Patent Application
20140168589
The present invention relates to a liquid crystal display panel and a liquid crystal display device. More specifically, the present invention relates to a liquid crystal display panel and a liquid crystal display device including a polymer layer for improving a property formed on a horizontal photo-alignment film.
Due to advantageous features such as thin profile, light weight, and low power consumption, liquid crystal display devices are used in a wide range of fields including mobile communication systems, monitors, and large televisions. Various performances are required in these fields, and various display modes have been developed. As the fundamental structure and principle, these liquid crystal display devices include a pair of substrates for interposing a liquid crystal layer therebetween; and control the transmission/shielding of light (on/off of the display) by appropriately applying a voltage to electrodes disposed on the liquid crystal layer side of at least one of the pair of substrates, and by controlling the alignment direction of liquid crystal molecules in the liquid crystal layer, thus achieving liquid crystal displays.
Examples of the display modes of recent liquid crystal display devices include a vertical alignment (VA) mode in which liquid crystal molecules having negative anisotropy of dielectric constant are aligned vertically to the substrate surface; and an in-plane switching (IPS) mode and a fringe field switching (FFS) mode in which liquid crystal molecules having positive or negative anisotropy of dielectric constant are aligned horizontally to the substrate surface, and a horizontal electric field is applied to the liquid crystal layer.
Herein, as a method of obtaining a high-luminance and high-speed response liquid crystal display device, alignment stabilization techniques using a polymer (hereinafter, also referred to as “polymer sustained (PS) treatment”) have been suggested (for example, see Patent Literatures 1 to 9). Among these, according to pre-tilt angle imparting techniques using a polymer (hereinafter, also referred to as “polymer sustained alignment (PSA) technique”), polymerizable components such as a polymerizable monomer and a polymerizable oligomer are mixed to obtain a liquid crystal composition, which is then sealed between the substrates; a voltage is applied between the substrates to tilt liquid crystal molecules; and the monomer is polymerized to form a polymer, with the liquid crystal molecules being tilted. This results in liquid crystal molecules that are tilted at a certain pre-tilt angle even after the voltage application is stopped, and thus the liquid crystal molecules can be aligned in a certain direction. Materials that are polymerizable by heat, light (ultraviolet light), and the like are selected as monomers to form a polymer.
According to another disclosed document, for example, one substrate was subjected to photo-alignment treatment and PS treatment and the other substrate was subjected to rubbing treatment, in a liquid crystal display device; and the influence of hysteresis and the like on the monomer concentration for PS treatment in liquid crystal were investigated (for example, see Non-Patent Literature 1).
The present inventors have been studying photo-alignment technique that allows the liquid crystal alignment direction to be controlled in multiple directions when a voltage is applied, without the need of rubbing treatment on an alignment film, and that provides excellent viewing angle characteristic. The photo-alignment technique is a technique of irradiating an alignment film, which is formed from a light-active material, with light such as ultraviolet light, and thereby causing the alignment film to have an alignment regulating force. According to the photo-alignment technique, since alignment treatment can be performed on a film surface in a non-contact manner, the occurrence of contaminants, dust and the like during alignment treatment can be suppressed. Additionally, unlike rubbing treatment, the photo-alignment technique can be suitably applied even to large panels, and can achieve excellent manufacturing yield.
The current photo-alignment technique has been adopted mainly for the mass production of televisions in which a vertical alignment film is used (for example, VA mode). The current photo-alignment technique has not been adopted for the mass production of televisions in which a horizontal alignment film is used (for example, IPS mode). This is because the use of a horizontal alignment film causes image sticking in a conspicuous manner. The image sticking is a phenomenon in which when the same amount of voltage is continuously applied for a certain period of time to a liquid crystal cell, brightness appears different between a portion where the voltage is continuously applied and a portion where the voltage is not applied.
The present inventors have found that forming a polymer layer stabilized by PS treatment is suitable to reduce the occurrence of image sticking caused by weak anchoring of the photo-alignment film. Therefore, it is important to promote polymerization to allow PS treatment. In addition, as described in Japanese Patent Application No. 2011-084755, a combination of a specific liquid crystal component with PS treatment process is suitable. This increases a polymer layer formation rate (i.e., the rate at which a polymer layer is formed, as a polymerizable monomer in the liquid crystal layer initiates chain polymerization such as radical polymerization, and the polymerized product is deposited on the surface on the liquid crystal layer side of the alignment film), and allows the formation of a polymer layer having a stable alignment regulating force (i.e., a PS layer). Further, the effect of reducing image sticking is particularly excellent when the alignment film is a horizontal alignment film because it increases the polymerization rate and the polymer layer formation rate.
Herein, for example, when PS treatment is performed in order to prevent image sticking in a horizontal electric field alignment mode such as an IPS mode or an FFS mode in which a horizontal photo-alignment film is used, alignment defects in the panel, if occurred, will be immobilized, leading to display defects. Among alignment defects, the occurrence of a string-like defect is particularly problematic. The string-like defect refers to a phenomenon that causes light leakage due to a string-like alignment defect in liquid crystal. The impacts of the light leakage on the quality of the liquid crystal display device are as follows: black appears grayish black; the contrast is poor; and the display becomes rough. None of the above-mentioned Patent Literatures 1 to 8 describes the horizontal photo-alignment film and the occurrence of a string-like defect caused by weak anchoring.
The importance of an object to reduce string-like defects is particularly significant when aiming to mass-produce liquid crystal display devices including a horizontal photo-alignment film having a weak alignment regulating force. It is considered to be a novel object in the technical field of the present invention.
For example, Patent Literature 9 mentioned above provides a liquid crystal display device having improved light transmittance, without decreasing the response speed when a change occurs in the gray scale. According to Embodiment 6-2 of Patent Literature 9, alignment defects occur due to the unevenness of the uneven reflective electrodes, and rubbing treatment fails to provide sufficient alignment treatment on the bottom of the uneven surface. In this respect, the occurrence of disclinations due to alignment disturbance can be suppressed by forming a polymer layer on the uneven reflective electrodes. However, this does not solve the problem of disclinations resulting from immobilization of alignment defects during PS treatment in the liquid crystal display device including a horizontal photo-alignment film having a weak alignment regulating force. Unfortunately, disclinations that occur before PS treatment are strongly immobilized as the disclinations by PS treatment. The technique disclosed in Non-Patent Literature 1 has a room for further improvement to suitably reduce disclinations that occur in display pixels due to PS treatment in the liquid crystal display device including a horizontal photo-alignment film.
The present invention is achieved in view of the current situation described above. It is an object of the present invention to provide a liquid crystal display panel and a liquid crystal display device having excellent display quality, with reduced string-like defects that occur in display pixels.
The present inventors conducted extensive studies and found that the above type of string-like defects occurs due to the following three factors. The first factor is weak anchoring of the alignment film itself. The present inventors found that weak anchoring of the alignment film results in a weak alignment regulating force, causing liquid crystal molecules in the bulk to easily stray from the direction in which the alignment film is treated. In other words, a method of increasing the anchoring strength of the alignment film itself is considered as a possible solution to the problem; however, usually, the anchoring energy of a horizontal photo-alignment film is remarkably small, compared to a horizontal alignment film to be rubbed. Thus, the approach to the problem by improving the properties of a material of the horizontal photo-alignment film has been difficult to apply. The second factor is a small elastic constant of liquid crystal. The present inventors found that when the elastic constant is small, liquid crystal molecules tend to undergo elastic deformation, and alignment disturbance is thus likely to occur. The string-like defect is considered to be an alignment defect resulting from splay deformation and/or bend deformation; thus, liquid crystal having a large elastic constant for splay deformation and bend deformation is considered to be less likely to produce alignment defects. The third factor is the presence of spacers. The present inventors found that a spacer is present at both ends of each string-like defect. For example, even when string-like defects occurred at the moment of phase transition from the isotropic phase to the liquid crystal phase, the string-like defects in the area where no spacer is present were observed to be unstable and disappear in a finite time. In other words, the spacer is considered to have an effect of stabilizing string-like defects, and the present inventors examined a method of destabilizing these defects.
For example, even when string-like defects occurred at the moment of phase transition from the isotropic phase to the liquid crystal phase, the string-like defects in the area where no spacer is present were observed to be unstable and disappear in a finite time. In other words, the spacer is considered to have an effect of stabilizing string-like defects, and the present inventors examined a method of destabilizing these defects.
Then, the present inventors found three suggestions for improvement. The first suggestion is as follows: a detailed analysis of the liquid crystal alignment of string-like defects under a polarizing microscope found that the deformation mode of liquid crystal mainly includes splay and bend deformations. The splay deformation is dominant at both ends of a string-like defect (i.e., around a spacer such as a bead), and the splay and bend deformations are dominant in the internal portion of a string-like defect. Thus, an increase in the energy of the alignment deformation leads to destabilization of string-like defects. It is therefore important to increase an elastic constant K1 (splay) and/or an elastic constant K3 (bend) of liquid crystal. The present inventors have already filed an application relating to the first suggestion in Japanese Patent Application No. 2011-051532.
The second suggestion for improvement is to increase the film thickness of the horizontal alignment film because a larger film thickness leads to a smaller exposed area of the photospacer, and this is considered to destabilize string-like defects. The third suggestion for improvement is to form a groove between the spacers to confine a string-like defect in the groove, which is then shielded by the BM or the like. In this way, the present inventors found that the above problem can also be successfully solved by the second and third suggestions for improvement, and thus accomplished the present invention.
That is, a first embodiment of the present invention relates to a liquid crystal display panel including a pair of substrates, and a liquid crystal layer interposed between the pair of substrates, wherein at least one of the pair of substrates includes a photo-alignment film, the photo-alignment film aligns liquid crystal molecules horizontally to a main surface of the at least one of the pair of substrates, and the photo-alignment film has a film thickness of 50 nm or more.
The photo-alignment film aligns the liquid crystal molecules horizontally to the main surface of the at least one of the pair of substrates (the photo-alignment film as used herein is also referred to as “horizontal photo-alignment film”). The horizontal photo-alignment film is not limited as long as it aligns at least liquid crystal molecules adjacent thereto, substantially horizontally to the surface of the horizontal photo-alignment film.
A second embodiment of the present invention relates to a liquid crystal display panel including a pair of substrates, and a liquid crystal layer interposed between the pair of substrates, wherein at least one of the pair of substrates includes a photo-alignment film, the photo-alignment film aligns liquid crystal molecules horizontally to a main surface of the at least one of the pair of substrates, the liquid crystal display panel includes photospacers between the pair of substrates, the photospacers are disposed on the at least one of the pair of substrates and project toward the liquid crystal layer, and the at least one of the pair of substrates includes a groove disposed in at least a portion of the area between the photospacers.
Both the first and second embodiments of the present invention can suitably solve the problem of the occurrence of string-like defects in a structure having such a problem. In this respect, these embodiments at least have common or closely related technical significance of the present invention, and these embodiments are considered to have the same or corresponding special technical feature.
Hereinafter, features common to the first and second embodiments of the present invention and preferred features thereof are described in detail. Specifically, the features described below are suitably applicable to both the first and second embodiments of the present invention described above, as long as the effects of the present invention are achieved.
Preferably, the at least one of the pair of substrates further includes a polymer layer on the liquid crystal layer side of the horizontal photo-alignment film. The horizontal photo-alignment film preferably has a film thickness of 85 nm or more. The horizontal photo-alignment film particularly preferably has a film thickness of 125 nm or more. An increase in the film thickness further improves the effect of reducing string-like defects of the present invention. It also results in a good voltage holding ratio, suppresses defects in the alignment film, and provides a good yield. The horizontal photo-alignment film preferably has a film thickness of 200 nm or less. This results in a sufficient reduction in the unevenness of coating (including coating by printing and inkjet) on the alignment film. It can also sufficiently prevent image sticking caused by residual DC. The film thickness of the horizontal photo-alignment film can be determined by measuring the film thickness at an opening of a pixel. When the film thickness varies depending on the type of the substrate (an array substrate or a counter substrate) or when the film thickness varies depending on the position in an opening of a pixel, the portion having the largest film thickness is regarded as the film thickness of the horizontal photo-alignment film.
The spacers may be disposed by being dispersed or the like. Preferably, the spacers are photospacers disposed on the at least one of the pair of substrates and project toward the liquid crystal layer. The spacers disposed on the substrate(s) in advance are usually formed of resin. The spacers disposed by being dispersed or the like are usually formed of glass or plastic. The above spacers are preferably those formed of resin, disposed on the substrate(s). More preferably, the resin is acrylic resin. Examples of the shape of each spacer include cylinder, prism, truncated cone, and sphere. Cylinder, prism, and truncated cone are preferred. The spacer may be coated with the horizontal photo-alignment film. The spacer is regarded as being coated with the horizontal photo-alignment film, as long as at least a portion of the spacer in contact with the liquid crystal layer (usually, a lateral side) is coated with the horizontal photo-alignment film. The substrate on which the spacers are disposed is preferably a counter substrate (color filter substrate). For example, the film thickness of the horizontal photo-alignment film included in the counter substrate including the spacers is preferably larger than that of the horizontal photo-alignment film included in a thin film transistor array substrate including no spacers.
Each of the photospacers preferably has a diameter of 14 μm or less as measured on the base (the surface in contact with the at least one of the pair of substrates) in order to more sufficiently achieve the effects of the present invention. The diameter is more preferably 12 μm or less. The diameter of the base is described later.
At least one of the pair of substrates included in the liquid crystal display panel of the present invention includes a polymer layer and a horizontal photo-alignment film, for example, in the stated order from the liquid crystal layer side. Preferably, the other one of the pair of substrates included in the liquid crystal display panel of the present invention includes a polymer layer, a horizontal photo-alignment film, and an electrode in the stated order from the liquid crystal layer side. A different layer may be present between the polymer layer and the horizontal photo-alignment film and/or between the horizontal photo-alignment film and the electrode. As long as the effects of the present invention are achieved, another layer may be provided between the polymer layer and the horizontal photo-alignment film, and/or between the horizontal photo-alignment film and the electrode. Usually, the polymer layer and the horizontal photo-alignment film are in contact with each other. In addition, preferably, each of the pair of substrates includes the horizontal photo-alignment film and the polymer layer. Preferably, the at least one of the pair of substrates further includes a linear electrode.
The horizontal photo-alignment film of the present invention is preferably, but not limited to, an alignment film having a property of aligning liquid crystal molecules adjacent thereto in a certain direction. The horizontal photo-alignment film also encompasses a film on which alignment treatment or the like is not performed and thus has no alignment property. In other words, the present invention is applicable to: polymer stabilization treatment to extend the BP temperature range in a polymer-stabilized blue phase (BP) display device in which alignment treatment is not required in the first place; a process for partially polymerizing a liquid crystal layer in a polymer dispersed liquid crystal (PDLC) display device; and other various applications. Specifically, the present invention is not only applicable to PS treatment to prevent image sticking, but is also applicable to other applications that require the formation of a polymer from a polymerizable monomer in a liquid crystal layer, as long as the present invention is a liquid crystal display panel including a polymer layer. Photo-alignment treatment is preferred as a method of performing alignment treatment because the effects of the present invention will be more significant, and excellent viewing angle characteristic can be obtained. Alignment treatment may also be performed by rubbing or the like.
The horizontal photo-alignment film achieves photo-alignment treatment that imparts an alignment property to the substrate surfaces through light irradiation with certain conditions. Hereinafter, a polymer film having a property of controlling the alignment of liquid crystal through photo-alignment treatment is also referred to as “photo-alignment film”.
A polymer constituting the horizontal photo-alignment film is preferably polysiloxane, polyamide acid, or polyimide, in terms of heat resistance.
The photo-alignment film is a polymer film having anisotropy induced by polarized or non-polarized light irradiation and having a property of imparting an alignment regulating force to liquid crystal. More preferably, the horizontal photo-alignment film is a photo-alignment film on which photo-alignment treatment is performed by ultraviolet light, visible light, or both of them. The size of the pretilt angle that is imparted to the liquid crystal molecules by the photo-alignment film can be adjusted by the type of light, light irradiation time, irradiation direction, irradiation intensity, type of photofunctional groups, and the like. It should be noted that because the alignment is immobilized by the formation of the polymer layer, there is no need to prevent ultraviolet light or visible light from entering the liquid crystal layer after the production process, and thus the range of selection of the production processes is broadened. In addition, when the horizontal photo-alignment film having a property of aligning liquid crystal molecules vertically to irradiated polarized light is irradiated with p-polarized light in a normal direction of the substrate or in an oblique direction to the substrate, the pretilt angle is 0°.
The photoactive material is preferably a material of the photo-alignment film. The material of the photo-alignment film may be a single polymer or a mixture containing other molecules as long as the material has the property described above. For example, the material may also be a mixture obtained by adding other low molecular weight molecules such as additives or other photo-inactive polymers to a polymer containing a functional group having photo-alignment ability. As the material of the photo-alignment film, a material which induces photodissociation, photoisomerization, or photodimerization is selected. Generally, photoisomerization and photodimerization allow alignment at a longer wavelength with a smaller exposure dose and thus exhibit excellent mass productivity, compared to photodissociation. Representative materials that induce photoisomerization or photodimerization include azobenzene derivatives, cinnamoyl derivatives, chalcone derivatives, cinnamate derivatives, coumarin derivatives, diarylethene derivatives, stilbene derivatives, and anthracene derivatives. The material for photoisomerization or photodimerization is preferably a cinnamate group or a derivative thereof. The benzene ring that is present in these functional groups may be a heterocyclic ring. A representative material that induces photodissociation is a material including a cyclobutane skeleton in a repeating unit. Examples thereof include polyimide including a cyclobutane ring.
The horizontal photo-alignment film may be a horizontal photo-alignment film irradiated with ultraviolet light from the outside of the liquid crystal cell. In this case, when the horizontal photo-alignment film is formed through photo-alignment treatment, and the polymer layer is formed through photopolymerization, it is preferred that the horizontal photo-alignment film and the polymer layer be simultaneously formed by using the same light. This provides a liquid crystal display panel with high production efficiency.
The polymer layer of the present invention is preferably a polymerized product of a monomer contained in the liquid crystal layer. In other words, the polymer layer is preferably the PS layer described above. The transfer of the excitation energy from the alignment film to the monomer when the horizontal photo-alignment film is irradiated with light is more efficiently performed in a horizontal alignment film than in a vertical alignment film. Thus, it is possible to form a more stable PS layer in the present invention. Usually, the PS layer controls the alignment of liquid crystal molecules adjacent thereto. A polymerizable functional group of the monomer is preferably at least one selected from the group consisting of acrylate, methacrylate, vinyl, vinyloxy, and epoxy groups. Among these, an acrylate group and/or a methacrylate group is more preferred. These polymerizable functional groups are highly likely to produce radicals, and are effective in reducing manufacturing cycle time. In addition, the monomer preferably includes at least two polymerizable functional groups because the reaction efficiency is higher when the number of polymerizable functional groups is larger. Further, an upper limit of the number of polymerizable functional groups in the monomer is preferably four, so that the molecular weight is sufficiently reduced and the monomer can thus be easily dissolved in liquid crystal. In addition, the monomer is preferably a monomer that initiates polymerization by light irradiation (i.e., photopolymerization) or a monomer that initiates polymerization by heating (i.e., thermal polymerization). In other words, the polymer layer is preferably formed by photopolymerization or thermal polymerization. Photopolymerization is particularly preferred because the polymerization reaction can be easily initiated at normal temperature. The light used for photopolymerization is preferably ultraviolet light, visible light, or a combination thereof.
In the present invention, the type of polymerization reaction to form the PS layer is not particularly limited, and examples thereof include step-growth polymerization in which a bifunctional monomer is polymerized stepwise while forming a new bond; and chain polymerization in which a monomer is sequentially bonded to active species generated from a small amount of catalyst (initiator) and are grown in a chain reaction. Examples of the step-growth polymerization include polycondensation and polyaddition. Examples of the chain polymerization include radical polymerization and ionic polymerization (for example, anionic polymerization and cationic polymerization).
The polymer layer improves the alignment regulating force of the horizontal photo-alignment film on which alignment treatment has been performed, and can reduce the occurrence of image sticking in display. In addition, in the case where a voltage of a threshold or higher is applied to the liquid crystal layer to polymerize a monomer in a state where liquid crystal molecules are aligned at a pre-tilt angle so as to form a polymer layer, the thus-obtained polymer layer includes a structure that allows the liquid crystal molecules to be aligned at a pre-tilt angle with respect to the polymer layer.
The pair of substrates included in the liquid crystal display panel of the present invention is used for interposing a liquid crystal layer therebetween. Each substrate is produced by, for example, forming a wiring, an electrode, a color filter, and the like on an insulating substrate as a base formed of glass, resin, or the like.
The liquid crystal molecules in the liquid crystal layer of the present invention may include a mixture of plural kinds of liquid crystal molecules. The liquid crystal layer may be a mixture of plural kinds of liquid crystal molecules for at least one of the following purposes: ensuring reliability; improving the response speed; and adjusting the liquid crystal phase temperature range, other elastic constants, anisotropy of dielectric constant, and refractive index anisotropy. In the case where the liquid crystal molecules in the liquid crystal layer include a mixture of plural kinds of liquid crystal molecules, the liquid crystal molecules as a whole must be designed to have an elastic coefficient of the present invention. In addition, the liquid crystal molecules in the liquid crystal layer may have either positive anisotropy of dielectric constant (positive type) or negative anisotropy of dielectric constant (negative type).
The alignment mode of the liquid crystal layer is preferably an alignment mode in which a horizontal alignment film can be used. Preferred examples thereof include in-plane switching (IPS), fringe field switching (FFS), optically compensated birefringence (OCB), twisted nematic (TN), super twisted nematic (STN), ferroelectrics liquid crystal (FLC), anti-ferroelectrics liquid crystal (AFLC), polymer dispersed liquid crystal (PDLC), and polymer network liquid crystal (PNLC) modes. Among these, the IPS, FFS, FLC, and AFLC modes are more preferred, and the IPS and FFS modes are still more preferred. In addition, a blue phase mode in which the formation of an alignment film is unnecessary is also preferred as the above alignment mode. Further, a mode in which the at least one of the pair of substrates includes a multi-domain structure for improving viewing angle characteristic is also preferred as the above alignment mode. The multi-domain structure refers to a structure including plural areas in which the liquid crystal molecules have different alignment forms (for example, in terms of bend directions in the OCB mode or twist directions in the TN and STN modes) or different alignment directions during either or both voltage application and non-voltage application. Forming the multi-domain structure actively requires patterning of an electrode into an appropriate form, and/or irradiation of a photoactive material with light using a photomask or the like.
As described above, the present invention is suitably applicable for display devices having excellent viewing angles such as an IPS mode or an FFS mode. A technique that provides good viewing angles is required in applications such as medical monitors, electronic books, smartphones, and the like.
The photospacers are regularly disposed in the non-display area of the liquid crystal display panel. The liquid crystal layer in at least a portion of the area between the photospacers is preferably thicker than the liquid crystal layer in the display area of the liquid crystal display panel. For example, the at least one of the pair of substrates preferably includes a groove disposed in at least a portion of the area between the photospacers. As a result of the formation of a groove as described above so as to increase the thickness of the liquid crystal layer between the adjacent photospacers, a string-like defect will be formed along the groove between the photospacers (under the black matrix), and this allows to reduce the number of string-like defects in the display pixels. The reason for the above phenomenon is considered as follows: 1) the elastic energy density of a string-like defect decreases in the groove; and 2) the horizontal photo-alignment film flows into the groove formed, and thus the alignment film surface of the horizontal photo-alignment film becomes less flat on the groove, reducing the anchoring energy of the alignment film on the groove and therefore allowing a string-like defect to be stably present in the groove. The groove may be formed not only in the substrate including the photospacers but also in the counter substrate.
Preferably, an electrode is disposed on a lateral side and base of the groove, and the groove is a contact hole for connecting the electrodes in layers above and below an interlayer insulation film including the groove to the same potential. The contact hole formed as described above also results in an increased thickness of the liquid crystal layer in a portion where the contact hole is formed between the adjacent photospacers, compared to the thickness of the liquid crystal layer in the active area. Consequently, a string-like defect is pulled to the portion where the contact hole is formed between the photospacers (under the black matrix), thus reducing the number of string-like defects that occur in the display pixels.
The present invention further provides a liquid crystal display panel including a pair of substrates and a liquid crystal layer interposed between the pair of substrates, wherein at least one of the pair of substrates includes: a polymer layer and a horizontal photo-alignment film in the stated order from the liquid crystal layer side; several photospacers; and a groove disposed in at least a portion of the area between the photospacers. Other constituent members of the liquid crystal display panel of the present invention are the same as those of the liquid crystal display panel of the present invention described above, and preferred embodiment of thereof are also the same as those of the liquid crystal display panel of the present invention described above.
The present invention also provides a liquid crystal display device including the liquid crystal display panel of the present invention. Preferred embodiments of the liquid crystal display panel included in the liquid crystal display device of the present invention are the same as those of the liquid crystal display panel of the present invention described above. In one preferred embodiment of the present invention, the liquid crystal display device of the present invention is a liquid crystal display device of an IPS mode. In another preferred embodiment of the present invention, the liquid crystal display device of the present invention is a liquid crystal display device of an FFS mode. The liquid crystal display device of an IPS mode is a liquid crystal display device of a horizontal electric field mode in which, usually, one of the pair of substrates includes two types of electrodes, which are opposed to each other when the main surface of the substrate is viewed in plane. In addition, the liquid crystal display device of an FFS mode is a liquid crystal display device of a fringe electric field mode in which, usually, one of the pair of substrates includes a planar electrode, and a slit electrode disposed in a layer different from a layer including the planar electrode, with an insulation layer between these layers. These liquid crystal display devices are described in further detail in embodiments.
As long as the above-described constituent elements are included as essential elements, the liquid crystal display panel and the liquid crystal display device of the present invention are not particularly limited by other constituent elements, and may appropriately include other elements that are commonly included in liquid crystal display panels and liquid crystal display devices.
Each of the embodiments described above may be appropriately combined without departing from the scope of the present invention.
The present invention provides a liquid crystal display panel and a liquid crystal display device having excellent display quality, with reduced string-like defects that occur in display pixels. When the present invention is applied to, for example, a liquid crystal display device of an IPS mode or an FFS mode including a photo-alignment film, an excellent viewing angle is achieved owing to the properties of a photo-alignment film, and the effect of reducing image sticking is also achieved at the same time.
Hereinafter, the present invention is described in further detail by explaining embodiments with reference to the drawing, but it not limited to these embodiments. The term “pixel” as used herein may refer to a subpixel, unless otherwise specified. In addition, the substrate including a thin film transistor element is also referred to as a TFT substrate, and a color filter substrate is also referred to as a CF substrate. In the embodiments, string-like defects were measured by observing every pixel of a panel prepared, under a polarizing microscope. Members and parts having the same functions are denoted by the same reference numerals except for the hundred's digit throughout the embodiments, unless otherwise specified. The terms “or more” and “or less” as used herein are inclusive. In other words, the term “or more” means “greater than and equal to” the value specified.
The TFT substrate 10 also includes an alignment film (horizontal photo-alignment film) 16, and the counter substrate 20 also includes an alignment film (horizontal photo-alignment film) 26d. The alignment films 16 and 26d are films mainly including polyimide, polyamide, polyvinyl, polysiloxane, and the like. Forming these alignment films allows liquid crystal molecules to be aligned in a certain direction. Each of these horizontal photo-alignment films preferably includes a photoreactive functional group that can undergo photoisomerization or photodimerization. It is more preferred that a photoisomerizable functional group be included. Examples of the photoisomerizable functional group include cinnamate, azo, chalcone, and stilbene groups. Among these, a cinnamate group is preferred. In other words, it is particularly preferred that the horizontal photo-alignment films each include a functional group having a cinnamate derivative.
The alignment film 16 included in the TFT substrate 10 has a film thickness of 75 nm in the active area. The alignment film 26d included in the counter substrate 20 has a film thickness of 85 nm in the active area. The alignment film 26d included in the counter substrate 20 is formed to have a larger film thickness as described above so as to reduce the exposed area of each photospacer 29, thereby destabilizing string-like defects. In addition, each photospacer 29 formed on the counter substrate 20 has a diameter of 12 μm as measured on the bottom (base) thereof.
Prior to a PS polymerization process, the liquid crystal layer 30 contains a polymerizable monomer. The polymerizable monomer initiates polymerization by the PS polymerization process to form PS layers 17 and 27 on the alignment films 16 and 26d, respectively, as shown in
The PS layers 17 and 27 can be formed by injecting a liquid crystal composition containing a liquid crystal material and a polymerizable monomer into a gap between the TFT substrate 10 and the counter substrate 20, and by irradiating the liquid crystal layer 30 with a certain amount of light or applying heat thereto to polymerize the polymerizable monomer. At this time, the polymerization is performed in a state where no voltage or a voltage less than the threshold is applied to the liquid crystal layer 30 so as to form the PS layers 17 and 27 that are aligned with the initial alignment of the liquid crystal molecules. As a result, the PS layers 17 and 27 each having a higher alignment stability can be achieved. A polymerization initiator may be added to the liquid crystal composition, if necessary.
The liquid crystal display panel according to Embodiment 1 includes the TFT substrate 10, the liquid crystal layer 30, and the counter substrate 20, which are laminated in the stated order from a back surface to an observation surface side of the liquid crystal display device. Linear polarizing plates 18 and 28 are disposed on the back surface side of the TFT substrate 10 and the observation surface side of the counter substrate 20, respectively. Each of these linear polarizing plates 18 and 28 may further be provided with a retarder, and may be a circularly polarizing plate.
The liquid crystal display panel according to Embodiment 1 may include a color-filter-on-array structure in which a color filter is disposed on the TFT substrate 10 instead of on the counter substrate. The liquid crystal display panel according to Embodiment 1 may also be a monochrome display device or a field sequential color device. In that case, the color filter is unnecessary.
The liquid crystal layer 30 is filled with a liquid crystal material having a property of being aligned in a specific direction when a certain voltage is applied thereto. The alignment of liquid crystal molecules in the liquid crystal layer 30 is controlled by the application of a threshold or higher voltage.
In
Hereinafter, an example of actual production of the liquid crystal display panel according to Embodiment 1 is described.
A 10-inch IGZO-TFT substrate including an FFS structure, and a color filter as a counter substrate were provided, and a polyvinyl cinnamate solution was applied to both substrates by spin coating. The IGZO-TFT substrate is a thin film transistor array substrate in which indium gallium zinc complex oxide is used as a semiconductor. In addition, the width L of the slit electrode on the upper layer was 3 μm, and the distance between the linear portions of the electrode (slit width S) was 5 μm (L/S=3 μm/5 μm). The polyvinyl cinnamate solution was prepared by dissolving 3% by weight of polyvinyl cinnamate in a solvent obtained by mixing N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether in equal amount. After application by spin coating, the alignment film was temporarily dried at 100° C. for 1 minute, and then baked at 215° C. for 40 minutes while purging nitrogen gas.
As described above, the alignment film (the uppermost layer) on the transparent electrode on the TFT has a film thickness of 75 nm in the active area. The alignment film on the CF has a film thickness of 85 nm in the active area. The diameter of the photospacer formed on the CF is 12 μm, as measured on the bottom (base).
The bottom diameter (diameter as measured on the bottom (base)) of the PS is now described.
These substrates were irradiated with linearly polarized ultraviolet light having a wavelength of 313 nm and an intensity of 5 J/cm2 from the normal direction of the substrates for liquid crystal alignment treatment. The angle formed between the direction of the slit of the electrode formed of ITO and the polarization direction is 10°.
Next, a thermosetting seal (HC1413FP: manufactured by Mitsui Chemicals, Inc.) was printed on the TFT substrate by using a screen plate. The height of each photospacer is set such that the liquid crystal layer in the active area has a thickness of 3.5 μm. These two kinds of substrates were bonded to each other such that the polarization direction of irradiated ultraviolet light is consistent between the substrates. Next, the bonded substrates were heated at 130° C. for 60 minutes in a nitrogen-purged furnace while applying a pressure of 0.5 kgf/cm2 thereto, and the seal was thus cured.
Liquid crystal was injected under vacuum into a panel produced by above-described method. In the present embodiment, a mixture, which was obtained by adding 5% by weight of trans-4-propyl-4′-vinyl-1,1′-bicyclohexane to 100% by weight of MLC-6610 (manufactured by Merck KGaA) and by further adding 1% by weight of biphenyl-4,4′-diyl bis(2-methylacrylate) as a polymerizable additive thereto, was used as the liquid crystal. An inlet of a cell through which the liquid crystal was injected was sealed with an epoxy adhesive (ARALDITE AR-S30, manufactured by NICHIBAN Co., Ltd.). At this time, the electrodes were short-circuited and the charge removing on the glass surface was performed so that the liquid crystal alignment would not be disturbed by an external electric field. Next, in order to remove the liquid crystal flow alignment and to simulate the curing of the seal in the one drop fill (ODF) process during mass production, the panel was heated at 130° C. for 40 minutes to transform liquid crystal into the isotropic phase for realignment treatment. As a result, an FFS liquid crystal panel in which the liquid crystal molecules were uniaxially aligned in a direction perpendicular to the polarization direction of ultraviolet light with which the alignment films were irradiated was obtained. All the processes were performed under yellow fluorescent light to prevent the liquid crystal panel from being exposed to ultraviolet light emitted from a fluorescent lamp.
The panel was further heated at 130° C. for 40 minutes immediately before PS treatment to carefully remove charge.
Subsequently, in order to perform PS treatment on this panel, the panel was irradiated with ultraviolet light (1.5 J/cm2) by using a black light unit (FHF32BLB, manufactured by TOSHIBA Corporation). As a result, biphenyl-4,4′-diyl bis(2-methylacrylate) was polymerized.
Four liquid crystal display panels of the same type were produced by the method described above. String-like defects occurred in only one of these panels.
The liquid crystal display device including the above-described liquid crystal display panel of Embodiment 1 may further appropriately include other members (for example, light source such as a back light) that are included in common liquid crystal display devices. The liquid crystal display device of Embodiment 1 is suitably applicable to TV panels, digital signage, medical monitors, electronic books, PC monitors, portable terminal panels, and the like. Liquid crystal display panels according to the later-described embodiments are also applicable in the same manner.
The type of the liquid crystal display device according to Embodiment 1 may be any of transmissive type, reflective type, and reflective-transmissive combination type. In the case of the transmissive or reflective-transmissive combination type, the liquid crystal display device of Embodiment 1 includes a back light. The back light is disposed on the back surface side of the liquid crystal cell such that the light is transmitted through the TFT substrate 10, the liquid crystal layer 30, and the counter substrate 20 in the stated order. In the case of the refractive or reflective-transmissive combination type, the TFT substrate 10 includes a reflector to reflect outside light. In addition, the polarizing plate on the counter substrate 20 must be a circularly polarizing plate at least in the area where the reflected light is used as display light.
The liquid crystal display device according to Embodiment 1 is disassembled, and the collected liquid crystal is enclosed in a cell. In this way, the elastic constant can be measured by using EC-1 manufactured by TOYO Corporation. The measurement temperature is 20° C. In addition, a chemical analysis using gas chromatograph mass spectrometry (GC-MS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the like can be carried out to analyze the components of a horizontal photo-alignment film and the components in the polymer layer. Furthermore, the cross-sectional shape of a liquid crystal cell containing an alignment film and a PS layer can be confirmed by microscopic observation using a scanning transmission electron microscope (STEM), a scanning electron microscope (SEM), or the like.
In Embodiment 2, four liquid crystal display panels were produced in the same manner as in Embodiment 1 except that the film thickness of the alignment film on the CF substrate was 50 nm in the active area. String-like defects occurred in two panels.
In Embodiment 3, four liquid crystal display panels were produced in the same manner as in Embodiment 1 except that the film thickness of the alignment film on the CF substrate was 125 nm in the active area. String-like defects did not occur in any of these panels.
In Embodiment 4, four liquid crystal display panels were produced in the same manner as in Embodiment 1 except that the baking temperature of alignment film was changed from 215° C. to 200° C. String-like defects occurred in two panels.
In Embodiment 5, four liquid crystal display panels were produced in the same manner as in Embodiment 1 except that the temporary drying temperature of alignment film was changed from 100° C. to 80° C. String-like defects occurred in two panels.
In Embodiment 6, eight liquid crystal display panels were produced in the same manner as in Embodiment 1 except that the diameter of the bottom (base) of each photospacer formed on the CF substrate was changed from 12 μm to 14 μm. String-like defects occurred in four panels.
In Embodiment 7, eight liquid crystal display panels were produced in the same manner as in Embodiment 1 except that the diameter of the bottom (base) of each photospacer formed on the CF substrate was changed from 12 μm to 17 μm. String-like defects occurred in five panels.
In Embodiment 8, eight liquid crystal display panels were produced in the same manner as in Embodiment 1 except that the diameter of the bottom (base) of each photospacer formed on the CF substrate was changed from 12 μm to 9 μm. String-like defects occurred in only one panel.
The points of the invention include the following: (1) the alignment film on the substrate on which the photospacers are formed preferably has a film thickness of 125 nm or more (Embodiments 1 to 3); (2) the baking temperature of the alignment film is preferably 215° C. or higher (this is considered to increase the alignment regulating force) (Embodiments 1 and 4); (3) the temporary drying temperature of the alignment film is preferably 100° C. or higher (instant evaporation of the solvent prevents the alignment film from flowing down the photospacers) (Embodiments 1 and 5); and (4) it is particularly preferred that the diameter of each photospacer be 12 μm or less (this reduces the non-aligned area and suppresses the occurrence of disclinations) (Embodiments 1 and 6 to 8).
The alignment film on the substrate on which the photospacers are formed has a film thickness of 50 nm or more, preferably 85 nm or more, and more preferably 125 nm or more. This makes the effects of the present invention more significant; provides a good voltage holding ratio; suppresses the occurrence of alignment film defects; and improves yield. In addition, the alignment film on the substrate on which the photospacers are formed preferably has a film thickness of 200 nm or less. This can sufficiently reduce the unevenness of coating (including coating by printing and inkjet) on the alignment film. It can also sufficiently prevent image sticking caused by residual DC.
Embodiment 9 solves a problem of string-like defects that extend into the active area (non-shielded display area). In other words, the present inventors focused on the confinement of disclinations under the BM to reduce the number of string-like defects that occur in the display pixels, and arrived at the idea of forming a groove between each photospacers to solve the problem. Combination of the constitution of each embodiment described above and the constitution including a groove between each photospacers can achieves a significant reduction of string-like defects that occur in the display pixels. Even if the alignment film has a film thickness of less than 50 nm, the constitution including a groove between each photospacers can achieve the effect of reducing string-like defects.
In the case of a liquid crystal display panel in which the liquid crystal layer in the active area has a thickness of 3.5 μm whereas the liquid crystal layer between the photospacers (between the photospacers along the gate wiring) has a thickness of 2.5 μm, a string-like defect (disclination) extends into the active area as shown in
In Embodiment 10, a contact hole (CH) was formed between a photospacer 429a and a photospacer 429b along a gate bus line G, and also between a photospacer 429c and a photospacer 429d along the gate bus line G in the IGZO-TFT substrate. The CH is a kind of a groove as described herein, and has an electrode on its lateral side and base, and is used for connecting electrodes in layers above and below the interlayer insulation film including the CH to the same potential. The CH has a depth of 2 μm. The liquid crystal layer in the active area has a thickness of 3.5 μm, whereas the liquid crystal layer in the CH portion has a thickness of 4.0 μm. The alignment film in the CH portion has a film thickness of 500 nm. For example, a string-like defect 434 between the photospacer 429c and photospacer 429d is pulled by the CH where the liquid crystal layer is thick, and the string-like defect 434 is thus hidden under the BM. As a result, no string-like defect is observed. Although the CH was formed between the photospacers along the gate bus line G in the present embodiment, the CH may be formed between the photospacers along a source bus line S.
In Embodiment 10, the diameter of each photospacer is 14 μm; the pixel pitch in the gate direction is 30 μm; and the diameter of each contact hole is 8 μm. The pixel pitch in the gate direction is preferably 40 μm or less for making the effects of the present invention more significant. The diameter of each contact hole is preferably 3 to 10 μm. Other elements of Embodiment 10 are the same as those of Embodiment 1.
In
The pair of combteeth electrodes 513 is formed such that, as shown in
Other elements of the modified example of the present embodiment may be the same as those of each embodiment described above. The advantageous effects of the present invention can also be achieved by such liquid crystal display panel of an IPS mode. The present invention is also applicable to liquid crystal display panels of other modes such as an FLC, AFLC modes.
In the liquid crystal display devices of a PS-FFS (PS-treated FFS) mode of Embodiments 1 to 9 described above and the liquid crystal display device of a PS-IPS (PS-treated IPS) mode of the modified example of the present embodiment, alignment of liquid crystal molecules by photo-alignment is more preferred than alignment thereof by rubbing because it can suppress the alignment unevenness and the generation of dust. Photo-alignment is further preferred because it does not cause a pretilt in liquid crystal, unlike rubbing, and provides good viewing angle characteristic. However, because the horizontal photo-alignment film generally has a weak alignment regulating force, severe image sticking is observed, which makes mass production difficult. (Herein, the horizontal photo-alignment film refers to the horizontal alignment film that is also a photo-alignment film. It aligns liquid crystal molecules substantially horizontally to the substrate; contains a functional group that causes photoisomerization, photodimerization, photodissociation in molecules of the alignment film by light irradiation; and is also capable of aligning the liquid crystal molecules by polarized light irradiation.) Thus, the present inventors solved this problem through PS (polymer sustained) treatment. However, the horizontal photo-alignment film, in particular, can be a factor that causes string-like defects because of its weak alignment regulating force. The present inventors successfully solved this problem by selecting a suitable direction of liquid crystal alignment. Thus, it is considered that the present invention also provides a very simple method of achieving photo-aligned IPS liquid crystal device.
In the actual usage, in the case of an application that involves exposure to visible light (for example, in the case of a liquid crystal TV), the use of visible light for alignment treatment of the photo-alignment film should be avoided as much as possible. However, in the embodiments described above, the alignment film surface is covered by the PS layer as a result of PS treatment, and the alignment is thus immobilized. This is advantageous in that a material whose sensitivity wavelength includes a visible light wavelength range may be used as the material of the photo-alignment film.
Conventionally, an ultraviolet absorption layer needed to be provided in order to prevent exposure to weak ultraviolet light from a back light and the surrounding environment, even when the sensitivity wavelength of the material of the photo-alignment film included an ultraviolet wavelength range. In this respect, the present invention provides another advantage in that the PS process eliminates the need to provide an ultraviolet absorption layer.
When PS treatment is performed by using ultraviolet light, the voltage holding ratio (VHR) may decrease due to irradiation of liquid crystal with ultraviolet light. However, efficient PS treatment as in the embodiments described above can reduce the ultraviolet irradiation time, and a decrease in the voltage holding ratio can thus be avoided.
In addition, the PS exposure dose (time) can be decreased because of reduced image sticking. In the production of liquid crystal panels, a decrease in the exposure dose (time) results in an increase in the throughput. Furthermore, because the irradiation apparatus can be made smaller, it leads to a reduction in the capital investment.
The irradiation of linearly polarized ultraviolet light for photo-alignment treatment in the above-described embodiments is performed before the bonding of the pair of substrates. However, the pair of substrates may be bonded first, and then photo-alignment treatment may be performed from the outside of the liquid crystal cell. It does not matter whether photo-alignment treatment is performed before or after liquid crystal filling; however, when photo-alignment treatment by irradiation of linearly polarized ultraviolet light is performed after liquid crystal filling, it makes it possible to simultaneously perform photo-alignment treatment and the PS process, which advantageously reduces the process time.
The polymer layer of the present embodiment may be a polymerized product of a monomer polymerizable by irradiation of visible light. The monomer used for the formation of the polymer layer of the present invention can be confirmed by confirming the molecular structure of the monomer unit in the polymer layer of the present invention.
The polymer layer is preferably a polymerized product of a monomer polymerizable by light irradiation. In particular, the polymer layer is preferably formed by polymerization of a monomer polymerizable by ultraviolet irradiation.
Hereinafter, a preferred monomer of the present invention is described in detail.
The polymer layer is also preferably formed by polymerization of a monomer including a monofunctional or polyfunctional polymerizable group including at least one kind of ring structure. Examples of the monomer include compounds represented by the following chemical formula (1):
[Chem. 1]
P1—Sp1—R2-A1-(Z-A2)m-R1 (1)
In the formula, R1 represents a —R2—Sp1—P1 group, a hydrogen atom, a halogen atom, a —CN group, an —NO2 group, an —NCO group, an —NCS group, an —OCN group, an —SCN group, an —SF5 group, or a C1 to C12 linear or branched alkyl group. P1 represents a polymerizable group. Sp1 represents a C1 to C6 linear, branched, or cyclic alkylene group or alkyleneoxy group, or a direct bond. A hydrogen atom in R1 may be substituted with a fluorine atom or a chlorine atom. A —CH2— group in R1 may be substituted with an —O— group, an —S— group, an —NH— group, a —CO— group, a —COO— group, an —COO— group, an —O—COO— group, an —OCH2— group, a —CH2O— group, an —SCH2— group, a —CH2S— group, an —N(CH3)— group, an —N(C2H5)— group, an —N(C3H7)— group, an —N(C4H9)— group, a —CF2O— group, an —OCF2— group, a —CF2S— group, an —SCF2— group, an —N(CF3)— group, a —CH2CH2— group, a —CF2CH2— group, a —CH2CF2— group, a —CF2CF2— group, a —CH═CH— group, a —CF═CF— group, a —C≡C— group, a —CH═CH—COO— group, or an —OCO—CH═CH— group, as long as an oxygen atom and a sulfur atom are not adjacent to each other. R2 represents an —O— group, an —S— group, an —NH— group, a —CO— group, a —COO— group, an —OCO— group, an —O—COO— group, an —OCH2— group, a —CH2O— group, an —SCH2— group, a —CH2S— group, an —N(CH3)— group, an —N(C2H5)— group, an —N(C3H7)— group, an —N(C4H9)— group, a —CF2O— group, an —OCF2— group, a —CF2S— group, an —SCF2— group, an —N(CF3)— group, a —CH2CH2— group, a —CF2CH2— group, a —CH2CF2— group, a —CF2CF2— group, a —CH═CH— group, a —CF═CF— group, a —C≡C— group, a —CH═CH—COO— group, an —OCO—CH═CH— group, or a direct bond. A1 and A2 are the same or different, and each represents a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a naphthalene-1,4-diyl group, a naphthalene-1,5-diyl group, a naphthalene-2,6-diyl group, a 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, a 1,4-bicyclo[2.2.2]octylene group, a piperidine-1,4-diyl group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, an indane-1,3-diyl group, an indane-1,5-diyl group, an indane-2,5-diyl group, a phenanthrene-1,6-diyl group, a phenanthrene-1,8-diyl group, a phenanthrene-2,7-diyl group, a phenanthrene-3,6-diyl group, an anthracene-1,5-diyl group, an anthracene-1,8-diyl group, an anthracene-2,6-diyl group, or an anthracene-2,7-diyl group. —CH2— groups in A1 and A2 each may be substituted with an —O— group or an —S— group, as long as they are not adjacent to each other. Hydrogen atoms in A1 and A2 each may be substituted with a fluorine atom, a chlorine atom, a —CN group, or a C1 to C6 alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, or alkyl carbonyloxy group. Each Z are the same or different, and represents an —O— group, an —S— group, an —NH— group, a —CO— group, a —COO— group, an —OCO— group, an —O—COO— group, an —OCH2— group, a —CH2O— group, an —SCH2— group, a —CH2S— group, an —N(CH3)— group, an —N(C2H5)— group, an —N(C3H7)— group, an —N(C4H9)— group, a —CF2O— group, an —OCF2— group, a —CF2S— group, an —SCF2— group, an —N(CF3)— group, a —CH2CH2— group, a —CF2CH2— group, a —CH2CF2— group, a —CF2CF2— group, a —CH═CH— group, a —CF═CF— group, a —C≡C— group, a —CH═CH—COO group, an —OCO—CH═CH— group, or a direct bond; and m is 0, 1, or 2.
More specific examples thereof include any of compounds represented by the following chemical formulae (2-1) to (2-5):
In each formula, each P1 are the same or different, and each represents a polymerizable group.
Examples of P1 above include an acryloyloxy group, a methacryloyloxy group, a vinyl group, a vinyloxy group, an acryloylamino group, and a methacryloylamino group. Herein, hydrogen atoms in benzene rings and fused rings in the compounds represented by the above chemical formulae (2-1) to (2-5) may be partially or fully substituted with halogen atoms, or C1 to C12 alkyl or alkoxy groups. In addition, hydrogen atoms in alkyl and alkoxy groups may be partially or fully substituted with halogen atoms. Further, the bonding positions of P1 to the benzene rings and the fused rings are not limited to the ones shown.
The polymer layer of the present embodiment may be a polymerized product of a monomer polymerizable by visible light irradiation.
Monomers for forming the polymer layer include two or more types of monomers. The monomer polymerizable by visible light irradiation may be a monomer that polymerizes another monomer. The monomer that polymerizes another monomer refers to, for example, a monomer that undergoes a chemical reaction upon visible light irradiation; initiates and promotes polymerization of another monomer that does not polymerize by itself by visible light irradiation; and polymerizes itself, while the wavelength range that induces reaction is different depending on the molecular structure. Owing to the monomer that polymerizes another monomer, a large number of existing monomers that do not polymerize by light irradiation (such as visible light) can be used as materials of the polymer layer. Examples of the monomer that polymerizes another monomer include a monomer including a structure that generates a radical by visible light irradiation.
Examples of the monomer that polymerizes another monomer include compounds represented by the following chemical formula (3):
In the formula, A3 and A4 are the same or different, and each represents a benzene ring, a biphenyl ring, or a C1 to C12 linear or branched alkyl or alkenyl group. At least one of A3 and A4 includes an —Sp2—P2 group. A hydrogen atom in A3 and A4 each may be substituted with an —Sp2—P2 group, a halogen atom, a —CN group, an —NO2 group, an —NCO group, an —NCS group, an —OCN group, an —SCN group, an —SF5 group, or a C1 to C12 linear or branched alkyl, alkenyl, or aralkyl group. Two adjacent hydrogen atoms in A3 and A4 each may be substituted with a C1 to C12 linear or branched alkylene or alkenylene group to form a cyclic structure. A hydrogen atom in an alkyl, alkenyl, alkylene, alkenylene, or aralkyl group in A3 and A4 each may be substituted with an —Sp2—P2 group. A —CH2— group in an alkyl, alkenyl, alkylene, alkenylene, or aralkyl group in A3 and A4 each may be substituted with an —O— group, an —S— group, an —NH— group, a —CO— group, a —COO— group, an —OCO— group, an —O—COO— group, an —OCH2— group, a —CH2O— group, an —SCH2— group, a —CH2S— group, an —N(CH3)— group, an —N(C2H5)— group, an —N(C3H7)— group, an —N(C4H9)— group, a —CF2O— group, an —OCF2— group, a —CF2S— group, an —SCF2— group, an —N(CF3)— group, a —CH2CH2— group, a —CF2CH2— group, a —CH2CF2— group, a —CF2CF2— group, a —CH═CH— group, a —CF═CF— group, a —C≡C— group, a —CH═CH—COO— group, or an —OCO—CH═CH— group, as long as an oxygen atom, a sulfur atom, and a nitrogen atom are not adjacent to one another. P2 represents a polymerizable group. Sp2 represents a C1 to C6 linear, branched, or cyclic alkylene or alkyleneoxy group, or a direct bond; and n is 1 or 2. A dotted line connecting A3 with Y and a dotted line connecting A4 with Y indicate that a Y-mediated bond may be present between A3 and A4. Y represents a —CH2— group, a —CH2CH2— group, a —CH═CH— group, an —O— group, an —S— group, an —NH— group, an —N(CH3)— group, an —N(C2H5)— group, an —N(C3H7)— group, an —N(C4H9)— group, an —OCH2— group, a —CH2O— group, an —SCH2— group, or a —CH2S— group, or a direct bond.
More specific examples thereof include any of compounds represented by the following chemical formulae (4-1) to (4-8):
In the formula, R3 and R4 are the same or different, and each represents an —Sp2—P2 group, a hydrogen atom, a halogen atom, a —CN group, an —NO2 group, an —NCO group, an —NCS group, an —OCN group, an —SCN group, an —SF5 group, or a C1 to C12 linear or branched alkyl, aralkyl, or phenyl group. At least one of R3 and R4 includes an —Sp2—P2 group. P2 represents a polymerizable group. Sp2 represents a C1 to C6 linear, branched, or cyclic alkylene or alkyleneoxy group, or a direct bond. When at least one of R3 and R4 represents a C1 to C12 linear or branched alkyl, aralkyl, or phenyl group, a hydrogen atom in at least one of R3 and R4 above may be substituted with a fluorine atom, a chlorine atom, or an —Sp2—P2 group. A —CH2— group in R3 and R4 each may be substituted with an —O— group, an —S— group, an —NH— group, a —CO— group, a —COO— group, an —OCO— group, an —O—COO— group, an —OCH2— group, a —CH2O— group, an —SCH2— group, a —CH2S— group, an —N(CH3)— group, an —N(C2H5)— group, an —N(C3H7)— group, an —N(C4H9)— group, a —CF2O— group, an OCF2— group, a —CF2S— group, an —SCF2— group, an —N(CF3)— group, a —CH2CH2— group, a —CF2CH2— group, a —CH2CF2— group, a —CF2CF2— group, a —CH═CH— group, a —CF═CF— group, a —C≡C— group, a —CH═CH—COO— group, or an —OCO—CH═CH— group, as long as an oxygen atom, a sulfur atom, and a nitrogen atom are not adjacent to one another.
Examples of P2 above include an acryloyloxy group, a methacryloyloxy group, a vinyl group, a vinyloxy group, an acryloylamino group, and a methacryloylamino group. Herein, hydrogen atoms in benzene rings in the compounds represented by the above chemical formulae (4-1) to (4-8) may be partially or fully substituted with halogen atoms or C1 to C12 alkyl or alkoxy groups. In addition, hydrogen atoms in alkyl and alkoxy groups may be partially or fully substituted with halogen atoms. Further, the bonding positions of R3 and R4 to the benzene rings are not limited to the ones shown.
The monomers for forming the polymer layer (for example, the compounds represented by the chemical formulae (2-1) to (2-5), and the compounds represented by the chemical formulae (4-1) to (4-8)) preferably include two or more polymerizable groups. For example, monomers including two polymerizable groups are preferred.
In the present invention, the above-described monomers may be added to liquid crystal without using a conventional polymerization initiator. This results in a significant improvement in electric properties because there is no residual polymerization initiator that can be an impurity in the liquid crystal layer. In other words, a polymerization initiator for the monomers can be substantially absent in the liquid crystal layer when the monomers are polymerized.
In the present embodiment, for example, a biphenyl-based bifunctional methacrylate monomer represented by the following chemical formula (5) may be used.
In this case, the formation of a polymer can be ensured without mixing a photopolymerization initiator. The radical generation process represented by the following formulae (6-1) and (6-2) is considered to be induced by light irradiation.
In addition, the present of a methacrylate group helps the monomer to form a polymer by radical polymerization.
Monomers that dissolves in liquid crystal are preferred as the monomers. Rod-like molecules are preferred as the monomers. Examples thereof may include naphthalene-based, phenanthrene-based, and anthracene-based monomers, in addition to the biphenyl-based monomer. In addition, hydrogen atoms therein may be partially or fully substituted with halogen atoms, alkyl groups, or alkoxy groups (hydrogen atoms in these groups may be partially or fully substituted with halogen atoms).
Examples of polymerizable groups may also include an acryloyloxy group, a vinyloxy group, an acryloylamino group, and a methacryloylamino group, in addition to the methacryloyloxy group. These monomers can generate radicals by light having a wavelength ranging from about 300 to 380 nm.
In addition to the above monomers, monomers such as acrylate and diacrylate having no photopolymerization initiating function may be mixed. The photopolymerization reaction rate can be adjusted with these monomers.
In addition, in the present embodiment, a mixture of a monomer represented by the following chemical formula (7A) and a monomer represented by the following chemical formula (7B) can also be used.
In this case, the PS process may be performed with visible light irradiation. This reduces damage to the liquid crystal and the photo-alignment film. Other examples of monomers that can be used include benzoin ether-based, acetophenone-based, benzil ketal-based, and ketone-based monomers, which generate radicals by photofragmentation and hydrogen abstraction. A polymerizable group must be attached to these monomers. Examples of the polymerizable group include an acryloyloxy group, a vinyloxy group, an acryloylamino group, and a methacryloylamino group, in addition to the methacryloyloxy group.
In addition, in the present embodiment, a polyimide including a cyclobutane skeleton may be used as the main chain of a polymer of an alignment film material.
Finally, a preferred embodiment of the liquid crystal layer in the liquid crystal display device of the present embodiment will be described. The liquid crystal layer contains liquid crystal molecules including, in a molecular structure thereof, a multiple bond other than conjugated double bonds of a benzene ring. The liquid crystal molecules may have either positive anisotropy of dielectric constant (positive type) or negative anisotropy of dielectric constant (negative type). The liquid crystal molecules are preferably nematic liquid crystal molecules having a high symmetric property in the liquid crystal layer.
The multiple bond does not include conjugated double bonds of a benzene ring because the benzene ring has low reactivity. However, as long as the liquid crystal molecule includes, as an essential bond, a multiple bond other than conjugated double bonds of a benzene ring, the liquid crystal molecules of the present embodiment may include conjugated double bonds of a benzene ring: the conjugated double bonds does not have to be particularly excluded. In addition, in the present embodiment, the liquid crystal molecules contained in the liquid crystal layer may be a mixture of plural kinds thereof. A liquid crystal material may be a mixture of plural kinds of liquid crystal molecules in order to secure the reliability, to improve the response speed, and to adjust the liquid crystal phase temperature range, elastic constant, anisotropy of dielectric constant, and refractive index anisotropy.
The multiple bond is preferably a double bond, and it is more preferred that the double bond be present in an ester group or an alkenyl group. For example, it is preferred that the double bond is present in an alkenyl group. The double bond has a higher reactivity than a triple bond. The multiple bond may be a triple bond, and in that case, the triple bond is preferably present in a cyano group. Further, each liquid crystal molecule preferably includes two or more kinds of multiple bonds.
Each liquid crystal molecule preferably contains at least one molecular structure selected from the group consisting of structures represented by the following formulae (8-1) to (8-6). Among these, a molecular structure represented by the following formula (8-4) is particularly preferred.
In Embodiment 11, a cell was completed in the same manner as in Embodiment 9, except for the below-described alignment film material and alignment treatment conditions.
A polyimide solution including a cyclobutane skeleton was used as an alignment film material. The alignment film material was applied to the substrates and dried in the same manner as in Embodiment 1.
The surface of each substrate was irradiated with polarized ultraviolet light having a wavelength of 254 nm with an intensity of 500 mJ/cm2 from the normal direction of each substrate for alignment treatment. As a result, the alignment film material applied to the substrates caused photodissociation, and horizontal alignment films were thus formed.
This panel was observed in reflective mode under a polarizing microscope. Disclinations were present between the photospacers and under the BM in the same manner as in Embodiment 9. Thus, the disclinations could not be observed with transmitted light.
Each of the embodiments described above may be suitably combined without departing from the scope of the present invention.
The present application claims priority to Patent Application No. 2011-189835 filed in Japan on Aug. 31, 2011 under the Paris Convention and provisions of national law in a designated State, the entire contents of which are hereby incorporated by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2011-189835 | Aug 2011 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/071256 | 8/23/2012 | WO | 00 | 2/6/2014 |
