JP2019113675A - Method for manufacturing liquid crystal display element - Google Patents

Abstract

To provide a method for manufacturing a liquid crystal display element, by which, in a polymerization step of irradiating a liquid crystal composition containing a polymerizable compound with light in a method of manufacturing a PSA type liquid crystal display device, the polymerizable compound is polymerized at a suitable polymerization speed so as to prevent or extremely minimize display failures due to changes in a pretilt angle and to decrease or suppress reduction of a VHR and display failures caused by the reduction of the VHR.SOLUTION: The present invention provides a method for manufacturing a liquid crystal display element, in which after a liquid crystal composition comprising a polymerizable compound and a non-polymerizable liquid crystal compound are deposited on a substrate, a light irradiation step (A) of irradiating the liquid crystal composition with irradiation light having light at a wavelength of 370 nm or more as an essential component is performed once or more times.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a liquid crystal display device using a liquid crystal composition containing a polymerizable compound.

  PSA (Polymer Sustained Alignment) type liquid crystal display device has a structure in which a polymer structure is formed in the cell to control the pretilt angle of liquid crystal molecules, and developed as a liquid crystal display element from high speed response and high contrast Is in progress.

  In the production of a PSA type liquid crystal display element, a liquid crystal composition containing a polymerizable compound is injected between the substrates, and a voltage is applied to irradiate liquid crystal molecules in a state in which liquid crystal molecules are aligned to irradiate ultraviolet light to polymerize the polymerizable compound. A method is used in which the alignment of liquid crystal molecules is fixed by controlling the pretilt angle of the liquid crystal molecules with the formed polymer structure (Patent Document 1).

  In such a PSA type liquid crystal display element, a liquid crystal exhibiting a low VHR (voltage retention) value when the polymerizable compound used to generate the pretilt angle remains in the display as an unpolymerized substance even after the polymerization step. Since it becomes a display element and a display defect such as burn-in may occur, a polymerizable compound or the like in which an unpolymerized substance does not remain or hardly remains has been developed (Patent Documents 1 and 2).

  Specifically, according to Patent Document 1, while applying a voltage between a pair of transparent electrodes, it is directly bonded to one or more ring structures or condensed ring structures and the ring structures or condensed ring structures 2 It is described that sticking can be reduced by polymerizing a monomer having two functional groups to form a polymer structure.

  Further, according to Patent Document 2, negative dielectric anisotropy including one or more types of polymerizable compounds having two polymerizable groups and one or more types of polymerizable compounds having three or more polymerizable groups can be obtained. A liquid crystal medium having the same and a liquid crystal display device using the same, exhibiting particularly good UV absorption at longer wavelengths, RM contained in the LC medium polymerizing rapidly and completely, and as quickly as possible low tilt angles Produces and enables high stability of pretilts even after prolonged UV exposure and / or after UV exposure, reduces or prevents the occurrence of image sticking in the display and reduces or prevents the occurrence of ODF unevenness in the display It is described.

JP 2003-307720 JP, 2016-108558, A

  The above Patent Documents 1 and 2 are both techniques focusing on the structure of the polymerizable compound used in the polymerization step and the content of the polymerizable compound, and, for example, Patent Document 1 specifies the direction in which the liquid crystal molecules fall. It is described that the burn-in is reduced by restricting by the polymerizable compound having the chemical structure of (1), but the decrease in VHR caused by the unpolymerized polymerizable compound and the display failure caused thereby, the non-polymerizable liquid crystal by light irradiation A new problem of compound degradation arises. Further, Patent Document 2 focuses on the number of polymerizable groups and the content of a polymerizable compound, and polymerizes using a fluorescent UV lamp type C (305 to 355 nm) as a light irradiation condition. Therefore, a new problem of deterioration of the non-polymerizable liquid crystal compound by the fluorescent UV lamp arises.

  Therefore, the problem to be solved by the present invention is that the polymerization step of irradiating a liquid crystal composition containing a polymerizable compound and a non-polymerizable liquid crystal compound of the manufacturing method for producing a PSA type liquid crystal display device is suitable. It is an object of the present invention to provide a method for producing a liquid crystal display element by reducing and suppressing display defects caused by a decrease in VHR due to deterioration of a nonpolymerizable liquid crystal compound and deterioration of a nonpolymerizable liquid crystal compound by performing light irradiation conditions Do.

  As a result of intensive investigations by the present inventors, after a liquid crystal composition containing a polymerizable compound and a non-polymerizable liquid crystal compound is attached onto a substrate, the liquid crystal composition is irradiated with light having a wavelength of 370 nm or more as the main component. It has been found that the above-mentioned problems can be solved by the method for producing a liquid crystal display device in which the light irradiation step (A) is performed one or more times, and the present invention has been completed.

  The liquid crystal display element using the method for manufacturing a liquid crystal display element of the present invention suppresses / reduces the decrease in VHR.

  The liquid crystal display device using the method for manufacturing a liquid crystal display device of the present invention has no or very few display defects due to the change of the pretilt angle.

  The liquid crystal display device using the method for manufacturing a liquid crystal display device according to the present invention exhibits excellent display quality with high voltage holding ratio (VHR) and high-speed response, and without or suppressed display defects such as alignment defects and burn-in. Show.

  The liquid crystal display element using the method for manufacturing a liquid crystal display element of the present invention has an appropriately short irradiation time of ultraviolet light, and can easily improve the production efficiency by optimization and reduction of energy cost.

FIG. 1 is a diagram showing an emission spectrum of a light source. FIG. 2 is a diagram showing an emission spectrum of the light source used in the comparative example. FIG. 3 is a diagram showing the emission spectrum of the light source used in the example.

  In the first aspect of the present invention, a liquid crystal composition containing a polymerizable compound and a non-polymerizable liquid crystal compound is attached to a substrate, and then light is emitted to the liquid crystal composition mainly containing light with a wavelength of 370 nm or more. It is a manufacturing method of the liquid crystal display element which performs an irradiation process (A) once or more.

  In the manufacturing method according to the present invention, since the liquid crystal composition containing the polymerizable compound and the non-polymerizable liquid crystal compound is irradiated with light whose main component is a wavelength of 370 nm or more, the polymerization becomes relatively mild. The liquid crystal display device using the method for producing a liquid crystal display device of the present invention can reduce deterioration of a liquid crystal composition, particularly a non-polymerizable liquid crystal compound, and a liquid crystal composition resulting from the deterioration of a non-polymerizable liquid crystal compound The decrease in VHR of

  The term “irradiation light mainly composed of light with a wavelength of 370 nm or more” as used herein refers to light with a wavelength of 370 nm or more and 500 nm or less in the emission spectrum of a light source that enables irradiation of light overlapping with the wavelength range of 300 nm to 500 nm. The integrated intensity which is an integral value of is divided by the integrated intensity which is an integral value of light of 300 nm or more and 500 nm or less is a light of 0.9 or more. The main component means that the integrated intensity of light of at least the selected wavelength region of 370 nm or more and 500 nm has an integrated intensity of at least 90% or more in 300 nm or more and 500 nm. Therefore, the light from the light source or the “light mainly composed of light with a wavelength of 370 nm or more” may include light with a wavelength of less than 300 nm or light with a wavelength of more than 500 nm. Further, the light from the light source may be only light within the range of 370 nm to 500 nm, as long as irradiation of light overlapping with a wavelength range of 300 nm to 500 nm can be performed.

In addition, in the manufacturing method according to the present invention, a method of calculating the irradiation light whose main component is light having a wavelength of 370 nm or more will be described below with reference to FIG. That is, FIG. 1 is a diagram showing the emission spectrum of the light source, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (μW / cm ² ). Since the line in the spectrum represents the intensity at each wavelength, the integrated value (a) (the area in the range of 300 nm to 500 nm), which is the sum of the intensities of each wavelength 300 nm to 500 nm, is the integrated intensity of light of 300 nm to 500 nm It is. Moreover, integral value (b) (area of the range of 370 nm-500 nm) which is the sum total of the intensity | strength of each wavelength of 370 nm-500 nm is integrated intensity of the light of 370 nm-500 nm. Therefore, when the integral value (b) / the integral value (a) is 0.9 or more, it corresponds to "irradiation light mainly composed of light with a wavelength of 370 nm or more". In this specification, it is calculated from the area ratio of the light emission spectrum of the light source whether it is the "main component" or not. That is, the area ratio is 90% or more to be the main component, and the area ratio is less than 90% not to be the main component.

  In the present specification, the wavelength range of ultraviolet light is 200 to 380 nm, and the wavelength range of visible light is 380 to 780 nm.

  In general, a method of manufacturing a liquid crystal display element is a method of filling a liquid crystal composition containing a polymerizable compound and a nonpolymerizable liquid crystal compound between a pair of (electrode) substrates by vacuum injection (a so-called vacuum injection method) The method is broadly divided into a method (so-called ODF method) of dropping a liquid crystal composition onto at least one (electrode) substrate of the electrodes). When the method of manufacturing a liquid crystal display element according to the present invention is performed by the former vacuum injection method, a liquid crystal cell forming step of manufacturing a liquid crystal cell provided with a pair of (electrode) substrates provided with an alignment film if necessary; An injection step of attaching and filling a liquid crystal composition containing a polymerizable compound onto the (electrode) substrate by vacuum injection into a cell, and a wavelength of 370 nm or more on the liquid crystal composition attached onto the (electrode) substrate It is preferable to have the light irradiation process (A) which irradiates the irradiation light which has as a main component the light of 4, and the process of bonding a polarizing plate.

  In the above manufacturing method, if necessary, after the injection step, the liquid crystal cell filled with the liquid crystal composition may be annealed at 60 to 130 ° C. before the light irradiation step. Moreover, it is preferable to perform the process (The said light irradiation process (A) and process of irradiating the light of a wavelength other than the said) of irradiating light to a liquid crystal composition once or more.

  In the step of irradiating the liquid crystal composition with light (step of irradiating the light irradiation step (A) and light of a wavelength other than the above), the light irradiation step may be performed one or more times in a state where a voltage is applied. preferable.

  When the method of manufacturing a liquid crystal display element according to the present invention is performed by the latter ODF method, a pair of (electrode) substrates provided with an alignment film is provided if necessary (electrode) substrate forming step, and at least one of the above (electrodes) The step of drawing the bonding area over the entire periphery with the bonding sealing agent on the outer periphery of one side of the substrate, and the polymerizable compound and the nonpolymerizable liquid crystal compound inside the bonding area on one side of the (electrode) substrate. A step of adhering a liquid crystal composition to be contained and then bonding it to the other (electrode) substrate to cure the sealing agent for bonding, and a liquid crystal composition containing a polymerizable compound attached onto the (electrode) substrate It is preferable to have the light irradiation process (A) which applies the irradiation light which has the light of wavelength 370 nm or more as a main component to a thing, and the process of bonding a polarizing plate.

  In the above manufacturing method, if necessary, after the injection step, the liquid crystal cell filled with the liquid crystal composition may be annealed at 60 to 130 ° C. before the light irradiation step. Moreover, it is preferable to perform the process (The said light irradiation process (A) and process of irradiating the light of a wavelength other than the said) of irradiating light to a liquid crystal composition once or more.

  The (electrode) substrate according to the present invention may or may not have an alignment layer on the surface. Further, one of the pair of substrates may have an alignment layer, and both may have an alignment layer. A preferred liquid crystal display device according to the present invention comprises an electrode layer comprising a first polarizing layer on one surface and a thin film transistor for controlling the pixel electrode and the pixel electrode provided in each pixel on the other surface. And a second substrate comprising a second polarizing layer on one side and a (transparent) electrode layer (also called common electrode) and a color filter on the other side. And a liquid crystal layer (formed of a liquid crystal composition containing a polymerization compound) sandwiched between the first substrate and the second substrate. In the liquid crystal display element, the long axis direction of the liquid crystal molecules in the liquid crystal layer when the voltage is not applied is substantially perpendicular to the substrate, and the long axis direction of the liquid crystal molecules in the voltage application is the above This is a liquid crystal display element in which the liquid crystal molecules are aligned substantially parallel to the substrate and reversibly controls the long axis direction of the liquid crystal molecules in response to a voltage.

  Furthermore, an alignment layer may be formed on at least one of the electrode (layer) or the surface of the common electrode layer if necessary so as to be adjacent to the liquid crystal layer and in direct contact with the liquid crystal composition constituting the liquid crystal layer. It is not necessary to form an alignment layer on the surface.

  In the step (A) of irradiating the liquid crystal composition with light, it is preferable to perform the light irradiation step once or more in a state where a voltage is applied, which will be described in detail later.

  The bonding sealing agent is preferably cured by a UV or heat-curable resin, and a known thermosetting sealing agent is preferably used.

  In the method of manufacturing a liquid crystal display device according to the present invention, light irradiation is performed by applying irradiation light mainly composed of light having a wavelength of 370 nm or more to a liquid crystal composition containing a polymerizable compound and a nonpolymerizable liquid crystal compound attached on a substrate. Step (A) is preferably performed 1 to 5 times, more preferably 1 to 4 times, further preferably 1 to 3 times, particularly preferably 1 to 2 times.

  In the light irradiation step (A) of the method for producing a liquid crystal display element according to the present invention, as means for generating irradiation light mainly composed of light with a wavelength of 370 nm or more, a high pressure mercury lamp, a halogen lamp, a metal halide lamp, fluorescent UV There are lamps and LED lamps. A filter that cuts a specific wavelength range, such as a band pass filter, a low pass filter, or a high pass filter may be used.

  In the light irradiation step (A), h-ray (405 nm), g-ray (436 nm) and the like are also preferable. The irradiation light may be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as necessary, and ultraviolet light may be cut and used as necessary.

In the method of manufacturing a liquid crystal display device according to the present invention, a liquid crystal composition containing a polymerizable compound and a nonpolymerizable liquid crystal compound attached on a substrate is irradiated with a light having a wavelength of 370 nm or more as necessary. You may perform the light irradiation process (B) which irradiates light other than light. In other words, in the method of manufacturing a liquid crystal display element according to the present invention, the light irradiation step (B) may be performed in which irradiation light which does not have light with a wavelength of 370 nm or more as the main component.
In this case, the lower limit of the wavelength of light to be irradiated in the step (B) of irradiating light is preferably 300 nm, more preferably 305 nm, and still more preferably 310 nm. 800 nm is preferable, 700 nm is preferable, 600 nm is preferable, 500 nm is preferable, and the upper limit of the wavelength of the light to be irradiated in the step (B) of irradiating light is preferably 400 nm.

  A low pressure mercury lamp, a metal halide lamp, a high pressure mercury lamp, a fluorescent UV lamp, a super high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used as a light source generating light in the wavelength range. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as (313 nm), i-line (365 nm), h-line (405 nm), g-line (436 nm), can preferably be used, and j-line (313 nm) or i-line (365 nm) The actinic ray which does not have light with a wavelength of 370 nm or more as a main component is preferable.

  The light used in the light irradiation step (B) according to the present invention preferably has a peak near 313 nm or a peak near 365 nm, more preferably a peak near 313 nm and a peak near 365 nm It is particularly preferable to have a peak in the vicinity of 313 nm. When the peak is in the vicinity of 313 nm, the reaction rate of the polymerizable compound is fast, so that the light irradiation time is short, and there is an advantage that VHR decrease due to long light irradiation does not easily occur. Further, if necessary, light having a specific wavelength or a specific wavelength or less may be cut using a known cut filter. In the light irradiation according to the present invention, it is preferable to cut light in the range of 300 to 350 nm or less, for example, a mode in which light of 320 nm or less is cut and light of 325 nm or less is cut.

  This has the advantage that the reaction rate of the polymerizable compound can be easily adjusted.

  Furthermore, as the wavelength of the ultraviolet light to be irradiated in the light irradiation step (B) according to the present invention, it is sufficient to include the above-mentioned ultraviolet light of 300 to 370 nm wavelength, and the ultraviolet light in the wavelength region other than the absorption wavelength region of the polymerizable compound It may be irradiated. The active energy ray such as ultraviolet rays to be irradiated preferably has a plurality of spectra, and preferably has a plurality of spectra. By irradiation with active energy rays having a plurality of spectra, the polymerizable compound can be polymerized by active energy rays of a spectrum (wavelength) suitable for each type, and in this case, the alignment direction of liquid crystal molecules can be controlled. Polymers are formed more efficiently.

  In order to polymerize the polymerizable compound contained in the liquid crystal composition of the present invention to obtain a good alignment performance of the liquid crystal, an appropriate polymerization rate is desirable. It may be a method of polymerizing by irradiating one or in combination or sequentially.

  In the process for producing a liquid crystal display device according to the present invention, the step (B) of irradiating light to a liquid crystal composition containing a polymerizable compound and a nonpolymerizable liquid crystal compound attached on a substrate is preferably 0 to 5 times. More preferably 1 to 4 times, still more preferably 1 to 3 times, particularly preferably 1 to 2 times.

  In the method for producing a liquid crystal display element according to the present invention, the step (B) of irradiating light may be performed before the light irradiation step (A), and the light is irradiated after the light irradiation step (A) Step (B) may be performed.

  In the method for producing a liquid crystal display device according to the present invention, a preferred embodiment of a light irradiation step for a liquid crystal composition containing a polymerizable compound and a non-polymerizable liquid crystal compound attached on a substrate comprises light of only 370 nm or more wavelength. It is preferable to perform the light irradiation process (A) which irradiates 1 to 2 times, and to perform the process (B) which irradiates light 0 to 4 times after a light irradiation process (A).

  By performing the light irradiation step a plurality of times, it is possible to form a reduction in the amount of residual monomer that causes a decrease in VHR and a desired pretilt angle.

The lower limit value of the illuminance of light irradiated in the light irradiation step (B) according to the present invention is preferably 10 mW / cm ² , more preferably 20 mW / cm ² , and still more preferably 30 mW / cm ² . Intensity upper limit value of the light the irradiation is preferably 1500 mW / cm ^2, more preferably 1000 mW / cm ^2, further preferably 800 mW / cm ^2.

  The method of measuring the illuminance of light to be irradiated according to the present invention is not particularly limited and can be carried out by a known method or apparatus, but the method of measuring the illuminance of light to be irradiated in the present specification is 313 nm For illumination, UVD-S313 manufactured by Ushio Inc. is used, and for illumination with 365 nm, UVD-S365 manufactured by Ushio Inc. is used.

Light irradiation time of the light irradiation process according to the present invention _(A) (t A) is suitably determined in such times of light irradiation step is preferably 0.5 to 150 minutes. The lower limit value of the irradiation time in the light irradiation step is more preferably 0.5 minutes, still more preferably 1 minute, and particularly preferably 1.5 minutes. The upper limit value of the irradiation time of the ultraviolet light is more preferably 120 minutes, more preferably 100 minutes, more preferably 90 minutes, more preferably 60 minutes, and 40 minutes. Is particularly preferred.

The irradiation time (t _A ) of light in the light irradiation step (B) according to the present invention is appropriately determined by the number of light irradiation steps and the like, but is preferably 0.5 to 100 minutes. The lower limit value of the irradiation time in the light irradiation step is more preferably 0.5 minutes, still more preferably 1 minute, and particularly preferably 1.5 minutes. The upper limit of the irradiation time of the ultraviolet light is more preferably 60 minutes, still more preferably 50 minutes, and particularly preferably 45 minutes.

  When a strong ultraviolet ray is irradiated for a long time in the polymerization step, the size of the production apparatus is increased and the production efficiency is lowered, and deterioration of the liquid crystal composition, particularly the nonpolymerizable liquid crystal compound, is caused by the ultraviolet ray. On the other hand, if the irradiation time of ultraviolet light is shortened, the occurrence of burn-in, which is one of display defects caused by the remaining polymerizable compound, can not be avoided. If the light irradiation process is the above-described conditions, as will be described later, the unreacted polymerizable compound in the entire composition is intentionally left to remain, and the unreacted polymerizable compound remaining by performing the light irradiation process Can be used.

  The temperature range of the atmosphere in the light irradiation steps (A) and (B) according to the present invention is preferably 19 ° C. to 63 ° C., and more preferably 20 ° C. to 50 ° C.

  In the present specification, the wavelength range of ultraviolet light is 200 to 380 nm, and the wavelength range of visible light is 380 to 780 nm.

  In the light irradiation steps (A) and (B) according to the present invention, when ultraviolet light is used, a polarized light source may be used or a non-polarized light source may be used, but non-polarized ultraviolet light may be irradiated. preferable.

  In the light irradiation steps (A) and (B) according to the present invention, the atmosphere in the light irradiation is not particularly limited, and may be an air atmosphere, or may be an atmosphere of nitrogen or a rare gas.

  Irradiation methods that can be used in the light irradiation steps (A) and (B) according to the present invention are not particularly limited, and known irradiation methods can be used.

  Moreover, when irradiating an ultraviolet-ray in the state which clamped the polymeric compound containing liquid crystal composition between 2 sheets of substrates (it superposes | polymerizes), the board | substrate of the irradiation side at least has the appropriate transparency with respect to an ultraviolet-ray Is preferably given. In addition, after only a specific part is polymerized using a mask at the time of light irradiation, the alignment state of the unpolymerized part is changed by changing the conditions such as the electric field and the magnetic field, and the ultraviolet ray is further irradiated to polymerize. The following means may be used.

  In the method of manufacturing a liquid crystal display element according to the present invention, it is preferable to irradiate light in a state where a voltage is applied in the light irradiation step (A) or (B).

  By irradiating light of a predetermined wavelength in a state where a voltage is applied to a liquid crystal composition containing a polymerizable compound, a stable pretilt angle of liquid crystal molecules is formed by the polymer derived from the remaining polymerizable compound. be able to. More specifically, the alignment direction of the liquid crystal molecules constituting the liquid crystal composition containing a polymerizable compound from the polymer polymerized in the light irradiation steps (A) and (B) is a specific direction (for example, Liquid crystal molecules can be fixed in vertical alignment by orientating in a direction perpendicular to the substrate) and forming a stable pretilt angle by a polymer polymerized in a light irradiation step if necessary. Thus, for example, the liquid crystal molecules at the time of voltage ON are aligned in parallel with the direction from the outside to the center of the fishbone structure, so that a multi-domain liquid crystal display element can be manufactured.

  When irradiating ultraviolet rays in the light irradiation steps (A) and (B) according to the present invention, it is preferable to irradiate the ultraviolet rays while applying an alternating voltage or a direct current voltage, and irradiate the ultraviolet rays while applying an alternating voltage. Is more preferred.

  The lower limit value of the frequency of the AC voltage to be applied is preferably 10 Hz, and more preferably 60 Hz. The upper limit of the frequency of the alternating voltage to be applied is preferably 10 kHz, more preferably 1 kHz.

  The magnitude of the voltage applied in the light irradiation steps (A) and (B) according to the present invention is selected depending on the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. The lower limit of the magnitude of the voltage applied in the light irradiation steps (A) and (B) is preferably 0.1 V, more preferably 0.2 V, and still more preferably 0.5 V. The upper limit of the magnitude of the voltage applied in the light irradiation step is preferably 30 V, more preferably 20 V, and still more preferably 10 V.

  The temperature of the liquid crystal composition containing the polymerizable compound and the nonpolymerizable liquid crystal compound at the time of voltage application in the light irradiation steps (A) and (B) according to the present invention is a temperature close to room temperature, preferably 14 to 62 ° C. It is preferable to apply a voltage to the polymerizable compound-containing liquid crystal composition at a temperature of 16 to 55 ° C., more preferably 18 to 52 ° C.

  The liquid crystal composition containing the polymerizable compound and the nonpolymerizable liquid crystal compound at the time of voltage application in the light irradiation step according to the present invention is preferably in a nematic phase state.

  In order to irradiate an ultraviolet-ray in the state which applied the voltage, it is preferable that the liquid crystal composition containing a polymeric compound and a non-polymerizable liquid crystal compound is a nematic phase from a viewpoint of uniform alignment.

  Hereinafter, a preferred embodiment of the method of manufacturing a liquid crystal display device according to the present invention will be described.

  One embodiment of a method of manufacturing a liquid crystal display device according to the present invention comprises irradiating a liquid crystal composition containing a polymerizable compound and a nonpolymerizable liquid crystal compound onto a substrate and then irradiating the substrate with light having a wavelength of 370 nm or more as the main component. Performing the light irradiation step (A) of applying the liquid crystal composition to the liquid crystal composition once, and performing the light irradiation step (B) of irradiating the liquid crystal composition with irradiation light not mainly containing light of a wavelength of 370 nm or more; The polymerizable compound is a group consisting of compounds represented by Formulas (XX-14) to (XX-21), Formulas (M-3) to (M-6), and Formula (RM-2-1) described later. Or at least one or more selected from

  In the preferred embodiment, the light irradiation step (A) may apply a voltage as necessary to apply irradiation light to the liquid crystal composition, and in the light irradiation step (B), the liquid crystal in a voltage non-applied state The composition is irradiated.

  In the above preferred embodiment, the polymerizable compound is represented by Formulas (XX-14) to (XX-21), Formulas (M-3) to (M-6), and Formula (RM-2-1) described later. At least one or more selected from the group consisting of the compounds represented, polymerization proceeds without delay even under relatively mild light irradiation conditions, so that the tilt angle is stable over time The voltage holding ratio can be maintained high because it can be formed and the light irradiation conditions are relatively mild.

  In the manufacturing method according to the present invention, the method for attaching a liquid crystal composition containing a polymerizable compound onto a substrate is not particularly limited, and the inside of a cell in which a pair of (electrode) substrates are bonded via a spacer. Method of attaching a polymerizable compound-containing liquid crystal composition onto an (electrode) substrate by injecting a liquid crystal composition containing a polymerizable compound into the substrate (vacuum injection method), one of a pair of (electrode) substrates and And / or a method (ODF method) of dropping a polymerizable compound-containing liquid crystal composition onto both substrates. In the substrate according to the present invention, it is preferable that an electrode layer (a pixel electrode including a TFT, a common electrode) and an alignment film be formed on the (transparent) support substrate as necessary.

  The method for dropping the polymerizable compound-containing liquid crystal composition according to the present invention is not particularly limited, but for example, methods using screen printing, offset printing, flexographic printing, ink jet, a droplet discharge device, a dispenser or the like are common. Other methods include dip, roll coater, slit coater, spinner and the like, and these may be used according to the purpose.

  The substrate according to the present invention preferably has an electrode layer for vertical electric field drive or horizontal electric field drive. Examples of the electrode layer include transparent conductive materials such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), IZTO (Indium Zinc Tin Oxide), etc. when the liquid crystal display element is of a transmission type. It is not limited to these. In the case of a reflective liquid crystal display element, examples of the electrode layer include materials such as aluminum that reflect light, but are not limited thereto.

  A conventionally known method can be used as a method of forming an electrode layer on a substrate according to the present invention. It is preferable that the liquid crystal display element which concerns on embodiment has a pair of transparent substrate which mutually opposes, and the said electrode layer is formed in the at least one board | substrate. The electrode layer preferably has a slit formed in a predetermined pattern (fishbone structure), and a transparent insulating film, a planarizing film, or the like may be laminated on the electrode layer. . Furthermore, a vertical or horizontal alignment film may be formed on the insulating film or the electrode layer, if necessary. The alignment film is preferably an organic polymer film such as a polyimide film, a nylon film, or a polyvinyl alcohol film.

  In the present invention, an alignment film may be formed on at least one of the pair of substrates, or it is preferable to use a substrate on which no alignment film is formed.

  A liquid crystal display device according to the present invention comprises a first support substrate and a second support substrate arranged in an opposite manner, a common electrode provided on the first support substrate or the second support substrate, and the first electrode. And a liquid crystal layer containing a liquid crystal composition provided between the first support substrate and the second support substrate, provided on the second support substrate or the second support substrate and having a thin film transistor. Is preferred. If necessary, an alignment film for controlling the alignment direction of liquid crystal molecules may be provided on the opposite surface side of at least one of the first support substrate and / or the second support substrate so as to abut on the liquid crystal layer. . Furthermore, a color filter may be appropriately provided on the first support substrate or the second support substrate, and a color filter may be provided on the pixel electrode or the common electrode. Also, two polarizing plates may be provided on the outside of the first support substrate or the second support base plate.

  The support substrate according to the present invention can use a flexible transparent material such as glass or plastic (acrylic, polycarbonate, etc.), and in view of application to a reflective liquid crystal display element, it is opaque such as a silicon wafer Materials are also acceptable. In addition, the pair of substrates is bonded by a sealing material and a sealing material such as an epoxy-based thermosetting composition disposed in the peripheral region, and in order to maintain the distance between the substrates, for example, glass particles Particulate spacers such as plastic particles and alumina particles or spacer posts made of a resin formed by photolithography may be disposed.

  When the liquid crystal display element according to the present invention is driven by a vertical electric field, it is preferable to provide an electrode layer on both of the pair of substrates. More specifically, the vertical electric field drive liquid crystal display device (VA) according to the present invention comprises a second support substrate disposed opposite to each other, a common electrode provided on the second support substrate, and the first electrode. It is preferable to have a pixel electrode having a thin film transistor, which is provided on the supporting substrate, and a liquid crystal layer containing a liquid crystal composition provided between the first supporting substrate and the second supporting substrate.

  Therefore, one of the substrates has a support substrate, a thin film transistor (TFT), a pixel electrode, and a wiring (a gate line, a data bus line, a Cs electrode, a contact hole, etc.), and the other substrate has a support substrate It is preferable to have a common electrode and a color filter. In addition, a color filter may be provided on the pixel electrode or the common electrode (color filter on array).

  When the liquid crystal display device according to the present invention is driven by a horizontal electric field, it is preferable that an electrode layer is formed only on one of the pair of substrates, and more specifically, the one substrate is a support substrate It is preferable that the semiconductor device includes a wiring (a gate line, a data bus line, a Cs electrode, a contact hole, and the like), a thin film transistor (TFT), a common electrode, and a pixel electrode. The other substrate preferably includes a support substrate and, if necessary, a color filter.

  In the light irradiation step according to the present invention, a substrate to which a liquid crystal composition containing a polymerizable compound and a nonpolymerizable liquid crystal compound is attached is the above (first or second) supporting substrate, a transparent substrate, one of the above substrates Or any of the other substrates described above.

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

  It is preferable that the first substrate and the second substrate be opposed so that the common electrode and the pixel electrode layer are inside.

  The distance between the first substrate and the second substrate may be adjusted via a spacer. At this time, it is preferable to adjust the thickness of the obtained light control layer to 1 to 100 μm. The thickness is more preferably 1.5 to 10 μm, and in the case of using a polarizing plate, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so as to maximize the contrast. When two polarizing plates are provided, the polarizing axis of each polarizing plate can be adjusted to adjust the viewing angle and contrast to be good. Furthermore, retardation films for widening the viewing angle can also be used.

  As a polymeric compound which concerns on this invention, the compound represented by the following general formula (I) is preferable.

(In the general formula ^{(I), R 101, R} 102, R 103, R 104, R 105, R 106, R 107, R 108, R 109 and ^{R 110} are each ^{independently,} P ^{21 -S} 21 - And an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, and P ²¹ represents a group represented by the following formula (R-I) to formula (R-IX) Any group represented by),

(In the above formulas (R-I) to (R-IX), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms) Or a halogenated alkyl group having 1 to 5 carbon atoms, W ¹ is a single bond, -O- or a methylene group, T ¹ is a single bond or COO-, p ¹ , t ¹ and q ¹ Are each independently 0, 1 or 2, and one or more hydrogen atoms of the above formulas (R-I) to (R-IX) may be substituted by the polar group. * Represents a bond.)
The above S ²¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkylene group is —O— so that oxygen atoms are not directly adjacent to each other. And -OCO- or -COO- may be substituted,
n ¹¹ represents 0, 1 or 2;
n ¹² and n ¹³ each independently represent 0 or 1;
represents n ¹¹ + n ¹² + n ¹³ = 1, 2, 3 or 4;
A ¹¹ is a group (a), a group (b) and a group (c) shown below:
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (c) Naphthalene-2,6-diyl group, 2,7-phenanthrendiyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6 -One -CH = or two or more non-adjacent -CH = present in the -diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is replaced by -N = May be.)
Group (a), group (b) and group (c) are each independently an alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms alkoxy group, a halogen, a cyano group, a nitro group, or ^P 21 ^{-S 21} - be substituted with good,
L ¹⁰ and ^{L 11} are each independently a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - OC 2 H 4 O -, - COO -, - OCO -, - CH = CR ^a -COO-, -CH = CR ^a -OCO-, -COO-CR ^a = CH-, -OCO-CR ^a = CH-, -O- (CH ₂ ) _z -O-,-(CH _{2) z -COO -, - (} CH 2) z -OCO -, - OCO- (CH 2) z -, - COO- (CH 2) z -, - CH = CH -, - CF 2 O -, - CO— (CH ₂ ) z —CO—, OCF ₂ — or —C≡C— (wherein, each R ^a independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, z each independently represents an integer of 0 to 4);
When a plurality of P ²¹ , S ²¹ , L ¹¹ and A ¹¹ exist, they may be the same or different. )
In the polymerizable compound-containing liquid crystal composition according to the present invention, the content of the polymerizable compound represented by the general formula (I) relative to the whole liquid crystal composition is 0.01 to 5% by mass, but the lower limit of the content 0.02% by mass is preferable, 0.03% by mass is preferable, 0.04% by mass is preferable, 0.05% by mass is preferable, 0.06% by mass is preferable, 0.07% by mass is preferable, and 0% is preferable. .08 mass% is preferable, 0.09 mass% is preferable, 0.1 mass% is preferable, 0.15 mass% is preferable, 0.2 mass% is preferable, 0.25 mass% is preferable, 0.3 % By mass is preferable, 0.35% by mass is preferable, 0.4% by mass is preferable, 0.5% by mass is preferable, 0.55% by mass is preferable, and the upper limit of the content is preferably 4.5% by mass, 4% by mass is preferable, 3.5% by mass is 3 mass% is preferable, 2.5 mass% is preferable, 2 mass% is preferable, 1.5 mass% is preferable, 1 mass% is preferable, 0.95 mass% is preferable, 0.9 mass% Is preferable, 0.85% by mass is preferable, 0.8% by mass is preferable, 0.75% by mass is preferable, 0.7% by mass is preferable, 0.65% by mass is preferable, and 0.6% by mass is preferable 0.55 mass% is preferable.

  The polymerizable compound according to the present invention has the following general formula (II):

(In the general formula ^{(II), R 201, R} 202, R 203, R 204, R 205, R 206, R 207, R 208, R 209 and ^{R 210} each ^{independently,} P 21 ^{-S 21} - A C 1 to C 18 alkyl group which may be substituted by a fluorine atom, an alkoxy group having 1 to 18 carbon atoms which may be substituted by a fluorine atom, a fluorine atom or a hydrogen atom, P ²¹ Represents a polymerizable group,
S ²¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkylene group is —O—, — so that oxygen atoms are not directly adjacent to each other. OCO- or -COO- may be substituted,
n ²¹ represents 0 or 1;
A ²¹ is
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (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 1,2 , And one or more non-adjacent -CH = present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by -N =).
Group (a), group (b) and group (c) are each independently an alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms alkoxy group, a halogen, a cyano group, a nitro group, or ^P 21 ^{-S 21} - be substituted with good,
At least one P ²¹ -S ^21- in one molecule of the general formula (I),
L ²¹ represents a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - OC 2 H 4 O -, - COO -, - OCO -, - CH = CR a -COO -, - ^{CH = CR a -OCO -, -} COO-CR a = CH -, - OCO-CR a = CH -, - (CH 2) z -COO -, - (CH 2) z -OCO -, - OCO- ( CH ₂ ) _z- , -COO- (CH ₂ ) _z- , -CH = CH-, -CF ₂ O-, -OCF ₂ -or -C≡C- (wherein each R ^a is independently hydrogen And each represents an alkyl group having 1 to 3 carbon atoms, wherein z independently represents an integer of 1 to 4).
When two or more P ²¹ , S ²¹ and A ²¹ exist, they may be the same or different. It is more preferable that the compound represented by 1.) be 1 type, or 2 or more types.

R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ and R ²¹⁰ are preferably substituted with an electron donating group, and have 1 to 18 carbon atoms An alkyl group or an alkoxy group having 1 to 18 carbon atoms is preferred.

  The compound represented by the general formula (I) according to the present invention is preferably a polymerizable compound represented by the general formula (IV).

In the above general formula (IV), R ⁷ and R ⁸ each independently represent any of the above formulas (R-I) to (R-IX), and X ¹ to X ⁸ are each independently And a trifluoromethyl group, a fluorine atom, a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms.

In the above general formula (IV), R ⁷ and R ⁸ are preferably each independently a methacryl group or an acryl group.

  The compound represented by the general formula (IV) is more preferably one or more selected from the group consisting of Formulas (IV-11) to (IV-19), and the compound represented by Formula (IV-) 16) Particularly preferred is the formula (IV-17).

  Specifically, the compounds represented by the general formula (I) according to the present invention are, for example, preferably compounds represented by the formulas (XX-1) to (XX-29), and the formula (XX-1) Formula (XX-7), Formula (XX-14) to Formula (XX-29) are more preferable, and Formula (XX-15) and Formula (XX-23) are particularly preferable.

In the general formulas (XX-1) to (XX-29), Sp ^xx is an alkylene group having 1 to 8 carbon atoms or O- (CH ₂ ) _s- (wherein, s is an integer of 1 to 7) And an oxygen atom is to be bonded to a ring).

In the general formula (XX-29) from the formula (XX-1), a hydrogen atom in the 1,4-phenylene group, _{further, -F, -Cl, -CF 3,} -CH 3 or ^P 21 ^{-S 21} - It may be replaced by any of

  Moreover, as a compound represented by General formula (I), the polymeric compound represented by Formula (M1)-Formula (M18) is preferable, for example.

In the above formulae, Rc represents a methyl group, an ethyl group or a propyl group, and Sp ^M represents a single bond, an alkylene group having 1 to 8 carbon atoms or -O- (CH ₂ ) _s- (wherein s is And an oxygen atom is taken to be attached to a ring.

  In addition, polymerizable compounds such as those represented by formulas (M19) to (M34) are also preferable.

Hydrogen atoms in the 1,4-phenylene group and naphthalene group in the formula (M34) from equation (M19) is further, -F, _-Cl, -CF 3, may be substituted by -CH _3.

  Moreover, the compound represented by general formula (I) is also preferable with the polymeric compound represented by Formula (M35)-Formula (M67).

(In the formula, Rc represents a methyl group, an ethyl group or propyl group, Sp ^M represents a single bond, an alkylene group or -O- _{(CH 2) s} 1 to 8 carbon atoms - (wherein, s Represents an integer of 1 to 7, and an oxygen atom is to be bonded to a ring.

  Moreover, the compound represented by general formula (I) is also preferable with the polymeric compound represented by Formula (RM-2-1)-Formula (RM-2-52).

  When the liquid crystal composition according to the present invention is a negative liquid crystal composition, the dielectric anisotropy (Δε) at 20 ° C. is from −2.0 to −8.0, but from −2.1 to −6. 2 is preferable, -2.2 to -5.3 is more preferable, and -2.5 to -5.0 is more preferable. -2.7 to -4.8 are particularly preferred.

  When the liquid crystal composition according to the present invention is a positive liquid crystal composition, the dielectric anisotropy (Δε) at 20 ° C. is 1.5 to 20, preferably 1.5 to 18.0. 5 to 15.0 is more preferable, 1.5 to 11 is more preferable, and 1.5 to 8 is particularly preferable.

  The liquid crystal composition according to the present invention has a refractive index anisotropy (Δn) at 20 ° C. of 0.08 to 0.14, preferably 0.09 to 0.13, more preferably 0.09 to 0.12. Is particularly preferred. More specifically, in the case of a thin cell gap, it is preferably 0.10 to 0.13, and in the case of a thick cell gap, it is preferably 0.08 to 0.11.

  The liquid crystal composition according to the present invention has a viscosity (η) at 10 ° C. of 10 to 50 mPa · s, preferably 10 to 45 mPa · s, and more preferably 10 to 40 mPa · s. The viscosity is preferably 35 mPa · s, more preferably 10 to 30 mPa · s, still more preferably 10 to 25 mPa · s, and particularly preferably 10 to 22 mPa · s.

The liquid crystal composition according to the present invention has a rotational viscosity (γ ₁ ) at 50 ° C. of 50 to 160 mPa · s, preferably 55 to 160 mPa · s, and more preferably 60 to 160 mPa · s, The viscosity is preferably 60 to 150 mPa · s, preferably 60 to 140 mPa · s, preferably 60 to 130 mPa · s, and more preferably 60 to 125 mPa · s.

The liquid crystal composition according to the present invention has a nematic phase-isotropic liquid phase transition temperature (T _ni ) of 60 ° C. to 120 ° C., preferably 70 ° C. to 100 ° C., particularly preferably 70 ° C. to 85 ° C. .

  The liquid crystal composition according to the present invention contains a non-polymerizable liquid crystal compound, and the non-polymerizable liquid crystal compound is a general compound of a dielectric substantially neutral compound (the value of Δε is -2 to 2) as the first component. It is preferable to contain one or more types of compounds represented by the formula (L).

  The compounds represented by the above general formula (L) are as follows.

(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-)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (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 1,2 , And one or more non-adjacent -CH = present in the 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 ^L2 is present, they may be May be the same or different. )
The liquid crystal composition according to the present invention contains a non-polymerizable liquid crystal compound, and the non-polymerizable liquid crystal compound has, as a second component, a general formula (J) of a dielectrically positive compound (Δε is larger than 2). And / or compounds represented by general formulas (N-1) to (N-3) of dielectrically negative compounds (the sign of Δε is negative and the absolute value is larger than 2) It is preferable to contain one or more kinds.

  The compound represented by General Formula (J) of the dielectrically positive compound (Δε is larger than 2) is as follows.

(Wherein, R ^J1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH ₂ -in the alkyl group are each independently -CH = CH-,- It may be substituted by C≡C-, -O-, -CO-, -COO- or -OCO-,
n ^J1 represents 0, 1, 2, 3 or 4;
A ^J1 , A ^J2 and A ^J3 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (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 1,2 , And one or more non-adjacent -CH = present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by -N =).
Group (a), group (b) and group (c) are each independently a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoro group It may be substituted by a methoxy group,
Z ^J1 and ^{Z J2} are each independently a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O -, -COO-, -OCO- or -C≡C-,
When n ^J1 is 2, 3 or 4 and there are a plurality of A ^J2 , they may be the same or different, and n ^J1 is 2, 3 or 4 and a plurality of Z ^J1 is present If they are identical or different,
X ^J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )
It is selected from the group consisting of the compounds represented by the general formulas (N-1) to (N-3) of the above-mentioned dielectrically negative compounds (the sign of Δε is negative and its absolute value is larger than 2) 1 type or 2 types or more are as follows.

(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 more of the alkyl groups are Adjacent two or more -CH ₂ -may be each independently substituted by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 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 d) represent a group selected from the group consisting of 1,4-cyclohexenylene groups, and the above groups (a), (b), (c) and (d) are each independently It may be substituted by 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 = CH-, -CF = CF- or -C≡C- Represent
X ^N21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents -CH ₂ -or an oxygen atom,
n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 each independently represent an integer of 0 to 3, but n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are each independently When there are a plurality of A ^{N11 to} A ^N32 and Z ^{N11 to} Z ^N32 , they may be the same or different. )
The compound represented by the above general formula (L) is preferably a compound represented by the following formulas (L-1) to (L-13).

(Wherein, R ^L1 and R ^L2 each independently represent the same meaning as in general formula (L), and A ^L1 and A ^L7 each independently represent the same meaning as in general formula (L); The hydrogen atom on ^L1 and A ^L2 may be each independently substituted by a fluorine atom, and Z ^L1 has the same meaning as Z ^L2 in formula (L), and X ^L1 and X ^L2 are each independently Represents a fluorine atom or a hydrogen atom)
The compound represented by the above general formula (J) is preferably a compound represented by the following formulas (M-1) to (M-18).

(In the ^formula, and ^{X M11} ~X ^M186 is each independently represent a hydrogen atom or a fluorine ^{atom, R J1 ~R J181} is each independently an alkyl group having 1 to 5 carbon atoms, 2 to 5 carbon atoms represents an alkenyl group or an alkoxy group having 1 to 4 carbon ^atoms, represents ^{X J11} ~X ^J181 mother fluorine atom, a chlorine atom or OCF _3,
Each of A ^M81 and A ^M82 is independently a 1,4-cyclohexylene group, a 1,4-phenylene group or

Represents a hydrogen atom on the 1,4-phenylene group may be substituted by a fluorine ^atom, W ^{M101 to W-M172} are each independently, -CH ₂ - represents a or -O-. )
The compound represented by the above general formula (J) is preferably a compound represented by the following formulas (K-1) to (K-6).

(Wherein, R ^K11 represents 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, and X ^{K11 to} X ^K14 are each independently hydrogen Represents an atom or a fluorine atom, and Y ^K11 represents a fluorine atom or OCF ₃ ))

(Wherein, R ^K21 represents 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, and X ^{K21 to} X ^K24 are each independently hydrogen Represents an atom or a fluorine atom, and Y ^K21 represents a fluorine atom or OCF ₃ ))

(Wherein, R ^K31 represents 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, and X ^{K31 to} X ^K36 are each independently hydrogen Represents an atom or a fluorine atom, and Y ^K31 represents a fluorine atom or OCF ₃ ))

(Wherein, R ^K41 represents 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, and X ^{K41 to} X ^K46 are each independently hydrogen Y ^{K 41} represents a fluorine atom or OCF ₃ , and Z ^{K 41} represents —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—.

(Wherein, R ^K51 represents 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, and X ^{K51 to} X ^K56 are each independently hydrogen Y ^{K 51} represents a fluorine atom or OCF ₃ , and Z ^{K 51} represents -OCH _2- , -CH ₂ O-, -OCF ₂ -or -CF ₂ O-.

( ^Wherein , R ^{K 61} represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^{K 61 to} X ^{K 68} each independently represent hydrogen) represents an atom or a fluorine ^{atom, Y K61} represents a fluorine atom or OCF ^{_3, Z K61} is _{-OCH 2 -, - CH 2 O} -, - OCF 2 - or an _-CF 2 O-).
As a compound represented by general formula (N-1) which concerns on this invention, the compound group represented by the following general formula (N-1a)-(N-1g) can be mentioned.

^{(Wherein, R N11} and ^{R N12} are as defined ^{R N11} and ^{R N12} in the general formula ^{(N-1), n Na12} represents 0 or ^{1, n NB11} is 1 or ^{2, n NC11} is N ^Nd11 represents 1 or 2; n ^Ne11 represents 1 or 2; n ^Nf12 represents 1 or 2; n ^Ng11 represents 1 or 2; A ^Ne11 represents trans-1,4 ^{-Represents a} cyclohexylene group or a 1,4-phenylene group, and A ^Ng11 represents a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group ^; If is ^{1, a NG11} represents cyclohexenylene ^group, when ^{n NG11} is 2, represents at least one ^{a NG11} 1,4-cyclohexenylene ^{group, Z NE11} is a single bond Represents an ethylene ^group, when ^{n NE11} is ^{1, Z NE11} if ^{.n NE11} representing the ethylene group is 2, represents at least one ^{Z NE11} ethylene group.)
When the whole liquid crystal composition containing the polymerizable compound according to the present invention exhibits positive dielectric anisotropy, the polymerizable compound represented by the general formula (I) and the compound represented by the general formula (J) It is preferable to include one or two or more compounds selected from and a compound represented by General Formula (L).

  The upper limit of the ratio occupied by the component composed of only the compounds represented by Formula (I), Formula (J) and Formula (L) in the entire liquid crystal composition containing the polymerizable compound according to the present invention The values are 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass% It is preferable that they are 88 mass%, 87 mass%, 86 mass%, 85 mass%, and 84 mass%.

  Further, the lower limit of the ratio of the component constituted only of the compounds represented by General Formula (I), General Formula (J) and General Formula (L) in the entire polymerizable compound-containing liquid crystal composition according to the present invention The values are 78 mass%, 80 mass%, 81 mass%, 83 mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, 90 mass%, 91 mass%, 92 mass% 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight.

  When the entire polymerizable compound-containing liquid crystal composition according to the present invention exhibits negative dielectric anisotropy, the polymerizable compound represented by the general formula (I) and the compound represented by the general formula (N-1) It is preferable to include one or two or more compounds selected from and a compound represented by General Formula (L).

  In the entire polymerizable compound-containing liquid crystal composition according to the present invention, the proportion of the component constituted only of the compound represented by General Formula (I), General Formula (N-1), and General Formula (L) The upper limit value is 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass %, 88% by mass, 87% by mass, 86% by mass, 85% by mass, 84% by mass.

  The liquid crystal display device using the polymerizable compound-containing liquid crystal composition of the present invention has the remarkable feature of high-speed response, and in addition, is sufficient tilt angle obtained and is there no unreacted polymerizable compound? Because the voltage holding ratio (VHR) is so small that there is no problem, problems such as alignment failure and display failure are sufficiently suppressed. In addition, since the tilt angle and the residual amount of the polymerizable compound can be easily controlled, it is easy to optimize and reduce the energy cost for manufacturing, which is optimal for improvement of production efficiency and stable mass production.

  The liquid crystal display device using the polymerizable compound-containing liquid crystal composition of the present invention is particularly useful for a liquid crystal display device for driving an active matrix, and is a PSA mode, PSVA mode, VA mode, PS-IPS mode or PS-FFS mode It can use for the liquid crystal display element for.

  Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited by these. The following abbreviations are used for the description of the compounds in the examples.

(Side chain)
-N -C _n H _{2n + 1} linear carbon number n alkyl group n-C _n H _{2n + 1-} linear carbon number n carbon group -On-OC _n H _{2n + 1} linear carbon number n alkoxy Group (linking group)
-1O- -CH ₂ -O-
(Ring structure)

  The characteristics measured in the examples are as follows.

T _ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
Δn: refractive index anisotropy at 20 ° C. :: viscosity at 20 ° C. (mPa · s)
γ ₁ : rotational viscosity (mPa · s) at 20 ° C
Δε: dielectric anisotropy at 20 ° C. (manufacturing method of liquid crystal display element and VHR evaluation method)
First, a liquid crystal composition containing a polymerizable compound is coated with a polyimide alignment film for inducing vertical alignment with a cell gap of 3.5 μm, and then a vacuum injection method is applied to a liquid crystal cell including a substrate with ITO where the polyimide alignment film is rubbed. The liquid crystal composition containing the polymerizable compound was attached to the alignment film, and the light irradiation process was performed under the following light conditions A to C to fabricate a liquid crystal display element. As a vertical alignment film forming material, JALS 2096 manufactured by JSR Corporation was used.

  Light sources A to C used in Examples and Comparative Examples are as follows.

  Light source A: Light was irradiated using a high-pressure mercury lamp (USH-500BY1 (manufactured by Ushio Denki Sangyo Co., Ltd.)) having a spectrum shown in FIG. 2 via a short wavelength cut filter having a cut on wavelength of 320 nm. The ratio of light having a wavelength of 370 nm or more to the light amount of 300 nm to 500 nm (area in a range of 370 nm to 500 nm ÷ area in a range of 300 nm to 500 nm) was 53%.

  Light source B: Using a high pressure mercury lamp (USH-500BY1 (manufactured by Ushio Inc.)) having a spectrum shown in FIG. 2, light was irradiated through a short wavelength cut filter having a cut on wavelength of 325 nm. The ratio of light having a wavelength of 370 nm or more to the light amount of 300 nm to 500 nm (area in a range of 370 nm to 500 nm ÷ area in a range of 300 nm to 500 nm) was 71%.

  Light source C: Light was emitted using an LED lamp showing the spectrum of FIG. The ratio of light having a wavelength of 370 nm or more to the light amount of 300 nm to 500 nm (area in a range of 370 nm to 500 nm ÷ area in a range of 300 nm to 500 nm) was 99%.

  In the example, “whether or not the main component is light with a wavelength of 370 nm or more (area in the range of 370 nm to 500 nm ÷ area in the range of 300 nm to 500 nm) is calculated from the area ratio of the light emission spectrum of the light source The ratio of the wavelength of 370 nm or more to the light amount of 300 nm or more and 500 nm or less is calculated using USR-30 (manufactured by Ushio Inc.).

  Next, using a liquid crystal display element manufactured by irradiating a liquid crystal cell with ultraviolet light under any of the light conditions A to C shown above, VHR at 333 K under a frequency of 0.6 Hz and an applied voltage of 1 V %) Was measured. For measurement of VHR, a 6424 type liquid crystal physical property evaluation apparatus (manufactured by Toyo Corporation) was used.

  Thereafter, display defect (burn-in) evaluation due to change in pretilt angle was performed. First, the pretilt angle of the liquid crystal display element produced above was measured and used as a pretilt angle (initial stage). The backlight was illuminated for 24 hours while applying a voltage of 30 V at a frequency of 100 Hz to the liquid crystal display element. After that, the pretilt angle was measured and used as the pretilt angle (after the test). A value obtained by subtracting the pretilt angle (after the test) from the measured pretilt angle (initial) is taken as a pretilt angle change amount (= absolute value of pretilt angle change) [°]. The pretilt angle was measured using Syntech OPTIPRO.

  As the amount of change in pretilt angle approaches 0 [°], the possibility of occurrence of display defects due to changes in pretilt angle decreases, and when it becomes 0.5 [°] or more, display defects due to changes in pretilt angle occur The possibility is higher.

(Comparative Example 1, Comparative Example 2, Example 1)
A liquid crystal composition of LC-001 was prepared, and its physical property values were measured. The composition of the liquid crystal composition and the results of the physical property values are as shown in Table 1.

  With a light source A, 90 spectral irradiation was performed on a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.6 wt% of the polymerizable compound RM-1 was added to 99.4 wt% of the liquid crystal composition LC-001. And Comparative Example 1.

  With a light source B, 90 spectral irradiation was performed on a cell injected with a polymerizable compound-containing liquid crystal composition obtained by adding 0.6 wt% of the polymerizable compound RM-1 to 99.4 wt% of the liquid crystal composition LC-001 And Comparative Example 2.

  90 spectral irradiation with a light source C was applied to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.6 wt% of the polymerizable compound RM-1 was added to 99.4 wt% of the liquid crystal composition LC-001. , Example 1.

  From Table 2 above, the VHR of Comparative Example 1 is 17%, the change in pretilt angle is 1.0 °, the VHR of Comparative Example 2 is 31%, and the change in pretilt angle is 0.5 °. Met. It was found that Comparative Example 1 and Comparative Example 2 had a low VHR and a large amount of change in pretilt angle. On the other hand, the VHR of Example 1 was 88 [%], and the pretilt angle change amount was 0.1 [°]. From this, it was found that Example 1 had a sufficiently high VHR and a sufficiently small amount of change in pretilt angle.

(Examples 2 to 7)
90 spectral irradiation with a light source C was applied to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-1 was added to 99.7% by weight of the liquid crystal composition LC-001. , Example 2.

  90 spectral irradiation with a light source C is applied to a cell into which a polymerizable compound-containing liquid crystal composition having 1.2% by weight of the polymerizable compound RM-1 added to 98.8% by weight of the liquid crystal composition LC-001 is injected. , Example 3.

  90 spectral irradiation with a light source C is applied to a cell into which a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-2 added to 99.7% by weight of the liquid crystal composition LC-001 is injected , Example 4.

  90 spectral irradiation with a light source C was applied to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-3 was added to 99.7% by weight of the liquid crystal composition LC-001. , Example 5.

  90 spectral irradiation with a light source C was applied to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-4 was added to 99.7% by weight of the liquid crystal composition LC-001. , Example 6.

  90 spectral irradiation with a light source C is applied to a cell into which a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-5 added to 99.7% by weight of the liquid crystal composition LC-001 is injected , Example 7.

  Similarly to Example 1, it was confirmed that VHR is sufficiently high in Examples 2 to 7 and the pretilt angle change amount is sufficiently small. In Examples 2 to 7 in which RM-1 to 4 were added, the change in pretilt angle was particularly small, and in Examples 2 and 3 in which RM-1 was added, VHR after irradiation was the highest, and RM-4 was added. Example 6 showed good storage stability.

(Comparative Example 3, Examples 8 to 9)
A light source is applied while applying 10 V of voltage to a cell injected with a polymerizable compound-containing liquid crystal composition obtained by adding 0.6 wt% of the polymerizable compound RM-1 to 99.4 wt% of the liquid crystal composition LC-001. After 15 spectral irradiation with B, 15 spectral irradiation with the light source B was made to be Comparative Example 3.

  A light source is applied while applying 10 V of voltage to a cell injected with a polymerizable compound-containing liquid crystal composition obtained by adding 0.6 wt% of the polymerizable compound RM-1 to 99.4 wt% of the liquid crystal composition LC-001. After 15 spectral irradiations with C, 15 spectral irradiations with a light source B are made to be Example 8.

  A light source is applied while applying 10 V of voltage to a cell injected with a polymerizable compound-containing liquid crystal composition obtained by adding 0.6 wt% of the polymerizable compound RM-1 to 99.4 wt% of the liquid crystal composition LC-001. After 5 spectral irradiations with B, 45 spectral irradiations with a light source C are made to be Example 9.

  While VHR of Comparative Example 3 was 72 [%] and the pretilt angle change amount was 0.5 [°], in Examples 8 to 9, VHR is sufficiently high similarly to Example 1, and the pretilt angle is It was confirmed that the amount of change was sufficiently small. In particular, the form of Example 8 had a smaller amount of change in pretilt angle than Examples 1 to 7 and Example 8, and the VHR after light irradiation was also good.

Claims (5)

  After a liquid crystal composition containing a polymerizable compound and a nonpolymerizable liquid crystal compound is attached to a substrate, a light irradiation step (A) of irradiating the liquid crystal composition with light having a wavelength of 370 nm or more as the main component The manufacturing method of the liquid crystal display element performed more than twice.   The manufacturing method of the liquid crystal display element of Claim 1 further including the light irradiation process (B) which irradiates the irradiation light which does not have light with a wavelength of 370 nm or more as a main component.   The manufacturing method of the liquid crystal display element of Claim 1 or 2 which performs a light irradiation process (A) or a light irradiation process (B) in the state which applied the voltage with respect to the said liquid crystal composition. The following general formula (I) as the polymerizable compound

(In the general formula ^{(I), R 101, R} 102, R 103, R 104, R 105, R 106, R 107, R 108, R 109 and ^{R 110} are each ^{independently,} P ^{21 -S} 21 - And an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, and P ²¹ represents a group represented by the following formula (R-I) to formula (R-IX) Any group represented by),

(In the above formulas (R-I) to (R-IX), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms) Or a halogenated alkyl group having 1 to 5 carbon atoms, W ¹ is a single bond, -O- or a methylene group, T ¹ is a single bond or COO-, p ¹ , t ¹ and q ¹ Are each independently 0, 1 or 2, and one or more hydrogen atoms of the above formulas (R-I) to (R-IX) may be substituted by the polar group. * Represents a bond.)
The above S ²¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkylene group is —O— so that oxygen atoms are not directly adjacent to each other. And -OCO- or -COO- may be substituted,
n ¹¹ represents 0, 1 or 2;
n ¹² and n ¹³ each independently represent 0 or 1;
represents n ¹¹ + n ¹² + n ¹³ = 1, 2 or 3;
A ¹¹ is a group (a), a group (b) and a group (c) shown below:
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (c) Naphthalene-2,6-diyl group, 2,7-phenanthrendiyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6 -One -CH = or two or more non-adjacent -CH = present in the -diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is replaced by -N = May be.)
Group (a), group (b) and group (c) are each independently an alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms alkoxy group, a halogen, a cyano group, a nitro group, or ^P 21 ^{-S 21} - be substituted with good,
L ¹⁰ and ^{L 11} are each independently a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - OC 2 H 4 O -, - COO -, - OCO -, - ^{CH = CR a -COO -, -} CH = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH -, - (CH 2) z -COO -, - (CH 2) _{z -OCO -, - OCO- (CH} 2) z -, - COO- (CH 2) z -, - CH = CH -, - CF 2 O -, - OCF 2 - or -C≡C- (wherein And ^Ra each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, each z independently represents an integer of 1 to 4).
When a plurality of P ²¹ , S ²¹ , L ¹¹ and A ¹¹ exist, they may be the same or different. The manufacturing method of the liquid crystal display element of any one of Claims 1-3 containing 1 type, or 2 or more types of compounds represented by these.   The substrate has an alignment layer on the surface, and a light irradiation step of irradiating the liquid crystal composition containing the polymerizable compound attached on the alignment layer with irradiation light mainly composed of light with a wavelength of 370 nm or more 1 The manufacturing method of the liquid crystal display element of any one of Claims 1-4 performed more than once.

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