Liquid crystal display panel incorporating an optical phase shifting substrate

Abstract: A liquid crystal display panel incorporating an optical phase shifting substrate which comprises a liquid crystal cell (1), a pair of polarizing sheets (2) disposed on opposing sides thereof, and a couple of substrates each having a transparent electrode layer, one of the substrates (3, 4) being either an optical phase shifting single oriented synthetic resin film or a laminate film comprising an optically isotropic amor­ phous film laminated to at least one side of the above optical phase shifting film and the other substrate being either a single-layer or multi-layer optically isotropic amorphous film or a glass sheet.

Description: BACKGROUND OF THE INVENTION This invention relates a liquid crystal display panel using an birefringent substrate and more particularly to a liquid crystal display panel of improved contrast and reduced angle-of-vision dependency. The liquid crystal display panel in general comprises a liquid crystal cell and a polarizer sheet disposed on either side of said cell and its basic structure may be represented by the scheme: Polarizer sheet/liquid crystal cell/polarizer sheet Of these constituent members, the liquid crystal cell comprises a pair of substrates each carrying a transparent electrode layer on one side thereof as disposed face-to-face with a spacer means interposed between the respective transparent electrode layers, with the gap between the two substrates having been filled with a liquid crystal material and the peripheral edges of the assembly sealed off with an epoxy or other adhesive. The schema of the assembly thus constructed is: Substrate/transparent electrode/liquid crystal/ transparent electrode/substrate Each of these substrates must be optically transparent and isotropic. Otherwise, the product liquid crystal display panel will be seriously colored to thereby interfere with a visual recognition of the information displayed. Therefore, it is essential that an amorphous material be chosen for the substrates and, for this reason, sheet glass substrates have been used almost exclusively. However, glass substrates are heavy in weight and cannot be thinned beyond a certain limit. Moreover, these substrates are liable to be broken, i.e. of poor impact resistance, and cannot be taken up on a roll or the like for mass production. Recently, therefore, synthetic resin films have come to be used for the substrates. Liquid crystal display panels are used in quantities today in the display units of office automation devices such as word processors, personal computers and so on, and recently STN (super-twisted nematic) liquid crystals have been developed and used especially for large-sized liquid crystal display panels. In this system, however, the background is colored yellow, green or deep blue and, therefore, provides only a poor contrast. Moreover, there is the problem of angle-of-vision dependency, which means that the contrast deteriolates when the display panel is viewed at an angle. Therefore, this system has not fully satisfied the users' demand for improvement in visual recognizability. Recently, however, thanks to the various improvements made in the aspect of liquid crystal structure and material, several large-capacity simple matrix liquid crystals with increased levels of blackness and, hence, enhanced contrast have been introduced one after another and high-contrast, substantially perfect black-and-white display panels and their color versions have been implemented. Of these newer panels, the most noteworthy is the panel in which the color of yellow, green or deep blue has been cancelled by the use of two STN liquid crystal cells in overlapping relation. In the cell forming the second layer of this panel structure, the orientation of liquid crystal molecules has been twisted in the reverse direction to cancel out the color produced in the first layer (Nikkei Micro Device, August 1987 issue, pp.36-38 and Nikkei Micro Device, October 1987 issue, pp.84-88). However, while the above published simple matrix liquid crystal panel for black-and-white high-contrast display has been designed to improve the contrast by superimposing a liquid crystal cell on another cell to render the color neutral (gray), the use of two liquid crystal cells of necessity makes the whole liquid crystal panel as much heavier and thicker, with the result that this system is contrary to the current trend toward reduced weight and thickness of the panel. Moreover, this display panel gives rise to a color when viewed at an angle and has room for improvement in the aspect of angle-of-vision dependency. A-0 311 339 discloses a liquid crystal display which comprises a liquid crystal panel having a liquid crystal layer disposed between electrode layers, polarizers disposed at both sides of the panel, and a solid birefringent film having the maximum refractive index direction varying with its depth and disposed at at least one side of the liquid crystal panel between the polarizers. It is described that the solid birefringent film compensates the dependence of the polarization characteristic on wave length, and would be capable of obtaining either a monochrome display or a display having an extremely low coloration. EP-A 0 297 841 discloses a thermoplastic polymer, preferably unoriented and amorphous, e.g. of polyester, polysulfone, polyvinyl chloride, polyacrylonitrile or acrylonitrile, is molded into a sheet or film and uniaxially stretched, preferably by tentering. The stretched film has (a) a low optical color unevenness expressed by its color difference (Δ E*) being such that the highest measured value thereof is not more than 30 as measured with a spectrophotometer on usually 10 locations of the sample whilst illuminated between crossed parallel polarizers with the sample optical axis at 45° to the phases of polarization, (b) a retardation value (R), i.e. the product of the thickness of the film and its birefringence, of 30 - 1200 nm, preferably 200 -1000 nm, and (c) an average visible light transmittance of at least 50%. It is reported that the film has fixed optical axis and a retardation value suitable for its use as an optical phase retarder and that it further could be placed against one of a pair of polarizing sheets in a liquid crystal cell. JP-A-58-143319 describes a liquid crystal display element which consists of upper, lower electrode substrates provided with electrode substrate functions on the polarizing plates. The substrates consist of the polarizing plate construction wherein a polarizer is sandwiched with supports which are uniaxially oriented polyethylene terephthalate films. Transparent electrode films are formed respectively on the surfaces of the substrates and are etched, whereby required electrode patterns are formed and the liquid crystal molecules are oriented. The substrates are adhered to each other by means of sealing materials, whereafter liquid crystals 4 are sealed therebetween. A reflection plate is adhered to the substrate, whereby the liquid crystal display element is constituted. JP-A-60-26322 describes a TN liquid crystal layer which is sandwiched with two linearly polarizing plates each having a polarizing axis crossing each other at right angles, and a transparent film having a polymer oriented in a specified direction and exhibiting optical birefringence and erasing coloring display phenomenon is inserted between one of the plates and the layer. Polycarbonate, a copolymer of tetrafluoroethylene and hexafluoroethylene, or polyfluoroethylene propylene ether is used for the material of this film. The rotation angle of this film is controlled so as to maximize the erasion effect of said phenomenon. As a result, the coloring phenomenon remarkably occurring especially in a large-sized cell can be easily erased, an off-grade rate in manufacture can be lowered, further, occurrence of elliptic polarization can be reduced, and contrast can be enhanced. It is an object of this invention to provide a liquid crystal display panel which, while satisfying the aforesaid requirements for reduced weight and reduced thickness, has realized a marked improvement in contract by way of color neutralization and, at the same time, virtually eliminated the problem of angle-of-vision dependency, thus overcoming the above-mentioned disadvantages of the prior art. SUMMARY OF THE INVENTION The liquid crystal display panel according to this invention comprises two opposed substrates supporting on their inner sucfaces transparent electrodes and enclosing super-twisted nematic liquid crystal material; two polarizer sheets stacked on the outer surface of the substrates, respectively; wherein one substrate consists of a stretched birefringent synthetic resin film backed on both sides thereof by optically isotropic multilayer amorphous films each including at least a gas-impermeable synthetic resin layer and a cured cross-linkable resin layer disposed adjointing to each other and wherein the other substrate consists of (i) an optically isotropic multilayer amorphous film including at least a gas-impermeable synthetic resin layer and a cured cross-linkable resin layer disposed adjointing to each other or (ii) a glass sheet. BRIEF DESCRIPTION OF THE DRAWING Fig. 1 is a cross-sectional view showing an example of the liquid crystal panel of this invention. DETAILED DESCRIPTION OF THE INVENTION Liquid crystal cell 1 The conventional liquid crystal cell in common use includes two juxtaposed glass sheets, both of which are optically isotropic, as substrates for supporting transparent electrodes. In contrast, the liquid crystal cell 1 used in this invention includes, as one substrate 3 for supporting one of transparent electrodes of the cell; a stretched birefringent synthetic resin film A backed on both sides thereof by optically isotropic multilayer amorphous films B each including at least a gas-impermeable synthetic resin layer and a cured cross-linkable resin layer disposed adjointing to each other and, as the other substrate 4 for supporting the other transparent electrode, (i) an optically isotropic multilayer amorphous film B including at least a gas-impermeable synthetic resin layer and a cured cross-linkable resin layer disposed adjointing to each other or (ii) a glass sheet C. Birefringent substrate As examples of said stretched birefringent synthetic resin film A, there may be mentioned stretched amorphous films of polymers with a glass transition temperature not less than 60°C, such as polycarbonate, phenoxy resin, polyparabanic acid resin, fumaric acid resin, polyamino acid resin, polystyrene, polysulfone, polyethersulfone, polyarylene ester, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polymethyl methacrylate, polyester and cellulosic and other polymers. The stretched birefringent synthetic resin film A can be manufactured by stretching the corresponding high polymer at a suitable temperature and, if necessary, subjecting the stretched film to aging. The conditions such as stretching temperature, draft ratio, aging temperature and aging time are dependent on the kind of polymer used and cannot be defined in general terms. Generally speaking, however, the stretching temperature is higher than the glass transition temperature of the material polymer (preferably higher than the glass transition temperature by at least 10°C), the draft ratio is about 1.1 to 8, the aging temperature is over said glass transition temperature, and the aging time is about 1 to 300 seconds. Stretching is generally monoaxial but biaxial stretching is applicable to some types of polymers. The optical stretched birefringent synthetic resin film A is used as laminated with an optically isotropic multilayer amorphous film B on both side thereof. Examples of such lamination are B/A/B, B/A/B/B, B/B/A/B/B etc.. An adhesive layer may be interposed between respective layers of the laminate. The total retardation value of the substrate is desirably not less than 60 nm and preferably not less than 70 nm Though the upper limit for this value is not critical, it is generally about 1000 nm. The transparency of the substrate is desirably not less than 60 percent, while its heat resistance is preferably not less than 60°C. This substrate is preferably resistant to chemicals (solvent resistance). The thickness of this birefringent substrate is desirably about 5 to 3000 µm and preferably about 7 to 3000 µm. The optically isotropic multilayer amorphous film B includes gas-impermeable synthetic resin layer and cured crosslinkable resin layer disposed adjointing to each other. The film (B) may further include film of polycarbonate, polyparabanic acid resin, fumaric acid resin, polystyrene, polyethersulfone, polyarylene ester, cellulosic polymer, polyester, polysulfone, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyacetate, poly-4-methylpentene-1, polyphenylene oxide, and so on. As examples of the cured film of crosslinkable resin, there may be mentioned the films formed from crosslinkable resin compositions each comprising at least one member of the group consisting of phenoxyether crosslinkable resin, epoxy resin, acrylic resin, acryl epoxy resin, melamine resin, phenolic resin and urethane resin and a crosslinking agent capable of reacting with active hydrogen. Particularly useful is the film formed from a phenoxyether type crosslinkable resin. The crosslinking agent capable of reacting with active hydrogen is a compound having an isocyanato, carboxy, mercapto or the like reactive group. The curing procedure may be simple heating or irradiation with an actinic radiation (ultraviolet light, electron beam, etc.). As examples of the gas-impermeable synthetic resin film, there may be mentioned polymer films having an oxygen permeability (as determined in accordance with ASTM D-1434-75) of not more than 30 cc/24 hr·m²·atm, preferably not more than 20 cc/24 hr·m²·atm, and more specifically the films formed from polymers each containing at least 50 mole percent of acrylonitrile, vinyl alcohol or vinylidene halide and any of the above-mentioned groups reactive to crosslinkable resins. Particularly useful, among such polymers, are OH-containing polymers such as polyvinyl alchol, either as such or as modified by copolymerization or graft copolymerization, and ethylene-vinyl alcohol copolymer with an ethylene content of 15 to 50 mole percent. When the above-mentioned cured crosslinkable resin film and gas-impermeable synthetic resin film layers are disposed adjoining to each other, the crosslinking agent used in the curing of the former film advantageously insures an intimate adhesion of the two layers without the aid of an adhesive layer. Moreover, in this laminar construction, the latter layer makes up for the disadvantage, i.e. brittleness, of the former layer, while the former layer makes up for the disadvantage, i.e. moisture permeability, of the latter layer. The above optically isotropic multilayer amorphous film B should have a retardation value of not more than 50 nm and preferably not more than 40 nm. The term "retardation value (R value)" as used in the specification means the product of the thickness d of the film multiplied by the absolute value of the difference between the refractive indexes of said film in two mutually perpendicular directions. R = d· | n¹ - n² | wherein n¹ is the refractive index* in an optional direction and n² is the refractive index in the direction perpendicular to n1. Optically isotropic substrate As the optically isotropic multilayer substrate which is to constitute the other substrate 4 for supporting the other transparent electrode of liquid crystal cell 1, either (i) an optically isotropic multilayer amorphous film B including at least a gas-impermeable synthetic resin layer and a cured cross-linkable resin layer disposed adjointing to each other or (ii) a glass sheet C is employed. The above optically isotropic mulilayer amorphous film B may be the same as the one described hereinbefore for the birefringent substrate. The optically isotropic multilayer amorphous film B should have a retardation value of not more than 50 nm and preferably not more than 40 nm. The light transparency of the film is desirably not less than 60 percent, while its heat resistance is preferably not less than 60°C. The thickness of the optically isotropic substrate is preferably in the range of 20 to 1000 µm and, for still better results, about 50 to 800 µm. In the case of glass sheet C, its thickness may range from about 0.3 to 3 mm. Transparent electrodes The transparent electrode is a transparent electrode layer formed by a known procedure which may, for example, vacuum vapor deposition, sputtering, ion plating, metal spraying, metal plating, chemical vapor deposition or spraying. Among these techniques, vacuum vapor deposition and sputtering are preferred because a thin film of uniform thickness can be produced. As the material for said transparent electrode layer, various metals such as Sn, In, Ti, Pb, Tb, etc. and oxides thereof are generally employed. When an elementary metal is used, the resulting film on the substrate can be subsequently oxidized in situ . While a metal oxide layer may be directly formed on the substrate, it is also possible to form a metal film or a low-oxide film in the first place and, then, subject the film to oxidation or additional oxidation by, for example, thermal oxidation, anodic oxidation or liquid-phase oxidation technique to obtain a transparent film. When a low-temperature sputtering equipment is employed, the thermal oxidation can be omitted. Aside from the metals mentioned above, noble metals such as Au, Pt and Ag may also be used in certain cases. The above metal or metal oxide electrically conductive layer is formed in a thickenss suited to required characteristics such as transparency, electrical conductivity, etc. and is generally not less than 100 Å and, for insuring stable electrical conductivity, preferably not less than 300 Å. Liquid crystal As the liquid crystal, super-twisted nematic (STN) liquid crystals are employed with advantage. Polarizer sheet 2 As examples of the polarizer sheet 2, there may be mentioned polarizing films of the following systems, i.e. (a) polyvinyl alcohol-iodine, ethylene-vinyl alcohol copolymer/iodine, etc. and (b) polyvinyl alcohol/two-tone dye, ethylene-vinyl alcohol copolymer/two-tone dye, ethylene-vinyl alcohol copolymer/polyene, polyvinyl alcohol/polyene, polyvinyl halide/polyene, polyacrylonitrile/polyene, polyacrylate/polyene, polymethacrylate/polyene, etc. or laminates of such polarizing films with optically isotropic amorphous films B which have been described hereinbefore. In the liquid crystal display panel of this invention, as a substrate 3 for supporting one of transparent electrodes of a liquid crystal cell 1, the aforementioned birefringent substrate is used in lieu of the conventional glass substrate. Thus, it has been designed that this birefringent substrate may play not only the role of a substrate for supporting a transparent electrode but also the role of improving the contrast effect and eliminating the angle-of-vision dependency of the liquid crystal display panel. Furthermore, in this invention, the aforementioned optically isotropic multilayer substrate or a glass sheet, which is also optically isotropic, is used as the substrate 4 for supporting the other transparent electrode of liquid crystal cell 1. In the case of said optically isotropic multilayer substrate, compared with glass sheet, the weight and thickness of the liquid crystal cell can be decreased and, moreover, its impact resistance is improved. In the case of glass sheet, the total weight of the liquid crystal cell can be decreased because the substrate 3 for supporting the other transparent electrode is not made of glass. As described above, the liquid crystal display panel of this invention has fulfilled the long-standing need for neutralization of its color and consequent improvement of contrast and for improvement of angle-of-view dependency while satisfying the requirements of reduced panel weight and thickness. Furthermore, since the birefringent substrate itself functions as a substrate for supporting the transparent electrode of a liquid crystal cell, the liquid crystal display panel of this invention offers the following advantages over the known display panel in which the liquid crystal cell is provided with an independent phase sheet. Thus, the complicated step of attaching a phase plate to the liquid crystal panel with an adhesive is eliminated and both the "slip" phenomenon and "tunneling" phenomenon (formation of voids) due to thermal degradation or aging of the adhesive layer securing the phase sheet to the panel are also eliminated. Examples The following examples are further illustrative of this invention. In the examples, all parts are by weight. Example 1 Fig. 1 is a cross-sectional view showing an example of the liquid crystal display panel of this invention. Stretched birefringent synthetic resin film A In 150 parts of methylene chloride was dissolved 10 parts of a polycarbonate derived from bisphenol A, with stirring. The resulting solution was cast on a glass plate and dried at 40°C to give a transparent film with a thickness of 58 µm. This film was monoaxially stretched in a draft ratio of 3 in an atmosphere at 180°C and then aged. The above procedure provided an birefringent film which was 32 µm thick and had a retardation value of 143 nm. Optically isotropic multilayer amorphous film B On a biaxially stretched polyester film with a thickness of 188 µm was cast a 16% solution of an ethylene-vinyl alcohol copolymer (ethylene content 32 mole %) in a 50:50 (w/w) mixture of water and isopropyl alcohol, followed by drying to give a gas-impermeable synthetic resin layer B-1 with a thickness of 12 µm. On top of this layer was directly cast a phenoxyether crosslinkable resin composition shown below, followed by drying to form a cured crosslinkable resin layer B-2 with a thickness of 20 µm. Phenoxyether resin (Union Carbide) 40 Parts Methyl ethyl ketone 40 Parts Cellosolve acetate 20 Parts Tolylene diisocyanate-trimethylolpropane adduct, 75% solution (Coronate L, Japan Polyurethane) 40 Parts Then, the laminate film was peeled off the biaxially stretched polyester film to give a two-layer optically isotropic amorphous film of B-1/B-2 structure. Two optically isotropic films of B-1/B-2 structure as prepared by the above procedure were laminated to each other with an acrylic adhesive in such a manner that the respective B-1 layers would adjoin each other face-to-face to provide a four-layer optically isotropic amorphous film of B-2/B-1/B-1/B-2 structure. Substrate 3 Then, on either side of the above birefringent film A, the two-layer optically isotropic amorphous film (B-1/B-2) prepared as above was laminated using an acrylic adhesive to fabricate a birefringent substrate of the B-2/B-1/A/ B-1/B-2 structure. This birefringent substrate had a thickness of about 106 µm, a retardation value of 145 nm, a visible light transmittance of 87%, an oxygen permeability (as determined in accordance with ASTM D-1434-75) of 1.2 cc/24 hr·m²·atm, and a surface pencil hardness of 2H. The substrate was moisture-proof. Substrate 4 The four-layer optically isotropic amorphous film of B-2/B-1/B-1/B-2 structure described above was used as the optically isotropic substrate in this example. This optically isotropic substrate had a thickness of about 75 µm, a retardation value of 2 nm, a visible light transmittance of 92%, an oxygen permeability (as determined in accordance with ASTM D-1434-75) of 0.8 cc/24 hr·m²·atm., and a surface pencil hardness of 2H. This substrate was moisture-proof. Formation of transparent electrodes An indium tin oxide (ITO) layer with a thickness of 320 Å is formed on one side of each of the above birefringent substrate and optically isotropic substrate. Fabrication of liquid crystal cell 1 After the above formation of transparent electrodes, using an epoxy adhesive as a sealant an STN (super-twisted nematic) liquid crystal with a twist angle of about 210° was filled into the gap between the birefringent substrate and the optically isotropic substrate to fabricate an STN liquid crystal cell. Liquid crystal display panel A pair of an iodine type polarizer sheets 2, 2 each having a visible light transmission of 42% and a degree of polarization of 86% were laid with the respective optical axes at right angles on both sides of the above liquid crystal cell to fabricate the product liquid crystal display panel. This liquid crystal display panel had a neutral color under no energization but when an electric voltage of 7 volts was applied, the display area turned deep gray-blue with a satisfactory contrast ratio of 9:1 and an improved angle-of-view dependency. Comparative Example 1 A liquid crystal display panel was fabricated in the same manner as Example 1 except that an STN liquid crystal was sealed into the gap between two optically isotropic sheets each carrying a transparent electrode. This display panel was green under no energization but when a voltage of several volts was applied, assumed a deep blue color. The contrast ratio was as small as 3:1. Example 2 Stretched birefringent synthetic resin film A In a 1:1 (w/w) mixture of tetrahydrofuran and dimethylformamide were dissolved 22 parts of polyvinyl chloride resin and 6 parts of polymethyl methacrylate and the solution was cast on a glass plate and dried at 85°C to give a film with a thickness of 82 µm. This film was monoaxially stretched in a draft ratio of 5 in an atmosphere at 130°C and, then, aged at the same temperature. The above procedure provided an birefringent film A having a thickness of 43 µm and a retardation value of 138 nm. Substrate 3 A two-layer optically isotropic amorphous film of B-1/B-2 structure, similar to the one used in Example 1, was laminated onto either side of the above birefringent film A to give an birefringent substrate. This birefringent substrate had a thickness of about 117 µm, a retardation value of 141 nm, a visible light transmittance of 86%, an oxygen permeability (as determined in accordance with ASTM D-1434-75) of 0.9 cc/24 hr·m²·atm, and a surface pencil hardness of 2H. The substrate was moisture-proof. Substrate 4 A two-layer optically isotropic amorphous film of B-1/B-2 structure, similar to the one used in Example 1, was laminated onto either side of a polycarbonate film (manufactured by Mitsubishi Chemical Industries, Ltd.) having a thickness of 90 µm and a retardation value of 18 nm to give an optically isotropic substrate. This optically isotropic substrate had a thickness of about 164 µm, a retardation value of 23 nm, a visible light transmittance of 90%, an oxygen permeability (as determined in accordance with ASTM D-1434-75) of 0.7 cc/24 hr·m²·atm, and a surface pencil hardness of 2H. This substrate was moisture-proof. Formation of transparent electrodes Transparent electrodes were formed in the same manner as Example 1; provided, however, that the thickness of the ITO layer was 460 Å. Fabrication of liquid crystal cell 1 A liquid crystal cell was fabricated in the same manner as Example 1. Liquid crystal display panel A pair of iodine type polarizer sheets 2, 2 each having a visible light transmittance of 38% and a degree of polarization of 98% were set up with the respective optical axes at right angles on either side of the above liquid crystal cell to fabricate a liquid crystal display panel. This liquid crystal display panel had a neutral color under no energization but when a voltage of 7 volts was applied, its display area turned deep gray-blue with a satisfactory contrast ratio of 8:1 and an improved angle-of-vision dependency. Example 3 Stretched birefringent synthetic resin film A In a mixture of 50 parts of methyl ethyl ketone and 50 parts of cellosolve acetate were dissolved 55 parts of phenoxyether resin (same as that used in Example 1) and 50 parts of Coronate L with stirring at room temperature. This solution was cast on a glass plate and allowed to stand in an atmosphere at 70°C for about 40 minutes, whereby a homogenous cured crosslinkable resin film with a thickness of 80 µm was obtained. The above film was monoaxially stretched at 150°C in a draft ratio of 3.6 and further aged at the same temperature for 20 minutes. The above procedure provided a birefringent film A having a thickness of 53 µm and a retardation value of 125 nm. Optically isotropic multilayer amorphous film B An ethylene-vinyl alcohol copolymer solution, similar to the one used in Example 1, was cast on a 100 µm-thick biaxially stretched polyester film and dried to give a gas-impermeable synthetic resin layer B-1 with a thickness of 25 µm. On top of this layer was directly cast a phenoxyether crosslinkable resin composition similar to that used in Example 1. After drying, aging was performed at 130°C for 20 minutes to give a cured crosslinkable resin layer B-2 with a thickness of 18 µm. Then, this laminate was peeled off the biaxially stretched polyester film to give a two-layer optically isotropic amorphous film of B-1/B-2 structure having a thickness of 43 µm. A couple of optically isotropic amorphous films of the above B-1/B-2 structure were laminated together with the aid of an acrylic adhesive in such a manner that the respective B-1 layers would adjoin each other face-to-face to give a four-layer optically isotropic amorphous film of B-2/B-1/B-1/B-2 structure. Substrate 3 Then, the above two-layer optically isotropic amorphous film of B-1/B-2 structure was laminated onto either side of the above birefringent film with the aid of an acrylic adhesive to prepare a birefringent substrate which had the B-2/B-1/A/B-1/B-2 structure. The above birefringent substrate had a thickness of about 149 µm, a retardation value of 127 nm, a visible light transmittance of 87%, an oxygen permeability (as determined in accordance with ASTM D-1434-75) of 0.6 cc/24 hr·m²·atm and a surface pencil hardness of 2H. This substrate was moisture-proof. Substrate 4 The above 4-layer optically isotropic amorphous film of B-2/B-1/B-1/B-2 structure was used as the optically isotropic substrate in this example. This optically isotropic substrate had a thickness of about 202 µm, a reatardation value of 4 nm, a visible light transmittance of 89%, an oxygen permeability (as determined in accordance with ASTM D-1434-75) of 0.6 cc/24 hr·m²·atm, and a surface pencil hardness of 2H. This substrate was moisture-proof. Liquid crystal display panel A liquid crystal display panel was fabricated under otherwise the same conditions as Example 1. In color, display-background contrast and angle-of-view dependency, this display panel was comparable to the panel obtained in Example 1. Example 4 Stretched birefringent synthetic resin film A In 80 parts of dimethylformamide was dissolved 10 parts of an acrylonitrile-methyl acrylate copolymer consisting of 95 parts of acrylonitrile and 5 parts of methyl acrylate at a temperature of about 60°C and the resulting solution was cast on a glass plate and dried in an atmosphere at about 75°C to give a transparent film with a thickness of 115 µm. Then, in an atmosphere at 130-140°C, this film was first stretched monoaxially in a draft ratio of 1.5 and, then, stretched at an angle of 90° with the direction of the first stretching in a draft ratio of 5. The resulting stretched film having a thickness of 46 µm and a retardation value of 280 nm was used as the birefringent film A in this example. Substrate 3 Using an urethane adhesive, an optically isotropic film of B-1/B-2 structure having a retardation value of 3 nm and a thickness of 33 µm, to be described below was laminated onto either side of the above birefringent film A in such a manner that the B-1 side would adjoin the film A to give a birefringent substrate of B-2/B-1/A/B-1/B-2 structure having a thickness of 130 µm. This substrate had a retardation value of 292 nm, a visible light transmittance of 85%, and an oxygen permeability of 1.4 cc/24 hr·m²·atm. The composition of the urethane adhesive mentioned above was as follows. Takelac A-371 (manufactured by Takeda Chemical Industries, Ltd.) 45 Parts Takenate A-10 (Curing agent) (manufactured by Takeda Chemical Industries, Ltd.) 7 Parts Ethyl acetate 50 Parts Optically isotropic multilayer amorphous film B In a 50/50 (w/w) mixture of water and isopropyl alcohol was dissolved an ethylene-vinyl alcohol copolymer with an ethylene content of 28% at a final concentration of 13% and the solution was cast on a 100 µm-thick biaxially stretched polyester film and dried to form a moisture-proof synthetic resin layer B-1 with a thickness of 9 µm. On top of this layer was directly cast a photocurable resin composition of the following composition and dried at 80°C. Then, the whole surface was irradiated with ultraviolet light using a 200-watt chemical lamp for 5 minutes to provide a UV-cured resin layer B-2 with a thickness of 24 µm. Phenoxyether resin (manufactured by Union Carbide) 40 Parts Trimethylolpropane triacrylate 20 Parts Bisphenol A-diglycidylether-acrylic acid adduct 20 Parts Benzoin ethyl ether 3 Parts Dioxane 300 Parts Then, this laminate B-1/B-2 film was peeled off the biaxially stretched polyester film to give an optically isotropic amorphous film with a thickness of 33 µm and a retardation value of 3 nm. Substrate 4 Using the same urethane adhesive as described above, the above optically isotropic amorphous film of B-1/B-2 structure was laminated onto either side of a polycarbonate film having a thickness of 50 µm and a retardation value of 7 nm in such a manner that the B-1 side adjoined the polycarbonate film. The resulting optically isotropic substrate of B-2/B-1/polycarbonate/B-1/B-2 structure had a thickness of 126 µm, a visible light transmittance of 89% and an oxygen permeability of 1.8 cc/24 hr·m²·atm. Formation of transparent electrodes Under the following sputtering conditions, an ITO film having a thickness of 420 Å was formed on one side of each of the above birefringent substrate and optically isotropic substrate. Target In₂O₃ 95 Weight % SnO₂ 5 Weight % Pressure 4 x 10⁻³ Torr Output 450 Watt Deposition speed 8 Å/second Fabrication of liquid crystal cell 1 A liquid crystal cell 1 was fabricated in the same manner as Example 1. Liquid crystal display panel A pair of iodine type polarizer sheets 2, 2 each having a visible light transmittance of 42% and a degree of polarization of 86% were set up with the respective optical axes at right angles on the respective sides of the above liquid crystal cell to fabricate a liquid crystal display panel. The resulting liquid crystal display panel had a neutral color under no energization but when a voltage of 10 volts was applied, its display area assumed a deep gray-blue color with a satisfactory contrast ratio of 6:1 and an improved angle-of-vision dependency. Example 5 Glass sheet The 0.7 mm-thick glass plate hithereto used for liquid crystal cells was used. Stretched birefringent synthetic resin film A In 150 parts of methylene chloride was dissolved 15 parts of a bisphenol A-based polycarbonate with stirring and the resulting solution was cast on a glass sheet and dried at 40°C to give a transparent film with a thickness of 70 µm. This film was monoaxially stretched in a draft ratio of 3 in an atmosphere at 180°C and, then, aged. The above procedure gave a birefringent film A having a thickness of 43 µm and a retardation value of 152 nm. Optically isotropic mulilayer amorphous film B The procedure described in Example 1 was followed to provide a two-layer optically isotropic amorphous film of B-1/B-2 structure. However, the thickness of B-1 layer and that of B-2 layers were set at 10 µm and 15 µm, respectively. Substrate 3 Then, using an acrylic adhesive, the two-layer optically isotropic amorphous film of B-1/B-2 structure prepared as above was laminated onto either side of the above birefringent film A to fabricate a birefringent substrate of B-2/B-1/A/B-1/B-2 structure. The above birefringent substrate had a thickness of about 113 µm, a retardation value of 158 nm, a visible light transmittance of 87%, an oxygen permeability (as determined in accordance with ASTM D-1434-75) of 1.8 cc/24 hr·m²·atm, and a surface pencil hardness of 2H. This substrate was moisture-proof Formation of transparent electrodes By the sputtering technique, a ITO layer with a thickness of 380 Å was formed on one side of each of the above 0.7 mm-thick glass sheet and birefringent substrate. Fabrication of liquid crystal cell 1 Two transparent electrodes were formed each on the above glass sheet and birefringent substrate and, then, using an epoxy adhesive as a sealant, an STN (super-twisted nematic) liquid crystal with a twist angle of about 220° was sealed into the gap between the glass sheet and the birefringent substrate to fabricate an STN liquid crystal cell. Liquid crystal display panel A pair of iodine type polarizer sheets 2, 2 each having a visible light transmittance of 42% and a polarization degree of 86% were set up with the respective optical axes at right angles on either side of the above liquid crystal cell to construct a liquid crystal display panel. This liquid crystal display panel had a neutral color under no energization but when a voltage of 6 volts was applied, its display area assumed a deep gray-blue color with a satisfactory contrast ratio of 8:1 and an improved angle-of-view dependency. Comparative Example 2 A liquid crystal display panel was fabricated in the same manner as Example 5 except that the STN liquid crystal was sealed between the two glass sheets after formation of transparent electrodes as in Example 5. This liquid crystal display panel was green under no energization but when a voltage of several volts was applied, the display area turned deep blue with a contrast ratio of 3:1. Example 6 Glass sheet The 1.2 mm-thick glass sheet of the type hithereto used for liquid crystal cells was employed. Stretched birefringent synthetic resin film A In a 1:1 (w/w) mixture of tetrahydrofuran and dimethylformamide were dissolved 24 parts of polyvinyl chloride resin and 7 parts of polymethyl methacrylate resin and the solution was cast on a glass sheet and dried at 85°C, whereby a film with a thickness of 90 µm was obtained. The above film was monoaxially stretched in a draft ratio of 4 in an atmosphere at 130°C and, then, aged at the same temperature. The above procedure gave a birefringent film A having a thickness of 46 µm and a retardation value of 135 nm. Substrate 3 A two-layer optically isotropic amorphous film of B-1/B-2 structure, similar to that used in Example 5, was laminated onto either side of the above birefringent film A to give a birefringent substrate. This birefringent substrate had a thickness of about 120 µm, a retardation value of 138 nm, a visible light transmission of 86%, an oxygen permeability (as determined in accordance with ASTM D-1434-75) of 1.2 cc/24 hr·m²·atm., and a surface pencil hardness of 2H. This substrate was moisture-proof. Formation of transparent electrodes Transparent electrodes were formed in the same manner as Example 5; provided, however, that the thickness of the ITO layer was 460 Å. Fabrication of liquid crystal cell 1 A liquid crystal cell was fabricated in the same manner as Example 5. Liquid crystal display panel A pair of iodine type polarizer sheets 2, 2 each having a visible light transmission of 38% and a polarization degree of 98% were set up with the respective optical axes at right angles on either side of the above liquid crystal cell to manufacture a liquid crystal display panel. This liquid crystal display panel had a neutral color under no energization but when a voltage of 6 volts was applied, its display area turned deep gray-blue with a satisfactory contrast ratio of 7:1 and an improved angle-of-view dependency.

Claims: A liquid crystal display panel comprising two opposed substrates supporting on their inner surfaces transparent electrodes and enclosing super-twisted nematic liquid crystal material; two polarizer sheets stacked on the outer surfaces of the substrates, respectively; wherein one substrate consists of a stretched birefringent synthetic resin film backed on both sides thereof by optically isotropic multilayer amorphous films each including at least a gas-impermeable synthetic resin layer and a cured cross-linkable resin layer disposed adjoining to each other and wherein the other substrate consists of (i) an optically isotropic multilayer amorphous film including at least a gas-impermeable synthetic resin layer and a cured cross-linkable resin layer disposed adjoining to each other or (ii) a glass sheet.

Inventors: HASHIMOTO KENJI C O FUJIMORI K, ICHIKAWA RINJIRO C O FUJIMORI, HASHIMOTO, KENJI C/O FUJIMORI KOGYO CO., LTD., ICHIKAWA, RINJIRO C/O FUJIMORI KOGYO  CO., LTD., Ichikawa, Rinjiro c/o Fujimori Kogyo Co., Ltd.
Applicants: FUJIMORI KOGYO CO, FUJIMORI KOGYO CO., LTD.
Application year: 1989
Main classification: G02F1
IPC codes: G02F1