JPWO2018180850A1 - Method of manufacturing liquid crystal display device - Google Patents

Abstract

A method for producing a liquid crystal display device, comprising a light irradiation step of irradiating a light having a peak at 300 to 400 nm to a liquid crystal composition containing a polymerizable compound attached on a substrate separately 1 to n independently.
Light is applied for 5 minutes to the liquid crystal composition containing 0.3% by mass of the polymerizable compound under the light irradiation condition of the k-th light irradiation step (S _k ) among the 1 to n light irradiation steps. If the concentration of the polymerizable compound after irradiation with (C _k), density variation V _k per unit of density difference of 0.3 mass% is expressed for each step in equation (1), The average reaction rate V _ave of the polymerizable compound in the total light irradiation step (ΣS _k ) represented by the formula (2) is controlled to 0.030 to 0.048 (mass% / min), Provided is a method of manufacturing a liquid crystal display device.

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 a voltage is applied 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, a radically polymerizable monomer generates a radical upon irradiation with light such as ultraviolet light and forms a polymer structure by polymerization, but, for example, lauryl acrylate has only one polymerizable group. Since it does not have, the polymerization rate is reduced, and the radical generated in the polymerizable group which is the polymerization end remains in the liquid crystal layer as an impurity and causes the VHR to be reduced, as a cyclic aliphatic compound or aromatic compound When a radically polymerizable monomer formed by bonding a hydrocarbon group having 12 or more carbon atoms to a compound formed by bonding two polymerizable groups is used to align liquid crystal molecules. It is described that it is possible to maintain high VHR.

JP 2003-307720 JP, 2016-6130, A

  The above Patent Documents 1 and 2 are both techniques focusing on the structure of the polymerizable compound used in the polymerization step. For example, Patent Document 1 discloses a polymerizable compound having a specific chemical structure in which the liquid crystal molecules fall Although it is described that the burn-in is reduced by the regulation, a new problem such as a decrease in VHR due to an unpolymerized polymerizable compound and a display failure resulting therefrom occurs. Further, in Patent Document 2, when the number of polymerization sites is one, the polymerization rate of the polymerizable compound is slow and VHR decreases, but when the number of polymerization sites is two, the polymerization rate of the polymerizable compound is fast. It is stated to maintain high VHR. Since the polymerization rate of the polymerizable compound affects the shortening of the manufacturing process of the liquid crystal display device as a product and the reduction of the energy cost, there is a demand for increasing the polymerization rate of the polymerizable compound. However, in the step of polymerizing the polymerizable compound in the liquid crystal composition used for the PSA type liquid crystal display element, if the polymerization rate of the polymerizable compound is fast, the residual amount of the polymerizable compound decreases in a short ultraviolet irradiation time. Although the decrease in VHR derived from the polymerizable compound described in Patent Document 2 can be reduced, a new problem arises that display defects are likely to occur due to changes in the pretilt angle. On the other hand, when the polymerization rate of the polymerizable compound is slow, a long ultraviolet irradiation time is required to reduce the residual amount of the polymerizable compound. Therefore, when a strong ultraviolet ray is irradiated for a long time in the polymerization step, the enlargement of the manufacturing apparatus and the reduction of the manufacturing efficiency are caused, and a new problem of deterioration of the liquid crystal composition by the ultraviolet ray occurs.

  Therefore, the problem to be solved by the present invention is that the polymerization rate at which the polymerizable compound is suitably polymerized in the polymerization step of irradiating the liquid crystal composition containing the polymerizable compound of the manufacturing method of producing the PSA type liquid crystal display It is an object of the present invention to provide a method of manufacturing a liquid crystal display element which has no or extremely low display defects due to a change in pretilt angle, and reduces and suppresses display defects due to a drop in VHR and the same.

  As a result of intensive investigations by the present inventors, it was found that the above-mentioned problems could be solved by setting the polymerizable compound to a suitable polymerization rate, and the present invention was 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 has a small residual amount of a polymerizable compound, exhibits high voltage holding ratio (VHR) and high-speed response, and does not have display defects such as alignment defects or burn-in. It shows excellent display quality which is suppressed.

  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.

In the manufacturing method of the liquid crystal display element of this invention, it is a graph which shows the relationship between voltage retention VHR and light irradiation time.

A first aspect of the present invention is a liquid crystal display device comprising a light irradiation step of irradiating a light having a peak at 300 to 400 nm to a liquid crystal composition containing a polymerizable compound attached on a substrate, independently from 1 to n times. Manufacturing method of
Light is applied for 5 minutes to the liquid crystal composition containing 0.3% by mass of the polymerizable compound under the light irradiation condition of the k-th light irradiation step (S _k ) among the 1 to n light irradiation steps. the concentration of the polymerizable compound after irradiation with (C _k), density variation V _k per unit of density difference of 0.3 mass% is expressed for each step by the following equation (1) In the case where the average reaction rate V _ave of the polymerizable compound in the total light irradiation step (ΣS _k ) represented by the following formula (2) is controlled to 0.030 to 0.048 (mass% / min) It is a manufacturing method of a liquid crystal display element characterized by the above.

(In the above formula (1), C _k was applied to the liquid crystal composition containing 0.3% by mass of the polymerizable compound for 5 minutes under light irradiation conditions in the k-th light irradiation step (S _k ) Represents the concentration (% by mass) of the polymerizable compound contained in the subsequent liquid crystal composition, and in the above formula (2), V _k is represented by the above formula (1), and t _k is the kth light irradiation step Represents the light irradiation time (minutes) for irradiating the polymerizable compound with light.)
Thus, the liquid crystal display device using the method of manufacturing a liquid crystal display device of the present invention can suppress or reduce the decrease in VHR, and can reduce or eliminate the display defect due to the change of the pretilt angle.

  In general, in the method of manufacturing a liquid crystal display element, a method (so-called vacuum injection method) of filling a liquid crystal composition between a pair of (electrode) substrates by vacuum injection, and at least one (electrode) substrate of the pair of (electrodes) And the method of dropping liquid crystal composition (so-called ODF method). 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 liquid crystal composition containing the polymerizable compound attached onto the (electrode) substrate It is preferable to have the light irradiation process of irradiating the thing which has the light which has a peak in 300-400 nm, 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 said light irradiation process once or more, and to perform a light irradiation process once or more in the state which applied the voltage.

  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) A step of drawing the bonding area over the entire periphery with a bonding sealing agent on the outer periphery of one side of the substrate, and a liquid crystal composition containing a polymerizable compound inside the bonding area on one side of the (electrode) substrate The step of bonding with the other (electrode) substrate after curing and curing the bonding sealing agent, and the liquid crystal composition containing the polymerizable compound attached onto the (electrode) substrate to a thickness of 300 to 400 nm. It is preferable to have the light irradiation process of irradiating the light which has a peak, and the process of bonding a polarizing plate together. Moreover, it is preferable to perform the said light irradiation process once or more, and to perform a light irradiation process once or more in the state which applied the voltage.

  The bonding sealing agent is preferably cured by a UV or thermally 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, the light irradiation step of irradiating the liquid crystal composition containing the polymerizable compound attached on the substrate with light having a peak at 300 to 400 nm is performed 1 to n times. It 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.

  By performing the light irradiation step 1 to n 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.

In the manufacturing method according to the present invention, the light irradiation step of irradiating light having a peak at 300 to 400 nm to the liquid crystal composition containing the polymerizable compound attached on the substrate, which is performed 1 to n times, is independent of each other For example, assuming that the k-th (1 ≦ k ≦ n) light irradiation process of ₁ to n times is S _k , the f-th (1 ≦ f ≦ n, k ≠ f) of 1 to n times When the light irradiation process is S _f , irradiation conditions (wavelength of light to be irradiated, integrated light quantity or illuminance, atmosphere, etc.) in the k-th light irradiation process (S _k ) are f-th light irradiation process (S _f ) It may be the same as or different from the irradiation conditions (wavelength of light to be irradiated, integrated light quantity or illuminance, atmosphere, etc.) in the above. Moreover, when performing a light irradiation process once, it is natural that 1 time irradiation conditions are independent.

Formula (1) which concerns on this invention is the said polymeric compound after irradiating light for 5 minutes with respect to the liquid crystal composition containing 0.3 mass% of polymeric compounds under the light irradiation conditions of a certain light irradiation process. Represents the concentration change amount per unit minute of the concentration difference between the concentration (C _k ) of 0.3% by mass and the concentration change amount (V _k ) of the light irradiation process in the above-mentioned certain light irradiation step. An index indicating the reactivity of the polymerizable compound under the conditions is set. In other words, the concentration of the polymerizable compound contained in the liquid crystal composition is 0.3% by mass (= the reference concentration) in order to calculate the index indicating the reactivity of the polymerizable compound under the light irradiation conditions of the light irradiation step. And the rate of change based on the light irradiation time of 5 minutes. For example, the measurement when _{V k} in the manufacturing method of the liquid crystal display device polymerizable compound performs 1~n times the light irradiation step of irradiating light having a peak at 300~400nm at 20 ° C. a liquid crystal composition containing 0.2 wt% When preparing a liquid crystal composition containing 0.3% by mass of the polymerizable compound, the polymerizable compound-containing liquid crystal composition is filled between 1 to k pairs of (electrode) substrates, Under the same conditions as the light irradiation conditions in the light irradiation steps (S ₁ ) to (S _k ) at 20 ° C. for each of a pair of (electrode) substrates filled with the k polymerizable compound-containing liquid crystal compositions in the concentration of the polymerizable compound contained in each of the liquid crystal composition after 5 minutes was measured _{C 1, C 2 ··· C k} , to calculate the _{V 1, V} 2 ··· _{V k} corresponding thereto. Similarly, for example, in a method of manufacturing a liquid crystal display device, the liquid crystal composition containing 0.4% by mass of a polymerizable compound is irradiated with light having a peak at 300 to 400 nm at 25 ° C. for 1 to n times. _{When k} is measured, a liquid crystal composition containing 0.3% by mass of the polymerizable compound is prepared, and the polymerizable compound-containing liquid crystal composition is filled between 1 to k pairs of (electrode) substrates Light irradiation conditions in a light irradiation step (S ₁ ) to (S _k ) at 25 ° C. to each of a pair of (electrode) substrates filled with 1 to k of the polymerizable compound-containing liquid crystal compositions the concentration of the polymerizable compound contained in each of the liquid crystal composition after 5 minutes under the same conditions to measure the _{C 1, C 2 ··· C k} , the _{V 1, V} 2 ··· _{V k} corresponding thereto calculate. Further, the temperature of the polymerizable compound at the time of measuring V _k (or the temperature of the atmosphere in the step of measuring V _k ) is the temperature of the polymerizable compound at the time of light irradiation in each light irradiation step (S _k ) It is preferable that it is the same as the temperature of the atmosphere in the corresponding light irradiation step (S _k ).

The irradiation conditions (liquid crystal cell (pair of (electrode) substrates), wavelength of light to be irradiated, integrated light quantity or illuminance, atmosphere) at the time of measuring the V _k are the irradiation conditions in each actual light irradiation step (S _k ) It is preferable that it is the same as (liquid crystal cell (pair of (electrode) substrates), wavelength of light to be irradiated, integrated light amount or illuminance, atmosphere).

In the formula (2) according to the present invention, the concentration change rate of the polymerizable compound under the light irradiation conditions in each light irradiation step (S _k ) and the irradiation time and product in each light irradiation step are apparent in each light irradiation step. The concentration of the reduced polymerizable compound is shown, and the sum of the concentration in all steps represents the total concentration of the “apparently” decreased polymerizable compound in the all light irradiation step, and “total” in the all light irradiation step The reduced concentration of the polymerizable compound is divided by the total light irradiation time to express the reaction rate of the "appearing" polymerizable compound in the total light irradiation step. Therefore, the average reaction rate V _ave according to the present invention represents the reaction rate of the “appearing” polymerizable compound in the all light irradiation step. Therefore, by controlling the average reaction speed V _ave in a specific range, there is no display defect due to the change of the pretilt angle, or there is very few, and a drop in VHR and a reduction in the display defect resulting therefrom / suppressed liquid crystal display A method of manufacturing a device can be provided.

The lower limit value of the average reaction rate V _ave (% by mass) according to the present invention is preferably 0.030 or more, 0.031 or more, 0.032 or more, 0.033 or more, 0.034 or more, The upper limit value of the average reaction rate V _{ave according to} the present invention is preferably 0.048 or less, 0.047 or less, 0.046 or less, 0.045 or less, 0.044 or less, 0.043 or less. Further, the average reaction rate V _{ave according} to the present invention is preferably 0.030 to 0.048, more preferably 0.032 to 0.048, still more preferably 0.032 to 0.047, and 0.032 to 0 .045 is more preferable, 0.033 to 0.045 is still more preferable, and 0.033 to 0.045 is particularly preferable.

When the lower limit value of the average reaction rate V _{ave according to} the present invention is 0.030, there is a merit that the decrease of VHR by light irradiation for a long time does not easily occur, and when the upper limit value is 0.048, the pretilt angle There is an advantage that the burn-in due to change is unlikely to occur.

The light irradiation conditions in the light irradiation step (S _k ) according to the present invention preferably include the peak wavelength of the light to be irradiated and / or the illuminance of the light to be irradiated.

In the method for producing a liquid crystal display element according to the present invention, the light irradiated to the polymerizable compound is light having a peak at 300 to 400 nm, and is preferably ultraviolet light. The light used in the light irradiation step (S _k ) 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.

The lower limit value of the illuminance of light having a peak at 300 to 400 nm irradiated in the light irradiation step (S _k ) according to the present invention is preferably 10 mW / cm ² , more preferably 20 mW / cm ² , 30 mW / cm ² is more preferable. 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.

In the light irradiation step (S _k ) according to the present invention, the light irradiation step (S _k ) according to the present invention is performed under light irradiation conditions in which light having a peak in the vicinity of 313 nm and / or a peak in the vicinity of 365 nm is irradiated. The lower limit value of the illuminance of the light (313 nm) to be irradiated is preferably 0.1 mW / cm ² , more preferably 0.3 mW / cm ² , and still more preferably ² mW / cm ² . The upper limit value of the illuminance of the light (313 nm) to be irradiated is preferably 30 mW / cm ² , more preferably 25 mW / cm ² , and still more preferably 20 mW / cm ² .

It is preferable from the viewpoint that the average reaction rate of the polymerizable compound can be controlled in the range of 0.030 to 0.048 when the lower limit value of the illuminance of light (313 nm) to be irradiated is ² mW / cm ² . When the upper limit of the illuminance of the ultraviolet ray to be used is at 20 mW / cm ^2, preferably in the viewpoint of controlling the average reaction rate of the photopolymerizable compound in the range of 0.030 to 0.048.

In the light irradiation step (S _k ) according to the present invention, the light irradiation step (S _k ) according to the present invention is performed under light irradiation conditions in which light having a peak in the vicinity of 313 nm and / or a peak in the vicinity of 365 nm is irradiated. the lower limit of the illuminance of the irradiated light (365 nm) is more preferably it is 0.1 mW / cm ² is preferably ^{0.5mW / cm 2, 1mW / cm} 2 is more preferred. The upper limit of the illuminance of light (365 nm) for the irradiation is preferably 150 mW / cm ^2, more preferably from 130 mW / cm ^2, further preferably 120 mW / cm ^2.

It is preferable from the viewpoint that the average reaction rate of the polymerizable compound can be controlled in the range of 0.030 to 0.048 when the lower limit value of the illuminance of light (365 nm) to be irradiated is 1 mW / cm ² . When the upper limit of the illuminance of the ultraviolet ray to be used is a 120 mW / cm ^2, preferably in the viewpoint of controlling the average reaction rate of the photopolymerizable compound in the range of from 0.030 to 0.048.

  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 process according to the present invention (S _k) in the light irradiation time (t _k) is suitably determined in such times of light irradiation step 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 manufacturing apparatus is increased and the manufacturing efficiency is lowered, and deterioration of the liquid crystal composition due to the ultraviolet ray occurs. 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.

All light irradiation process according to the present invention ([sigma] s _k) in the light irradiation time (.SIGMA.t _k) is suitably determined in such times of light irradiation step is preferably 5 to 100 minutes. The lower limit value of the irradiation time in the light irradiation step is more preferably 5 minutes, still more preferably 10 minutes, and particularly preferably 15 minutes. The upper limit value of the irradiation time of the ultraviolet light is more preferably a minute, further preferably 70 minutes, and particularly preferably 60 minutes.

The temperature range of the atmosphere in the light irradiation step (S _k ) according to the present invention is preferably 19 ° C. to 63 ° C., and more preferably 20 ° C. to 50 ° C. Further, it is preferable that the temperature of the atmosphere in the calculation of the concentration change rate (V _k) corresponding to the light irradiation step (S _k), and the temperature of the atmosphere in the light irradiation step (S _k) are identical. That is, the temperature of the atmosphere (or polymerizable compound) in the calculation of the reduced concentration (V _{k + 1} ) after 5 minutes from the reference concentration of 0.3 mass% of the polymerizable compound contained in the liquid crystal composition and V _{k + 1} It is preferable that the temperature of the atmosphere in the corresponding light irradiation step (S _{k + 1} ) be the same.

  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 step (S _k ) according to the present invention, when using ultraviolet light, a polarized light source may be used or a non-polarized light source may be used, but it is preferable to irradiate non-polarized ultraviolet light.

In the light irradiation step (S _k ) 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.

The irradiation method that can be used in the light irradiation step (S _k ) according to the present invention is not particularly limited, and any known irradiation method can be used.

In the present invention, 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. Actinic radiation having a wavelength of 300 nm or more and 450 nm or less, such as j-ray (313 nm), i-ray (365 nm), h-line (405 nm), g-line (436 nm), can preferably be used. An actinic ray having a wavelength of 300 nm or more and 400 nm or less is preferable.
In addition, 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.

Furthermore, as the wavelength of the ultraviolet light to be irradiated in the light irradiation step (S _k ) according to the present invention, it is sufficient to include the above-mentioned ultraviolet light of 300 to 400 nm wavelength, and the ultraviolet light in the wavelength region other than the absorption wavelength region of the polymerizable compound. You may irradiate. 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.

  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 in which a voltage is applied in at least one light irradiation step (S _k ) of the 1 to n light irradiation steps.

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 the polymerizable compound from the polymer polymerized in the light irradiation step (S _k ) is a specific direction with respect to the substrate (for example, with respect to the substrate) The liquid crystal molecules can be fixed in a vertical alignment by forming a stable pretilt angle by the polymer polymerized in the light irradiation step, if necessary, by aligning in the vertical direction. 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 the ultraviolet light in the light irradiation step (S _k ) according to the present invention, it is preferable to irradiate the ultraviolet light while applying an alternating voltage or a direct current voltage, and it is more preferable to irradiate the ultraviolet light while applying an alternating voltage. preferable.

  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 step (S _k ) 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 step (S _k ) 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 at the time of voltage application in the light irradiation step (S _k ) according to the present invention is a temperature close to room temperature, preferably 14 to 62 ° C., more preferably 16 to 55 ° C., further Preferably, a voltage is applied to the polymerizable compound-containing liquid crystal composition at 18 to 52 ° C.

  It is preferable that the liquid crystal composition containing the polymeric compound at the time of voltage application in the light irradiation process which concerns on this invention is 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 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 one light irradiation step of irradiating a liquid crystal composition containing a polymerizable compound attached onto a substrate with light having a peak at 300 to 400 nm. A method of manufacturing a liquid crystal display device, comprising
Under the light irradiation conditions of the _first light irradiation step (S ₁ ), the concentration of the above-mentioned polymerizable compound after irradiating the liquid crystal composition containing 0.3% by mass of the light for 5 minutes with light (C _{When 1} ) and the density | concentration change amount V ₁ per unit minute of the density | concentration difference of 0.3 mass% are represented by the following formula | equation (1-1),
Control of the average reaction rate V _ave of the polymerizable compound in the _first light irradiation step (S ₁ ) represented by the following formula (2-1) to 0.030 to 0.048 (% by mass / minute) It is to be.

(In the above formula (1-1), C ₁ represents the concentration (% by mass) of the polymerizable compound contained in the liquid crystal composition after 5 minutes under light irradiation conditions in the _first light irradiation step (S ₁ ) Represents
In the above formula (2-1), V ₁ is represented by the above formula (1-1), and t ₁ is a light irradiation time (light irradiation time) for irradiating light to the polymerizable compound in the _first light irradiation step (S ₁ ) Represents minutes). )
When the light irradiation process is performed once, a desired pretilt angle can be formed in one irradiation process, the number of processes can be omitted, and there is a merit that only one light irradiation apparatus can be used. is there.

When irradiating light, preferably ultraviolet light, in the light irradiation step (S ₁ ) according to the present invention, it is preferable to irradiate ultraviolet light while applying an alternating voltage or a direct current voltage. It is more preferable to irradiate.

  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 step (S ₁ ) 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 step (S ₁ ) 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 atmosphere at the time of voltage application in the light irradiation step (S ₁ ) according to the present invention is a temperature close to room temperature, preferably 14 to 62 ° C., more preferably 16 to 55 ° C., still more preferably 18 to 52 ° C. It is preferable to apply a voltage to the liquid crystal composition containing a liquid crystal compound.

When the light irradiation step is performed once, the concentration (C ₁ ) of the polymerizable compound after the light is irradiated to the liquid crystal composition containing 0.3% by mass of the polymerizable compound for 5 minutes; The temperature of the atmosphere for irradiating light for 5 minutes when measuring the concentration variation V ₁ per unit minute of the concentration difference with 3% by mass is a light having a peak at 300 to 400 nm in the light irradiation step (S ₁ ) The temperature is preferably the same as the temperature of the atmosphere to be irradiated.

When performing one of the above light irradiation process, the concentration of the polymerizable compound after irradiation with 5 minutes light polymerizable compound to the liquid crystal composition containing 0.3 wt% and (C _1), 0.3 It is preferable that the illuminance of the light irradiated for 5 minutes when measuring the density variation V ₁ per unit minute of the density difference with the mass% is the same as the illuminance of the light irradiated in the light irradiation step (S ₁ ) .

When performing one of the above light irradiation process, the concentration of the polymerizable compound after irradiation with 5 minutes light polymerizable compound to the liquid crystal composition containing 0.3 wt% and (C _1), 0.3 light irradiated 5 minutes in measuring the concentration variation V ₁ of the per unit amount of the density difference between the mass% is preferably the same as the light to be irradiated in the light irradiation step (S _1).

The other form of the manufacturing method of the liquid crystal display element which concerns on this invention separates independently the light irradiation process which irradiates the light which has a peak in 300-400 nm to the liquid crystal composition containing the polymeric compound attached on the board | substrate. It is a manufacturing method of the liquid crystal display element equipped twice, and is for 5 minutes on the light irradiation conditions of the _1st light irradiation process (S1) with respect to the liquid crystal composition containing 0.3 mass% of said polymeric compounds. The concentration change amount per unit minute V ₁ of the concentration difference (C ₁ ) of the polymerizable compound after irradiation with light and the concentration difference between 0.3 mass% is represented by the following formula (1-1): A concentration of the polymerizable compound after the liquid crystal composition containing 0.3% by mass of the polymerizable compound is irradiated with light for 5 minutes under the light irradiation condition of the _second light irradiation step (S ₂ ) The concentration change amount V ₂ per unit minute of the concentration difference between C ₂ ) and 0.3% by mass, When it is represented by the following formula (1-2), the average reaction rate V _ave of the polymerizable compound represented by the following formula (2-2) is 0.030 to 0.048 (% by mass / minute) Control.

(In the above formulas (1-1) and (1-2), C ₁ represents the light of the first light irradiation step (S ₁ ) with respect to the liquid crystal composition containing 0.3% by mass of the polymerizable compound) The concentration (% by mass) of the polymerizable compound after irradiation with light for 5 minutes under the irradiation conditions, C ₂ represents the _second light for the liquid crystal composition containing 0.3% by mass of the polymerizable compound Represents the concentration (% by mass) of the polymerizable compound after being irradiated with light for 5 minutes under light irradiation conditions in the irradiation step (S ₂ ),
The formula (2-2), _{V 1} and _{V 2} represents the formula (1-1) and concentration change amount per unit of the formula _(1-2), t 1, _{t 2} is The light irradiation time (minutes) which irradiates light to the polymeric compound in each process is represented. )
When the light irradiation step is divided into two steps, the number of liquid crystal panels that can be processed at one time increases, which is preferable from the viewpoint of mass production of liquid crystal display elements. Further, since the step of forming the pretilt application by the first light irradiation and the step of reducing the concentration of the polymerizable compound remaining by the second light irradiation can be divided, the reduction of the remaining amount of the polymerizable compound or the desired Easy to adjust the operation of pretilt formation.

In the method for producing a liquid crystal display element according to the present invention, the liquid crystal composition containing the polymerizable compound attached on the substrate is provided with two separate light irradiation steps of irradiating light having a peak at 300 to 400 nm. In the case where the voltage is applied in the _first light irradiation step (S ₁ ), it is preferable to irradiate light having a peak at 300 to 400 nm.

First, a liquid crystal composition containing a polymerizable compound is irradiated with light of a predetermined wavelength in a state where a voltage is applied, that is, a polymer derived from the polymerizable compound by the _first light irradiation step (S ₁ ) The shape of the polymer structure is reinforced by the liquid crystal molecules forming a desired pretilt angle by (polymer structure) and performing the _second light irradiation step (S ₂ ) without applying a voltage. Residual polymerizable compounds can be reduced. For example, a VA liquid crystal display element in which the liquid crystal composition is aligned in the direction perpendicular to the substrate when no voltage is applied will be described as an example. That is, by performing the light irradiation step (S ₁ ) in a state where a voltage is applied, the liquid crystal molecules constituting the liquid crystal composition containing the polymerizable compound have a specific orientation direction with respect to the substrate, for example, the substrate when voltage is applied. The polymerizing compound polymerizes in a state in which the liquid crystal molecules follow the horizontal direction, and when no voltage is applied thereafter, the liquid crystal molecules are aligned with the substrate by the polymer structure in which the polymerizing compound is polymerized. The shape of the polymer structure can be fixed in a state of being slightly inclined toward the substrate side from the vertical direction (pretilt angle), and further performing the _second light irradiation step (S ₂ ) without applying a voltage. Can be reinforced and residual polymerizable compounds can be reduced. Thus, it is possible to manufacture a liquid crystal display device that achieves a desired pretilt angle and a high VHR value. Further, in the present invention, since the average reaction rate of the polymerizable compound is controlled within a predetermined range, in the first light irradiation step (S ₁ ) and / or the second light irradiation step (S ₂ ) Since the formation speed and the shape of the polymer structure to be formed can be controlled, it is considered that it is possible to manufacture a liquid crystal display element in which an appropriate pretilt angle and the amount of the remaining polymerizable compound are reduced.

When irradiating the ultraviolet light in the light irradiation step (S ₁ ) according to the present invention, it is preferable to irradiate the ultraviolet light while applying an alternating voltage or a direct current voltage, and it is more preferable to irradiate the ultraviolet light while applying an alternating voltage. preferable.

  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 step (S ₁ ) 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 step (S ₁ ) 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.

In the method for producing a liquid crystal display element according to the present invention, the liquid crystal composition containing the polymerizable compound attached on the substrate is provided with two separate light irradiation steps of irradiating light having a peak at 300 to 400 nm. In the case, after the first light irradiation step (S ₁ ), the second light irradiation step (S ₂ ) is provided, and the light irradiation time t ₂ in the _second light irradiation step (S ₂ ) is it is preferably longer than the light irradiation time t ₁ of the first round of the light irradiation step (S _1).

  As a result, there is an advantage that formation of a predetermined pretilt angle is possible, and burn-in due to a change in pretilt angle can be reduced.

  In the method of manufacturing a liquid crystal display element according to the present invention, the light irradiation step is preferably performed once or twice. For example, from the viewpoint of only one irradiation device, it is preferable to perform one light irradiation step. On the other hand, from the viewpoint of easiness of control of the pretilt angle of liquid crystal molecules, it is preferable to carry out two light irradiation steps. From the ease of control of the pretilt angle of liquid crystal molecules, the embodiment of the above-mentioned two light irradiation steps is more preferable.

  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 substrate 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 disposed in opposition, a common electrode provided on the first support substrate or the second support substrate, and the first electrode. And a pixel electrode having a thin film transistor, and a liquid crystal layer containing a liquid crystal composition provided between the first support substrate and the second support substrate. 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, the substrate to which the polymerizable compound-containing liquid crystal composition is attached is any of the (first or second) supporting substrate, the transparent substrate, the one substrate, and the other substrate. It may be

  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.

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

(In the general formula ^{(I), 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, 1 or 2;
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 preferable that the compound represented by 1.) be 1 type, or 2 or more types.

With a polymerizable compound of such a specific structure, the average reaction rate V _ave can be easily controlled to 0.030 to 0.048 (% / min).

  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-1) to (R-9), and X ¹ to X ⁸ are each independently And represents 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 above general formula (IV) is more preferably one or more selected from the group consisting of formulas (IV-11) to (IV-19), and 11), Formula (IV-16) and Formula (IV-17) are particularly preferable.

  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) to Formula (XX-14) to Formula (XX-29) are more 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 the oxygen atom is taken to be attached to the 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 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 (M65).

  In the polymerizable compound-containing liquid crystal composition according to the present invention, the content of the polymerizable compound represented by Formula (M1) to Formula (M65) with respect to the whole liquid crystal composition is 0.01 to 5% by mass. The lower limit of the content is preferably 0.02 mass%, preferably 0.03 mass%, preferably 0.04 mass%, preferably 0.05 mass%, and preferably 0.06 mass%, 0.07 mass%. Is preferable, 0.08% by mass is preferable, 0.09% by mass is preferable, 0.1% by mass is preferable, 0.15% by mass is preferable, 0.2% by mass is preferable, and 0.25% by mass is preferable 0.3 mass% is preferable, 0.35 mass% is preferable, 0.4 mass% is preferable, 0.5 mass% is preferable, 0.55 mass% is preferable, and the upper limit of the content is 4.5 mass % Is preferable, 4% by mass is preferable, and 3 5 mass% is preferable, 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 mass% is preferable, 0.8 mass% is preferable, 0.75 mass% is preferable, 0.7 mass% is preferable, 0.65 mass% is preferable, 0.6 mass % Is preferable and 0.55 mass% is preferable.

  As a preferable example of a compound represented by general formula (I) which concerns on this invention, the polymeric compound represented by a following formula (RM-2-1)-a formula (RM-2-52) is mentioned.

  Moreover, as a specific content of the polymerizable monomer represented by said Formula (RM-2-1)-(RM-2-52), 5 mass% or less is preferable, and 3 mass% or less is more preferable, 2 mass% or less is more preferable, 1 mass% or less is especially preferable, and 0.8 mass% or less is the most preferable.

  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 comprises, as a first component, one or two kinds of compounds represented by the general formula (L) of a dielectric substantially neutral compound (the value of Δε is −2 to 2) It is preferable to contain more than.

  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 comprises, as a second component, a compound represented by General Formula (J) of a dielectrically positive compound (Δε is larger than 2) and / or a dielectrically negative compound ( Preferably, the sign of Δε is negative and its absolute value is greater than 2).

  The compounds represented by the above general formula (J) are 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. )
One or more selected from the group consisting of the compounds represented by the general formulas (N-1) to (N-3) 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.)
The compound represented by General Formula (N-2) according to the present invention is a compound selected from the group of compounds represented by the following General Formulas (N-2-1) to (N-2-3) Is preferred.

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

^{(Wherein, R N221} and ^{R N222} each independently represents the same meaning as ^{R N21} and ^{R N22} in the general formula (N-2).)

^{(Wherein, R N231} and ^{R N232} each independently represents the same meaning as ^{R N21} and ^{R N22} in the general formula (N-2).)
The compound represented by General Formula (N-3) is preferably a compound selected from the group of compounds represented by General Formula (N-3-2).

^{(Wherein, R N321} and ^{R N322} each independently represents the same meaning as ^{R N31} and ^{R N32} in the general formula (N-3).)
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 proportion occupied by the components consisting of only the compounds represented by general formula (I), general formula (J) and general 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.

(Method of manufacturing liquid crystal display device)
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 display element was manufactured.

(Measurement of V _k )
About the liquid crystal cell containing the liquid crystal composition containing a polymerizable compound, the residual quantity of the polymerizable compound in the liquid crystal display element after irradiating light for 5 minutes on light irradiation conditions of AD mentioned later in air | atmosphere of 25 degreeC measured (mass%) in accordance with equation (1) and (2) were calculated when _{V k} and _{V ave} of the polymerizable compound [wt% / min]. The measuring method of the residual amount ( _Ck ) of the polymeric compound in that case is demonstrated. First, the liquid crystal display element was disassembled to obtain an acetonitrile solution of an eluted component containing a liquid crystal composition, a polymer, and an unreacted polymerizable compound. This was analyzed by high performance liquid chromatograph, and the peak area of each component was measured. The amount of the remaining polymerizable compound was determined from the peak area of the liquid crystal compound as the index and the peak area ratio of the unreacted polymerizable compound. The residual amount of the polymerizable compound was determined from this value and the amount of the polymerizable compound initially added. The detection limit of this measurement was 100 ppm. Light irradiation conditions and the temperature during the measurement of V _k is carried out under the same conditions as the corresponding respective light irradiation step (S _k).

  The light irradiation conditions A to D used in Examples and Comparative Examples are as follows.

Light irradiation conditions A: Light was irradiated using a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less. In this case, illuminance illuminance measured at the center wavelength of 365nm condition is measured at 100 mW / cm ^2, the central wavelength 313nm condition was 24 mW / cm ^2.

Light irradiation condition B: Light was irradiated using a high pressure mercury lamp through a filter that cuts off light of 325 nm or less. At this time, the illuminance measured under the condition of center wavelength 365 nm was 120 mW / cm ² and the illuminance measured under the condition of center wavelength 313 nm was 18 mW / cm ² .

Light irradiation conditions C: Light was irradiated using a fluorescent UV lamp. In this case, illuminance measured at the center wavelength of 365nm conditions 2 mW / cm ^2, illuminance measured under the conditions of a central wavelength 313nm was 3 mW / cm ^2.

Light irradiation conditions D: Light was irradiated using a fluorescent UV lamp. In this case, illuminance measured at the center wavelength of 365nm conditions 3 mW / cm ^2, illuminance measured under the conditions of a central wavelength 313nm was 0.3 mW / cm ^2.

(Measurement of the amount of change in pretilt angle in the manufacturing method of an actual liquid crystal display element once in the case of light irradiation (in the case of n = 1)
In the atmosphere at 25 ° C., light irradiation was performed for the time described in the following table under the above light irradiation conditions A to D, and display defect (burn-in) evaluation due to change in pretilt angle was performed. The light irradiation time was until the residual amount of the polymerizable compound became less than the detection lower limit. First, the pretilt angle of the liquid crystal display element was measured and used as a pretilt angle (initial). 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 Examples 1 to 5)
Nematic liquid crystal phase-isotropic phase transition point (T _NI ) is 74 ° C, Δn (20 ° C) is 0.11, Δε (20 ° C) is -3.2, γ ₁ (20 ° C) is 125 mPa · s. The liquid crystal composition exhibiting a dielectric anisotropy of 1% was designated as a liquid crystal composition LC-001. LC-001 is a composition comprising the general formulas (L-1), (L-3), (L-10), (N-1c) and (N-1d).

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-2 is added to 99.7 parts by mass of the liquid crystal composition LC-001. Irradiation was conducted under the light irradiation condition A for 15 times to obtain Comparative Example 1.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-3 added to 99.7 parts by mass of the liquid crystal composition LC-001. Irradiation was carried out under the light irradiation condition A for 15 spectra, and a comparative example 2 was obtained.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-3 added to 99.7 parts by mass of the liquid crystal composition LC-001. Irradiation was conducted under the light irradiation condition B for 15 spectra, and the comparative example 3 was obtained.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-4 added to 99.7 parts by mass of the liquid crystal composition LC-001. Irradiation was performed under the light irradiation condition A for 5 spectra to obtain Comparative Example 4.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-4 added to 99.7 parts by mass of the liquid crystal composition LC-001. Irradiation was carried out under the light irradiation condition B for 15 spectra, and a comparative example 5 was obtained.

V _{ave in} Comparative Example 1 was 0.055 [mass% / min]. The pretilt angle change amount of Comparative Example 1 was 1.1 [°]. From these results, it was found that in Comparative Example 1, although the reaction rate of the polymerizable compound was fast, the amount of change in pretilt angle was large.

  Similar to Comparative Example 1, Comparative Examples 2 to 5 also show that although the reaction rate of the polymerizable compound is fast, the amount of change in pretilt angle is large.

(Examples 1 to 6)
A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-1 is added to 99.7 parts by mass of the liquid crystal composition LC-001. 30 spectral irradiation was carried out under light irradiation condition A, and it was referred to as Example 1.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-2 is added to 99.7 parts by mass of the liquid crystal composition LC-001. 30 spectral irradiation was performed under light irradiation condition B, and it was set as Example 2.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-2 is added to 99.7 parts by mass of the liquid crystal composition LC-001. 60 spectral irradiation was performed under light irradiation condition C, and it was set as Example 3.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-3 added to 99.7 parts by mass of the liquid crystal composition LC-001. 30 spectral irradiation was performed under light irradiation condition C, and it was set as Example 4.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-4 added to 99.7 parts by mass of the liquid crystal composition LC-001. 30 spectral irradiation was performed under the light irradiation condition C, and the working example 5 was obtained.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-4 added to 99.7 parts by mass of the liquid crystal composition LC-001. 60 spectral irradiation was performed under light irradiation condition D, and it was set as Example 6.

V _{ave in} Example 1 was 0.042 [mass% / min]. The amount of change in pretilt angle in Example 1 was 0.3 [°]. From these results, it was found that in Example 1, the reaction rate of the polymerizable compound was moderately fast, and the pretilt angle change amount was small.

  Similar to Example 1, Examples 2 to 6 also showed that the reaction rate of the polymerizable compound was moderately fast, and the amount of change in pretilt angle was small. In Examples 1 to 6, it was confirmed that a sufficient pretilt angle was given, the response was sufficiently fast, and the VHR was sufficiently high. The measurement conditions of the response speed were 6 V for Von, 1 V for Voff, and a measurement temperature of 25 ° C., and a measurement instrument used was DMS 703 manufactured by AUTRONIC-MELCHERS.

(Measurement of pretilt angle change amount in the manufacturing method of the actual liquid crystal display element of light irradiation process 2 times (in the case of n = 2))
After the first light irradiation in the air at 25 ° C. while applying a voltage, the second light irradiation was performed without applying a voltage. The light irradiation conditions and the light irradiation time in the first and second light irradiation steps are as shown in the following table. The light irradiation time was until the residual amount of the polymerizable compound became less than the detection lower limit. Next, display defect (burn-in) evaluation due to change in pretilt angle was performed. First, the pretilt angle of the liquid crystal display element was measured and used as a pretilt angle (initial). 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 6)
A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-3 added to 99.7 parts by mass of the liquid crystal composition LC-001. Then, ultraviolet light was irradiated for 600 seconds under the ultraviolet light irradiation condition B, and then 5 spectral irradiations were performed under the light irradiation condition C, whereby Comparative Example 6 was obtained.

  Similar to Comparative Example 1, Comparative Example 6 also showed that the reaction rate of the polymerizable compound was fast, but the amount of change in pretilt angle was large.

(Examples 7 to 13)
A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-2 is added to 99.7 parts by mass of the liquid crystal composition LC-001. Then, 1.25 spectral irradiation was performed under the light irradiation condition B, and then 60 spectral irradiation was performed under the light irradiation condition C, whereby Example 7 was obtained.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-2 is added to 99.7 parts by mass of the liquid crystal composition LC-001. Then, 2.5 spectral irradiation was performed under the light irradiation condition B, and then 50 spectral irradiation was performed under the light irradiation condition C, whereby Example 8 was obtained.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-2 is added to 99.7 parts by mass of the liquid crystal composition LC-001. Irradiation was performed under the light irradiation condition B for 5 spectra, and then under the light irradiation condition C for 45 spectra, to obtain Example 9.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-2 is added to 99.7 parts by mass of the liquid crystal composition LC-001. Under the light irradiation condition B, 10 spectral irradiation was performed, and then the 30 spectral irradiation was performed under the irradiation condition C, to obtain Example 10.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-3 added to 99.7 parts by mass of the liquid crystal composition LC-001. Irradiation was performed under 1.25 irradiation conditions under irradiation condition B, and then under 30 irradiation conditions under irradiation condition C to obtain Example 11.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-3 added to 99.7 parts by mass of the liquid crystal composition LC-001. Then, 2.5 spectral irradiation was performed under the light irradiation condition B, and then 20 spectral irradiation was performed under the light irradiation condition C, whereby Example 12 was obtained.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-3 added to 99.7 parts by mass of the liquid crystal composition LC-001. Irradiation was performed under the light irradiation condition B for 5 spectra, and then under the irradiation condition C for 10 spectra, to obtain Example 13.

  Also in Examples 7 to 13, as in Example 1, it was found that the reaction rate of the polymerizable compound was moderately fast, and the pretilt angle change amount was small.

  Moreover, in Examples 7 to 13, a sufficient pretilt angle was given, which was a sufficiently high-speed response, and it was confirmed that VHR was sufficiently high. The measurement conditions of the response speed were 6 V for Von, 1 V for Voff, and a measurement temperature of 25 ° C., and a measurement instrument used was DMS 703 manufactured by AUTRONIC-MELCHERS.

(Relationship between voltage holding ratio VHR and light irradiation time)
In order to confirm the relationship between VHR and light irradiation time, the liquid crystal display element was evaluated in one light irradiation process. The evaluation method will be described below. After heating at 120 ° C. for 1 hour, light was irradiated at 25 ° C. in the atmosphere under the conditions described in the following table, and VHR was measured. The measurement conditions of the said VHR are 1V, 0.6 Hz, and 60 degreeC.

(Comparative Example 7, Examples 14 to 16)
A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-1 is added to 99.7 parts by mass of the liquid crystal composition LC-001. 90 spectral irradiation was performed under the light irradiation condition C, and the comparative example 7 was obtained.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition in which 0.3% by weight of the polymerizable compound RM-2 is added to 99.7 parts by mass of the liquid crystal composition LC-001. Irradiation was carried out under the irradiation conditions C for 60 spectrally to obtain Example 14.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-3 added to 99.7 parts by mass of the liquid crystal composition LC-001. 30 spectral irradiation was performed under the light irradiation condition C, and the working example 15 was obtained.

  A voltage of 10 V is applied at a frequency of 100 Hz to a cell injected with a polymerizable compound-containing liquid crystal composition having 0.3% by weight of the polymerizable compound RM-4 added to 99.7 parts by mass of the liquid crystal composition LC-001. 30 spectral irradiation was performed under the light irradiation condition C, and the working example 16 was obtained.

V _{ave in} Comparative Example 7 was 0.029 [mass% / min]. The pretilt angle change amount of Comparative Example 1 was 0.1 [°]. The VHR after ultraviolet irradiation in Comparative Example 1 was 71%.

V _{ave in} Example 14 was 0.034 [mass% / min]. The amount of change in pretilt angle in Example 14 was 0.2 [°]. The VHR after ultraviolet irradiation in Example 14 was 76 [%].

V _{ave in} Example 15 was 0.041 [mass% / min]. The amount of change in pretilt angle in Example 15 was 0.1 [°]. The VHR after ultraviolet irradiation in Example 15 was 79%.

The V _{ave in} Example 16 was 0.047 [mass% / min]. The amount of change in pretilt angle in Example 16 was 0.2 [°]. The VHR after ultraviolet irradiation in Example 16 was 80%.

  The graph (The comparative example 7 is described as com7, and Examples 14-16 are described as exp14-16.) Which plotted the ultraviolet irradiation time and VHR of Comparative Example 7, Example 14-Example 16 is shown in FIG.

From the graph shown in FIG. 1, it was found that VHR is higher as V _ave is larger, and when V _ave is smaller than 0.030 (mass% / min), VHR saturates at a low value. From this, it was found that when the V _ave is appropriately large, the residual amount of the polymerizable compound becomes equal to or less than the detection lower limit in a short light irradiation time, so that deterioration or the like of the liquid crystal composition due to light does not easily occur.

Claims (7)

A method for producing a liquid crystal display device, comprising a light irradiation step of irradiating a light having a peak at 300 to 400 nm to a liquid crystal composition containing a polymerizable compound attached on a substrate separately 1 to n independently.
Light is applied for 5 minutes to the liquid crystal composition containing 0.3% by mass of the polymerizable compound under the light irradiation condition of the k-th light irradiation step (S _k ) among the 1 to n light irradiation steps. the concentration of the polymerizable compound after irradiation with (C _k), density variation V _k per unit of density difference of 0.3 mass% is expressed for each step by the following equation (1) In the case where the average reaction rate V _ave of the polymerizable compound in the total light irradiation step (ΣS _k ) represented by the following formula (2) is controlled to 0.030 to 0.048 (mass% / min) The manufacturing method of the liquid crystal display element characterized by the above.

(In the above formula (1), C _k was applied to the liquid crystal composition containing 0.3% by mass of the polymerizable compound for 5 minutes under light irradiation conditions in the k-th light irradiation step (S _k ) Represents the concentration (% by mass) of the polymerizable compound contained in the subsequent liquid crystal composition, and in the above formula (2), V _k is represented by the above formula (1), and t _k is the kth light irradiation step Represents the light irradiation time (minutes) for irradiating the polymerizable compound with light.) The manufacturing method of the liquid crystal display element of Claim 1 which irradiates light in the state which applied the voltage in at least 1 light irradiation process ( _Sk ). A method for producing a liquid crystal display device, comprising a light irradiation step of irradiating a liquid crystal composition containing a polymerizable compound attached on a substrate with light having a peak at 300 to 400 nm once.
Under the light irradiation conditions of the _first light irradiation step (S ₁ ), the concentration of the above-mentioned polymerizable compound after irradiating the liquid crystal composition containing 0.3% by mass of the light for 5 minutes with light (C _{When 1} ) and the density | concentration change amount V ₁ per unit minute of the density | concentration difference of 0.3 mass% are represented by the following formula | equation (1-1),
Control of the average reaction rate V _ave of the polymerizable compound in the _first light irradiation step (S ₁ ) represented by the following formula (2-1) to 0.030 to 0.048 (% by mass / minute) A method of manufacturing a liquid crystal display device according to claim 1 or 2, characterized in that:

(In the above formula (1-1), C ₁ represents the concentration (% by mass) of the polymerizable compound contained in the liquid crystal composition after 5 minutes under light irradiation conditions in the _first light irradiation step (S ₁ ) Represents
In the above formula (2-1), V ₁ is represented by the above formula (1-1), and t ₁ is a light irradiation time (light irradiation time) for irradiating light to the polymerizable compound in the _first light irradiation step (S ₁ ) Represents minutes). ) A method of manufacturing a liquid crystal display device, comprising separately and independently performing a light irradiation step of irradiating a liquid crystal composition containing a polymerizable compound attached on a substrate with light having a peak at 300 to 400 nm separately and separately.
The concentration (C) of the polymerizable compound after the liquid crystal composition containing 0.3% by mass of the polymerizable compound is irradiated with light for 5 minutes under the light irradiation condition of the _first light irradiation step (S ₁ ) ₁ ) and the concentration change amount V ₁ per unit minute of the concentration difference between 0.3 mass% is represented by the following equation (1-1),
The concentration (C) of the polymerizable compound after the liquid crystal composition containing 0.3% by mass of the polymerizable compound is irradiated with light for 5 minutes under the light irradiation condition of the _second light irradiation step (S ₂ ) _When the concentration variation V ₂ per unit minute of the concentration difference between ₂ ) and 0.3 mass% is represented by the following equation (1-2),
The average reaction rate V _ave of the polymerizable compound represented by the following formula (2-2) is controlled to 0.030 to 0.048 (% by mass / minute), The manufacturing method of the liquid crystal display element as described in-.

(In the above formulas (1-1) and (1-2), C ₁ represents the light of the first light irradiation step (S ₁ ) with respect to the liquid crystal composition containing 0.3% by mass of the polymerizable compound) The concentration (% by mass) of the polymerizable compound after irradiation with light for 5 minutes under the irradiation conditions, C ₂ represents the _second light for the liquid crystal composition containing 0.3% by mass of the polymerizable compound Represents the concentration (% by mass) of the polymerizable compound after being irradiated with light for 5 minutes under light irradiation conditions in the irradiation step (S ₂ ),
The formula (2-2), _{V 1} and _{V 2} represents the formula (1-1) and concentration change amount per unit of the formula _(1-2), t 1, _{t 2} is The light irradiation time (minutes) which irradiates light to the polymeric compound in each process is represented. ) In the first light irradiation step (S _1), it is irradiated with light having a peak at 300~400nm while applying a voltage, a method of manufacturing a liquid crystal display device according to claim 3 or 4. After the first light irradiation step _{(S 1),} comprising a second light irradiation step _{(S 2),} the irradiation time _{t 2} of the second light irradiation step _{(S 2),} the first light irradiation step ( S ₁₎ longer than the irradiation time t ₁ of the manufacturing method of the liquid crystal display device according to claim 4 or 5.
Production method. The following general formula (I) as the polymerizable compound

(In the general formula ^{(I), 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, 1 or 2;
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. The liquid crystal display element according to any one of claims 1 to 6, wherein the average reaction rate V _ave is controlled to 0.030 to 0.048 (% by mass / minute), and the compound represented by Method.

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