WO2018180850A1 - 液晶表示素子の製造方法 - Google Patents

液晶表示素子の製造方法 Download PDF

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Publication number
WO2018180850A1
WO2018180850A1 PCT/JP2018/011312 JP2018011312W WO2018180850A1 WO 2018180850 A1 WO2018180850 A1 WO 2018180850A1 JP 2018011312 W JP2018011312 W JP 2018011312W WO 2018180850 A1 WO2018180850 A1 WO 2018180850A1
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Prior art keywords
liquid crystal
light irradiation
polymerizable compound
mass
light
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PCT/JP2018/011312
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English (en)
French (fr)
Japanese (ja)
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麻里奈 後藤
雄一 井ノ上
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Dic株式会社
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Priority to JP2019509642A priority Critical patent/JP6573145B2/ja
Priority to CN201880016151.2A priority patent/CN110383158B/zh
Priority to KR1020197026010A priority patent/KR20190131484A/ko
Publication of WO2018180850A1 publication Critical patent/WO2018180850A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering

Definitions

  • the present invention relates to a method for producing a liquid crystal display device using a liquid crystal composition containing a polymerizable compound.
  • the PSA (Polymer Sustained Alignment) type liquid crystal display device has a structure in which a polymer structure is formed in the cell in order to control the pretilt angle of the liquid crystal molecules, and has been developed as a liquid crystal display device due to its high-speed response and high contrast. Is underway.
  • a PSA type liquid crystal display device is manufactured by injecting a liquid crystal composition containing a polymerizable compound between substrates, irradiating ultraviolet rays in a state where liquid crystal molecules are aligned by applying a voltage, and polymerizing the polymerizable compound.
  • a method of fixing the alignment of the liquid crystal molecules by controlling the pretilt angle of the liquid crystal molecules with the formed polymer structure is used (Patent Document 1).
  • Patent Document 1 while applying a voltage between a pair of transparent electrodes, one or more ring structures or condensed ring structures and the ring structure or condensed ring structure 2 are directly bonded. It is described that image sticking can be reduced by polymerizing a monomer having two functional groups to form a polymer structure.
  • a radical polymerizable monomer generates a radical upon irradiation with light such as ultraviolet rays and polymerizes to form a polymer structure.
  • lauryl acrylate has only one polymerizable group. Since it does not have, the polymerization rate is reduced, radicals generated in the polymerizable group which is the polymerization terminal remain as impurities in the liquid crystal layer, and causes a reduction in VHR.
  • a radical polymerizable monomer formed by further bonding a hydrocarbon group having 12 or more carbon atoms to a compound formed by bonding two polymerizable groups is used, liquid crystal molecules are aligned. And a high VHR can be maintained.
  • Patent Document 1 describes a polymerizable compound having a specific chemical structure in the direction in which the liquid crystal molecules are tilted. Although it is described that the burn-in is reduced by restricting by the above, there arises a new problem of a decrease in VHR due to an unpolymerized polymerizable compound and a display defect resulting therefrom. 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 increases. Maintaining high VHR is described.
  • the polymerization rate of the polymerizable compound affects the shortening of the manufacturing process of the liquid crystal display element as a product and the reduction of the energy cost, there is a demand for increasing the polymerization rate of the polymerizable compound.
  • the polymerization rate of the polymerizable compound is high, the residual amount of the polymerizable compound decreases in a short ultraviolet irradiation time.
  • the decrease in VHR derived from the polymerizable compound described in Patent Document 2 can be reduced, there arises a new problem that display defects are likely to occur due to changes in the pretilt angle.
  • an object of the present invention is to provide a method for manufacturing a liquid crystal display element in which there is no or very little display failure due to a change in pretilt angle, and VHR is reduced and display failure is reduced or suppressed.
  • the liquid crystal display element using the method for manufacturing a liquid crystal display element of the present invention suppresses or reduces the decrease in VHR.
  • the liquid crystal display element using the liquid crystal display element manufacturing method of the present invention has no or very little display defect due to a change in the pretilt angle.
  • the liquid crystal display element using the method for producing a liquid crystal display element of the present invention has a small residual amount of the polymerizable compound, exhibits a high voltage holding ratio (VHR) and a high-speed response, and does not have a display defect such as alignment failure or image sticking. Suppressed and excellent display quality.
  • VHR voltage holding ratio
  • the liquid crystal display element using the method for manufacturing a liquid crystal display element of the present invention has a reasonably short ultraviolet irradiation time, and can easily improve production efficiency by optimizing and reducing energy costs.
  • a first aspect of the present invention is a liquid crystal display device comprising a light irradiation step of irradiating 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 times.
  • a manufacturing method of Of the 1 to n light irradiation steps the liquid crystal composition containing 0.3% by mass of the polymerizable compound is irradiated with light for 5 minutes under the light irradiation conditions of the kth light irradiation step (S k ).
  • the concentration change amount V k per unit of the concentration difference between the polymerizable compound after irradiation (C k ) and 0.3% by mass is expressed for each step by the following formula (1).
  • the average reaction rate V ave of the polymerizable compound in the all-light irradiation step ( ⁇ S k ) represented by the following formula (2) is controlled to 0.030 to 0.048 (mass% / min). This is a method for manufacturing a liquid crystal display element.
  • the liquid crystal display element using the manufacturing method of the liquid crystal display element of the present invention can suppress or reduce the decrease in VHR, and can display the display defect due to the change in the pretilt angle or can extremely reduce it.
  • a method for manufacturing a liquid crystal display element includes a method in which a liquid crystal composition is filled between a pair of (electrode) substrates by vacuum injection (so-called vacuum injection method), and a method on at least one (electrode) substrate of a pair of (electrodes). And a method of dropping a liquid crystal composition (so-called ODF method).
  • the liquid crystal cell filled with the liquid crystal composition may be annealed at 60 to 130 ° C. after the injection step and 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.
  • a pair of (electrode) substrates provided with an alignment film as necessary (electrode) substrate preparation step and at least one of the above (electrodes) A step of drawing a bonding region over the entire circumference with a bonding sealant on the outer peripheral portion of one side of the substrate, and a liquid crystal composition containing a polymerizable compound inside the bonding region on one side of the (electrode) substrate.
  • the step of bonding the other (electrode) substrate to cure the bonding sealant, and the liquid crystal composition containing the polymerizable compound attached on the (electrode) substrate to 300 to 400 nm It is preferable to have a light irradiation step of irradiating light having a peak and a step of bonding a polarizing plate. 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 sealant is preferably cured by a resin that is cured by UV or heat, and a known thermosetting sealant is preferably used.
  • 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, still more preferably 1 to 3 times, and particularly preferably 1 to 2 times.
  • the light irradiation step of irradiating light having a peak at 300 to 400 nm to the liquid crystal composition containing the polymerizable compound deposited on the substrate 1 to n times is independent and independent.
  • the irradiation conditions (wavelength of light to be irradiated, integrated light amount or illuminance, atmosphere, etc.) in the k-th light irradiation step (S k ) are the f-th light irradiation step (S f ).
  • irradiation conditions Wavelength of irradiated light, integrated light quantity or illuminance, atmosphere, etc.
  • the irradiation conditions of 1 time are independent.
  • the formula (1) according to the present invention is obtained by irradiating the liquid crystal composition containing 0.3% by mass of the polymerizable compound with light for 5 minutes under the light irradiation condition of a certain light irradiation step.
  • the concentration change amount (V k ) represents the light irradiation in the so-called light irradiation step described above because it represents the concentration change amount per unit portion of the concentration difference between the concentration (C k ) and 0.3 mass%.
  • An index indicating the reactivity of the polymerizable compound under the conditions is set.
  • the rate of change when the light irradiation time of 5 minutes is used as a reference.
  • V k is measured in a method of manufacturing a liquid crystal display device in which a light irradiation step of irradiating light having a peak at 300 to 400 nm at 20 ° C.
  • a liquid crystal composition containing 0.2% by mass of a polymerizable compound is prepared, and the polymerizable compound-containing liquid crystal composition is filled between 1 to k pairs of (electrode) substrates.
  • a light irradiation step of irradiating light having a peak at 300 to 400 nm at 25 ° C. for a liquid crystal composition containing 0.4% by mass of a polymerizable compound is performed 1 to n times.
  • measuring k 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.
  • the temperature of the polymerizable compound when measuring V k is the temperature of the polymerizable compound during light irradiation in each light irradiation step (S k ) (or It is preferably the same as the temperature of the atmosphere in the corresponding light irradiation step (S k ).
  • the irradiation conditions (liquid crystal cell (a pair of (electrode) substrates), the wavelength of light to be irradiated, the integrated light amount or illuminance, and the atmosphere) when measuring the above V k are the irradiation conditions in each actual light irradiation step (S k ). It is preferably the same as (liquid crystal cell (a pair of (electrode) substrates), wavelength of light to be irradiated, integrated light amount or illuminance, atmosphere).
  • the concentration change rate of the polymerizable compound under the light irradiation condition in each light irradiation step (S k ) and the irradiation time and product in each light irradiation step are the apparent values in each light irradiation step.
  • the total concentration of the polymerizable compound in all steps represents the total concentration of the polymerizable compound in which the “apparent” decreased in the total light irradiation step.
  • Dividing the reduced polymerizable compound concentration by the total light irradiation time represents the reaction rate of the “apparent” polymerizable compound in the total light irradiation step.
  • the average reaction rate V ave according to the present invention represents the reaction rate of the “apparent” polymerizable compound in the total light irradiation step. Therefore, by controlling the average reaction speed V ave within a specific range, there is no display defect due to a change in the pretilt angle, or it is extremely small, and the liquid crystal display reduces or suppresses the decrease in VHR and the display defect caused by it.
  • An element manufacturing method can be provided.
  • the lower limit value of the average reaction rate V ave (mass% / min) 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, or 0.043 or less.
  • 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, further preferably 0.032 to 0.047, and 0.032 to 0. 0.045 is more preferable, 0.033 to 0.045 is still more preferable, and 0.033 to 0.045 is particularly preferable.
  • the lower limit value of the average reaction rate V ave according to the present invention is 0.030, there is an advantage that VHR is hardly lowered by long-time light irradiation, and when the upper limit value is 0.048, the pretilt angle There is a merit that seizure due to change hardly occurs.
  • the light irradiation conditions in the light irradiation step (S k ) according to the present invention preferably include the peak wavelength of the irradiated light and / or the illuminance of the irradiated light.
  • the light irradiated to the polymerizable compound is light having a peak at 300 to 400 nm, and preferably ultraviolet light.
  • the light used in the light irradiation step (S k ) according to the present invention preferably has a peak in the vicinity of 313 nm or has a peak in the vicinity of 365 nm, preferably has a peak in the vicinity of 313 nm and has a peak in the vicinity of 365 nm. Preferably, it has a peak in the vicinity of 313 nm.
  • light having a specific wavelength or a specific wavelength or less may be cut by a known cut filter.
  • the lower limit 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.
  • the light irradiation step (S k ) according to the present invention in the light irradiation condition (S k ) according to the present invention, in the light irradiation condition of irradiating light having a peak near 313 nm and / or a peak near 365 nm.
  • the lower limit of the illuminance of the irradiated light (313 nm) is preferably 0.1 mW / cm 2 , more preferably 0.3 mW / cm 2 , and even more preferably 2 mW / cm 2 .
  • the upper limit of the illuminance of the irradiation light (313 nm) is preferably 30 mW / cm 2, more preferably from 25 mW / cm 2, further preferably 20 mW / cm 2.
  • the lower limit of the illuminance of the irradiated light (313 nm) is preferably 2 mW / cm 2 from the viewpoint that the average reaction rate of the polymerizable compound can be controlled in the range of 0.030 to 0.048.
  • the upper limit of the illuminance of ultraviolet rays to be used is preferably 20 mW / cm 2 from the viewpoint that the average reaction rate of the photopolymerizable compound can be controlled in the range of 0.030 to 0.048.
  • 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.
  • the lower limit of the illuminance of irradiated light is preferably 1 mW / cm 2 from the viewpoint that the average reaction rate of the polymerizable compound can be controlled in the range of 0.030 to 0.048.
  • the upper limit of the illuminance of ultraviolet rays to be used is preferably 120 mW / cm 2 from the viewpoint that the average reaction rate of the photopolymerizable compound can be controlled in the range of 0.030 to 0.048.
  • the method for measuring the illuminance of the irradiating light according to the present invention is not particularly limited and can be performed by a known method or apparatus.
  • Ushio Electric UVD-S313 is used for the illuminance
  • Ushio Electric UVD-S365 is used for the illuminance of 365 nm.
  • 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, further preferably 1 minute, and particularly preferably 1.5 minutes.
  • the upper limit of the irradiation time of the ultraviolet rays is more preferably 60 minutes, further preferably 50 minutes, and particularly preferably 45 minutes.
  • the production apparatus When strong ultraviolet rays are irradiated for a long time in the polymerization step, the production apparatus is increased in size and the production efficiency is lowered, and the liquid crystal composition is deteriorated by the ultraviolet rays. On the other hand, if the irradiation time of ultraviolet rays is shortened, the occurrence of image sticking, which is one of display defects caused by the remaining polymerizable compound, cannot be avoided. If the light irradiation step is as described above, as will be described later, the unreacted polymerizable compound remaining in the entire composition after leaving the unreacted polymerizable compound dared to remain is further treated. 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, further preferably 10 minutes, and particularly preferably 15 minutes.
  • the upper limit value of the ultraviolet irradiation time is more preferably minutes, 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. Moreover, 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 the same.
  • the wavelength region of ultraviolet rays is 200 to 380 nm
  • the wavelength region of visible light is 380 to 780 nm.
  • the light irradiation step (S k ) when ultraviolet rays are used, a polarized light source or a non-polarized light source may be used, but it is preferable to irradiate non-polarized ultraviolet rays.
  • the atmosphere in the light irradiation is not particularly limited, and may be an air atmosphere or a nitrogen or rare gas atmosphere.
  • the irradiation method that can be used in the light irradiation step (S k ) according to the present invention is not particularly limited, and a known irradiation method can be used.
  • a low-pressure mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a fluorescent UV lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. are used as a lamp that generates light to be irradiated to the polymerizable compound.
  • Actinic rays having a wavelength of 300 nm or more and 450 nm or less such as j-line (313 nm), i-line (365 nm), h-line (405 nm), and g-line (436 nm), can be preferably used.
  • Actinic rays having a wavelength of 300 nm or more and 400 nm or less are preferred.
  • 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, if necessary, and the ultraviolet light may be cut as necessary.
  • the wavelength of the ultraviolet ray irradiated in the light irradiation step (S k ) according to the present invention only needs to include the ultraviolet ray having the wavelength of 300 to 400 nm, and the ultraviolet ray having a wavelength region that is not the absorption wavelength region of the polymerizable compound. May be irradiated.
  • Active energy rays such as ultraviolet rays to be irradiated preferably have a plurality of spectra, and ultraviolet rays having a plurality of spectra are preferable.
  • the polymerizable compound can be polymerized with active energy rays having a spectrum (wavelength) suitable for each type, and in this case, the orientation direction of liquid crystal molecules can be controlled. A polymer is formed more efficiently.
  • an appropriate polymerization rate is desirable. Therefore, an active energy ray such as an electron beam is used separately from ultraviolet rays. It may be a method of polymerizing by irradiating one or in combination or sequentially.
  • the substrate on the irradiated surface side is suitable for ultraviolet rays. Is preferably given.
  • the orientation state of the unpolymerized part is changed by changing conditions such as an electric field and a magnetic field, and further ultraviolet rays are irradiated to polymerize. You may use the means.
  • a stable pretilt angle of liquid crystal molecules is formed by the polymer derived from the remaining polymerizable compound by further irradiating light of a predetermined wavelength with a voltage applied to the liquid crystal composition containing the polymerizable compound.
  • the orientation direction of the liquid crystal molecules constituting the liquid crystal composition containing the polymerizable compound by the polymer polymerized in the light irradiation step (S k ) is determined in a specific direction (for example, with respect to the substrate).
  • the liquid crystal molecules can be fixed in the vertical alignment by forming a stable pretilt angle with the polymer polymerized in the light irradiation step if necessary.
  • the liquid crystal molecules when the voltage is turned 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.
  • irradiating ultraviolet rays in the light irradiation step (S k ) according to the present invention it is preferable to irradiate ultraviolet rays while applying an alternating voltage or a direct current voltage, and more preferably irradiating ultraviolet rays while applying an alternating voltage. preferable.
  • the lower limit value of the frequency of the AC voltage to be applied is preferably a frequency of 10 Hz, and more preferably a frequency of 60 Hz.
  • the upper limit value of the frequency of the AC voltage to be applied is preferably 10 kHz, and 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 value 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 even more preferably 0.5 V.
  • the upper limit value of the voltage applied in the light irradiation step is preferably 30V, more preferably 20V, and even more preferably 10V.
  • the temperature of the liquid crystal composition containing the polymerizable compound at the time of voltage application is close to room temperature, preferably 14 to 62 ° C., more preferably 16 to 55 ° C. It is preferable to apply a voltage to the polymerizable compound-containing liquid crystal composition at 18 to 52 ° C.
  • the liquid crystal composition containing a polymerizable compound at the time of voltage application is preferably in a nematic phase state.
  • the liquid crystal composition containing a polymerizable compound is preferably a nematic phase from the viewpoint of uniform alignment.
  • One embodiment of the method for producing a liquid crystal display element according to the present invention includes 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.
  • a method of manufacturing a liquid crystal display element The concentration (C) of the polymerizable compound after irradiating the liquid crystal composition containing 0.3% by mass of the polymerizable compound under the light irradiation conditions of the first light irradiation step (S 1 ) for 5 minutes.
  • 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) is controlled to 0.030 to 0.048 (mass% / min). It is to be.
  • C 1 is the concentration (mass%) of the polymerizable compound contained in the liquid crystal composition after 5 minutes under the light irradiation condition in the first light irradiation step (S 1 ).
  • V 1 is represented by the above formula (1-1)
  • t 1 is a light irradiation time for irradiating the polymerizable compound with light in the first light irradiation step (S 1 ) ( Minutes).
  • the light irradiation step (S 1 ) when irradiating light, preferably ultraviolet rays, it is preferable to irradiate ultraviolet rays while applying an AC voltage or a DC voltage, and light (ultraviolet rays) while applying an AC voltage. ) Is more preferable.
  • the lower limit value of the frequency of the AC voltage to be applied is preferably a frequency of 10 Hz, and more preferably a frequency of 60 Hz.
  • the upper limit value of the frequency of the AC voltage to be applied is preferably 10 kHz, and 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 value of the voltage applied in the light irradiation step is preferably 30V, more preferably 20V, and even more preferably 10V.
  • the temperature of the atmosphere during voltage application is close to room temperature, preferably 14 to 62 ° C., more preferably 16 to 55 ° C., and further preferably 18 to 52 ° C. It is preferable to apply a voltage to the liquid crystal composition-containing liquid crystal composition.
  • the temperature of the atmosphere in which light is irradiated for 5 minutes when measuring the concentration change amount V 1 per unit of the concentration difference from 3% by mass is 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.
  • the light irradiated for 5 minutes when measuring the concentration change amount V 1 per unit of the concentration difference from the mass% is preferably the same as the light irradiated in the light irradiation step (S 1 ).
  • 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 is independent.
  • the concentration change amount V 1 per unit portion of the concentration difference between the polymerizable compound after irradiation with light (C 1 ) and 0.3% by mass is expressed by the following formula (1-1).
  • the average reaction rate V ave of the polymerizable compound represented by the following formula (2-2) is 0.030 to 0.048 (mass% / min).
  • C 1 represents the light in the first light irradiation step (S 1 ) for the liquid crystal composition containing 0.3% by mass of the polymerizable compound. This represents the concentration (% by mass) of the polymerizable compound after irradiation with light for 5 minutes under irradiation conditions, and C 2 represents the second light for the liquid crystal composition containing 0.3% by mass of the polymerizable compound.
  • V 1 and V 2 represent the concentration change amount per unit represented by the above formula (1-1) and formula (1-2), and t 1 and t 2 are The light irradiation time (minutes) for irradiating the polymerizable compound with light in each step is represented. ) If the light irradiation step is divided into two steps, the number of liquid crystal panels that can be processed at a time increases, which is preferable from the viewpoint of mass production of liquid crystal display elements.
  • the remaining amount of the polymerizable compound can be reduced or desired Easy to adjust pretilt forming operation.
  • 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 is provided twice separately.
  • the first light irradiation step (S 1 ) it is preferable to irradiate light having a peak at 300 to 400 nm with a voltage applied.
  • a polymer derived from a polymerizable compound is obtained by first irradiating light having a predetermined wavelength with a voltage applied to a liquid crystal composition containing the polymerizable compound, that is, by a first light irradiation step (S 1 ).
  • the liquid crystal molecules form a desired pretilt angle by the (polymer structure), and the second light irradiation step (S 2 ) is performed without applying a voltage, thereby reinforcing the shape of the polymer structure, and
  • the remaining polymerizable compound can be reduced.
  • a VA liquid crystal display element that is aligned in a direction perpendicular to the substrate when no voltage is applied will be described as an example.
  • the liquid crystal molecules constituting the liquid crystal composition containing the polymerizable compound are in a specific orientation direction with respect to the substrate, for example, when the voltage is applied, the substrate Since the polymerizable compound is polymerized in a state of following the horizontal direction with respect to the liquid crystal molecule, when no voltage is applied thereafter, the liquid crystal molecules are aligned with the substrate by the polymer structure in which the polymerizable compound is polymerized.
  • the polymer structure can be fixed in a state where it is slightly tilted toward the substrate side from the vertical direction (pretilt angle), and the second light irradiation step (S 2 ) is performed without applying a voltage.
  • the remaining polymerizable compound can be reduced.
  • achieves a desired pretilt angle and high VHR value can be manufactured.
  • 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 shape of the polymer structure to be formed can be controlled, it is considered that a liquid crystal display element in which an appropriate pretilt angle and the amount of the remaining polymerizable compound are reduced can be produced.
  • irradiating ultraviolet rays in the light irradiation step (S 1 ) it is preferable to irradiate ultraviolet rays while applying an alternating voltage or a direct current voltage, and more preferably irradiating ultraviolet rays while applying an alternating voltage. preferable.
  • the lower limit value of the frequency of the AC voltage to be applied is preferably a frequency of 10 Hz, and more preferably a frequency of 60 Hz.
  • the upper limit value of the frequency of the AC voltage to be applied is preferably 10 kHz, and 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 value of the voltage applied in the light irradiation step is preferably 30V, more preferably 20V, and even more preferably 10V.
  • 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 is provided twice separately.
  • a 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 preferable that the first light irradiation step (S 1 ) is longer than the light irradiation time t 1 .
  • the light irradiation step is preferably performed once or twice.
  • the viewpoint that only one irradiation device is required it is preferable to perform one light irradiation step.
  • the method for attaching the liquid crystal composition containing the polymerizable compound on the substrate is not particularly limited, and the inside of the cell in which a pair of (electrode) substrates are bonded together via a spacer.
  • a liquid crystal composition containing a polymerizable compound into the (electrode) substrate to attach the polymerizable compound-containing liquid crystal composition (vacuum injection method)
  • one of the pair of (electrode) substrates and Examples thereof include a method (ODF method) of dropping a polymerizable compound-containing liquid crystal composition on both substrates.
  • the substrate according to the present invention preferably has an electrode layer (a pixel electrode including a TFT, a common electrode) and an alignment film formed on a (transparent) support substrate as necessary.
  • the method of dropping the polymerizable compound-containing liquid crystal composition according to the present invention is not particularly limited, but for example, a method of performing screen printing, offset printing, flexographic printing, ink jetting, a droplet discharge device or a dispenser is 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 driving or lateral electric field driving.
  • the electrode layer include transparent conductive materials such as ITO (Indium Tin Oxide), IZO (Indium Zinc Tin Oxide), etc., when the liquid crystal display element is a transmissive type. It is not limited to these.
  • examples of the electrode layer include, but are not limited to, a material that reflects light such as aluminum.
  • the liquid crystal display element according to the embodiment preferably includes a pair of transparent substrates facing each other, and the electrode layer is preferably formed on at least one of the substrates.
  • the electrode layer preferably has slits 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.
  • 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.
  • an alignment film may be formed on at least one of the pair of substrates, or a substrate on which no alignment film is formed is preferably used.
  • the liquid crystal display element includes a first support substrate and a second support substrate which are disposed opposite to each other, a common electrode provided on the first support substrate or the second support substrate, and the first support substrate.
  • an alignment film for controlling the alignment direction of the liquid crystal molecules may be provided on the opposing surface side of at least one of the first support substrate and / or the second support substrate so as to contact the liquid crystal layer.
  • a color filter may be provided as appropriate 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.
  • two polarizing plates may be provided outside the first support substrate or the second support base plate.
  • a transparent material having flexibility such as glass or plastic (acrylic, polycarbonate, etc.) can be used.
  • an opaque material such as a silicon wafer is used. Any material may be used.
  • the pair of substrates is bonded by a sealing material and a sealing material such as an epoxy thermosetting composition disposed in the peripheral region, and in order to maintain the distance between the substrates, for example, glass particles Alternatively, granular spacers such as plastic particles and alumina particles, or spacer columns made of a resin formed by a photolithography method may be disposed.
  • the vertical electric field drive type liquid crystal display element (VA) includes a second support substrate disposed oppositely, a common electrode provided on the second support substrate, and the first electrode. It is preferable to include 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.
  • one substrate includes a support substrate, a thin film transistor (TFT), a pixel electrode, and wiring (a gate line, a data bus line, a Cs electrode, a contact hole, and the like), and the other substrate includes 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).
  • the liquid crystal display element according to the present invention When the liquid crystal display element 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. More specifically, the one substrate is a support substrate. And a wiring (gate line, data bus line, Cs electrode, contact hole, etc.), a thin film transistor (TFT), a common electrode, and a pixel electrode.
  • the other substrate preferably has a support substrate and, if necessary, a color filter.
  • the substrate to which the polymerizable compound-containing liquid crystal composition is attached is any one of the above (first or second) support substrate, the transparent substrate, the one substrate, and the other substrate. It may be.
  • the color filter according to the present invention can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method.
  • a method for producing a color filter by a pigment dispersion method will be described as an example.
  • a curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created.
  • 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 on the substrate.
  • first substrate and the second substrate face each other 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.
  • it is preferable to adjust so that the thickness of the obtained light control layer is 1 to 100 ⁇ m. More preferably, the thickness is 1.5 to 10 ⁇ m.
  • a polarizing plate it is preferable to adjust the product of the refractive index anisotropy ⁇ n of the liquid crystal and the cell thickness d so that the contrast is maximized.
  • the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good.
  • a retardation film for widening the viewing angle can also be used.
  • the polymerizable compound according to the present invention has the following 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 - an alkyl group substituted by fluorine atoms from a good carbon atoms 1 also 18, an alkoxy group having from good carbon atoms 1 be substituted by a fluorine atom 18, represent either 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 an oxygen atom is not directly adjacent to each other.
  • 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) a 1,4-phenylene group (one —CH ⁇ present in the 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 , 3,4-tetrahydronaphthalene-2,6-diyl group, one —CH ⁇ or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ .
  • 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).
  • 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 A trifluoromethyl group, a fluorine atom, a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms.
  • R 7 and R 8 are preferably each independently a methacryl group or an acryl group.
  • the compound represented by the general formula (IV) is more preferably one or more selected from the group consisting of the formulas (IV-11) to (IV-19). 11), formula (IV-16), and formula (IV-17) are particularly preferable.
  • the compound represented by the general formula (I) according to the present invention is preferably a compound represented by the general formula (XX-1) to the general formula (XX-29), for example, the formula (XX-1) To formula (XX-7), and formula (XX-14) to formula (XX-29) are more preferable.
  • Sp xx represents an alkylene group having 1 to 8 carbon atoms or —O— (CH 2 ) s — (wherein s represents an integer of 1 to 7) And an oxygen atom is bonded to the ring).
  • the hydrogen atom in the 1,4-phenylene group is further —F, —Cl, —CF 3 , —CH 3 or P 21 —S 21 —. It may be replaced by any of the above.
  • a polymerizable compound represented by the formula (M1) to the formula (M18) is preferable.
  • polymerizable compounds such as formula (M19) to formula (M34) are also preferable.
  • the hydrogen atoms in the 1,4-phenylene group and naphthalene group in the formulas (M19) to (M34) may be further substituted with —F, —Cl, —CF 3 , or —CH 3 .
  • the compound represented by the general formula (I) is also preferably a polymerizable compound represented by the formula (M35) to the formula (M65).
  • the content of the polymerizable compound represented by the formulas (M1) to (M65) with respect to the entire 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%, preferably 0.06 mass%, 0.07 mass% 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% by mass 0.35% by mass is preferable, 0.4% by mass is preferable, 0.5% by mass is preferable, 0.55% by mass is preferable, and the upper limit of the content is 4.5% by mass % Is preferred, 4% by weight is preferred, 0.5% by mass is preferable, 3% by mass is preferable, 2.5% by mass is preferable, 2% by mass is preferable, 1.5% by mass is preferable, 1% by mass is preferable, 0.95% by mass is preferable, and 0% is preferable. 0.9% by mass, 0.85% by mass is preferable, 0.8% by mass is preferable, 0.75% by mass is preferable, 0.7% by mass is preferable, 0.65% by mass is preferable, and 0.6% by mass is preferable. % By mass is preferable, and 0.55% by mass is preferable.
  • Preferred examples of the compound represented by the general formula (I) according to the present invention include polymerizable compounds represented by the following formulas (RM-2-1) to (RM-2-52).
  • the specific content of the polymerizable monomer represented by the above formulas (RM-2-1) to (RM-2-52) is preferably 5% by mass or less, more preferably 3% by mass or less. It is more preferably 2% by mass or less, particularly preferably 1% by mass or less, and most preferably 0.8% by mass or less.
  • the dielectric anisotropy ( ⁇ ) at 20 ° C. is from ⁇ 2.0 to ⁇ 8.0, but from ⁇ 2.1 to ⁇ 6. 2 is preferred, -2.2 to -5.3 is more preferred, and -2.5 to -5.0 is even more preferred. -2.7 to -4.8 are particularly preferred.
  • the dielectric anisotropy ( ⁇ ) 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 ( ⁇ n) at 20 ° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and 0.09 to 0.12. Is particularly preferred. More specifically, it is preferably 0.10 to 0.13 when dealing with a thin cell gap, and preferably 0.08 to 0.11 when dealing with a thick cell gap.
  • the liquid crystal composition according to the present invention has a viscosity ( ⁇ ) at 20 ° C. of 10 to 50 mPa ⁇ s, preferably 10 to 45 mPa ⁇ s, and preferably 10 to 40 mPa ⁇ s. It is preferably 35 mPa ⁇ s, preferably 10 to 30 mPa ⁇ s, 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 ( ⁇ 1 ) at 20 ° C. of 50 to 160 mPa ⁇ s, preferably 55 to 160 mPa ⁇ s, and preferably 60 to 160 mPa ⁇ s.
  • 60 to 150 mPa ⁇ s is preferable, 60 to 140 mPa ⁇ s is preferable, 60 to 130 mPa ⁇ s is preferable, and 60 to 125 mPa ⁇ s is preferable.
  • 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., more preferably 70 ° C. to 100 ° C., and particularly preferably 70 ° C. to 85 ° C. .
  • the liquid crystal composition according to the present invention includes, as a first component, one or two compounds represented by the general formula (L) of a dielectrically neutral compound ( ⁇ value is ⁇ 2 to 2). It is preferable to contain above.
  • the compound represented by the general formula (L) is as follows.
  • R L1 and R L2 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH 2 — in the alkyl group are each independently Optionally substituted by —CH ⁇ CH—, —C ⁇ C—, —O—, —CO—, —COO— or —OCO—, n L1 represents 0, 1, 2 or 3,
  • a L1 , A L2 and A L3 each independently represent (a) a 1,4-cyclohexylene group (one —CH 2 — present in the group or two or more —CH 2 — not adjacent to each other).
  • 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
  • the compound represented by the general formula (J) is as follows.
  • 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—, — Optionally 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-.)
  • the group (a), the group (b) and the group (c) are each independently selected from the group consisting of cyano group, fluorine atom, chlorine atom, methyl group, trifluoromethyl group or trifluoro May be substituted with a methoxy group
  • Z J1 and Z J2 each independently represent 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-
  • n J1 is 2, 3 or 4 and a plurality of A J2 are present, they may be the same or different, and n J1 is 2, 3 or 4 and a plurality of Z J1 is present.
  • 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.
  • 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 non- Two or more adjacent —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 —CH ⁇ that are not adjacent to each other may be replaced by —N ⁇ )
  • (d) represents a group selected from the group consisting of 1,4-cyclohexenylene groups, and the groups (a), (b), (c) and (d) are each independently May be substituted with a cyano group, a fluorine atom or a chlorine atom, Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2.
  • XN21 represents a hydrogen atom or a fluorine atom
  • T N31 represents —CH 2 — or an oxygen atom
  • n N11 , n N12 , n N21 , n N22 , n N31, and n N32 each independently represent an integer of 0 to 3, but n N11 + n N12 , n N21 + n N22, and n N31 + n N32 are each independently When there are a plurality of A N11 to A N32 and Z N11 to Z N32 , they may be the same or different.
  • the compound represented by the general formula (L) is preferably a compound represented by the following formulas (L-1) to (L-13).
  • R L1 and R L2 each independently represent the same meaning as in the general formula (L), and A L1 and A L7 each independently represent the same meaning as in the general formula (L),
  • the hydrogen atoms on L1 and A L2 may be each independently substituted with a fluorine atom
  • Z L1 represents the same meaning as Z L2 in formula (L)
  • X L1 and X L2 each independently Represents a fluorine atom or a hydrogen atom.
  • the compound represented by the general formula (J) is preferably a compound represented by the following formulas (M-1) to (M-18).
  • X M11 ⁇ X M186 each independently represent a hydrogen atom or a fluorine atom
  • R J1 ⁇ R J181 is independently an alkyl group having 1 to 5 carbon atoms, 2 to 5 carbon atoms
  • X J11 to X J181 represents a fluorine atom, a chlorine atom or OCF 3
  • a M81 and A M82 are each independently 1,4-cyclohexylene group, 1,4-phenylene group or
  • a hydrogen atom on the 1,4-phenylene group may be substituted with a fluorine atom
  • W M101 to W M172 each independently represents —CH 2 — or —O—.
  • the compound represented by the general formula (J) is preferably a compound represented by the following formulas (K-1) to (K-6).
  • R K11 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
  • X K11 to X K14 are each independently hydrogen. represents an atom or a fluorine atom
  • Y K11 represents a fluorine atom or OCF 3.
  • R K21 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
  • X K21 to X K24 are each independently hydrogen. represents an atom or a fluorine atom
  • Y K21 represents a fluorine atom or OCF 3.
  • R K31 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
  • X K31 to X K36 are each independently hydrogen.
  • Y K31 represents a fluorine atom or OCF 3.
  • R K41 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
  • X K41 to X K46 are each independently hydrogen.
  • An atom or a fluorine atom Y K41 represents a fluorine atom or OCF 3
  • Z K41 represents —OCH 2 —, —CH 2 O—, —OCF 2 —, or —CF 2 O—.
  • R K51 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
  • X K51 to X K56 are each independently hydrogen.
  • An atom or a fluorine atom Y K51 represents a fluorine atom or OCF 3
  • Z K51 represents —OCH 2 —, —CH 2 O—, —OCF 2 —, or —CF 2 O—.
  • R K61 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
  • X K61 to X K68 are each independently 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-).
  • Examples of the compound represented by the general formula (N-1) according to the present invention include compounds represented by the following general formulas (N-1a) to (N-1g).
  • 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 Represents 0 or 1, 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, but n Ng11 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
  • R N211 and R N212 each independently represents the same meaning as R N21 and R N22 in the general formula (N-2).
  • R N221 and R N222 each independently represents the same meaning as R N21 and R N22 in the general formula (N-2).
  • the compound represented by the general formula (N-3) is preferably a compound selected from the group of compounds represented by the general formula (N-3-2).
  • R N321 and R N322 each independently represent the same meaning as R N31 and R N32 in formula (N-3)).
  • the polymerizable compound represented by the general formula (I) and the compound represented by the general formula (J) It is preferable that 1 type or 2 types or more of compounds chosen from are included, and the compound represented by general formula (L).
  • the upper limit of the ratio which the component comprised only from the compound represented by general formula (I), general formula (J), and general formula (L) among the whole liquid crystal composition containing the polymeric compound which concerns on this invention Values are 100% by weight, 99% by weight, 98% by weight, 97% by weight, 96% by weight, 95% by weight, 94% by weight, 93% by weight, 92% by weight, 91% by weight, 90% by weight, 89% by weight. 88 mass%, 87 mass%, 86 mass%, 85 mass%, and 84 mass%.
  • Values are 78%, 80%, 81%, 83%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92% by weight.
  • the polymerizable compound represented by the general formula (I) and the compound represented by the general formula (N-1) It is preferable that 1 type or 2 types or more of compounds chosen from are included, and the compound represented by general formula (L).
  • the proportion of components composed only of the compounds represented by formula (I), formula (N-1), and formula (L) are 100%, 99%, 98%, 97%, 96%, 95%, 95%, 94%, 93%, 92%, 91%, 90%, 89% %, 88% by mass, 87% by mass, 86% by mass, 85% by mass, and 84% by mass are preferable.
  • the liquid crystal display device using the polymerizable compound-containing liquid crystal composition of the present invention has a remarkable characteristic of high-speed response, and in addition, whether a tilt angle is sufficiently obtained and there is no unreacted polymerizable compound. Since the voltage holding ratio (VHR) is so high that it does not become a problem and there is no problem such as alignment failure or display failure, it is 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 production, which is optimal for improving production efficiency and stable mass production.
  • VHR voltage holding ratio
  • 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 be used for a liquid crystal display element.
  • a liquid crystal composition containing a polymerizable compound is coated with a polyimide alignment film that induces vertical alignment at a cell gap of 3.5 ⁇ m, and then vacuum injection is performed on a liquid crystal cell including a substrate with ITO that is rubbed with the polyimide alignment film.
  • the liquid crystal display element was produced.
  • the liquid crystal display element was disassembled to obtain an acetonitrile solution of an elution component containing a liquid crystal composition, a polymer, and an unreacted polymerizable compound. This was analyzed with a high performance liquid chromatograph, and the peak areas of each component were measured. The amount of the remaining polymerizable compound was determined from the peak area ratio of the liquid crystal compound as an 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 lower limit of this measurement was 100 ppm.
  • the light irradiation conditions and temperature at the time of measuring V k are the same as the corresponding light irradiation steps (S k ).
  • Light irradiation condition A Using a high-pressure mercury lamp, light was irradiated through a filter that cuts out 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 Using a high-pressure mercury lamp, light was irradiated through a filter that cuts light of 325 nm or less. At this time, the illuminance measured under the condition of the center wavelength 365 nm was 120 mW / cm 2 , and the illuminance measured under the condition of the center wavelength 313 nm was 18 mW / cm 2 .
  • Light irradiation condition 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 condition 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.
  • pretilt angle change amount is to 0 [°]
  • the pretilt angle change amount exceeds 0.5 [°]
  • a display failure due to the change in the pretilt angle will occur. More likely.
  • liquid crystal composition 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 was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-2 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 15 spectral irradiations were performed under the light irradiation condition A to obtain Comparative Example 1.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-3 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 15 spectral irradiations were performed under the light irradiation condition A to obtain Comparative Example 2.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-3 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 15 spectral irradiations were performed under the light irradiation condition B to obtain Comparative Example 3.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition containing 0.3 wt% of the polymerizable compound RM-4 was injected with respect to 99.7 parts by mass of the liquid crystal composition LC-001. Then, 5 spectral irradiations were performed under the light irradiation condition A to obtain Comparative Example 4.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition containing 0.3 wt% of the polymerizable compound RM-4 was injected with respect to 99.7 parts by mass of the liquid crystal composition LC-001. Then, 15 spectral irradiations were performed under the light irradiation condition B to obtain Comparative Example 5.
  • V ave in Comparative Example 1 was 0.055 [% by mass / min].
  • the amount of change in the pretilt angle of Comparative Example 1 was 1.1 [°]. From these results, it was found that in Comparative Example 1, the reaction rate of the polymerizable compound was fast, but the amount of change in the pretilt angle was large.
  • Comparative Examples 2 to 5 like Comparative Example 1, it was found that the reaction rate of the polymerizable compound was fast, but the amount of change in the pretilt angle was large.
  • Example 1 A voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition containing 0.3 wt% of the polymerizable compound RM-1 was injected with respect to 99.7 parts by mass of the liquid crystal composition LC-001. Then, 30 spectral irradiations were performed under the light irradiation condition A to obtain Example 1.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-2 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 30 spectral irradiations were performed under the light irradiation condition B, and Example 2 was obtained.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-2 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 60 spectral irradiation was performed under the light irradiation condition C to obtain Example 3.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-3 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 30 spectral irradiations were performed under the light irradiation condition C to obtain Example 4.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition containing 0.3 wt% of the polymerizable compound RM-4 was injected with respect to 99.7 parts by mass of the liquid crystal composition LC-001. Then, 30 spectral irradiations were performed under the light irradiation condition C to obtain Example 5.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition containing 0.3 wt% of the polymerizable compound RM-4 was injected with respect to 99.7 parts by mass of the liquid crystal composition LC-001. Then, 60 spectral irradiation was performed under the light irradiation condition D to obtain Example 6.
  • V ave in Example 1 was 0.042 [% by mass / min].
  • the amount of change in the 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 high and the amount of change in the pretilt angle was small.
  • Example 2 As in Example 1, it was found that the reaction rate of the polymerizable compound was moderately high 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 6V for Von, 1V for Voff, 25 ° C for measurement temperature, and DMS703, manufactured by AUTRONIC-MELCHERS, as the measuring instrument.
  • the pretilt angle of the liquid crystal display element was measured and set as the pretilt angle (initial).
  • the liquid crystal display element was irradiated with a backlight for 24 hours while applying a voltage of 30 V at a frequency of 100 Hz. Thereafter, the pretilt angle was measured to obtain a pretilt angle (after the test).
  • the pretilt angle was measured using an OPTIPRO made by Shintec.
  • pretilt angle change amount is to 0 [°]
  • the pretilt angle change amount exceeds 0.5 [°]
  • a display failure due to the change in the pretilt angle will occur. More likely.
  • Comparative Example 6 A voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-3 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, ultraviolet light was irradiated for 600 seconds under the ultraviolet irradiation condition B, and then 5 spectral irradiations were performed under the light irradiation condition C to obtain Comparative Example 6.
  • Comparative Example 6 was found to have a large reaction rate of the polymerizable compound but a large amount of change in the pretilt angle.
  • Example 7 A voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-2 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. 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 to obtain Example 7.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-2 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. 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 to obtain Example 8.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-2 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 5 spectral irradiations were performed under the light irradiation condition B, and then 45 spectral irradiations were performed under the light irradiation condition C to obtain Example 9.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-2 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 10 spectral irradiations were performed under the light irradiation condition B, and then 30 spectral irradiations were performed under the irradiation condition C to obtain Example 10.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-3 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 1.25 spectral irradiation was performed under irradiation condition B, and then 30 spectral irradiations were performed under irradiation condition C to obtain Example 11.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-3 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 2.5 spectral irradiation was performed under the light irradiation condition B, and then 20 spectral irradiations were performed under the light irradiation condition C to obtain Example 12.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-3 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 5 spectral irradiations were performed under the light irradiation condition B, and then 10 spectral irradiations were performed under the irradiation condition C to obtain Example 13.
  • Examples 7 to 13 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 6V for Von, 1V for Voff, 25 ° C for measurement temperature, and DMS703, manufactured by AUTRONIC-MELCHERS, as the measuring instrument.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-2 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected. Then, 60 spectral irradiation was performed under the light irradiation condition C to obtain Example 14.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition in which 0.3 wt% of the polymerizable compound RM-3 was added to 99.7 parts by mass of the liquid crystal composition LC-001 was injected.
  • the sample was irradiated with 30 spectra under the light irradiation condition C to obtain Example 15.
  • a voltage of 10 V was applied at a frequency of 100 Hz to a cell into which a polymerizable compound-containing liquid crystal composition containing 0.3 wt% of the polymerizable compound RM-4 was injected with respect to 99.7 parts by mass of the liquid crystal composition LC-001. Then, 30 spectral irradiations were carried out under the light irradiation condition C to obtain Example 16.
  • V ave in Comparative Example 7 was 0.029 [% by mass / min].
  • the amount of change in the pretilt angle of Comparative Example 1 was 0.1 [°].
  • VHR of the comparative example 1 after ultraviolet irradiation was 71 [%].
  • V ave in Example 14 was 0.034 [% by mass / min].
  • the amount of change in pretilt angle of Example 14 was 0.2 [°].
  • the VHR after ultraviolet irradiation in Example 14 was 76 [%].
  • V ave in Example 15 was 0.041 [% by 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 [%].
  • V ave in Example 16 was 0.047 [% by mass / min].
  • the amount of change in pretilt angle in Example 16 was 0.2 [°].
  • VHR after ultraviolet irradiation of Example 16 was 80 [%].
  • FIG. 1 shows a graph in which the ultraviolet irradiation time and VHR of Comparative Example 7 and Examples 14 to 16 are plotted (Comparative Example 7 is described as com7 and Examples 14 to 16 are described as exp14 to 16).
  • VHR was higher as V ave was larger, and when V ave was smaller than 0.030 (mass% / min), VHR was saturated at a lower value. From this, it was found that when V ave is moderately large, the residual amount of the polymerizable compound falls below the detection lower limit in a short light irradiation time, so that the liquid crystal composition is not easily deteriorated by light.

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