TW200420919A - Method for manufacturing a phase plate - Google Patents

Abstract

The present invention provides a method for manufacturing a thin phase plate with no appearance defects and with high performance. First, as shown in Fig. 1A, a solution of a liquid crystalline compound is applied to a transparent base (1) and dried, or a melted liquid crystalline compound is applied to a transparent base (1), thereby forming a liquid crystalline compound-containing layer (2a). Then, as shown in Fig. 1B, the liquid crystalline compound-containing layer (2a) is turned liquid crystalline or liquefied to be a melted layer (2b). An alignment substrate (3) is brought into contact with the melted layer (2a) to align the liquid crystalline compound in a specific direction. Thereafter, as shown in Fig. 1C, the melted liquid crystalline compound-containing layer (2b) is solidified, and the alignment substrate (3) is removed, thus manufacturing a phase plate (4) composed of a transparent base (1) and an optically anisotropic layer (2c).

Description

200420919 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for manufacturing a retardation plate suitable for use in an image display device, such as a liquid crystal display device (LCD). [Prior art] In a video display device such as a liquid crystal display device, a phase difference plate is an important component that achieves an increase in contrast and an enlarged viewing angle range by optical compensation. As the type of the retardation plate, a polymer film is stretched to impart optical anisotropy, or a glass or a polymer film is coated with an optically anisotropic layer containing a liquid crystal compound on a substrate. With the recent reduction in the thickness of liquid crystal display devices, the latter is particularly valued. In the manufacture of retardation plates, in order to form an optically anisotropic layer containing a liquid crystal compound, the alignment direction of the entire molecules of the liquid crystal compound or the meso portion showing liquid crystallinity must be in a certain direction or in a continuously changing manner. Do regular alignment. The method includes, for example, a method of forming an alignment film on a substrate and coating a liquid crystal compound on the substrate (hereinafter referred to as "alignment film formation method"), refer to Japanese Patent Application Laid-Open No. 2002-14233, and US Patent No. 621 5539. (No. 6,300,991 and US Patent No. 6300991)) Furthermore, the optical anisotropy layer is formed by coating a liquid crystal compound on an alignment substrate prepared separately, and then the optical anisotropy is transferred onto a substrate. "'Is called" transfer method ", refer to Japanese Patent No. 2631 01 5). The outline of the alignment film formation method is as follows. That is, first, 200420919, a transparent substrate is prepared, and a liquid for forming an alignment film is coated thereon to form a smooth film. Then, a rubbing treatment is performed on the film to give the liquid crystal alignment force to form an alignment film. Next, a liquid crystal compound solution is applied to the alignment film and dried or a liquid crystal compound melt is applied to align the liquid crystal compound. Next, if necessary, the liquid crystal compound is hydrated and cooled to be solidified 'to form an optically anisotropic layer, thereby manufacturing a retardation plate. Furthermore, there is another method of preparing a substrate for forming an alignment film on a transparent substrate, and sandwiching the aforementioned liquid crystalline compound with the alignment film forming surface of the two substrates to align it (for example, refer to JP 9_28148). Bulletin). There is also a method in which rubbing treatment is performed instead of forming an alignment film on a transparent substrate (for example, refer to Japanese Patent Application Laid-Open No. 9-281481). The outline of the transfer method is as follows. That is, first of all, prepare the orientation group with the anisotropy, such as a uniaxially stretched polymer film. Next, the liquid crystalline compound is applied and dried, or a molten liquid of the liquid crystalline compound is applied to align the liquid crystalline compound. Next, if necessary, the aforementioned liquid crystalline compound is polymerized and cooled to solidify, thereby fixing the alignment state to form an optically anisotropic layer. On the other hand, a substrate is prepared and an adhesive or an adhesive is applied thereon. As the aforementioned substrate, an optically isotropic transparent film or an optically anisotropic film (having an optical axis in which the alignment direction of the liquid crystal compound is different) can be used. Next, after the optically anisotropic layer is bonded to the adhesive layer, the alignment substrate is removed and transferred to form a retardation plate. 70 However, in the aforementioned alignment film formation method, the alignment pattern 9 remained in the retardation plate, and in the aforementioned transfer method, the adhesive agent &# in the retardation plate 200420919. From the viewpoint of the optical performance of the retardation plate, these residues are unnecessary, and in order to reduce the thickness, it is better to reduce the residue as much as possible. Furthermore, in the aforementioned alignment film forming method, the adhesion between the alignment film and the optically anisotropic layer may be poor. Japanese Patent Application Laid-Open No. 9_1 525009 discloses that a modified PVA alignment film is formed on a transparent substrate after performing an undercoating treatment (gelatin, etc.), and has good adhesion to the liquid crystal layer. The thickness of the retardation plate will be increased, and the manufacturing process will become more complicated. In the aforementioned alignment film forming method, scratches may be left on the surface of the alignment film during the aforementioned rubbing treatment. In addition, since the alignment film will remain directly in the retardation plate, if the surface of the alignment film is scratched, it will become an appearance defect of the retardation plate. Furthermore, there is a possibility that, during the rubbing process, 'foreign matter' and the like are fixed on the surface of the alignment film and stay with the alignment film-and remain inside the retardation plate. Even the method of directly performing rubbing treatment without forming an alignment film on a transparent substrate has the same disadvantage. Further, in the aforementioned transfer method, when an adhesive agent is applied, the surface may be damaged by the adhesion of the surface and foreign matter, or the optical anisotropic layer may not be partially transferred. SUMMARY OF THE INVENTION Accordingly, the present invention aims to provide a method for manufacturing a retardation plate that is thin, has no appearance defects, and has high properties. In order to solve the above-mentioned problems, an optically anisotropic layer is formed, which is characterized by (1) having no liquid crystal alignment ability, the manufacturing method of the present invention is characterized in that the transparent substrate includes the following processes (1) to (4). A process for forming a liquid crystalline 200420919 compound-containing layer on the aforementioned transparent substrate. (2) A process in which the liquid crystal compound-containing layer is brought into contact with an alignment substrate having liquid crystal alignment capability, and the liquid crystal compound of the aforementioned layer is aligned. (3) A process for forming the optically anisotropic layer by fixing the aforementioned alignment state of the liquid crystal compound of the aforementioned layer. (4) a process of removing the aforementioned alignment substrate. As described above, according to the manufacturing method of the present invention, unlike the prior art, since no alignment film, adhesive, friction, or the like is left on the transparent substrate, it is possible to manufacture a thin, non-defective, and high-performance retardation plate. . Furthermore, when an optically anisotropic layer containing a liquid crystal compound is laminated on the transparent substrate, since the lamination can be performed without transmitting the alignment film, there is no reason for the adhesion between the alignment film and the optically anisotropic layer. Problems caused by weak sex. [Embodiment] Next, an embodiment of the present invention will be described. Although the thickness of the aforementioned transparent substrate is not particularly limited, in order to reduce the thickness of the retardation plate, it is better to use a thinner one, such as α 2 (M2 (^ is preferred, and 20 ~ 80 # m is ideal, and It is more preferable to be 20 to 40 ym. The so-called "transparent clasp ^ ^ β" of the transparent substrate mentioned above has a light transmittance that can be applied to the phase and the plate. The light transmittance is described above. The side sheep, as long as it is in the actual application range, is not particularly limited, but it is considered from the perspective of the relative performance of the phase difference plate, and the ideal state is 100%. Moreover, although the aforementioned transparent substrate It can be an optically hypertropic, but depending on the performance required for a liquid crystal display device with a 10 200420919 retardation plate, the aforementioned transparent substrate is preferably an optically anisotropic. Optical anisotropy here There is no particular limitation: 'It may be an optical anisotropy having positive or negative AP late phase difference characteristics. [A person having an optical anisotropy having positive or negative C-Plate phase difference characteristics, a positive or negative one. -Plate optical anisotropy or refractive index with anisotropy in different directions The biaxial optical anisotropy by (i.e. also 'has two optical axes.) Also, the so-called A-Plate, C-Plate with a square

Plate refers to a layer with uniaxial optical anisotropy. The optical axis of the aforementioned a-Plate is in the in-plane direction, and those whose optical characteristics meet the following formula (I) are called P0SltlVe (positive) A-Plate; $ Those who have the following formula (II) are called negative (negative) A- Plate. , 3 nz nx > ny (I) nx < ny = nz -run (II) complex light :; God: the optical axis of te is in the z-axis direction ', that is, in the thickness direction, p, late stem, 1Γ foot 1 ^ ⑴ 1) is called posltive (positive) C-nx nx axis meets the following formula (IV) is called negativeU) c_piate. nv ~ ny < nz ny > nz (I ⑴ In the above formula ⑴ ~ uv), the nx (:) γ axis and the z square, and the ⑽ system are absent # ^, the refractive index. Among them, whether it is the aforementioned X-axis or γ system, the largest fold in the plane of the layer: γ is the direction perpendicular to the axis, +, and :, and the other axis is the thickness perpendicular to the axis ::: two axes It refers to the X axis, the Υ direction, and the ζ axis direction. In the "late", the optical axis is in the plane. , Thickness direction perpendicular to the in-plane direction) are tilted when viewed. 200420919 The method for imparting optical anisotropy is not limited. It is only necessary to apply general methods, such as the optically isotropic transparent film. Optical anisotropy, and can be used as the aforementioned transparent Mozambique substrate. For example, you can also buy a commercially available optical molecular anisotropic rain molecular thin ^ aD & D, find the film, and use it directly as the aforementioned transparent The base material of the aforementioned transparent base material is particularly special (P ~ ...). It can be glass or Gao Weizi, etc. There is no particular limitation on the I compound that can be used for the aforementioned polymer film. Polyethylene terephthalate vinegar, polyethylene terephthalate _ and other polymer brewing polymers; cellulose diethylene glycol, = ethyl cellulose and other cellulose polymer figures; polymethyl acrylic acid Acrylic polymers such as vinegar; styrene polymers such as polystyrene, fluorinated nitrile-styrene copolymer (US resin); polycarbonate polymers such as bisphenol "carbonic acid copolymer"; polyethylene, poly Linear or branched polyolefins such as propylene and ethylene copolymers, polynorbornenes, etc.

Polyolefins with a cyclic structure; Gas-based polymers such as vinyl polymers, nylons, and aromatic S-amines; fluorenimine-based polymers; mill-based polymerization = poly # polyether boron-based polymers; poly Ether ether ketone polymer; polyphenylene sulfide polymer · 'vinyl alcohol polymer; vinyl chloride polymer; polyvinyl butyral polymer; acrylic polymer; polyoxymethylene polymer; Alkaline polymer is preferred. It can be used alone or in combination of two or more. In the aforementioned polymer, cellulose based polymer such as triethyl cellulose and other polymers are used. Polycarbonate polymers such as polymers, octacyclic structured polyolefins such as polynorbornene, and fluorene polymers such as aromatic polyfluorene are preferably fluorene-based polymers, among which Cellulose-based kappa products are most preferable. As for the transparent base material, a polymer film described in Japanese Patent Application Laid-Open No. 2001-343529 (WOO 1/37007) can also be cited. As the polymer film, a resin composition that can be used is, for example, a thermoplastic resin containing a bond /, a substituted or unsubstituted fluorene imine group, and a thermoplastic resin having a substituted or unsubstituted phenyl group and a cyano group in a side chain. As an example, examples of the t include a resin composition containing an interactive copolymer composed of isobutylene and N-methylmaleamidine, and an acrylonitrile-styrene copolymer. The polymer film may be an extruded product of the resin composition, for example.

To improve the aforementioned transparent substrate and-, day by day, the soil can be treated with corona discharge treatment, UV-ozone treatment, 4 inspections, etc. Especially, when using a polymer thin film with optical anisotropy as another transparent substrate, the polymer film itself may have a crystal alignment ability, so in order to eliminate the liquid crystal alignment ability It is also possible to apply the light pre-isotropic layer. Also, even if the transparent substrate is optically isotropic,

Alternatively, an optically isotropic layer may be coated on the A, m, and t or both sides. The thickness of the aforementioned light (^ layer) is not particularly limited, and may be, for example, 0.05 to 10 # m, where 箄 乂 Ideal 'is more preferably 0.5 to 2. The aforementioned light d rabbit: the material of the f layer is not In particular, a resin layer or the like can be used, and ^ can be appropriately selected as the material of the polymer film, and the like can be made of: the same material. If necessary, the tree can be covered by don The adhesiveness between the aforementioned optically anisotropic layer of the liquid crystal compound and the transparent substrate. The method of coating the orientation-oriented layer is described, and the method 13 is specifically limited. The coating method, casting method 1, L coating method, printing, the aforementioned polymer, etc. are also printed in the 03 version of the printing method. Here it is used in the form of β I liquid or y knife powder, although missing two; τ From the viewpoint of polymer films, etc., from the viewpoint of water dispersion: :: A solution of hydrocarbon solvents such as methyl ethyl acetate, cyclopentamine, cyclohexyl, etc., and ethyl acetate, such as toluene, etc. can be used. : Although it includes the optically anisotropic layer of the aforementioned liquid crystalline compound:: Do not restrict, in order to achieve the thinness of the retardation plate & Yes, /, ',,, and soil' can be, for example, 0.5 to 10 # m, and 1-10 " is more ideal 'and 2 ~ 8 // m is more reasonable. Especially ^ p, +, and only Sister Tian, in the other anisotropic layer, the orientation direction of the liquid crystal material is not particularly limited. It can be set appropriately to obtain optimized optical compensation, for example, to tilt in the same direction. (―Naguantilt‖ alignment, hybrid alignment, palmar nematic alignment, co-horizontal alignment, vertical homeotropic alignment, etc. are preferred. The aforementioned liquid crystalline compound is not particularly limited, and may be a liquid crystal monomer or For example, a rod-shaped liquid crystal compound, a plate-shaped liquid crystal compound, and a polymer of these compounds can be used as the polymer, and they can be used alone or in combination of two or more. When a polymer is used, it can be a liquid crystal polymer. The liquid crystal compound may be a homopolymer or a heteropolymer (copolymer). The liquid crystal compounds include fluorenimines, azo oxides, cyanobiphenyls, cyanophenyls, and benzoates. Type, phenyl cyclohexane carboxylic acid, cyanobenzene cyclohexane, cyano-substituted phenylpyrimidine Liquid crystal compounds such as alkoxy-substituted phenylpyrimidines, phenyl difluorenes, diphenylethanes, aliphatic alkenylcyclohexylbenzonitrile, and polymers of these compounds are preferred. Furthermore, In order to make the alignment temperature low and easy to process 14 200420919, it is desirable that the liquid crystal compound contains at least one of a liquid crystal prepolymer and a liquid crystal monomer. In addition, the temperature range of the liquid crystal compound containing layer exhibiting a liquid crystal state. (Liquid crystal temperature range) It is appropriately determined according to the type of the liquid crystal compound, etc. The liquid crystal temperature range is not particularly limited. It is considered from the viewpoint of the manufacture and use of the retardation plate, especially considering that the transparent substrate is heated during the manufacturing process. And deformation, etc., the temperature is not too high

More ideal. The aforementioned liquid crystal temperature range may be 20 to 150 ° C, and more preferably 20 to 120 ° C, and more preferably 20 to 80 ° C. Further, as long as the retardation plate performance is not impaired, the liquid crystal compound-containing layer may be appropriately added with substances other than the liquid crystal compound, such as a photopolymerization initiator, a leveling agent, and a viscosity modifier. The aforementioned alignment substrate is also not particularly limited, and it is possible to use a stretched product of a polymer film such as polyethylene terephthalate, a person who directly rubs a triethyl cellulose film, or a liquid crystal alignment on a substrate. Capability of alignment film and so on. The aforementioned alignment film is not particularly limited, and can be provided with a liquid crystal alignment ability by rubbing treatment. Depending on the type of the alignment film, the liquid crystal alignment ability can be made by light irradiation without rubbing treatment. When the alignment film is formed on the polymer film by applying the alignment film forming liquid, it is preferable that the solvent and the polymer film are appropriately selected so that the polymer film is not easily attacked by the solvent in the liquid. ^ The alignment direction of the liquid crystal compound can be controlled by the surface state of the alignment substrate and the transparent substrate and the type of the liquid crystal compound, and can be controlled by the same method as the previous conventional rules. For example, p apply a nematic liquid crystal compound 15 200420919 on a transparent substrate without liquid crystal alignment ability, and use a uniaxially stretched polymer film such as polyethylene terephthalate for the alignment substrate. Alignment to obtain the alignment state such as the same-direction alignment (co-horizontal alignment) along the stretching direction. If the alignment substrate has a liquid crystal oblique alignment capability, it is desirable to obtain an optically anisotropic layer having an inclination angle, for example, the above-mentioned characteristics such as an O-plate. Although the alignment substrate having the liquid crystal oblique alignment capability is not particularly limited, examples thereof include an alignment substrate including an oblique vapor deposition film, a light alignment film, or a rubbing film. These films can be formed on a suitable substrate such as glass or bi-molecular film, and can be used as an alignment substrate having the aforementioned liquid crystal tilt alignment capability. Among the aforementioned alignment substrates, an alignment substrate including a photo-alignment film or a friction film can be manufactured without using a high-temperature process that may damage the aforementioned substrate, and is therefore preferable. The material of the alignment substrate having the aforementioned liquid crystal oblique alignment ability is not particularly limited, but an alignment substrate containing a long-bond fluorinated polyfluorene imide or polylithium sintered oxygen is preferred. The aforementioned alignment substrate can form a long-chain alkyl polyimide rubbing film or a polysiloxane friction film on the front substrate, and the long-chain alkyl polyimide can also form the aforementioned substrate itself, and then: Friction acts as an alignment substrate. The manufacturing method of the alignment earth plate having the above-mentioned liquid crystal oblique alignment ability is not particularly limited ^, and the previous method can be appropriately used. Secondly, as described in Japanese Patent Application Laid-Open No. 5-1 1252 and the like, oblique steaming ore is described, and Japanese Patent Application Laid-Open No. 30016 and the like describe a friction film of polyoxysilane. An example of the manufacturing method of this invention is demonstrated using the process drawing of FIG. That is, the property is: 10 kg, firstly, as an optical anisotropy, is formed on the transparent substrate 1: the liquid crystal compound of the driver contains ... a. Although the formation method does not include a method of coating the liquid crystal compound solution on the transparent base 16 200420919 and drying it, or a method of combining the aforementioned liquid crystal properties: cloth on a transparent substrate 1 Better. The "melting" of the neutral compound of the present invention means a liquid crystal state or a liquefied state. Japan and Japan Shitian applies optical isotropy on one or both sides of the translucent substrate 1: Japan: It is preferable to form a liquid crystal compound-containing layer Z a on the aforementioned optically isotropic layer. Say

It is stated that the liquid crystalline compound contains a liquid crystal prepolymer or a liquid crystal monomer, and it is preferable to add a photopolymerization initiator when photopolymerization is performed thereafter. Although the former = 光 Α "initiator is not particularly limited ^, Chiba Specialty Chemicals Corporation

Irgacure907 > Irgacure369 > Irgacurel84 (^ ^ ^ A ^) or eight is better. Although the addition amount of the aforementioned photopolymerization initiator is not particularly limited, it may be from 0 to 5% by weight relative to the liquid crystal prepolymer and the liquid crystal monomer, and preferably from 0.1 to 1% by weight. In the solution of the liquid crystal compound, the solvent is not particularly limited as long as the solvent can dissolve the liquid crystal compound. When the solution is directly coated on the transparent substrate, the transparent substrate is not easily etched. 1 is better. Examples of the solvent include ketones such as methyl ethyl ketone, cyclopentanone, and cyclohexanone; esters such as ethyl acetate; and hydrocarbons such as toluene.

The coating method of the liquid crystal compound solution or melt is not particularly limited, and a spin coating method, a roll coating method, a flow coating method, a printing method, a dip coating, a cast film method, a rod coating method, Gravure printing and so on. Next, the alignment substrate is brought into contact with the liquid crystal compound-containing layer, and the liquid crystal compound of the aforementioned layer is aligned. In this process, the liquid crystal compound-containing layer 2a is heated to a temperature above its liquid crystal temperature, and the liquid crystal compound-containing layer 2a is contacted with the alignment substrate 17 200420919 in this state. It is preferably above the liquid crystal temperature. That is, as shown in FIG. 1B, 'the liquid crystal compound-containing layer 2a is heated to its liquid crystal temperature to form a liquid crystal state or a liquefied state layer 2b, and in this state, it contacts the alignment substrate 3' to align the liquid crystal compound as described above. Alternatively, the liquid crystal compound-containing layer 2a may be brought into contact with the alignment substrate 3, and the liquid crystal compound-containing layer 2a may be heated to a temperature equal to or higher than the aforementioned liquid / day / degree to form a liquid crystal state or a liquefied state layer 2b. The liquid crystal temperature range is as described above. In addition, although the liquid crystal compound-containing layer 2a is formed as a solid as shown in FIG. 1A, it is not particularly limited, but the aforementioned layer that is in a liquid crystal state or a liquefied state can be omitted from the heating process, which is preferable. . For example, after the molten liquid of the liquid crystal compound is applied, the liquid crystal compound may be brought into contact with the alignment substrate immediately, or after the solution of the liquid crystal compound is coated and dried at the liquid crystal temperature or higher, the aligned substrate may be immediately contacted. The time during which the alignment substrate 3 contacts the liquid crystalline compound-containing layer 2b is not particularly limited, but may be from 100 to 120 seconds, and more preferably from 300 to 600 seconds. The contact direction of the alignment substrate 3 is not particularly limited, and may be appropriately set according to the purpose. For example, when the transparent substrate 1 and the alignment substrate 3 are both uniaxially stretched polymer films, and the aforementioned liquid crystal compound is a nematic liquid crystal compound, in order to obtain appropriate optical compensation performance, the transparent substrate 丨 and alignment It is preferable that the optical axes of the substrate 3 cross at an appropriate angle. Then, the alignment state of the liquid crystal compound in the liquid crystal compound-containing layer is fixed to form an optically anisotropic layer. When the liquid crystal compound is at least one of a liquid crystal prepolymer or a liquid crystal monomer, a method of performing photopolymerization of the liquid crystal compound to achieve the fixed alignment of the alignment state is performed. The irradiation light here is not particularly limited, but ultraviolet rays are preferred, and the wavelength of the ultraviolet rays described in the first 18 200420919 is preferably 200 to 400 nm. The light intensity, irradiation time, and amount of the aforementioned irradiation light are not particularly limited as long as the aforementioned alignment state can be sufficiently fixed. The irradiation direction of the irradiation light is not particularly limited as long as it does not interfere with the irradiation of the liquid crystal compound-containing layer. The irradiation may be performed from the transparent substrate side or the alignment substrate side.

When the liquid crystal compound is a liquid crystal polymer, it is preferable to fix the alignment state just described by cooling the liquid crystal compound-containing layer to a temperature below the liquid crystal temperature. The cooling method is not particularly limited, and it can be left at room temperature, or it can be quickly cooled by using an appropriate cooler. Further, as shown in Fig. 1C, the alignment substrate 3 is removed to produce a retardation plate 4 composed of a transparent substrate 1 and an optically anisotropic layer 2c. Although the manufacturing method of the present invention can be implemented as described above, it is only one embodiment of the present invention. Any change can be made as long as it does not deviate from the gist of the present invention. For example, the aforementioned manufacturing process (1) to ( 4) Other processes. When photopolymerizing the liquid crystalline compound, the conventional method is mostly carried out under a nitrogen atmosphere. This is because most photopolymerization is so-called free-radical polymerization 'and oxygen in the atmosphere will hinder polymerization (hardening)', resulting in poor hardness or durability of the optically anisotropic layer. However, when photopolymerization is performed by the manufacturing method of the present invention, as long as the liquid crystal compound-containing layer is irradiated with light in a state sandwiched between the transparent substrate and the alignment substrate, the liquid crystal compound is inevitably difficult to interact with. Photopolymerization is carried out in the atmosphere. With this, even without nitrogen washing, a retardation plate with good hardness and durability can be easily obtained, and it also has the advantages of improving the manufacturing efficiency of the retardation plate.

As an example, the present invention is not limited to this embodiment. Method of another embodiment. However, this also

It is preferable that the alignment substrate is a 胄 -shaped alignment substrate, and is continuously sent out and the above processes ⑺ to ⑷ are continuously performed. Here, it is more preferable that at least one of the transparent substrate and the alignment substrate is fed out by using a roller. In addition, the winding process (5) which further includes the aforementioned retardation plate is more desirable. The manufacturing method is not particularly limited in its specific implementation method, and it can be used as a so-called roll-to-roll (roll tQ r.) Process. Perform, for example, the following method: Material supply light 13, liquid crystal compound solution coating device 15, 5, alignment substrate supply roller 16, heating device 1, 7, Figure 2 shows an example of the device for implementing the manufacturing method of the present invention 2 Do not think about the diagram. However, this diagram is only an example, and does not represent the entire content of the present invention. As shown in the figure, the main constituent elements of the device are rollers 5 to 12, transparent base ^ 14, liquid crystal alignment fixed clothing of the drying device. Set 18, the alignment substrate winding device 19, and the retardation plate winding device 20. Among the rollers 5 to 12, 5, 9 and 10 are guide rollers, 6 is a coating roller, and 7 and 8 are opposite to each other. The laminating rolls, 11 and 12 are opposite pairs. The materials of the rolls 5 to 12 are not limited. Metals such as stainless steel, rubber, and silicone 5 to 12 can be used as smooth as possible. In addition, if necessary, you can connect the thermostat to a temperature control device to make the temperature changeable. The liquid crystal compound solution coating device 14 is not particularly limited, and a 200420919 garment having a coating mechanism such as a coating machine can be used. The coating machine is not particularly limited, considering the liquid crystal properties used. For the physical properties of the lingering fluid, coating machines such as gravure, wire bar, and plastic core can be used. The liquid crystal alignment and fixing device 1S can appropriately select a cooling device or a light irradiation device according to the type of liquid crystal compound used. The relationship between the type of the liquid crystal substrate and the method of fixing the alignment state is as described above. The light source of the light irradiation device is not particularly limited, and general equipment, external lamps, etc. can be used as appropriate. Transparent substrate supply roller 13 With the alignment substrate supply roller 16, the τ-shaped transparent substrate 2 丨 and the belt-shaped alignment substrate 22 are rolled into a roll shape, and the transparent substrate 21 and the alignment substrate 22 can be continuously sent out by the rollers 5 to 12. The arrows in the figure indicate the sending direction of the transparent substrate 2 and the alignment substrate 22. The method of manufacturing the retardation plate using the device of FIG. 2 can be applied as follows, that is, firstly, the transparent substrate 21 is made of a transparent substrate. Timber supply roller 1 3 is sent out, and the obtained transparent substrate 21 passes the guide roller 5 and passes between the coating roller 6 and the liquid crystal compound solution coating device 14. At this time, the liquid crystal compound solution is applied by the liquid crystal compound solution coating device 14. It is coated on the transparent substrate 21. Furthermore, the applied liquid crystal compound solution is dried by a drying device 1 to form a liquid crystal compound-containing layer on the transparent substrate 2. It is supplied from an alignment substrate. The alignment substrate 22 sent out from the roller 丨 6 is fired by the laminating rollers 7 and 8 so that the upper surface of the transparent substrate 21 (the surface on which the liquid crystal compound-containing layer is coated) is brought into close contact with the alignment substrate 22. The state of the compound-containing layer is not particularly limited, and it is preferable that the compound-containing layer is in a liquefied state (isotropic state) or a liquid crystal state, and is easy to adhere to the alignment substrate 22. After the liquid crystal compound-containing layer is formed, in order to further improve its tightness with the alignment substrate 22, 200420919, the viscosity can also be controlled. This control method is not particularly limited, and a general infrared heater can be appropriately used (Fig. (Not marked) or warm air. Next, the transparent substrate 21 (which is in contact with the alignment substrate 22 through the liquid crystal compound-containing layer) is further sent out and passed through a heating device, and the liquid crystal compound-containing layer is liquefied by heating, and then sent out The inside of the fixing device 18 is aligned by the liquid crystal. The heating temperature inside the heating device Η is not particularly limited, and may be appropriately selected depending on the type of the liquid crystal compound and the like. The liquid crystal compound is aligned therebetween, and the alignment state is fixed inside the liquid crystal alignment fixing device 18 to form an optically anisotropic layer. The method of fixing the alignment state varies depending on the type of the liquid crystal compound. When it is a liquid crystal polymer (non-photoreactive compound), the alignment state of the liquid crystal compound can be maintained by cooling. Method of curing (vitrification). The cooling method is not limited, and may be a method of rapid cooling by cold air or the like, or only exposure to room temperature. When it is a liquid crystal monomer or a liquid crystal prepolymer (photoreactive compound), this state can be fixed by photopolymerization (light curing). The amount of light irradiation is not particularly limited, as long as the liquid crystal compound can be sufficiently hardened. As described above, this photopolymerization is a highly efficient method because a retardation plate having excellent hardness and durability can be easily obtained without performing nitrogen washing. In addition, the transparent substrate 21 forming the aforementioned optically anisotropic layer is further sent out after passing through the liquid crystal fixed orientation f18, passing through the guide 9 and then passing through the guide roller 10 to pass through the roller 12 . When passing, the alignment substrate 22 is peeled and removed from the transparent substrate 21 by the alignment substrate winding device 19 to form the required retardation plate 23, and then wound by the retardation plate winding device 20 to 22 200420919-stepwise winding . As described above, a method for manufacturing a board can be implemented. According to the above-mentioned embodiment, the phase difference of Ling Zhi can be mass-produced because the manufacturing process from sending the transparent substrate to the winding process of the phase difference plate can be continuously connected to the manufacturing efficiency of the phase difference plate. Again: The case where the π process is performed discontinuously separately ’is more advantageous in the manufacture of the test of the accessory I :. The phase difference plate manufactured by the manufacturing method of the present invention is thin, does not have “appearance defects” and high performance. Its use method is widely recognized by ▲ ▲, and it is widely used in various optical elements. Or a liquid crystal display element, etc. The optical element includes the phase difference plate and the polarizing element m of the present invention, and has a transparent protective film ', and this transparent protective film is placed between: the two difference plates and the aforementioned polarizing element. For example The optical element of the present invention can be formed by laminating the phase J plate of the present invention on a polarizing plate with a transparent protective film laminated on the polarized light = cow. Furthermore, the optical element of the present invention may include in addition to these polarizing elements or transparent Any of the components outside the protective film should be i or less, and the constituent elements of the optical element of the present invention will be described more specifically. The aforementioned polarizing element is not particularly limited, but a stretched film is preferred because it can obtain good optical characteristics. For example, it can be dyed by inhaling dichroic substances such as iodine or dichroic dyes into various films by a conventionally known method, and then performing crosslinking, stretching, and drying to adjust The film which can produce the required material, and which can make the linear polarized light penetrate when natural light is incident is 23 200420919, and the one with excellent light transmittance and polarization is better. As various films that can inhale dichroic materials, Examples include hydrophilic polymer films such as polyvinyl alcohol (PVA) -based films, partially formaldehyde PVA-based films, ethylene-vinyl acetate copolymer-based partially saponified films, and cellulose-based films, among others. A dehydration-treated product of m or a polyvinyl chloride-aligned film of a dehydrochlorinated product of polyvinyl chloride, etc. In t, a polyvinyl alcohol-based film is preferred because it is easy to obtain good optical characteristics. In addition, the thickness of the aforementioned polarizing element For example, a range of 1 to 80 // m is not limited to this.

The aforementioned transparent baffle film is not particularly limited, and a conventionally known transparent film 'may be used, and it is preferable to be excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, and the like. Examples of such transparent protective films include polyethylene terephthalate, polyethylene terephthalate, and other polymers such as ethyl acetate, cellulose Cellulose polymers such as acetocellulose, and acrylic polymers such as polymethyl methacrylate. Polymers, polystyrene, acrylonitrile-styrene copolymer (As resin), styrene-based polymers, etc., fluorene A-carbonic acid copolymers, such as polycarbonate polymers, polyethylene, polypropylene, ethylene_propylene Straight-chain or branched polyolefins such as copolymers, cyclic structured polyolefins such as polynorbornene, vinyl chloride polymers, nylon, aromatic polyamines, and other amine-based polymers, fluorenimines Based polymers, maple based polymers, polyether boron based polymers, polyether ether ketone based polymers, polyphenylene sulfur based polymers, vinyl alcohol based polymers, partial vinyl polymers, vinyl butyral based polymers Polymers, acrylic polymers, polyoxymethylene polymers, and epoxy polymers. These can be used alone or in combination of two or more. Based on the polarization characteristics and durability considerations, it is better to use a surface-treated TAC film with a base 24 200420919. Alternatively, the polymer film described in Japanese Patent Application Publication No. 200343343 (WO01 / 37007) can be used. The transparent protective film is preferably colorless. Specifically, the phase difference value (Rth) in the thin thickness direction is preferably in the range of -90nm ~ + 75nm, more preferably in the range of -80nm ~ + 60nm, and the core in the range of -70nm ~ + 45nm, Although the above-mentioned phase difference value is in the range of -90nm ~ + 75nm, the phenomenon of coloring (optical coloring) caused by the protection of thin cymbals can be fully eliminated. Among them, here ^

Rth is represented by the following formula (v). In the following formulas, the definitions of nx, ny & nz are the same as the formulae ⑴ to (IV), and d represents the film thickness of the transparent protective film.

Rth = [{(nx + ny) / 2} -nz] xd (V) The thickness of the aforementioned transparent protective film is not particularly limited, and can be appropriately selected according to the phase difference or protection strength, etc., generally less than 500 // m, 5 ~ 3〇〇 # m is preferable, and 5 ~ 15 0 // m is more preferable. The transparent protective film may be appropriately formed by a conventionally known method such as a method of coating the various transparent resins on a polarizing element, a method of laminating the transparent resin film on the polarizing element, or a commercially available product. X 'The transparent I material of the retardation plate of the present invention can also serve as the aforementioned transparent protective film. The transparent protective film may be further subjected to a purpose such as hard film treatment, anti-reflection treatment, adhesion prevention or diffusion, anti-glare, and the like. The aforementioned hard film treatment is based on the purpose of preventing surface scratches. For example, the surface of a transparent protective film is formed by a hardened resin. 25 200420919 A hardened film with excellent hardness and smoothness. As the curable resin, for example, a silicone-based, urethane-based, acrylic, epoxy-based UV-curable resin, etc. can be used, and the aforementioned treatment can be performed by a conventionally known method. Adhesion prevention is based on the purpose of preventing close contact with adjacent layers. The anti-reflection treatment is performed for the purpose of preventing reflection of light from the outside on the surface of the polarizing plate, and can be performed by forming a conventionally known anti-reflection layer or the like. The & glare s urged by the IJ face is for the purpose of preventing the visual obstruction of penetrating light caused by external & line reflection, etc., and forming a fine uneven structure on the surface of a transparent protective film by a method known in the past, for example get on. Examples of the method for forming such an uneven structure k include, for example, a sandblasting method or an embossing method, and a method in which transparent fine particles are mixed with the transparent resin as described above to form a translucent moon 5 蒦 溥 film. For example, the above-mentioned transparent particles can be exemplified by stone dioxide, oxidation, etc. In addition, conductive inorganic inorganic systems can be used, such as dioxin, emulsification, tin oxide, copper oxide, ore, and antimony oxide furnace. Micro-particles, organic micro-particles composed of cross-linked polymer particles, etc. "Transparent 2: There is no particular limitation on the average particle size of the particles. _ Limit two =: Also, the mixing ratio of transparent particles is not The range of special parts ^ Γ general transparent resin 1⑽f parts are preferably in the range of 2 to 70 mass, more preferably in the range of 5 to 50 parts by mass. The anti-glare film itself is used in combination with the above-mentioned transparent microparticles, and 7.j is formed as a transparent protective film. In addition, ㈣: on the surface of the transparent protective thin 臈 as a coating layer, etc. "" Several glare layers can also double as a diffusion layer (visual compensation function, etc.) that diffuses the transmitted light to magnify the viewing angle of 26 200420919. The aforementioned anti-reflection layer, etc. may be laminated with the aforementioned transparent protective film to form an anti-adhesion layer, a diffusion layer, and an anti-glare layer formed on the polarizing plate. For example, an optical layer can be laminated in a stacked manner. As for the polarizing plate, the aforementioned polarizing plate may further include other optical layers (such as a reflective plate, a transflective reflective plate, and a brightness-enhancing film, which are various conventional optical layers used in forming a liquid crystal display device). The layer can be one type or can be used in combination of two or more types, X, can be __ layer can also be laminated more than two layers. The following is a description of this integrated polarizing plate. The first S 'is for reflective M plate or An example of the transflective type reflective plate is described. The aforementioned reflective type polarizing plate is obtained by further laminating the reflective plate with the polarizing element and the transparent protective film, and the transflective type polarizing plate is based on The polarizing element and the transparent protective film are further laminated with a semi-transmissive reflective plate. The reflective polarizing plate is usually disposed inside the liquid crystal cell, and can be used to reflect incident light from the visual side (display side) for display. Type of liquid crystal display device (reflective liquid crystal display device), etc. This reflective polarizer can omit the built-in light source of the backlight, etc., so the thickness of the liquid crystal display device can be reduced, which is its advantage. It can be produced by a conventional method such as a method of forming a reflective plate made of a metal or the like on one side of a polarizing plate exhibiting elasticity. Specifically, S 'includes, for example, one side of the transparent protective film of the polarizing plate. (Exposed surface) Reflective polarizing plates made of metal or a bell box made of 27 200420919 reflective metal such as aluminum are formed on this surface as a matting treatment. The aforementioned various transparent resins contain fine particles to transform the ^ ★ into a transparent protective film with a micro, rugged structure. Jl t can reflect the reflective plate formed by the reflective plate with the fine uneven structure, such as flat reflectors with fine uneven structures on the surface, so that incident light can be irregularly reflected and diffused. This can prevent directivity or dazzling appearance, can suppress The unevenness of light and dark is the advantage. Such a reflecting plate can be, for example, a vacuum evaporation method, an ion implantation method, a Φ-year-old plating method, or a key bond method on the uneven surface of the foregoing transparent protective film (ie, Conventional method) It is directly formed in the form of a metal foil or a metal vapor-deposited film. Alternatively, instead of forming the reflective plate directly from the transparent protective film on the polarizing plate, a suitable film arrangement such as the aforementioned transparent protective film can be used instead. A reflecting sheet made of a reflecting layer is used as a reflecting plate. The reflecting layer S of the reflecting plate is made of metal, so for example, to prevent a decrease in the reflectance caused by oxidation, or to maintain the initial reflectance for a long time, or This is to avoid the need to form a transparent protective film, etc., and its use form is to cover the reflective surface of the summer heat with the aforementioned film or polarizer. Better state. On the other hand, the aforementioned semi-transmissive polarizing plate is one in which the reflective plate in the reflective polarizing plate is changed to a semi-transmissive reflecting plate. As for the semi-transmissive reflection plate, for example, a semi-transmissive polarizing plate that reflects light with a reflective layer and transmits the light, etc. A semi-transmissive polarizing plate is usually provided inside a liquid crystal element, and can be used in the following Type of liquid crystal display device and the like. That is, when the liquid crystal display device 28 200420919 is used in a bright environment of bismuth, the incident light from the visual side (display •) is reflected and the image is displayed. In a relatively dark environment, semi-transparent is used. A built-in light source such as a backlight light source built into the backlight side of the transmissive polarizer displays images. Therefore, this semi-transmissive polarizing plate is useful for the formation of a backlight source that can save energy in bright% i, and a liquid crystal display device with a built-in light source in a relatively dark environment. . ‘其 夂’ An example of a polarizing plate in which the brightness-improving film is further laminated on the polarizing element and the transparent protective film will be described. There is no particular limitation on the 7C degree-improving film. For example, a dielectric layer or a multilayer laminated body of a film having a different refractive index anisotropy can be used. These can allow a linearly polarized light of a predetermined polarization axis to pass through but The other lights are reflected. Examples of such a shell-enhancing film include the product name Γ D-RFF 荣 丄 2 J # manufactured by ⑽ Corporation. In addition, a cholesteric liquid crystal layer (especially an alignment film of XK compound of cholesteric hydration solution) can be used, or an alignment liquid crystal layer is supported on the film. These systems reflect the circularly polarized light on the left and right sides so as to allow other light to pass through. Examples include the product name PCF350 manufactured by Nitto Denko Corporation, and the product name "Transmax" manufactured by Merck Corporation. In the optical element # of the present invention, only the constituent elements (such as a retardation plate, 70 polarizing elements, a transparent protective film, etc.) can be laminated, and for example, the constituent elements can be further included, and a part of all the & It is preferable to laminate the foregoing adhesive layers. The manufacturing method of the optical element is not particularly limited, and it can be manufactured by a general method. For example, an adhesive layer or an adhesive may be applied to each constituent element to form an adhesive layer, and the foregoing constituent elements 29 200420919 may be bonded through the adhesive layer. Method manufacturing. For example, first prepare the retardation plate of the present invention and the polarizing element followed by the transparent protective film, and then apply one side of the retardation plate or the transparent protective film to an adhesive, and then paste the retardation plate. Combined with the aforementioned transparent protective film, the required optical element can be manufactured. The type of the adhesive or the adhesive is not particularly limited, and may be appropriately selected according to the materials and the like of the respective constituent elements, and examples thereof include acrylic acid-based, vinyl alcohol-based, lithone-based, polyacetate-based, Adhesives made of polymers such as polyamines, poly-baseds, and rubber knee adhesives. In the present invention, there is no obvious difference between the "adhesive" and the "adhesive", which means that it is relatively easy to peel off the adherends from each other in the adhesive, and the adherence is called an "adhesive". The above-mentioned adhesives, adhesives, and the like are difficult to peel off even under the influence of humidity or heat, and are excellent in light transmittance and polarization. Specifically: when the polarizing element is a PVA-based film, based on considerations such as the safety of subsequent processing, a pVA-based bonding agent is preferred. These adhesives or adhesives can be directly coated on the surface of the transparent protective film of the Kelly, Kelly and Nine Elements, and a strip of uranium K td or adhesive can be arranged on the uranium surface. Layer or sheet. In addition, for example, it can be prepared as an aqueous solution, and other additives or catalysts such as acids can be added as appropriate. In the case of coating a different type of adhesive, for example, in the aqueous solution of the adhesive, one cow ^ is mixed with other additives, such as an acid, and other media. The thickness 1η of the adhesive layer is not particularly limited, and is, for example, 1 nm to 500 nm, preferably 1 nm, 9λλ, 10,300 nm, and more preferably 20.100 nm. Formation of the above-mentioned pore film of the present invention, # and Jg. Bovine polarizing element, transparent protective sheet, photon layer, adhesive layer and other long-term compounds, each layer can also be used for example Ketone-based compounds, | Benzodisuccinic compounds, acrylic acid 30 200420919 Nitrogen compounds, ultraviolet absorbing agents, etc. are properly treated to impart ultraviolet absorbing ability. In the manufacturing process of a liquid crystal display device, the optical element of the present invention, the method of sequentially stacking the respective constituent elements on the surface of the liquid crystal cell, and the like, and the foregoing constituent elements are laminated in advance to form the optical element of the present invention The method provided to the manufacturing of the liquid crystal display device and the like has excellent quality son-in-law and assembly operability, so it has the advantage of improving the manufacturing efficiency of the liquid crystal display device and the like, which is ideal.

For unknown optical elements, based on the consideration that they can be easily laminated to other components of the liquid crystal cell, it is preferable that one or both sides of the outer side further have a typical adhesive layer or adhesive layer. The aforementioned adhesive layer or the like may be a layered body or a laminated body. As for the laminated body, for example, a laminated body composed of different groups or different types of single layers can be used. In addition, when disposed on both sides of the optical element, they may be the same adhesive layer, or they may be adhesive layers of the same composition or different types. When provided on the optical element: The case where the surface of the agent layer is exposed ’Before the adhesive layer is put to practical use, the purpose of ^ # is to prevent the dyeing, and the separator is used to cover the desired one. This spacer can be peeled off by a suitable peeling agent such as Shixue-based, long-chain-fired, Dun-based, vulcanized, etc. on the appropriate film. To form. The material of the film is not particularly limited. For example, the same material as the transparent protective film can be used. ^ c The method of using the light of the present invention is not particularly limited. It is used for various image display devices arranged on the surface of a liquid crystal cell, etc .: 31 200420919 Secondly, the image display device of the present invention will be described. The image display device includes the retardation plate of the present invention or the optical element of the present invention. Other than that, the image display device of the present invention is not particularly limited, and its manufacturing method, structure, and use method are arbitrary, and conventionally known forms can be suitably used. The type of the image display device of the present invention is not particularly limited. For example, A liquid crystal display device is preferred. For example, the phase difference plate or optical element of the present invention can be arranged on one or both sides of a liquid crystal cell to form a liquid crystal panel, and can be used for reflective or semi-transmissive, transmissive-reflective liquid crystal displays, etc. Device. The type of the liquid crystal cell forming the liquid crystal display device can be arbitrarily selected. For example, an active array driving type represented by a thin film transistor type, a simple array driving type represented by a twisted nematic type or a super twisted nematic type, can be used. For example, various types of liquid crystal cells can be used. The cell just mentioned is usually a structure that injects liquid crystal into the gap between the substrates of the liquid crystal cell. There is no particular limitation on the substrate of the liquid crystal substrate. For example, a glass substrate or a plastic substrate can be used. ^ The material of the plastic substrate is not particularly limited, and conventionally known materials can be mentioned. ,, Σ, and 々, Japanese-Japanese 7L t single-sided surface, when the above-mentioned optical elements and other components are arranged on both sides of the liquid crystal cell, these can be the same type or different. x, on the handle of the liquid crystal display, it can be further arranged at a suitable position-one layer: mirror row sheet, lens row sheet, light diffusion plate or backlight element, etc.

The structure of the liquid crystal panel in China is not limited to 32 200420919, and may include, for example, a liquid crystal cell, a retardation plate of the present invention, a polarizing element, and a transparent protective film. The one side of the liquid crystal cell is sequentially laminated with the retardation plate and the polarizing element. And the aforementioned transparent protective film is preferred. The arrangement of the retardation plate of the present invention is not particularly limited, and examples thereof include an arrangement method in which the optically anisotropic side faces the liquid crystal cell and a transparent substrate side faces the polarizing element. When the liquid crystal display device of the present invention further includes a light source, the light source is not particularly limited, but from the viewpoint of effective use of light energy, for example, a planar light source capable of emitting polarized light is preferred. Furthermore, the image display device of the present invention is not limited to the aforementioned liquid crystal display device, and can also be used in, for example, organic electroluminescence (EL) displays, plasma displays (PDs), and FED (Electric Field Emission Display: Field Emissi⑽ D1 sp 1 ay ) And other self-luminous image display devices. In the case of a self-emitting flat display device, by setting the in-plane retardation value of the optically anisotropic layer of the retardation plate of the present invention to / 4, circularly polarized light can be obtained, so it can be used as anti-reflection Filter used. The following is a description of the electroluminescence (EL) display device of the present invention. The EL display device of the present invention is a display device having the retardation plate or optical components of the present invention. The EL display device may be any of an organic EL display device and an inorganic EL display device. Recently, in the EL display device, an optical film such as a polarizing element or a polarizing plate and an I / 4 plate have been proposed to prevent reflection from an electrode in a black state. The retardation plate or optical element of the present invention, in particular, emits any of linearly polarized light, circularly polarized light, or elliptical polarized light from the el layer, 200420919, or emits natural light toward the front direction, and the emitted light toward the oblique direction is partially polarized. The situation is very useful. First, a general organic EL display device will be described. Generally, an organic EL display device includes a light emitting body (organic EL light emitting body) formed by sequentially stacking a transparent electrode (anode), an organic light emitting layer, and a metal electrode (cathode) on a transparent substrate. The organic light-emitting layer is a laminate of various organic thin films. For example, a laminate including a hole-implanted layer composed of a triphenylamine derivative and a light-emitting layer composed of a crab light f organic solid is known. Various combinations of a light-emitting layer and an electron-implanted layer composed of a forbidden benzene derivative or the like, or a hole-implanted layer, a light-emitting layer, and an electron-implanted layer. The organic EL device emits light based on the following principles. That is, voltage is applied to the foregoing anode and cathode to implant holes and electrons in the organic light-emitting layer. The energy generated by the recombination of these holes and electrons will excite the fluorescent substance. When it reaches the ground state, it emits light. Electron holes and electrons combined with this mechanism are similar to ordinary diodes in that current and luminous intensity show strong non-linearity accompanied by rectification for the application of electric dust. In the organic EL display device, 'in order to derive light from the organic light emitting layer, == the electrode needs to be a transparent electrode'. Generally, a transparent electrode formed of a steel tin oxide (ιτ〇) lunar transmissive conductor is used as an anode. On the other hand, in order to make it easier to implant the electrons to improve the luminous efficiency, it is important to use a substance with a small function of two functions. Usually, two A1 Li metal electrodes can be used. In the organic EL display device having the foregoing configuration, the organic light emitting layer is preferably formed as a thin film having a thickness of 34 200420919 to about 10 nm. This is because the organic light-emitting layer can make light almost completely penetrate the same as the transparent electrode. Therefore, light that is incident from the surface of the transparent substrate and penetrates the transparent electrode and the organic light-emitting layer when it is not emitting light, and the light that is reflected at the metal electrode is emitted to the surface side of the transparent substrate again. Therefore, when viewed from the outside, the display surface of the organic EL display device will be a mirror surface.

In the organic EL display device of the present invention, the retardation plate or optical element of the present invention is preferably provided on the surface side of the transparent electrode. With this configuration, an organic EL display device exhibiting effects of suppressing external reflection and improving visibility can be obtained. For example, the 'optical element of the present invention including the aforementioned retardation plate and polarizing plate' has a function of polarizing light incident from the outside and reflected on a metal electrode ', so that its polarizing effect can be used to avoid confirming the metal electrode from the outside. This is the mirror effect. In particular, as long as the retardation plate of the present invention is constituted by a 1/4 wavelength plate and the angle of polarization of the polarizing plate disc retardation plate is adjusted to redundant / 4, the mirror surface of the metal electrode can be completely shielded. In other words, only the linearly polarized light component can be transmitted by the polarizing plate with respect to the external light emitted by the EL device. This linearly polarized retardation plate can be generally elliptical, but when the retardation plate & ^ long plate and the aforementioned angle is r / 4, it becomes circularly polarized light. This circularly polarized light usually penetrates the transparent substrate, the transparent electrode, and the organic thin film and is reflected by the metal electrode, and penetrates the organic thin film, the transparent electrode, and the transparent substrate again. The phase difference plate becomes linearly polarized light again. This linearly polarized light cannot penetrate the polarizing plate because it is orthogonal to the polarization direction of the polarizing plate. Therefore, the mirror surface of the metal electrode can be completely shielded as described above. 35 200420919 Next, an embodiment of the present invention will be described. However, the present invention is not limited to the following examples. (Example 1) A retardation plate was manufactured as follows. That is, first, the externally polymerizable nematic liquid crystal compound (PaHocollol LC242 (trade name) manufactured by BASF Co., Ltd.) is not provided in the following chemical formula (1), and light of 0.5 g polymerization

Starter (Irgacure 907, manufactured by Chiba Tetsu Chemical Co., Ltd. (trade name D is added with 曱 $ 'stirring # 10 minutes to completely dissolve the solid to prepare a liquid crystalline compound solution (to become coating liquid A). Here, The addition amount of toluene was adjusted to a concentration of 20% by weight. On the other hand, a saponified cellulose acetate (TAC) film was prepared as a transparent substrate. Another TAC film (Fuji film) Co., Ltd.), and rubbing was performed on one side thereof as an alignment substrate.

On the cited transparent substrate, the coating liquid A was coated with a bar coater, and heated and dried at 120 ° C for 2 minutes to form a liquid crystal compound-containing layer and cooled to room temperature. The liquid crystalline compound contains ^^ The friction surface of the alignment substrate is closely adhered. After keeping the adhesive sheet heated at 15 ° C. for 2 minutes, it was cooled at room temperature to cool the temperature of the habitual compound-containing layer to about 40 ° C. In addition, the aforementioned $ [Biochemical substance-containing layer is irradiated with ultraviolet light with a cumulative light amount of 200mJ / cm2: 36 200420919] polymerizes the liquid crystal compound to form an optically anisotropic layer, and then peels and removes the alignment substrate to form the required Phase difference plate. (Example 2) A retardation plate was manufactured as follows. That is, first, in the same manner as in Example j, a coating liquid A was prepared. On the other hand, a 2% by weight aqueous solution (as coating liquid B) of a water-dispersible polyester resin (manufactured by Toyobo Co., Ltd. under the trade name Rib_1245) was prepared. Furthermore, a saponified triacetyl cellulose (TAC) film was prepared, and the coating solution B was coated on one side by a bar coater, and heated and dried at 120 ° C for 3 minutes. An optically isotropic polymer resin layer is used as a transparent substrate. Furthermore, another TAC film (manufactured by Fuji Negative Film Co., Ltd.) was prepared as an alignment substrate by rubbing on one side thereof. Next, the coating solution A 'was applied on a polyacetate resin layer of the transparent substrate with a bar coater, followed by heating and drying for 2 minutes to form a liquid crystal compound-containing layer. The cooled room temperature 'brings the surface of the liquid crystal compound-containing layer into close contact with the friction surface of the alignment substrate at this temperature. After maintaining the tight state, 120 T of heating for 30 seconds' cooled and cooled at room temperature, and cooled the temperature of the liquid crystal compound-containing layer to 40 ° C.] (: about. Further, the liquid crystal compound-containing layer was The ultraviolet light body t with a cumulative light amount of 200 mJ / cm2 polymerizes the liquid crystal compound to form an optically anisotropic layer. Then, the alignment substrate is peeled and removed to form a required retardation plate. (Example 3) Glass Plate instead of TAC film as a transparent substrate 'The rest are manufactured in the same manner as in Example 1. 37 200420919, Fruit Example 4) Uniaxially stretched polyethylene terephthalate (PET) Film instead of hook

The ΔΛ ^ ^ of the rubbing treatment was taken as an alignment substrate, and the rest were manufactured in the same manner as in the embodiment to produce a retardation plate. (Comparative example 1)

~ Manufacturing a retardation plate as follows. That is, first, the coating liquid A is prepared in the same manner as in Example 2 and Example 2. On the other hand, the coating liquid B was prepared in the same manner as in Example 2. Further, a glass substrate was prepared, and the aforementioned coating was applied with a bar coater on the glass substrate, and night B was dried for 3 minutes in one stroke. Then, the coating liquid A was applied with a bar coater, and was dried at 120 QC for 2 minutes, and dried to form a liquid crystal compound-containing layer. Next, it was cooled, and the liquid crystal compound-containing layer was irradiated with ultraviolet rays having a cumulative light amount of 200 mj / cm2 to polymerize the liquid crystal compound as described above to produce a retardation plate required. (Evaluation of liquid crystal alignment)

Regarding the retardation plates of Example 4 and Comparative Example 1, the alignment state of the liquid crystalline compound was evaluated by the following method. That is, first, two polarizing plates' are prepared, and a retardation plate serving as an evaluation target is sandwiched therebetween. Here, the polarizing axes of the two polarizing plates are perpendicular to each other. Next, light is irradiated from one side of the polarizing plate and it is confirmed whether the light passes through the other side. Furthermore, 'the polarizing axis is kept in a vertical state, and only the retardation plate is rotated, and its light transmittance is confirmed at various angles, and the alignment state of the liquid crystal compound is further evaluated. According to the above evaluation ', the alignment axis of each of the retardation plates of Examples 1 to 4 and the polarizing axis clip 45 of either of the two polarizing plates described above. It can be confirmed that the light passes through the polarizing plate. In addition, when the alignment axis is parallel or perpendicular to the polarization axis of either of the two polarizing plates, it can be confirmed that light does not pass through the polarizing plates. However, before the above-mentioned alignment axis is peeled and removed from each phase difference plate, it is the friction axis of the above-mentioned alignment substrate in the implementation of combination 3; in Example 4, it is the friction axis with the above-mentioned alignment substrate. The axis of the stretching axis is parallel. From this evaluation, it can be seen that in each of the phase difference plates of the yoke examples 1 to 4, each of the liquid crystal compounds is aligned in parallel with the alignment axis. In comparison, according to the above-mentioned Ping Shi κ juice estimation, the phase difference handle in Comparative Example 1

In all directions, light will read through & T a, J & A J 9 teeth through without disappearing. In addition, the phase difference plate of Comparative Example 1 can be visually inspected, and it is possible to make a complaint about the brother. From this, it is understood that the aforementioned liquid crystalline compounds are not regularly aligned. (Example 5) As described below, a phase difference plate was manufactured by the roll-to-light method using the manufacturing method of the present invention. First, a coating solution containing the following compounds is prepared as follows. That is, first, in the ultraviolet-polymerizable nematic liquid not represented by the following chemical formula (n Q), a compound of 1 kg and 5 Og of a daily compound, such as ，, Λ. I starter (Irgacure907 manufactured by Chiba Special Chemicals Co., Ltd. (trade name φ 4) added toluene to dissolve and prepare a solution. Here, the amount of toluene was adjusted to $, and the concentration of Fenbe was 20% by weight. 〇Stir for 60 minutes and fill the solute with the starfish w. Mouthpiece / Filling knife> Gu Jie, and then use a transitional strain with a diameter of 2.5 // m (made by the Japanese company Paul) to borrow and transfer it to the required one. Coating liquid. On the other hand, prepare a transparent substrate. That is, firstly, prepare triethyl cellulose with a width of 300 mm and a length of 300 m. After the saponification treatment, apply polyisocyanate resin (manufactured by Toyobo Co., Ltd. ^ ^ "Baro Nalu MD-1245 (transparent substrate required for product 39. Prepare a width of 300mm and a length of 300m 'Rewind it to the name of the winding)' 'Rewind it to ^ to get re Or, prepare an alignment substrate. That is, triethyl cellulose with a surface treated with rubbing can be used to find the required transparent substrate. Second, 'assemble into a device with the structure shown in Figure 2, use the device and a shovel The coating liquid, transparent substrate, and substrate are required for manufacturing. Retardation plate schematic of the process as aforesaid, and the specific conditions are as follows. That 'First, the transparent substrate 13 and the alignment of the feed line speed of the substrate 16 to 4m /

Minute. Using the aforementioned coating solution as a helmet, the right θ k ^ A soil suppression solution is a liquid crystal compound solution, and a micro gravure printing coater was used on the liquid crystal compounding solution coating device 14 towels to wind the wire. The rods control the thickness of the coating. A drying device 15 was used to set the drying temperature to 100 ° C. The time from entering the drying device 15 to the drying device 15 was 1 minute. The heating temperature was set to 150 using a heating device. . The time from the point i between the transparent substrate 13 and the alignment substrate 16 from entering the heating clothing 17 to exiting the heating device is 3 Q seconds. A high-pressure mercury lamp with an output of 120 w / cm was used in the liquid crystal alignment fixing chemical set 18, and the irradiation amount was 600 mJ / cm2. The final retardation plate 20 is transparent and has excellent light penetrability without white turbidity. Similar to Example 4 & Comparative Example, this phase difference plate was evaluated for liquid crystal alignment with a polarizing microscope, and the same characteristics as those of Examples 1 to 4 were observed. That is, it can be confirmed that the retardation plate of this embodiment is an optical anisotropy having uniaxial alignment. The phase difference was measured with a spectroscopic ellipsometer ("M-220 model (trade name)" manufactured by Spectroscopy Corporation). The results are shown in Fig. 3. It can be seen from the figure that the phase difference characteristic of the phase difference plate of this embodiment is 200420919 bilaterally symmetrical. In addition, the method of measuring the phase difference is in accordance with the general use method of the spectrometer. (Example 6) A retardation plate having a tilt angle as described below was manufactured. That is, first, the coating liquid A was prepared in the same manner as in Example 1. On the other hand, the coating liquid B was prepared in the same manner as in Example 2. In addition, a saponified cellulose triacetate (TAC) film was prepared, and the coating solution B was coated on one side by a bar coater, followed by heating and drying at 120 ° C for 2 minutes to form an optical isotropy. Polyester resin layer as a transparent substrate. Next, the above-mentioned coating liquid A 'was applied onto the polyacetate resin layer of the transparent substrate at 120 ° C. (; Heating and drying for 2 minutes; forming a liquid crystal compound-containing layer. On the other hand, an easily-adhesive polyethylene terephthalate film is prepared, and a polysiloxane compound is coated on one side of the film. Manufactured by N Specialty Co., Ltd., under the trade name Pelgaut P). It is heated and dried for 1 minute to form a polysiloxane layer, and then rubbed on its surface to become an alignment film, thereby obtaining an alignment substrate with tilting alignment ability of liquid crystals. Next, the liquid crystal compound-containing layer is brought into close contact with the friction surface of the alignment film, and the heating is performed at 120 ° C for 2 minutes while maintaining the state. Then, the liquid crystal compound-containing layer is cooled at room temperature to make the temperature of the liquid crystal compound-containing layer. Cooling = about 40 ° C, and irradiation with ultraviolet light with a cumulative light amount of 200 mJ / cm2, so that the former = = said: polymer is polymerized to form an optically anisotropic layer. Then the aforementioned alignment soil plate is peeled to obtain the required retardation plate. The obtained retardation plate is transparent and free from white turbidity and other phenomena.

Light tooth permeability. This retardation plate was retarded from that of Example 5. 1 Ai method to measure I 〃 ,,,. The results are shown in Figure 4. It can be seen from the figure that the phase difference characteristics of the differential plate in this implementation are asymmetrical left and right, so it is a differential plate. << Phase (Example 7) A retardation plate having an inclination angle is manufactured in the following manner. That is, in Baixian ', 20 parts by weight of the liquid crystalline copolymeric human compound represented by the following chemical formula (i) was dissolved in 80 parts by weight of Diqi Yiyuan to obtain a liquid crystalline compound solution. Wherein 'η' and .η in the chemical formula 表示 respectively represent the ratio of monomer units (Mole and 0-100, in this embodiment, 0M. Also, in this embodiment, R1 in the chemical formula 为 is a hydrogen atom. The weight-average molecular weight of the liquid crystalline copolymer compound is 5000. With R1-C-

h2c c-o-ch2-ch2-o ο 100-π ο η (2) # A phase difference plate was manufactured in the same manner as in Example 6 except that the solution was used in place of the aforementioned coating solution A and was not irradiated with ultraviolet rays. The obtained retardation plate is transparent and has excellent light penetrability without white turbidity and the like. Furthermore, it was measured in the same manner as in Example 5 and Example 6. It was found that the phase difference characteristic was a left-right asymmetrical phase difference plate with an inclination angle (Example 8). 42 200420919 Manufactured as follows Phase difference plate with tilt angle. That is, first, an acrylic liquid crystal compound (Vantico Corporation | y, CB483 (trade name)) was dissolved in toluene to obtain a 30% by weight liquid crystal compound solution. Next, a transparent beauty material was produced in the same manner as in Example 6. The liquid crystal compound solution was coated on the polyester layer and heated at 12% for 2 minutes to dry it to form a liquid crystal compound-containing layer. On the other hand, a photo-alignment film-forming liquid (manufactured by Fantec, LPPF301 (trade name)) was applied on one side of the glass plate to 150. (: Heating and drying for 10 minutes, and then forming an alignment film by obliquely irradiating polarized ultraviolet rays to obtain an alignment substrate having a liquid crystal oblique alignment ability. Next, the transparent substrate and the alignment substrate are coated with the liquid crystal compound-containing layer. And the alignment film can be adhered in such a manner that the alignment film can be closely adhered, and the state is maintained at 120. (: Heating for 2 minutes. After that, it is cooled to a temperature. The temperature of the liquid crystal compound-containing layer is cooled to about left and right, and the accumulated light amount is The above-mentioned liquid crystal compound is polymerized to form an optically anisotropic layer by irradiating ultraviolet light at 20 mJ / cm2 to form an optically anisotropic layer. Then, the alignment substrate is peeled off to form a required retardation plate. The obtained retardation plate is free from white turbidity and the like. It is transparent and has excellent light penetrability. Measure the phase difference in the same way as the implementation of your "~ 7": the result is shown in Figure 5. It can be seen that the phase difference and the property of the phase difference plate of this embodiment are The left and right sides are asymmetric, so it is a phase with an inclination angle (Comparative Example 2). A single phase two is used to manufacture a retardation plate as follows. That is, first, a glass plate: a surface is mainly used for forming a light alignment film. (LppF30i (manufactured by Ticco) (products are dried by heating at 150 ° C for 10 minutes, and then polarized by oblique irradiation 43 200420919 ', Youkai / Chenghayou liquid day-to-day tilting alignment ability alignment film, Make a transparent substrate. Then, prepare a liquid crystal :::: material solution in the same manner as in the Example &quot; and apply it to the aforementioned alignment film, and dry it for 12 minutes in pure 2 minutes. 'Cool in a room temperature environment to cool the liquid crystal: the temperature of the material-containing layer is cooled to about ㈣. Then, the liquid crystal compound is irradiated with ultraviolet rays with a cumulative light # 2GGmJ / cm2 under a nitrogen atmosphere. Required phase difference plate.

The phase difference plate was obtained by polymerizing it to form an optically anisotropic layer. (Comparative Example 3) A phase difference plate was produced in the same manner as in Comparative Example 2 except that the ultraviolet irradiation was performed in the atmosphere instead of the nitrogen washing atmosphere. The retardation plate has a tilt angle. (Hardness test and checkerboard peel test)

The hardness test and checkerboard peel test of the optical anisotropic layer of the retardation plates of Example 8, Comparative Examples 2 and 3 were performed. The hardness test was performed using a machine MHA-400 (trade name) manufactured by NEC Corporation in accordance with jis-K5401. The substrate grid peeling test is an adhesive tape (manufactured by Nitto Denko Corporation, No. 720 (trade name)) is closely adhered to the optical anisotropic layer of each retardation plate, and then peeled off to observe the peeling of the optical anisotropic layer. situation. As a result of the hardness test, in Comparative Example 2 (irradiation of the liquid crystal compound-containing layer with ultraviolet rays in a nitrogen-washed atmosphere), the press-in hardness of the optically anisotropic layer was 0 · 5OGPa, which corresponds to pencil hardness B. In contrast, the retardation plate of Comparative Example 3, which was irradiated with ultraviolet rays in the atmosphere, had an optical anisotropic layer having a press-in hardness of 0.20 GPa (corresponding to a pencil hardness of 4B), which was insufficient in hardness. Moreover, in the retardation plate of Example 8 of 2004 200420919, the liquid crystal compound-containing layer was irradiated with ultraviolet rays in the atmosphere without being washed with nitrogen, but was the same as the retardation plate of Comparative Example 2. Its optical anisotropic layer Its indentation hardness is 0.50GPa. In the checkerboard peeling test, the retardation plate of Example 8 had almost no peeling of the optical anisotropic layer and showed good adhesion. In comparison, in Comparative Examples 2 and 3, the optical anisotropic layer was large. Partial peeling with poor results. That is, compared with Comparative Examples 2 and 3 in which the optically anisotropic layer was formed on the alignment film, the retardation plate of Example 8 had better adhesion between the transparent substrate and the optically anisotropic layer. Industrially, as described above, according to the present invention, it is possible to manufacture a thin phase retardation plate with low performance and no appearance defects. Because the manufacturing method of the present invention allows the optically anisotropic layer having a liquid crystal compound to be laminated on the substrate without passing through an alignment film or an adhesive, it is advantageous for achieving the optical performance and thinning of the retardation plate. The rubbing-treated alignment film does not remain in the retardation plate, so there are no appearance defects caused by rubbing treatment. Furthermore, there is no problem caused by poor adhesion between the alignment film and the aforementioned optically anisotropic layer. In addition, when the liquid crystal compound is photopolymerized by the manufacturing method of the present invention, a phase difference plate having excellent hardness and durability can be easily obtained even if nitrogen washing is not performed, so it is also beneficial to improve the manufacturing efficiency of the phase difference plate. In addition, the manufacturing efficiency can be further improved if the light-to-light manufacturing process is used. The retardation plate manufactured by the manufacturing method of the present invention can be widely used in various optical elements, image display devices, and the like, and particularly contributes to the reduction in thickness of liquid crystal displays. 45 ^ 00420919 [Brief description of the drawings] (I) Schematic part Fig. 1 is a process drawing showing an example of the manufacturing method of the present invention. Fig. 2 is a schematic diagram showing an example of an apparatus for implementing the manufacturing method of the present invention. FIG. 3 shows the phase difference characteristics of the phase difference plate of the fifth embodiment. FIG. 4 shows the phase difference characteristics of the phase difference plate of the sixth embodiment. Fig. 5 shows the phase difference characteristics of the phase difference plate of the eighth embodiment. (II) Symbols for components 1 Transparent substrates 2a, 2b Liquid crystal compound-containing layer 3 Alignment substrate 4 Phase difference plate 5-12 Roller 13 Transparent substrate supply roller 14 Liquid crystal compound> Valley coating device 15 Drying device 16 Alignment Substrate supply pro 17 Heating device 18 Liquid crystal alignment fixing device 19 Alignment substrate winding device 20 Phase difference plate winding device 46 200420919 21 Transparent substrate 22 Alignment substrate 23 Phase difference plate

47

Claims (1)

200420919 Patent application scope: 1 · A method for manufacturing a retardation plate, which is used to manufacture a retardation plate with an optically anisotropic layer formed on a transparent substrate; it is characterized by including the following process (1) ~ (4): process (1) forming a liquid crystal compound-containing layer on the transparent substrate without liquid crystal alignment capability; process (2) making the liquid crystal compound-containing layer contact with an alignment substrate with liquid crystal alignment capability, so that the The liquid crystal compound alignment of the layer; the process (3) fixes the alignment state of the liquid crystal compound of the layer to form an optically anisotropic layer; the airtight (4) removes the alignment substrate. 2. The manufacturing method according to item 1 of the scope of patent application, wherein one side or both sides of the transparent substrate is coated with an optical isotropic layer, and in the process (1), the optical isotropic layer is coated on the optical isotropic layer. This liquid crystal compound-containing layer is formed. 3. The manufacturing method according to item 1 of the patent application scope, wherein the liquid crystal compound contains at least one of a liquid crystal prepolymer and a liquid crystal monomer, and in the process (3), the liquid crystal compound is subjected to light irradiation. The polymerization method fixes the alignment state. 4. The manufacturing method according to item i of the application, wherein the liquid crystal compound is a liquid crystal polymer. In the process (3), the alignment is performed by cooling the liquid crystal compound-containing layer to a temperature below its liquid crystal temperature. Immobilization of state. 5. The manufacturing method according to item 丨 in the scope of application for a patent, wherein, in the process 液晶, the method for forming the liquid crystal compound-containing layer on the transparent substrate 48 200420919 method is to apply a solution of the liquid crystal compound A method of drying the transparent substrate, or a method of applying the molten liquid crystal compound to the transparent substrate. 6 · The manufacturing method according to item 1 of the patent application scope, wherein, in the process (2), 'the liquid crystal compound-containing layer is heated to exceed its liquid crystal temperature, and in this state, is brought into contact with the alignment substrate, or The liquid crystal compound-containing layer is in contact with the alignment substrate, and is heated to exceed the liquid crystal temperature in this state. 7. The manufacturing method according to item 1 of the patent application scope, wherein the transparent substrate has optical anisotropy. 8. If the base material is a band-shaped transparent base material, perform the processes (1) to (4). The manufacturing method of item 1 is sent continuously while “the transparent output is continuously fed into 9”. For example, the manufacturing method of the item 1 of the patent application scope, Ά, y, and again, the alignment soil plate is a belt-shaped alignment substrate, This process (2) ~ (4) is performed continuously. Marching in succession Transparent Further one item 10. If the manufacturing method of the scope of patent application item 8 or 9 is applied, at least one of the base material and the alignment substrate is sent out using a roller. 11. If the manufacturer of the scope of patent application item 8 or 9 is used. The step includes a winding process (5) of the phase difference plate. Among them, 12 · -type retardation plates are characterized by being manufactured by the manufacturing method thereof. Ming patent scope 13 · An optical element characterized by the phase difference plate and polarizing element of item 12. Ming Patent Scope 49 200420919 14 · Rushen's patent includes a transparent protective film plate and the polarizing element. The optical element around item 13, among them, further, the transparent protective film is arranged in the phase difference. [5] If the optical element in the U range of the patent application, the pot step includes an adhesive layer, and constitutes the light wind_ 再 欣 4 7b The components of the learning element are laminated through the adhesive layer. ^ 次 '1 6. — A type of LCD panel, basin win, and temple sign, is the phase difference plate or the patent application for the phase difference plate of the 12 items in the scope of the patent application. Obtained on one or both sides of the liquid crystal cell. The 17th-type image display device includes a phase difference plate of the 12th patent application or the 18th type of liquid crystal display device of the optical element of the 13th patent application, which is characterized by including the first Phase difference plate with 12 items, optical element with patent application No. 13 or liquid crystal panel with patent application No. 16. Pick up, schema: as next page 50