JPWO2017183683A1 - Liquid crystal display device and method of manufacturing the same - Google Patents

Abstract

It is difficult to generate drip marks during production without deteriorating various characteristics as liquid crystal display elements such as dielectric anisotropy, viscosity, upper limit temperature of nematic phase, rotational viscosity (γ1), etc. and burn-in characteristics of liquid crystal display elements Provided are a highly reliable liquid crystal display element having various characteristics as a liquid crystal display element and a method of manufacturing the same. The liquid crystal display device of the present invention comprises a first substrate, a second substrate, and a liquid crystal composition layer sandwiched between the first substrate and the second substrate, and the first substrate and the second substrate Of at least one of the first substrate and the second substrate, the weight of a compound having a polymerizable group for controlling the orientation direction of liquid crystal molecules in the liquid crystal composition layer on at least one of the first substrate and the second substrate It has a united film and an alignment film containing a polymer having a thermally decomposable group.

Description

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

  Liquid crystal display devices are used in watches, calculators, various measurement devices, panels for automobiles, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, and the like. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type (vertical alignment; VA) using a TFT (thin film transistor), and IPS. (In-plane switching) type etc. are mentioned. The liquid crystal composition used in these liquid crystal display devices is stable against external factors such as moisture, air, heat, light and the like, and exhibits a liquid crystal phase in a temperature range as wide as possible around room temperature, and is low It is required to be viscous and to have a low drive voltage. Furthermore, the liquid crystal composition has several to dozens of compounds in order to make the dielectric anisotropy (Δε), the refractive index anisotropy (Δn), etc. optimum values for each liquid crystal display element. It consists of

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

  On the other hand, in order to improve the viewing angle characteristics of the VA type display, an MVA (multi-domain vertical alignment) type in which the alignment direction of liquid crystal molecules in a pixel is divided into a plurality by providing projection structures on the substrate. Liquid crystal display devices have come into widespread use. Although the MVA type liquid crystal display device 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 distant portion, 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 protrusion structure. In order to solve this problem, unlike ordinary MVA liquid crystal display devices, PSA is used as a method of providing a uniform pretilt angle in divided pixels without providing a non-transmissive protrusion structure in the cell. Liquid crystal display devices (including polymer sustained alignment: including polymer stabilized alignment, and PS liquid crystal display devices (including polymer stabilized)) have been developed. In a PSA liquid crystal display element, a small amount of reactive monomer is added to a liquid crystal composition, and after introducing the liquid crystal composition into a liquid crystal cell, a voltage is applied between the electrodes and irradiation of active energy rays results in the liquid crystal composition. Manufactured by polymerizing a reactive monomer of Therefore, it is possible to provide an appropriate pretilt angle in the divided pixels, and as a result, it is possible to achieve an improvement in contrast by transmittance improvement and a high-speed response by applying a uniform pretilt angle (see, for example, Patent Document 1). However, in the PSA liquid crystal display element, it is necessary to add a reactive monomer to the liquid crystal composition, and in the active matrix liquid crystal display element where high voltage holding ratio is required, there are many problems and display defects such as burn-in There was also a problem that occurred.

  Reactive monomers are mixed into the alignment film material as a method of improving the defects of the PSA liquid crystal display element and providing a uniform pretilt angle to liquid crystal molecules without mixing foreign substances other than the liquid crystal material into the liquid crystal composition. After introducing the liquid crystal composition into the liquid crystal cell, a system has been developed in which reactive monomers in the alignment film are polymerized by irradiation of active energy rays while applying a voltage between the electrodes (for example, Patent Document 2, 3 and 4).

  On the other hand, with the increase in the screen size of liquid crystal display elements, the manufacturing method of liquid crystal display elements has also undergone great changes. That is, since the conventional vacuum injection method requires a long time for the manufacturing process when manufacturing a large panel, in the manufacture of a large panel, the manufacturing method by an ODF (one-drop-fill) method is the mainstream (See, for example, Patent Document 5). Since this method can shorten the injection time as compared with the vacuum injection method, it is the mainstream of the manufacturing method of the liquid crystal display element. However, the phenomenon in which the dripping marks on which the liquid crystal composition is dropped remains in the dropped shape on the liquid crystal display element even after the liquid crystal display element is manufactured has become a new problem. In addition, with a dripping mark, when displaying in black, it defines as the phenomenon in which the mark which dripped the liquid-crystal composition floats up white. In particular, in the above-described system in which reactive monomers are added to the alignment film material to impart a pretilt angle to liquid crystal molecules, reactive monomers that are foreign substances are present in the alignment film when the liquid crystal composition is dropped onto the substrate. Therefore, the problem of drip marks is likely to occur. Also, in general, the generation of the dripping marks often occurs due to the selection of the liquid crystal material, and the cause is not clear.

  As a method of suppressing the dripping 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 dripping mark generated in relation to the alignment control film. Japanese Patent Application Laid-Open Publication No. 2000-147118 discloses a method of However, this method alone has the problem of burn-in of the display caused by the reactive monomer added to the liquid crystal composition as in the PSA method and the like, and the effect is also insufficient for suppression of dripping marks. There has been a demand for the development of a liquid crystal display element which hardly causes burn-in and dripping marks while maintaining the basic characteristics as a display element. Furthermore, since the liquid crystal display element is exposed to UV light at the time of its production and use, it is important that these UV irradiations do not affect the display even if degradation or the like does not occur.

Therefore, in Japanese Patent No. 05299595 (Patent Document 12), etc., a reactive monomer is contained in the vertical alignment film, and the liquid crystal composition is introduced into the liquid crystal cell and then activated while applying a voltage between the electrodes. The liquid crystal display element which combined a specific liquid crystal composition was proposed in the system which polymerizes the reactive monomer in alignment film by irradiation of an energy ray. By this liquid crystal display element, various characteristics as a liquid crystal display element such as dielectric anisotropy, viscosity, upper limit temperature of nematic phase, rotational viscosity (γ ₁ ) and the like, and the burn-in characteristics of the liquid crystal display element are not deteriorated. It has become possible to provide a liquid crystal display element in which a dripping mark is unlikely to occur and a method of manufacturing the same. However, with the advancement of requirements for liquid crystal display elements, there has been a demand for further improvement of various properties as liquid crystal display elements, in particular, development of liquid crystal display elements having a stable pretilt angle.

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

The present invention has been made in view of the above circumstances, and has various characteristics as a liquid crystal display element such as dielectric anisotropy, viscosity, upper limit temperature of nematic phase, rotational viscosity (γ ₁ ), and burn-in of the liquid crystal display element A liquid crystal display device having various characteristics as a liquid crystal display device which is hard to generate dripping marks at the time of manufacture without deteriorating the characteristics, and is stably provided with a pretilt angle, and a method of manufacturing the same. I assume.

  As a result of examining various liquid crystal compositions in order to solve the above problems, the present inventors have found that the problems can be solved by containing a polymer having a thermally decomposable group in an alignment film. We came to complete the invention.

  That is, the present invention comprises a first substrate, a second substrate, and a liquid crystal composition layer sandwiched between the first and second substrates, and the first substrate and the second substrate A polymer of a compound having an electrode on at least one side and having a polymerizable group on at least one of the first substrate and the second substrate to control the alignment direction of liquid crystal molecules in the liquid crystal composition layer And an alignment film containing a thermally degradable polymer having a thermally degradable group, wherein the dielectric anisotropy (Δε) of the liquid crystal composition constituting the liquid crystal composition layer is negative. It is a manufacturing method of the liquid crystal display element made into said, and the said liquid crystal display element.

  According to the present invention, the liquid crystal display device is excellent in high-speed response, less occurrence of burn-in, less generation of drip marks at the time of manufacture, excellent in various characteristics as liquid crystal display device, and stably pretilt angle Can be effectively used as a display element such as a liquid crystal TV, a monitor or the like.

  Further, according to the present invention, it is possible to manufacture an efficient liquid crystal display element in which a dripping mark hardly occurs.

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

The present embodiment is specifically described in order to better understand the spirit of the invention, and does not limit the present invention unless otherwise specified.
[Liquid crystal display element]
The liquid crystal display device of the present invention is a liquid crystal display device having a liquid crystal composition layer sandwiched between a pair of substrates, wherein a voltage is applied to the liquid crystal composition layer to convert liquid crystal molecules in the liquid crystal composition layer into Frederickis. The transfer is based on the principle of acting as an optical switch, and in this respect, well known conventional techniques can be used.

  In a conventional vertical alignment liquid crystal display device having two substrates for conducting a free-radical transfer of liquid crystal molecules, in general, a method of applying charges vertically between the two substrates is employed. In this case, one electrode is a common electrode, and the other electrode is a pixel electrode. The following shows the most typical embodiment of this scheme.

  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 the present 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 A common electrode 14 provided on the surface of the substrate 11 facing the liquid crystal composition layer 13, a pixel electrode 15 provided on the surface facing the liquid crystal composition layer 13 of the second substrate 12, and a common electrode Vertical alignment film 16 provided on the surface facing liquid crystal composition layer 13 in 14, the vertical alignment film 17 provided on the surface facing liquid crystal composition layer 13 in pixel electrode 15, 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 of

  A glass substrate or a plastic substrate is used as the first substrate 11 and the second substrate 12.

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

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

  The pixel electrode 15 is usually made of a transparent material such as indium-doped tin oxide (ITO).

  The pixel electrodes 15 are arranged in a matrix on the second substrate 12. The pixel electrode 15 is controlled by the drain electrode of an active element represented by a TFT switching element, and the TFT switching element has gate lines which are address signal lines and source lines which are data lines in a matrix. Here, the configuration of the TFT switching element is not shown.

  In the case of performing pixel division in which the falling direction of liquid crystal molecules in the pixel is divided into several regions in order to improve the viewing angle characteristics, a slit (forming an electrode having a stripe or V-shaped pattern in each pixel) The pixel electrode may be provided with a portion that is not

  FIG. 2 is a schematic plan view showing a typical form of a slit electrode (comb electrode) in the case of dividing the inside of a pixel into four regions. The slit electrode has a slit in the form of a comb in four directions from the center of the pixel, so that liquid crystal molecules in each pixel, which are approximately vertically aligned with the substrate when no voltage is applied, are accompanied by the voltage application. Direct the director of the liquid crystal molecules in four different directions and approach the horizontal alignment. As a result, since the alignment orientation of the liquid crystal in the pixel can be divided into a plurality, it has extremely wide viewing angle characteristics.

  As a method for dividing the pixel, in addition to the 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, etc. are used. . Although the alignment direction of liquid crystal molecules can be divided by these methods, a configuration using a slit electrode is preferable in terms of transmittance and easiness of production. Since the pixel electrode provided with the slit does not have a driving force with respect to the liquid crystal molecules when no voltage is applied, it can not apply a pretilt angle to the liquid crystal molecules. However, by using the alignment film material used in the present invention in combination, a pretilt angle can be given, and by combining with the slit electrode in which the pixel is divided, a wide viewing angle by the pixel division can be achieved.

In the present invention, having a pretilt angle refers to the direction 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) and the liquid crystal molecules in the no voltage applied state. The director's 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 liquid crystal molecules is substantially vertically aligned with the substrate surface when no voltage is applied. In order to vertically align liquid crystal molecules, a (vertical) alignment film is generally used. 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 polyimide is used as an alignment film material for forming a vertical alignment film, a mixture of tetracarboxylic acid dianhydride and diisocyanate as a polymer compound precursor, a polyamic acid, a polyimide solution in which polyimide is dissolved or dispersed in a solvent is used. In this case, the content of the polyimide 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 10% by mass or less Is more preferred.

  In addition, in the case of using a polysiloxane-based material 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. It is possible to use a polysiloxane solution in which the resulting polysiloxane is dissolved.

  In the liquid crystal display device of the present invention, the vertical alignment films 16 and 17 formed of polyimide or the like include a polymer or the like formed by polymerization of a polymerizable compound having a polymerizable group. The polymerizable compound has a function of fixing the pretilt angle of liquid crystal molecules. That is, by using a slit electrode or the like, it becomes possible to tilt the director of liquid crystal molecules in the pixel in different directions at the time of voltage application. However, even in the configuration using the slit electrode, the liquid crystal molecules are almost vertically aligned with the substrate surface when no voltage is applied, and a pretilt angle is not generated, but a voltage is applied between the electrodes to slightly In the state of being tilted, an appropriate pretilt angle is given by irradiating ultraviolet rays etc. and polymerizing the reactive monomer in the liquid crystal composition.

  In addition, if necessary, the polymer layers 20 and 21 may be polymerized by curing the polymerizable compound while applying a voltage after sandwiching the polymerizable compound contained in the liquid crystal composition between the substrates. The compound may be formed as a polymer on the surface of the vertical alignment films 16 and 17 while the phase separation of the compound.

  The orientation of liquid crystal molecules is determined by 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 formed as necessary. The amount is high, the occurrence of burn-in is small, and the occurrence of dripping marks at the time of production is small.

  In the present invention, substantially vertical means that the director of liquid crystal molecules in vertical alignment is slightly tilted from the vertical direction to give a pretilt angle. Assuming that the pretilt angle is 90 ° in the case of perfect vertical alignment and 0 ° in the case of homogeneous alignment (alignment in the direction horizontal to the substrate surface), substantially vertical is preferably 89.5 to 85 °, 89. More preferably, it is 5 to 87 °.

  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, although it is presumed that the vertical alignment film and the polymerizable compound are intertwined in a complex manner to form a kind of polymer alloy, it can not show the correct structure.

In addition, the polymer layers 20 and 21 formed as needed are separated 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 uniformly formed on the entire surface of the vertical alignment film or formed with a nonuniform sea-island structure is considered to be different depending on the conditions to be manufactured, and the accurate structure is shown I can not do it. FIG. 1 shows the case of uniform formation.
(A thermally decomposable polymer having a thermally decomposable group incorporated in an alignment film)
The alignment film used in the present invention needs to have an alignment control ability to control the alignment direction of the liquid crystal molecules, as well as the vertical alignment ability to align liquid crystal molecules in the liquid crystal composition layer in a direction perpendicular to the substrate surface. Furthermore, in order to stably provide a pretilt angle, it is necessary to make the surface of the alignment film smooth and not to affect the alignment of the liquid crystal composition in contact with the alignment film.

  Therefore, the present invention is characterized in that the alignment film contains at least one or more polymers having a thermally decomposable group. The polymer having a thermally decomposable group is used by being added to the alignment film material, and the surface of the alignment film can be smoothed through the heating step. As a result, an effect of uniformly and stably imparting a pretilt angle formed by a polymer of a compound having a polymerizable group, which controls the alignment direction of liquid crystal molecules in a liquid crystal composition layer described later, is controlled. It is considered as having.

  As a polymer which has the said thermally decomposable group, the polymer whose thermally decomposable group contains a fluorine atom and / or a silicon atom can be mentioned specifically.

  Moreover, it is preferable that the polymer which has a thermally degradable group contains the structural unit represented by the following general formula (I-1-1) or general formula (I-1-2) as a side chain.

(In the general formula (I-1-1) and the general formula (I-1-2), R ¹ and R ² each independently represent a hydrogen atom or a linear or branched C 1-18 carbon atom Represents an organic group, Y ¹ represents an oxygen atom or a sulfur atom, R ⁴ represents a fluorine atom and / or an organic group having a silicon atom, and * represents a bonding site. Is preferred.

In the general formula (I-1-1) and the general formula (I-1-2), ^{R 1} is a hydrogen atom or a linear or branched 1-18 organic group carbon atoms, ^{R 1} Is preferably a hydrogen atom or a methyl group, and R ¹ is more preferably a hydrogen atom.

In General Formula (I-1-1) and General Formula (I-1-2), R ² represents a hydrogen atom or a linear or branched organic group having 1 to 18 carbon atoms, but R ² Is preferably a linear alkyl group having 1 to 12 carbon atoms, and R ² is more preferably a methyl group.

In General Formula (I-1-1) and General Formula (I-1-2), Y ¹ represents an oxygen atom or a sulfur atom, but Y ¹ is preferably an oxygen atom.

In General Formula (I-1-1) and General Formula (I-1-2), R ⁴ represents an organic group having a fluorine atom and / or a silicon atom, but R ⁴ exhibits excellent smoothness. Therefore, a fluorinated alkyl group, a fluorinated alkenyl group, a fluorinated aromatic group, a poly (perfluoroalkylene ether) group, and one or more hydrogen atoms bonded to a silicon atom are each independently a methyl group and a phenylene group Preferred is a polysiloxane group which may be substituted by a group selected from the following: a fluorinated alkyl group having 1 to 12 carbon atoms to which a fluorine atom is directly bonded, and one or more hydrogens bonded to a silicon atom More preferred is a polysiloxane group which may be substituted by a group independently selected from a methyl group and a phenylene group, and the number of carbon atoms to which a fluorine atom is directly bonded is 1 to 8 Fluorinated alkyl group is particularly preferred.

Examples of ^{R 4,} for example, group is preferably represented by the following formula (I-R4-1) ~ formula (I-R4-19).

In the above formulae, * represents a bonding site to Y ¹ , R ^{51 to} R ⁵⁶ each independently represent a hydrogen atom, a methyl group or a phenyl group, and R ^{57 to} R 59 each independently have 1 to 3 carbon atoms And an alkyl group having 1 to 3 carbon atoms, and n5 represents an integer of 1 to 150.

  The polymer having a thermally decomposable group according to the present invention is not limited to the structural units represented by the general formula (I-1-1) or the general formula (I-1-2) within the range not impairing the effects of the present invention. It may contain a structural unit. Specifically, the side chain can be exemplified by the following general formula (I-2-1) or general formula (I-2-2).

(In the general formula (I-2-1) and the general formula (I-2-2), R ¹¹ and R ²¹ each independently represent a hydrogen atom or a linear or branched C 1-18 carbon atom R ¹¹ is an organic group, Y ¹¹ is an oxygen atom or a sulfur atom, R ⁴¹ is an organic group having 1 to 18 carbon atoms, and R ²¹ and R ⁴¹ are bonded to each other to form Y ¹¹ as a hetero atom It may form a ring, and * represents a binding site.)
In the above general formula (I-2-1) and general formula (I-2-2), R ¹¹ represents a hydrogen atom, R ²¹ represents a methyl group, and Y ¹¹ is an oxygen atom or a sulfur atom However, the difference in polarity between the blocked carboxyl group and the regenerated carboxyl group is large, which is preferable. Moreover, as a side chain represented by said general formula (I-2-1) or general formula (I-2-2), following formula (I-2-1-1) or a formula (I-2-2) is mentioned. The side chain represented by -1) is more preferable.

  The polymer having a thermally decomposable group of the present invention can be efficiently produced, for example, by the following method.

  Production method 1: A polymerizable monomer (α) having a hydroxyl group or a carboxyl group and the following general formula (IA)

(In the general formula (IA), R ¹ , R ²¹ and R ²² each is a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is an organic group having a fluorine atom and / or a silicon atom .]
A method of polymerizing the polymerizable monomer after reaction with a vinyl ether compound represented by to obtain a polymerizable monomer having a blocked carboxyl group.

  Production method 2: A method in which a polymer obtained by using a polymerizable monomer (α) having a hydroxyl group or a carboxyl group is reacted with a vinyl ether compound represented by the above general formula (IA).

  Examples of the polymerizable monomer (α) having a hydroxyl group or a carboxyl group include (meth) acrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate and carboxypentyl (meth) ) Acrylate, 2- (Meth) acryloyloxyethyl hexahydrophthalic acid, 2- (Meth) acryloyloxypropyl hexahydrophthalic acid, 2- (Meth) acryloyloxyethyl phthalic acid, 2- (Meth) acryloyl Roxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid and the like can be preferably exemplified. Among them, (meth) acrylic acid is preferable and methacrylic acid is more preferable because it is inexpensive and easy to handle.

  In the present invention, "(meth) acrylate" refers to one or both of methacrylate and acrylate, "(meth) acryloyl group" refers to one or both of methacryloyl group and acryloyl group, and The term "acrylic acid" refers to one or both of methacrylic acid and acrylic acid.

  In the production method 1, after obtaining a polymerizable monomer having a blocked hydroxyl group or carboxyl group, when polymerizing the polymerizable monomer, or in the production method 2, it has a hydroxyl group or carboxyl group When obtaining a polymer obtained using the polymerizable monomer (α), a polymerizable monomer (A) other than the polymerizable monomer (α) is used in combination as long as the effects of the present invention are not impaired. It is also possible to obtain a polymer. Examples of the polymerizable monomer (A) include acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

  Examples of the acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, chlorethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydro Furfuryl acrylate and the like can be mentioned.

  Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydrofuran Furfuryl methacrylate and the like can be mentioned.

  Examples of the acrylamides include acrylamide, N-alkyl acrylamide (as an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl and propyl), N, N-dialkyl acrylamide (as an alkyl group) Are those having 1 to 3 carbon atoms), N-hydroxyethyl-N-methyl acrylamide, N-2-acetamidoethyl-N-acetyl acrylamide and the like.

  Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamide (as an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl and propyl), N, N-dialkyl methacrylamide Examples of the alkyl group include those having 1 to 3 carbon atoms, N-hydroxyethyl-N-methyl methacrylamide, N-2-acetamidoethyl-N-acetyl methacrylamide and the like.

  Examples of the allyl compound include allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.) Allyloxy ethanol etc. are mentioned.

  Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, Hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butyl aminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc., Vinyl esters: vinyl bitylate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate ,vinyl Rate, vinyl caproate, vinyl chloroacetate, vinyl di- chloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl -β- phenyl butyrate, vinyl cyclohexyl carboxylate.

  Examples of the dialkyl itaconic acid include dimethyl itaconate, diethyl itaconate and dibutyl itaconate. Examples of dialkyl esters or monoalkyl esters of fumaric acid include dibutyl fumarate and the like, as well as crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleironitrile, styrene and the like.

  Moreover, the radically polymerizable monomer which has an oxyalkylene group can also be used as a polymerizable monomer (A). As a radically polymerizable monomer having an oxyalkylene group, for example, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, poly (ethylene glycol propylene glycol) mono (meth) acrylate, polyethylene glycol Polypropylene glycol mono (meth) acrylate, poly (ethylene glycol tetramethylene glycol) mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol tetramethylene glycol) mono (meth) acrylate , Polypropylene glycol polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol butylene g) Cole) mono (meth) acrylate, polypropylene glycol polybutylene glycol mono (meth) acrylate, poly (ethylene glycol butylene glycol) mono (meth) acrylate polyethylene glycol polybutylene glycol mono (meth) acrylate poly (tetra ethylene) Glycol butylene glycol) mono (meth) acrylate, polytetraethylene glycol polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly (ethylene glycol trimethylene glycol) mono (meth) acrylate polyethylene Glycol polytrimethylene glycol mono (meth) acrylate, poly (propylene glycol trimethylene glycol) mono (Meth) acrylate, polypropylene glycol polytrimethylene glycol mono (meth) acrylate, poly (trimethylene glycol tetramethylene glycol) mono (meth) acrylate polytrimethylene glycol polytetramethylene glycol mono (meth) acrylate poly ( Examples include butylene glycol trimethylene glycol) mono (meth) acrylate, polybutylene glycol polytrimethylene glycol mono (meth) acrylate and the like.

  In addition, said "poly (ethylene glycol propylene glycol)" means the random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol polypropylene glycol" is the block copolymer of ethylene glycol and propylene glycol. And so on.

  As a commercial item of the radically polymerizable monomer which has the said oxyalkylene group, "NK ester AMP-10G" by Shin-Nakamura Chemical Co., Ltd. make, "NK ester AMP-20G", "NK ester AMP-60G" are mentioned, for example. “NOM, Inc.,“ Blenmer PME-100 ”,“ Blenmer PME-200 ”,“ Blenmer PME-400 ”,“ Blenmer PME-4000 ”,“ Blenmer PP-1000 ”,“ Blenmer PP-500 ” "Blenmer PP-800", "Blenmer 70 PEP-350B", "Blenmer 55 PET-800", "Blenmer 50 POEP-800B", "Blenmer 10PPB-500B", "Blenmer NKH-5050", "Brenmer AP-400", Sartomer Company-made "SR604" etc. That. The radically polymerizable monomers (γ) can be used alone or in combination of two or more.

  Furthermore, a radically polymerizable monomer having a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain can also be used as the polymerizable monomer (A) within the range that does not impair the effect of the present invention. As this radically polymerizable monomer, what is represented with the following general formula (A0) can be illustrated preferably, for example.

[In the above general formula (A0), R represents a hydrogen atom or a methyl group, L represents any one group of the following formulas (L-1) to (L-10), and Rf represents a following formula (Rf -1)-(Rf-7) any one group is represented. ]

(N in the above formulas (L-1), (L-3), (L-5), (L-6) and (L-7) represents an integer of 1 to 8. The above formula (L-8) M) in (L-9) and (L-10) represents an integer of 1 to 8, and n represents an integer of 0 to 8. In the above formulas (L-6) and (L-7) R f ′ ′ represents any one group of the following formulas (R f-1) to (R f -7).

(N in the above formulas (Rf-1) to (Rf-4) is an integer of 1 to 6, for example, preferably an integer of 4 to 6. m in the above formula (Rf-5) is For example, it is an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23. Preferably, m is an integer of 1 to 5 and n is 0 to 4 And the sum of m and n is 4 to 5. In the above formula (Rf-6), m is, for example, an integer of 1 to 6, n is an integer of 1 to 3, and l is It is an integer of 1 to 20, p is an integer of 0 to 5, and the sum of m, p and the product of n and 1 is 2 to 71. Preferably, m is an integer of 1 to 3 N is an integer of 1 to 3; l is an integer of 1 to 6; p is an integer of 0 to 2; and the sum of m, p and the product of n and l is 2 to 23 Is)
As specific examples of the radically polymerizable monomer having the fluorinated alkyl group or poly (perfluoroalkylene ether) chain, for example, the following polymerizable monomers (A-1) to (A-15) etc. It can be preferably exemplified.

  N in Formula (A-13) to Formula (A-15) is, for example, 0 to 20.

  Examples of the vinyl ether compounds represented by the above general formula (IA) include 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1 -Vinyloxyoctane, 3,3,4,4,5,5,6,6,6-nonafluoro-1-vinyloxyhexane etc. are mentioned. Among them, the reaction with the polymer obtained using the polymerizable monomer (α) proceeds easily, and the difference in polarity before and after heating becomes large, which is preferable. In addition, from the viewpoint of the coatability of a polymerizable liquid crystal composition containing a polymer having a thermally degradable group and the ease of lamination after film formation, 3, 3, 4, 5, 4, 5, 6, 7, 6, 7,8,8,8-Tridecafluoro-1-vinyloxyoctane is preferred.

  In order to obtain the thermally degradable group-containing polymer of the present invention, a vinyl ether compound other than the compound represented by the above general formula (IA) can be obtained by combining a vinyl ether compound represented by the general formula (IA) It can also be used together in the range which does not impair the effect of this invention. As such vinyl ether compounds, for example, aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, etc .; Aliphatic vinyl thioether compounds; 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy- 2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, 3,4-dihydro-2H-pyran-2- Cyclic vinyl such as sodium carboxylate Ether compounds, cyclic vinyl thioether compounds corresponding to these.

  In the said manufacturing method 1, the polymerizable monomer ((alpha)) which has a carboxyl group and the vinyl ether compound represented by the said general formula (IA) are made to react. A polymerizable monomer having a blocked carboxyl group is thus obtained. The reaction conditions may include, for example, heating to about 20 to 100 ° C. in the presence of an acid catalyst. And when polymerizing the polymerizable monomer which has the block-ized carboxyl group, it can carry out on the conditions which polymerize the polymerizable monomer ((alpha)) mentioned later.

  Although there is no restriction | limiting in particular as a method to obtain a polymer using a polymerizable monomer ((alpha)) in the said manufacturing method 2, For example, a polymerizable monomer ((alpha)) and a radically polymerizable monomer as needed The method etc. which polymerize ((gamma)) in an organic solvent using a radical polymerization initiator etc. are mentioned. As the organic solvent to be used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like can be mentioned. These are suitably selected in consideration of boiling point, compatibility, and polymerizability. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide, and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethyl thioglycolic acid, octyl thioglycolic acid and the like can be used as required.

  In the production method 2, the polymer and the vinyl ether compound represented by the general formula (IA) can be reacted, for example, by heating to about 20 to 100 ° C. in the presence of an acid catalyst. . The carboxyl group which a polymer has is blocked by this reaction, and the polymer which has a structure represented by said general formula (I-1-1) or general formula (I-1-2) is obtained. The blocked vinyl group is released from the vinyl ether blocked in a high temperature environment, for example, an environment of 150 to 300 ° C., and the carboxyl group is regenerated.

  As a polymer which has the said thermally-degradable group, the polymer which has a structural unit selected from the following general formula (I-1-1-1)-general formula (I-1-2-2) is preferable.

(In the general formula (I-1-1-1) to the general formula (I-1-2-2), R ¹ represents a hydrogen atom or a linear or branched organic group having 1 to 18 carbon atoms R ⁴¹ and R ⁵ each independently represent an alkylene group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 4 to 12 carbon atoms R ⁶ represents a hydrogen atom or a methyl group R ⁴² represents a fluorine atom and / or an organic group having a silicon atom, n represents an integer of 0 to 12)
In the general formula (I-1-1-1) to the general formula (I-1-2-2), a preferable group of R ^{42 is} a group represented by the general formula (I-1-1) or the general formula (I-1) It is the same as the preferable group of R ⁴ described in 2).

  When an alignment film material containing a polymer having a thermally decomposable group is applied to a substrate, the polymer having a thermally decomposable group containing a fluorine atom and / or a silicon atom segregates on the coating film surface. The surface of the film obtained by detachment of the group having a fluorine atom and / or a silicon atom from the polymer in a state of being segregated on this surface becomes smooth. As a result of such a phenomenon, the pretilt angle formed by the polymer of the compound having a polymerizable group, which controls the alignment direction of liquid crystal molecules in the liquid crystal composition layer described later, is uniformly stabilized on the alignment film layer. Can be given.

  The number average molecular weight (Mn) of the polymer having a thermally decomposable group used in the present invention, which is represented by the general formula (I-1-1-1) to the general formula (I-1-2-2) or the like, is The range of 1,000 to 50,000 is preferable, the range of 1,500 to 20,000 is more preferable, and the range of 2,000 to 8,000 is more preferable. The weight average molecular weight (Mw) is preferably in the range of 1,000 to 100,000, and more preferably in the range of 5,000 to 70,000. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.

  The polymer having a thermally decomposable group used in the alignment film of the present invention can be used singly or in combination of two or more.

  The total blending amount of the polymer having a thermally decomposable group used in the present invention in the alignment film material is preferably 0.01 to 5% by mass with respect to the total amount of the solid content of the alignment film material. The content is preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, and still more preferably 0.2 to 1% by mass.

As a method of obtaining an alignment film having two functions of the vertical alignment ability and the alignment control ability, a polymer having the above-mentioned thermally decomposable group and a polymerizable compound having a polymerizable group in an alignment film material usually used A method of blending, a method of blending a polymer having a thermally degradable group further using a polymer of a polymerizable compound having a crosslinkable functional group in a side chain portion as an alignment film material, a polymerizable liquid crystal compound and the above thermal There is a method of using a cured product of a polymerizable liquid crystal composition containing a polymer having a degradable group. Each method will be described below.
(Method of blending a polymer having a thermally degradable group and a polymerizable compound having a polymerizable group in an alignment film material)
As a method of blending the polymer having the above-mentioned heat-degradable group and the polymerizable compound having the above-mentioned polymerizable group into the alignment film material, the above-mentioned heat-degradable group is added to the above-mentioned polymer compound precursor as the alignment film material. The method of mix | blending the polymer which it has, and the polymeric compound which has a polymeric group is mentioned. And the alignment film surface can be made smooth by the heating process (baking) of the said high molecular compound precursor. As a result, the pretilt angle formed by the polymer of the compound having a polymerizable group can be stably provided on the alignment film layer, and the alignment direction of liquid crystal molecules in the liquid crystal composition layer described later can be uniformly controlled. can do.

  The polymerizable compound having a reactive group contained in the alignment film material may or may not contain the mesogenic site. The polymer of the polymerizable compound having a reactive group preferably has a crosslinked structure from the viewpoint of durability, and from the viewpoint of durability, the polymerizable compound having a reactive group has a bifunctional or trifunctional structure. Polymerizable compounds having two or more reactive groups such as functional groups are preferred.

  In the polymerizable compound having a reactive group, the reactive group is preferably a substituent having polymerizability by light. In particular, when the vertical alignment film is formed by thermal polymerization, since the reaction of the polymerizable compound having a reactive group can be suppressed during thermal polymerization of the vertical alignment film material, the reactive group has polymerizability by light. Substituents are particularly preferred.

  Specifically as the polymerizable compound having a reactive group, 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, OCOOO, OCO, or COO, and X is to be 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 However, the alkylene group in the polyvalent alkylene group or the alkenylene group in the polyvalent alkenylene group may be substituted by -O-, -CO-, or -CF ₂ -to the extent that the oxygen atom is not adjacent to the carbon atom; Alkyl group of 5 to 20 (alkylene in the group Group may be substituted by an oxygen atom as long as the oxygen atom is not adjacent), or may be substituted by a cyclic substituent, and k represents a polymerization of 0 to 5). Compounds are preferred.

In the above general formula (V), X ⁷ and X ⁸ each independently represent a hydrogen atom or a methyl group, but when importance is placed on the reaction rate, a hydrogen atom is preferable, and emphasis is placed on reducing the amount of residual reaction. If it is a methyl group is preferred.

In the above 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) And X represents O, OCOO, or COO, and X represents an aromatic ring present in U. However, it is preferable that the carbon chain is not very long, and a single bond or A C1-C5 alkylene group is preferable, and a single bond or a C1-C3 alkylene group is more preferable. In addition, when Sp ¹ and Sp ^{2 each} 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. It is more preferable that any of them is a single bond.

  In the above general formula (V), k represents an integer of 0 to 5, but k represents an integer of 1 to 5 when importance is placed on controllability of the alignment direction of liquid crystal molecules in the liquid crystal composition layer. Is more preferable, k is more preferably an integer of 1 to 3, and k is more preferably 1 or 2.

In the above 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 group having 5 to 30 carbon atoms A cyclic substituent is represented, but the alkylene group in the polyvalent alkylene group may be substituted by -O-, -CO-, or -CF _2- within the range where 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 by an oxygen atom within the range where the oxygen atom is not adjacent), or a cyclic substituent, and may be substituted by two or more cyclic substituents Is preferred.

  In the general formula (V), U preferably specifically represents the following formula (Va-1) to the formula (Va-6), and the formula (Va-1), the formula (Va-2), It is more preferable to represent Formula (Va-6), and it is particularly preferable to represent Formula (Va-1).

(In the formula, both ends are Sp¹Or Sp²If k is an integer of 2 to 5 (in the case of k = 1 above), and the number of linked bases is correspondingly increased. Z¹, Z²And Z³Are each independently -OCH₂-, -CH₂O-, -COO-, -OCO-, -CF₂O-, -OCF ₂-, -CH₂CH₂-, -CF₂CF₂-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH₂CH₂-, -OCO-CH₂CH₂-, -CH₂CH₂-COO-, -CH₂CH₂-OCO-, -COO-CH₂-, -OCO-CH₂-, -CH₂-COO-, -CH₂-OCO-, -O (CH₂)_m1 Represents an O- or a single bond, wherein m1 represents an integer of 1 to 6, and in all the aromatic rings in the formula, any hydrogen atom may be substituted by a fluorine atom. )
  In the above U, Z¹, Z²And Z³Are each independently -OCH₂-, -CH₂O-, -COO-, -OCO-, -CF₂O-, -OCF₂-, -CH₂CH₂-, -CF ₂CF₂-Or a single bond is preferable, -COO-, -OCO-, -OCH₂CH₂O- or single bond is more preferred.

When U has the above ring structure, at least one of Sp ¹ and Sp ² preferably represents a single bond, and it is also preferred 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 a trifunctional compound of k = 2.

  Specifically, the compounds represented by General Formula (Va-1-1) to (Va-5-3) below are preferable as the compounds represented by General Formula (V).

  Further, among the compounds represented by the above formulas (Va-1-1) to (Va-5-10), the formulas (Va-1-1) to (Va-1-34), the formulas (Va- 2-1) to the formula (Va-2-21), the formula (Va-2-24) to the formula (Va-2-39), and the formula (Va-5-4) to the formula (Va-5-10) The compound represented is preferable, and Formula (Va-1-1)-Formula (Va-1-13), Formula (Va-1-17)-Formula (Va-1-26), Formula (Va-1-29) ) To formula (Va-1-34), formula (Va-2-4) to formula (Va-2-8), formula (Va-2-14), formula (Va-2-17), formula (Va) −20), formula (Va-2-21), formula (Va-2-24) to formula (Va-2-39), formula (Va-5-5) to formula (Va-5-9) The compound represented by is more preferable.

  Among the polymerizable compounds having the reactive group, the content of the compound represented by the general formula (V) in the alignment film material forming the alignment film is relative to the total amount of the solid content of the alignment film material And 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.

  As a polymerizable compound having a polymerizable group contained in the alignment film material, in addition to the compound represented by the above general formula (V), a polymerizable compound represented by the following general formula (V-1) is contained Also good.

(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 a phenanthrene ring; In the formula, any hydrogen atom may be substituted by a fluorine atom).
In the above general formula (V-1), X ¹⁰ and X ¹¹ each independently represent a hydrogen atom or a methyl group, but when importance is placed on the reaction rate, a hydrogen atom is preferable, and the reaction residual amount is reduced When importance is placed on methyl, methyl is preferred.

In the above general formula (V-1), 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 Represents an integer of -7, X represents -O-, -OCOO- or -COO-, and X represents a bond to a phenanthrene ring), but preferably the carbon chain is 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 preferable. Also, Sp ³ and Sp ⁴ is -X- _{(CH 2) t} - may represent a, t is preferably 1 to 5, more preferably 1 to 3, at least one of Sp ³ and Sp ⁴ is a single bond It is more preferable that any of them is a single bond.

  Specifically, the compounds represented by the general formula (V-1) are preferably compounds represented by the following general formulas (V-1-1) to (V-1-52).

  Among the polymerizable compounds having the reactive group, the content of the compound represented by the general formula (V-1) in the alignment film material forming the alignment film is the total content of the solid content of the alignment film material. On the other hand, it is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.

  The content of the entire polymerizable compound having a polymerizable group (total amount of compounds represented by general formula (V) and / or general formula (V-1)) in the alignment film material forming the alignment film is And 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.

In addition, the total blending amount of the solid content to be blended in the alignment film material of the polymer having a thermally decomposable group is preferably 0.01 to 5% by mass with respect to the total amount of the alignment film material, and 0. It is preferable that it is 05-3 mass%, It is more preferable that it is 0.1-2 mass%, It is further more preferable that it is 0.2-1 mass%.
(Method of using a polymer of a polymerizable compound having a crosslinkable functional group in a side chain as an alignment film material and further blending a polymer having the above-mentioned thermally degradable group)
As a method of obtaining an alignment film having two functions of vertical alignment ability and alignment control ability, a method using a polymer of a polymerizable compound having a crosslinkable functional group in a side chain portion as an alignment film material is also preferable. Moreover, also when using the said method, the alignment film surface can be made smooth by the subsequent heating process (baking) using the polymer which has the said thermally-degradable group. As a result, the pretilt angle formed by the polymer of the compound having a polymerizable group can be stably provided on the alignment film layer, and the alignment direction of liquid crystal molecules in the liquid crystal composition layer described later can be uniformly controlled. can do. As the polymerizable compound having a crosslinkable functional group in the side chain portion, the main 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 containing a crosslinkable functional group as a side chain in a repeating unit (main chain portion) constituting the polyimide structure. Be Then, the crosslinkable functional group becomes a polymerization reaction initiation point, and a polymerizable compound having a polymerizable group blended in the alignment film material radically reacts to form a side chain, thereby forming liquid crystal molecules in the liquid crystal composition layer. It has an orientation control ability to control the orientation direction of. The crosslinkable functional group may have any structure as long as it can undergo radical reaction, but groups represented by (P2-1) to (P2-7) shown below are preferable, The groups represented by (P2-1) to (P2-3) are more preferable, and the group represented by (P2-1) or (P2-2) is more preferable.

(R ¹ represents an alkyl group of 1 to 5 carbon atoms.)
The crosslinkable functional group may 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. , 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 polymeric compound which has a polyimide skeleton as a principal chain and has a crosslinkable functional group as a side chain, the compound represented by general formula (V-3) shown below can be illustrated, for example.

(In General Formula (V-3), R ³ represents any one of the groups represented by (V-3-A) to (V-3-F) below, and R ⁴ and R ⁵ are And each independently represents an alkylene group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ are each independently any of the groups represented by (P2-1) to (P2-7) above. N represents an integer of 1 or more; m1 and m2 each represent 0 or 1; m3 and m4 each represent an integer of 0 or 1; m5 and m6 each represent 0 or 1; , M5 and m6 represent 1).

  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 a crosslinkable functional group as a side chain is represented by the above general formula (V) And the same compounds as the compounds represented by the above general formula (V-1).

  The total blending amount of the compound represented by the above general formula (V) and the compound represented by the above general formula (V-1) to be blended in the alignment film material is 1 to 5 with respect to the total amount of the alignment film material The content is preferably 40% by mass, preferably 3 to 35% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.

  In addition, when using the polymer of the polymeric compound which has a crosslinkable functional group in a side chain part as said alignment film material, you may use together and use the above-mentioned well-known polyimide-type material.

In addition, the total blending amount of the solid content to be blended in the alignment film material of the polymer having a thermally decomposable group is preferably 0.01 to 5% by mass with respect to the total amount of the alignment film material, and 0. It is preferable that it is 05-3 mass%, It is more preferable that it is 0.1-2 mass%, It is further more preferable that it is 0.2-1 mass%.
(Method using cured product of polymerizable liquid crystal compound as alignment film)
As a method of obtaining an alignment film having two functions of vertical alignment ability and alignment control ability, a method of using a cured product of a polymerizable liquid crystal compound as the alignment film is also preferable. Moreover, also when using the said method, alignment film is obtained by heating (baking) the polymerizable liquid crystal composition which is an alignment film material containing the said polymeric liquid crystal compound and the polymer which has the said thermally-degradable group. The surface can be smoothed. As a result, the pretilt angle formed by the polymer of the compound having a polymerizable group can be stably provided on the alignment film layer, and the alignment direction of liquid crystal molecules in the liquid crystal composition layer described later can be uniformly controlled. can do.

  When a cured product of a polymerizable liquid crystal compound is used as the alignment film, an alignment film composed of the above-mentioned polyimide material or polysiloxane material may be used as the undercoat alignment film.

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

(In the formula, X¹Represents a hydrogen atom or a methyl group, and Sp¹And Sp²Each independently represents a single bond, an alkylene group having 1 to 8 carbon atoms, or -O- (CH₂)_s-(Wherein, s represents an integer of 2 to 7 and an oxygen atom is bonded to an aromatic ring), and Z¹Is -OCH₂-, -CH₂O-, -COO-, -OCO-, -CF₂O-, -OCF₂-, -CH₂CH ₂-, -CF₂CF₂-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH₂CH₂-, -OCO-CH ₂CH₂-, -CH₂CH₂-COO-, -CH₂CH₂-OCO-, -COO-CH₂-, -OCO-CH₂-, -CH₂-COO-, -CH₂-OCO-, -CY¹= CY²-(Y¹And Y²Each independently represents a hydrogen atom or a fluorine atom. And —C≡C— or a single bond, Y represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 carbon atoms -8 alkenyloxy group, hydrogen atom, fluorine atom or cyano group, or the following structure

(Wherein, X ² represents a hydrogen atom or a methyl group), ring C represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and in ring C, it is 1,4 -Any hydrogen atom of -phenylene group may be substituted by fluorine atom. )
In the above general formula (V3), X ¹ and X ² each independently represent a hydrogen atom or a methyl group, but when importance is placed on the reaction rate, a hydrogen atom is preferable, and it is emphasized to reduce the residual amount of reaction If it is a methyl group is preferred.

In the above general formula (V3), Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or -O- (CH ₂ ) _s- (wherein s is 2 to 7) And the oxygen atom is to be bonded to an aromatic ring), but the carbon chain is preferably not so long, preferably a single bond or an alkylene group having 1 to 5 carbon atoms, 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 each} represent —O— (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. It is more preferable that any of them is a single bond.

In the general formula (V3), ^{Z 1} is _{-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 represents 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 preferable, and -COO- , -OCO- or a single bond is more preferable, and a single bond is particularly preferable.

  In the above general formula (V3), C represents a 1,4-phenylene group in which any hydrogen atom may be substituted by a fluorine atom, a trans-1,4-cyclohexylene group or a single bond; -A phenylene group or a single bond is preferred.

When C represents a ring structure other than a single bond, Z ¹ is also preferably a linking group other than a single bond, and when C is a single bond, Z ¹ 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 The compound representing a cyano group is a monofunctional polymerizable liquid crystal compound, and Y is a compound having no polymerizable skeleton. On the other hand, the compound in which Y represents the above-mentioned polymerizable skeleton is a bifunctional polymerizable liquid crystal compound. In the present invention, although any of monofunctional polymerizable liquid crystal compounds or bifunctional polymerizable liquid crystal compounds can be used, bifunctional polymerizable liquid crystal compounds are preferable from the viewpoint of heat resistance, and both of them are used simultaneously It can also be done.

  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 general formulas (V3-1) to (V3-3) are preferable. The compound represented by 4) is particularly preferable, and the compound represented by the general formula (V3-2) is most preferable.

In addition to the polymerizable liquid crystal compound represented by the above general formula (V3), a compound represented by the above general formula (V) (with the exception of the compound represented by the general formula (V3)), and / Or you may use together the compound represented by the said general formula (V-1) 1 or more types.

In addition, the total blending amount of the solid content to be blended in the alignment film material of the polymer having a thermally decomposable group is preferably 0.01 to 5% by mass with respect to the total amount of the alignment film material, and 0. It is preferable that it is 05-3 mass%, It is more preferable that it is 0.1-2 mass%, It is further more preferable that it is 0.2-1 mass%.
(A polymerizable compound contained in a liquid crystal composition to form a polymer layer on the surface of an alignment film)
In the liquid crystal display device of the present invention, the vertical alignment film contains a polymer formed by the 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 the liquid crystal composition is sandwiched between the substrates, the polymerizable compound is cured by applying a voltage to the polymerizable compound to form a phase. A liquid crystal is formed as a polymer layer on the surface of the vertical alignment film while being separated, and the alignment of liquid crystal molecules and the stability of the pretilt angle are high, the occurrence of burn-in is small, and the generation of drip marks during its manufacture is small. A display element can be obtained.

  The polymerizable compound for forming the polymerized layer may be a monofunctional polymerizable compound having one reactive group, a polyfunctional polymerizable compound having two or more reactive groups such as difunctional or trifunctional, etc. However, polyfunctional polymerizable compounds having two or more reactive groups such as difunctional or trifunctional are preferable. The polymerizable compound to be used may be one type or two or more types.

  As a polymerizable compound which forms a polymer layer, it is preferable to contain 1 or more types of compounds represented by above-mentioned compound represented by General formula (V), and / or said General formula (V-1).

1 type or 2 types selected from the compound represented by the above-mentioned general formula (V) and the compound represented by the said general formula (V-1) used in order to form a polymer layer in the vertical alignment film surface The total content of the above compounds in the liquid crystal composition is preferably 0 to 2% by mass, preferably 0.03 to 0.1% by mass, and 0.05 to 0.08% by mass. More preferably, it is%.
(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 ones in the alkyl group The above -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) 1,4-cyclohexylene group (one -CH _2- present in this group or adjacent thereto And two or more -CH _2- may be replaced by -O-) and (b) 1,4-phenylene group (one -CH = present in this group or not adjacent 2) Or more of -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 = or two or more non-adjacent —CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by —N =. )
And 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 = N-, -CH = CH-, -CF = CF- or -C≡C-,
X ^N21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents -CH ₂ -or -O-,
^{n N11, n N12, n N21} , n N22, n N31 and ^{n N32} each independently represents an integer of ^{0~3, n N11 + n N12,} n N21 + n N22 and ⁿ N31 ^{+ n N3 2} is independently And 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 in which Δε is negative and the absolute value is larger than 3.

  R in the general formulas (N-1), (N-2) and (N-3)^N11, R^N12, R^N21, R ^N22, R^N31And R^N32Each independently preferably represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms; An alkyl group of 1 to 5 atoms, an alkoxy group of 1 to 5 carbon atoms, an alkenyl group of 2 to 5 carbon atoms or an alkenyloxy group of 2 to 5 carbon atoms is preferable, and an alkyl of 1 to 5 carbon atoms Group or alkenyl group having 2 to 5 carbon atoms is more preferable, alkyl group having 2 to 5 carbon atoms or alkenyl group having 2 to 3 carbon atoms is more preferable, and alkenyl group having 3 carbon atoms (propenyl group) is more preferable Particularly preferred.

  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 Alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain Preferred is an alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, preferably linear.

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

A ^{N 11} , A ^{N 12} , A ^{N 21} , A ^{N 22} , A ^{N 31} and A ^{N 32} are each preferably aromatic when it is required to increase Δn independently, and in order to improve the response speed, it is preferable to use fat Group is preferred, and trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 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 Be 2,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl 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.

X ^N21 is preferably a fluorine atom.

T ^N31 is preferably -O-.

n ^{N 11} + n ^{N 12} , n N ²¹ + n N ²² and n ^{N 31} + n ^{N 32} are preferably 1 or 2, and combinations in which n ^{N 11} is 1 and n ^{N 12} is 0, n ^{N 11} is 2 and n ^{N 12} is 0, n ^A combination in which ^{N 11} is 1 and n ^{N 12} is 1, a combination in which n ^{N 11} is 2 and n ^{N 12} is 1, a combination in which n N ²¹ is 1 and n N ²² is 0, n N ²¹ is 2 and n N ²² is A combination of 0, a combination of n ^N31 of 1 and n ^N32 of 0, and a combination of n ^N31 of 2 and n ^N32 of 0 is preferred.

  The lower limit value of the preferable content of the compound represented by General Formula (N-1) to the total amount of the liquid crystal composition of the present invention (the total amount of liquid crystal compounds contained in the liquid crystal composition. The same applies hereinafter) is 1% by mass (hereinafter referred to simply as% by mass), 10%, 20%, 30%, 40%, 50%, 55%, 60% Yes, 65%, 70%, 75% and 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

  The lower limit value of the preferable content of the compound represented by General Formula (N-2) with respect to the total amount of the liquid crystal composition of the present invention is 1 mass% (hereinafter mass% is simply expressed as%), 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

  The lower limit value of the preferable content of the compound represented by General Formula (N-3) to the total amount of the liquid crystal composition of the present invention is 1 mass% (hereinafter mass% is simply expressed as%), 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

  When it is necessary to keep the viscosity of the liquid crystal composition of the present invention low and have a high response speed, it is preferable that the above lower limit is low and the upper limit is low. Furthermore, when the composition of the present invention is required to keep Tni high and a composition having good temperature stability is required, it is preferable that the above lower limit is low and the upper limit is 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 be high and the upper limit value be high.

  The compound represented by General Formula (N-1) is preferably a compound selected from the group of compounds represented by General Formulas (N-1-1) to (N-1-21).

  The compounds represented by General Formula (N-1-1) are the following compounds.

( ^Wherein , R ^N111 and R ^N112 each independently represent the same meaning as R ^{N 11} and R ^N12 in general formula (N-1).)
R ^{N 111} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably a propyl group or a pentyl group. R ^{N 112} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms, or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group or butoxy group.

    Although a compound denoted by a general formula (N-1-1) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content Setting a lower value is more effective. Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  Furthermore, the compound represented by General Formula (N-1-1) is a compound selected from the group of compounds represented by Formula (N-1-1. 1) to Formula (N- 1. 1. 14) And the compounds represented by formulas (N-1-1. 1) to (N- 1.1.4) are preferable, and the compounds represented by formulas (N- 1.1. 1) and (N- The compound represented by 1-1.3) is preferable.

  The compounds represented by formulas (N-1-1. 1) to (N- 1. 4) can be used alone or in combination, but the liquid crystal composition of the present invention The lower limit value of the preferable content of these compounds alone or in the total amount of these is 5% by mass (hereinafter referred to simply as% by mass), 10%, 13% and 15%. 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%. The upper limit of the preferred content is 50%, 40%, 38%, 35%, 33%, 30% with respect to the total amount of the liquid crystal composition of the present invention. 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6%, 5% and 3%.

  The compounds represented by General Formula (N-1-2) are the following compounds.

(Wherein, R ^N121 and R ^N122 each independently represent the same meaning as R ^{N 11} and R ^N12 in General Formula (N-1).)
^{RN 121} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group, a butyl group or a pentyl group. R ^{N 122} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, and a methyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group is preferred preferable.

    Although a compound denoted by a general formula (N-1-2) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher, and when importance is given to solubility at low temperature, setting it smaller is more effective, and when _TNI is emphasized, the content It is effective to set a larger value. Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

Furthermore, the compound represented by the general formula (N-1-2) is a compound selected from the group of compounds represented by the formula (N-2.1.) To the formula (N-1-2.13) It is preferable that 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 It is preferable that it is a compound represented by (N-1-2.13), and when importance is given to improvement of Δε, formula (N-1-2. 3) to 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.

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

  The compounds represented by General Formula (N-1-3) are the following compounds.

( ^Wherein , R ^{N 131} and R ^{N 132} each independently represent the same meaning as R ^{N 11} and R ^{N 12} in General Formula (N-1).)
R ^{N 131} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R ^{N 132} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group, a propoxy group or a butoxy group.

  Although the compound represented by general formula (N-1-3) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content It is effective to set up to Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  Furthermore, the compound represented by the general formula (N-1-3) is a compound selected from the group of compounds represented by the formula (N-3.1. 1) to the formula (N-1.3.1. 1) Are preferably compounds represented by the formulas (N-3.1.) To (N-1-3.7), and it is preferable that the compounds represented by the formulas (N-3.1. 1) and (N The compounds represented by the formula (1-3), the formula (N-1-3.3), the formula (N-1-3.4) and the formula (N-1-3.6) are preferable.

  The compounds represented by the formulas (N-1-3.1) to (N-1-3.4) and the formula (N-1-3.6) may be used alone or in combination. Although it is possible, a combination of the formula (N-3.1.) And the formula (N-1-3.2), a formula (N-1-3. 3), a formula (N-1-3.4) And combinations of two or three selected from formula (N-1-3.6) are preferable. The lower limit of the preferable content of one or more of these compounds to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13% Yes, 15%, 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20% with respect to the total amount of the liquid crystal composition of the present invention. It is 18%, 15% and 13%.

  The compounds represented by General Formula (N-1-4) are the following compounds.

( ^Wherein , each of R ^{N 141} and R ^{N 142} independently represents the same meaning as R ^{N 11} and R ^{N 12} in General Formula (N-1).)
Independently R ^N141 and ^{R N142} are each an alkyl group having 1 to 5 carbon atoms, preferably an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 4-5, methyl group, propyl group, ethoxy Preferred is a group or butoxy group.

  Although the compound represented by general formula (N-1-4) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content Setting a lower value is more effective. Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-4) relative to the total amount of the liquid crystal 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% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15%, 13%, 11%, 10% and 8%.

  Furthermore, the compound represented by the general formula (N-1-4) is a compound selected from the group of compounds represented by formula (N-4.1. 4) to formula (N-1-4. 14) And the compounds represented by the formulas (N-4.1.) To (N-1-4.4) are preferable, and the compounds represented by the formulas (N-4.1. The compound represented by -1-4.2) is preferable.

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

  The compounds represented by General Formula (N-1-5) are the following compounds.

( ^Wherein , R ^{N 151} and R ^{N 152} each independently represent the same meaning as R ^{N 11} and R ^{N 12} in General Formula (N-1).)
R ^{N 151} and R ^{N 152} are each independently an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms, or an alkoxy group of 1 to 4 carbon atoms, preferably an ethyl group, a propyl group or a butyl group Is preferred.

  Although a compound denoted by a general formula (N-1-5) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher, and when importance is given to solubility at low temperature, setting it smaller is more effective, and when _TNI is emphasized, the content It is effective to set a larger value. Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  Furthermore, 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) It is preferable that the compound represented by formula (N-1-3.2 and 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, but the liquid crystal composition of the present invention The lower limit value of the preferable content of these compounds alone or in the total amount of these is 5 mass% (hereinafter, mass% is simply expressed as%), 8%, 10%, 13% The upper limit value of the preferred content is 35%, 33%, and 30% with respect to the total amount of the liquid crystal composition of the present invention. , 28%, 25%, 23%, 20%, 18%, 15%, 13%.

  The compounds represented by General Formula (N-1-10) are the following compounds.

(Wherein, each of R N ¹¹⁰¹ and R N ¹¹⁰² independently represents the same meaning as R ^{N 11} and R ^{N 12} in General Formula (N-1).)
R N ¹¹⁰¹ is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N ¹¹⁰² is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group, a propoxy group or a butoxy group.

  Although a compound denoted by a general formula (N-1-10) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content It is effective to set up to Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  Furthermore, the compound represented by General Formula (N-1-10) is a compound selected from the compound group represented by Formula (N-1-10.1) to Formula (N-1-10.11) Are preferably compounds represented by the formulas (N-1-10.1) to (N-1-10.5), and the compounds of the formulas (N-1-10.1) and (N The compound represented by -1-1.2) is preferable.

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

  The compounds represented by General Formula (N-1-11) are the following compounds.

( ^Wherein , each of R N ¹¹¹¹ and R N ^{11 12} independently represents the same meaning as R ^{N 11} and R ^{N 12} in General Formula (N-1).)
R ^{N 1111} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R ^{N 1112} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group, a propoxy group or a butoxy group.

  Although a compound denoted by a general formula (N-1-11) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content It is effective to set up to Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  Furthermore, the compound represented by General Formula (N-1-11) is a compound selected from the compound group represented by Formula (N-1-11.1) to Formula (N-1-11.15) And the compounds represented by formulas (N-1-11.1) to (N-1-11.15) are preferable. The compound represented by 1-11.4) is preferable.

  Although 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 liquid crystal composition of the present invention can be used. The lower limit value of the preferable content of these compounds alone or in the total amount of these is 5% by mass (hereinafter referred to simply as% by mass), 10%, 13% and 15%. The upper limit of the preferred content is 35%, 30%, 28%, and 25% of the total content of the liquid crystal composition of the present invention. , 23%, 20%, 18%, 15%, 13%.

  The compounds represented by General Formula (N-1-12) are the following compounds.

^{(Wherein, R N1121} and ^{R N1122} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
R ^{N 1121} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R ^{N 1122} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms, or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group, a propoxy group or a butoxy group.

  Although the compound represented by general formula (N-1-12) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content It is effective to set up to Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  The compounds represented by General Formula (N-1-13) are the following compounds.

( ^Wherein , each of R N ¹¹³¹ and R ^{N 1132} independently represents the same meaning as R ^{N 11} and R ^{N 12} in General Formula (N-1).)
R ^{N 1131} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R ^{N 1132} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group, a propoxy group or a butoxy group.

  Although the compound represented by general formula (N-1-13) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content It is effective to set up to Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  The compounds represented by General Formula (N-1-14) are the following compounds.

( ^Wherein , each of R N ¹¹⁴¹ and R ^{N 114 2} independently represents the same meaning as R ^{N 11} and R ^{N 12} in General Formula (N-1).)
R ^{N 1141} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R ^{N 1142} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms, or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group, a propoxy group or a butoxy group.

  Although a compound denoted by a general formula (N-1-14) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content It is effective to set up to Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  The compounds represented by General Formula (N-1-15) are the following compounds.

^{(Wherein, R N1151} and ^{R N1152} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
R ^{N 1151} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R ^{N 1152} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group, a propoxy group or a butoxy group.

  Although a compound denoted by a general formula (N-1-15) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content It is effective to set up to Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  The compounds represented by General Formula (N-1-16) are the following compounds.

^{(Wherein, R N1161} and ^{R N1162} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
R ^{N 1161} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R ^{N 1162} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group, a propoxy group or a butoxy group.

  Although the compound represented by general formula (N-1-16) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content It is effective to set up to Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  The compounds represented by General Formula (N-1-17) are the following compounds.

^{(Wherein, R N1171} and ^{R N1172} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
R ^{N 1171} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R ^{N 1172} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group, a propoxy group or a butoxy group.

  Although the compound represented by general formula (N-1-17) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content It is effective to set up to Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  The compounds represented by General Formula (N-1-18) are the following compounds.

( ^Wherein , each of R ^N1181 and R ^N1182 independently represents the same meaning as R ^{N 11} and R ^N12 in general formula (N).)
R ^{N 1181} is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R ^{N 1182} is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, and is preferably an ethoxy group, a propoxy group or a butoxy group.

  Although a compound denoted by a general formula (N-1-18) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

When importance is attached to improvement of Δε, it is preferable to set the content higher. When importance is given to solubility at low temperature, setting the content higher is more effective, and when _TNI is emphasized, the content It is effective to set up to Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  The compounds represented by General Formula (N-1-20) are the following compounds.

^{(Wherein, R N1201} and ^{R N1202} each independently represents the same meaning as ^{R N 11} and ^{R N12} in the general formula (N).)
The compounds represented by General Formula (N-1-21) are the following compounds.

^{(Wherein, R N1211} and ^{R N1212} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
The compound represented by Formula (N-2) is preferably a compound selected from the group of compounds represented by Formulas (N-2-1) to (N-2-3).

  The compounds represented by General Formula (N-2-1) are the following compounds.

^{(Wherein, R N211} and ^{R N212} are each independently of the general formula (N-2) represent the same meaning as ^{R N 21} and ^{R N22.)}
The compounds represented by General Formula (N-2-2) are the following compounds.

^{(Wherein, R N221} and ^{R N222} are each independently of the general formula (N-2) represent the same meaning as ^{R N 21} and ^{R N22.)}
The compounds represented by General Formula (N-2-3) are the following compounds.

^{(Wherein, R N231} and ^{R N232} are each independently the same meaning as ^{R N 31} and ^{R N32} in the general formula (N-3).)
It is preferable that the compound represented by general formula (N-3) is a compound chosen from the compound group represented by general formula (N-3-1)-(N-3-2).

  The compounds represented by General Formula (N-3-1) are the following compounds.

( ^Wherein , R ^{N 311} and R ^{N 312} each independently represent the same meaning as R ^{N 11} and R ^{N 12} in General Formula (N-1).)
The compounds represented by General Formula (N-3-2) are the following compounds.

( ^Wherein , R ^{N 321} and R ^{N 322} each independently represent the same meaning as R ^{N 11} and R ^{N 12} in General Formula (N-1).)
The general formula (N-1), the general formula (N-2), and the general formula (N-3) relative to the total amount of the liquid crystal composition of the present invention (the total amount of liquid crystal compounds contained in the liquid crystal composition) The total content of the compound represented by is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 20 to 70% by mass, and still more preferably 20 to 60% by mass. -55 mass% is further preferable, 25-55 mass% is further preferable, and 30-55 mass% is particularly preferable.

  More specifically, the total content of the compounds represented by General Formula (N-1), General Formula (N-2), and General Formula (N-3) is a lower limit value in the liquid crystal composition. It is preferable to contain 1% by mass (hereinafter referred to simply as% by mass), preferably 5% or more, preferably 10% or more, and preferably 13% or more. % Is preferable, 18% or more is preferable, 20% or more is preferable, 23% or more is preferable, 25% or more is preferable, and 28% or more is preferable. 30% or more is preferable, 33% or more is preferable, 35% or more is preferable, 38% or more is preferable, and 40% or more is preferable. Arbitrariness. The upper limit thereof 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 is preferable, 78% or less is preferable, 75% or less is preferable, 73% or less is preferable, 70% or less is preferable, and 68% or less Is preferably contained, preferably 65% or less, preferably 63% or less, preferably 60% or less, preferably 55% or less, and 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 General Formula (L). The compounds represented by the general formula (L) correspond to dielectric substantially neutral compounds (the value of Δε is −2 to 2).

(Wherein, R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH ₂ -in the alkyl group are independently of each other It may be 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 are each independently (a) 1,4-cyclohexylene group (one -CH _2- present in this group or two or more non-adjacent -CH _2- May be replaced by -O-) and (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = is -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 = or two or more non-adjacent —CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by —N =. )
And 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} each independently represent 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 -, - represents CF = CF- or -C≡C-,
When n ^L1 is 2 or 3 and a plurality of A ^L2 is present, they may be the same or different, and when n ^L1 is 2 or 3 and a plurality of Z ^L3 is present, they may be May be the same or different, but the compounds represented by the general formula (N-1), the general formula (N-2) and the general formula (N-3) are excluded. )
The compounds represented by formula (L) may be used alone or in combination. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the desired performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of compound used is, for example, one type in one embodiment of the present invention. Or in another embodiment of the present invention, there are 2 types, 3 types, 4 types, 5 types, 5 types, 6 types, 7 types, 8 types, 9 types and 10 It is more than kind.

  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 the 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 mass% (hereinafter mass% is simply expressed as%), and 10% Yes, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% is there. The upper limit value of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%.

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

When reliability is important, both R ^L1 and R ^L2 are preferably alkyl groups, and when importance is given to reducing the volatility of the compound, alkoxy groups are preferable, and viscosity reduction is important When doing, at least one is preferably an alkenyl group.

R ^L1 and R ^L2 are, when the ring structure to which they are bonded is a phenyl group (aromatic), a linear alkyl group of 1 to 5 carbon atoms, or a linear alkyl group of 1 to 4 carbon atoms Alkoxy groups and alkenyl groups having 4 to 5 carbon atoms are preferred, and in the case where the ring structure to which they are attached is a saturated ring structure such as cyclohexane, pyran and dioxane, a straight chain having 1 to 5 carbon atoms The alkyl group, the linear alkoxy group having 1 to 4 carbon atoms, and the linear alkenyl group having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, preferably linear.

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

n ^L1 is preferably 0 when importance is attached to the response speed, 2 or 3 is preferable to improve the upper limit temperature of the nematic phase, and 1 is preferable to balance them. Moreover, in order to satisfy the characteristics required as a composition, it is preferable to combine compounds of different values.

A ^{L 1} , A ^{L 2} and A ^{L 3} are preferably aromatic when it is required to increase Δn, and are preferably aliphatic to improve the response speed, and each of them is 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] octyrene group piperidine-1,4-diyl group naphthalene-2,6-diyl group decahydronaphthalene-2,6 -Preferably represents a diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, more preferably represents the following structure,

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

It is preferable that Z ^L1 and Z ^L2 be a single bond when the response speed is important.

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

  The compounds represented by General Formula (L-1) are the following compounds.

(In the formula, R^L11And R^L12Are each independently R in the general formula (L)^L1And R ^L2Represents the same meaning as. )
  R^L11And R^L12Is 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.

  Although the compound represented by general formula (L-1) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

  The lower limit value of the preferable content is 1% by mass (hereinafter, mass% is simply expressed as%), 2%, 3%, 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 preferred content is 95%, 90%, 85%, 80%, 75%, 70%, based on the total weight of the composition of the present invention. %, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%.

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

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

(Wherein, R ^L12 represents the same meaning as in the general formula (L-1).)
The compound represented by General Formula (L-1-1) is a compound selected from the compound group represented by Formula (L-1-1. 1) to Formula (L- 1-1. 3) It is preferable that it is a compound represented by formula (L-1-1.2) or formula (L-1-1.3), in particular, it is represented by formula (L-1-1.3) It is preferable that it is a compound.

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

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

(Wherein, R ^L12 represents the same meaning as in the general formula (L-1).)
The lower limit of the preferable content of the compound represented by the formula (L-1-2) relative 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 preferred content is 60%, 55%, 50%, 45%, 42%, 40%, based on the total weight of the composition of the present invention. %, 35%, 33%, and 30%.

  Furthermore, the compound represented by General Formula (L-1-2) is a compound selected from the group of compounds represented by Formula (L-2.1) to Formula (L-1-2.4) And the compounds represented by formulas (L-1-2.2) to (L-1-2.4) are preferable. In particular, a compound represented by the formula (L-1-2.2) is preferable in order to particularly improve the response speed of the composition of the present invention. When Tni higher than the response speed is to be determined, it is preferable to use a compound represented by Formula (L-1-2.3) or Formula (L-1-2.4). It is unpreferable to make content of the compound represented by Formula (L-1-2.3) and Formula (L-1-2.4) into 30 mass% or more in order to improve the solubility in low temperature .

  The lower limit of the preferable content of the compound represented by the formula (L- 1 -2.2) 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 preferred content is 60%, 55%, 50%, 45%, 43%, 40%, 60%, based on the total weight of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, 22%.

  Preferred content of the total of the compound represented by the formula (L-1-1.3) and the compound represented by the formula (L-1-2.2) relative 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%, 35% , 40%. The upper limit of the preferred content is 60%, 55%, 50%, 45%, 43%, 40%, 60%, based on the total weight of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, 22%.

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

(In the formula, R ^L13 and R ^L14 each independently represent 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 value of the preferable content of the compound represented by the formula (L-1-3) to the total amount of the liquid crystal composition of the present invention is 1 mass% (hereinafter mass% is simply expressed as%). , 5%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 30%. The upper limit of the preferred content is 60%, 55%, 50%, 45%, 40%, 37%, 35%, based on the total weight of the composition of the present invention. %, 33%, 30%, 27%, 25%, 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-3.1. 1) to the formula (L-1.3.1. 2) It is preferable that 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-3.1) is preferable in order to particularly improve the response speed of the composition of the present invention. In addition, when Tni higher than the response speed is to be determined, the formula (L-1-3.3), the formula (L-1-3.4), the formula (L-1-3.11) and the formula (L-) can be obtained. It is preferable to use the compound represented by 1-3.12). The total of the compounds represented by the formula (L-1-3.3), the formula (L-1-3.4), the formula (L-1.3.11) and the formula (L-1.3.12) It is not preferable to make the content of 20% by mass or more in order to improve the solubility at low temperature.

  The lower limit of the preferable content of the compound represented by the formula (L-3.1. 1) 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%, 7%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 20%, 17%, 15%, 13%, 10%, 8%, or 20%, based on the total weight of the composition of the present invention. % And 6%.

  The compound represented by formula (L-1) is preferably a compound selected from the group of compounds represented by 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) relative to the total amount of the liquid crystal composition of the present invention is 1 mass% (hereinafter mass% is simply expressed as%). 5%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferred content is 25%, 23%, 20%, 17%, 15%, 13%, 10%, based on the total weight of the composition of the present invention. %.

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

  Furthermore, the compounds represented by general formulas (L-1-4) and (L-1-5) are represented by formulas (L-4.1.) To (L-1-5.3) It is preferable that it is a compound selected from the compound group, and it is preferable that it is a compound represented by Formula (L-1-4.2) or Formula (L-1-5.2).

  The lower limit of the preferable content of the compound represented by the formula (L-1-4.2) 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%, 7%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 20%, 17%, 15%, 13%, 10%, 8%, or 20%, based on the total weight 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-1-1.3) 3.4), It is preferable to combine 2 or more types of compounds chosen from the compound represented by Formula (L-1-3.11) and Formula (L-1-3.12), It is preferable -1.3), formula (L-1-2.2), formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4) and It is preferable to combine two or more compounds selected from the compounds represented by the formula (L-1-4.2), and the lower limit value of the preferable content of the total content of these compounds is the liquid crystal composition of the present invention It is 1 mass% (Hereinafter, mass% is simply expressed as%.), 2%, 3%, 5%, 7%, 10%, 13% with respect to the total amount of substances. %, 15% and 18 20%, 23%, 25%, 27%, 30%, 33%, 35%, and the upper limit is the total amount of the liquid crystal composition of the present invention Against 80%, 70%, 60%, 50%, 45%, 40%, 37%, 35%, 33%, 30%. %, 28%, 25%, 23% and 20%. When importance is placed on the reliability of the composition, compounds represented by Formula (L-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 above, and when importance is attached to the response speed of the composition, it is represented by the formula (L-1-1.3) and the formula (L-1-2.2) It is preferable to combine two or more compounds selected from

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

(In the formula, R^L21And R^L22Are each independently R in the general formula (L)^L1And R ^L2Represents the same meaning as. )
  R^L21Is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and R^L22Is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms.

    Although the compound represented by general formula (L-1) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

  When importance is given to solubility at low temperature, setting the content higher is more effective, and conversely, when importance is placed on response speed, setting the content smaller is more effective. Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

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

  Furthermore, the compound represented by General Formula (L-2) is preferably a compound selected from the group of compounds represented by Formula (L-2.1) to Formula (L-2.6), It is preferable that it is a compound represented by (L-2.1), Formula (L-2.3), Formula (L-2.4), and Formula (L-2.6).

  The compounds represented by General Formula (L-3) are the following compounds.

(In the formula, R^L31And R^L32Are each independently R in the general formula (L)^L1And R ^L2Represents the same meaning as. )
  R^L31And R^L32Each independently preferably represent an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms.

  Although a compound denoted by a general formula (L-3) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

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

  In the case of obtaining a high birefringence, it is effective to set the content to a large value, and conversely, in the case of placing importance on high Tni, the effect is set to a small amount. Furthermore, in the case of improving the drop marks and the sticking characteristic, it is preferable to set the range of the content in the middle.

  Furthermore, the compound represented by General Formula (L-3) is preferably a compound selected from the group of compounds represented by Formula (L-3.1) to Formula (L-3.4), It is preferable that it is a compound represented by (L-3.2) to Formula (L-3.7).

  The compounds represented by General Formula (L-4) are the following compounds.

(In the formula, R^L41And R^L42Are each independently R in the general formula (L)^L1And R ^L2Represents the same meaning as. )
  R^L41Is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and R^L42Is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms. )
  Although a compound denoted by a general formula (L-4) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

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

  The lower limit of the preferable content of the compound represented by the formula (L-4) relative to the total amount of the liquid crystal composition of the present invention is 1 mass% (hereinafter mass% is simply expressed as%), and 2 %, 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) to the total amount of the liquid crystal composition of the present invention is 50%, 40%, 35%, 30% Yes, 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 required properties such as low temperature solubility, transition temperature, electrical reliability, birefringence, etc., the compound represented by the formula (L-4.1) may be represented by the formula (L-4.1) Even if it contains the compound represented by -4.2), it contains both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2) Or all of the compounds represented by Formula (L-4.1) to Formula (L-4.3) may be contained. The lower limit of the preferable content of the compound represented by the formula (L-4.1) or the formula (L-4.2) to the total amount of the liquid crystal composition of the present invention is 3%, 5% 7%, 9%, 11%, 12%, 13%, 18%, 21%, and the preferred upper limit is 45, 40% Yes, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% is there.

  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 value 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 General Formula (L-4) is preferably a compound represented by Formula (L-4.4) to Formula (L-4.6), for example. It is preferable that it is a compound represented by these.

  Depending on the required properties such as low temperature solubility, transition temperature, electrical reliability, birefringence, etc., the compound represented by formula (L-4.4) may also contain formula (L Even if it contains the compound represented by -4.5), it contains both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5) 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) to the total amount of the liquid crystal composition of the present invention is 3% by mass Is simply expressed as%), 5%, 7%, 9%, 11%, 12%, 13%, 18%, 21%. The preferred upper limit is 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 value 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 Formula (L-4) is preferably a compound represented by Formula (L-4.7) to Formula (L-4.10), and in particular, a compound represented by Formula (L-4. The compound represented by 9) is preferable.

  The compounds represented by General Formula (L-5) are the following compounds.

(In the formula, R^L51And R^L52Are each independently R in the general formula (L)^L1And R ^L2Represents the same meaning as. )
  R^L51Is preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, and R^L52Is preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 4 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms.

  Although the compound represented by general formula (L-5) can also be used independently, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

  In the composition of the present invention, the content of the compound represented by the general formula (L-5) is low temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping mark, It is necessary to appropriately adjust according to the required performance such as burn-in and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-5) relative to the total amount of the liquid crystal composition of the present invention is 1 mass% (hereinafter mass% is simply expressed as%), and 2 %, 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) to the total amount of the liquid crystal composition of the present invention is 50%, 40%, 35%, 30% The compound represented by the general formula (L-5), which is 20%, 15%, 10% and 5%, is a compound of the formula (L-5.1) or the formula (L-5. It is preferable that it is a compound represented by 2), and it is especially preferable that it is a compound represented by Formula (L-5.1).

  The lower limit value of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention is 1 mass% (hereinafter, mass% is simply expressed as%), 2%, and 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 General Formula (L-5) is preferably a compound represented by Formula (L-5.3) or Formula (L-5.4).

  The lower limit value of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention is 1 mass% (hereinafter, mass% is simply expressed as%), 2%, and 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 General Formula (L-5) is preferably a compound selected from the group of compounds represented by Formula (L-5.5) to Formula (L-5.7), and in particular It is preferable that it is a compound represented by L-5.7.

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

  The compounds represented by General Formula (L-6) are the following compounds.

(In the formula, R^L61And R^L62Are each independently R in the general formula (L)^L1And R ^L2Represents the same meaning as X^L61And X^L62Each independently represents a hydrogen atom or a fluorine atom. )
  R^L61And R^L62Each independently preferably represent an alkyl group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms;^L61And X^L62Preferably, one is a fluorine atom and the other is a hydrogen atom.

  Although a compound denoted by a general formula (L-6) can also be used alone, it can also be used combining two or more compounds. There is no particular limitation on the types of compounds that can be combined, but they are used in appropriate combination according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. The type of the compound used is, for example, one type, two types, three types, four types, five types or more as one embodiment of the present invention.

  The lower limit of the preferable content of the compound represented by the formula (L-6) relative to the total amount of the liquid crystal composition of the present invention is 1 mass% (hereinafter mass% is simply expressed as%), and 2 %, 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) to the total amount of the liquid crystal composition of the present invention is 50%, 40%, 35%, 30% Yes, 20%, 15%, 10%, 5%. When emphasis is placed on increasing Δn, it is preferable to increase the content, and when emphasis is put on precipitation at low temperature, it is preferable to reduce the content.

  The compound represented by General Formula (L-6) is preferably a compound represented by Formula (L-6.1) to Formula (L-6.9).

  Although there is no restriction | limiting in particular in the kind of compound which can be combined, It is preferable to contain 1 type-3 types in these compounds, and 1 type-4 types are more preferable to contain. In addition, since a broad molecular weight distribution of the selected compound is also effective for solubility, for example, one compound represented by the formula (L-6.1) or (L-6.2), a compound of the formula (L- 6.4) or (L-6.5) from the compound represented by the formula (L-6.6) or the formula (L-6.7) It is preferable to select one type of compound from the compounds represented by -6.8) or (L-6.9) and appropriately combine these. Among them, it is represented by the formula (L-6.1), the formula (L-6.3) the formula (L-6.4), the formula (L-6.6) and the formula (L-6.9) It is preferred to include a compound.

  Furthermore, the compound represented by General Formula (L-6) is preferably a compound represented by Formula (L-6.10) to Formula (L-6.17), for example. It is preferable that it is a compound represented by L-6.

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

  The compounds represented by General Formula (L-7) are the following compounds.

(In the formula, R^L71And R^L72Are each independently R in the general formula (L)^L1And R^{L 2}Represents the same meaning as^L71And A^L72Are each independently A in the general formula (L) ^L2And A^L3Represents the same meaning as^L71And A^L72Each of the above hydrogen atoms may be independently substituted by a fluorine atom, and Z^L71Is Z in the general formula (L)^L2Represents the same meaning as X^L71And X^L72Each independently represents a fluorine atom or a hydrogen atom. )
  In the formula, R^L71And R^L72Each independently preferably represent an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 2 to 5 carbon atoms or an alkoxy group of 1 to 4 carbon atoms;^L71And A^L72Each independently preferably represents 1,4-cyclohexylene or 1,4-phenylene;^L71And A^L72The above hydrogen atoms may each independently be replaced by a fluorine atom, and Q^L71Is preferably a single bond or COO-, preferably a single bond, X^{L 71}And X^L72Is preferably a hydrogen atom.

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

  In the liquid crystal composition of the present invention, the content of the compound represented by the general formula (L-7) is the solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping mark It is necessary to appropriately adjust according to the required performance such as burn-in and dielectric anisotropy.

  The lower limit of the preferable content of the compound represented by the formula (L-7) relative to the total amount of the liquid crystal composition of the present invention is 1 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) to the total amount of the composition of the present invention is 30%, 25%, 23%, and 20%. 18%, 15%, 10% and 5%.

  It is preferable to increase the content of the compound represented by formula (L-7) when the composition of the present invention is desired to have a high Tni embodiment, and the content is desired if a low viscosity embodiment is desired. It is preferable to reduce the

  Furthermore, the compound represented by General Formula (L-7) is preferably a compound represented by Formula (L-7.1) to Formula (L-7.4), and the compound represented by Formula (L-7. It is preferable that it is a compound represented by 2).

  Furthermore, the compound represented by General Formula (L-7) is preferably a compound represented by Formula (L-7. 11) to Formula (L-7. 13), and the compound represented by Formula (L-7. It is preferable that it is a compound represented by 11).

  Furthermore, the compound represented by General Formula (L-7) is a compound represented by Formula (L-7.21) to Formula (L-7.23). It is preferable that it is a compound represented by Formula (L-7.21).

  Furthermore, the compound represented by General Formula (L-7) is preferably a compound represented by Formula (L-7. 31) to Formula (L-7. 34), and the compound represented by Formula (L-7. 31) or / and a compound represented by the formula (L-7. 32) is preferable.

  Furthermore, the compound represented by General Formula (L-7) is preferably a compound represented by Formula (L-7.41) to Formula (L-7.44), and the compound represented by Formula (L-7. 41) or / and a compound represented by the formula (L-7. 42) are preferable.

  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 in the present invention can be used in a wide range of nematic phase-isotropic liquid phase transition temperature (Tni), but the nematic phase-isotropic liquid phase transition temperature (Tni) is 60 It is preferable that it is -120 degreeC, It is more preferable that it is 70-100 degreeC, It is especially preferable that it is 70-85 degreeC.

  The dielectric anisotropy Δε of the liquid crystal composition in the present invention is preferably −2.0 to −6.0 at 25 ° C., and more preferably −2.5 to −5.0. Particularly preferred is -2.5 to -3.5.

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

The upper limit value 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 value of the rotational viscosity (γ ₁ ) is preferably 20 (mPa · s) or more, more preferably 30 (mPa · s) or more, and still more preferably 40 (mPa · s) or more, 50 (mPa · s). s) or more is still more preferable, 60 (mPa · s) or more is still more preferable, and 70 (mPa · s) or more is particularly preferable.

  In the liquid crystal composition according to the present invention, Z which is a function of rotational viscosity and refractive index anisotropy preferably exhibits a specific value.

(In the above equation, γ ₁ represents rotational viscosity and Δ n represents refractive index anisotropy.)
13000 or less is preferable, 12000 or less is more preferable, 11000 or less is especially preferable.

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

The liquid crystal composition according to the present invention can use 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 preferable that 70-110 degreeC is more preferable, and 75-100 degreeC is especially preferable.
[Method of Manufacturing Liquid Crystal Display Device]
Next, with reference to FIG. 1, the manufacturing method of the liquid crystal display element of this invention is demonstrated.

  Alignment film material or 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 the surface of the second substrate 12 on which the pixel electrode 15 is formed The compounds are applied and heated to form vertical alignment films 16 and 17. When a polymerizable liquid crystal compound is used as an alignment film, it may have a normal alignment film as a base alignment film.

  Here, first, an alignment film material containing a polymer having a thermally decomposable group is prepared by any of the three methods described above.

  When the first polymer compound is a polyimide, for example, a mixture of tetracarboxylic acid dianhydride and diisocyanate, a polyamic acid, and a polyimide solution in which a polyimide is dissolved or dispersed as a polymer compound precursor. Etc. It is preferable that it is 1 to 10 mass%, and, as for content of the polyimide in this polyimide solution, it is more preferable that it is 3 to 5 mass%.

  When the first polymer compound is a polysiloxane, as the polymer compound precursor, for example, a silicon compound having an alkoxy group, a silicon compound having a halogenated alkoxy group, an alcohol, and an oxalic acid are compounded in a predetermined manner The polysiloxane is synthesized by mixing and heating in a quantitative ratio, and a polysiloxane solution in which the polysiloxane is dissolved in a solvent can be mentioned.

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

  After adjusting the alignment film material, 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 and the pixel electrode 15 and its slit portion (not shown). Or print. In addition, the polymer having a thermally decomposable group containing a fluorine atom and / or a silicon atom is segregated on the coated surface by passing through a drying step as necessary.

  Next, heat treatment (baking treatment) is performed in an environment of 120 to 300 ° C. Thereby, the polymer compound precursor contained in the coated or printed alignment film material and / or the compound represented by the above general formula (V-3), or the polymerizable liquid crystal compound is polymerized and cured to polymerize Among polymers having a thermally decomposable group containing a fluorine atom and / or a silicon atom which becomes a compound and at the same time segregated on the coated surface, the thermally decomposable group portion containing the fluorine atom and / or the silicon atom is optically anisotropic It desorbs from the polymer contained in the body and smoothes the coated surface.

  In addition, in order to desorb the thermally degradable group part which couple | bonds with the polymer which has a thermally degradable group, it is preferable to bake-process at 150-300 degreeC for 5 to 120 minutes, and 10-60 at 180-250 degreeC. It is more preferable to bake for a minute.

  At the stage of this heat treatment, vertical alignment ability to align liquid crystal molecules in the liquid crystal composition layer in a direction perpendicular to the substrate surface is formed. After this, processing such as rubbing may be performed if necessary.

  Next, the first substrate 11 and the second substrate 12 are stacked, and a liquid crystal composition layer 13 containing liquid crystal molecules is sealed therebetween.

  Specifically, spacer protrusions for securing a cell gap with respect to the surface on which the vertical alignment films 16 and 17 are formed in any one of the first substrate 11 and the second substrate 12, for example, , The plastic beads and the like are sprayed, and the seal portion is printed using, for example, an epoxy adhesive or the like by screen printing.

  Thereafter, the first substrate 11 and the second substrate 12 are bonded via the spacer protrusion and the seal portion so that the vertical alignment films 16 and 17 face each other, and the liquid crystal molecules and, if necessary, the polymerizability A liquid crystal composition containing a 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 a voltage application unit. The voltage is applied, for example, at a magnitude of 5 to 30 (V). The application may apply an electric 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 (the 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 is generated in a direction forming a predetermined angle with respect to the composition layer 13), and the liquid crystal molecules 19 are aligned in a predetermined direction from the normal direction of the first substrate 11 and the second substrate 12 It will be done. At this time, the tilt angle of the liquid crystal molecules 19 is approximately equal to the pretilt θ applied to the liquid crystal molecules 19 in the process described later. Therefore, it is possible to control the magnitude of the pretilt θ of the liquid crystal molecules 19 by appropriately adjusting the magnitude of the voltage (see FIG. 3).

  Furthermore, while the voltage is applied, ultraviolet light UV is applied to the liquid crystal composition layer 13 from the outside of the first substrate 11, for example, in the liquid crystal composition layers in the vertical alignment films 16 and 17. The compound having a polymerizable group that controls the alignment direction of the liquid crystal molecules or the polymerizable liquid crystal compound, and the polymerizable compound in the liquid crystal composition are polymerized to form a polymer.

In this case, the intensity of the ultraviolet light UV to be applied may or may not be constant, and the irradiation time at each intensity when changing the irradiation intensity is also arbitrary, but two or more irradiation processes When using it, it is preferable to select an intensity lower than the irradiation intensity of the 1st step in the irradiation intensity of the irradiation step of the 2nd step and subsequent steps, and the total irradiation time of the 2nd step and later is from the irradiation time of the 1st step It is also preferred that the energy content be long and have a large total energy content. Also, when changing the irradiation intensity discontinuously, it is desirable that the average irradiation light intensity in the first half of the total irradiation process time be stronger than the average irradiation intensity in the second half, and that the intensity immediately after the start of irradiation be the strongest More desirably, it is more preferable that the irradiation intensity always keep decreasing to a certain value as the irradiation time passes. In that case, the ultraviolet light UV intensity is preferably ² mW / cm ^{-2 to} 100 mW / cm ^-2, but in the first step in the case of multi-step irradiation or during all irradiation steps in the case of changing the irradiation intensity discontinuously it highest illumination intensity is ^{10mW / cm -2 ~100mW / cm -2} , and a minimum irradiation intensity when changing the second stage or later, or discontinuously irradiation intensity in the case of multi-stage irradiation 2 mW / cm ^- and more preferably ^{2 ~50mW} / ^{cm -2.} Moreover, although it is preferable that irradiation total energy amount is 10J-300J, it is more preferable that it is 50J-250J, and it is further more preferable that it is 100J-250J.

  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 the vertical alignment film material fixed to the alignment control part of the vertical alignment films 16 and 17, and further, if necessary, the polymer layer 20 , 21 are formed. This alignment control unit has a function (alignment) to impart pretilt θ to liquid crystal molecules 19 located in the vicinity of the interface with the polymer layers 20 and 21 (vertical alignment films 16 and 17) in the liquid crystal composition layer 13 in the non-driven state. Control ability). 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 of the first substrate 11 and the second substrate 12 may be irradiated. It may be irradiated from the outside of the substrate.

  As described above, in the liquid crystal display layer 13 of the present invention, the liquid crystal molecules 19 have a predetermined pretilt θ in the liquid crystal composition layer 13. As a result, the response speed to the drive voltage can be significantly improved as compared with the liquid crystal display element which is not subjected to the pretilt processing and the liquid crystal display device including the same.

  In the liquid crystal display element of the present invention, a polyimide precursor which is not photosensitive is preferable as the polymer compound precursor constituting the vertical alignment films 16 and 17.

  Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. Moreover, "%" in the composition of the following example and a comparative example 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 at 25 ° C. γ ₁ : rotational viscosity at 25 ° C. (mPa · s)
K ₃₃ : Elastic constant of bending at 20 ° C. (pN)
Pre-UV irradiation voltage holding ratio (initial VHR): Voltage holding ratio at 343 K under frequency 60 Hz, applied voltage 1 V (%)
VHR after UV irradiation: after UV irradiation to the liquid crystal display elements of the following examples and comparative examples, the voltage holding ratio (%) at 343 K under the conditions of frequency 60 Hz and applied voltage 1 V
In the following examples and comparative examples, the burn-in, drop marks and pretilt angle of the liquid crystal display element were evaluated by the following methods.
(Burned)
The burn-in evaluation of the liquid crystal display element is carried out by displaying a predetermined fixed pattern in the display area for 1000 hours and thereafter visually observing the level of the residual image of the fixed pattern when uniform display is performed over the entire screen by the following four steps. went.
:: no afterimage 残: a slight afterimage even acceptable level 許 容: afterimage unacceptable level ×: afterimage with appreciably poor (drop marks)
The evaluation of the drop marks of the liquid crystal display device was performed by the following four-step evaluation by visual observation of the drop marks that appear white when the entire surface was displayed black.
:: no afterimage 残: a slight afterimage but acceptable level :: afterimage unacceptable level ×: afterimage with very poor (pretilt angle)
The surface of the liquid crystal display element was randomly measured at five points, and the average value was taken as the pretilt angle. In addition, when the stability of the pretilt angle was evaluated, changes in the pretilt angle before and after stress were compared. The stress was applied by placing the liquid crystal display 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 descriptions of compounds. Here, n represents a natural number.
(Side chain)
-N-C _n H _{2 n + 1} straight-chain alkyl group having n carbon atoms n-C _n H _{2 n + 1-} straight-chain alkyl group having n carbon atoms-On-OC _n H _{2 n + 1} straight chain having n carbon atoms Jo alkoxyl group nO- _C n _{H 2n} + 1 O- carbon atoms n linear alkoxyl group -V -CH = CH ₂
V- CH ₂ = CH-
-V1 -CH = CH-CH ₃
1V- CH ₃ -CH = CH-
_{-2V -CH 2 -CH 2 -CH = CH} 3
_{V2- CH 3 = CH-CH 2} -CH 2 -
-2V 1 -CH ₂ -CH ₂ -CH = CH-CH _{3
1V2- CH 3 -CH = CH-CH} 2 -CH 2
(Linking group)
-N--C _n H ₂ n-
-NO--C _n H _{2 n-} O-
-On--O-C _n H _{2 n-}
-COO- -C (= O) -O-
-OCO- -O-C (= O)-
-CF2O- -CF ₂ -O-
-OCF2- -O-CF ₂ -
D -C = C-
T-C ≡ C-
(Ring structure)

Synthesis Example 1
[Synthesis of Polymer (A-1) Having Thermally Degradable Group]
26.8 g of acrylic acid and 3,3,4,4,5,5,6,6,7,7,8,8,8-8 in a glass flask equipped with a stirrer, thermometer, condenser, and dropping device. 30.0 g of tridecafluoro-1-vinyloxyoctane was charged, and the mixture was stirred at room temperature for 21 hours under a stream of dry air. Next, 0.003 g of methoquinone and 107.6 g of diisopropyl ether were added, and 161.4 g of a saturated aqueous solution of sodium carbonate and 161.4 g of ion exchanged water were added to separate the layers. Next, after removing the upper layer, 161.4 g of ion exchanged water was added to separate the layers. Furthermore, after removing the upper layer, the solvent was removed to obtain a polymerizable monomer having a blocked carboxyl group represented by the general formula (1).

In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 50 g of propylene glycol monomethyl ether acetate was charged as a solvent, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. Next, a monomer solution in which 17.5 g of the polymerizable monomer having a blocked carboxyl group and 32.5 g of polypropylene glycol monomethacrylate are dissolved in 40.0 g of propylene glycol monomethyl ether acetate (PGMEA), and a radical polymerization initiator The two drops of the polymerization initiator solution in which 1.5 g of 2,2'-azobis (methyl isobutyrate) was dissolved in 17 g of propylene glycol monomethyl ether acetate were set in separate dropping devices, respectively, and the inside of the flask was The dropwise addition was started at the same time while keeping the temperature at ° C, and each was dropped over 3 hours. After completion of the dropwise addition, after stirring at 80 ° C. for 10 hours, propylene glycol monomethyl ether acetate was further added to obtain a propylene glycol monomethyl ether acetate solution containing 20 mass% of a polymer (A-1) having a thermally degradable group . As a result of measuring the molecular weight of the obtained polymer (A-1) having a thermally degradable group by GPC (molecular weight in terms of polystyrene), it has a number average molecular weight of 2,500, a weight average molecular weight of 9,000 and a maximum molecular weight of 90,000 there were.
(Composition example 2)
[Synthesis of Polymer (A-2) Having Thermally Degradable Group]
In a glass flask equipped with a stirrer, thermometer, and dropping device, 25.0 g of hydroxyphenyl methacrylate and 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-8 82.0 g of decafluoro-1-vinyloxyoctane, 1.6 g of trifluoroacetic acid, and 200 g of tetrahydrofuran were charged, and reacted while maintaining at 60 ° C. for 9 hours under a nitrogen atmosphere. After cooling, 1.7 g of pyridine was added to the reaction solution, and the obtained reaction solution was washed with water, separated, desolventized, and unreacted components were removed by distillation under reduced pressure to obtain an acetalized product.

  In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 200 g of diethylene glycol dimethyl ether, 8.0 g of dimethyl-2,2'-azobis (2-methylpropionate), 2,4-diphenyl as a solvent 2.0 g of -4-methyl-1-pentene was charged. Then, 75.0 g of the acetalized product and 25.0 g of benzyl methacrylate are charged, and while gently stirring under a nitrogen atmosphere, the inside of the flask is raised to 80 ° C. and the heat is decomposed by stirring at 80 ° C. for 4 hours A diethylene glycol dimethyl ether solution containing 35% by mass of the polymer (A-2) having a functional group was obtained. As a result of measuring the molecular weight of the obtained polymer (A-2) having a thermally degradable group by GPC (molecular weight in terms of polystyrene), it has a number average molecular weight of 9,900, a weight average molecular weight of 21,800 and a maximum molecular weight of 70,000 there were.

Moreover, Megafac F-554 (made by DIC Corporation) was used as a polymer (A-3) which does not have a thermally decomposable group.
(Liquid crystal composition)
The following liquid crystal compositions (LC-A1) to (LC-A6), (LC-B1), and (LC-B2) were used in Examples and Comparative Examples of the present invention.

(Compound having a polymerizable group for controlling the alignment direction of liquid crystal molecules in the liquid crystal composition layer)
As a compound which has a polymeric group which controls the orientation direction of the liquid crystal molecule in a liquid-crystal composition layer, the compound represented by the following formula was used.

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

  In each pixel electrode substrate, in order to divide the alignment of liquid crystal molecules, each pixel electrode was etched with ITO so that a slit having no electrode exists.

  A vertical alignment film material containing a polyimide precursor and a polymerizable compound having a polymerizable group is applied to each of a common electrode substrate and a pixel electrode substrate by spin coating, and the coated 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 above formula (Va-1-3) in a polyimide solution (trade name: JALS2131-R6, manufactured by JSR Corporation) containing 3% by mass of a polyimide precursor as a solid content A solution containing 0.5% by mass of the polymer (A-1) and 0.01% by mass of the polymer (A-1) having the thermally degradable group was used.

  The liquid crystal composition (LC-A1) was sandwiched between the common electrode substrate on which the vertical alignment film was formed and the pixel electrode substrate, and then the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.0 μm by using a spacer having a thickness of 3.0 μm.

  The liquid crystal display element thus obtained was irradiated with ultraviolet light in the state where a rectangular alternating current electric field was applied, and the compound represented by the formula (Va-1-3) was cured. The liquid crystal display device of Example 1 is irradiated with ultraviolet light for 300 seconds at 20 mW as a UV light together with UIS-S2511RZ made by Ushio Inc. as an irradiation device and using USH-250BY made by Ushio Inc. as an ultraviolet lamp. I got By this step, a vertical alignment film containing the compound represented by the formula (Va-1-3) is formed, and liquid crystal molecules in the liquid crystal composition layer are provided with a pretilt angle.

  Here, the pretilt angle is defined as shown in FIG. In the case of perfect 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 a pretilt angle in different directions in the four sections according to the slits of the pixel electrode as shown in FIG. 2, and even after the curing of the polymerizable compound, the AC electric field is cut off. The pretilt angle was maintained. In addition, almost no change in pretilt angle was observed even after stress.

  Physical properties of liquid crystal composition used in liquid crystal display element of Example 1, VHR after UV irradiation, evaluation of dripping marks of obtained liquid crystal display element, evaluation of burn-in, pretilt angle before stress, pretilt change after stress Are shown in the following table. As a result, in the liquid crystal composition used in the liquid crystal display element of Example 1, no large change in pretilt angle is observed before and after stress. This is because the polymer (A-1) having a thermally degradable group in the material for the alignment film makes the alignment film smoother, and since the polymer is stable to the liquid crystal composition, the pretilt angle is also stable. It is considered to be

(Examples 2 to 11, Comparative Examples 1 to 2)
Example except that the compound having a polymerizable group to be used, the polymer having a thermal decomposable group or the polymer having no thermal decomposable group to be used, and the liquid crystal composition to be used have been changed to those described in the above table, respectively The liquid crystal display elements of Examples 2 to 11 and Comparative examples 1 to 2 were produced under the same conditions as Example 1. Each physical property of the liquid crystal composition used for the obtained liquid crystal display element, VHR after UV irradiation, evaluation of dripping marks of the obtained liquid crystal display element, evaluation of burn-in, pretilt angle before stress, pretilt change after stress , According to the above table.
(Example 12)
A first substrate (common electrode substrate) having a transparent electrode layer formed of a transparent common electrode and a color filter layer, and a second substrate (pixel) having a pixel electrode layer having a transparent pixel electrode driven by an active element An electrode substrate) was produced.

  In each pixel electrode substrate, in order to divide the alignment of liquid crystal molecules, each pixel electrode was etched with ITO so that a slit having no electrode exists.

  A vertical alignment film material including a polyimide precursor, a polymerizable compound having a polymerizable group, and a polymer having a thermally degradable group is applied to each of the common electrode substrate and the pixel electrode substrate by spin coating, and the application is performed. By heating the film at 200 ° C., the polyimide precursor in the vertical 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 vertical alignment film forming material, a polyimide derivative represented by the following formula has a solid content of 3% by mass, a polymerizable compound represented by the formula (Va-1-3) is 0.5% by mass, and a thermal decomposition A N-methyl-2-pyrrolidone / 2-butoxyethanol = 70/30 (mass ratio) solution containing 0.01% by mass of the polymer (A-1) having a group was used.

  The liquid crystal composition (LC-A1) was sandwiched between the common electrode substrate on which the vertical alignment film was formed and the pixel electrode substrate, and then the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.0 μm by using a spacer having a thickness of 3.0 μm.

  The liquid crystal display element thus obtained was irradiated with ultraviolet light in the state where a rectangular alternating current electric field was applied, and the compound represented by the formula (Va-1-3) was cured. The liquid crystal display element of Example 12 is irradiated with ultraviolet light for 300 seconds at 20 mW as a UV light together with UIS-S2511RZ manufactured by USHIO Inc. as an irradiation apparatus and using USH-250BY manufactured by USHIO INC. As a UV lamp. I got By this process, 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 liquid crystal molecules in the liquid crystal composition layer. Ru.

  The liquid crystal display element of Example 12 has pretilt angles in different directions in four sections according to the slits of the pixel electrode as shown in FIG. 2, and even after the curing of the polymerizable compound, the AC electric field is cut off. The pretilt angle was maintained. In addition, almost no change in pretilt angle was observed even after stress.

  Physical properties of liquid crystal composition used for liquid crystal display element of Example 12, VHR after UV irradiation, evaluation of dripping marks of obtained liquid crystal display element, evaluation of burn-in, pretilt angle before stress, pretilt change after stress Are shown in the following table. As a result, in the liquid crystal composition used for the liquid crystal display element of Example 12, no significant change in the pretilt angle is observed before and after stress. This is because the polymer (A-1) having a thermally degradable group in the material for the alignment film makes the alignment film smoother, and since the polymer is stable to the liquid crystal composition, the pretilt angle is also stable. It is considered to be

(Examples 13 to 18, Comparative Examples 3 to 4)
Example except that the compound having a polymerizable group to be used, the polymer having a thermal decomposable group or the polymer having no thermal decomposable group to be used, and the liquid crystal composition to be used have been changed to those described in the above table, respectively The liquid crystal display elements of Examples 13 to 18 and Comparative Examples 3 to 4 were produced under the same conditions as Example 12. Each physical property of the liquid crystal composition used for the obtained liquid crystal display element, VHR after UV irradiation, evaluation of dripping marks of the obtained liquid crystal display element, evaluation of burn-in, pretilt angle before stress, pretilt change after stress , According to the above table.
(Example 19)
A first substrate (common electrode substrate) having a transparent electrode layer formed of a transparent common electrode and a color filter layer, and a second substrate (pixel) having a pixel electrode layer having a transparent pixel electrode driven by an active element An electrode substrate) was produced.

  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 spin coating to form a precursor layer of a vertical alignment film with a thickness of 200 nm. As a material for forming a vertical alignment film, 5.0% by mass of the polymerizable compound represented by the formula (Va-1-3), and 0.1% by mass of the polymer (A-1) having a thermally decomposable group %, And 95.0 mass% of UCL-011-K1 (made by DIC Corporation) polymeric compound were used.

  Each of the substrates coated with the vertical alignment film forming material is heated for 5 minutes in a constant temperature bath at 70 ° C., and further heated on a hot plate at 180 ° C. for 15 minutes to polymerize the coated vertical alignment film forming material The liquid crystal compound was an isotropic liquid.

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

  A magnetic field inclined 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 light was irradiated to cure the polymerizable liquid crystal compound to form a vertical alignment film.

  The liquid crystal composition (LC-A1) was sandwiched between the common electrode substrate on which the vertical alignment film was formed and the pixel electrode substrate, and then the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.0 μm by using a spacer having a thickness of 3.0 μm.

  The liquid crystal display element thus obtained was irradiated with ultraviolet light in the state where a rectangular alternating current electric field was applied, and the compound represented by the formula (Va-1-3) was cured. The liquid crystal display element of Example 19 is irradiated with ultraviolet light for 300 seconds at 20 mW using a Ushio Inc. USH-250BY as an ultraviolet lamp together with a UIS-S2511 RZ manufactured by Ushio Inc. as an irradiation apparatus. I got By this step, a vertical alignment film containing the polymer of the above formula (Va-1-3) is formed, and a pretilt angle is given to liquid crystal molecules in the liquid crystal composition layer.

  The liquid crystal display element of Example 19 has pretilt angles in different directions in four sections according to the slits of the pixel electrode as shown in FIG. 2, and after curing of the polymerizable liquid crystal compound, the AC electric field is cut off. But the pretilt angle was maintained. In addition, almost no change in pretilt angle was observed even after stress.

  Physical properties of liquid crystal composition used for liquid crystal display element of Example 19, VHR after UV irradiation, evaluation of dripping marks of obtained liquid crystal display element, evaluation of burn-in, pretilt angle before stress, pretilt change after stress Are shown in the following table. As a result, in the liquid crystal composition used for the liquid crystal display element of Example 19, no significant change in pretilt angle is observed before and after stress. This is because the polymer (A-1) having a thermally degradable group in the material for the alignment film makes the alignment film smoother, and since the polymer is stable to the liquid crystal composition, the pretilt angle is also stable. It is considered to be

(Examples 20 to 25, Comparative Examples 5 to 6)
Example except that the compound having a polymerizable group to be used, the polymer having a thermal decomposable group or the polymer having no thermal decomposable group to be used, and the liquid crystal composition to be used have been changed to those described in the above table, respectively The liquid crystal display elements of Examples 20 to 25 and Comparative Examples 5 to 6 were produced under the same conditions as in Example 19. Each physical property of the liquid crystal composition used for the obtained liquid crystal display element, VHR after UV irradiation, evaluation of dripping marks of the obtained liquid crystal display element, evaluation of burn-in, pretilt angle before stress, pretilt change after stress , According to the above table.

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 molecules, 20 ... polymer layer, 21 ... polymer layer

Claims (16)

  A first substrate, a second substrate, and a liquid crystal composition layer sandwiched between the first and second substrates, and an electrode is provided on at least one of the first substrate and the second substrate. A polymer of a compound having a polymerizable group which controls the alignment direction of liquid crystal molecules in the liquid crystal composition layer on at least one of the first substrate and the second substrate; A liquid crystal display device comprising an alignment film containing a polymer having a group, wherein the dielectric anisotropy (Δε) of the liquid crystal composition constituting the liquid crystal composition layer is negative. The liquid crystal composition 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 represent an alkyl group having 1 to 8 carbon atoms, and one or two non-adjacent ones in the alkyl group Or more of -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) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ -. May be replaced by -O-) and (B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -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 = or two or more non-adjacent —CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by —N =. )
And 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 = N-, -CH = CH-, -CF = CF- or -C≡C-,
X ^N21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents -CH ₂ -or -O-,
^{n N11, n N12, n N21} , n N22, n N31 and ^{n N32} each independently represents an integer of ^{0~3, n N11 + n N12,} n N21 + n N22 and ⁿ N31 ^{+ n N3 2} is independently And 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 liquid crystal display element of Claim 1 containing the 1 type (s) or 2 or more types of compound chosen from the compound group represented by these.   The liquid crystal display element according to claim 1 or 2, wherein the thermally decomposable group contains a fluorine atom and / or a silicon atom. The thermally decomposable group is represented by the following general formula (I-1-1) or general formula (I-1-2)

(In the general formula (I-1-1) and the general formula (I-1-2), R ¹ and R ² each independently represent a hydrogen atom or a linear or branched C 1-18 carbon atom Represents an organic group, Y ¹ represents an oxygen atom or a sulfur atom, R ⁴ represents a fluorine atom and / or an organic group having a silicon atom, and * represents a bonding site. The liquid crystal display device according to any one of claims 1 to 3.   The liquid crystal display element according to any one of claims 1 to 4, comprising a plurality of pixels, and having two or more regions having different pretilt angles in the pixels.   The liquid crystal display element according to any one of claims 1 to 5, wherein the first substrate has a common electrode and the second substrate has a pixel electrode.   Between the common electrode and the pixel electrode, an electric charge is applied substantially perpendicularly to the first substrate and the second substrate, and the alignment film for controlling liquid crystal molecules in the liquid crystal composition layer is provided. The liquid crystal display element as described in.   The said alignment film contains the polymer which controls the orientation direction of the liquid crystal molecule in the said liquid-crystal composition layer, or is formed from the hardened | cured material of a polymerizable liquid crystal compound. The liquid crystal display element as described in.   The polymer for controlling the alignment direction of 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 liquid crystal display element according to claim 8, comprising a polymer of a polymerizable compound having   The liquid crystal display device according to any one of claims 1 to 9, further comprising, on the surface of the alignment film, a polymer of one or more polymerizable compounds that control and stabilize the alignment of liquid crystal molecules. An alignment material containing a polymer having a thermally degradable group is applied to at least one of the first substrate and the second substrate to form an alignment film material, and then the first substrate having an electrode on at least one of the first substrate and the second substrate. And the second substrate sandwiching the liquid crystal composition, and irradiating the electrode with an active energy ray while applying a voltage, the polymerizability of the compound having a polymerizable group contained in the alignment film material The liquid crystal composition has an alignment film that controls the alignment direction of liquid crystal molecules in the liquid crystal composition layer by polymerizing a group, 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 represent an alkyl group having 1 to 8 carbon atoms, and one or two non-adjacent ones in the alkyl group Or more of -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) 1,4-cyclohexylene group (one -CH _2- present in this group or adjacent thereto And two or more -CH _2- may be replaced by -O-) and (b) 1,4-phenylene group (one -CH = present in this group or not adjacent 2) Or more of -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 = or two or more non-adjacent —CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by —N =. )
And 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 = N-, -CH = CH-, -CF = CF- or -C≡C-,
X ^N21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents -CH ₂ -or -O-,
^{n N11, n N12, n N21} , n N22, n N31 and ^{n N32} each independently represents an integer of ^{0~3, n N11 + n N12,} n N21 + n N22 and ⁿ N31 ^{+ n N3 2} is independently And 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 manufacturing method of the liquid crystal display element containing the 1 type (s) or 2 or more types of compound chosen from the compound group represented by these.   The said alignment film material contains the polymer which controls the orientation direction of the liquid crystal molecule in the said liquid-crystal composition layer, or, the said alignment film material is a hardened | cured material of a polymerizable liquid crystal compound. Method of manufacturing a liquid crystal display device.   The polymer for controlling the alignment direction of 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 12 containing the polymer of the polymeric compound which has these.   The method for producing a liquid crystal display device according to claim 12 or 13, further comprising a polymer of one or more polymerizable compounds which control and stabilize the alignment of liquid crystal molecules on the surface of the alignment film. The said active energy ray is an ultraviolet-ray, The intensity | strength is ² mW / cm ^<-2 > -100mW / cm ^{< -2} >, The irradiation total energy amount is 10J-300J as described in any one of Claims 12-14. Method of manufacturing a liquid crystal display device   An alignment film material comprising a polymer of a compound having a polymerizable group which controls the alignment direction of liquid crystal molecules, and a polymer having a thermally degradable group.

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