WO2019009166A1 - Dispositif d'affichage à cristaux liquides et son procédé de fabrication - Google Patents

Dispositif d'affichage à cristaux liquides et son procédé de fabrication Download PDF

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Publication number
WO2019009166A1
WO2019009166A1 PCT/JP2018/024479 JP2018024479W WO2019009166A1 WO 2019009166 A1 WO2019009166 A1 WO 2019009166A1 JP 2018024479 W JP2018024479 W JP 2018024479W WO 2019009166 A1 WO2019009166 A1 WO 2019009166A1
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Prior art keywords
liquid crystal
monomer
display device
group
substrates
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PCT/JP2018/024479
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English (en)
Japanese (ja)
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真伸 水▲崎▼
博司 土屋
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シャープ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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

Definitions

  • the present invention relates to a liquid crystal display device and a method of manufacturing the liquid crystal display device. More specifically, the present invention relates to a liquid crystal display device having an alignment control layer, and a method of manufacturing the liquid crystal display device.
  • Liquid crystal display devices are used in applications such as televisions, smartphones, tablets, PCs, and car navigation systems. In these applications, various performances are required, and various display modes have been developed.
  • a vertical alignment mode such as a VA (Vertical Alignment) mode may be adopted because a high contrast can be easily obtained.
  • VA Vertical Alignment
  • it has also been proposed to use means instead of the conventional alignment film see, for example, Patent Document 1).
  • the display area for displaying an image is widened, and the frame area not contributing to the display of the image is narrowed.
  • the frame becomes narrower, peeling between a pair of substrates constituting the liquid crystal display device may be facilitated.
  • FIG. 6 is a schematic cross-sectional view showing a liquid crystal display device having a conventional alignment film.
  • an alignment film 116a is formed on the surface of the substrate 102a, and an alignment film 116b is formed on the surface of the substrate 102b.
  • the substrate 102a having the alignment film 116a formed on the surface thereof and the substrate 102b having the alignment film 116b formed on the surface thereof are bonded by the sealing material 104, and the liquid crystal layer 103 is formed between the substrate 102a and the substrate 102b.
  • the area surrounded by the sealing material 104 corresponds to the display area
  • the area surrounding the display area is the frame area I think that corresponds to.
  • the alignment film 116 a exists between the substrate 102 a and the seal material 104
  • the alignment film 116 b exists between the substrate 102 b and the seal material 104.
  • the adhesive strength between the alignment films 116a and 116b and the sealing material 104 is originally low, and thus the alignment films 116a and 116b and the sealing material 104 Peeling from the interface of
  • the width of the sealing material 104 is reduced and the frame area is narrowed, the adhesion area between the alignment films 116a and 116b and the sealing material 104 is reduced, so the seal with the alignment films 116a and 116b is performed. It may be easier to peel off from the interface with the material 104.
  • the present inventors examined a method for preventing the adhesion between the alignment films 116a and 116b and the sealing material 104.
  • the position of the alignment films 116 a and 116 b is controlled so that the alignment film 116 a is not disposed between the substrate 102 a and the sealant 104 and the alignment film 116 b is not disposed between the substrate 102 b and the sealant 104. Is difficult in terms of the accuracy of the film forming apparatus (printing apparatus).
  • Patent Document 1 uses a polymer layer formed by polymerizing one or more radically polymerizable monomers added in the liquid crystal layer. Is described.
  • the invention described in Patent Document 1 since the conventional alignment film is not used, the problem of peeling from the interface between the alignment film and the sealing material as described above can be avoided.
  • the invention described in Patent Document 1 has room for improvement in that it suppresses the decrease in voltage holding ratio (VHR) caused by the unpolymerized monomer remaining in the liquid crystal layer.
  • VHR voltage holding ratio
  • the liquid crystal layer is irradiated with ultraviolet light under a high temperature environment higher than the nematic phase-isotropic phase transition temperature of the liquid crystal material in the liquid crystal layer.
  • the present invention has been made in view of the above-mentioned present situation, and provides a liquid crystal display device which is difficult to be separated even if the frame is narrowed and which has high voltage holding ratio and manufacturing efficiency, and a method of manufacturing the liquid crystal display device. Purpose.
  • the inventors of the present invention conducted various studies on a liquid crystal display device having a high voltage holding ratio and a high production efficiency, and a method for producing the above liquid crystal display device, even if the frame is narrowed. It focused on utilizing the orientation control layer formed by polymerizing at least two types of monomers (including the first monomer and the second monomer) added to the liquid crystal layer. Then, it has been found that, by using such an orientation control layer, it is possible to realize a configuration in which a pair of substrates and a sealing material are in contact without interposing a conventional alignment film.
  • the alignment control layer when forming an alignment control layer, if a monomer having a predetermined structure is used as the first monomer of the at least two types of monomers, the polymerization rate is increased, and a monomer in an unpolymerized state in the liquid crystal layer Was found to be difficult to survive. Furthermore, it has been found that the alignment control layer can also be formed by irradiating the liquid crystal layer with light in a normal temperature environment. The present invention has been achieved with the above in mind that it is possible to solve the above problems clearly.
  • one embodiment of the present invention includes a pair of substrates disposed opposite to each other, a liquid crystal layer disposed between the pair of substrates, and a liquid crystal layer disposed between the pair of substrates, and surrounds the liquid crystal layer in plan view And a sealing material disposed between the pair of substrates and in contact with the pair of substrates, in a region surrounded by the sealing material in a plan view, disposed between the pair of substrates and the liquid crystal layer in a cross sectional view And an alignment control layer in contact with the liquid crystal layer, wherein the alignment control layer contains a polymer including a unit derived from the first monomer and a unit derived from the second monomer, and the liquid crystal molecules in the liquid crystal material are
  • the first monomer may be a liquid crystal display device represented by the following chemical formula (1), which is oriented in the vertical direction with respect to the surfaces of the pair of substrates.
  • X 1 and X 2 are the same or different and each represents H, CH 3 or C 2 H 5 .
  • Y 1 and Y 2 are the same or different, and H, F, Cl, Br, linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or linear, branched or cyclic carbon It represents an alkyloxy group of the formulas 1 to 6.
  • Z represents O, S, NH, CO, COO, OCO, or a direct bond.
  • m represents an integer of 6 to 16; n represents an integer of 8 to 24.
  • the first monomer may contain at least one of the monomers represented by the following chemical formulas (2-1) to (2-8).
  • the second monomer may be represented by the following chemical formula (3).
  • P 1 and P 2 are the same or different and each represents an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group or a vinyloxy group.
  • Sp 1 and Sp 2 are the same or different, and are linear, branched or cyclic alkylene groups having 1 to 6 carbon atoms, linear, branched or cyclic alkylene oxy groups having 1 to 6 carbon atoms, or , Represents a direct bond.
  • the second monomer may contain at least one of the monomers represented by the following chemical formulas (4-1) and (4-2).
  • the nematic phase-isotropic phase transition temperature of the liquid crystal material may be 80 ° C. or higher.
  • the nematic phase-isotropic phase transition temperature of the liquid crystal material may be 90 ° C. or higher.
  • Another embodiment of the present invention is a step of forming a liquid crystal layer by sealing a liquid crystal composition containing a liquid crystal material, a first monomer, and a second monomer between a pair of substrates bonded by a sealing material 1) An alignment in contact with the liquid crystal layer between the pair of substrates and the liquid crystal layer by polymerizing at least the first monomer and the second monomer by irradiating the liquid crystal layer with light.
  • Forming the control layer (2), wherein the alignment control layer aligns liquid crystal molecules in the liquid crystal material in a direction perpendicular to the surfaces of the pair of substrates, and the first monomer May be a method of manufacturing a liquid crystal display device represented by the following chemical formula (1).
  • X 1 and X 2 are the same or different and each represents H, CH 3 or C 2 H 5 .
  • Y 1 and Y 2 are the same or different, and H, F, Cl, Br, linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or linear, branched or cyclic carbon It represents an alkyloxy group of the formulas 1 to 6.
  • Z represents O, S, NH, CO, COO, OCO, or a direct bond.
  • m represents an integer of 6 to 16; n represents an integer of 8 to 24.
  • the first monomer may contain at least one of the monomers represented by the following chemical formulas (2-1) to (2-8).
  • the second monomer may be represented by the following chemical formula (3).
  • P 1 and P 2 are the same or different and each represents an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group or a vinyloxy group.
  • Sp 1 and Sp 2 are the same or different, and are linear, branched or cyclic alkylene groups having 1 to 6 carbon atoms, linear, branched or cyclic alkylene oxy groups having 1 to 6 carbon atoms, or , Represents a direct bond.
  • the second monomer may contain at least one of the monomers represented by the following chemical formulas (4-1) and (4-2).
  • the liquid crystal layer in the step (2), may be irradiated with light in a state where the temperature of the liquid crystal layer is set to 20 to 100 ° C.
  • the present invention it is possible to provide a liquid crystal display device which is difficult to be separated even when the frame is narrowed and which has high voltage holding ratio and manufacturing efficiency, and a method of manufacturing the liquid crystal display device.
  • FIG. 1 is a schematic plan view showing a liquid crystal display device of an embodiment. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the liquid crystal display device of embodiment, (a) shows the state before formation of an orientation control layer, (b) shows the state after formation of an orientation control layer. It is a perspective view showing a first sample for adhesive strength evaluation. It is a perspective view showing a second sample for adhesive strength evaluation. It is a cross-sectional schematic diagram which shows the liquid crystal display device which has the conventional alignment film.
  • X to Y means “X or more and Y or less”.
  • FIG. 1 is a schematic cross-sectional view showing the liquid crystal display device of the embodiment.
  • FIG. 2 is a schematic plan view showing the liquid crystal display device of the embodiment.
  • the liquid crystal display device 1 includes a substrate 2a, a substrate 2b, a liquid crystal layer 3, a sealing material 4, an orientation control layer 5a, and an orientation control layer 5b.
  • the substrates 2a and 2b are disposed to face each other.
  • the liquid crystal layer 3 is disposed between the substrate 2a and the substrate 2b.
  • the sealing material 4 surrounds the liquid crystal layer 3 in a plan view, is disposed between the substrate 2 a and the substrate 2 b in a cross sectional view, and is in contact with the substrates 2 a and 2 b.
  • the alignment control layer 5 a is disposed between the substrate 2 a and the liquid crystal layer 3 in cross section and in contact with the liquid crystal layer 3 in a region surrounded by the sealing material 4 in plan view.
  • the orientation control layer 5 b is disposed between the substrate 2 b and the liquid crystal layer 3 in cross section and in contact with the liquid crystal layer 3 in a region surrounded by the sealing material 4 in plan view.
  • the conventional alignment film is not disposed, and the sealing material 4 is in contact with the substrates 2a and 2b. Therefore, since the adhesive strength between the sealing material 4 and the substrates 2a and 2b is sufficiently secured, peeling between the substrate 2a and the substrate 2b occurs even if the width of the sealing material 4 is reduced for narrowing the frame. It becomes difficult to do.
  • the alignment film is not required to be disposed at a position in contact with the sealing material 4 between the substrates 2a and 2b and the sealing material 4.
  • controlling the position of the alignment film in this way is a film forming apparatus (printing apparatus It is difficult on the accuracy of). Therefore, it is preferable that the alignment film is not disposed on the surfaces of the substrates 2a and 2b.
  • the alignment film is at least one compound selected from the group consisting of polyimide, polyamic acid, polymaleimide, polyamide, polysiloxane, polyphosphazene, polysilsesquioxane, and copolymers thereof.
  • a film which may be either a single layer film or a laminated film
  • an alignment film is formed by applying or depositing an alignment film material on the surface of a substrate constituting a display region.
  • the presence or absence in particular of the orientation process for example, a photo-alignment process, a rubbing process, etc.
  • the orientation process for example, a photo-alignment process, a rubbing process, etc.
  • the substrate 2a has a support base 6a and a pixel electrode 7 disposed on the surface of the support base 6a on the liquid crystal layer 3 side.
  • Examples of the material of the support base 6 a include glass, plastic and the like.
  • Examples of the material of the pixel electrode 7 include transparent materials (inorganic materials) such as indium tin oxide (ITO) and indium zinc oxide (IZO).
  • transparent materials inorganic materials
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • the substrate 2a may be an active matrix substrate having thin film transistor elements.
  • the thin film transistor element includes a semiconductor layer, various electrodes (a gate electrode, a source electrode, a drain electrode), and the like.
  • the thin film transistor elements are formed between the pixel electrodes 7 arranged in a matrix and peripheral wirings (gate bus lines and source bus lines) partitioning the pixel electrodes 7. It intervenes electrically.
  • the signal voltage is applied to the pixel electrode 7 through the thin film transistor element to charge the pixel. Then, when the thin film transistor element is turned off, the charge stored in the pixel is held.
  • the voltage holding ratio indicates the ratio of the amount of charge held in one frame (for example, 16.67 ms) to the amount of charge charged. That is, when the voltage holding ratio is low, the voltage applied to the liquid crystal layer 3 is easily attenuated with the passage of time, and as a result, it is difficult to obtain a desired voltage application state. Therefore, in the liquid crystal display device 1, it is required to increase the voltage holding ratio.
  • Examples of the material of the semiconductor layer of the thin film transistor element include amorphous silicon, polycrystalline silicon, an oxide semiconductor, and the like.
  • an oxide semiconductor is preferable from the viewpoint of low power consumption and high-speed driving.
  • the oxide semiconductor low power consumption can be realized because off leakage current (leakage current when the thin film transistor element is in the off state) is small, and on current (current when the thin film transistor element is in the on state) is Because there are many, high speed driving can be realized.
  • the oxide semiconductor for example, a compound including indium, gallium, zinc, and oxygen, a compound including indium, tin, zinc, and oxygen, and the like can be given.
  • the substrate 2 b includes a support base 6 b, color filter layers 8 R (red), 8 G (green), 8 B (blue), and a black matrix 9 disposed on the surface of the support base 6 b on the liquid crystal layer 3 side; A common electrode 10 covering the color filter layers 8R, 8G, 8B and the black matrix 9 is provided.
  • the black matrix 9 may be arranged in a grid so as to partition the color filter layers 8R, 8G, 8B corresponding to the respective pixels.
  • Examples of the material of the support base 6 b include glass, plastic and the like.
  • Examples of the material of the color filter layers 8R, 8G, and 8B include a pigment-dispersed color resist and the like.
  • the combination of colors of the color filter layer is not particularly limited, and in addition to the combination of red, green and blue as shown in FIG. 1, for example, a combination of red, green, blue and yellow, etc. may be mentioned.
  • the thicknesses of the color filter layers 8R, 8G, 8B may be the same as or different from each other.
  • the thickness of the color filter layer 8B may be larger than the thickness of the color filter layers 8R and 8G. According to such a configuration, the thickness (cell gap) of the liquid crystal layer 3 can be optimized in a small state.
  • Examples of the material of the black matrix 9 include black resists and the like.
  • Examples of the material of the common electrode 10 include transparent materials (inorganic materials) such as indium tin oxide (ITO) and indium zinc oxide (IZO).
  • transparent materials inorganic materials
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • the liquid crystal layer 3 contains a liquid crystal material.
  • the liquid crystal material is preferably a nematic liquid crystal material. In this case, it is preferable that the liquid crystal material undergoes a phase transition from the nematic phase to the isotropic phase in the temperature rising process.
  • the nematic phase-isotropic phase transition temperature of the liquid crystal material may be 80 ° C. or higher, and may be 90 ° C. or higher. As described above, the liquid crystal display device 1 can be used even when a liquid crystal material having a high nematic phase-isotropic phase transition temperature is required for applications such as on-vehicle and digital signage.
  • the liquid crystal material of the liquid crystal layer 3 may be a negative liquid crystal material having negative dielectric anisotropy ( ⁇ ⁇ 0), and a positive liquid crystal material having positive dielectric anisotropy ( ⁇ > 0) It may be In FIG. 1, liquid crystal molecules in a negative liquid crystal material are exemplified as the liquid crystal molecules 11.
  • the sealing material 4 examples include those containing a resin such as an epoxy resin and a (meth) acrylic resin, and may contain an inorganic filler, an organic filler, a curing agent and the like as appropriate.
  • the sealing material 4 may be one that is cured by light (photo-curing type) or one that is cured by heat (thermo-setting type), or one that is cured by both of them (light and heat) It may be a curing type. More specifically, the sealing material 4 may be one that is cured by ultraviolet light (ultraviolet curing type), or may be one that is cured by heat (thermosetting type), or cured by both of them. (UV / heat curing type) may be used.
  • the width of the sealing material 4 may be 0.4 to 1.5 mm in a plan view.
  • the width of the sealing material 4 is, for example, 1.5 mm for narrowing the frame. Even if the size is made smaller, peeling between the substrate 2a and the substrate 2b is difficult.
  • the orientation control layers 5a and 5b contain a polymer including units derived from the first monomer and units derived from the second monomer.
  • the first monomer is represented by the following chemical formula (1).
  • X 1 and X 2 are the same or different and each represents H, CH 3 or C 2 H 5 .
  • Y 1 and Y 2 are the same or different, and H, F, Cl, Br, linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or linear, branched or cyclic carbon It represents an alkyloxy group of the formulas 1 to 6.
  • Z represents O, S, NH, CO, COO, OCO, or a direct bond.
  • m represents an integer of 6 to 16; n represents an integer of 8 to 24.
  • the first monomer may contain at least one of the monomers represented by the following chemical formulas (2-1) to (2-8).
  • the liquid crystal molecules 11 in the liquid crystal material of the liquid crystal layer 3 are aligned in the direction perpendicular to the surface of the substrates 2a and 2b by the action of the unit derived from the first monomer in the polymer. It can be done. That is, the liquid crystal display device 1 is a liquid crystal display device in the vertical alignment mode (for example, VA mode). In the liquid crystal display device 1, alignment control of the liquid crystal molecules 11 when the voltage applied to the liquid crystal layer 3 is less than the threshold voltage (including when no voltage is applied) is performed by the alignment control layers 5a and 5b.
  • VA mode vertical alignment mode
  • liquid crystal molecules 11 are aligned in a direction perpendicular to the surface of the substrates 2a and 2b (hereinafter, also referred to simply as “vertically aligned”) means that the pretilt angle of the liquid crystal molecules 11 is the surface of the substrates 2a and 2b. To 86 ° to 90 °, preferably 88.5 ° to 90 °. When the voltage applied to the liquid crystal layer 3 is less than the threshold voltage (including when no voltage is applied), the major axis of the liquid crystal molecules 11 is tilted with respect to the surface of the substrates 2a and 2b. Means an angle.
  • the first monomer is composed of an aliphatic compound except for the end of the side chain, and has a flexible flexible molecular structure. Therefore, in the formation of the alignment control layers 5a and 5b, when polymerizing at least the first monomer and the second monomer, the environment under the nematic phase-isotropic phase transition temperature of the liquid crystal material of the liquid crystal layer 3, for example, Even when light is irradiated in a normal temperature environment, an alignment regulating force for vertically aligning the liquid crystal molecules 11 is sufficiently obtained.
  • normal temperature means 15 to 45 ° C.
  • the first monomer is a bifunctional monomer having two acryloyl groups as a polymerizable group
  • the polymerization rate is increased when forming the alignment control layers 5a and 5b, and the liquid crystal layer 3 is not polymerized.
  • the monomer is less likely to remain.
  • the liquid crystal display device 1 having a high voltage holding ratio can be obtained.
  • the polymerization rate becomes slow and many monomers in the unpolymerized state remain in the liquid crystal layer 3, so the voltage holding ratio is large. It will decrease.
  • the second monomer is preferably represented by the following chemical formula (3).
  • the second monomer has a polymerization initiation function to start the polymerization reaction of at least the first monomer and the second monomer.
  • P 1 and P 2 are the same or different and each represents an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group or a vinyloxy group.
  • Sp 1 and Sp 2 are the same or different, and are linear, branched or cyclic alkylene groups having 1 to 6 carbon atoms, linear, branched or cyclic alkylene oxy groups having 1 to 6 carbon atoms, or , Represents a direct bond.
  • the second monomer may contain at least one of the monomers represented by the following chemical formulas (4-1) and (4-2).
  • the second monomer When the second monomer is represented by the above chemical formula (3) (including the above chemical formulas (4-1) and (4-2)), the second monomer has a polymerization initiation function, and thus forms the orientation control layers 5a and 5b. At the same time, if the first monomer and the second monomer are used in combination, the polymerization rate is faster and the production efficiency is further enhanced. Moreover, the irradiation amount of the light at the time of forming alignment control layer 5a, 5b can also be reduced.
  • the polymer constituting the orientation control layers 5a and 5b includes, in addition to the unit derived from the first monomer and the unit derived from the second monomer, a unit derived from a monomer having a structure other than the first monomer and the second monomer. It may further be included.
  • the liquid crystal display device 1 further includes a polarizing plate 12a on the side opposite to the liquid crystal layer 3 of the substrate 2a (supporting base 6a) and a polarizing plate 12b on the opposite side of the liquid crystal layer 3 of the substrate 2b (supporting base 6b). You may have.
  • polarizing plates 12a and 12b for example, a linear polarizing plate (absorption type polarizing plate) in which an anisotropic material such as iodine complex (or dye) is dyed and adsorbed to a polyvinyl alcohol (PVA) film and then stretched and oriented Etc. can be used.
  • a linear polarizing plate absorption type polarizing plate
  • an anisotropic material such as iodine complex (or dye) is dyed and adsorbed to a polyvinyl alcohol (PVA) film and then stretched and oriented Etc.
  • the transmission axis of the polarizing plate 12a and the transmission axis of the polarizing plate 12b are preferably orthogonal to each other. According to such a configuration, since the polarizing plates 12a and 12b are disposed in cross nicol, it is possible to effectively realize the black display state when no voltage is applied.
  • that the two transmission axes are orthogonal means that the angle between them is 88 to 92 °, preferably 89.5 to 90.5 °, particularly preferably 90 ° (completely orthogonal) ).
  • the liquid crystal display device 1 may further have a backlight 13 on the side of the substrate 2 a (polarizing plate 12 a) opposite to the liquid crystal layer 3.
  • the liquid crystal display device 1 is a transmissive liquid crystal display device.
  • the method of the backlight 13 is not particularly limited, and examples thereof include an edge light method and a direct type.
  • the type of light source of the backlight 13 is not particularly limited, and examples thereof include a light emitting diode (LED), a cold cathode tube (CCFL), and the like.
  • the liquid crystal display device 1 may further have a member generally used in the field of liquid crystal display devices in addition to the members described above.
  • a member generally used in the field of liquid crystal display devices for example, a tape carrier package (TCP), a printed circuit board (PCB) Or the like; an optical film such as a viewing angle widening film, a brightness enhancement film, etc .; a bezel (frame) or the like, as appropriate.
  • FIG. 3 is a schematic cross-sectional view for explaining the method of manufacturing the liquid crystal display device of the embodiment, wherein (a) shows a state before formation of the alignment control layer, and (b) shows after the formation of the alignment control layer. Indicates the status.
  • description of the point which overlaps with the content mentioned above is abbreviate
  • a liquid crystal material liquid crystal molecules 11
  • a first monomer and a second monomer monomer 14
  • the liquid crystal composition 3 is enclosed to form a liquid crystal layer 3.
  • the liquid crystal layer 3 can be formed, for example, by sealing a liquid crystal composition between the substrate 2 a and the substrate 2 b by a method such as a dropping method or an injection method.
  • the liquid crystal layer 3 is formed by a dropping method, for example, the following process is adopted. First, after the sealing material 4 is applied on the surface of one of the substrates 2 a and 2 b, the liquid crystal composition is dropped in the area surrounded by the sealing material 4. Then, the substrate 2 a and the substrate 2 b are bonded with the sealing material 4 to form the liquid crystal layer 3.
  • the sealing material 4 is applied onto one surface of the substrates 2 a and 2 b, and then the substrate 2 a and the substrate 2 b are bonded together by the sealing material 4. Then, a liquid crystal composition is injected between the substrate 2 a and the substrate 2 b to form the liquid crystal layer 3.
  • a vacuum may be applied between the substrate 2a and the substrate 2b.
  • the sealing material 4 may be hardened in advance or may not be hardened.
  • the curing of the sealing material 4 may be performed at a different timing from the formation of the orientation control layers 5a and 5b described later, or may be performed at the same timing.
  • the first monomer in the liquid crystal composition is represented by the following chemical formula (1).
  • X 1 and X 2 are the same or different and each represents H, CH 3 or C 2 H 5 .
  • Y 1 and Y 2 are the same or different, and H, F, Cl, Br, linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or linear, branched or cyclic carbon It represents an alkyloxy group of the formulas 1 to 6.
  • Z represents O, S, NH, CO, COO, OCO, or a direct bond.
  • m represents an integer of 6 to 16; n represents an integer of 8 to 24.
  • the first monomer may contain at least one of the monomers represented by the following chemical formulas (2-1) to (2-8).
  • the content of the first monomer in the liquid crystal composition is preferably 0.3 to 5% by weight.
  • the content of the first monomer in the liquid crystal composition is less than 0.3% by weight, it may be difficult to obtain a state in which the liquid crystal molecules 11 are uniformly and stably vertically aligned in the liquid crystal layer 3.
  • the content of the first monomer in the liquid crystal composition is more than 5% by weight, it takes time for the first monomer to be completely polymerized in the formation of the orientation control layers 5a and 5b described later. This may cause a decrease in the voltage holding ratio due to the remaining unpolymerized monomer.
  • the second monomer in the liquid crystal composition is preferably represented by the following chemical formula (3).
  • P 1 and P 2 are the same or different and each represents an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group or a vinyloxy group.
  • Sp 1 and Sp 2 are the same or different, and are linear, branched or cyclic alkylene groups having 1 to 6 carbon atoms, linear, branched or cyclic alkylene oxy groups having 1 to 6 carbon atoms, or , Represents a direct bond.
  • the second monomer may contain at least one of the monomers represented by the following chemical formulas (4-1) and (4-2).
  • the content of the second monomer in the liquid crystal composition is preferably 0.03 to 0.3% by weight.
  • the second monomer is a compound represented by the above chemical formula (3) (the above chemical formulas (4-1) and (4-2)
  • the orientation control layers 5a and 5b described later are formed, it is difficult for the polymerization initiation function of the second monomer to be exhibited, and it takes time to complete the polymerization reaction. is there.
  • the second monomer is a compound represented by the chemical formula (3) (the above chemical formulas (4-1) and (4-2)
  • the generation of a large number of radicals may accelerate the polymerization rate, but may lower the voltage holding ratio. .
  • the content of the first monomer is preferably equal to or greater than the content of the second monomer.
  • the weight ratio of the first monomer to the second monomer is preferably 140: 1 to 1: 1.
  • the liquid crystal layer 3 is irradiated with light (arrows in FIG. 3 (a)) to polymerize at least the first monomer and the second monomer, as shown in FIG. 3 (b).
  • the alignment control layer 5a in contact with the liquid crystal layer 3 is formed between the substrate 2a and the liquid crystal layer 3
  • the alignment control layer 5b in contact with the liquid crystal layer 3 is formed between the substrate 2b and the liquid crystal layer 3 Do.
  • the orientation control layers 5 a and 5 b are layers formed by phase separation of a polymer produced by polymerizing at least a first monomer and a second monomer from the liquid crystal layer 3.
  • the liquid crystal display device 1 is completed by appropriately arranging members (not shown) such as a polarizing plate and a backlight.
  • the light irradiated to the liquid crystal layer 3 may be ultraviolet light or visible light (wavelength: 380 nm or more), and among them, ultraviolet light is preferable. .
  • the ultraviolet light may be unpolarized ultraviolet light or polarized ultraviolet light.
  • the wavelength of the ultraviolet light is preferably 280 to 430 nm.
  • the wavelength of the ultraviolet light irradiated to the liquid crystal layer 3 is shorter than 280 nm, the liquid crystal material (liquid crystal molecules 11) and the first monomer and the second monomer (monomer 14) are decomposed to lower the voltage holding ratio It may be triggered.
  • the polymerization reaction proceeds even with the irradiation of the ultraviolet light having a wavelength longer than 430 nm, for example, the polymerization reaction also progresses by the light (ultraviolet light) emitted from the backlight. AC afterimage may occur.
  • the amount of irradiation of the ultraviolet light is preferably 0.01 to 10 J / cm 2 .
  • the irradiation amount of the ultraviolet light irradiated to the liquid crystal layer 3 is less than 0.01 J / cm 2 , the polymerization reaction does not proceed sufficiently and an AC residual image may be generated.
  • the liquid crystal material (liquid crystal molecules 11) and the first monomer and the second monomer (monomer 14) are decomposed (or The polymerization of the first monomer and the second monomer causes decomposition of the produced polymer), which may cause a decrease in voltage retention.
  • the orientation control layers 5a and 5b contain a polymer including units derived from the first monomer and units derived from the second monomer. According to the alignment control layers 5a and 5b, the liquid crystal molecules 11 in the liquid crystal material of the liquid crystal layer 3 are aligned in the direction perpendicular to the surface of the substrates 2a and 2b by the action of the unit derived from the first monomer in the polymer. It can be done. That is, according to the method of manufacturing a liquid crystal display device of the present embodiment, a liquid crystal display device of vertical alignment mode (for example, VA mode) can be manufactured as the liquid crystal display device 1.
  • VA mode vertical alignment mode
  • the liquid crystal material of the liquid crystal layer 3 is used to use the first monomer having the molecular structure excellent in flexibility when forming the alignment control layers 5a and 5b. Even when the liquid crystal layer 3 is irradiated with light in an environment below the nematic phase-isotropic phase transition temperature, for example, in a normal temperature environment, an alignment control force for vertically aligning the liquid crystal molecules 11 can be sufficiently obtained. That is, when forming the alignment control layers 5a and 5b, it is not necessary to perform light irradiation to the liquid crystal layer 3 in a high temperature environment higher than the nematic phase-isotropic phase transition temperature of the liquid crystal material, so the manufacturing efficiency Increase.
  • the temperature environment for irradiating light to the liquid crystal layer 3 is not limited to a special one.
  • the temperature of the liquid crystal layer 3 is set to 20 to 100.degree. In the state as described above, the liquid crystal layer 3 may be irradiated with light.
  • the first monomer which is a bifunctional monomer
  • the first monomer which is a bifunctional monomer
  • the alignment film is formed on the surfaces of the substrates 2a and 2b before bonding the substrate 2a and the substrate 2b with the sealing material 4 as members responsible for controlling the alignment of the liquid crystal molecules 11. Since the alignment control layers 5a and 5b are formed after the substrate 2a and the substrate 2b are attached to each other by the sealing material 4 instead of forming a, it is possible to realize a configuration in which the sealing material 4 is in contact with the substrates 2a and 2b. Therefore, since the adhesive strength between the sealing material 4 and the substrates 2a and 2b is sufficiently secured, peeling between the substrate 2a and the substrate 2b occurs even if the width of the sealing material 4 is reduced for narrowing the frame. It becomes difficult to do.
  • the liquid crystal composition may further contain a monomer having a structure other than the first monomer and the second monomer, in addition to the liquid crystal material, the first monomer and the second monomer. That is, when forming the orientation control layers 5a and 5b, in addition to the first monomer and the second monomer, a monomer having a structure other than the first monomer and the second monomer may be polymerized. As a result, the polymer constituting the orientation control layers 5a and 5b is derived from a monomer having a structure other than the first monomer and the second monomer in addition to the unit derived from the first monomer and the unit derived from the second monomer. The unit may be further included.
  • the liquid crystal composition used when manufacturing a liquid crystal display device in an Example and a comparative example was as follows.
  • a liquid crystal material L1 (nematic phase-isotropic phase transition temperature: 80 ° C., dielectric anisotropy ( ⁇ ): ⁇ 3.4, refractive index anisotropy ( ⁇ n): 0.095), A monomer M1 (first monomer) represented by 2-1) and a monomer N1 (second monomer) represented by the following chemical formula (4-1) were added. Thereafter, the obtained mixture was left to stand at 25 ° C. for 24 hours to completely dissolve the monomers M1 and N1 in the liquid crystal material L1, thereby preparing a liquid crystal composition A1.
  • the content of the monomer M1 in the liquid crystal composition A1 was 1.5% by weight.
  • the content of the monomer N1 in the liquid crystal composition A1 was 0.3% by weight.
  • a liquid crystal material L1 (nematic phase-isotropic phase transition temperature: 80 ° C., dielectric anisotropy ( ⁇ ): ⁇ 3.4, refractive index anisotropy ( ⁇ n): 0.095), A monomer M2 (first monomer) represented by 2-2) and a monomer N2 (second monomer) represented by the following chemical formula (4-2) were added. Thereafter, the resulting mixture is left to stand at 25 ° C. for 24 hours to completely dissolve the monomers M2 and N2 in the liquid crystal material L1, thereby preparing a liquid crystal composition A2.
  • the content of the monomer M2 in the liquid crystal composition A2 was 1.3% by weight.
  • the content of the monomer N2 in the liquid crystal composition A2 was 0.3% by weight.
  • a liquid crystal material L1 (nematic phase-isotropic phase transition temperature: 80 ° C., dielectric anisotropy ( ⁇ ): ⁇ 3.4, refractive index anisotropy ( ⁇ n): 0.095), A monomer M3 (first monomer) represented by 2-3) and a monomer N2 (second monomer) represented by the above chemical formula (4-2) were added. Thereafter, the obtained mixture was left to stand at 25 ° C. for 24 hours to completely dissolve the monomers M3 and N2 in the liquid crystal material L1, thereby preparing a liquid crystal composition A3.
  • the content of the monomer M3 in the liquid crystal composition A3 was 1.2% by weight.
  • the content of the monomer N2 in the liquid crystal composition A3 was 0.2% by weight.
  • a liquid crystal material L1 (nematic phase-isotropic phase transition temperature: 80 ° C., dielectric anisotropy ( ⁇ ): ⁇ 3.4, refractive index anisotropy ( ⁇ n): 0.095)
  • a monomer M4 (first monomer) represented by 2-4)
  • a monomer N2 (second monomer) represented by the above chemical formula (4-2) were added.
  • the resulting mixture is left to stand at 25 ° C. for 24 hours to completely dissolve the monomers M4 and N2 in the liquid crystal material L1, thereby preparing a liquid crystal composition A4.
  • the content of the monomer M4 in the liquid crystal composition A4 was 1.4% by weight.
  • the content of the monomer N2 in the liquid crystal composition A4 was 0.2% by weight.
  • a liquid crystal material L1 (nematic phase-isotropic phase transition temperature: 80 ° C., dielectric anisotropy ( ⁇ ): ⁇ 3.4, refractive index anisotropy ( ⁇ n): 0.095), A monomer M5 (first monomer) represented by 2-5) and a monomer N2 (second monomer) represented by the above chemical formula (4-2) were added. Then, the resulting mixture was left to stand at 25 ° C. for 24 hours to completely dissolve the monomers M5 and N2 in the liquid crystal material L1, thereby preparing a liquid crystal composition A5.
  • the content of the monomer M5 in the liquid crystal composition A5 was 1.3% by weight.
  • the content of the monomer N2 in the liquid crystal composition A5 was 0.3% by weight.
  • a liquid crystal material L2 (nematic phase-isotropic phase transition temperature: 92 ° C., dielectric anisotropy ( ⁇ ): -3.2, refractive index anisotropy ( ⁇ n): 0.095), the above chemical formula ( A monomer M1 (first monomer) represented by 2-1) and a monomer N1 (second monomer) represented by the chemical formula (4-1) are added. Thereafter, the resulting mixture was left to stand at 25 ° C. for 24 hours to completely dissolve the monomers M1 and N1 in the liquid crystal material L2, thereby preparing a liquid crystal composition A6.
  • the content of the monomer M1 in the liquid crystal composition A6 was 1.5% by weight.
  • the content of the monomer N1 in the liquid crystal composition A6 was 0.3% by weight.
  • a liquid crystal material L3 (nematic phase-isotropic phase transition temperature: 110 ° C., dielectric anisotropy ( ⁇ ): ⁇ 3.5, refractive index anisotropy ( ⁇ n): 0.100) to the above chemical formula ( A monomer M1 (first monomer) represented by 2-1) and a monomer N1 (second monomer) represented by the chemical formula (4-1) are added. Thereafter, the resulting mixture is allowed to stand at 25 ° C. for 24 hours to completely dissolve the monomers M1 and N1 in the liquid crystal material L3, thereby preparing a liquid crystal composition A7.
  • the content of the monomer M1 in the liquid crystal composition A7 was 1.5% by weight.
  • the content of the monomer N1 in the liquid crystal composition A7 was 0.3% by weight.
  • ⁇ Liquid crystal composition B1> First, a liquid crystal material L1 (nematic phase-isotropic phase transition temperature: 80 ° C., dielectric anisotropy ( ⁇ ): ⁇ 3.4, refractive index anisotropy ( ⁇ n): 0.095), A monomer Q1 represented by 5) and a monomer N1 (second monomer) represented by the chemical formula (4-1) were added. Thereafter, the resulting mixture was left to stand at 25 ° C. for 24 hours to completely dissolve the monomers Q1 and N1 in the liquid crystal material L1, thereby preparing a liquid crystal composition B1. The content of the monomer Q1 in the liquid crystal composition B1 was 1.5% by weight.
  • the content of the monomer N1 in the liquid crystal composition B1 was 0.3% by weight.
  • the liquid crystal composition B1 contained two kinds of monomers Q1 and N1, but did not contain a monomer corresponding to the above-mentioned first monomer (the above chemical formula (1)).
  • ⁇ Liquid crystal composition B2> First, a liquid crystal material L1 (nematic phase-isotropic phase transition temperature: 80 ° C., dielectric anisotropy ( ⁇ ): ⁇ 3.4, refractive index anisotropy ( ⁇ n): 0.095), the above chemical formula ( Only the monomer M1 (first monomer) represented by 2-1) was added. Thereafter, the resulting mixture was allowed to stand at 25 ° C. for 24 hours to completely dissolve the monomer M1 in the liquid crystal material L1, thereby preparing a liquid crystal composition B2. The content of the monomer M1 in the liquid crystal composition B2 was 1.5% by weight.
  • the liquid crystal composition B2 contained the monomer M1 corresponding to the above-mentioned first monomer (the above-mentioned chemical formula (1)), but did not contain any other monomer (second monomer).
  • Example 1 The liquid crystal display device of Example 1 was manufactured by the following method. First, two substrates having transparent electrodes made of indium tin oxide (ITO) on the surface were prepared. Then, after applying a sealing material "Photolec (registered trademark)" manufactured by Sekisui Chemical Co., Ltd. on the surface of one substrate on the transparent electrode side, the liquid crystal composition A1 is dropped in the area surrounded by the sealing material. did. After that, both substrates were bonded with a sealing material to form a liquid crystal layer. In the following description, for convenience, the liquid crystal cell manufactured in this process is referred to as "liquid crystal cell”.
  • ITO indium tin oxide
  • the temperature of the liquid crystal cell (liquid crystal layer) is set to 25 ° C., and the black light “FHF-32BLB” (having a small emission intensity at a wavelength of 310 nm and a large emission intensity at a wavelength of 330 nm or more) manufactured by Toshiba Lighttech Co., Ltd.
  • Non-polarizing ultraviolet light (irradiation intensity: 0.33 mW / cm 2 ) was irradiated from the normal direction to the liquid crystal cell using an ultraviolet light source).
  • the irradiation amount of non-polarization ultraviolet light was three specifications of 0 J / cm 2 (hereinafter, specification 1), 0.5 J / cm 2 (hereinafter, specification 2), and 2 J / cm 2 (hereinafter, specification 3).
  • specification 1 0 J / cm 2
  • specification 2 0.5 J / cm 2
  • specification 3 2 J / cm 2
  • an alignment control layer was formed between the two substrates and the liquid crystal layer, and the sealing material was cured (except for the specification 1).
  • the width of the sealing material after curing was 0.5 mm.
  • Comparative example 1 A liquid crystal display device of Comparative Example 1 was manufactured in the same manner as Example 1, except that the liquid crystal composition B1 was used instead of the liquid crystal composition A1.
  • the alignment state was visually confirmed in a state in which the liquid crystal display was sandwiched between two linear polarizing plates (absorption-type polarizing plates) arranged in cross nicol.
  • a black display state was realized, it was determined that liquid crystal molecules were vertically aligned, and a liquid crystal display device of vertical alignment mode (VA mode) was obtained.
  • VA mode liquid crystal display device of vertical alignment mode
  • the voltage holding ratio was measured under the conditions of an applied voltage of 1 V, an applied time of 60 ⁇ s, a one frame period of 16.67 ms, and a measurement temperature of 70 ° C. using a liquid crystal physical property evaluation system “type 5254” manufactured by Toyo Corporation.
  • Example 1 As shown in Table 1, in Example 1, the liquid crystal display device in the vertical alignment mode was realized, and the voltage holding ratio was high. In particular, in specification 3, no alignment defect was present, and an alignment control force for vertically aligning liquid crystal molecules was sufficiently obtained.
  • Example 1 when forming an orientation control layer, a polymerization reaction is started by the polymerization start function of monomer N1 in liquid crystal composition A1, and the liquid crystal molecule is vertically aligned by the side chain group of monomer M1. It is considered that the orientation control force was developed.
  • the voltage holding ratio was high because the polymerization rate was high because the monomer M1 was a bifunctional monomer, and the monomer in the unpolymerized state was unlikely to remain in the liquid crystal layer.
  • the alignment control layer when forming the alignment control layer, even if the liquid crystal layer is irradiated with ultraviolet light (in Example 1, non-polarized ultraviolet light) in a normal temperature environment of 25 ° C., the alignment control power to vertically align liquid crystal molecules is sufficient. It was confirmed that it could be obtained.
  • ultraviolet light in Example 1, non-polarized ultraviolet light
  • Comparative Example 1 the liquid crystal display device in the vertical alignment mode was not realized, and in the specifications 2 and 3, the voltage holding ratio was lower than that in Example 1.
  • the temperature at the time of irradiating the liquid crystal layer with ultraviolet light is changed to 90 ° C. (more than the nematic phase-isotropic phase transition temperature of the liquid crystal material L1) in Comparative Example 1 to perform evaluation. It has been found that a liquid crystal display device of the vertical alignment mode is realized.
  • the alignment control layer when the liquid crystal layer is irradiated with ultraviolet light (non-polarizing ultraviolet light in Comparative Example 1) in a normal temperature environment of 25 ° C., liquid crystal molecules are randomly aligned and vertically aligned. The liquid crystal display of the mode was not realized. It is considered that this is because the monomer Q1 in the liquid crystal composition B1 is a monofunctional monomer, and the polymerization rate is slow in a normal temperature environment of 25 ° C.
  • the monomer Q1 is a monofunctional monomer and has a rigid molecular structure in which a biphenyl group is introduced in the central part, the alignment state of the liquid crystal molecules is random alignment of specification 1 (initial state) It is also possible that the polymerization reaction has progressed.
  • Example 2 Example 1 was carried out in the same manner as Example 1, except that the liquid crystal composition A2 was used instead of the liquid crystal composition A1 and that the irradiation amount of non-polarization ultraviolet light was 2 J / cm 2 (only specification 3). The liquid crystal display of Example 2 was manufactured.
  • Example 3 A liquid crystal display device of Example 3 was manufactured in the same manner as Example 2 except that liquid crystal composition A3 was used instead of liquid crystal composition A2.
  • Example 4 A liquid crystal display device of Example 4 was manufactured in the same manner as Example 2 except that liquid crystal composition A4 was used instead of liquid crystal composition A2.
  • Example 5 A liquid crystal display device of Example 5 was manufactured in the same manner as Example 2 except that liquid crystal composition A5 was used instead of liquid crystal composition A2.
  • Comparative example 2 A liquid crystal display device of Comparative Example 2 was manufactured in the same manner as Example 2, except that liquid crystal composition B2 was used instead of liquid crystal composition A2.
  • the liquid crystal display device in the vertical alignment mode was realized, and the voltage holding ratio was high.
  • the alignment control layer when the alignment control layer is formed, the polymerization reaction is started by the polymerization initiation function of the monomer N2 in the liquid crystal compositions A2 to A5, and the side chain group of the monomers M2 to M5 is used. It is considered that an alignment control force for vertically aligning liquid crystal molecules is developed.
  • the monomers M2 to M5 are bifunctional monomers, the polymerization rate is fast, and monomers in an unpolymerized state are less likely to remain in the liquid crystal layer, so that it is considered that the voltage holding ratio is high.
  • the liquid crystal display device of the vertical alignment mode was not realized. It is considered that this is because the liquid crystal composition B2 does not contain a monomer having a polymerization initiation function (for example, a monomer N2) and the polymerization reaction does not proceed.
  • a monomer having a polymerization initiation function for example, a monomer N2
  • Example 6 A liquid crystal display device of Example 6 was manufactured in the same manner as Example 2, except that liquid crystal composition A6 was used instead of liquid crystal composition A2.
  • Example 7 A liquid crystal display device of Example 7 was manufactured in the same manner as Example 2 except that liquid crystal composition A7 was used instead of liquid crystal composition A2.
  • the liquid crystal display device in the vertical alignment mode was realized, and the voltage holding ratio was high.
  • the polymerization initiation function is initiated by the polymerization initiation function of the monomer N1 in the liquid crystal compositions A6 and A7, and the side chain group of the monomer M1 causes liquid crystal molecules. It is considered that an alignment control force to vertically align the is expressed.
  • the voltage holding ratio was high because the polymerization rate was high because the monomer M1 was a bifunctional monomer, and the monomer in the unpolymerized state was unlikely to remain in the liquid crystal layer.
  • the alignment control layer when forming the alignment control layer, the alignment control force to vertically align the liquid crystal molecules even if the liquid crystal layer is irradiated with ultraviolet light (non-polarized ultraviolet light in Examples 6 and 7) under a normal temperature environment of 25 ° C. It was confirmed that it could be obtained sufficiently. Therefore, the liquid crystal display device of the present invention can be used even in cases where a liquid crystal material having a high nematic phase-isotropic phase transition temperature is required as in the sixth and seventh embodiments for use in vehicles, digital signage, etc. It was confirmed that there is.
  • Adhesive strength evaluation Three types of samples were produced by the following method for adhesive strength evaluation, and the adhesive strength of the sealing material was evaluated.
  • FIG. 4 is a schematic perspective view showing a first sample for adhesive strength evaluation.
  • two glass substrates 15a and 15b on which an alignment film was not formed were prepared.
  • the sealing material 4 was dripped so that a diameter might be set to 2 mm on one surface among glass substrate 15a, 15b.
  • the glass substrates 15a and 15b were bonded by the sealing material 4 so that the longitudinal directions were orthogonal to each other.
  • the sealing material 4 was cured by heating after being irradiated with ultraviolet light to produce a first sample. In the first sample, the sealing material 4 was in contact with the glass substrates 15a and 15b.
  • glass substrates 15a and 15b a non-alkali glass substrate having a size of 15 mm ⁇ 40 mm and a thickness of 0.7 mm was used.
  • sealing material 4 a sealing material "Photo Rec” manufactured by Sekisui Chemical Co., Ltd. was used.
  • FIG. 5 is a schematic perspective view showing a second sample for adhesive strength evaluation.
  • two glass substrates 115a and 115b were prepared.
  • a horizontal alignment type polyimide alignment film 116a was formed on the surface of the glass substrate 115a
  • a horizontal alignment type polyimide alignment film 116b was formed on the surface of the glass substrate 115b.
  • the alignment films 116a and 116b were formed by applying an alignment film material containing a horizontal alignment type polyamic acid and then baking it at 200 ° C. for 30 minutes.
  • the sealing material 104 was dropped onto one surface of the alignment films 116 a and 116 b so as to have a diameter of 2 mm. After that, the glass substrates 115 a and 115 b were pasted together by the sealing material 104 so that the longitudinal directions were orthogonal to each other and the alignment films 116 a and 116 b were opposed to each other. Finally, the sealing material 104 was cured by heating after being irradiated with ultraviolet light to produce a second sample. In the second sample, the seal material 104 was in contact with the alignment films 116a and 116b.
  • glass substrates 115a and 115b substrates made of non-alkali glass having a size of 15 mm ⁇ 40 mm and a thickness of 0.7 mm were used.
  • sealing material 104 a sealing material "PHOTOREC" manufactured by Sekisui Chemical Co., Ltd. was used.
  • a third sample was produced in the same manner as the second sample except that a vertical alignment type polyimide alignment film was formed instead of the horizontal alignment type polyimide alignment film as the alignment films 116a and 116b.
  • the seal material 104 was in contact with the alignment films 116a and 116b.
  • the first sample, the second sample, and the third sample are tested for 100 hours in a high-temperature, high-humidity environment with a temperature of 60 ° C. and a humidity of 90%, and adhesion strengths before and after the test are It was measured.
  • the results are shown in Table 4.
  • adhesive strength as shown in FIGS. 4 and 5, a load is applied to each sample in the direction of the arrow, and in the first sample, the adhesive strength when peeled off at the interface between the sealing material and In the second sample and the third sample, the adhesion when peeled off at the interface between the seal material and the alignment film was measured.
  • the first sample maintained an adhesive strength of 2.8 kgf / mm higher than that of the second and third samples, with no change in adhesive strength before and after the test.
  • the adhesion strength before the test was 2.6 kgf / mm, a value close to the adhesion strength before the test of the first sample, but the adhesion strength after the test was 1.5 kgf / mm Down to.
  • the adhesion strength before the test is 1.1 kgf / mm, which is lower than the adhesion strength before the test of the first sample and the second sample, and the peel strength after the test is 0. It further decreased to .2 kgf / mm or less.
  • One embodiment of the present invention includes a pair of substrates disposed opposite to each other, a liquid crystal layer including a liquid crystal material, and a liquid crystal layer disposed between the pair of substrates, and surrounds the liquid crystal layer in a plan view, and the cross section view
  • a sealing material disposed between a pair of substrates and in contact with the pair of substrates, and in a region surrounded by the sealing material in a plan view, disposed between the pair of substrates and the liquid crystal layer in a cross sectional view
  • An alignment control layer in contact with the liquid crystal layer, wherein the alignment control layer contains a polymer including a unit derived from the first monomer and a unit derived from the second monomer, the liquid crystal molecules in the liquid crystal material
  • the liquid crystal display device may be one that is oriented in a direction perpendicular to the surface of the substrate, and the first monomer is represented by the following chemical formula (1). According to this aspect, it is possible to realize a liquid crystal display device which is difficult to be separated even when the frame is
  • X 1 and X 2 are the same or different and each represents H, CH 3 or C 2 H 5 .
  • Y 1 and Y 2 are the same or different, and H, F, Cl, Br, linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or linear, branched or cyclic carbon It represents an alkyloxy group of the formulas 1 to 6.
  • Z represents O, S, NH, CO, COO, OCO, or a direct bond.
  • m represents an integer of 6 to 16; n represents an integer of 8 to 24.
  • the first monomer may contain at least one of the monomers represented by the following chemical formulas (2-1) to (2-8). According to such a configuration, the first monomer can be effectively used. Further, according to the monomers represented by the following chemical formulas (2-1) to (2-8), since the halogen group (F, Cl, Br) is introduced to the biphenyl group, the liquid crystal molecules are vertically aligned. The alignment control force becomes stronger.
  • the second monomer may be represented by the following chemical formula (3). According to such a configuration, since the second monomer has a polymerization initiation function to start the polymerization reaction of at least the first monomer and the second monomer, the polymerization when forming the orientation control layer The speed is faster and the manufacturing efficiency is higher.
  • P 1 and P 2 are the same or different and each represents an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group or a vinyloxy group.
  • Sp 1 and Sp 2 are the same or different, and are linear, branched or cyclic alkylene groups having 1 to 6 carbon atoms, linear, branched or cyclic alkylene oxy groups having 1 to 6 carbon atoms, or , Represents a direct bond.
  • the second monomer may contain at least one of the monomers represented by the following chemical formulas (4-1) and (4-2). According to such a configuration, the second monomer can be effectively used.
  • the nematic phase-isotropic phase transition temperature of the liquid crystal material may be 80 ° C. or higher. In one embodiment of the present invention, the nematic phase-isotropic phase transition temperature of the liquid crystal material may be 90 ° C. or more. According to such a configuration, the liquid crystal display device can be used even when the liquid crystal material having a high nematic phase-isotropic phase transition temperature is required for applications such as car-mounted and digital signage.
  • Another embodiment of the present invention is a step of forming a liquid crystal layer by sealing a liquid crystal composition containing a liquid crystal material, a first monomer, and a second monomer between a pair of substrates bonded by a sealing material 1) An alignment in contact with the liquid crystal layer between the pair of substrates and the liquid crystal layer by polymerizing at least the first monomer and the second monomer by irradiating the liquid crystal layer with light.
  • Forming the control layer (2), wherein the alignment control layer aligns liquid crystal molecules in the liquid crystal material in a direction perpendicular to the surfaces of the pair of substrates, and the first monomer May be a method of manufacturing a liquid crystal display device represented by the following chemical formula (1). According to this aspect, it is possible to manufacture a liquid crystal display device which is difficult to be separated even if the frame is narrowed and which has high voltage holding ratio and manufacturing efficiency.
  • X 1 and X 2 are the same or different and each represents H, CH 3 or C 2 H 5 .
  • Y 1 and Y 2 are the same or different, and H, F, Cl, Br, linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or linear, branched or cyclic carbon It represents an alkyloxy group of the formulas 1 to 6.
  • Z represents O, S, NH, CO, COO, OCO, or a direct bond.
  • m represents an integer of 6 to 16; n represents an integer of 8 to 24.
  • the first monomer may contain at least one of the monomers represented by the following chemical formulas (2-1) to (2-8). According to such a configuration, the first monomer can be effectively used. Further, according to the monomers represented by the following chemical formulas (2-1) to (2-8), since the halogen group (F, Cl, Br) is introduced to the biphenyl group, the liquid crystal molecules are vertically aligned. The alignment control force becomes stronger.
  • the second monomer may be represented by the following chemical formula (3). According to such a configuration, since the second monomer has a polymerization initiation function to start the polymerization reaction of at least the first monomer and the second monomer, the polymerization when forming the orientation control layer The speed is faster and the manufacturing efficiency is higher.
  • P 1 and P 2 are the same or different and each represents an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group or a vinyloxy group.
  • Sp 1 and Sp 2 are the same or different, and are linear, branched or cyclic alkylene groups having 1 to 6 carbon atoms, linear, branched or cyclic alkylene oxy groups having 1 to 6 carbon atoms, or , Represents a direct bond.
  • the second monomer may contain at least one of the monomers represented by the following chemical formulas (4-1) and (4-2). According to such a configuration, the second monomer can be effectively used.
  • the liquid crystal layer in the step (2), may be irradiated with light in a state where the temperature of the liquid crystal layer is set to 20 to 100 ° C.
  • the temperature environment when the light is irradiated to the liquid crystal layer is, for example, special conditions such as a high temperature environment above the nematic phase-isotropic phase transition temperature of the liquid crystal material. The manufacturing efficiency is further enhanced because it is not necessary to limit to the ones.
  • 103 liquid crystal layer 4

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Abstract

La présente invention concerne un dispositif d'affichage à cristaux liquides qui est peu susceptible de provoquer un pelage même si un cadre associé est rétréci, et qui présente un taux de rétention de tension élevé et permet un rendement de fabrication élevé. Le dispositif d'affichage à cristaux liquides selon la présente invention comprend : une paire de substrats (2a, 2b) disposés de manière à être opposés l'un à l'autre ; une couche de cristaux liquides (3) qui contient un matériau à cristaux liquides et est disposé entre la paire de substrats ; un matériau d'étanchéité (4) qui entoure la couche de cristaux liquides dans une vue en plan, est disposé entre la paire de substrats dans une vue en coupe transversale, et est en contact avec la paire de substrats ; des couches de commande d'alignement (5a, 5b) qui, dans une zone entourée par le matériau d'étanchéité dans une vue en plan, sont disposées entre la paire de substrats et la couche de cristaux liquides dans une vue en coupe transversale et sont en contact avec la couche de cristaux liquides. Les couches de commande d'alignement contiennent un polymère qui comprend une unité dérivée d'un premier monomère et une unité dérivée d'un second monomère. Des molécules de cristaux liquides dans le matériau à cristaux liquides sont alignées dans la direction perpendiculaire aux surfaces de la paire de substrats. Le premier monomère est représenté par une formule chimique prédéterminée.
PCT/JP2018/024479 2017-07-05 2018-06-28 Dispositif d'affichage à cristaux liquides et son procédé de fabrication WO2019009166A1 (fr)

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WO2021117104A1 (fr) * 2019-12-09 2021-06-17 シャープ株式会社 Film d'alignement, dispositif d'affichage, procédé de production de dispositif d'affichage, agent d'alignement de cristaux liquides et composition de cristaux liquides

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JPH107617A (ja) * 1996-02-26 1998-01-13 Sharp Corp 重合性化合物およびそれを用いた液晶表示素子
WO2012121321A1 (fr) * 2011-03-09 2012-09-13 シャープ株式会社 Dispositif d'affichage à cristaux liquides et procédé de production de dispositif d'affichage à cristaux liquides

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Publication number Priority date Publication date Assignee Title
JPH107617A (ja) * 1996-02-26 1998-01-13 Sharp Corp 重合性化合物およびそれを用いた液晶表示素子
WO2012121321A1 (fr) * 2011-03-09 2012-09-13 シャープ株式会社 Dispositif d'affichage à cristaux liquides et procédé de production de dispositif d'affichage à cristaux liquides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021117104A1 (fr) * 2019-12-09 2021-06-17 シャープ株式会社 Film d'alignement, dispositif d'affichage, procédé de production de dispositif d'affichage, agent d'alignement de cristaux liquides et composition de cristaux liquides

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