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WO2013031497A1 - Dispositif d'affichage à cristaux liquides et composition de cristaux liquides - Google Patents

Dispositif d'affichage à cristaux liquides et composition de cristaux liquides Download PDF

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Publication number
WO2013031497A1
WO2013031497A1 PCT/JP2012/070178 JP2012070178W WO2013031497A1 WO 2013031497 A1 WO2013031497 A1 WO 2013031497A1 JP 2012070178 W JP2012070178 W JP 2012070178W WO 2013031497 A1 WO2013031497 A1 WO 2013031497A1
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Prior art keywords
liquid crystal
group
crystal display
display device
monomer
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PCT/JP2012/070178
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English (en)
Japanese (ja)
Inventor
仲西　洋平
真伸 水▲崎▼
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シャープ株式会社
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Publication of WO2013031497A1 publication Critical patent/WO2013031497A1/fr

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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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
    • 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
    • C09K19/542—Macromolecular compounds
    • C09K2019/548—Macromolecular compounds stabilizing the alignment; Polymer stabilized alignment
    • 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
    • G02F1/133753—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle
    • G02F1/133757—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle with different alignment orientations
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • G02F1/1341—Filling or closing of cells
    • G02F1/13415—Drop filling process
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G02F2202/022—Materials and properties organic material polymeric
    • G02F2202/023—Materials and properties organic material polymeric curable

Definitions

  • the present invention relates to a liquid crystal display device and a liquid crystal composition. More specifically, a liquid crystal composition containing a monomer that reacts (polymerizes) with light or light and heat, and the liquid crystal composition is sealed between a pair of substrates, and the monomer is polymerized to align the liquid crystal.
  • the present invention relates to a liquid crystal display device that forms a polymer layer for controlling the temperature.
  • a liquid crystal display is characterized by thinness, light weight, and low power consumption, and is widely used in various fields.
  • an active matrix type liquid crystal display device in which an active element is arranged for each pixel is widely adopted.
  • the display method (mode) of the liquid crystal display device is determined by how the liquid crystals are arranged in the cell, and the TN (twisted nematic) mode has been the mainstream before.
  • MVA multidomain vertical alignment
  • PVA Powerned vertical alignment
  • CPA Continuous Pinwheel Alignment
  • IPS Intelligent Pinwheel Alignment
  • IPS Intelligent Pinwheel Alignment
  • FFS Frringe Field
  • the liquid crystal is aligned perpendicularly to the substrate, and liquid crystal molecules are aligned by a slit (bank) provided on the transparent electrode (ITO film) of the active matrix substrate and a protrusion (bank) provided on the counter substrate.
  • a slit bank
  • ITO film transparent electrode
  • a protrusion bank
  • the substantial aperture ratio decreases due to the slits and protrusions, so that the light transmittance in the MVA mode is lower than that in the TN mode. Therefore, the MVA mode cannot be adopted for a display device for a portable terminal that requires low power consumption.
  • the protrusions and the slits are arranged in a complicated manner so that the liquid crystal molecules are tilted in four directions when a voltage is applied to the liquid crystal layer, the light transmittance is lowered. If these arrangements are simplified and the interval between the protrusions or slits is increased, the light transmittance can be increased. However, if the interval between the protrusions or slits is increased, it takes time to propagate the tilt of the liquid crystal molecules, and the response of the device tends to be slow when a voltage is applied to the device for display.
  • a liquid crystal composition containing a polymerizable monomer is injected between the substrates, and the monomer is polymerized in a state where a voltage is applied, thereby liquid crystal molecules.
  • PSA Polymer sustained alignment
  • PSA monomers contained in the liquid crystal composition to form a polymer and the concentration of the polymerization initiator
  • a liquid crystal dropping method (ODF process; One drop fill process) has come to be used as a technique for filling a liquid crystal in the panel.
  • ODF process before adhering one substrate to the other substrate, the sealing resin is applied to one substrate to prevent the liquid crystal composition from leaking, and then the liquid crystal composition is dropped. Then, the opposing substrates are bonded together. Because they are bonded together in a vacuum state, no air enters between the substrates.
  • a photocurable resin is often used. After the substrates are bonded together, the sealing resin is cured by irradiating light from the outside of the panel to form a sealing material. Confine inside the pair of substrates and the sealant. At this time, a shading mask is also used so that light other than the sealing resin is not irradiated. In the present specification, light is not limited to visible light, but may be ultraviolet light.
  • a liquid crystal display device using a liquid crystal dropping method (ODF process; one drop fill process) of a liquid crystal display panel (hereinafter also referred to as a liquid crystal dropping process) and the PSA technique has a poor alignment. May occur.
  • An object of the present invention is to provide a liquid crystal display device in which alignment defects are effectively reduced in a liquid crystal display device using both a liquid crystal dropping step and a PSA technique.
  • the PSA monomer reacts by irradiation with ultraviolet rays even without a polymerization initiator. Therefore, when the liquid crystal composition is exposed to light in the process of manufacturing the liquid crystal display device, the PSA monomer in the liquid crystal composition causes a polymerization reaction. Taking the liquid crystal dropping process as an example, when light is irradiated to cure the sealing resin, the liquid crystal composition is irradiated with light that could not be blocked by the light shielding mask, and the PSA monomer in the liquid crystal composition is polymerized.
  • the PSA monomer reacts and polymerizes by irradiation with ultraviolet rays even without a polymerization initiator.
  • This reaction is considered to generate radicals by photo-Fries rearrangement and promote polymerization.
  • the photofleece rearrangement means that an aryl ester of the following formula (3-1) is converted into a hydroxyacetophenone of the following formulas (3-2) and (3-3) by light and the following formula: It rearranges to (3-4) phenols.
  • an acyloxy bond is cleaved to generate a radical.
  • This radical serves as a polymerization initiator, and the PSA monomer is polymerized.
  • the conventional PSA monomer has two or more reactive functional groups, and each functional group is directly bonded to a core benzene ring or condensed ring structure. Yes. That is, in the conventional PSA monomer, as shown in the following chemical formulas (5-2) and (5-3), there are two or more places where the bond may be cleaved by light irradiation. Therefore, the conventional PSA monomer has a high radical generation probability due to light irradiation. As described above, since the conventional PSA monomer has a relatively high reactivity, a polymerization reaction progresses during a liquid crystal display manufacturing process, for example, a liquid crystal dropping process, and a polymer that fixes a disordered state is formed. It has been found that orientation failure may occur.
  • the present inventors insert a spacer portion between the reactive functional group and the ring structure so that the vicinity of the reactive functional group is not cleaved, and the radical generation position of the PSA monomer is assumed to be one place and only one place.
  • the reactivity of the PSA monomer is suppressed to some extent, and even when irradiated with light, the polymerization is suppressed to such an extent that no polymer is generated to fix the alignment disorder. It was found that it can be suppressed.
  • a PSA monomer having two or more reactive functional groups only one functional group is directly bonded to a ring structure such as a benzene ring or a condensed ring structure, and other reactivity
  • a spacer portion between the functional group and the ring structure as shown in the following chemical formula (6-2)
  • the vicinity of the reactive functional group that binds to the spacer portion is not cleaved, but directly into the ring structure. Only one reactive functional group to be bonded is cleaved.
  • a reactive functional group is bonded to the benzene ring, but the same applies to a condensed ring structure.
  • the polymerization rate can be adjusted by setting the position where the light fleece rearrangement is performed to one position.
  • a pair of substrates, a sealing material, the pair of substrates, a liquid crystal composition held by the sealing material, and a surface of the pair of substrates in contact with the liquid crystal composition A pair of polymer layers each formed, wherein the pair of polymer layers includes one or more ring structures, a spacer part directly bonded to the ring structure, a first reactive functional group bonded via the spacer part,
  • the spacer portion is formed by polymerizing a monomer (PSA monomer) including a second reactive functional group directly bonded to the ring structure, and the spacer portion includes a liquid crystal display device that does not include an unsaturated bond (hereinafter referred to as the present invention). It is also referred to as a first liquid crystal display device).
  • Examples of the ring structure include aromatic rings such as a benzene ring, a condensed benzene ring, and a heteroaromatic ring.
  • Examples of the condensed benzene ring include naphthalene, anthracene, phenanthrene and the like obtained by condensation polymerization of benzene.
  • the ring structure may be an allocyclic ring in which a ring is formed with the same kind of atoms, or a heterocyclic ring in which a ring is formed with two or more kinds of atoms.
  • the number of rings included in the ring structure is not limited.
  • the spacer portion is a chemical structure that connects the ring structure and the first reactive functional group in the molecule of the PSA monomer, so that the first reactive functional group does not cause or is less likely to cause photofleece rearrangement.
  • a chemical structure is preferred.
  • the said spacer part does not have an unsaturated bond.
  • Examples of the structure of the spacer portion include an alkylene group or an oxyalkylene group. The number of carbon atoms of the alkylene group or oxyalkylene group is not particularly limited, but is preferably 1-8. In these groups, a hydrogen atom may be substituted with another atom or may have a side chain.
  • the said 1st and 2nd reactive functional group should just be a group which has a functional group which shows the reactivity by light, and it is preferable that a light Fleece rearrangement is produced.
  • the structures of the first and second reactive functional groups include, independently of each other, an acrylamide group, a methacrylamide group, an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, and an epoxy group.
  • the second reactive functional group is preferably a group having a functional group causing a polymerization reaction
  • the first reactive functional group is more preferably a group having a functional group causing a polymerization reaction.
  • the first reactive functional group and the second reactive functional group may be bonded to the same ring structure, or may be bonded to different ring structures. That is, the spacer part that connects the first reactive functional group and the ring structure and the second reactive functional group may be bonded to the same ring structure, or may be bonded to different ring structures. Good.
  • the PSA monomers may be polymerized to form an oligomer.
  • the monofunctional monomer can be cleaved at one position as in the case of the PSA monomer according to the present invention.
  • the polymer is formed by the PSA monomer according to the present invention, the polymer is formed by the monofunctional monomer.
  • the stability of the orientation is superior to that of the formation.
  • the pretilt angle imparted by the polymer formed by the monofunctional monomer disappears, but is imparted by the polymer formed by the PSA monomer according to the present invention. The pretilt angle is maintained.
  • another aspect of the present invention includes a pair of substrates, a sealing material, the pair of substrates, a liquid crystal composition held by the sealing material, and the liquid crystal of the pair of substrates.
  • PSA monomer a monomer containing only one reactive functional group that generates fleece rearrangement by light irradiation.
  • It is also a liquid crystal display device that is formed (hereinafter also referred to as a second liquid crystal display device of the present invention).
  • another aspect of the present invention is a liquid crystal composition containing at least one monomer, and the at least one monomer is directly bonded to one or more ring structures, the ring structure.
  • a liquid crystal composition comprising a spacer part, a first reactive functional group bonded via the spacer part, and a second reactive functional group directly bonded to the ring structure, wherein the spacer part does not contain an unsaturated bond But there is.
  • the first and second liquid crystal display devices of the present invention and the liquid crystal composition of the present invention are not particularly limited by other configurations as long as such a configuration is essential. Absent.
  • the sealing material is preferably formed from a photocurable resin.
  • the first reactive functional group is represented by P1
  • the second reactive functional group is represented by P2
  • the spacer portion is represented by Z1
  • the ring structure is represented by A1 and A2
  • the monomer is represented by the following formula (1).
  • the liquid crystal display device (hereinafter also referred to as the first embodiment) is preferable.
  • P1 and P2 are each independently an acrylamide group, a methacrylamide group, an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, or an epoxy group
  • A1 and A2 are each independently 1 , 4-phenylene group or naphthalene-2,6-diyl group
  • Z1 is an alkylene group or oxyalkylene group having 1 to 8 carbon atoms
  • n is 0, 1 or 2.
  • P1 and P2 are each independently an acrylate group or a methacrylate group, the Z1 is —CH 2 —, and n is more preferably 1.
  • the monomer is more preferably represented by the following formula (2).
  • P1 and P2 are each independently an acrylamide group, a methacrylamide group, an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group or an epoxy group, and Z1 is an alkylene having 1 to 8 carbon atoms Group or an oxyalkylene group.
  • a polymerization reaction is caused in the ODF process, for example, in accordance with conditions such as a production line, a liquid crystal composition, and an alignment film. It is difficult to design a PSA monomer that causes a polymerization reaction in the process of forming a polymer layer.
  • the first and second liquid crystal display devices of the present invention preferably have a vertical alignment film under the polymer layer (hereinafter also referred to as a second embodiment).
  • the present invention can be applied to a liquid crystal display device such as a mode in which liquid crystal molecules are aligned substantially vertically, such as an MVA mode, a PVA mode, or a CPA mode.
  • the first and second liquid crystal display devices of the present invention preferably have a horizontal alignment film under the polymer layer (hereinafter also referred to as a third mode).
  • the liquid crystal display device is More preferably, the liquid crystal molecules are driven using a lateral electric field.
  • the present invention can be applied to a liquid crystal display device such as a mode in which liquid crystal molecules are aligned substantially horizontally, such as an IPS mode or an FFS mode.
  • the first and second liquid crystal display devices of the present invention preferably have a photo-alignment film under the polymer layer.
  • the present invention can be applied to a liquid crystal display device using a photo-alignment film, for example, a UV 2 A (ultraviolet induced multi-domain vertical alignment) mode liquid crystal display device in which the photo-alignment film is aligned and divided.
  • a photo-alignment film for example, a UV 2 A (ultraviolet induced multi-domain vertical alignment) mode liquid crystal display device in which the photo-alignment film is aligned and divided.
  • the UV 2 A mode it is possible to use a simple pixel structure without a bank, an ITO slit, etc. by controlling liquid crystal molecules with an alignment-divided photo-alignment film, and a vertical alignment with a very high transmittance. A mode can be realized.
  • the monomer preferably contains a reactive functional group that does not cause fleece rearrangement by light irradiation. Thereby, alignment stability can be improved.
  • the liquid crystal display device which used the liquid crystal dripping process and PSA technique together, the liquid crystal display device which reduced the orientation defect effectively can be provided.
  • FIG. 1 is a schematic plan view of an MVA mode liquid crystal display device according to Embodiment 1.
  • FIG. FIG. 2 is a schematic cross-sectional view of the liquid crystal display device taken along line AA ′ shown in FIG. It is a cross-sectional schematic diagram which shows the state which formed the seal pattern on the board
  • FIG. 3 is a schematic cross-sectional view showing a polymerization step of a PSA monomer in the liquid crystal display device according to Embodiment 1.
  • FIG. 6 is a schematic plan view showing a photo-alignment processing direction for a pair of substrates and a domain division pattern in a UV 2 A mode liquid crystal display device according to Example 2.
  • 6 is a schematic plan view of an IPS mode liquid crystal display device according to Embodiment 3.
  • FIG. 6 is a schematic plan view of an FFS mode liquid crystal display device according to Embodiment 4.
  • FIG. 6 is a schematic plan view of another FFS mode liquid crystal display device according to Embodiment 4.
  • FIG. 1 is a schematic cross-sectional view showing a polymerization step of a PSA monomer in the liquid crystal display device according to Embodiment 1.
  • FIG. 6 is a schematic plan view showing a photo-alignment processing direction for a pair of substrates and a domain division pattern in a UV 2 A mode liquid crystal display device according
  • Embodiment 1 As an embodiment of the present invention, an MVA mode liquid crystal display device will be described as an example.
  • the liquid crystal display device 1 includes a liquid crystal display panel 10.
  • the liquid crystal display panel 10 includes an active matrix substrate 11 that is a pair of substrates arranged opposite to each other, and an opposing substrate.
  • a substrate 12 and a liquid crystal layer (liquid crystal composition) 13 sandwiched between them are included.
  • a pair of polarizing plates (not shown) is provided on the surface opposite to the liquid crystal layer 13 of the active matrix substrate 11 and the counter substrate 12.
  • the substrates 11 and 12 are bonded together by a sealing material 14 provided so as to surround the display area. Moreover, the board
  • the counter substrate 12 includes a colorless and transparent transparent substrate 22 made of glass, plastic, or the like.
  • a black matrix (not shown) layer that shields light between the sub-pixels.
  • the common electrode 15 is formed from a transparent conductive film such as ITO.
  • the liquid crystal display device of this embodiment is an active matrix type liquid crystal display device for color display having a color layer on the counter substrate 12, and includes R (red), G (green), and B (blue).
  • One pixel is composed of three sub-pixels that output each color light.
  • the type and number of colors of the sub-pixels constituting each sub-pixel are not particularly limited and can be set as appropriate. That is, in the liquid crystal display of the present embodiment, each pixel may be composed of, for example, three sub-pixels of C (cyan), M (magenta), and Y (yellow), for example, four or more colors such as RGBY. May be composed of the sub-pixels.
  • the active matrix substrate 11 includes a colorless and transparent transparent substrate 21 made of glass, plastic or the like.
  • a gate bus line 17, a Cs electrode 19, and a data bus On the main surface of the transparent substrate 21 on the liquid crystal layer 13 side, a gate bus line 17, a Cs electrode 19, and a data bus.
  • the line 18 includes a TFT 40 that is a switching element and is provided for each sub-pixel, and an alignment film 31 that covers these components and is provided on the surface on the liquid crystal layer 13 side.
  • the TFT 40 includes a drain electrode 41, a gate electrode 42, a semiconductor layer 43, and a source electrode 44.
  • the alignment films 31 and 32 provided on the active matrix substrate 11 and the counter substrate 12 are vertical alignment films, and are formed by coating from a known alignment film material such as partially chemically imidized polyamic acid.
  • the vertical alignment film is not usually rubbed, but can align the liquid crystal composition (liquid crystal molecules) substantially perpendicular to the film surface when no voltage is applied.
  • an MVA mode liquid crystal display device including a vertical alignment film is taken as an example.
  • An alignment film may be formed.
  • a photo-alignment film may be formed by using a known photo-alignment film material as the alignment film material, and the photo-alignment film may be a horizontal photo-alignment film or a vertical photo-alignment film.
  • the alignment may be divided by changing the direction of light irradiated for each alignment region.
  • An image signal (video signal) is supplied to the pixel electrode 16 from the data bus line 18 extending vertically between adjacent subpixels via the TFT 40.
  • a rectangular wave is applied to the pixel electrode 16 according to the image signal.
  • Each pixel electrode 16 is electrically connected to the drain electrode 41 of the TFT 40 through a contact hole provided in the interlayer insulating film 36.
  • a common signal common to the sub-pixels is supplied to the common electrode 15.
  • the common electrode 15 is connected to a common voltage generation circuit and is set to a predetermined potential (typically 0 V).
  • the data bus line 18 is connected to a data driver (data line driving circuit).
  • a gate bus line 17 connected to a gate driver (scanning line driving circuit) extends in the left-right direction between adjacent sub-pixels.
  • the gate bus line 17 also functions as a gate electrode 42 of the TFT 40, and the gate A scanning signal supplied in a pulse manner from the driver to the gate bus line at a predetermined timing is applied to each TFT 40 in a line sequential manner.
  • An image signal supplied from the data bus line 18 is applied at a predetermined timing to the pixel electrode 16 connected to the TFT 40 which is turned on for a certain period by the input of the scanning signal.
  • the image signal of a predetermined level written in the liquid crystal layer 13 is held for a certain period between the pixel electrode 16 to which the image signal is applied and the common electrode 15.
  • a storage capacitor is formed between the pixel electrode 16 and the common electrode 15 and between the pixel electrode 16 and the Cs electrode 19.
  • the pixel electrode 16 is formed of a transparent conductive film such as ITO, a metal film such as aluminum or chromium, and the like. As shown in FIG. 1, the shape of the pixel electrode 16 when the liquid crystal display panel 1 is viewed in plan has a fishbone structure including a trunk and a plurality of branches branched from the trunk. The branches extend in four directions and constitute four domains.
  • the active matrix substrate 11 and the counter substrate 12 have polymer layers 33 and 34 on the surfaces in contact with the liquid crystal layer 13, respectively.
  • the polymer layers 33 and 34 assist the alignment films 31 and 32 in controlling the alignment of the liquid crystal molecules, or the polymer layers 33 and 34 themselves control the alignment of the liquid crystal molecules.
  • the polymer layers 33 and 34 are formed in the liquid crystal composition by irradiating the liquid crystal composition with light (for example, ultraviolet irradiation) after the liquid crystal composition is sandwiched between the active matrix substrate 11, the counter substrate 12, and the sealing material 14.
  • the PSA monomer is polymerized and formed.
  • the liquid crystal composition includes a PSA monomer that forms the polymer layers 33 and 34 and a liquid crystal material such as liquid crystal molecules.
  • the PSA monomer contained in the liquid crystal composition will be described in detail below.
  • the PSA monomer includes one or more ring structures, a first reactive functional group bonded to the ring structure via a spacer portion, and a second reactive functional group directly bonded to the ring structure.
  • the PSA monomer is represented by the following formula (1). It is preferable (hereinafter also referred to as the first PSA monomer). P1-Z1-A1- (A2) n-P2 (1)
  • P1 and P2 are each independently acrylamide group, methacrylamide group, acrylate group, methacrylate group, vinyl group, vinyloxy group or epoxy group, and A1 and A2 are each independently 1,4-phenylene group or naphthalene.
  • a -2,6-diyl group, Z1 is an alkylene group or oxyalkylene group having 1 to 8 carbon atoms, and n is 0, 1 or 2.
  • the P1 and P2 each independently, an acrylate or methacrylate group, Z1 is CH 2, n is more preferably 1.
  • the first PSA monomer is more preferably represented by the following formula (2).
  • each of P1 and P2 is independently an acrylamide group, a methacrylamide group, an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, or an epoxy group
  • Z1 is an alkylene group having 1 to 8 carbon atoms or an oxyalkylene group It is a group.
  • PSA monomers may be polymerized to form an oligomer and dissolved in the liquid crystal composition.
  • the core characteristics are important. For example, since the absorption region extends from the low wavelength side to the long wavelength side in the order of anthracene, phenanthrene, naphthalene ring, and biphenyl, the PSA monomer is easily excited. If the effect of reducing the reaction rate due to the introduction of the spacer portion into the PSA monomer is insufficient, that is, if the PSA monomer is relatively susceptible to polymerization even when the spacer portion is introduced, a core portion that is difficult to be excited is introduced. It is possible.
  • the ease of the polymerization reaction required for the PSA monomer of the present invention may vary depending on the conditions of the production line, the liquid crystal to be selected, the alignment film, etc., but the first and second reactive functional groups are changed to the spacer part, and An optimal PSA monomer can be obtained by appropriately combining ring structures.
  • the concentration of the PSA monomer added to the liquid crystal composition is, for example, 0.1 wt% to 0.5 wt% with respect to the entire liquid crystal composition including the PSA monomer if the PSA monomer is represented by the above formula (2). % Is preferred.
  • concentration of the PSA monomer represented by the above formula (2) is less than 0.1 wt%, a polymer layer is formed, but there is not a sufficient layer thickness. Therefore, a desired pretilt angle (in the vertical alignment mode such as MVA mode) , 87 ° to 88.5 ° is preferable).
  • MVA mode vertical alignment mode
  • dielectric breakdown occurs due to excessively high voltage.
  • the liquid crystal display panel may be destroyed.
  • the PSA monomer represented by the above formula (2) when the concentration of the PSA monomer represented by the above formula (2) is higher than 0.5 wt%, the PSA monomer may not be completely dissolved in the liquid crystal composition and may cause display defects such as bright spots. is there.
  • the addition concentration of the PSA monomer can be appropriately set in consideration of the function of the polymer layer to be formed and the solubility of the PSA monomer in the liquid crystal material.
  • each of the active matrix substrate 11 and the counter substrate 12 can be manufactured by a conventionally known method.
  • a photocurable resin 24 is applied to the substrate 11 or 12 so as to surround the display area to form a rectangular frame-shaped seal pattern (FIG. 3). 1, a seal pattern is formed on the substrate 11).
  • the photocurable resin 24 has a property of being cured by visible light or ultraviolet light.
  • the photocurable resin 24 may also have a property of curing by heating (thermosetting) in addition to photocuring properties.
  • fine droplets of the liquid crystal composition 13 are applied dropwise onto the entire surface of the frame of the substrate 11 or 12 on which the seal pattern is formed, with the photocurable resin 24 being uncured. Thereafter, as shown in FIG.
  • the other substrate is overlaid in a vacuum atmosphere, for example, using a UV lamp as a light source, and irradiating ultraviolet rays with an energy of about 3 J / cm 2 to cure the seal pattern. Then, the liquid crystal layer 13 is formed. At this time, it is preferable that the area other than the area where the photocurable resin 24 is applied is covered with a mask. However, when the liquid crystal display panel is small and medium and it is difficult to dispose a mask, the mask does not have to be provided.
  • the liquid crystal composition contains a PSA monomer having photoreactivity, but the photoreactivity is poorer than that of the conventional PSA monomer. Therefore, alignment is performed during light irradiation (ultraviolet irradiation) for curing the seal pattern. No polymer is produced to fix the turbulence.
  • the mask is removed, and thereafter, as shown in FIG. 3-4, heating is performed to harden the seal pattern to form a seal material 14.
  • the photocurable resin 24 which comprises a seal pattern has only photocurability and does not have thermosetting, it is not necessary to heat.
  • the liquid crystal composition is sandwiched between the active matrix substrate 11, the counter substrate 12, and the sealing material. As described above, the liquid crystal display panel 10 is formed by the ODF process.
  • the liquid crystal display panel 10 is irradiated with ultraviolet rays with an energy of about 4 J / cm 2 by an ultraviolet lamp, for example.
  • the PSA monomer in the product is polymerized to form polymer layers 33 and 34 on the alignment films 31 and 32, respectively.
  • the applied voltage can be appropriately adjusted according to a desired pretilt angle, and includes 0 volt.
  • the PSA monomer is polymerized to form the polymer layers 33 and 34.
  • the liquid crystal display panel according to Embodiment 1 is manufactured through the ODF process and the polymerization step of the PSA monomer.
  • the PSA monomer can be suppressed from being polymerized by light (for example, ultraviolet rays) irradiated for curing the seal pattern during the ODF process, the polymer generated during the ODF process. It is possible to suppress the occurrence of orientation failure due to.
  • the MVA mode liquid crystal display device has been described as an example.
  • any liquid crystal display device manufactured using both the ODF process and the PSA technology may be used.
  • the mode is not particularly limited.
  • a mode in which liquid crystal molecules are aligned by a vertical electric field or an oblique electric field such as a PVA mode and a CPA mode may be used.
  • a mode in which liquid crystal molecules are aligned by a lateral electric field such as an IPS mode and an FFS mode may be used.
  • a UV 2 A mode in which liquid crystal molecules are controlled by an alignment-divided photo-alignment film may be used.
  • the IPS mode liquid crystal display device requires a strong backlight.
  • the FFS mode is the same as the IPS mode in that an electrode is provided on one side of the substrate. However, a single insulating layer is provided on one electrode and a comb electrode is provided thereon to switch liquid crystal molecules in a horizontal plane.
  • the liquid crystal display device according to the embodiment of the present invention was actually manufactured and designated as Examples 1 to 4.
  • Example 1 As Example 1, an MVA mode liquid crystal display device was manufactured.
  • As the alignment film a vertical alignment film made of partially chemically imidized polyamic acid was used.
  • a liquid crystal composition having a negative dielectric anisotropy was used so that the director of liquid crystal molecules when no voltage was applied was approximately perpendicular to the substrate. Since the polarizing plate is attached to both sides of the liquid crystal display device in crossed Nicol, it is normally black, and the polarizing axis of the polarizing plate is parallel to the bus line.
  • the panel size was 10 type and the resolution was XGA.
  • a light blocking black matrix and a color filter were formed on a glass substrate, and a common electrode made of ITO was formed on the upper surface of the color filter.
  • a common electrode made of ITO was formed on the upper surface of the color filter.
  • an active matrix substrate on the other glass substrate, a plurality of parallel gate bus lines, a plurality of data bus lines formed in parallel to the gate bus lines in the vertical direction, and intersections of the gate bus lines and the data bus lines A thin film transistor (TFT) formed in a matrix and a pixel electrode made of ITO were formed.
  • the gate bus line is separated from the data bus line by an insulating film, and a source electrode and a drain electrode of the TFT are formed in the same layer as the data bus line.
  • the pixel electrode has a fine structure (fishbone structure) as shown in FIG. 1, and stabilizes the potential of each pixel electrode at a position parallel to the gate bus line and in the middle of the adjacent gate bus line. For this purpose, a Cs electrode was provided.
  • a liquid crystal composition was dropped on the active matrix substrate after applying a mixture of ultraviolet curing and thermosetting materials.
  • a PSA monomer represented by the following chemical formula (7) was added so as to be 0.3 wt% with respect to the entire liquid crystal composition containing the PSA monomer. Note that the liquid crystal composition may be dropped by applying a seal to the counter substrate.
  • the substrates were bonded together in a vacuum atmosphere and returned to atmospheric pressure.
  • the sealing material was cured by irradiating ultraviolet rays from the outside of the substrate. A mask that shields ultraviolet rays was not used. Thereafter, firing was performed to completely cure the seal. After curing the seal, ultraviolet rays were irradiated at 20 J / cm 2 at room temperature while applying a voltage of 10V.
  • Comparative Example 1 The liquid crystal display of Example 1 except that 0.3 wt% of dimethacrylate represented by the following chemical formula (8) was added to the liquid crystal composition instead of the PSA monomer represented by the above chemical formula (7) as the PSA monomer.
  • An MVA mode liquid crystal display device which is the same as the device was manufactured.
  • Example 2 As Example 2, a UV 2 A mode liquid crystal display device was manufactured. In each of the active matrix substrate and the counter substrate, each pixel was aligned and divided at an equal pitch so as to divide each pixel into two, thereby forming a photo-alignment film. Then, both substrates were bonded so that the orientation-divided directions were orthogonal to each other when the substrates were viewed in plan. As a result, as shown in FIG. 4, four divided domains having different alignment directions of liquid crystal molecules located in the vicinity of the center in the thickness direction of the liquid crystal layer were formed in four regions (i to iv in FIG. 4). More specifically, the dotted arrow in FIG.
  • Example 4 indicates the tilt direction of the liquid crystal molecules on the lower substrate, and the solid arrow indicates the tilt direction of the liquid crystal molecules on the upper substrate.
  • the liquid crystal molecules appear to fall down in the direction opposite to the arrow. Therefore, as shown in FIG. 4, the liquid crystal molecules fall down in different directions in the four regions.
  • a liquid crystal having a negative dielectric anisotropy is used as in Example 1.
  • the PSA monomer represented by the above chemical formula (7) is used as a liquid crystal composition containing the PSA monomer. It added so that it might become 0.3 wt% with respect to the whole.
  • Comparative Example 2 The liquid crystal display of Example 2 except that 0.3 wt% of dimethacrylate represented by the chemical formula (8) was added to the liquid crystal composition instead of the PSA monomer represented by the chemical formula (7) as the PSA monomer. A liquid crystal display device of UV 2 A mode, which is the same as the device, was produced.
  • Example 3 As Example 3, an IPS mode liquid crystal display device was manufactured. As shown in FIG. 5, in the liquid crystal display device 101 in the IPS mode, the common electrode 115 formed in a comb shape on the active matrix substrate and the pixel electrode 116 formed in a comb shape are formed on the same substrate. Arranged. Liquid crystal molecules were horizontally aligned using a polyimide alignment film that had been rubbed as an alignment film. A liquid crystal having a positive dielectric anisotropy was used.
  • the PSA monomer represented by the chemical formula (7) is added to 0.3 wt% with respect to the entire liquid crystal composition, A liquid crystal composition was dropped on the active matrix substrate. Note that the liquid crystal composition may be dropped by applying a seal to the counter substrate.
  • the substrates were bonded together in a vacuum atmosphere and returned to atmospheric pressure.
  • the sealing material was cured by irradiating ultraviolet rays from the outside of the substrate. Thereafter, firing was performed to completely cure the seal. After curing the seal, ultraviolet rays were irradiated at 20 J / cm 2 at room temperature while applying a voltage of 0V. A mask that shields ultraviolet rays was not used.
  • Comparative Example 3 The liquid crystal display of Example 3 except that 0.3 wt% of dimethacrylate represented by the chemical formula (8) was added to the liquid crystal composition instead of the PSA monomer represented by the chemical formula (7) as the PSA monomer.
  • An IPS mode liquid crystal display device which is the same as the device was manufactured.
  • Example 4 As Example 4, an FFS mode liquid crystal display device was manufactured. As shown in FIG. 6A, in the FFS mode liquid crystal display device 201, a planar common electrode 215 made of ITO and a pixel electrode 216 having an opening made of ITO are formed on an active matrix substrate. Are arranged in this order. In FIG. 6A, the shape of the opening is a parallelogram, and the opening is arranged obliquely with respect to the long side and the short side of the rectangular pixel. Since the upper half and the lower half have different opening inclination directions with respect to the long side direction of the pixel, the upper half and the lower half have different rotation directions in the liquid crystal alignment direction.
  • the boundary between the two regions is formed in parallel to the short side direction of the pixel at the center of the pixel where the TFT and the through hole are present.
  • the shape of the opening is V-shaped, and the bent portion of the V-shape is a boundary between two regions having different rotation directions in the liquid crystal alignment direction, and the boundary between the two regions is the long side of the pixel. It may be formed parallel to the direction.
  • Liquid crystal molecules were horizontally aligned using a photo-alignment film as the alignment film. A liquid crystal having a positive dielectric anisotropy was used.
  • the PSA monomer represented by the chemical formula (7) was added to 0.3 wt% with respect to the entire liquid crystal composition including the PSA monomer, and the liquid crystal composition was dropped onto the active matrix substrate. did.
  • ultraviolet rays were irradiated at room temperature at 20 J / cm 2 while applying a voltage of 0V. At this time, a mask for shielding ultraviolet rays was not used. Note that the liquid crystal composition may be dropped by applying a seal to the counter substrate.
  • Comparative Example 4 The liquid crystal display of Example 4 except that 0.3 wt% of dimethacrylate represented by the chemical formula (8) was added to the liquid crystal composition instead of the PSA monomer represented by the chemical formula (7) as the PSA monomer.
  • An FFS mode liquid crystal display device which is the same as the device was manufactured.
  • liquid crystal display device 10 liquid crystal display panel 11: active matrix substrate 12: counter substrate 13: liquid crystal layer (liquid crystal composition) 14: Sealing material 15, 115, 215: Common electrode 16, 116, 216: Pixel electrode 17: Gate bus line 18: Data bus line 19: Cs electrode 21, 22: Transparent substrate 24: Photocurable resin 31, 32: Alignment films 33, 34: polymer layer 35: protrusion 36: interlayer insulating film 40: TFT 41: drain electrode 42: gate electrode 43: semiconductor layer 44: source electrode 50: power supply

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  • Spectroscopy & Molecular Physics (AREA)
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Abstract

La présente invention concerne un dispositif d'affichage à cristaux liquides, à l'aide d'une étape de dépôt de gouttes de cristaux liquides et de la technique PSA, les problèmes d'alignement étant efficacement réduits. Ledit dispositif d'affichage à cristaux liquides est doté d'une paire de substrats, d'un matériau d'étanchéité, d'une composition de cristaux liquides contenue par lesdits substrats et ledit matériau d'étanchéité, et d'une couche polymère formée sur chaque substrat, en particulier sur les surfaces de celui-ci qui sont en contact avec la composition de cristaux liquides. Lesdites couches polymères sont formées par la polymérisation d'un monomère contenant les éléments suivants : au moins une structure annulaire, une section espaceur directement liée à celle-ci, un premier groupe fonctionnel réactif lié par le biais de la section espaceur, et un second groupe fonctionnel réactif lié directement à la structure annulaire. La section espaceur ne contient pas de liaisons insaturées.
PCT/JP2012/070178 2011-08-31 2012-08-08 Dispositif d'affichage à cristaux liquides et composition de cristaux liquides WO2013031497A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009064035A (ja) * 2001-10-02 2009-03-26 Sharp Corp 液晶表示装置用基板及びそれを用いた液晶表示装置
WO2010061490A1 (fr) * 2008-11-27 2010-06-03 シャープ株式会社 Écran à cristaux liquides et procédé de production correspondant
JP2010537256A (ja) * 2007-08-30 2010-12-02 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 液晶ディスプレイ
JP2011076065A (ja) * 2009-09-02 2011-04-14 Jsr Corp 液晶表示素子の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009064035A (ja) * 2001-10-02 2009-03-26 Sharp Corp 液晶表示装置用基板及びそれを用いた液晶表示装置
JP2010537256A (ja) * 2007-08-30 2010-12-02 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 液晶ディスプレイ
WO2010061490A1 (fr) * 2008-11-27 2010-06-03 シャープ株式会社 Écran à cristaux liquides et procédé de production correspondant
JP2011076065A (ja) * 2009-09-02 2011-04-14 Jsr Corp 液晶表示素子の製造方法

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