as a side chain include compounds having a crosslinkable functional group as a side chain in the repeating unit (main chain portion) constituting the polyimide structure. It is done. And the said crosslinkable functional group becomes a polymerization reaction start point, and the polymerizable compound which has a polymerizable group mix | blended in alignment film material carries out a radical reaction, and forms a side chain, The liquid crystal molecule in a liquid crystal composition layer It has the orientation control ability to control the orientation direction. The crosslinkable functional group may have any structure as long as it is capable of radical reaction, but groups represented by the following (V2-1) to (V2-7) are preferable, A group represented by (V2-1) to (V2-3) is more preferred, and a group represented by (V2-1) or (V2-2) is more preferred.

(R ¹ represents an alkyl group having 1 to 5 carbon atoms.)
The crosslinkable functional group only needs to be bonded to the main chain portion via a covalent bond, and may be directly bonded to the main chain portion or may be bonded to the main chain portion via a linking group. As the linking group, —O—C ₆ H ₄ — or —O—C ₆ H ₄ — (R ² O) r— is preferably used (R ² represents an alkylene group having 1 to 20 carbon atoms). R represents an integer of 1 or more.)

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

(In the general 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 carbon. Represents an alkylene group having 1 to 20 atoms, and R ⁶ and R ⁷ each independently represents any one of the groups represented by the above (V2-1) to (V2-7), and n Represents an integer of 1 or more, m1 and m2 each represents 0 or 1, m3 and m4 each represents 0 or an integer of 1 or more, m5 and m6 each represent 0 or 1, and at least m5 and m6 One represents 1.)

As the polymerizable compound having a polymerizable group to be blended in the alignment film material together with the polymerizable compound having a polyimide skeleton in the main chain portion and having a crosslinkable functional group as a side chain, the general formula (I) and the above Although the same thing as the compound represented by general formula (V) is mentioned, it is characterized by necessarily containing the compound represented by general formula (I). By containing the compound represented by the general formula (I), the side chain can be formed with a small amount of energy, that is, the irradiation dose such as ultraviolet rays can be reduced.

The compounding amount of the compound represented by the general formula (I) in the alignment film material is preferably 0.1 to 6% by mass, and more preferably 0.5 to 5% by mass. More preferably, it is 1 to 4% by mass.

The blending amount of the whole polymerizable compound having a polymerizable group in the alignment film material is preferably 0.1 to 6% by mass, more preferably 0.5 to 5% by mass. More preferably, it is ˜4% by mass.

In addition, when using the polymer of the polymeric compound which has a crosslinkable functional group in a side chain part as the said alignment film material, you may use together with the above-mentioned well-known polyimide-type material.
(Method using cured product of polymerizable liquid crystal compound as alignment film)
When a cured product of a polymerizable liquid crystal compound is used as the alignment film, an alignment film made of the above-described polyimide material or polysiloxane material may be used as the undercoat alignment film.

When a cured product of a polymerizable liquid crystal compound is used as the alignment film, it must contain the compound represented by the above general formula (I) together with the polymerizable liquid crystal compound represented by the following general formula (V3). Yes. By containing the compound represented by the general formula (I), a cured product of the polymerizable liquid crystal compound can be obtained with a small amount of energy, that is, it is possible to reduce the irradiation amount of ultraviolet rays or the like. It becomes.

When producing an alignment film using a cured product of a polymerizable liquid crystal compound, the above general formula is used with respect to the total amount of the compound represented by the general formula (I) and the polymerizable liquid crystal compound represented by the general formula (V3). The content of the compound represented by the formula (I) is preferably 0.1 to 50% by mass, more preferably 0.3 to 30% by mass, and even more preferably 0.5 to 10% by mass. .

Specifically, as the polymerizable liquid crystal compound forming the alignment film, the following general formula (V3)

(Wherein X ¹ represents a hydrogen atom or a methyl group, and Sp ⁵ and Sp ⁶ each independently represents a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s — ( In the formula, s represents an integer of 2 to 7, and an oxygen atom is bonded to an aromatic ring.), 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 - ^{(Y 1} and ^{Y 2} each independently represent a hydrogen atom, a fluorine atom.), - C≡C- or a single bond, Y is an alkyl group having 1 to 8 carbon atoms, carbon atoms An alkenyl group having 2 to 8 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), the C ring represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, -Any hydrogen atom of the phenylene group may be substituted with a fluorine atom. It is preferable to contain one or more polymerizable liquid crystal compounds represented by

In the general formula (V3), X ¹ and X ² each independently represent a hydrogen atom or a methyl group. However, when importance is attached to the reaction rate, a hydrogen atom is preferable, and importance is placed on reducing the residual amount of the reaction. In this case, a methyl group is preferred.

In the general formula (V3), Sp ⁵ and Sp ⁶ are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s — (wherein s is 2 to 7). Wherein the oxygen atom is bonded to the aromatic ring), the carbon chain is preferably not so long, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or An alkylene group having 1 to 3 carbon atoms is more preferred. Further, when Sp ⁵ and Sp ⁶ represent —O— (CH ₂ ) _s —, s is preferably 1 to 5, more preferably 1 to 3, and at least one of Sp ⁵ and Sp ⁶ is a single bond. More preferably, it is particularly preferable that both are single bonds.

In the general formula (V3), 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 — (Y ¹ and Y ² each independently represents a hydrogen atom or a fluorine atom), —C≡C— or a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —C H ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond is preferable, —COO—, —OCO— or a single bond is more preferable, and a single bond is particularly preferable.

In the above general formula (V3), the ring 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 by a fluorine atom. A 4-phenylene group or a single bond is preferred.

When C ring represents a ring structure other than a single bond, Z ⁴ is preferably a linking group other than a single bond. When C ring is a single bond, Z ⁴ is preferably a single bond.

Y is 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 A compound representing a cyano group is a monofunctional polymerizable liquid crystal compound, and Y does not have a polymerizable skeleton. On the other hand, the compound in which Y represents the above-described polymerizable skeleton is a bifunctional polymerizable liquid crystal compound. In the present invention, either a monofunctional polymerizable liquid crystal compound or a bifunctional polymerizable liquid crystal compound can be used, but a bifunctional polymerizable liquid crystal compound is preferable from the viewpoint of heat resistance, and both of them are used simultaneously. You can also.

From the above, as the polymerizable liquid crystal compound having a ring structure, compounds represented by the following general formulas (V3-1) to (V3-6) are preferable, and the general formulas (V3-1) to (V3- The compound represented by 4) is particularly preferred, and the compound represented by the general formula (V3-2) is most preferred.

(In the above formula, Sp ⁵ and Sp ⁶ are each independently the same as defined above.)
When a cured product of a polymerizable liquid crystal compound is used as an alignment film, the polymerizable liquid crystal compound in the alignment film forming material is heated to an isotropic liquid, and then the temperature is lowered to make the alignment of the polymerizable liquid crystal compound a vertical alignment. There is a need. Thereafter, a pretilt angle is applied in a state where a magnetic field inclined by a specific angle from the substrate surface is applied, and in this state, ultraviolet rays are irradiated to cure the polymerizable liquid crystal compound to obtain an alignment film.

The alignment film may have a horizontal alignment film as a base layer of the alignment film. Specifically, using a polyimide-based horizontal alignment film material, etc., the horizontal alignment film material is applied onto the substrate by a spin coating method, the solvent is removed by heating or the like, and then baked to create a base layer, which is rubbed. You may have the horizontal alignment film which gave the horizontal orientation by processing.
(Polymerizable compound included in liquid crystal composition to form polymer layer on alignment film surface)
In the liquid crystal display element of the present invention, the vertical alignment film includes a polymer formed by polymerization of a polymerizable compound having a reactive group, and the polymer can give an appropriate pretilt angle. If necessary, the polymerizable compound is contained in the liquid crystal composition, and after sandwiching the liquid crystal composition between the substrates, the polymerizable compound is cured by applying the voltage to cure the polymerizable compound. Liquid crystal formed as a polymer layer on the surface of the vertical alignment film while being separated, liquid crystal molecule orientation and pretilt angle stability are high, there is little occurrence of image sticking, and there are few occurrences of dripping marks during its production A display element can be obtained.

The polymerizable compound for forming the polymerization layer is a monofunctional polymerizable compound having one reactive group, a polyfunctional polymerizable compound having two or more reactive groups such as bifunctional or trifunctional, etc. However, a polyfunctional polymerizable compound having two or more reactive groups such as bifunctional or trifunctional is preferable. The polymerizable compound used may be one type or two or more types.

As the polymerizable compound for forming the polymer layer, it is preferable to contain the compound represented by the aforementioned general formula (I). By using the compound represented by the general formula (I), the polymer layer can be formed on the surface of the alignment film with a small amount of energy, that is, the irradiation amount of ultraviolet rays or the like is reduced. Is possible.

Further, as the polymerizable compound for forming the polymer layer, the general formula (V1) is the same as the general formula (V) described above.

(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 ) _r — (wherein _r represents an integer of 2 to 7, X represents O, OCOO, OCO, or COO, and X is bonded to an aromatic ring present in U) U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms, a linear or branched polyvalent alkenylene group having 3 to 20 carbon atoms, or a polyvalent cyclic substituent having 5 to 30 carbon atoms. The alkylene group in the polyvalent alkylene group or the alkenylene group in the polyvalent alkenylene group may be substituted with —O—, —CO—, —CF ₂ — within the range in which the oxygen atom is not adjacent, An alkyl group of 5 to 20 (alkylene in the group) The oxygen group may be substituted with an oxygen atom in the range where the oxygen atoms are not adjacent to each other)), or may be substituted with a cyclic substituent, and k represents an integer of 0 to 5.) Are preferred.

In the general formula (V1), X ⁷ and X ⁸ each independently represent a hydrogen atom or a methyl group. However, when importance is attached to the reaction rate, a hydrogen atom is preferable, and importance is placed on reducing the residual amount of the reaction. In this case, a methyl group is preferred.

In the general formula (V1), Sp ¹ and Sp ² are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —X— (CH ₂ ) _r — (wherein r is 2 to 7). X represents O, OCOO, or COO, and X is bonded to an aromatic ring present in U.), but the carbon chain is preferably not so long, and a single bond or An alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or an alkylene group having 1 to 3 carbon atoms is more preferable. Also, when Sp ¹ and Sp ² represent —X— (CH ₂ ) _s —, r is preferably 1 to 5, more preferably 1 to 3, and at least one of Sp ¹ and Sp ² is a single bond. More preferably, it is particularly preferable that both are single bonds.

In the general formula (V1), k represents an integer of 0 to 5. However, when emphasizing controllability of the alignment direction of liquid crystal molecules in the liquid crystal composition layer, k represents an integer of 1 to 5. More preferably, k represents an integer of 1 to 3, and k represents more preferably 1.

In the above general formula (V1), U is a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms, a linear or branched polyvalent alkenylene group having 3 to 20 carbon atoms, or a polyvalent having 5 to 30 carbon atoms. Represents a cyclic substituent, and the alkylene group in the polyvalent alkylene group may be substituted with —O—, —CO—, —CF ₂ — in the range in which the oxygen atom is not adjacent, and has 5 to 20 carbon atoms. An alkyl group (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent), or may be substituted with a cyclic substituent, and may be substituted with two or more cyclic substituents; It is preferable. Specifically, U preferably represents the following formula (V1a-1) to formula (V1a-6), and represents formula (V1a-1), formula (V1a-2), or formula (V1a-6). It is more preferable that the formula (V1a-1) is represented.

The compound represented by the general formula (V1) is preferably a compound represented by the following general 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 of 2 to 7 and an oxygen atom is bonded to an aromatic ring), 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 -, - _{^{^{H 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, C ring 1 Represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and all of the 1,4-phenylene groups in the formula may have an arbitrary hydrogen atom substituted with a fluorine atom.)
In the general formula (V1b), X ¹ and X ² each independently represent a hydrogen atom or a methyl group, both of which are diacrylate derivatives each representing a hydrogen atom, or both of which are methyl methacrylate groups. A compound in which one represents a hydrogen atom and the other represents a methyl group is also preferable. The polymerization rate of these compounds is the fastest for diacrylate derivatives, slow for dimethacrylate derivatives, and intermediate for asymmetric compounds, and a preferred embodiment can be used depending on the application.

In the general 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—, at least one of which is a single bond A compound in which both represent a single bond or one in which one represents a single bond and the other represents an alkylene group having 1 to 8 carbon atoms or —O— (CH ₂ ) s— is preferable. In this case, an alkylene group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4.

In the above general 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, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond is preferred, and —CO O—, —OCO— or a single bond is more preferred, and a single bond is particularly preferred.
When C ring represents a ring structure other than a single bond, Z ⁴ is preferably a linking group other than a single bond. When C ring is a single bond, Z ⁴ is preferably a single bond.

As described above, in the general formula (V1b), it is preferable that the C ring represents a single bond and the ring structure is formed of two rings. Specific examples of the polymerizable compound having a ring structure include Compounds represented by formulas (V1b-1) to (V1b-6) are preferred, compounds represented by general formulas (V1b-1) to (V1b-4) are particularly preferred, and compounds represented by general formula (V1b-2) The compounds represented are most preferred.

(Sp ^1b and Sp ^2b represent the same meanings as Sp ¹ and Sp ² described in the general formula (V1b), respectively.)
Specifically, the compound represented by the general formula (V1) is also preferably a compound represented by the following general formula (V1c).

(In the formula, 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 having 1 to 8 carbon atoms. Represents an alkylene group or —O— (CH ₂ ) _s — (wherein _s represents an integer of 2 to 7 and an oxygen atom is bonded to an 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, and the J ring represents a 1,4-phenylene group or a single bond, In any of the 1,4-phenylene groups, any hydrogen atom may be replaced by a fluorine atom.)
The total content of the compounds represented by the general formula (I) used for forming the polymer layer on the surface of the vertical alignment film in the liquid crystal composition is preferably 0 to 1% by mass, The content is preferably 0.8 to 0.8% by mass, and more preferably 0.05 to 0.6% by mass.

In addition, the total content of the polymerizable compound represented by the general formula (V1) used for forming the polymer layer on the surface of the vertical alignment film in the liquid crystal composition is preferably 0 to 1% by mass. 0.03-0.8% by mass is preferable, and 0.05-0.6% by mass is more preferable.

The total content of the polymerizable compounds used for forming the polymer layer on the surface of the vertical alignment film in the liquid crystal composition is preferably 0 to 1% by mass, and 0.03 to 0.8% by mass. Preferably, the content is 0.05 to 0.6% by mass.
(Liquid crystal composition)
The liquid crystal composition in the present invention contains one or more compounds represented by general formula (N-1), general formula (N-2), and general formula (N-3).

In the formula, R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two non-adjacent groups in the alkyl group The above —CH ₂ — may be independently substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31, and A ^N32 are each independently (a) a 1,4-cyclohexylene group (one —CH ₂ — or adjacent to each other in this group). And two or more —CH ₂ — may be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or not adjacent 2 More than one -CH = may be replaced by -N =.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—. , —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—,
^XN21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents —CH ₂ — or an oxygen atom,
n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31, and n ^N32 each independently represent an integer of 0 to 3, but n ^N11 + n ^N12 , n ^N21 + n ^N22, and n ^N31 + n ^N32 are each independently When there are a plurality of A ^N11 to A ^N32 and Z ^N11 to Z ^N32 , they may be the same or different.

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

In the general formulas (N-1), (N-2) and (N-3), R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 each independently represent 1 to 8 carbon atoms. An alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, An alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is preferable. More preferably, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable.

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

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

A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31, and A ^N32 are preferably aromatic when it is required to increase Δn independently, and in order to improve the response speed, fat Preferably a trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5 -Difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1 , 4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Preferred, it is more preferable that represents the following structures,

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

^{^{^{^{Z N11, Z N12, Z N21}}}} , Z N22, Z N31 and ^{Z N32} _-CH 2 each _{independently} _{O -, - CF 2 O -} , - CH 2 CH 2 -, - CF 2 CF 2 - or a single bond preferably represents _{_{an, -CH 2 O -, - CH}} 2 CH 2 - or a single bond is more preferable, _-CH 2 O-or a single bond is particularly preferred.

^XN21 is preferably a fluorine atom.

T ^N31 is preferably an oxygen atom.

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

The lower limit of the preferable content of the compound represented by the general formula (N-1) with respect to the total amount of the composition of the present invention (the total amount of liquid crystal compounds contained in the liquid crystal composition; the same shall apply hereinafter) is 1 Mass% (hereinafter, mass% is simply expressed as%), 10%, 20%, 30%, 40%, 50%, 55%, and 60%. 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

The lower limit of the preferable content of the compound represented by the general formula (N-2) with respect to the total amount of the composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). %, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% %. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

The lower limit of the preferable content of the compound represented by the general formula (N-3) with respect to the total amount of the composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). %, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% %. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

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

The compound represented by the general formula (N-1) is preferably a compound selected from the group of compounds represented by the general formulas (N-1-1) to (N-1-21).

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

( ^Wherein , R ^N111 and R ^N112 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
R ^N111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a propyl group or a pentyl group. ^RN112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group or a butoxy group.

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

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-1) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.

Further, the compound represented by the general formula (N-1-1) is a compound selected from the group of compounds represented by the formula (N-1-1.1) to the formula (N-1-1.14). Preferably, it is a compound represented by the formulas (N-1-1.1) to (N-1-1.4), and the formula (N-1-1.1) and the formula (N The compound represented by -1-1.3) is preferable.

The compounds represented by the formulas (N-1-1.1) to (N-1-1.4) can be used alone or in combination. The lower limit of the preferred content of these compounds alone or with respect to the total amount is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.

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

(In the formula, R ^N121 and R ^N122 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
^RN121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, a butyl group or a pentyl group. ^RN122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and includes a methyl group, a propyl group, a methoxy group, an ethoxy group, or a propoxy group. preferable.

The compound represented by the general formula (N-1-2) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

When emphasizing the improvement of Δε, it is preferable to set the content higher. When emphasizing the solubility at low temperature, it is more effective to set the content lower. When emphasizing T _NI , the content is preferable. Setting a large number of is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-2) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 7%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37%, 40%, 42%. The upper limit of the preferable content is 50%, 48%, 45%, 43%, 40%, 38%, and 35% with respect to the total amount of the composition of the present invention. %, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% %, 8%, 7%, 6%, 5%.

Further, the compound represented by the general formula (N-1-2) is a compound selected from the group of compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13). Preferably, the formula (N-1-2.3) to the formula (N-1-2.7), the formula (N-1-2.10), the formula (N-1-2.11) and the formula The compound represented by (N-1-2.13) is preferable, and when importance is placed on the improvement of Δε, the formula (N-1-2.3) to the formula (N-1-2.7) in the compounds _represented, when emphasizing improvements in _{T NI} formula (N-1-2.10), formula (N-1-2.11) and formula (N-1-2.13) It is preferable that it is a compound represented by these.

The compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13) can be used alone or in combination. The lower limit of the preferred content of these compounds alone or with respect to the total amount is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, and 15%. 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.

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

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

The compound represented by the general formula (N-1-3) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-3) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

Further, the compound represented by the general formula (N-1-3) is a compound selected from the group of compounds represented by the formula (N-1-3.1) to the formula (N-1-3.11). Preferably, it is a compound represented by the formulas (N-1-3.1) to (N-1-3.7), and the formula (N-1-3.1) and the formula (N -1-3.2), formula (N-1-3.3), formula (N-1-3.4) and compounds represented by formula (N-1-3.6) are preferred.

The compounds represented by formula (N-1-3.1) to formula (N-1-3.4) and formula (N-1-3.6) may be used alone or in combination. Is possible, but the combination of formula (N-1-3.1) and formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) ) And a combination of two or three selected from formula (N-1-3.6) are preferred. The lower limit of the preferable content of these compounds alone or with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, and 13%. 15%, 17%, and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

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

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

The compound represented by the general formula (N-1-4) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-4) with respect to the total amount of the composition of the present invention is 3% by mass (hereinafter, mass% is simply expressed as%), 5%, 7%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, and 8%.

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

The compounds represented by formulas (N-1-4.1) to (N-1-4.4) can be used singly or in combination, but the compounds of the present invention The lower limit of the preferable content of these compounds alone or with respect to the total amount is 3% by mass (hereinafter, mass% is simply expressed as%), 5%, 7%, 10%, 13%, 15%, 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, and 8%.

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

(In the formula, R ^N151 and R ^N152 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
R ^N151 and R ^N152 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethyl group, a propyl group, or a butyl group. Is preferred.

The compound represented by the general formula (N-1-5) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-5) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 8%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 33%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the composition of the present invention. %, 18%, 15% and 13%.

Further, the compound represented by the general formula (N-1-5) is a compound selected from the group of compounds represented by the formula (N-1-5.1) to the formula (N-1-5.6). The compound represented by the formula (N-1-3.2 and the formula (N-1-3.4) is preferable.

The compounds represented by formula (N-1-3.2) and formula (N-1-3.4) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount is 5% by mass (hereinafter, mass% is simply expressed as%), 8%, 10%, 13%, 15%, 17%, and 20% The upper limit of the preferred content is 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%.

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

(In the formula, R ^N1101 and R ^N1102 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
R ^N1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1102 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-10) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-10) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

Further, the compound represented by the general formula (N-1-10) is a compound selected from the group of compounds represented by the formula (N-1-10.1) to the formula (N-1-10.11). Preferably, it is a compound represented by the formulas (N-1-10.1) to (N-1-10.5), and the formula (N-1-10.1) and the formula (N The compound represented by (1-10.2) is preferable.

The compounds represented by the formula (N-1-10.1) and the formula (N-1-10.2) can be used alone or in combination. The lower limit of the preferred content of these compounds alone or with respect to the total amount is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, and 15%. 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

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

(In the formula, R ^N1111 and R ^N1112 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
R ^N1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

The compound represented by the general formula (N-1-11) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-11) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

Further, the compound represented by the general formula (N-1-11) is a compound selected from the group of compounds represented by the formula (N-1-11.1) to the formula (N-1-11.15). Preferably, it is a compound represented by the formulas (N-1-11.1) to (N-1-11.15), and is preferably a compound represented by the formula (N-1-11.2) or the formula (N-- The compound represented by 1-11.4) is preferable.

The compounds represented by the formula (N-1-11.2 and the formula (N-1-11.4) can be used alone or in combination. The lower limit of the preferred content of these compounds alone or with respect to the total amount is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, The upper limit of the preferable content is 35%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition of the present invention. %, 20%, 18%, 15%, 13%.

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

( ^Wherein , R ^N1121 and R ^N1122 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
^RN1121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. ^RN1122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-12) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-12) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

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

( ^Wherein , R ^N1131 and R ^N1132 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
R ^N1131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-13) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-13) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

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

( ^Wherein , R ^N1141 and R ^N1142 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
R ^N1141 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1142 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-14) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-14) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

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

( ^Wherein , R ^N1151 and R ^N1152 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
^RN1151 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1152 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-15) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-15) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

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

(In the formula, R ^N1161 and R ^N1162 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
R ^N1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1162 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-16) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-16) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

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

( ^Wherein , R ^N1171 and R ^N1172 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
^RN1171 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1172 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-17) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-17) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

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

( ^Wherein , R ^N1181 and R ^N1182 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N)).
^RN1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1182 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-18) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-18) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

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

(In the formula, R ^N1201 and R ^N1202 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N)).
The compound represented by the general formula (N-1-21) is the following compound.

(In the formula, R ^N1211 and R ^N1212 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
The compound represented by the general formula (N-2) is preferably a compound selected from the group of compounds represented by the general formulas (N-2-1) to (N-2-3).

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

^{(Wherein, R N211} and ^{R N212} each independently represents the same meaning as ^{R N21} and ^{R N22} in the general formula (N-2).)
The compound represented by the general formula (N-2-2) is the following compound.

^{(Wherein, R N221} and ^{R N222} each independently represents the same meaning as ^{R N21} and ^{R N22} in the general formula (N-2).)
The compound represented by the general formula (N-2-3) is the following compound.

^{(Wherein, R N231} and ^{R N232} each independently represents the same meaning as ^{R N31} and ^{R N32} in the general formula (N-3).)
The compound represented by the general formula (N-3) is preferably a compound selected from the group of compounds represented by the general formulas (N-3-1) to (N-3-2).

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

(In the formula, R ^N311 and R ^N312 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
The compound represented by the general formula (N-3-2) is the following compound.

(In the formula, R ^N321 and R ^N322 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
In general formula (N-1), general formula (N-2), and general formula (N-3) with respect to the total amount of the composition of the present invention (total amount of liquid crystal compounds contained in the liquid crystal composition) The total content of the compounds represented is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 20 to 70% by mass, further preferably 20 to 60% by mass, 55 mass% is more preferable, 25 to 55 mass% is further preferable, and 30 to 55 mass% is particularly preferable.

More specifically, the total amount of the compounds represented by the general formula (N-1), the general formula (N-2), and the general formula (N-3) is set as a lower limit in the composition. It is preferably contained in an amount of 1% by mass (hereinafter referred to simply as%), preferably 5% or more, preferably 10% or more, preferably 13% or more, 15% It is preferably contained, preferably contained 18% or more, preferably contained 20% or more, preferably contained 23% or more, preferably contained 25% or more, and contained 28% or more. Preferably, it contains 30% or more, preferably contains 33% or more, preferably contains 35% or more, preferably contains 38% or more, and preferably contains 40% or more. There. Further, the upper limit value is preferably 95% or less, preferably 90% or less, preferably 88% or less, preferably 85% or less, and preferably 83% or less. 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 less, preferably 63% or less, preferably 60% or less, preferably 55% or less, preferably 50% or less, It is preferable to contain 40% or less.

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

(Wherein R ^L1 and R ^L2 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently Optionally substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^L1 represents 0, 1, 2 or 3,
A ^L1 , A ^L2 and A ^L3 each independently represent (a) a 1,4-cyclohexylene group (one —CH ₂ — present in the group or two or more —CH ₂ — not adjacent to each other). May be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or two or more —CH═ not adjacent to each other —N May be replaced by =.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and Z ^L2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —OCF ₂ -, -CF ₂ O-, -CH = NN-CH-, -CH = CH-, -CF = CF- or -C≡C-
When n ^L1 is 2 or 3, and a plurality of A ^L2 are present, they may be the same or different, and when n ^L1 is 2 or 3, and a plurality of Z ^L3 are present, May be the same or different, but excludes compounds represented by general formula (N-1), general formula (N-2) and general formula (N-3). )
Although the compound represented by general formula (L) may be used independently, it can also be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to desired properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention. Alternatively, in another embodiment of the present invention, there are two types, three types, four types, five types, six types, seven types, eight types, nine types, 10 types, More than types.

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

The lower limit of the preferable content of the compound represented by the formula (L) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), which is 10%. Yes, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% is there. The upper limit of the preferable content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, and 25%.

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

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

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

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

A ^L1 , A ^L2, and A ^L3 are preferably aromatic when it is required to increase Δn, and are preferably aliphatic for improving the response speed, and are each independently trans- 1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 -It preferably represents a diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents the following structure:

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

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

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

(In the formula, R ^L11 and R ^L12 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L11 and R ^L12 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

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

The lower limit of the preferable content is 1% by mass (hereinafter, mass% is simply expressed as%), 2%, 3%, and 5% with respect to the total amount of the liquid crystal composition of the present invention. Yes, 7%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% Yes, 55%. The upper limit of the preferable content is 95%, 90%, 85%, 80%, 75%, 70%, 65%, based on the total amount of the composition of the present invention. %, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%.

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

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

(Wherein R ^L12 represents the same meaning as in general formula (L-1).)
The compound represented by the general formula (L-1-1) is a compound selected from the group of compounds represented by the formula (L-1-1.1) to the formula (L-1-1.3). And is preferably a compound represented by formula (L-1-1.2) or formula (L-1-1.3), and particularly represented by formula (L-1-1.3). It is preferable that it is a compound.

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

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

(Wherein R ^L12 represents the same meaning as in general formula (L-1).)
The lower limit of the preferable content of the compound represented by the formula (L-1-2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 5%, 10%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 35% . The upper limit of the preferable content is 60%, 55%, 50%, 45%, 42%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 33%, and 30%.

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

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

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

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

(Wherein R ^L13 and R ^L14 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ^L13 and R ^L14 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

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

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

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

(In the formula, R ^L15 and R ^L16 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ^L15 and R ^L16 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

The lower limit of the preferable content of the compound represented by the formula (L-1-4) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 5%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 25%, 23%, 20%, 17%, 15%, 13%, and 10% with respect to the total amount of the composition of the present invention. %.

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

Furthermore, the compounds represented by the general formulas (L-1-4) and (L-1-5) are represented by the formulas (L-1-4.1) to (L-1-5.3). And a compound represented by the formula (L-1-4.2) or the formula (L-1-5.2) is preferable.

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

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

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

(In the formula, R ^L21 and R ^L22 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L22 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable.

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

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

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

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

(In the formula, R ^L31 and R ^L32 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L).)
R ^L31 and R ^L32 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

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

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

When a high birefringence is obtained, the effect is high when the content is set to be large. On the other hand, when high Tni is emphasized, the effect is high when the content is set low. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

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

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

(In the formula, R ^L41 and R ^L42 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L).)
R ^L41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L42 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable. )
The compound represented by the general formula (L-4) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

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

The lower limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass% is simply expressed as%). %, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30% %, 35%, and 40%. The upper limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, and 30%. 20%, 15%, 10%, 5%.

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

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

When both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2) are contained, both compounds relative to the total amount of the liquid crystal composition of the present invention The lower limit of the preferable content of is 15% by mass (hereinafter, mass% is simply expressed as%), 19%, 24%, 30%, and the preferable upper limit is 45. 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.

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

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

The lower limit of the preferable content of the compound represented by the formula (L-4.4) or the formula (L-4.5) with respect to the total amount of the liquid crystal composition of the present invention is 3% by mass (hereinafter referred to as mass%). Is simply expressed as%), 5%, 7%, 9%, 11%, 12%, 13%, 18%, and 21%. Preferred upper limit values are 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13% %, 10%, and 8%.

When both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5) are contained, both compounds relative to the total amount of the liquid crystal composition of the present invention The lower limit of the preferable content of is 15% by mass (hereinafter, mass% is simply expressed as%), 19%, 24%, 30%, and the preferable upper limit is 45. 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.

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

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

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

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

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

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

The lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), 2%, 3%, 5% and 7%. The upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.

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

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

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

(In the formula, R ^L61 and R ^L62 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L), and X ^L61 and X ^L62 each independently represent a hydrogen atom or a fluorine atom. )
R ^L61 and R ^L62 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and one of X ^L61 and X ^L62 is a fluorine atom and the other is a hydrogen atom. Is preferred.

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

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

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

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

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

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

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

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

In the liquid crystal composition of the present invention, the content of the compound represented by the general formula (L-7) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, dropping trace Therefore, it is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

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

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

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

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

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

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

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

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

The liquid crystal composition of the present invention can use a nematic phase-isotropic liquid phase transition temperature (Tni) in a wide range, but the nematic phase-isotropic liquid phase transition temperature (Tni) is 60. It is preferably from ˜120 ° C., more preferably from 70 to 100 ° C., particularly preferably from 70 to 85 ° C.

The dielectric anisotropy Δε of the liquid crystal composition in the present invention is preferably −2.0 to −6.0, more preferably −2.5 to −5.0 at 25 ° C. A value of −2.5 to −3.5 is particularly preferable.

The refractive index anisotropy Δn of the liquid crystal composition in the present invention is preferably 0.08 to 0.13 at 25 ° C., more preferably 0.09 to 0.12. More specifically, the refractive index anisotropy of the liquid crystal composition in the present invention is preferably 0.10 to 0.12 at 25 ° C. when dealing with a thin cell gap. When it corresponds to a cell gap (cell gap of 3.4 μm or less), it is preferably about 0.9 to about 0.12, and when it corresponds to a thick cell gap (cell gap of 3.5 μm or more), it is about 0. It is preferably about 08 to about 0.1.

The upper limit of the rotational viscosity (γ ₁ ) of the liquid crystal composition according to 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 50 (mPa · s). s) or more is more preferable, 60 (mPa · s) or more is further more preferable, and 70 (mPa · s) or more is particularly preferable.

In the liquid crystal composition according to the present invention, it is preferable that Z as a function of rotational viscosity and refractive index anisotropy shows a specific value.

(In the above formula, γ ₁ represents rotational viscosity and Δn represents refractive index anisotropy.)
Z is preferably 13000 or less, more preferably 12000 or less, and particularly preferably 11000 or less.

When used in an active matrix display device, the liquid crystal composition according to the present invention needs to have a specific resistance of 10 ¹¹ (Ω · m) or more, preferably 10 ¹² (Ω · m). ¹³ (Ω · m) or more is more preferable.

The liquid crystal composition according to the present invention can use a nematic phase-isotropic liquid phase transition temperature (T _NI ) in a wide range, and the phase transition temperature (T _NI ) is 60 to 120 ° C. It is preferably 70 to 110 ° C, particularly preferably 75 to 100 ° C.
[Method of manufacturing liquid crystal display element]
Next, with reference to FIG. 1, the manufacturing method of the liquid crystal display element of this invention is demonstrated.

An alignment film material or a polymerizable liquid crystal containing a polymerizable compound having a polymerizable group on the surface of the first substrate 11 on which the common electrode 14 is formed and on the surface of the second substrate 12 on which the pixel electrode 15 is formed. The

vertical alignment films

16 and 17 are formed by applying a compound and heating. In addition, when using a polymerizable liquid crystal compound as the alignment film, a normal alignment film may be provided as the base alignment film.

Here, first, the polymer compound precursor to be the first polymer compound and / or the compound represented by the above general formula (V2), the compound represented by the above general formula (I), and the necessity Correspondingly, a polymerizable compound such as a compound represented by the general formula (V), or an alignment film material containing a compound having photopolymerizability and photocrosslinkability, or a compound represented by the general formula (I) and polymerization An alignment film material made of a conductive liquid crystal compound is prepared.

When the first polymer compound is polyimide, examples of the polymer compound precursor include a mixture of tetracarboxylic dianhydride and diisocyanate, polyamic acid, and a polyimide solution in which polyimide is dissolved or dispersed in a solvent. Etc. The polyimide content in the polyimide solution is preferably 1% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 5% by mass or less.

When the first polymer compound is polysiloxane, examples of the polymer compound precursor include a silicon compound having an alkoxy group, a silicon compound having a halogenated alkoxy group, alcohol, and oxalic acid. Examples thereof include a polysiloxane solution prepared by synthesizing polysiloxane by mixing at a quantitative ratio and heating, and dissolving it in a solvent.

In addition, you may add the compound which has photocrosslinkability, a photoinitiator, a solvent, etc. to alignment film material as needed.

After the alignment film material is adjusted, the alignment film material is applied to each of the first substrate 11 and the second substrate 12 so as to cover the common electrode 14, the pixel electrode 15, and its slit portion (not shown). Alternatively, after printing, a process such as heating is performed. As a result, the polymer compound precursor and / or the compound represented by the general formula (V2) or the polymerizable liquid crystal compound contained in the coated or printed alignment film material is polymerized and cured to form a polymer compound. A compound represented by general formula (I) and a compound represented by general formula (V), if necessary, or a compound represented by general formula (I) and a polymerizable liquid crystal

Vertical alignment films

16 and 17 in which the compound is semi-cured are formed.

Here, when the heat treatment is performed, the temperature is preferably 80 ° C. or higher, and more preferably 150 to 200 ° C.

In this stage, the vertical alignment ability to align the liquid crystal molecules in the liquid crystal composition layer in the direction perpendicular to the substrate surface is formed. Thereafter, a process such as rubbing may be performed as necessary.

Next, 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, spacer protrusions for securing a cell gap with respect to the surface on which the

vertical alignment films

16 and 17 are formed on either one of the first substrate 11 and the second substrate 12, for example, In addition to spraying plastic beads or the like, for example, the seal portion is printed using an epoxy adhesive or the like by a screen printing method.

Thereafter, the first substrate 11 and the second substrate 12 are bonded together through spacer protrusions and a seal portion so that the

vertical alignment films

16 and 17 are opposed to each other, and liquid crystal molecules and, if necessary, polymerizable. A liquid crystal composition containing the compound is injected.

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

Next, a voltage is applied between the common electrode 14 and the pixel electrode 15 using voltage applying means. The voltage is applied with a magnitude of 5 to 30 (V), for example. The application may apply a charge substantially perpendicularly to the first substrate and the second substrate. Thereby, the surface adjacent to the liquid crystal composition layer 13 in the first substrate 11 (surface facing the liquid crystal composition layer 13) and the surface adjacent to the liquid crystal composition layer 13 in the second substrate 12 (liquid crystal An electric field in a direction forming a predetermined angle with respect to the surface facing the composition layer 13 is generated, and the liquid crystal molecules 19 are oriented in a predetermined direction with respect to the normal direction of the first substrate 11 and the second substrate 12. Will be. At this time, the tilt angle of the liquid crystal molecules 19 is approximately equal to the pretilt θ given to the liquid crystal molecules 19 in a process described later. Therefore, the magnitude of the pretilt θ of the liquid crystal molecules 19 can be controlled by appropriately adjusting the magnitude of the voltage (see FIG. 3).

Furthermore, the ultraviolet light UV is irradiated to the liquid crystal composition layer 13 from the outside of the first substrate 11 with the voltage applied, for example, by the general formula (I) in the

vertical alignment films

16 and 17. A compound represented by formula (V) or a polymerizable liquid crystal compound and a polymerizable compound in the liquid crystal composition are polymerized to produce a polymer.

In this case, the intensity of the ultraviolet light UV to be irradiated may or may not be constant, and the irradiation time at each intensity when the irradiation intensity is changed is arbitrary, but two or more stages of irradiation processes are performed. When employed, it is preferable to select an irradiation intensity in the irradiation process in the second stage and after that which is weaker than the irradiation intensity in the first stage, and the total irradiation time in the second stage and after is more than the irradiation time in the first stage. It is preferable that the total irradiation energy amount is long and long. When the irradiation intensity is changed discontinuously, it is desirable that the average irradiation light intensity in the first half of the entire irradiation process time is stronger than the average irradiation intensity in the second half, and the intensity immediately after the start of irradiation is the strongest. More desirably, it is further preferable that the irradiation intensity always decreases to a certain value as the irradiation time elapses. In this case, the ultraviolet UV intensity is preferably ² mW / cm ⁻² to 100 mW / cm ⁻² , but the first stage in the case of multi-stage irradiation or the entire irradiation process in the case of changing the irradiation intensity discontinuously. The maximum irradiation intensity is 10 mW / cm ⁻² to 100 mW / cm ⁻² , and the minimum irradiation intensity is 2 mW / cm ⁻ after the second stage in the case of multistage irradiation or when the irradiation intensity is changed discontinuously. More preferably, it is ² to 50 mW / cm ⁻² . The total irradiation energy is preferably 10 J to 300 J, more preferably 50 J to 250 J, and even more preferably 100 J to 250 J.

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

As a result, it has an alignment control ability (not shown) including a vertical alignment film material fixed to the alignment control portions of the

vertical alignment films

16 and 17, and further, the polymer layer 20 is formed on the surface thereof as necessary. , 21 are formed. This alignment control unit has a function of imparting a pretilt θ to the liquid crystal molecules 19 located in the vicinity of the interface of the liquid crystal composition layer 13 with the polymer layers 20 and 21 (vertical alignment films 16 and 17) in the non-driven state (alignment). Controllability). Here, although the ultraviolet light UV is irradiated from the outside of the first substrate 11, it may be irradiated from the outside of the second substrate 12, and both the first substrate 11 and the second substrate 12 may be irradiated. You may irradiate from the outer side of a board | substrate.

Thus, in the liquid crystal display element of the present invention, the liquid crystal molecules 19 in the liquid crystal composition layer 13 have a predetermined pretilt θ. As a result, the response speed to the drive voltage can be greatly improved as compared with a liquid crystal display element that has not been subjected to any pretilt processing and a liquid crystal display device having the liquid crystal display element.

In the liquid crystal display element of the present invention, the polymer compound precursor constituting the

vertical alignment films

16 and 17 is preferably a non-photosensitive polyimide precursor.

Hereinafter, the present invention will be described more specifically with reference to 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 “mass%”.

In the following Examples and Comparative Examples, Tni, Δn, Δε, η , γ 1 respectively are defined as follows.
T _ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
T _cn : solid phase-nematic phase transition temperature (° C.)
Δn: refractive index anisotropy at 25 ° C. Δε: dielectric anisotropy γ _{1 at} 25 ° C .: rotational viscosity at 25 ° C. (mPa · s)
K ₃₃ : Elastic constant of bending at 20 ° C. (pN)
Voltage holding ratio before UV irradiation (initial VHR): voltage holding ratio (%) at 343 K under conditions of frequency 60 Hz and applied voltage 1 V
VHR after UV irradiation: The liquid crystal display elements of the following examples and comparative examples were irradiated with UV, and then measured under the same conditions as in the VHR measurement method described above.

In the following examples and comparative examples, image sticking, drop marks, and pretilt angles of liquid crystal display elements were evaluated by the following methods.
(Burn in)
The burn-in evaluation of the liquid crystal display element is based on the following four-level evaluation of the afterimage level of the fixed pattern when the predetermined fixed pattern is displayed in the display area for 1000 hours and then the entire screen is uniformly displayed. went.
◎: No afterimage ○: Level of afterimage is slightly acceptable but acceptable △: Level of afterimage is unacceptable ×: Image retention is quite poor (drop mark)
Evaluation of the drop marks of the liquid crystal display device was performed by the following four-stage evaluation of the drop marks that appeared white when the entire surface was displayed in black.
◎: No afterimage ○: Even afterimage is slightly acceptable level △: Afterimage is unacceptable level ×: Afterimage is fairly poor (pretilt angle)
The in-plane of the liquid crystal display element was randomly measured at five locations, and the average value was defined as the pretilt angle. When evaluating the stability of the pretilt angle, the change in the pretilt angle before and after the stress was compared. The stress was applied by putting 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 change angle (°): pretilt angle after stress-pretilt angle before stress In the examples, the following abbreviations are used for the description of compounds. Note that n represents a natural number.
(Side chain)
-N -C _n H _{2n + 1} linear alkyl group with n carbon atoms n- C _n H _{2n + 1} -linear alkyl group with n carbon atoms -On -OC _n H _{2n + 1} linear chain with n carbon atoms -Like alkoxyl group nO- C _n H _{2n + 1} O- linear alkoxyl group having n carbon atoms -V -CH = CH ₂
V- CH ₂ = CH-
-V1 -CH = CH-CH ₃
1V- CH ₃ —CH═CH—
_{_{-2V -CH 2 -CH 2 -CH = CH}} 3
V2- CH ₃ = CH-CH ₂ -CH _2-
-2V1 -CH ₂ -CH ₂ -CH = CH-CH ₃
1V2- CH ₃ —CH═CH—CH ₂ —CH ₂
(Linking group)
-N- -C _n H _2n-
—NO— —C _n H _2n —O—
—On— —O—C _n H _2n —
—COO— —C (═O) —O—
-OCO- -OC (= O)-
—CF ₂ O——CF ₂ —O—
-OCF2- -O-CF _2-
D -C = C-
T -C≡C-
(Ring structure)

(Example 1)
A first substrate (common electrode substrate) having a transparent electrode layer and a color filter layer made of a transparent common electrode, and a second substrate (pixel) having a pixel electrode layer having a transparent pixel electrode driven by an active element Electrode substrate).

In the pixel electrode substrate, each pixel electrode was obtained by etching ITO so that a slit having no electrode was present in the pixel electrode in order to divide the orientation of liquid crystal molecules.

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

As a material for forming a vertical alignment film, a compound represented by the following formula (I-1) is added to a polyimide solution containing 3% of a polyimide precursor (trade name: JALS2131-R6, manufactured by JSR) with 3.0% The containing solution was used.

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

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied to cure the compound represented by the formula (I-1). As the irradiation device, UIS-S2511RZ manufactured by Ushio Electric Co., Ltd. and USH-250BY manufactured by Ushio Electric Co., Ltd. are used as an ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 300 seconds. Got. By this step, a vertical alignment film containing the compound represented by the formula (I-1) is formed, and a pretilt angle is given to the liquid crystal molecules in the liquid crystal composition layer.

Here, the pretilt angle is defined as shown in FIG. In the case of complete vertical alignment, the pretilt angle (θ) is 90 °, and when the pretilt angle is given, the pretilt angle (θ) is smaller than 90 °.

The liquid crystal display element of Example 1 has pretilt angles in different directions in the four sections according to the slits of the pixel electrode as shown in FIG. 2, and the AC electric field is turned off after the polymerizable compound is cured. The pretilt angle was maintained.

Table 2 below shows each physical property of the liquid crystal composition used in the liquid crystal display element of Example 1, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 1 does not show a significant decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Comparative Example 1)
As a material for forming a vertical alignment film, a compound represented by the following formula (Va-1-1) is added to a polyimide solution containing 3% of a polyimide precursor (trade name: JALS2131-R6, manufactured by JSR). A liquid crystal display element of Comparative Example 1 was obtained in the same manner as in Example 1 except that a solution containing 1% was used.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied, and the polymerizable compound having a reactive group in the alignment film was cured. As the irradiation device, UIS-S2511RZ manufactured by Ushio Electric Co., Ltd. and USH-250BY manufactured by Ushio Electric Co., Ltd. are used as the ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 600 seconds. Got. The liquid crystal display element was irradiated with ultraviolet rays under the same conditions as in Example 1 (20 mW for 300 seconds) to give a pretilt angle, but the polymerizable compound having a reactive group in the alignment film was not sufficiently cured. Since the pretilt angle was not stably given, irradiation of 20 mW and 600 seconds was required to maintain the pretilt angle.

Table 3 below shows each physical property of the liquid crystal composition used in the liquid crystal display element of Comparative Example 1, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, since the alignment film material of Comparative Example 1 does not contain the polymerizable compound represented by the general formula (I), UV irradiation for curing the polymerizable compound having the polymerizable property in the alignment film is performed. As a result of an increase in the total energy amount, a decrease in VHR was observed, and a decrease in physical properties due to decomposition of the liquid crystal compound in the liquid crystal composition was confirmed.

(Example 2)
A liquid crystal composition (LC-A2) containing the compounds 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 a liquid crystal display element of Example 2 was obtained.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied to cure the compound represented by the formula (I-1). As the irradiation device, UIS-S2511RZ made by Ushio Electric Co., Ltd. and USH-250BY made by Ushio Electric Co., Ltd. are used as an ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 300 seconds. Got. The liquid crystal display element of Example 2 had a pretilt angle as in Example 1, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured.

Table 5 below shows each physical property of the liquid crystal composition used in the liquid crystal display element of Example 2, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 2 does not show a decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

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

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied to cure the compound represented by the formula (I-1). As the irradiation device, UIS-S2511RZ manufactured by USHIO INC. And USH-250BY manufactured by USHIO ELECTRIC CO., LTD. Are used as UV lamps, and the liquid crystal display device is irradiated with UV rays at 20 mW for 300 seconds. Got. The liquid crystal display element of Example 3 had a pretilt angle as in Example 1, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured.

Table 7 below shows the physical properties of the liquid crystal composition used in the liquid crystal display element of Example 3, the VHR before and after UV irradiation, the drop mark evaluation and the burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 3 does not show a significant decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

Example 4
A liquid crystal composition (LC-A4) containing the compounds shown in the following table was prepared, and the liquid crystal composition was used. As a material for forming a vertical alignment film, a compound 1.5 represented by the following formula (I-1) is added to a polyimide solution containing 3% of a polyimide precursor (trade name: JALS2131-R6, manufactured by JSR). % And a solution containing 1.5% of the compound represented by the formula (Va-1-1) was used. Other conditions were the same as in Example 1, and a 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, and the compound represented by the formula (I-1) and the compound represented by the formula (Va-1-1) are cured. I let you. As the irradiation device, UIS-S2511RZ manufactured by Ushio Electric Co., Ltd. and USH-250BY manufactured by Ushio Electric Co., Ltd. are used as an ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 300 seconds. Got. The liquid crystal display element of Example 4 had a pretilt angle as in Example 1, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured.

Table 9 below shows properties of the liquid crystal composition used in the liquid crystal display element of Example 4, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 4 does not show a significant decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Example 5)
A liquid crystal composition (LC-A5) containing the compounds shown in the following table was prepared, and the liquid crystal composition was used. Further, as a material for forming a vertical alignment film, a compound 3.0 represented by the following formula (I-21) is added to a polyimide solution containing 3% of a polyimide precursor (trade name: JALS2131-R6, manufactured by JSR). % Containing solution was used. The other conditions were the same as in Example 1, and a liquid crystal display element of Example 5 was obtained.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied to cure the compound represented by the formula (I-21). As the irradiation device, UIS-S2511RZ manufactured by Ushio Electric Co., Ltd. and USH-250BY manufactured by Ushio Electric Co., Ltd. are used as an ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 300 seconds. Got. The liquid crystal display element of Example 5 had a pretilt angle as in Example 1, and the pretilt angle was maintained even when the alternating electric field was turned off after the polymerizable compound was cured.

Table 11 below shows properties of the liquid crystal composition used in the liquid crystal display element of Example 5, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 5 does not show a significant decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Example 6)
A liquid crystal composition (LC-A6) containing the compounds shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 5, and the liquid crystal display element of Example 6 was obtained.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied to cure the compound represented by the formula (I-21). As the irradiation device, UIS-S2511RZ manufactured by USHIO INC. And USH-250BY manufactured by USHIO ELECTRIC CO., LTD. Are used as UV lamps, and the liquid crystal display device is irradiated with UV rays at 20 mW for 300 seconds. Got. The liquid crystal display element of Example 6 had a pretilt angle similar to that of Example 5, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured.

Table 13 below shows the physical properties of the liquid crystal composition used in the liquid crystal display element of Example 6, the VHR before and after UV irradiation, the drop mark evaluation and the burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 6 does not show a significant decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Example 7)
A liquid crystal composition (LC-B) containing the compounds shown in the following table was prepared, and the liquid crystal composition was used. Further, as a material for forming a vertical alignment film, a compound 3.0 represented by the following formula (I-33) is added to a polyimide solution containing 3% of a polyimide precursor (trade name: JALS2131-R6, manufactured by JSR). % Containing solution was used. Other conditions were the same as in Example 1, and a liquid crystal display element of Example 7 was obtained.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied to cure the compound represented by the formula (I-33). As the irradiation device, UIS-S2511RZ made by Ushio Electric Co., Ltd. and USH-250BY made by Ushio Electric Co., Ltd. are used as an ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 300 seconds. Got. The liquid crystal display element of Example 7 had a pretilt angle as in Example 1, and the pretilt angle was maintained even when the alternating electric field was turned off after the polymerizable compound was cured.

Table 15 below shows the physical properties of the liquid crystal composition used in the liquid crystal display element of Example 7, the VHR before and after UV irradiation, the drop mark evaluation and the burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 7 does not show a significant decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Comparative Example 2)
As a material for forming a vertical alignment film, a compound represented by the following formula (Va-1-1) is added to a polyimide solution containing 3% of a polyimide precursor (trade name: JALS2131-R6, manufactured by JSR). A liquid crystal display element of Comparative Example 2 was obtained in the same manner as in Example 7 except that a solution containing 1% was used.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied, and the polymerizable compound having a reactive group in the alignment film was cured. As the irradiation device, UIS-S2511RZ made by USHIO ELECTRIC CO., LTD. And USH-250BY made by USHIO ELECTRIC CO., LTD. Are used as an ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 600 seconds. Got. The liquid crystal display element was irradiated with ultraviolet rays under the same conditions as in Example 7 (300 msec at 20 mW) to give a pretilt angle, but the polymerizable compound having a reactive group in the alignment film was insufficiently cured. Since the pretilt angle was not stably given, irradiation of 20 mW and 600 seconds was required to maintain the pretilt angle.

Table 16 below shows each physical property of the liquid crystal composition used in the liquid crystal display element of Comparative Example 2, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, since the alignment film material of Comparative Example 2 does not contain the polymerizable compound represented by the general formula (I), UV irradiation for curing the polymerizable compound having the polymerizable property in the alignment film is performed. As a result of an increase in the total energy amount, a decrease in VHR was observed, and a decrease in physical properties due to decomposition of the liquid crystal compound in the liquid crystal composition was confirmed.

(Example 8)
A liquid crystal composition (LC-B2) containing the compounds 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 8 was obtained.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied to cure the compound represented by the formula (I-1). As the irradiation device, UIS-S2511RZ manufactured by USHIO INC. And USH-250BY manufactured by USHIO ELECTRIC CO., LTD. Are used as UV lamps, and the liquid crystal display device is irradiated with UV rays at 20 mW for 300 seconds. Got. The liquid crystal display element of Example 8 had a pretilt angle as in Example 1, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured.

Table 18 below shows the physical properties of the liquid crystal composition used in the liquid crystal display element of Example 8, the VHR before and after UV irradiation, the drop mark evaluation and the burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 8 does not show a decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

Example 9
A first substrate (common electrode substrate) having a transparent electrode layer and a color filter layer made of a transparent common electrode, and a second substrate (pixel) having a pixel electrode layer having a transparent pixel electrode driven by an active element Electrode substrate).

A vertical alignment film material containing a polyimide precursor and a polymerizable compound having a polymerizable group is applied to each of the common electrode substrate and the pixel electrode substrate by spin coating, and the applied film is heated at 200 ° C. The polyimide precursor in the alignment film material was cured to form a 100 nm vertical alignment film on the surface of each substrate. At this stage, the polymerizable compound having a polymerizable group is not cured in the vertical alignment film.

As a material for forming a vertical alignment film, an N-methyl-2-pyrrolidone solution containing 3% of a polyimide derivative represented by the following formula and 3.0% of a polymerizable compound represented by the formula (I-1) is used. It was.

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

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied to cure the polymerizable compound having the reactive group. As an irradiation device, UIS-S2511RZ manufactured by USHIO INC. And USH-250BY manufactured by USHIO ELECTRIC CO., LTD. Are used as UV lamps, and the liquid crystal display device is irradiated with UV rays at 20 mW for 300 seconds. Got. By this step, a vertical alignment film containing a polymer of a polymerizable compound having a polyimide skeleton as a main chain and a polymerizable group as a side chain is formed, and a pretilt angle is given to the liquid crystal molecules in the liquid crystal composition layer. The

The liquid crystal display element of Example 9 has pretilt angles in different directions in the four sections according to the slits of the pixel electrode as shown in FIG. 2, and the AC electric field is turned off after the polymerizable compound is cured. The pretilt angle was maintained.

Table 20 below shows each physical property of the liquid crystal composition used in the liquid crystal display element of Example 9, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 9 does not show a significant decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Comparative Example 3)
As a material for forming a vertical alignment film, an N-methyl-2-pyrrolidone solution containing 3% of a polyimide derivative represented by the following formula and 3% of a polymerizable compound represented by the formula (Va-1-1) is used. A liquid crystal display element of Comparative Example 3 was obtained in the same manner as Example 9 except for the above.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied, and the polymerizable compound having a reactive group in the alignment film was cured. As the irradiation device, UIS-S2511RZ made by USHIO ELECTRIC CO., LTD. And USH-250BY made by USHIO ELECTRIC CO., LTD. Are used as an ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 600 seconds. Got. The liquid crystal display element was irradiated with ultraviolet rays under the same conditions as in Example 9 (300 msec at 20 mW) to give a pretilt angle, but the polymerizable compound having a reactive group in the alignment film was not sufficiently cured. Since the pretilt angle was not stably given, irradiation of 20 mW and 600 seconds was required to maintain the pretilt angle.

Table 21 below shows the physical properties of the liquid crystal composition used in the liquid crystal display element of Comparative Example 3, the VHR before and after UV irradiation, the drop mark evaluation and the burn-in evaluation of the obtained liquid crystal display element. As a result, since the alignment film material of Comparative Example 3 does not contain the polymerizable compound represented by the general formula (I), UV irradiation for curing the polymerizable compound having the polymerizable property in the alignment film is performed. As a result of an increase in the total energy amount, a decrease in VHR was observed, and a decrease in physical properties due to decomposition of the liquid crystal compound in the liquid crystal composition was confirmed.

(Example 10)
A liquid crystal composition (LC-A3) containing the compounds shown in the following table was prepared, and the liquid crystal composition was used. Otherwise, the conditions were the same as in Example 9, and the liquid crystal display element of Example 10 was obtained.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied to cure the polymerizable compound having the reactive group. The liquid crystal display element of Example 10 was irradiated with UV light at 20 mW for 600 seconds using USH-250BY manufactured by USHIO INC. As a UV lamp as well as UIS-S2511RZ manufactured by USHIO ELECTRIC CO., LTD. Got. The liquid crystal display element of Example 10 had a pretilt angle as in Example 9, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured.

Table 23 below shows properties of the liquid crystal composition used in the liquid crystal display element of Example 10, VHR before and after UV irradiation, drop mark evaluation and image sticking evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 10 does not show a significant decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Example 11)
A liquid crystal composition (LC-A6) containing the compounds shown in the following table was prepared, and the liquid crystal composition was used. Further, as a material for forming a vertical alignment film, an N-methyl-2-pyrrolidone solution containing 3% of a polyimide derivative represented by the following formula and 3% of a polymerizable compound represented by the following formula (I-21) Was used. Otherwise, the conditions were the same as in Example 9, and the liquid crystal display element of Example 11 was obtained.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied to cure the polymerizable compound having the reactive group. The liquid crystal display element of Example 11 was irradiated with UV light at 20 mW for 600 seconds using USH-250BY made by USHIO ELECTRIC CO., LTD. Together with UIS-S2511RZ made by USHIO ELECTRIC CO., LTD. Got. The liquid crystal display element of Example 11 had a pretilt angle as in Example 9, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured.

Table 25 below shows the physical properties of the liquid crystal composition used in the liquid crystal display element of Example 11, the VHR before and after UV irradiation, the drop mark evaluation and the burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 11 does not show a significant decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

Example 12
A liquid crystal composition (LC-B) containing the compounds shown in the following table was prepared, and the liquid crystal composition was used. Further, as a material for forming a vertical alignment film, an N-methyl-2-pyrrolidone solution containing 3% of a polyimide derivative represented by the following formula and 3% of a polymerizable compound represented by the following formula (I-33) Was used. Otherwise, the conditions were the same as in Example 9, and the liquid crystal display element of Example 12 was obtained.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied to cure the polymerizable compound having the reactive group. The liquid crystal display element of Example 12 was irradiated with UV light at 20 mW for 600 seconds using USH-250BY made by USHIO ELECTRIC CO., LTD. Got. The liquid crystal display element of Example 12 had a pretilt angle as in Example 9, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured.

Table 27 below shows properties of the liquid crystal composition used in the liquid crystal display element of Example 12, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 12 does not show a significant decrease in VHR before and after UV irradiation. Since the alignment film material contains the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy when the polymerizable compound having a polymerizable group in the alignment film is polymerized is determined. This is considered to be because it can be kept low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Comparative Example 4)
As a material for forming a vertical alignment film, an N-methyl-2-pyrrolidone solution containing 3% of a polyimide derivative represented by the following formula and 3% of a polymerizable compound represented by the formula (Va-1-1) is used. A liquid crystal display element of Comparative Example 4 was obtained in the same manner as Example 12 except that.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied, and the polymerizable compound having a reactive group in the alignment film was cured. As the irradiation device, UIS-S2511RZ manufactured by USHIO INC. And USH-250BY manufactured by USHIO ELECTRIC CO., LTD. Are used as UV lamps, and the liquid crystal display device is irradiated with UV rays at 20 mW for 600 seconds. Got. The liquid crystal display element was irradiated with ultraviolet rays under the same conditions as in Example 12 (20 mW for 300 seconds) to give a pretilt angle, but the polymerizable compound having a reactive group in the alignment film was not sufficiently cured. Since the pretilt angle was not stably given, irradiation of 20 mW and 600 seconds was required to maintain the pretilt angle.

Table 28 below shows properties of the liquid crystal composition used in the liquid crystal display element of Comparative Example 4, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, since the alignment film material of Comparative Example 4 does not contain the polymerizable compound represented by the general formula (I), UV irradiation for curing the polymerizable compound having the polymerizable property in the alignment film is performed. As a result of an increase in the total energy amount, a decrease in VHR was observed, and a decrease in physical properties due to decomposition of the liquid crystal compound in the liquid crystal composition was confirmed.

(Example 13)
A first substrate (common electrode substrate) having a transparent electrode layer and a color filter layer made of a transparent common electrode, and a second substrate (pixel) having a pixel electrode layer having a transparent pixel electrode driven by an active element Electrode substrate).

A vertical alignment film material containing a polymerizable liquid crystal compound and a polymerization initiator was applied to each of the common electrode substrate and the pixel electrode substrate by a spin coating method to form a precursor layer of a vertical alignment film having a thickness of 200 nm. As a material for forming a vertical alignment film, 3.0% of a polymerizable compound represented by the following formula (I-1) and 97.0% of UCL-011-K1 (DIC Corporation) polymerizable compound were used. .

Each of the substrates coated with the vertical alignment film forming material was heated in a constant temperature bath at 70 ° C. for 15 minutes, whereby the polymerizable liquid crystal compound in the applied vertical alignment film forming material was changed to an isotropic liquid.

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

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

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied, and the polymerizable compound was cured. As the irradiation device, UIS-S2511RZ made by USHIO ELECTRIC CO., LTD. And USH-250BY made by USHIO ELECTRIC CO., LTD. Are used as an ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 300 seconds. Got. By this step, a vertical alignment film containing a polymer of a polymerizable liquid crystal compound is formed, and a pretilt angle is imparted to the liquid crystal molecules in the liquid crystal composition layer.

The liquid crystal display element of Example 13 has pretilt angles in different directions in the four sections according to the slits of the pixel electrode as shown in FIG. 2, and the AC electric field is turned off after the polymerizable liquid crystal compound is cured. But the pretilt angle was maintained.

The following table shows each physical property of the liquid crystal composition used in the liquid crystal display element of Example 13, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 13 does not show a significant decrease in VHR before and after UV irradiation. This is because the alignment film material contains the polymerizable compound represented by the general formula (I), so that the total amount of UV irradiation energy when polymerizing the polymerizable liquid crystal compound in the alignment film can be kept low. Therefore, it is considered that decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Comparative Example 5)
A liquid crystal display element of Comparative Example 5 was obtained in the same manner as in Example 13 except that 100% of UCL-011-K1 (manufactured by DIC Corporation) was used as the vertical alignment film forming material. It was.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied, and the polymerizable compound was cured. As an irradiation device, UIS-S2511RZ made by USHIO ELECTRIC CO., LTD. And USH-250BY made by USHIO ELECTRIC CO., LTD. Are used as an ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 600 seconds. Got. The liquid crystal display element was irradiated with ultraviolet rays under the same conditions as in Example 13 (20 mW for 300 seconds) to give a pretilt angle. However, the polymerizable liquid crystal compound in the alignment film was insufficiently cured and stable. Since the pretilt angle was not given, the irradiation of 600 m at 20 mW was required to maintain the pretilt angle.

Table 31 below shows properties of the liquid crystal composition used in the liquid crystal display element of Comparative Example 5, VHR before and after UV irradiation, drop mark evaluation of the obtained liquid crystal display element, and burn-in evaluation. As a result, since the alignment film material of Comparative Example 5 does not contain the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy for curing the polymerizable liquid crystal compound in the alignment film As a result, the VHR decreased, and the physical properties decreased due to the decomposition of the liquid crystal compound in the liquid crystal composition.

(Example 14)
A liquid crystal composition (LC-A3) containing the compounds shown in the following table was prepared, and the liquid crystal display element of Example 14 was obtained under the same conditions as in Example 13 except that the liquid crystal composition was used.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied, and the polymerizable compound was cured. The liquid crystal display element of Example 14 was irradiated with UV light at 20 mW for 300 seconds using USH-250BY made by USHIO ELECTRIC CO., LTD. Together with UIS-S2511RZ made by USHIO ELECTRIC CO., LTD. Got. The liquid crystal display element of Example 14 had a pretilt angle as in Example 13, and the pretilt angle was maintained even when the alternating electric field was turned off after the polymerizable compound was cured.

Table 33 below shows properties of the liquid crystal composition used in the liquid crystal display element of Example 14, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 14 does not show a significant decrease in VHR before and after UV irradiation. This is because the alignment film material contains the polymerizable compound represented by the general formula (I), so that the total amount of UV irradiation energy when polymerizing the polymerizable liquid crystal compound in the alignment film can be kept low. Therefore, it is considered that decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Example 15)
A liquid crystal composition (LC-A6) containing the compounds shown in the following table was prepared, and the liquid crystal composition was used. As the material for forming the vertical alignment film, 3.0% of a polymerizable compound represented by the following formula (I-21) and 97.0% of UCL-011-K1 (manufactured by DIC Corporation) were used. Otherwise, the liquid crystal display element of Example 15 was obtained under the same conditions as in Example 13.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied, and the polymerizable compound was cured. As the irradiation device, UIS-S2511RZ manufactured by USHIO INC. And USH-250BY manufactured by USHIO ELECTRIC CO., LTD. Are used as UV lamps, and the liquid crystal display device is irradiated with UV rays at 20 mW for 300 seconds. Got. The liquid crystal display element of Example 15 had a pretilt angle similar to that of Example 13, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured.

Table 35 below shows properties of the liquid crystal composition used in the liquid crystal display element of Example 15, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 15 does not show a significant decrease in VHR before and after UV irradiation. This is because the alignment film material contains the polymerizable compound represented by the general formula (I), so that the total amount of UV irradiation energy when polymerizing the polymerizable liquid crystal compound in the alignment film can be kept low. Therefore, it is considered that decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Example 16)
A liquid crystal composition (LC-B) containing the compounds shown in the following table was prepared, and the liquid crystal composition was used. As a material for forming the vertical alignment film, 3.0% of a polymerizable compound represented by the following formula (I-33) and 97.0% of UCL-011-K1 (manufactured by DIC Corporation) were used. Otherwise, the liquid crystal display element of Example 16 was obtained under the same conditions as in Example 13.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied, and the polymerizable compound was cured. The liquid crystal display element of Example 16 was irradiated with UV light at 20 mW for 300 seconds using USH-250BY made by USHIO INC. With UIS-S2511RZ made by USHIO ELECTRIC CO., LTD. Got. The liquid crystal display element of Example 16 had a pretilt angle similar to that of Example 13, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured.

Table 37 below shows properties of the liquid crystal composition used in the liquid crystal display element of Example 16, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, the liquid crystal composition used in the liquid crystal display element of Example 16 does not show a significant decrease in VHR before and after UV irradiation. This is because the alignment film material contains the polymerizable compound represented by the general formula (I), so that the total amount of UV irradiation energy when polymerizing the polymerizable liquid crystal compound in the alignment film can be kept low. Therefore, it is considered that decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(Comparative Example 6)
A liquid crystal display device of Comparative Example 6 was obtained in the same manner as in Example 16 except that 100% of UCL-011-K1 (manufactured by DIC Corporation) was used as the vertical alignment film forming material. It was.

The obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular AC electric field was applied, and the polymerizable compound was cured. As the irradiation device, UIS-S2511RZ manufactured by USHIO INC. And USH-250BY manufactured by USHIO ELECTRIC CO., LTD. Are used as UV lamps, and the liquid crystal display device is irradiated with UV rays at 20 mW for 600 seconds. Got. The liquid crystal display element was irradiated with ultraviolet rays under the same conditions as in Example 16 (300 msec at 20 mW) to give a pretilt angle, but the polymerizable liquid crystal compound in the alignment film was not sufficiently cured and stable. Since the pretilt angle was not given, the irradiation of 600 m at 20 mW was required to maintain the pretilt angle.

Table 38 below shows properties of the liquid crystal composition used in the liquid crystal display element of Comparative Example 6, VHR before and after UV irradiation, drop mark evaluation and burn-in evaluation of the obtained liquid crystal display element. As a result, since the alignment film material of Comparative Example 6 does not contain the polymerizable compound represented by the general formula (I), the total amount of UV irradiation energy for curing the polymerizable liquid crystal compound in the alignment film As a result, the VHR decreased, and the physical properties decreased due to the decomposition of the liquid crystal compound in the liquid crystal composition.

DESCRIPTION OF SYMBOLS 10 ... Liquid crystal display element, 11 ... 1st board | substrate, 12 ... 2nd board | substrate, 13 ... Liquid crystal composition layer, 14 ... Common electrode, 15 ... Pixel electrode, 16 ... Vertical alignment film, 17 ... Vertical alignment film, 18 ... Color filter, 19 ... Liquid crystal molecule, 20 ... Polymer layer, 21 ... Polymer layer

Claims

A pair of substrates having a first substrate and a second substrate; a liquid crystal composition layer sandwiched between the substrates; and electrodes on at least one of the first substrate and the second substrate. And controlling 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 on at least one of the first substrate and the second substrate. A liquid crystal composition having an alignment film containing a polymer and constituting the liquid crystal composition layer has the following general formula (N-1), general formula (N-2), and general formula (N-3):

(Wherein, R N11 , R N12 , R N21 , R N22 , R N31 and R N32 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or non-adjacent 2 in the alkyl group Two or more —CH 2 — may be each independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
A N11 , A N12 , A N21 , A N22 , A N31, and A N32 are each independently (a) a 1,4-cyclohexylene group (one —CH 2 — or adjacent to each other in this group). And two or more —CH 2 — may be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or not adjacent 2 More than one -CH = may be replaced by -N =.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—. , —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—,
XN21 represents a hydrogen atom or a fluorine atom,
T N31 represents —CH 2 — or an oxygen atom,
n N11 , n N12 , n N21 , n N22 , n N31, and n N32 each independently represent an integer of 0 to 3, but n N11 + n N12 , n N21 + n N22, and n N31 + n N32 are each independently When there are a plurality of A N11 to A N32 and Z N11 to Z N32 , they may be the same or different. ) Containing one or more compounds selected from the group of compounds represented by
The compound having a polymerizable group is represented by the general formula (I)

(Wherein X 10 and X 11 each independently represent a hydrogen atom or a methyl group, and Sp 3 and Sp 4 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —X— ( CH 2 ) t — (wherein t represents an integer of 2 to 7, X represents —O—, —OCOO—, —OCO—, or —COO—, and X is bonded to the phenanthrene ring) .), And the phenanthrene ring in the formula is a liquid crystal display element containing one or more compounds represented by the following formula: any hydrogen atom may be substituted with a fluorine atom.
The liquid crystal display element according to claim 1, comprising a plurality of pixels, and having two or more regions having different pretilt angles in the pixels.
3. The liquid crystal display element according to claim 1, wherein the first substrate has a common electrode and the second substrate has a pixel electrode.
4. The alignment film for applying a charge substantially perpendicularly to the first substrate and the second substrate between the common electrode and the pixel electrode to control liquid crystal molecules in the liquid crystal composition layer. A liquid crystal display element according to 1.
5. The alignment film according to claim 1, wherein the alignment film includes a polymer that controls an alignment direction of liquid crystal molecules in the liquid crystal composition layer, or is formed from a cured product of a polymerizable liquid crystal compound. A liquid crystal display element according to 1.
The polymer for controlling the orientation direction of the liquid crystal molecules in the liquid crystal composition layer includes a polymer of a compound having a polymerizable group, or a polyimide skeleton as a main chain and a crosslinkable functional group as a side chain. The liquid crystal display element of Claim 5 containing the polymer of the polymeric compound which has.
The liquid crystal display device according to any one of claims 1 to 6, further comprising a polymer of one or more polymerizable compounds that controls and stabilizes alignment of liquid crystal molecules on the surface of the alignment film.
After applying an alignment material to at least one of the first substrate and the second substrate and forming the alignment film material by heating, the first substrate and the second substrate having electrodes on at least one of them By sandwiching a liquid crystal composition and irradiating the electrode with active energy rays in a state where a voltage is applied, the polymerizable group of the compound having a polymerizable group contained in the alignment film material is polymerized to form the liquid crystal. The liquid crystal composition has an alignment film that controls the alignment direction of liquid crystal molecules in the composition layer, and the liquid crystal composition has the following general formula (N-1), general formula (N-2), and general formula (N-3):

(Wherein, R N11 , R N12 , R N21 , R N22 , R N31 and R N32 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or non-adjacent 2 in the alkyl group Two or more —CH 2 — may be each independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
A N11 , A N12 , A N21 , A N22 , A N31, and A N32 are each independently (a) a 1,4-cyclohexylene group (one —CH 2 — or adjacent to each other in this group). And two or more —CH 2 — may be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or not adjacent 2 More than one -CH = may be replaced by -N =.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—. , —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—,
XN21 represents a hydrogen atom or a fluorine atom,
T N31 represents —CH 2 — or an oxygen atom,
n N11 , n N12 , n N21 , n N22 , n N31, and n N32 each independently represent an integer of 0 to 3, but n N11 + n N12 , n N21 + n N22, and n N31 + n N32 are each independently When there are a plurality of A N11 to A N32 and Z N11 to Z N32 , they may be the same or different. ) Containing one or more compounds selected from the group of compounds represented by
The compound having a polymerizable group is represented by the general formula (I)

(Wherein X 10 and X 11 each independently represent a hydrogen atom or a methyl group, and Sp 3 and Sp 4 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —X— (CH 2 ) t — (wherein t represents an integer of 2 to 7, X represents —O—, —OCOO—, —OCO—, or —COO—, and X represents a bond to the phenanthrene ring. The phenanthrene ring in the formula represents a method for producing a liquid crystal display device containing one or more compounds represented by the following formula: any hydrogen atom may be substituted with a fluorine atom.
The liquid crystal display element according to claim 8, wherein the alignment film material includes a polymer that controls an alignment direction of liquid crystal molecules in the liquid crystal composition layer, or is formed from a cured product of a polymerizable liquid crystal compound. Production method.
The polymer for controlling the alignment direction of the liquid crystal molecules in the liquid crystal composition layer includes a polymer of a compound having a polymerizable group, or has a polyimide skeleton as a main chain and a crosslinkable functional group as a side chain. The manufacturing method of the liquid crystal display element of Claim 9 containing the polymer of the polymeric compound which has this.
The method for producing a liquid crystal display element according to claim 9 or 10, further comprising a polymer of one or more polymerizable compounds that controls and stabilizes the alignment of liquid crystal molecules on the surface of the alignment film.
The active energy ray is ultraviolet light, the intensity thereof is 2 mW / cm −2 to 100 mW / cm −2 , and the total irradiation energy amount is 10 J to 300 J. Liquid crystal display element manufacturing method.