This invention relates to an optical compensator for improving viewing angle characteristics of liquid crystal displays having a substrate, an orientation layer, and an optical anisotropic layer containing a high molecular weight polymer.
Current rapid expansion in the liquid crystal display (LCD) applications in various areas of information display is largely due to improvements of display qualities. Contrast, color reproduction, and stable gray scale intensities are important quality attributes for electronic displays, which employ liquid crystal technology. The primary factor limiting the contrast of a liquid crystal display is the propensity for light to “leak” through liquid crystal elements or cell, which are in the dark or “black” pixel state. Furthermore, the leakage and hence contrast of a liquid crystal display are also dependent on the angle from which the display screen is viewed. Typically the optimum contrast is observed only within a narrow viewing angle centered about the normal incidence to the display and falls off rapidly as the viewing angle is increased. In color displays, the leakage problem not only degrades the contrast but also causes color or hue shifts with an associated degradation of color reproduction. In addition to black-state light leakage, the narrow viewing angle problem in typical twisted nematic liquid crystal displays is exacerbated by a shift in the brightness-voltage curve as a function of viewing angle because of the optical anisotropy of the liquid crystal material.
Thus, one of the major factors measuring the quality of such displays is the viewing angle characteristic, which describes a change in contrast ratio from different viewing angles. It is desirable to be able to see the same image from a wide variation in viewing angles and this ability has been a shortcoming with liquid crystal display devices. One way to improve the viewing angle characteristic is to insert a compensator (also referred as compensation film, retardation film, or retarder) with proper optical properties between the polarizer and liquid crystal cell, such as disclosed in U.S. Pat. No. 5,583,679 (Ito et al.), U.S. Pat. No. 5,853,801 (Suga et al.), U.S. Pat. No. 5,619,352 (Koch et al.), U.S. Pat. No. 5,978,055 (Van De Witte et al.), and U.S. Pat. No. 6,160,597 (Schadt et al.). A compensation film according to U.S. Pat. No. 5,583,679 (Ito et al.) and U.S. Pat. No. 5,853,801 (Suga et al.), based on discotic liquid crystals which have negative birefringence, is widely used. It offers improved contrast over wider viewing angles, however, it suffers larger color shift for gray level images, compared to a compensator made of liquid crystalline materials with positive birefringence, according to Satoh et al. (“Comparison of nematic hybrid and discotic hybrid films as viewing angle compensator for NW-TN-LCDs”, SID 2000 Digest, pp. 347-349, (2000)). To achieve comparable performance in the contrast ratio while reducing color shift, one alternative is to use a pair of crossed liquid crystal polymer films (LCP) on each side of liquid crystal cell, as discussed by Chen et al. (“Wide Viewing Angle Photoaligned Plastic Films”, SID 99 Digest, pp.98-101 (1999)). This paper states that “since the second LPP/LCP retarder film is coated directly on top of the first LCP retarder film, the total thickness of the final wide-view retarder stack is only a few microns thin”. Although they provide very compact optical component, one of the challenges of this method is to make two LCP layers crossed, particularly in a continuous roll to roll manufacturing process.
U.S. Pat. No. 5,583,679 teaches that a variety of materials (polymers and surfactants) can be added to discotic liquid crystals to affect the optical performance of the resultant discotic optical compensator film by changing the tilt angle of this film. It also mentions that these materials can only be added in small amounts so as to be compatible with the discotic liquid crystal. If too much of this new material is added to the discotic then the optical compensator film will not have the desired anisotropic optical properties (optical alignment and retardation). This patent pertains only to optical compensator films made from discotic (disc shaped) liquid crystals, it does not mention nematic (rod shaped) liquid crystals. It also does not mention use of such additives to affect film uniformity.
It is a problem to be solved to provide an optical compensator that widens the viewing angle characteristics of liquid crystal displays, in particular Twisted Nematic (TN), Super Twisted Nematic (STN), Optically Compensated Bend (OCB), In Plane Switching (IPS), or Vertically Aligned (VA) liquid crystal displays (these various liquid crystal display technologies have been reviewed in U.S. Pat. No. 5,619,352 (Koch et al.), U.S. Pat. No. 5,410,422 (Bos), and U.S. Pat. No. 4,701,028 (Clerc et al.)), is readily manufactured in a roll-to-roll process. Such roll- to-roll processes require coating of an optically anisotropic layer on an orientation layer. Such layers can generally be prepared by coating solutions of polymerizable nematic liquid crystal on an orientation layer. Usually very low viscosity solutions are used in coating liquid crystals which causes many coating defects (i.e. mottle), leading to severely diminished performance of the optical compensator film and thus the complete liquid crystal display. Adding a high molecular weight polymer in coating solvents, provided they do not affect alignment and tilt angle of liquid crystals, can reduce these coating defects. While U.S. Pat. No. 5,583,679 mentions addition of such materials to discotic liquid crystals layer changes optical properties, in the present invention addition of a variety of high molecular weight polymers did not detrimentally affect the optical performance of the compensator film.
It is a problem to be solved to provide an optical compensator that widens the viewing angle characteristics of liquid crystal displays, and in particular of Twisted Nematic (TN), Super Twisted Nematic (STN), Optically Compensated Bend (OCB), In Plane Switching (IPS), or Vertically Aligned (VA) liquid crystal displays, is readily manufactured in a roll-to-roll coatable process with excellent layer uniformities and optical properties.
The invention provides an optical compensator for a liquid crystal display comprising a transparent polymeric support, an orientation layer, and an optically anisotropic layer, in order, wherein the anisotropic layer comprises a nematic liquid crystalline polymer, and a separate colorless polymer having a weight average molecular weight that is greater that the entanglement molecular weight of the polymer. The invention also provides a process for making such a compensator.
In a desirable embodiment the separate polymer comprises from 2 to 20 wt % of the anisotropic layer and is prepared using ethylenically unsaturated monomers. In another desirable embodiment, the colorless polymer is an amorphous polymer.
The uniformity and quality of this film is enhanced by the use of a high molecular weight polymer.
The current invention regarding the optical compensator for liquid crystal displays is described by referring to the drawings as follows.
On the substrate 10, an orientation layer 20 is applied, and an anisotropic layer 30 is disposed on top of layer 20.
The orientation layer 20 can be oriented by various techniques. In one example, the orientation layer contains a rubbing-orientable material such as a polyimide or polyvinyl alcohol and can be oriented by a rubbing technique. In another example, the orientation layer contains a shear-orientable material and can be oriented by a shear-alignment technique. In another example, the orientation layer contains an electrically- or magnetically -orientable material and can be oriented by an electrical- or magnetic-alignment technique. In another example, the orientation layer can also be a layer of SiOx fabricated by oblique deposition. In another example, the orientation layer contains a photo-orientable material and can be oriented by a photo-alignment technique. Photo-orientable materials include, for example, photo isomerization polymers, photo dimerization polymers, and photo decomposition polymers. In a preferred embodiment, the photo-orientable materials are cinnamic acid derivatives as disclosed in U.S. Pat. No. 6,160,597. Such materials may be oriented and simultaneously crosslinked by selective irradiation with linear polarized UV light.
The anisotropic layer 30 is typically a nematic liquid crystalline prepolymer when it is first disposed on the orientation layer 20, and is cross-linked by a further UV irradiation, or by other means such as heat. In a preferred embodiment, the anisotropic layer contains a material such as a diacrylate or diepoxide with positive birefringence as disclosed in U.S. Pat. No. 6,160,597 (Schadt et al.) and U.S. Pat. No. 5,602,661 (Schadt et al.). The optic axis in the anisotropic layer 30 is usually tilted relative to the layer plane, and varies across the thickness direction. The anisotropic layer 30 in accordance with the present invention is applied from a liquid medium containing an organic solvent mixture and a high molecular weight polymer.
The high molecular weight polymer is chemically separate from the nematic crystalline polymer and improves the dried coating uniformity of the anisotropic layer 30 without detrimentally affecting its adhesion to orientation layer 20 or its overall optical properties.
In general these high molecular weight polymers are amorphous and colorless (no appreciable absorption between 400-800 nm) and are soluble in the coating solvent, and whose weight average molecular weight is greater than the entanglement molecular weight (i.e., a term often used to describe the molecular weight at which polymer entanglements become significant enough to contribute heavily to viscosity). More preferably their weight average molecular weight will be above 45,000. Most preferably their weight average molecular weight will be above 99,000. Furthermore, such polymers will not change the average tilt angle of the anisotropic layer 30 by more than about ±10 degrees. More preferably such polymers will not change the average tilt angle of the anisotropic layer 30 by more than about ±5 degrees. Most preferably such polymers will not change the average tilt angle of the anisotropic layer 30 by more than about ±2 degrees. In addition, such polymers will not decrease the optical retardation of the anisotropic layer 30 by more than about 50%. More preferably such polymers will not decrease the optical retardation of the anisotropic layer 30 by more than about 35%. Most preferably such polymers will not decrease optical retardation of the anisotropic layer 30 by more than about 5%.
In this case amorphous as used with respect to the polymers means that the polymer does not produce any sharp diffraction peaks when exposed to X-ray diffraction analysis. Crystalline polymers, liquid crystal molecules and crystalline inorganic materials would produce such sharp peaks when subjected to such X-ray diffraction analysis. See Chung .Frank H. and Deane K. Smith, Industrial Applications X-Ray Diffraction By comparison, Marcel Dekker, Inc; (2000) pp 495-6). Such amorphous materials are desirably suitable to be solvent cast or coated such as TAC, polycarbonates, cyclic polyolefins, polyesters, and polyimides
The high molecular weight polymer useful in the present invention include: condensation polymers such as, polyesters, polyurethanes, polyamides, and polyimides; interpolymers prepared from ethylenically unsaturated monomers such as ethylene, vinyl acetate, vinyl halide, vinylidene halide, acrylonitrile, alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, (meth)acrylic acid, methacrylonitrile, glycidyl acrylate, glycidyl methacrylate, liquid crystal acrylates, styrene and its derivatives, vinyl alkyl ethers, vinyl alkyl ketones, butadiene, vinyl silanes; and others, and mixtures thereof; derivatives of poly(vinylacetate) or poly(vinyl alcohol) such as poly(vinylbutyral), poly(vinyl formal), poly(vinylcinnamate) and others; cellulose esters; and others.
Preferred polymers for use in the present invention include: poly(vinylformal), poly(vinylacetate), poly(vinylbutyral) and poly(vinylcinnamate).
The high molecular weight polymer is added from 2% to 20 wt % of the anisotropic layer 30. More preferably such polymers are added from 2% to 10 wt % of the anisotropic layer 30. Most preferably such polymers are added from 2% to 5 wt % of the anisotropic layer 30. The amount of the high molecular weight polymer added is dependent on both the composition and molecular weight of the polymer employed since both of these can impact coating viscosity throughout the drying process.
The anisotropic layer may also contain addenda such as surfactants, light stabilizers and UV initiators. UV initiatiors include materials such as benzophenone and acetophenone and their derivatives; benzoin, benzoin ethers, benzil, benzil ketals, fluorenone, xanthanone, alpha and beta naphthyl carbonyl compounds and ketones. Preferred initiators are alpha-hydroxyketones.
While this type of compensator described above provides some desired optical properties, it is not sufficient in many applications, for example, as a compensator for Twisted Nematic (TN) Liquid Crystal Displays (LCDs).
It should be understood that the optic axis in each of the anisotropic layers 30 and 50 can have a variable tilt angle and/or variable azimuthal angle. For example, the optic axis 84 in the anisotropic layer 30 has a variable tilt angle θ across the Z-axis ranging from θ1 to θ2. In another example, the optic axis 84 has a fixed tilt angle θ across the Z-axis, namely, θ1=θ2. In another example, the optic axis 84 is contained in one plane such as the XZ plane and consequently has a fixed azimuthal angle φ across the Z-axis. In another example, although the anisotropic layer 30 is still oriented along the preferred direction forced by the orientation layer at their interface, the optic axis 84 has a variable azimuthal angle φ across the Z-axis. The azimuthal angle of the optic axis 84 can be varied by adding a proper amount of chiral dopant into the anisotropic layer 30. In another example, the optic axis 84 has a variable tilt angle θ and a variable azimuthal angle φ across the Z-axis. Like the optic axis 84 of the anisotropic layer 30, the optic axis 86 of the anisotropic layer 50 can also have a fixed tilt angle, a variable tilt angle, a fixed azimuthal angle, a variable azimuthal angle, or a variable tilt angle and a variable azimuthal angle across the Z-axis. The anisotropic layers 30 and 50 typically have different optic axis. Preferably the anisotropic layer 30 is positioned orthogonally relative to the respective optic axis of the anisotropic layer 50 about an axis perpendicular to the plane of the substrate. Even though the optic axis of the anisotropic layer 30 is preferred to be orthogonal (or ±90 degrees) relative to the respective (or counterpart) optic axis of the anisotropic layer 50 about an axis perpendicular to the plane of the substrate, it should be understood that the angle between the optic axis of the two anisotropic layers can be in a range of 85 to 95 degrees to be considered as orthogonal.
For the manufacture of more complex layer structures than that illustrated in
In one embodiment, the orientation layer is oriented by rubbing the orientation layer in a direction 94 of 90 degrees (φ=90°) relative to the roll moving direction 92. In another embodiment, the orientation layer is oriented by a photo-alignment technique, for example, the orientation layer is exposed to a linearly polarized ultraviolet (UV) light indicated by 90. It may or may not be collimated, however, the projection (pointing along 94) of the principal ray of the light 90 onto the roll makes an angle of about 90 degrees relative to the roll moving direction.
The invention may be used in conjunction with electronic imaging device comprising a liquid crystal display device. The energy required to achieve this control is generally much less than that required for the luminescent materials used in other display types such as cathode ray tubes. Accordingly, liquid crystal technology is used for a number of applications, including but not limited to digital watches, calculators, portable computers, electronic games for which light weight, low power consumption and long operating life are important features.
The present invention is illustrated in more detail by the following non-limiting examples.
Coating of Photo-Aligned Anisotropic Layer for Layer Uniformity.
Onto a photo-aligned orientation layer prepared from a mixture of VANTICO Staralign 2110 and Staralign 2100 photo-aligning vinyl cinnamate polymers on cellulose triacetate support, a methyl ethyl ketone solution of crosslinkable diacrylate nematic liquid crystalline compound (7 wt %) (obtained by diluting 30 wt % stock solution of VANTICO LCP 483) was slot hopper cast. The sample was then heated to 55° C. to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and anisotropic layer fixed by exposing to 365 nm light (300-1000 mJ/cm2) under an atmosphere of nitrogen. The sample was the viewed between crossed polarizers and judged for appearance.
Coating of Photo-Aligned Anisotropic Layer Containing a High Molecular Weight Polymer to Improve Layer Uniformity.
Onto a photo-aligned orientation layer prepared from a mixture of VANTICO Staralign 2110 and Staralign 2100 photo-aligning vinyl cinnamate polymers on cellulose triacetate support, a methyl ethyl ketone solution of crosslinkable diacrylate nematic liquid crystalline compound (7 wt %) (obtained by diluting 30 wt % stock solution of VANTICO LCP 483) and poly(vinylacetate) having a weight average molecular weight of 185,000 (2.4 wt % of dried anisotropic film) was slot hopper cast. The sample was then heated to 55° C. to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and anisotropic layer fixed by exposing to 365 nm light (300-1000 mJ/cm2) under an atmosphere of nitrogen.
Comparison Example A and Example 1 were then viewed between crossed polarizing filters to determine the effect of the high molecular weight polymer on the resulting dried anisotropic layer uniformity, and a visual rating was assigned. The rating considered all obvious post-application imperfections, including mottle, drying convection cells, and repellencies. A rating of 1 corresponds to the poorest possible quality and a rating of 10 the best possible quality.
Preparation of Photo-Aligned Anisotropic Layer.
On a clean glass plate, a coating solution containing a mixture of VANTICO Staralign 2110 and Staralign 2100 photo-aligning vinyl cinnamate polymers (1 wt % total solids in MEK) was spun cast (@ 1000 rpm). Sample was dried at 55° C. for 5 min. and then exposed to 308 nm polarized light (15-30 mJ/cm2) at an inclination of 20 degrees away from normal angle of incidence to obtain a photo-aligned orientation layer. Typically this will produce a layer thickness between 30-100 nm as measured by ellipsometry (J. A. Woollam Co., Model M2000V). On the orientation layer a methyl ethyl ketone solution of crosslinkable diacrylate nematic liquid crystalline compound (7 wt %) (obtained by diluting 30 wt % stock solution of VANTICO LCP 483) was spun cast (@ 1000 rpm). The sample was then heated at a temperature of 55° C. for 3 minutes to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and anisotropic layer fixed by exposing to 365 nm light (300-1000 mJ/cm2) under an atmosphere of nitrogen. In-plane retardation, average tilt angle, and thickness of the anisotropic layer were measured by ellipsometry (J. A. Woollam Co., Model M2000V). The measured average tilt angle method had errors of ±2.0 degrees.
Preparation of Photo-Aligned Anisotropic Layer with Added Poly(Vinylacetate)
On a clean glass plate, a coating solution containing a mixture of VANTICO Staralign 2110 and Staralign 2100 photo-aligning polymers (1 wt % solids in MEK) was spun cast (@ 1000 rpm). Sample was dried at 55° C. for 5 min. and then exposed to 308 nm polarized light (15-30 mJ/cm2) at an inclination of 20 degrees away from normal angle of incidence to obtain a photo-aligned orientation layer. Typically this will produce a layer thickness between 30-100 nm as measured by ellipsometry (J. A. Woollam Co., Model M2000V).
On the orientation layer a methyl ethyl ketone solution of crosslinkable diacrylate nematic liquid crystalline compound (7 wt %) (obtained by diluting 30 wt % stock solution of VANTICO LCP 483) and a high molecular weight polymer (at a wt % of dried anisotropic film as indicated in Table 2) was spun cast (@ 1000 rpm). The sample was then heated at a temperature of 55° C. for 3 minutes to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and anisotropic layer fixed by exposing to 365 nm light (300-1000 mJ/cm2) under an atmosphere of nitrogen. In-plane retardation, average tilt angle, and thickness of the anisotropic layer were measured by ellipsometry (J. A. Woollam Co., Model M2000V). The measured average tilt angles had errors of ±2.0 degrees.
The aforementioned examples clearly demonstrate that compared to comparison example B addition of a high molecular weight polymer does not change optical properties of anisotropic layer.
The entire contents of the patents and other publications referred to in this specification are incorporated herein by reference.
This is a Continuation-in-Part of application Ser. No. 10/194,097 filed Jul. 12, 2002. This application is cofiled as part of a group of the following commonly assigned applications under Ser. Nos. 10/194,162, 10/195,093, 10/195,094, 10/194,097, 10/194,823, 10/194,750, 10/194,130, and 10/194,100, the contents of which are incorporated herein by reference.
Number | Date | Country | |
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Parent | 10194097 | Jul 2002 | US |
Child | 10985612 | Nov 2004 | US |