CA2248214A1 - An optical film - Google Patents
An optical film Download PDFInfo
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- CA2248214A1 CA2248214A1 CA002248214A CA2248214A CA2248214A1 CA 2248214 A1 CA2248214 A1 CA 2248214A1 CA 002248214 A CA002248214 A CA 002248214A CA 2248214 A CA2248214 A CA 2248214A CA 2248214 A1 CA2248214 A1 CA 2248214A1
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- optical body
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3008—Polarising elements comprising dielectric particles, e.g. birefringent crystals embedded in a matrix
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
- G02F1/133545—Dielectric stack polarisers
Abstract
An optical film is provided which comprises a disperse phase of polymeric particles disposed within a continuous birefringent matrix. The film is oriented, typically by stretching, in one or more directions. The size and shape of the disperse phase particles, the volume fraction of the disperse phase, the film thickness, and the amount of orientation are chosen to attain a desired degree of diffuse reflection and total transmission of electromagnetic radiation of a desired wavelength in the resulting film.
Description
W O 97132224 PCT~US97/00981 AN OPTICAL FILM
Field of the Invention s This invention relates to optical materials which contain structures suitable for controlling optical characteristics, such as reflectance and tr~ncmic.cion. In a further aspect, it relates to control of specific polarizations of reflected or transmitted light.
Background Optical films are known to the art which are constructed from inclusions dispersed within a continuous matrix. The characteristics of these inclusions can be manipulated to provide a range of reflective and tr~ncmicsive properties to the film. These characteristics include inclusion size with respect to wavelength s within the film, inclusion shape and alignment, inclusion volumetric fill factor and the degree of refractive index mi.cm~tch with the continuous matrix along the film's three orthogonal axes.
Conventional absorbing (dichroic) polarizers have, as their inclusion phase, inorg~nic rod-like chains of light-absorbing iodine which are aligned within a polymer matrix. Such a film will tend to absorb light polarized with its electric field vector aligned parallel to the rod-like iodine chains, and to transmit light polarized perpendicular to the rods. Because the iodine chains have two or more dimensions that are small compared to the wavelength of visible light, and because the number of chains per cubic wavelength of light is large, the optical plol)e-lies 2s of such a film are predominately specular, with very little diffuse tr~ncmiccion through the film or diffuse reflection from the film surfaces. Like most other commercially available polarizers, these polarizing films are based on polarization-selective absorption.
Films filled with inorganic inclusions with different characteristics can provide other optical tr~n.cmiccion and reflective properties. For example, coated mica flakes with two or more dimensions that are large compared with visible wavelengths, have been incorporated into polymeric films and into paints to impart a metallic glitter. These flakes can be manipulated to lie in the plane of the film, thereby illlp~ Lhlg a strong directional dependence to the reflective appearance.
Such an effect can be used to produce security screens that are highly reflective for 5 certain viewing angles, and tr~ncmi~sive for other viewing angles. Large flakes having a coloration (specularly selective reflection) that depends on alignment with respect to incident light, can be incorporated into a film to provide evidence of tampering. In this application, it is necessary that all the flakes in the film be similarly aligned with respect to each other.
Io However, optical films made from polymers filled with inorganic inclusions suffer from a variety of infirmities. Typically, adhesion between theinorganic particles and the polymer matrix is poor. Consequently, the optical ~lo~e~lies of the film decline when stress or strain is applied across the matrix, both because the bond between the matrix and the inclusions is complonlised, andbecause the rigid inorganic inclusions may be fractured. Furtherrnore, ~ nment of inorganic inclusions requires process steps and considerations that complicate manufacturing.
Other films, such as that disclosed in U.S. 4,688,900 (Doane et. al.), consists of a clear light-transmitting continuous polymer matrix, with droplets of 20 light mod~ ting liquid crystals dispersed within. Stretching of the material reportedly results in a distortion of the liquid crystal droplet from a spherical to an ellipsoidal shape, with the long axis of the ellipsoid parallel to the direction of stretch. U.S. 5,301,041 (Konuma et al.) make a similar disclosure, but achieve the distortion of the liquid crystal droplet through the application of pressure. A.25 Aphonin, "Optical Properties of Stretched Polymer Dispersed Liquid Crystal Films: Angle-Dependent Polarized Light Scattering, Liquid Crystals, Vol. 19, No.4, 469-480 (1995), discusses the optical properties of stretched films consisting of liquid crystal droplets disposed within a polymer matrix. He reports that the elongation of the droplets into an ellipsoidal shape, with their long axes parallel to 30 the stretch direction, imparts an oriented birefringence (refractive index difference among the dimensional axes of the droplet) to the droplets, resulting in a relative refractive index mi~m~tch between the dispersed and continuous phases along certain film axes, and a relative index match along the other film axes. Such liquid crystal droplets are not small as compared to visible wavelengths in the film, and thus the optical properties of such films have a substantial diffuse component to their reflective and tr~n~mi~sive properties. Aphonin suggests the use of these materials as a polarizing diffuser for backlit twisted nematic LCDs. However, optical films employing liquid crystals as the disperse phase are substantially limited in the degree of refractive index mi~m~tch between the matrix phase and the dispersed phase. Furthermore, the birefringence of the liquid crystal component of such films is typically sensitive to tel,lpeld~ lre.
U. S. 5,268,225 (Isayev) discloses a composite l~min~te made from thermotropic liquid crystal polymer blends. The blend consists of two liquid crystal polymers which are immiscible with each other. The blends may be cast into a film consisting of a dispersed inclusion phase and a continuous phase. When the film is stretched, the dispersed phase forms a series of fibers whose axes are aligned in the direction of stretch. While the film is described as having improved mechanical properties, no mention is made of the optical properties of the film.However, due to their liquid crystal nature, films of this type would suffer from the infirmities of other liquid crystal materials discussed above.
Still other films have been made to exhibit desirable optical properties through the application of electric or magnetic fields. For example, U. S.
5,008,807 (Waters et al.) describes a liquid crystal device which consists of a layer of fibers permeated with liquid crystal material and disposed between two electrodes. A voltage across the electrodes produces an electric field which changes the birefringent properties of the liquid crystal material, resulting invarious degrees of mi.cm~tch between the refractive indices of the fibers and the liquid crystal. However, the requirement of an electric or magnetic field is inconvenient and undesirable in many applications, particularly those where existing fields might produce interference.
Other optical films have been made by incorporating a dispersion of inclusions of a first polymer into a second polymer, and then stretching the W O 97/32224 PCT~US97/00981 resulting composite in one or two directions. U. S. 4,871,784 (Otonari et al. ) is exemplative of this technology. The polymers are selected such that there is lowadhesion between the dispersed phase and the surrounding matrix polymer, so thatan elliptical void is formed around each inclusion when the film is stretched. Such s voids have dimensions of the order of visible wavelengths. The refractive index mi.cm~tch between the void and the polymer in these "microvoided" films is typically quite large (about 0.5), causing substantial diffuse reflection. However, the optical properties of microvoided materials are difficult to control because of variations of the geometry of the interfaces, and it is not possible to produce a film 10 axis for which refractive indices are relatively matched, as would be useful for polarization-sensitive optical properties. Furthermore, the voids in such material can be easily collapsed through exposure to heat and pressure.
Optical films have also been made wherein a dispersed phase is deterministically arranged in an ordered pattern within a continuous matrix. U. S.
5,217,794 (Schrenk) is exemplative ofthis technology. There, a lamellar polymeric film is disclosed which is made of polymeric inclusions which are large compared with wavelength on two axes, disposed within a continuous matrix of another polymeric material. The refractive index of the dispersed phase differs significantly from that of the continuous phase along one or more of the l~min~te's axes, and is relatively well matched along another. Because of the ordering of the dispersed phase, films of this type exhibit strong iridescence (i.e., interference-based angle dependent coloring) for instances in which they are substantially reflective. As a result, such films have seen limited use for optical applications where optical diffusion is desirable.
There thus remains a need in the art for an optical m~teri~l consisting of 2 continuous and a dispersed phase, wherein the refractive index mi.~m~tch betweenthe two phases along the material's three dimensional axes can be conveniently and permanently manipulated to achieve desirable degrees of diffuse and specular reflection and tr~n~mi~ion, wherein the optical material is stable with respect to stress, strain, temperature differences, and electric and magnetic fields, and wherein the optical material has an in~i~nificant level of iridescence. These and other needs are met by the present invention, as hereinafter disclosed.
Brief description of the Drawings s FIG. I is a schematic drawing illustrating an optical body made in accordance with the present invention, wherein the disperse phase is arranged as a series of elongated masses having an essentially circular cross-section;
FIG. 2 is a s~h~m~tic drawing illustrating an optical body made in accordance with the present invention, wherein the disperse phase is arranged as a o series of elongated masses having an essenti~lly elliptical cross-section;
FIGS. 3a-e are sçhem~tic drawings illustrating various shapes of the disperse phase in an optical body made in accordance with the present invention;FIG. 4a is a graph of the bidirectional scatter distribution as a function of scattered angle for an oriented film in accordance with the present invention for light polarized perpendicular to orientation direction;
FIG. 4b is a graph of the bidirectional scatter distribution as a function of scattered angle for an oriented film in accordance with the present invention for light polarized parallel to orientation direction; and FIG. 5 is a s~hPm~tic representation of a multilayer film made in accordance with the present invention.
Summary of the Invention In one aspect, the present invention relates to a diffusely reflective film or other optical body comprising a birefringent continuous polymeric phase and a subst~nti~lly nonbirefringent disperse phase disposed within the continuous phase.
The indices of refraction of the continuous and disperse phases are substantially mi~m~tch~od (i.e., differ from one another by more than about 0.05) along a first of three mutually orthogonal axes, and are substantially matched (i.e., differ by less than about 0.05) along a second of three mutually orthogonal axes. In some emborliment~, the indices of refraction of the continuous and disperse phases can - be substantially matched or mi.cm~tched along, or parallel to, a third of three mutl]~lly orthogonal axes to produce a mirror or a polarizer. Incident light polarized along, or parallel to, a mi~mz~tche~l axis is scattered, resulting in significant diffuse reflection. Incident light polarized along a matched axis isscattered to a much lesser degree and is significantly specularly transmitted. These 5 properties can be used to make optical films for a variety of uses, including low loss (significantly nonabsorbing) reflective polarizers for which polarizations of light that are not significantly transmitted are diffusely reflected.
In a related aspect, the present invention relates to an optical film or other optical body comprising a birefringent continuous phase and a disperse phase, o wherein the indices of refraction of the continuous and disperse phases are substantially matched (i.e., wherein the index dirr~lence between the continuousand disperse phases is less than about 0.05) along an axis perpendicular to a surface of the optical body.
In another aspect, the present invention relates to a composite optical body 5 comprising a polymeric continuous birefringent first phase in which the disperse second phase may be birefringent, but in which the degree of match and mi~m~tch in at least two orthogonal directions is primarily due to the birefringence of the first phase.
In still another aspect, the present invention relates to a method for 20 obtaining a diffuse reflective polarizer, comprising the steps of: providing a first resin, whose degree of birefringence can be altered by application of a force field, as through dimensional orientation or an applied electric field, such that the resulting resin material has, for at least h,vo orthogonal directions, an index of refraction difference of more than about 0.05; providing a second resin, dispersed 25 within the first resin; and applying said force field to the composite of both resins such that the indices of the two resins are approximately matched to within lessthan about 0.05 in one of two directions, and the index difference between first and second resins in the other of two directions is greater than about 0.0~. In a related embodiment, the second resin is dispersed in the first resin after imposition of the 30 force field and subsequent alteration of the birefringence of the first resin.
In yet another aspect, the present invention re}ates to an optical body acting as a reflective polarizer with a high extinction ratio. In this aspect, the index difference in the match direction is chosen as small as possible and the difference in the mi.em~tch direction is maximized. The volume fraction, thickness, and disperse phase particle size and shape can be chosen to maximize the extinction ratio, although the relative importance of optical tr~nemieeion and reflection for the different polarizations may vary for different applications.
In another aspect, the present invention relates to an optical body comprising a continuous phase, a disperse phase whose index of refraction differs o from said continuous phase by greater than about 0.05 along a first axis and by less than about 0.05 along a second axis orthogonal to said first axis, and a dichroic dye. The optical body is preferably oriented along at least one axis. The dichroic dye improves the extinction coefficient of the optical body by absorbing, in addition to scattering, light polarized parallel to the axis of orientation.
In the various aspects of the present invention, the reflection and tr~nemie.eion properties for at least two orthogonal polarizations of incident light are determined by the selection or manipulation of various parameters, includingthe optical indices of the continuous and disperse phases, the size and shape of the disperse phase particles, the volume fraction of the disperse phase, the thickness of the optical body through which some fraction of the incident light is to pass, and the wavelength or wavelength band of electromagnetic radiation of interest.
The magnitude of the index match or miem~t~h along a particular axis will directly affect the degree of scattering of light polarized along that axis. In general, scattering power varies as the square of the index mi.em~t~h. Thus, the larger the 2s index mi~m~tçh along a particular axis, the stronger the sC~ttering of light polarized along that axis. Conversely, when the miem~tçh along a particular axis is small,light polarized along that axis is scattered to a lesser extent and is thereby transmitted specularly through the volume of the body.
The size of the disperse phase also can have a significant effect on scattering. If the disperse phase particles are too small (i.e., less than about 1/30 the wavelength of light in the medium of interest) and if there are many particles per cubic wavelength, the optical body behaves as a medium with an effective index of refraction somewhat between the indices of the two phases along any given axis. In such a case, very little light is scattered. If the particles are too large, the light is specularly reflected from the particle surface, with very little s diffusion into other directions. When the particles are too large in at least two orthogonal directions, undesirable iridescence effects can also occur. Practicallimits may also be reached when particles become large in that the thickness of the optical body becomes greater and desirable mechanical properties are COlllp~ ised~
o The shape of the particles of the disperse phase can also have an effect on the scattering of light. The depolarization factors of the particles for the electric field in the index of refraction match and micm~trh directions can reduce or enhance the amount of scattering in a given direction. The effect can either add or detract from the amount of scattering from the index mi.cm~t~'h, but generally has a small influence on scattering in the preferred range of properties in the present invention.
The shape of the particles can also influence the degree of diffusion of light scattered from the particles. This shape effect is generally small but increases as the aspect ratio of the geometrical cross-section of the particle in the plane perpendicular to the direction of incidence of the light increases and as the particles get relatively larger. In general, in the operation of this invention, the disperse phase particles should be sized less than several wavelengths of light in one or two mutually orthogonal (limen~ions if diffuse, rather than specular, reflection is preferred.
Dimensional alignment is also found to have an effect on the SC~U~lillg behavior of the disperse phase. In particular, it has been observed, in optical bodies made in accordance with the present invention, that aligned scatterers will not scatter light symmetrically about the directions of specular tr~n~mis~ion orreflection as randomly aligned scatterers would. In particular, inclusions that have been elongated by orientation to resemble rods scatter light primarily along (ornear) a cone centered on the orientation direction and having an edge along the specularly transmitted direction. For example, for light incident on such an elongated rod in a direction perpendicular to the orientation direction, the scattered light appears as a band of light in the plane perpendicular to the orientation direction with an intensity that decreases with increasing angle away from the s specular directions. By tailoring the geometry of the inclusions, some control over the distribution of scattered light can be achieved both in the tr~n~micsive hemisphere and in the reflective hemisphere.
The volume fraction of the disperse phase also affects the scattering of light in the optical bodies of the present invention. Within certain limits, increasing the o volume fraction of the disperse phase tends to increase the amount of scattering that a light ray experiences after entering the body for both the match and mi~m~tch directions of polarized light. This factor is important for controlling the reflection and tr~n~mic~ion properties for a given application. However, if the volume fraction of the disperse phase becomes too large, light scattering Is dimini~hes. Without wishing to be bound by theory, this appears to be due to the fact that the disperse phase particles are closer together, in terms of the wavelength of light, so that the particles tend to act together as a smaller number of large effective particles.
The thickness of the optical body is also an important control parameter 20 which can be manipulated to affect reflection and tr~n~mi~sion properties in the present invention. As the thickness of the optical body increases, diffuse reflection also increases, and tr~n~mi~ion, both specular and diffuse, decreases.
While the present invention will often be described herein with reference to the visible region of the spectrum, various embodiments of the present invention25 can be used to operate at different wavelengths (and thus frequencies) of electrom~gnPtic radiation through ~plop,;ate scaling of the components of the optical body. Thus, as the wavelength increases, the linear size of the components of the optical body are increased so that the dimensions, measured in units of wavelength, remain approximately constant. Another major effect of ch~nging 30 wavelength is that, for most materials of interest, the index of refraction and the W O 97/32224 PCTrUS97/00981 absorption coefficient change. However, the principles of index match and mi.cm~tch still apply at each wavelength of interest.
Detailed Description of the Invention Introduction As used herein, the terms "specular reflection" and "specular reflectance"
refer to the reflectance of light rays into an emergent cone with a vertex angle of 16 degrees centered around the specular angle. The terms "diffuse reflection" or "diffuse reflectance" refer to the reflection of rays that are outside the specular I o cone defined above. The terms "total reflectance" or "total reflection" refer to the combined reflectance of all light from a surface. Thus, total reflection is the sum of specular and diffuse reflection.
Similarly, the terms "specular tr~n~mi~.~ion" and "specular tr~n~mitt~nce"
are used herein in reference to the tr~ncmi~ion of rays into an emergent cone with a vertex angle of 16 degrees centered around the specular direction. The ter~ns "diffuse tr~n.~mi~ion" and "diffuse transmittance" are used herein in reference to the tr~n~mi.~ion of all rays that are outside the specular cone defined above. The terms "total tr~n~mi~cion" or "total transmittance" refer to the combined tr~n~mis~ion of all light through an optical body. Thus, total tr~n.cmi~ion is the sum of specular and diffuse tr~n~mi~.~ion.
As used herein, the term "extinction ratio" is defined to mean the ratio of total light transmitted in one polarization to the light transmitted in an orthogonal polarization.
FIGS. 1-2 illustrate a first embodiment of the present invention. In accordance with the invention, a diffusely reflective optical film 10 or other optical body is produced which consists of a birefringent matrix or continuous phase 12 and a discontinuous or disperse phase 14. The birefringence of the continuous phase is typically at least about 0.05, preferably at least about 0.1, more preferably at least about 0.15, and most preferably at least about 0.2.
The indices of refraction of the continuous and disperse phases are substantially matched (i.e., differ by less than about 0.05) along a first of three CA 022482l4 l998-08-28 W O 97/32224 PCTAJS97tO0981 mutually orthogonal axes, and are substantially mi.~m~tched (i.e., differ by more than about 0.05) along a second of three mutually orthogonal axes. Preferably, the indices of refraction of the continuous and disperse phases differ by less than about 0.03 in the match direction, more preferably, less than about 0.02, and most 5 preferably, less than about 0.01. The indices of refraction of the continuous and disperse phases preferably differ in the mi~m~tch direction by at least about 0.07, more preferably, by at least about 0.1, and most preferably, by at least about 0.2.
The mi~m~tch in refractive indices along a particular axis has the effect that incident light polarized along that axis will be substantially scattered, resulting in a o significant amount of reflection. By contrast, incident light polarized along an axis in which the refractive indices are matched will be spectrally transmitted or reflected with a much lesser degree of scattering. This effect can be utilized to make a variety of optical devices, including reflective polarizers and mirrors.
The present invention provides a practical and simple optical body and s method for making a reflective polarizer, and also provides a means of obtaining a continuous range of optical properties according to the principles described herein.
Also, very efficient low loss polarizers can be obtained with high e~tinction ratios.
Other advantages are a wide range of practical materials for the disperse phase and the continuous phase, and a high degree of control in providing optical bodies of 20 consistent and predictable high quality performance.
Effect of Index Match/Mismatch In the preferred embodiment, the materials of at least one of the continuous and disperse phases are of a type that undergoes a change in refractive index upon 25 orientation. Consequently, as the film is oriented in one or more directions,refractive index m~tch~s or mi~m~tches are produced along one or more axes. By careful manipulation of orientation parameters and other proces~ing conditions, the positive or negative birefringence of the matrix can be used to induce diffuse reflection or tr~n.~mi.csion of one or both polarizations of light along a given axis.
30 The relative ratio between tr~n~mi~ion and diffuse reflection is dependent on the concentration of the disperse phase inclusions, the thickness of the film, the square W O 97/32224 PCTnJS97/00981 of the difference in the index of refraction between the continuous and dispersephases, the size and geometry of the disperse phase inclusions, and the wavelength or wavelength band of the incident radiation.
The magnitude of the index match or mi.cm~tch along a particular axis directly affects the degree of scattering of light polarized along that axis. Ingeneral, scattering power varies as the square of the index mi~m~tch Thus, the larger the index mi~m~tch along a particular axis, the stronger the scattering of light polarized along that axis. Conversely, when the mi.~m~tch along a particular axis is small, light polarized along that axis is scattered to a lesser extent and is 0 thereby transmitted specularly through the volume of the body.
FIGS. 4a-b demonstrate this effect in oriented films made in accordance with the present invention. There, a typical Bidirectional Scatter Distribution Function (BSDF) measurement is shown for normally incident light at 632.8 mn.
The BSDF is described in J. Stover, "Optical Scattering Measurement and Analysis" (1990). The BSDF is shown as a function of scattered angle for polarizations of light both perpendicular and parallel to the axis of orientation. A
scattered angle of zero corresponds to lm~c~ttçred (specularly transmitted) light.
For light polarized in the index match direction (that is, perpendicular to the orientation direction) as in FIG. 4a, there is a significant specularly transmitted peak with a sizable component of diffusely transmitted light (scattering angle between 8 and 80 degrees), and a small component of diffusely reflected light (scattering angle larger than 100 degrees). For light polarized in the index micm~tch direction (that is, parallel to the orientation direction) as in FIG. 4b, there is negligible specularly tr~n~mitted light and a greatly reduced component of 2s diffusely Lldn~ iLLed light, and a sizable diffusely reflected component. It should be noted that the plane of scattering shown by these graphs is the plane perpendicular to the orientation direction where most of the scattered light exists for these elongated inclusions. Scattered light contributions outside of this plane are greatly reduced.
If the index of refraction of the inclusions (i.e., the disperse phase) m~tches that of the continuous host media along some axis, then incident light polarized W O 97132224 PCTrUS97/00981 with electric fields parallel to this axis will pass through lln~c~ttered regardless of the size, shape, and density of inclusions. If the indices are not matched alongsome axis, then the inclusions will scatter light polarized along this axis. Forscatterers of a given cross-sectional area with dimensions larger than 5 approximately ~/30 ( where ~ is the wavelength of light in the media), the strength of the scattering is largely determined by the index mi~m~tch The exact size, shape and alignment of a mism~tched inclusion play a role in determining how much light will be scattered into various directions from that inclusion. If thedensity and thickness of the scattering layer is sufficient, according to multiple o scattering theory, incident light will be either reflected or absorbed, but not transmitted, regardless of the details of the scatterer size and shape.
When the material is to be used as a polarizer, it is preferably processed, as by stretching and allowing some dimensional relaxation in the cross stretch in-plane direction, so that the index of refraction difference between the continuous 1S and disperse phases is large along a first axis in a plane parallel to a surface of the material and small along the other two orthogonal axes. This results in a large optical anisotropy for electromagnetic radiation of dirrelent polarizations.
Some of the polarizers within the scope of the present invention are elliptical polarizers. In general, elliptical polarizers will have a difference in index 20 of refraction between the disperse phase and the continuous phase for both the stretch and cross-stretch directions. The ratio of forward to back scattering isdependent on the difference in refractive index between the disperse and continuous phases, the concentration of the disperse phase, the size and shape of the disperse phase, and the overall thickness of the film. In general, elliptical 25 diffusers have a relatively small difference in index of refraction between the particles of the disperse and continuous phases. By using a birefringent polymer-based diffuser, highly elliptical polarization sensitivity (i.e., diffuse reflectivity depending on the polarization of light) can be achieved. At an extreme, where the index of refraction of the polymers match on one axis, the elliptical polarizer will 30 be a diffuse reflecting polarizer.
W O 97/32224 PCT~US97/00981 Methods of Obl~inin~ Index Match/Mismatch The materials selected for use in a polarizer in accordance with the present invention, and the degree of orientation of these materials, are preferably chosen so that the phases in the finished polarizer have at least one axis for which the associated indices of refraction are substantially equal. The match of refractive indices associated with that axis, which typically, but not necessarily, is an axis transverse to the direction of orientation, results in substantially no reflection of light in that plane of polarization.
The disperse phase may also exhibit a decrease in the refractive index lo associated with the direction of orientation after stretching. If the birefringence of the host is positive, a negative strain ind~1ced birefringence of the disperse phase has the advantage of increasing the difference between indices of refraction of the adjoining phases associated with the orientation axis while the reflection of light with its plane of polarization perpendicular to the orientation direction is still negligible. Differences between the indices of refraction of adjoining phases in the direction orthogonal to the orientation direction should be less than about 0.05 after orientation, and preferably, less than about 0.02.
The disperse phase may also exhibit a positive strain in~ ced birefringence.
However, this can be altered by means of heat treatment to match the refractive index of the axis perpendicular to the orientation direction of the continuous phase.
The temperature of the heat treatment should not be so high as to relax the birefringence in the continuous phase.
Size of Disperse Phase The size of the disperse phase also can have a signific~nt effect on scattering. If the disperse phase particles are too small (i.e., less than about 1/30 the wavelength of light in the medium of interest) and if there are many particles pér cubic wavelength, the optical body behaves as a medium with an effective index of refraction somewhat between the indices of the two phases along any given axis. In such a case, very little light is scattered. If the particles are too large, the light is specularly reflected from the surface of the particle, with very W O 97/32224 PCTrUS97/00981 little diffusion into other directions. When the particles are too large in at least two orthogonal directions, undesirable iridescence effects can also occur. Practical limits may also be reached when particles become large in that the thickness of the optical body becomes greater and desirable mechanical properties are colllplolllised.
The dimensions of the particles of the disperse phase after alignment can vary depending on the desired use of the optical material. Thus, for example, the ~1imçn~ions of the particles may var,v depending on the wavelength of electromagnetic radiation that is of interest in a particular application, with o different ~limen~ions required for reflecting or transmitting visible, ultraviolet, infrared, and microwave radiation. Generally, however, the length of the particles should be such that they are approximately greater than the wavelength of electromagnetic radiation of interest in the medium, divided by 30.
Preferably, in applications where the optical body is to be used as a low loss reflective polarizer, the particles will have a length that is greater than about 2 times the wavelength of the electromagnetic radiation over the wavelength range of interest, and preferably over 4 times the wavelength. The average diameter of the particles is preferably equal or less than the wavelength of the electromagneticradiation over the wavelength range of interest, and preferably less than 0.5 of the desired wavelength. While the llimen~ions of the disperse phase are a secondary consideration in most applications, they become of greater hll~ol~lce in thin film applications, where there is comparatively little diffuse reflection.
Geometry of Disperse Phase While the index mi~m~t~.h is the predominant factor relied upon to promote scattering in the films of the present invention (i.e., a diffuse mirror or polarizer made in accordance with the present invention has a substantial mi~m~tch in the indices of refraction of the continuous and disperse phases along at least one axis), the geometry of the particles of the disperse phase can have a secondary effect on scattering. Thus, the depolarization factors of the particles for the electric field in the index of refraction match and mi~m~t~h directions can reduce or enhance the W O 97132224 PCT~US97/00981 amount of sc~ ring in a given direction. For example, when the disperse phase iselliptical in a cross-section taken along a plane perpendicular to the axis of orientation, the elliptical cross-sectional shape of the disperse phase contributes to the asymmetric diffusion in both back scattered light and forward scattered light.
5 The effect can either add or detract from the amount of scattering from the index mi.cm~tch, but generally has a small influence on scattering in the preferred range of properties in the present invention.
The shape of the disperse phase particles can also influence the degree of diffusion of light scattered from the particles. This shape effect is generally small o but increases as the aspect ratio of the geometrical cross-section of the particle in the plane perpendicular to the direction of incidence of the light increases and as the particles get relatively larger. In general, in the operation of this invention, the disperse phase particles should be sized less than several wavelengths of light in one or two mutually orthogonal tlimen~ions if diffuse, rather than specular, 5 reflection is preferred.
Preferably, for a low loss reflective polarizer, the plef~,.. d embodiment consists of a disperse phase disposed within the continuous phase as a series ofrod-like structures which, as a consequence of orientation, have a high aspect ratio which can enhance reflection for polarizations parallel to the orientation direction by increasing the scattering strength and dispersion for that polarization relative to polarizations perpendicular to the orientation direction. However, as indicated in FIGS. 3a-e, the disperse phase may be provided with many dirre.~l~l geometries.
Thus, the disperse phase may be disk-shaped or elongated disk-shaped, as in FIGS.
3a-c, rod-shaped, as in FIG. 3d-e, or spherical. Other embodiments are 2s contemplated wherein the disperse phase has cross sections which are approximately elliptical (including circular), polygonal, irregular, or a combination of one or more of these shapes. The cross-sectional shape and size of the particles of the disperse phase may also vary from one particle to another, or from one region of the film to another (i.e., from the surface to the core).
In some embodiments, the disperse phase may have a core and shell construction, wherein the core and shell are made out of the same or different W O 97132224 PCT~US97/00981 materials, or wherein the core is hollow. Thus, for example, the disperse phase may consist of hollow fibers of equal or random lengths, and of uniform or non-uniform cross section. The interior space of the fibers may be empty, or may be occupied by a suitable medium which may be a solid, liquid, or gas, and may be organic or inorganic. The refractive index of the medium may be chosen in consideration of the refractive indices of the disperse phase and the continuousphase so as to achieve a desired optical effect (i.e., reflection or polarization along a given ax1s).
The geometry of the disperse phase may be arrived at through suitable o orientation or processing of the optical material, through the use of particles having a particular geometry, or through a combination of the two. Thus, for example, adisperse phase having a substantially rod-like structure can be produced by orienting a film con.~isting of approximately spherical disperse phase particlesalong a single axis. The rod-like structures can be given an elliptical cross-section by orienting the film in a second direction perpendicular to the first. As a further example, a disperse phase having a substantially rod-like structure in which therods are rectangular in cross-section can be produced by orienting in a single direction a film having a disperse phase con~i~ting of a series of essPnti~lly rectangular flakes.
Stretching is one convenient manner for arriving at a desired geometry, since stretching can also be used to induce a difference in indices of refraction within the material. As indicated above, the orientation of films in accordance with the invention may be in more than one direction, and may be sequential or simultaneous.
In another example, the components of the continuous and disperse phases may be extruded such that the disperse phase is rod-like in one axis in the unoriented film. Rods with a high aspect ratio may be generated by orienting in the direction of the major axis of the rods in the extruded film. Plate-like structures may be generated by orienting in an orthogonal direction to the major axis of the rods in the extruded film.
W O 97/32224 PCTrUS97/00981 The structure in FIG. 2 can be produced by asymmetric biaxial orientation of a blend of es~enti~lly spherical particles within a continuous matrix.
Alternatively, the structure may be obtained by incorporating a plurality of fibrous structures into the matrix material, aligning the structures along a single axis, and 5 orienting the mixture in a direction transverse to that axis. Still another method for obtaining this structure is by controlling the relative viscosities, shear, or surface tension of the components of a polymer blend so as to give rise to a fibrous disperse phase when the blend is extruded into a film. In general, it is found that the best results are obtained when the shear is applied in the direction of extrusion.
Dimensional Alignment of Disperse Phase Dimensional alignment is also found to have an effect on the sc~ttering behavior of the disperse phase. In particular, it has been observed in optical bodies made in accordance with the present invention that aligned scatterers will not 5 scatter light symmetrically about the directions of specular tr~n~mi~ion or reflection as randomly aligned sc~ cl~ would. In particular, inclusions that have been elongated through orientation to resemble rods scatter light primarily along (or near) the surface of a cone centered on the orientation direction and along the specularly transmitted direction. This may result in an anisotropic distribution of 20 scattered light about the specular reflection and specular tr~n~mi.c~ion directions.
For example, for light incident on such an elongated rod in a direction perpendicular to the orientation direction, the scattered light appears as a band of light in the plane perpendicular to the orientation direction with an intensity that decreases with increasing angle away from the specular directions. By tailoring the 25 geometry of the inclusions, some control over the distribution of scattered light can be achieved both in the tr~n~mi~sive hemisphere and in the reflective hemisphere.
Dimensions of D;;,~ sc Phase In applications where the optical body is to be used as a low loss reflective 30 polarizer, the structures of the disperse phase preferably have a high aspect ratio, i.e., the structures are substantially larger in one dimension than in any other dimension. The aspect ratio is preferably at least 2, and more preferably at least 5.
The largest ~limencion (i.e., the length) is preferably at least 2 times the wavelength of the electromagnetic radiation over the wavelength range of interest, and morepreferably at least 4 times the desired wavelength. On the other hand, the smaller (i.e., cross-sectional) dimensions of the structures of the disperse phase are preferably less than or equal to the wavelength of interest, and more preferably less than 0.5 times the wavelength of interest.
Volume Fraction of Di~l.c. ~e Phase 0 The volume fraction of the disperse phase also affects the scattering of light in the optical bodies of the present invention. Within certain limits, increasing the volume fraction of the disperse phase tends to increase the amount of scatteringthat a light ray experiences after entering the body for both the match and mi~m~tch directions of polarized light. This factor is important for controlling the reflection and tr~mi~.cion properties for a given application. However, if the volume fraction of the disperse phase becomes too large, light scattering can ~limini~h Without wishing to be bound by theory, this appears to be due to the fact that the disperse phase particles are closer together, in terrns of the wavelength of light, so that the particles tend to act together as a smaller number of large effective particles.
The desired volume fraction of the disperse phase will depend on many factors, including the specific choice of materials for the continuous and disperse phase. However, the volume fraction of the disperse phase will typically be at least about 1% by volume relative to the continuous phase, more preferably within the range of about 5 to about 15%, and most preferably within the range of about l S to about 30%.
Thickness of Optical Body The thickness of the optical body is also an important parameter which can be manipulated to affect reflection and tr~n~mi~sion properties in the present invention. As the thickness of the optical body increases, diffuse reflection also W O 97/32224 PCTrUS97/00981 increases, and tr~n.smi.ssion, both specular and diffuse, decreases. Thus, while the thickness of the optical body will typically be chosen to achieve a desired degree of mechanical strength in the finished product, it can also be used to directly to control reflection and tr~n.smission properties.
Thickness can also be utilized to make final adjustments in reflection and tr~n~mi~sion properties of the optical body. Thus, for example, in film applications, the device used to extrude the film can be controlled by a downstream optical device which measures transmission and reflection values in the extrudedfilm, and which varies the thickness of the film (i.e., by adjusting extrusion rates or 0 ch~nging casting wheel speeds) so as to m~int:~in the reflection and tr~nsmiqsion values within a predet~ ed range.
Materials for Continuous/Di~ ,e Phases Many different materials may be used as the continuous or disperse phases in the optical bodies of the present invention, depending on the specific application to which the optical body is directed. Such materials include inorganic materials such as silica-based polymers, organic m~teri~ls such as liquid crystals, and polymeric materials, including monomers, copolymers, grafted polymers, and mixtures or blends thereof. The exact choice of materials for a given application will be driven by the desired match and mi.sm~tch obtainable in the refractive indices of the continuous and disperse phases along a particular axis, as well as the desired physical properties in the resulting product. However, the materials of the continuous phase will generally be characterized by being substantially transparent in the region of the spectrum desired.
A further consideration in the choice of materials is that the resulting product must contain at least two distinct phases. This may be accomplished by casting the optical material from two or more materials which are immiscible with each other. Alternatively, if it is desired to make an optical material with a first and second material which are not immiscible with each other, and if the first material has a higher melting point than the second material, in some cases it may - be possible to embed particles of applopliate dimensions of the first material W O 97132224 rCTrUS97/00981 within a molten matrix of the second material at a temperature below the meltingpoint of the first material. The resulting mixture can then be cast into a film, with or without subsequent orientation, to produce an optical device.
Suitable polymeric materials for use as the continuous or disperse phase in the present invention may be amorphous, semicrystalline, or crystalline polymeric materials, including materials made from monomers based on carboxylic acids such as isophthalic, azelaic, adipic, sebacic, dibenzoic, terephthalic, 2,7-naphthalene dicarboxylic, 2,6-naphthalene dicarboxylic, cyclohexanedicarboxylic,and bibenzoic acids (including 4,4t-bibenzoic acid), or materials made from the o corresponding esters of the aforementioned acids (i.e., dimethylterephth~l~tP). Of these, 2,6-polyethylene naphth~l~te (PEN) is especially preferred because of itsstrain induced birefringence, and because of its ability to remain permanently birefringent after stretching. PEN has a refractive index for polarized incident light of 550 nm wavelength which increases after stretching when the plane of polarization is parallel to the axis of stretch from about 1.64 to as high as about 1.9, while the refractive index decreases for light polarized perpendicular to the axis of stretch. PEN exhibits a birefringence (in this case, the difference between the index of refraction along the stretch direction and the index perpendicular to the stretch direction) of 0.25 to 0.40 in the visible spectrum. The birefringence can be increased by increasing the molecular orientation. PEN may be substantially heatstable from about 155~C up to about 230~C, depending upon the processing conditions utilized during the m~mlf~ture of the film.
Polybutylene naphth~l~te is also a suitable material as well as other crystalline naphthalene dicarboxylic polyesters. The crystalline naphthalene dicarboxylic polyesters exhibit a difference in refractive indices associated with different in-plane axes of at least 0.05 and preferably above 0.20.
When PEN is used as one phase in the optical material of the present invention, the other phase is preferably polymethylmethacrylate (PMMA) or a syndiotactic vinyl aromatic polymer such as polystyrene (sPS). Other preferred polymers for use with PEN are based on terephthalic, isophthalic, sebacic, azelaic or cyclohexanedicarboxylic acid or the related alkyl esters of these materials.
Naphthalene dicarboxylic acid may also be employed in minor amounts to improve adhesion between the phases. The diol component may be ethylene glycol or a related diol. Preferably, the index of refraction of the selected polymer is less than about 1.65, and more preferably, less than about 1.55, although a similar result may 5 be obtainable by using a polymer having a higher index of refraction if the same index difference is achieved.
Syndiotactic-vinyl aromatic polymers useful in the current invention include poly(styrene), poly(alkyl styrene), poly(styrene halide), poly(alkyl styrene), poly(vinyl ester benzoate), and these hydrogenated polymers and ~ es, or o copolymers co.~ g these structural units. Exarnples of poly(alkyl styrenes) include: poly(methyl styrene), poly(ethyl styrene), poly(propyl styrene), poly(butyl styrene), poly(phenyl styrene), poly(vinyl naphthalene), poly(vinylstyrene), and poly(acenaphthalene) may be mentioned. As for the poly(styrene halides), examples include: poly(chlorostyrene), poly(bromostyrene), 5 and poly(fluorostyrene). Examples of poly(alkoxy styrene) include: poly(methoxy styrene), and poly(ethoxy styrene). Among these exarnples, as particularly preferable styrene group polymers, are: polystyrene, poly(p-methyl styrene), poly(m-methyl styrene), poly(p-tertiary butyl styrene), poly(p-chlorostyrene), poly(m-chloro styrene), poly(p-fluoro styrene), and copolymers of styrene and p-20 methyl styrene may be mentioned.
Furthermore, as comonomers of syndiotactic vinyl-aromatic group copolymers, besides monomers of above explained styrene group polymer, olefin monomers such as ethylene, propylene, butene, hexene, or octene; diene monomers such as butadiene, isoprene; polar vinyl monomers such as cyclic diene monomer, 25 methyl methacrylate, maleic acid anhydride, or acrylonitrile may be mentioned.
The syndiotactic-vinyl aromatic polymers of the present invention may be block copolymers, random copolymers, or alternating copolymers.
The vinyl aromatic polymer having high level syndiotactic structure referred to in this invention generally includes polystyrene having syndiotacticity 30 of higher than 75% or more, as determined by carbon-13 nuclear magnetic W O 97/32224 PCTrUS97/00981 resonance. Preferably, the degree of syndiotacticity is higher than 85% racemic diad, or higher than 30%, or more preferably, higher than 50%, racemic pentad.
In addition, although there are no particular restrictions regarding the molecular weight of this syndiotactic-vinyl aromatic group polymer, preferably, the s weight average molecular weight is greater than 10,000 and less than 1,000,000, and more preferably, greater than 50,000 and less than 800,000.
As for said other resins, various types may be mentioned, including, for instance, vinyl aromatic group polymers with atactic structures, vinyl aromatic group polymers with isotactic structures, and all polymers that are miscible. For o example, polyphenylene ethers show good miscibility with the previous explained vinyl aromatic group polymers. Furthermore, the composition of these miscible resin components is preferably between 70 to 1 weight %, or more preferably, 50 to 2 weight %. When composition of miscible resin component exceeds 70 weight %, degradation on the heat resistance may occur, and is usually not 1 5 desirable.
It is not required that the selected polymer for a particular phase be a copolyester or copolycarbonate. Vinyl polymers and copolymers made from monomers such as vinyl n~phth~lenes, styrenes, ethylene, maleic anhydride, acrylates, and methacrylates may also be employed. Cond~n.c~tion polymers, otherthan polyesters and polycarbonates, can also be lltili7f?cl Suitable contlenc~tion polymers include polysulfones, polyamides, polyureth~nes, polyamic acids, and polyimides. Naphthalene groups and halogens such as chlorine, bromine and iodine are useful in increasing the refractive index of the selected polymer to the desired level (1.59 to 1.69) if needed to substantially match the refractive index if 2s PEN is the host. Acrylate groups and fluorine are particularly useful in decreasing the refractive index.
Minor amounts of comonomers may be substituted into the n~phth~lene dicarboxylic acid polyester so long as the large refractive index difference in the orientation direction(s) is not substantially compromised. A smaller index difference (and therefore decreased reflectivity) may be counterbalanced by advantages in any of the following: improved adhesion between the continuous W O 97/322Z4 PCTrUS97/00981 and disperse phase, lowered temperature of extrusion, and better match of melt viscosities.
Region of Spectrum s While the present invention is frequently described herein with reference to the visible region of the spectrum, various embo~limentc of the present invention can be used to operate at different wavelengths ~and thus frequencies) of electromagnetic radiation through a~lopliate scaling of the components of the optical body. Thus, as the wavelength increases, the linear size of the components o of the optical body may be increased so that the dimensions of these components, measured in units of wavelength, remain approximately constant.
Of course, one major effect of ch~nging wavelength is that, for most materials of interest, the index of refraction and the absorption coefficient change.
However, the principles of index match and mi~m~tch still apply at each 1S wavelength of interest, and may be utilized in the selection of materials for an optical device that will operate over a specific region of the spectrum. Thus, for example, proper scaling of ~iime~jons will allow operation in the infrared, near-ultraviolet, and ultra-violet regions of the spectrum. In these cases, the indices of refraction refer to the values at these wavelengths of operation, and the body thickness and size of the disperse phase scattering components should also be approximately scaled with wavelength. Even more of the electrom~gnetic spectrum can be used, including very high, ultrahigh, microwave and millimeter wave frequencies. Polarizing and diffusing effects will be present with proper scaling to wavelength and the indices of refraction can be obtained from the square 2s root of the dielectric function (including real and im~gin~ry parts). Useful products in these longer wavelength bands can be diffuse reflective polarizers and partial polarizers.
In some embodiments of the present invention, the optical pl~pCl lies of the optical body vary across the wavelength band of interest. In these embodiments, materials may be utilized for the continuous and/or disperse phases whose indices of refraction, along one or more axes, varies from one wavelength region to W O 97/32224 PCT~US97/00981 another. The choice of continuous and disperse phase materials, and the optical properties (i.e., diffuse and disperse reflection or specular tr~n~mi.csion) resulting from a specific choice of materials, will depend on the wavelength band of interest.
Skin Layers A layer of material which is substantially free of a disperse phase may be coextensively disposed on one or both major surfaces of the film, i.e., the extruded blend of the disperse phase and the continuous phase. The composition of the layer, also called a skin layer, may be chosen, for example, to protect the integrity o of the disperse phase within the extruded blend, to add mechanical or physical properties to the final film or to add optical functionality to the fina} film. Suitable materials of choice may include the material of the continuous phase or the material of the disperse phase. Other materials with a melt viscosity similar to the extruded blend may also be useful.
s A skin layer or layers may reduce the wide range of shear intensities the extruded blend might experience within the extrusion process, particularly at the die. A high shear environment may cause undesirable surface voiding and may result in a textured surface. A broad range of shear values throughout the thickness of the film may also prevent the disperse phase from forming the desired particle size in the blend.
A skin layer or layers may also add physical strength to the resulting composite or reduce problems during processing, such as, for example, reducing the tendency for the film to split during the orientation process. Skin layer materials which remain amorphous may tend to make films with a higher toughness, while skin layer materials which are semicrystalline may tend to makefilms with a higher tensile modulus. Other functional components such as ~nti~t~tic additives, UV absorbers, dyes, antioxidants, and pigments, may be added to the skin layer, provided they do not substantially interfere with the desiredoptical properties of the resulting product.
The skin layers may be applied to one or two sides of the extruded blend at some point during the extrusion process, i.e., before the extruded blend and skin W O 97132224 PCTrUS97100981 layer(s) exit the extrusion die. This may be accomplished using conventional coextrusion technology, which may include using a three-layer coextrusion die.
T ~min~tion of skin layer(s) to a previously formed film of an extruded blend is also possible. Total skin layer thicknesses may range from about 2% to about 50% of the total blend/skin layer thickness.
A wide range of polymers are suitable for skin layers. Predomin~ntly arnorphous polymers include copolyesters based on one or more of terephthalic acid, 2,6-naphthalene dicarboxylic acid, isophthalic acid phthalic acid, or their alkyl ester counterparts, and alkylene diols, such as ethylene glycol. Exarnples of o semicrystalline polymers are 2,6-polyethylene n~phth~l~te, polyethylene terephth~l~te, and nylon materials.
Antireflection Layers The films and other optical devices made in accordance with the invention may also include one or more anti-reflective layers. Such layers, which may or may not be polari_ation sensitive, serve to increase tr~n.cmi~sion and to reducereflective glare. An anti-reflective layer may be imparted to the films and optical devices of the present invention through ~propllate surface treatment, such as coating or sputter etching.
In some embodiments of the present invention, it is desired to maximize the tr~n~mi~sion and/or minimi7~ the specular reflection for certain polarizations of light. In these embodiments, the optical body may comprise two or more layers inwhich at least one layer comprises an anti-reflection system in close contact with a layer providing the continuous and disperse phases. Such an anti-reflection system acts to reduce the specular reflection of the incident light and to increase theamount of incident light that enters the portion of the body comprising the continuous and disperse layers. Such a function can be accomplished by a varietyof means well known in the art. Examples are ~uarter wave anti-reflection layers, two or more layer anti-reflective stack, graded index layers, and graded densitylayers. Such anti-reflection functions can also be used on the transmitted lightside of the body to increase transmitted light if desired.
W 097/32224 PCTrUS97/00981 Microvoiding In some embodiments, the materials of the continuous and disperse phases may be chosen so that the interface between the two phases will be sufficiently 5 weak to result in voiding when the film is oriented. The average dimensions of the voids may be controlled through careful manipulation of processing parameters and stretch ratios, or through selective use of compatibilizers. The voids may be back-filled in the finiched product with a liquid, gas, or solid. Voiding may beused in conjunction with the aspect ratios and refractive indices of the disperse and 0 continuous phases to produce desirable optical properties in the resulting film.
More Than Two Phases The optical bodies made in accordance with the present invention may also consist of more than two phases. Thus, for example, an optical material made in 5 accordance with the present invention can consist of two dirr~ disperse phaseswithin the continuous phase. The second disperse phase could be randomly or non-randomly dispersed throughout the continuous phase, and can be randomly aligned or aligned along a common axis.
Optical bodies made in accordance with the present invention may also 20 consist of more than one continuous phase. Thus, in some embodimentc, the optical body may include, in addition to a first continuous phase and a dispersephase, a second phase which is co-continuous in at least one ~iimencion with thefirst continuous phase. In one particular embodiment, the second continuous phase is a porous, sponge-like material which is coextensive with the first continuous25 phase (i.e., the first continuous phase extends through a network of channels or spaces exten~ling through the second continuous phase, much as water extends through a network of channels in a wet sponge). In a related embodiment, the second continuous phase is in the forrn of a dendritic structure which is coextensive in at least one dimension with the first continuous phase.
CA 022482l4 l998-08-28 W O 97132224 PCTrUS97/00981 Multilayer Combinations If desired, one or more sheets of a continuous/disperse phase film made in accordance with the present invention may be used in combination with, or as a component in, a multilayered film (i.e., to increase reflectivity). Suitable multilayered films include those of the type described in WO 95/17303 (Ouderkirket al.). In such a construction, the individual sheets may be l~min~ted or otherwise adhered together or may be spaced apart. If the optical thicknesses of the phases within the sheets are substantially equal (that is, if the two sheets present a substantially equal and large number of scatterers to incident light along a given axis), the composite will reflect, at somewhat greater efficiency, substantially the same band width and spectral range of reflectivity (i.e., "band") as the individual sheets. If the optical thickn~.ces of phases within the sheets are not substantially equal, the composite will reflect across a broader band width than the individual phases. A composite combining mirror sheets with polarizer sheets is useful for increasing total reflectance while still polarizing transmitted light. Alternatively, a single sheet may be asymmetrically and biaxially oriented to produce a film having selective reflective and polarizing plope, lies.
FIG. 5 illustrates one example of this embodiment of the present invention.
There, the optical body consists of a multilayer film 20 in which the layers alternate between layers of PEN 22 and layers of co-PEN 24. Each PEN layer includes a disperse phase of syndiotactic polystyrene (sPS) within a matrix of PEN.
This type of construction is desirable in that it promotes lower off-angle color.
Furthermore, since the layering or inclusion of scatterers averages out light leakage, control over layer thickness is less critical, allowing the film to be more tolerable of variations in processing parameters.
Any of the materials previously noted may be used as any of the layers in this embolliment, or as the continuous or disperse phase within a particular layer.
However, PEN and co-PEN are particularly desirable as the major components of adjacent layers, since these materials promote good laminar adhesion.
Also, a number of variations are possible in the arrangement of the layers.
Thus, for example, the layers can be made to follow a repeating sequence through W O 97/32224 PCTrUS97/0098 part or all of the structure. One example of this is a construction having the layer pattern ... ABCABC ..., wherein A, B, and C are distinct materials or distinct blends or mixtures of the same or different materials, and wherein one or more of A, B, or C contains at least one disperse phase and at least one continuous phase.
5 The skin layers are preferably the same or chemically similar materials.
Additives The optical materials of the present invention may also comprise other materials or additives as are known to the art. Such materials include pigments,o dyes, binders, coatings, fillers, compatibilizers, antioxidants (including sterically hindered phenols), surfactants, antimicrobial agents, zlnti~t~tic agents, flarneretardants, foaming agents, lubricants, reinforcers, light stabilizers (including UV
stabilizers or blockers), heat stabilizers, impact modifiers, plasticizers, viscosity modifiers, and other such materials. Furthermore, the films and other optical 5 devices made in accordance with the present invention may include one or more outer layers which serve to protect the device from abrasion, impact, or other damage, or which enhance the processability or durability of the device.
Suitable lubricants for use in the present invention include calcium sterate, zinc sterate, copper sterate, cobalt sterate, molybdenum neodocanoate, and 20 ruthenium (III) acetylacetonate.
Antioxidants useful in the present invention include 4,4'-thiobis-(6-t-butyl-m-cresol), 2,2'-methylenebis-(4-methyl-6-t-butyl-butylphenol), octadecyl-3,5-di-t-butyl-4-hydroxyhydrocinn~m:~te, bis-(2,4-di-t-butylphenyl) pentaerythritol diphosphite, IrganoxTM 1093 (1979)(((3,5-bis(1,1 -dimethylethyl)-4-25 hydroxyphenyl~methyl)-dioctadecyl ester phosphonic acid), IrganoxTM 1098 (N,N'-1,6-hexanediylbis(3,5-bis(1, I -dimethyl)-4-hydroxy-benzenepl opal1amide), NaugaardTM 445 (aryl arnine), IrganoxTM L 57 (alkylated diphenylarnine), IrganoxTM
L 115 (sulfur cont~ining bisphenol), IrganoxTM LO 6 (alkylated phenyl-delta-napthylamine), Ethanox 398 (flourophosphonite), and 2,2'-ethylidenebis(4,6-di-t-30 butylphenyl)fluorophosnite.
W O 97/32224 PCTrUS97100981 A group of antioxidants that are especially prefe,l~d are sterically hindered phenols, including butylated hydroxytoluene (BHT), Vitamin E (di-alpha-tocopherol), IrganoxTM 1425WL(calcium bis-(O-ethyl(3,5-di-t-butyl-4-hydroxybenzyl))phosphonate), IrganoxTM 1010 (tetrakis(methylene(3,5,di-t-butyl-4-hydroxyhydrocinn~m~te))methane), IrganoxTM 1076 (octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinn~m~te), EthanoxTM 702 (hindered bis phenolic), Etanox 330 (high molecular weight hindered phenolic), and EthanoxTM 703 (hindered phenolic amine).
Dichroic dyes are a particularly useful additive in some applications to o which the optical m~t~ri~ls of the present invention may be directed, due to their ability to absorb light of a particular polarization when they are molecularly aligned within the m~t~ri~l. When used in a film or other material which predomin~ntly scatters only one polarization of light, the dichroic dye causes the material to absorb one polarization of light more than another. Suitable dichroic dyes for use in the present invention include Congo Red (sodium diphenyl-bis-a-aphlhylamine sulfonate), methylene blue, stilbene dye (Color Index (CI) = 620), and 1,1 '-diethyl-2,2'-cyanine chloride (CI = 374 (orange) or CI = 518 (blue)). The properties of these dyes, and methods of m~king them, are described in E.H. Land, Colloid Chemistry (1946). These dyes have noticeable dichroism in polyvinyl alcohol and a lesser dichroism in cellulose. A slight dichroism is observed withCongo Red in PEN.
W O 97/32224 rCT~US97/00981 Other suitable dyes include the following materials:
(1) R~ R
where R is ~ CH=N~
,~ ,~i ~ ~ ~ O--C9HI9 O OH
J~ _ ~ OR
O NH2 o N--CH
O NH2 ~
The properties of these dyes, and methods of making them, are discussed in the Kirk Othmer Encyclopedia of Chemical Technology, Vol. 8, pp. 652-661 (4th Ed.
5 1993), and in the references cited therein.
When a dichroic dye is used in the optical bodies of the present invention, it may be incorporated into either the continuous or disperse phase. However, it is- preferred that the dichroic dye is incorporated into the disperse phase.
W O 97/32224 PCT~US97/00981 Dychroic dyes in combination with certain polymer systems exhibit the ability to polarize light to varying degrees. Polyvinyl alcohol and certain dichroic dyes may be used to make films with the ability to polarize light. Other polymers, such as polyethylene terephth~1~te or polyamides, such as nylon-6, do not exhibit s as strong an ability to polarize light when combined with a dichroic dye. The polyvinyl alcohol and dichroic dye combination is said to have a higher dichroism ratio than, for example, the same dye in other film forming polymer systems. A
higher dichroism ratio indicates a higher ability to polarize light.
Molecular alignment of a dichroic dye within an optical body made in 0 accordance with the present invention is preferably accomplished by stretching the optical body after the dye has been incorporated into it. However, other methodsmay also be used to achieve molecular ~lignment Thus, in one method, the dichroic dye is cryst~lli7~.1, as through sublimation or by cryst~11i7~tion fromsolution, into a series of elongated notches that are cut, etched, or otherwise formed 5 in the surface of a film or other optical body, either before or after the optical body has been oriented. The treated surface may then be coated with one or more surface layers, may be incorporated into a polymer matrix or used in a multilayer structure, or may be utilized as a component of another optical body. The notches may be created in accordance with a predetermined pattern or diagram, and with a20 predetermined amount of spacing between the notches, so as to achieve desirable optical properties.
In a related embodiment, the dichroic dye may be disposed within one or more hollow fibers or other conduits, either before or after the hollow fibers or conduits are disposed within the optical body. The hollow fibers or conduits may2s be constructed out of a m~t~ri~1 that is the same or different from the surrounding material of the optical body.
In yet another embodiment, the dichroic dye is disposed along the layer interface of a multilayer construction, as by sublimation onto the surface of a layer before it is incorporated into the multilayer construction. In still other 30 embo~iment~, the dichroic dye is used to at least partially backfill the voids in a microvoided film made in accordance with the present invention.
W O 97/32224 PCT~US97/00981 Applications of Present Invention The optical bodies of the present invention are particularly useful as diffuse polarizers. However, optical bodies may also be made in accordance with the 5 invention which operate as reflective polarizers or diffuse mirrors. In these applications, the construction of the optical material is similar to that in the diffuser applications described above. However, these reflectors will generally have a much larger difference in the index of refraction along at least one axis. This index difference is typically at least about 0.1, more preferably about 0.15, and mosto preferably about 0.2.
Reflective polarizers have a refractive index difference along one axis, and substantially m~t~h~cl indices along another. Reflective films, on the other hand, differ in refractive index along at least two in-film plane orthogonal axes.
However, the reflective properties of these embo-liment~ need not be ~ in~d 15 solely by reliance on refractive index mi~m~tches. Thus, for example, the thickness of the films could be adjusted to attain a desired degree of reflection. In some cases, adjustment of the thickness of the film may cause the film to go from being a tr~n~mi~ive diffuser to a diffuse reflector.
The reflective polarizer of the present invention has many different 20 applications, and is particularly useful in liquid crystal display panels. In addition, the polarizer can be constructed out of PEN or similar materials which are good ultraviolet filters and which absorb ultraviolet light efficiently up to the edge of the visible spectrum. The reflective polarizer can also be used as a thin infrared sheet polarizer.
2s Overview of Examples The following Examples illustrate the production of various optical materials in accordance with the present invention, as well as the spectral properties of these materials. Unless otherwise indicated, percent composition 30 refers to percent composition by weight. The polyethylene naphth~l~te resin used was produced for these samples using ethylene glycol and dimethyl-2,6-naphthalenedicarboxylate, available from Amoco Corp., Chicago, Illinois. These reagents were polymerized to various intrinsic viscosities (IV) using conventional polyester resin polymerization techniques. Syndiotactic polystyrene (sPS) may beproduced in accordance with the method disclosed in U. S. Patent 4,680,353 s (Ishihara et al). The examples includes various polymer pairs, various fractions of continuous and disperse phases and other additives or process changes as ~ cl-sse~
below.
Stretching or orienting of the samples was provided using either conventional orientation equipment used for making polyester film or a laboratory o batch orienter. The laboratory batch orienter used was designed to use a small piece of cast material (7.5cm by 7.5cm) cut from the extruded cast web and held by a square array of 24 ~,li~el~ (6 on each side). The orientation temp~ldlule ofthe sample was controlled a hot air blower and the film sample was oriented through a mechanical system that increased the distance between the gli~JpC;I~ in one or both directions at a controlled rate. Samples stretched in both directions could be oriented sequentially or simultaneously. For samples that were oriented in the constrained mode (C), all g~i~e-~ hold the web and the gli~)~Cl:i move only in one dimension. Whereas, in the unconslldined mode (U), the ~ri~ that hold the film at a fixed dimension perpendicular to the direction of stretch are not engaged and the film is allowed to relax or neckdown in that ~imçn.~ion.
Polarized diffuse tran~mi~ion and reflection were measured using a Perkin Elmer Lambda 19 ultravioletlvisible/near infrared spectrophotometer equipped with a Perkin Elmer Labsphere S900-1000 150 millimeter integrating sphere accessory and a Glan-Thompson cube polarizer. Parallel and crossed tran~mi~sion and reflection values were measured with the e-vector of the polarized light parallel or perpendicular, respectively, to the stretch direction of the film. All scans were continuous and were conducted with a scan rate of 480 nanometers per minute and a slit width of 2 nanometers. Reflection was performed in the "V-reflection"
mode. Tr~n~mi~.sion and reflectance values are averages of all wavelengths from 400 to 700 nanometers.
WO 97t32224 PCTtUS97/00981 EXAMPLE I
In Example 1, an optical film was made in accordance with the invention by extruding a blend of 75% polyethylene naphth~ te (PEN) as the continuous or major phase and 25% of polymethylmethacrylate (PMMA) as the disperse or minor s phase into a cast film or sheet about 380 microns thick using conventional extrusion and casting techniques. The PEN had an intrinsic viscosity (IV) of 0.52 (measured in 60% phenol, 40% dichlorobenzene). The PMMA was obtained from ICI Americas, Inc., Wilmington, Delaware, under the product designation CP82.
The extruder used was a 3.15 cm (1.24") Brabender with a 1 tube 60 ,~m Tegra o filter. The die was a 30.4 cm (12") EDI UltraflexTM 40.
About 24 hours after the film was extruded, the cast film was oriented in the width or transverse direction (TD) on a polyester film tentering device. Thestretching was accomplished at about 9.1 meters per minute (30 ft/min) with an output width of about 140 cm (55 inches) and a stretching temperature of about 160~C (320~F). The total reflectivity ofthe stretched sample was measured with an integrating sphere ~ chm~nt on a Lambda 19 spectrophotometer with the sarnple beam polarized with a Glan-Thompson cube polarizer. The sample had a 75% parallel reflectivity (i.e., reflectivity was measured with the stretch direction of the film parallel to the e-vector of the polarized light), and 52% crossed reflectivity (i.e., reflectivity was measured with the e-vector of the polarized light perpendicular to the stretch direction).
In Example 2, an optical film was made and evaluated in a manner similar to Example I except using a blend of 75% PEN, 25% syndiotactic polystyrene (sPS), 0.2% of a polystyrene glycidyl methacrylate compatibilizer, and 0.25% each of IrganoxTM 1010 and UltranoxTM 626. The synthesis of polystyrene glycidyl methacrylate is described in Polymer Processes, "Chemical Technology of Plastics, Resins, Rubbers, Adhesives and Fibers", Vol. 10, Chap. 3, pp. 69-109 (1956)(Ed.
by Calvin E. Schildknecht).
W O 97/32224 PCTrUS97/00981 The PEN had an intrinsic viscosity of 0.52 measured in 60% phenol, 40%
dichlorobenzene. The sPS was obtained from Dow Chemical Co. and had a weight average molecular weight of about 200,000, designated subsequently as sPS-200-0.The parallel reflectivity on the stretched film sample was determined to be 73.3%, s and the crossed reflectivity was determined to be 35%.
In Example 3, an optical film was made and evaluated in a manner similar to Example 2 except the compatibilizer level was raised to 0.6%. The resulting o parallel reflectivity was deterrnined to be 81 % and the crossed reflectivity was determined to be 35.6%.
In Example 4, an three layer optical film was made in accordance with the present invention ~ltili7ing conventional three layer coextrusion techniques. The film had a core layer and a skin layer on each side of the core layer. The core layer consisted of a blend of 75% PEN and 25% sPS 200-4 (the deci&n~tion sPS-200-4 refers to a copolymer of syndiotactic-polystyrene co~ g 4 mole % of para-methyl styrene), and each skin layer consisted of 100% PEN having an intrinsic viscosity of 0.56 measured in 60% phenol, 40% dichlorobenzene.
The resulting three-layer cast film had a core layer thickness of about 415 microns, and each skin layer was about 110 microns thick for a total thickness of about 635 microns. A laboratory batch stretcher was used to stretch the resulting three-layer cast film about 6 to 1 in the m~ehine direction (MD) at a tel,lpeldlllre of 2s about 129~C. Because the edges of the film sample parallel to the stretch direction were not gripped by the lab stretcher, the sample was unconstrained in the transverse direction (TD) and the sample necked-down in the TD about 50% as a result of the stretch procedure.
Optical performance was evaluated in a manner similar to Example l. The parallel reflectivity was deterrnined to be 80.1 %, and the crossed reflectivity was W O 97/32224 PCTrUS97/00981 determined to be 15%. These results demonstrate that the film perforrns as a lowabsorbing, energy conserving system.
In Examples 5-29, a series of optical films were produced and evaluated in a manner similar to Example 4, except the sPS fraction in the core layer and the IV
of the PEN resin used were varied as shown in Table 1. The IV of the PEN resin in the core layer and that in the skin layers was the same for a given sample. The total thickness of the cast sheet was about 625 microns with about two-thirds ofo this total in the core layer and the balance in the skin layers which were approximately equal in thickness. Various blends of PEN and sPS in the core layer were produced, as indicated in Table 1. The f1lms were stretched to a stretch ratio of about 6:1 in either the m~hine direction (MD) or in the transverse direction (TD) at various telllpe,~l lres as indicated in Table 1. Some of the samples were constrained (C) in the direction perpendicular to the stretch direction to prevent the sample from n~c~ing down during stretching. The samples labeled "U'~ in Table 1 were uncon~ hled and permitted to neckdown in the unconstrained dimension.
Certain optical properties of the stretched samples, including percent tr~n~mi~ion, reflection, and absorption, were measured along axes both parallel and crossed or perpendicular to the direction of stretch. The results are summarized in Table 1.
Heat setting, as indicated for Examples 24-27, was accomplished by manually constraining the two edges of the stretched sarnple which were perpendicular to the direction of stretch by clamping to an apl)lopliately sized rigid frame and placing the clamped sarnple in an oven at the indicated temperature for 1 minute. The two sides of the sample parallel to the direction of stretch were unconstrained (U) or not clamped and allowed to neckdown. The h~tsetting of Example 29 was similar except all four of the edges of the stretched sarnple were constrained (C) or clamped. Example 28 was not heat set.
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All of the above samples were observed to contain varying shapes of the disperse phase depending on the location of the disperse phase within the body of the film sarnple. The disperse phase inclusions located nearer the surfaces of the samples were observed to be of an elongated shape rather than more nearly spherical. The inclusions which are more nearly centered between the surfaces ofthe samples may be more nearly spherical. This is true even for the samples withthe skin layers, but the magnitude of the effect is reduced with the skin layers. The addition of the skin layers improves the processing of the films by reducing thetendency for splitting during the stretching operation.
o Without wishing to be bound by theory, the elongation of the inclusions(disperse phase) in the core layer of the cast film is thought to be the result of shear on the blend as it is transported through the die. This elongation feature may be altered by varying physical dimensions of the die, extrusion temperatures, flow rate of the extrudate, as well as chemical aspects of the continuous and disperse phase 1S materials which would alter their relative melt viscosities. Certain applications or uses may benefit from providing some elongation to the disperse phase during extrusion. For those applications which are subsequently stretched in the machine direction, starting with a disperse phase elongated during extrusion may allow ahigher aspect ratio to be reached in the resulting disperse phase.
Another notable feature is the fact that a noticeable improvement in performance is observed when the same sample is stretched unconstrained. Thus, in Exarnple 9, the % tr~n.cmi~ion was 79.5% and 20.3% in the parallel and perpendicular directions, respectively. By contrast, the tr~n~mi~.~ion in Exarnple 16 was only 75.8% and 28.7% in the parallel and perpendicular directions, respectively. There is a thickness increase relative to constrained stretching when samples are stretched unconstrained, but since both tr~n~mi~sion and extinction improve, the index match is probably being improved.
An alternative way to provide refractive index control is to modify the chemistry of the materials. For example, a copolymer of 30 wt % of interpolymerized units derived from terephthalic acid and 70 wt % of units derived from 2,6-naphthalic acid has a refractive index 0.02 units lower than a 100% PEN
W O 97/32224 PCTrUS97100981 polymer. Other monomers or ratios may have slightly different results. This typeof change may be used to more closely match the refractive indices in one axis while only causing a slight reduction in the axis which desires a large difference.
In other words, the benefits attained by more closely matching the index values in 5 one axis more than compensate for the reduction in an orthogonal axis in which a large difference is desired. Secondly, a chemical change may be desirable to alter the temperature range in which stretching occurs. A copolymer of sPS and varyingratios of para methyl styrene monomer will alter the optimum stretch-temperaturerange. A combination of these techniques may be necessary to most effectively 0 optimize the total system for processing and resulting refractive index matches and differences. Thus, an improved control of the final performance may be ~tt:~in~od by optimi7ing the process and chemistry in terms of stretching conditions and further adjusting the chemistry of the materials to maximize the difference in refractive index in at least one axis and minimi7ing the difference at least one15 orthogonal axis.
These samples displayed better optical performance if oriented in the MD
rather than TD direction (compare Examples 14-15). Without wishing to be bound by theory, it is believed that different geometry inclusions are developed with an MD orientation than with a TD orientation and that these inclusions have higher 20 aspect ratios, making non-ideal end effects less important. The non-ideal endeffects refers to the complex geometry/index of refraction relationship at the tip of each end of the elongated particles. The interior or non-end of the particles are thought to have a uniform geometry and refractive index which is thought to be desirable. Thus, the higher the percentage of the elongated particle that is uniform, 25 the better the optical performance.
The extinction ratio of these materials is the ratio of the tr~n~mi~.cion for polarizations perpendicular to the stretch direction to that parallel to the stretch direction. For the examples cited in Table 1, the extinction ratio ranges between about 2 and about 5, although extinction ratios up to 7 have been observed in 30 optical bodies made in accordance with the present invention. It is expected that W O 97/32224 PCTrUS97100981 even higher extinction ratios can be achieved by adjusting film thickness, inclusion volume fraction, particle size, and the degree of index match and mi~m~tr.1 In Examples 30-100, samples of the invention were made using various materials as listed in Table 2. PEN 42, PEN 47, PEN 53, PEN 56, and PEN 60 refer to polyethylene naphth~l~te having an intrinsic viscosity (IV) of 0.42, 0.47, 0.53, 0.56, and 0.60, respectively, measured in 60% phenol, 40% dichlorobenzene.The particular sPS-200-4 used was obtained from Dow Chemical Co. EcdelTM
o 9967 and EastarTM are copolyesters which are available commercially from F~tm~n Chemical Co., Rochester, New York. SurlynTM 1706 is an ionomer resin available from E.I. du Pont de Nemours & Co., Wilmington, Delaware. The materials listed as Additive 1 or 2 include polystyrene glycidyl methacrylate. The ~e~i~n~tions GMAPS2, GMAPS5, and GMAPS8 refer to glycidyl methacrylate having 2, 5, and 8% by weight, respectively, of glycidyl methacrylate in the total copolymer. ETPB refers to the cros~linkin~ agent ethyltriphenylphosphonium bromide. PMMA V044 refers to a polymethylmethacrylate available commercially from Atohaas North America, Inc.
The optical film samples were produced in a manner similar to Exarnple 4 except for the differences noted in Table 2 and discussed below. The continuous phase and its ratio of the total is reported as major phase. The disperse phase and its ratio of the total is reported as minor phase. The value reported for blend thickness represents the approximate thickness of the core layer in microns. Thethickness of the skin layers varied when the core layer thickness varied, but was kept to a constant ratio, i.e., the skin layers were approximately equal and the total of the two skin layers was about one-third of the total thickness. The size of the disperse phase was determined for some samples by either sc~nnincg electron microscope (SEM) or tr~n~mi.~ion electron microscope (TEM). Those examples which were subsequently stretched using the laboratory batch orienter are shown by an "X" in the column labeled Batch Stretched.
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s EXAMPLE 101 In Example 101, an optical film was made in a manner similar to Example 4 except the resulting core thickness was about 420 microns thick, and each skinlayer was about 105 microns thick. The PEN had a 0.56 IV. The cast film was oriented as in Example 1, except the temperature of stretch was 165~C and there o was a 15 day delay between casting and stretching. The tr~n~mi~ion was 87.1%and 39.7% for parallel and perpendicularly polarized light, respectively.
In Examples 102 - 121, optical films were made as in Example 101, except that orientation conditions were varied and/or the sPS-200-0 was replaced with either copolymers of sPS cont~ining either 4 or 8 mole % of para-methyl styrene or with an atactic-form of styrene, Styron 663 (available from Dow Chemical Company, Midland, Michigan) as listed in Table 3. Evaluations of tr~n~mi~ion properties are also reported. Tr~n~mi~ion values are averaged over all wavelengths between 450-700 nm.
Ex. % PS PEN Temper Rail Perpendicular Parallel sPS IV -ature Settin Tr~n~mi.csion Transmission of g (%) (%) Draw (cm) (~C) 101 25 200-0 0.56 165 152 87.1 39.7 102 35 200-0 0.56 165 152 87.8 44.4 103 15 200-4 0.56 165 152 86.1 43.5 104 25 200-4 0.56 165 152 86.5 43.6 105 35 200-4 0.56 165 152 88.2 50.7 W 097/32224 PCT~US97/00981 Ex. %PS PEN Temper Rail Perpendicular Parallel sPS IV -atureSettinTr~ncmic~cion Transmission of g (%) (%) Draw (cm) (~C) 106 l S200-8 0.56 165 152 89.3 40.7 107 25200-8 0.56 165 152 88.5 42.8 108 35200-8 0.56 165 152 88.6 43.3 109 15Styron0.56 165 152 89.3 45.7 110 25Styron 0.56 165 152 87.8 41.6 111 35Styron 0.56 165 152 88.8 48.2 112 15Styron 0.48 165 152 88.5 62.8 113 25Styron 0.48 165 152 87.1 59.6 114 35Styron 0.48 165 152 86.8 59.6 115 15 200-0 0.48 165 152 88.0 58.3 116 25 200-0 0.48 165 152 88.0 58.7 117 35 200-0 0.48 165 152 88.5 60.6 118 15 200-4 0.48 165 152 89.0 57.4 119 35 200-4 0.48 165 152 87.3 64.0 120 35 200-0 0.56 171 127 86.5 65.1 121 35 200-0 0.56 171 152 88.1 61.5 These examples indicate that the particles of the included phase are elongated more in the m~chine direction in high IV PEN than in low IV PEN. This is con.cictPnt with the observation that, in low IV PEN, elongation occurs to a 5 greater extent near the surface of the film than at points interior to the film, with s2 W O 97/32224 PCTrUS97/00981 the result that fibrillar structures are formed near the surface and spherical structures are formed towards the center.
Some of these Examples suggest that the orientation temperatures and degree of orientation are important variables in achieving the desired effect.
Examples 109 to 114 suggest that quiescent crystallization need not be the only reason for the lack of tr~n~mi~ion of a preferred polarization of light.
In Examplel 22, a multilayer optical film was made in accordance with the o invention by means of a 209 layer feedblock. The feedblock was fed with twomaterials: (1) PEN at 38.6 kg per hour (intrinsic viscosity of 0.48); and (2) a blend of 95% CoPEN and 5% by weight of sPS homopolymer (200,000 molecular weight). The CoPEN was a copolymer based on 70 mole % naphthalene dicarboxylate and 30 mole % dimethyl isophth~l~te polymerized with ethylene glycol to an intrinsic viscosity of 0.59. The CoPEN/sPS blend was fed into the feedblock at a rate of 34.1 kg per hour.
The CoPEN blend material was on the outside of the extrudate, and the layer composition of the resulting stack of layers alternated between the two materials. The thicknesses of the layers was designed to result in a one-quarterwavelength stack with a linear gradient of thicknesses, and having a 1.3 ratio from the thinnest to the thickest layer. Then, a thicker skin layer of CoPEN (made inaccordance with the method described above to make the CoPEN/sPS blend, except the molar ratios were 70/15/15 naphthalene dicarboxylate /dimethyl terephth~l~te/dimethyl isophth~l~te) devoid of sPS was added to each side of the209 layer composite. The total skin layer was added at a rate of 29.5 kg per hour, with about one-half of this quantity on each side or surface of the stack.
The resulting skin layer clad multilayer composite was extruded through a 1.2 ratio asymmetric multiplier to achieve a multilayer composite of 421 layers.The resulting multilayer composite was then clad with another skin layer of the 70/15/15 CoPEN on each surface at a total rate of 29.5 kg per hour with about one-half of this quantity on each side. Since this second skin layer may not be separately detectable from the existing skin layer (as the material is the same), for the purposes of this discussion, the resulting extra thick skin layer will be counted as only one layer.
The resulting 421 layer composite was again extruded through a 1.40 ratio asymmetric multiplier to achieve a 841 layer film which was then cast into a sheet by extruding through a die and quenching into a sheet about 30 mils thick. The resulting cast sheet was then oriented in the width direction using a conventional film making tentering device. The sheet was stretched at a temperature of about 300~F (149~C) to a stretch ratio of about 6: 1 and at a stretch rate of about 20% per o second. The resulting stretched film was about 5 mils thick.
In Exa~nple 123, a multilayer optical film was made as in Example 122, except that the amount of sPS in the CoPEN/sPS blend was 20% instead of 5%.
In Example 124, a multilayer optical film was made as in Example 122, except that no sPS was added to the film.
s The results reported in Table 4 include a measure of the optical gain of the film. The optical gain of a film is the ratio of light transmitted through an LCD
panel from a b~ light with the film inserted between the two to the light transmitted without the film in place. The significance of optical gain in the context of optical films is described in WO 95/17692 in relation to Figure 2 of that reference. A higher gain value is generally desirable. The tr~n~mi.csion values include values obtained when the light source was polarized parallel to the stretch direction (Tll) and light polarized perpendicular to the stretch direction (Tl). Off-angle-color (OAC) was measured using an Oriel spectrophotometer as the root mean square deviation of p-polarized tr~n~mi.~sion at 50 degree incident light of wavelength between 400 and 700 nm.
Ex.mole% sPS Gain Tl(%) Tll (%) OAC (%) 122 5 1.5 83 2 1.5 123 20 1.45 81 1.5 1.2 124 0 1.6 87 5 3.5 W O 97/32224 PCTrUS97/00981 The value of off-angle-color (OAC) demonstrates the advantage of using a multilayer construction within the context of the present invention. In particular, such a construction can be used to substantially reduce OAC with only a modest reduction in gain. This tradeoff may have advantages in some applications. The s values of Tll for the examples of the invention may be lower than expected because light scattered by the sPS dispersed phase may not be received by the detector.
The prece(ling description of the present invention is merely illustrative, and is not intendcd to be limiting. Therefore, the scope of the present invention should be construed solely by reference to the appended claims.
Field of the Invention s This invention relates to optical materials which contain structures suitable for controlling optical characteristics, such as reflectance and tr~ncmic.cion. In a further aspect, it relates to control of specific polarizations of reflected or transmitted light.
Background Optical films are known to the art which are constructed from inclusions dispersed within a continuous matrix. The characteristics of these inclusions can be manipulated to provide a range of reflective and tr~ncmicsive properties to the film. These characteristics include inclusion size with respect to wavelength s within the film, inclusion shape and alignment, inclusion volumetric fill factor and the degree of refractive index mi.cm~tch with the continuous matrix along the film's three orthogonal axes.
Conventional absorbing (dichroic) polarizers have, as their inclusion phase, inorg~nic rod-like chains of light-absorbing iodine which are aligned within a polymer matrix. Such a film will tend to absorb light polarized with its electric field vector aligned parallel to the rod-like iodine chains, and to transmit light polarized perpendicular to the rods. Because the iodine chains have two or more dimensions that are small compared to the wavelength of visible light, and because the number of chains per cubic wavelength of light is large, the optical plol)e-lies 2s of such a film are predominately specular, with very little diffuse tr~ncmiccion through the film or diffuse reflection from the film surfaces. Like most other commercially available polarizers, these polarizing films are based on polarization-selective absorption.
Films filled with inorganic inclusions with different characteristics can provide other optical tr~n.cmiccion and reflective properties. For example, coated mica flakes with two or more dimensions that are large compared with visible wavelengths, have been incorporated into polymeric films and into paints to impart a metallic glitter. These flakes can be manipulated to lie in the plane of the film, thereby illlp~ Lhlg a strong directional dependence to the reflective appearance.
Such an effect can be used to produce security screens that are highly reflective for 5 certain viewing angles, and tr~ncmi~sive for other viewing angles. Large flakes having a coloration (specularly selective reflection) that depends on alignment with respect to incident light, can be incorporated into a film to provide evidence of tampering. In this application, it is necessary that all the flakes in the film be similarly aligned with respect to each other.
Io However, optical films made from polymers filled with inorganic inclusions suffer from a variety of infirmities. Typically, adhesion between theinorganic particles and the polymer matrix is poor. Consequently, the optical ~lo~e~lies of the film decline when stress or strain is applied across the matrix, both because the bond between the matrix and the inclusions is complonlised, andbecause the rigid inorganic inclusions may be fractured. Furtherrnore, ~ nment of inorganic inclusions requires process steps and considerations that complicate manufacturing.
Other films, such as that disclosed in U.S. 4,688,900 (Doane et. al.), consists of a clear light-transmitting continuous polymer matrix, with droplets of 20 light mod~ ting liquid crystals dispersed within. Stretching of the material reportedly results in a distortion of the liquid crystal droplet from a spherical to an ellipsoidal shape, with the long axis of the ellipsoid parallel to the direction of stretch. U.S. 5,301,041 (Konuma et al.) make a similar disclosure, but achieve the distortion of the liquid crystal droplet through the application of pressure. A.25 Aphonin, "Optical Properties of Stretched Polymer Dispersed Liquid Crystal Films: Angle-Dependent Polarized Light Scattering, Liquid Crystals, Vol. 19, No.4, 469-480 (1995), discusses the optical properties of stretched films consisting of liquid crystal droplets disposed within a polymer matrix. He reports that the elongation of the droplets into an ellipsoidal shape, with their long axes parallel to 30 the stretch direction, imparts an oriented birefringence (refractive index difference among the dimensional axes of the droplet) to the droplets, resulting in a relative refractive index mi~m~tch between the dispersed and continuous phases along certain film axes, and a relative index match along the other film axes. Such liquid crystal droplets are not small as compared to visible wavelengths in the film, and thus the optical properties of such films have a substantial diffuse component to their reflective and tr~n~mi~sive properties. Aphonin suggests the use of these materials as a polarizing diffuser for backlit twisted nematic LCDs. However, optical films employing liquid crystals as the disperse phase are substantially limited in the degree of refractive index mi~m~tch between the matrix phase and the dispersed phase. Furthermore, the birefringence of the liquid crystal component of such films is typically sensitive to tel,lpeld~ lre.
U. S. 5,268,225 (Isayev) discloses a composite l~min~te made from thermotropic liquid crystal polymer blends. The blend consists of two liquid crystal polymers which are immiscible with each other. The blends may be cast into a film consisting of a dispersed inclusion phase and a continuous phase. When the film is stretched, the dispersed phase forms a series of fibers whose axes are aligned in the direction of stretch. While the film is described as having improved mechanical properties, no mention is made of the optical properties of the film.However, due to their liquid crystal nature, films of this type would suffer from the infirmities of other liquid crystal materials discussed above.
Still other films have been made to exhibit desirable optical properties through the application of electric or magnetic fields. For example, U. S.
5,008,807 (Waters et al.) describes a liquid crystal device which consists of a layer of fibers permeated with liquid crystal material and disposed between two electrodes. A voltage across the electrodes produces an electric field which changes the birefringent properties of the liquid crystal material, resulting invarious degrees of mi.cm~tch between the refractive indices of the fibers and the liquid crystal. However, the requirement of an electric or magnetic field is inconvenient and undesirable in many applications, particularly those where existing fields might produce interference.
Other optical films have been made by incorporating a dispersion of inclusions of a first polymer into a second polymer, and then stretching the W O 97/32224 PCT~US97/00981 resulting composite in one or two directions. U. S. 4,871,784 (Otonari et al. ) is exemplative of this technology. The polymers are selected such that there is lowadhesion between the dispersed phase and the surrounding matrix polymer, so thatan elliptical void is formed around each inclusion when the film is stretched. Such s voids have dimensions of the order of visible wavelengths. The refractive index mi.cm~tch between the void and the polymer in these "microvoided" films is typically quite large (about 0.5), causing substantial diffuse reflection. However, the optical properties of microvoided materials are difficult to control because of variations of the geometry of the interfaces, and it is not possible to produce a film 10 axis for which refractive indices are relatively matched, as would be useful for polarization-sensitive optical properties. Furthermore, the voids in such material can be easily collapsed through exposure to heat and pressure.
Optical films have also been made wherein a dispersed phase is deterministically arranged in an ordered pattern within a continuous matrix. U. S.
5,217,794 (Schrenk) is exemplative ofthis technology. There, a lamellar polymeric film is disclosed which is made of polymeric inclusions which are large compared with wavelength on two axes, disposed within a continuous matrix of another polymeric material. The refractive index of the dispersed phase differs significantly from that of the continuous phase along one or more of the l~min~te's axes, and is relatively well matched along another. Because of the ordering of the dispersed phase, films of this type exhibit strong iridescence (i.e., interference-based angle dependent coloring) for instances in which they are substantially reflective. As a result, such films have seen limited use for optical applications where optical diffusion is desirable.
There thus remains a need in the art for an optical m~teri~l consisting of 2 continuous and a dispersed phase, wherein the refractive index mi.~m~tch betweenthe two phases along the material's three dimensional axes can be conveniently and permanently manipulated to achieve desirable degrees of diffuse and specular reflection and tr~n~mi~ion, wherein the optical material is stable with respect to stress, strain, temperature differences, and electric and magnetic fields, and wherein the optical material has an in~i~nificant level of iridescence. These and other needs are met by the present invention, as hereinafter disclosed.
Brief description of the Drawings s FIG. I is a schematic drawing illustrating an optical body made in accordance with the present invention, wherein the disperse phase is arranged as a series of elongated masses having an essentially circular cross-section;
FIG. 2 is a s~h~m~tic drawing illustrating an optical body made in accordance with the present invention, wherein the disperse phase is arranged as a o series of elongated masses having an essenti~lly elliptical cross-section;
FIGS. 3a-e are sçhem~tic drawings illustrating various shapes of the disperse phase in an optical body made in accordance with the present invention;FIG. 4a is a graph of the bidirectional scatter distribution as a function of scattered angle for an oriented film in accordance with the present invention for light polarized perpendicular to orientation direction;
FIG. 4b is a graph of the bidirectional scatter distribution as a function of scattered angle for an oriented film in accordance with the present invention for light polarized parallel to orientation direction; and FIG. 5 is a s~hPm~tic representation of a multilayer film made in accordance with the present invention.
Summary of the Invention In one aspect, the present invention relates to a diffusely reflective film or other optical body comprising a birefringent continuous polymeric phase and a subst~nti~lly nonbirefringent disperse phase disposed within the continuous phase.
The indices of refraction of the continuous and disperse phases are substantially mi~m~tch~od (i.e., differ from one another by more than about 0.05) along a first of three mutually orthogonal axes, and are substantially matched (i.e., differ by less than about 0.05) along a second of three mutually orthogonal axes. In some emborliment~, the indices of refraction of the continuous and disperse phases can - be substantially matched or mi.cm~tched along, or parallel to, a third of three mutl]~lly orthogonal axes to produce a mirror or a polarizer. Incident light polarized along, or parallel to, a mi~mz~tche~l axis is scattered, resulting in significant diffuse reflection. Incident light polarized along a matched axis isscattered to a much lesser degree and is significantly specularly transmitted. These 5 properties can be used to make optical films for a variety of uses, including low loss (significantly nonabsorbing) reflective polarizers for which polarizations of light that are not significantly transmitted are diffusely reflected.
In a related aspect, the present invention relates to an optical film or other optical body comprising a birefringent continuous phase and a disperse phase, o wherein the indices of refraction of the continuous and disperse phases are substantially matched (i.e., wherein the index dirr~lence between the continuousand disperse phases is less than about 0.05) along an axis perpendicular to a surface of the optical body.
In another aspect, the present invention relates to a composite optical body 5 comprising a polymeric continuous birefringent first phase in which the disperse second phase may be birefringent, but in which the degree of match and mi~m~tch in at least two orthogonal directions is primarily due to the birefringence of the first phase.
In still another aspect, the present invention relates to a method for 20 obtaining a diffuse reflective polarizer, comprising the steps of: providing a first resin, whose degree of birefringence can be altered by application of a force field, as through dimensional orientation or an applied electric field, such that the resulting resin material has, for at least h,vo orthogonal directions, an index of refraction difference of more than about 0.05; providing a second resin, dispersed 25 within the first resin; and applying said force field to the composite of both resins such that the indices of the two resins are approximately matched to within lessthan about 0.05 in one of two directions, and the index difference between first and second resins in the other of two directions is greater than about 0.0~. In a related embodiment, the second resin is dispersed in the first resin after imposition of the 30 force field and subsequent alteration of the birefringence of the first resin.
In yet another aspect, the present invention re}ates to an optical body acting as a reflective polarizer with a high extinction ratio. In this aspect, the index difference in the match direction is chosen as small as possible and the difference in the mi.em~tch direction is maximized. The volume fraction, thickness, and disperse phase particle size and shape can be chosen to maximize the extinction ratio, although the relative importance of optical tr~nemieeion and reflection for the different polarizations may vary for different applications.
In another aspect, the present invention relates to an optical body comprising a continuous phase, a disperse phase whose index of refraction differs o from said continuous phase by greater than about 0.05 along a first axis and by less than about 0.05 along a second axis orthogonal to said first axis, and a dichroic dye. The optical body is preferably oriented along at least one axis. The dichroic dye improves the extinction coefficient of the optical body by absorbing, in addition to scattering, light polarized parallel to the axis of orientation.
In the various aspects of the present invention, the reflection and tr~nemie.eion properties for at least two orthogonal polarizations of incident light are determined by the selection or manipulation of various parameters, includingthe optical indices of the continuous and disperse phases, the size and shape of the disperse phase particles, the volume fraction of the disperse phase, the thickness of the optical body through which some fraction of the incident light is to pass, and the wavelength or wavelength band of electromagnetic radiation of interest.
The magnitude of the index match or miem~t~h along a particular axis will directly affect the degree of scattering of light polarized along that axis. In general, scattering power varies as the square of the index mi.em~t~h. Thus, the larger the 2s index mi~m~tçh along a particular axis, the stronger the sC~ttering of light polarized along that axis. Conversely, when the miem~tçh along a particular axis is small,light polarized along that axis is scattered to a lesser extent and is thereby transmitted specularly through the volume of the body.
The size of the disperse phase also can have a significant effect on scattering. If the disperse phase particles are too small (i.e., less than about 1/30 the wavelength of light in the medium of interest) and if there are many particles per cubic wavelength, the optical body behaves as a medium with an effective index of refraction somewhat between the indices of the two phases along any given axis. In such a case, very little light is scattered. If the particles are too large, the light is specularly reflected from the particle surface, with very little s diffusion into other directions. When the particles are too large in at least two orthogonal directions, undesirable iridescence effects can also occur. Practicallimits may also be reached when particles become large in that the thickness of the optical body becomes greater and desirable mechanical properties are COlllp~ ised~
o The shape of the particles of the disperse phase can also have an effect on the scattering of light. The depolarization factors of the particles for the electric field in the index of refraction match and micm~trh directions can reduce or enhance the amount of scattering in a given direction. The effect can either add or detract from the amount of scattering from the index mi.cm~t~'h, but generally has a small influence on scattering in the preferred range of properties in the present invention.
The shape of the particles can also influence the degree of diffusion of light scattered from the particles. This shape effect is generally small but increases as the aspect ratio of the geometrical cross-section of the particle in the plane perpendicular to the direction of incidence of the light increases and as the particles get relatively larger. In general, in the operation of this invention, the disperse phase particles should be sized less than several wavelengths of light in one or two mutually orthogonal (limen~ions if diffuse, rather than specular, reflection is preferred.
Dimensional alignment is also found to have an effect on the SC~U~lillg behavior of the disperse phase. In particular, it has been observed, in optical bodies made in accordance with the present invention, that aligned scatterers will not scatter light symmetrically about the directions of specular tr~n~mis~ion orreflection as randomly aligned scatterers would. In particular, inclusions that have been elongated by orientation to resemble rods scatter light primarily along (ornear) a cone centered on the orientation direction and having an edge along the specularly transmitted direction. For example, for light incident on such an elongated rod in a direction perpendicular to the orientation direction, the scattered light appears as a band of light in the plane perpendicular to the orientation direction with an intensity that decreases with increasing angle away from the s specular directions. By tailoring the geometry of the inclusions, some control over the distribution of scattered light can be achieved both in the tr~n~micsive hemisphere and in the reflective hemisphere.
The volume fraction of the disperse phase also affects the scattering of light in the optical bodies of the present invention. Within certain limits, increasing the o volume fraction of the disperse phase tends to increase the amount of scattering that a light ray experiences after entering the body for both the match and mi~m~tch directions of polarized light. This factor is important for controlling the reflection and tr~n~mic~ion properties for a given application. However, if the volume fraction of the disperse phase becomes too large, light scattering Is dimini~hes. Without wishing to be bound by theory, this appears to be due to the fact that the disperse phase particles are closer together, in terms of the wavelength of light, so that the particles tend to act together as a smaller number of large effective particles.
The thickness of the optical body is also an important control parameter 20 which can be manipulated to affect reflection and tr~n~mi~sion properties in the present invention. As the thickness of the optical body increases, diffuse reflection also increases, and tr~n~mi~ion, both specular and diffuse, decreases.
While the present invention will often be described herein with reference to the visible region of the spectrum, various embodiments of the present invention25 can be used to operate at different wavelengths (and thus frequencies) of electrom~gnPtic radiation through ~plop,;ate scaling of the components of the optical body. Thus, as the wavelength increases, the linear size of the components of the optical body are increased so that the dimensions, measured in units of wavelength, remain approximately constant. Another major effect of ch~nging 30 wavelength is that, for most materials of interest, the index of refraction and the W O 97/32224 PCTrUS97/00981 absorption coefficient change. However, the principles of index match and mi.cm~tch still apply at each wavelength of interest.
Detailed Description of the Invention Introduction As used herein, the terms "specular reflection" and "specular reflectance"
refer to the reflectance of light rays into an emergent cone with a vertex angle of 16 degrees centered around the specular angle. The terms "diffuse reflection" or "diffuse reflectance" refer to the reflection of rays that are outside the specular I o cone defined above. The terms "total reflectance" or "total reflection" refer to the combined reflectance of all light from a surface. Thus, total reflection is the sum of specular and diffuse reflection.
Similarly, the terms "specular tr~n~mi~.~ion" and "specular tr~n~mitt~nce"
are used herein in reference to the tr~ncmi~ion of rays into an emergent cone with a vertex angle of 16 degrees centered around the specular direction. The ter~ns "diffuse tr~n.~mi~ion" and "diffuse transmittance" are used herein in reference to the tr~n~mi.~ion of all rays that are outside the specular cone defined above. The terms "total tr~n~mi~cion" or "total transmittance" refer to the combined tr~n~mis~ion of all light through an optical body. Thus, total tr~n.cmi~ion is the sum of specular and diffuse tr~n~mi~.~ion.
As used herein, the term "extinction ratio" is defined to mean the ratio of total light transmitted in one polarization to the light transmitted in an orthogonal polarization.
FIGS. 1-2 illustrate a first embodiment of the present invention. In accordance with the invention, a diffusely reflective optical film 10 or other optical body is produced which consists of a birefringent matrix or continuous phase 12 and a discontinuous or disperse phase 14. The birefringence of the continuous phase is typically at least about 0.05, preferably at least about 0.1, more preferably at least about 0.15, and most preferably at least about 0.2.
The indices of refraction of the continuous and disperse phases are substantially matched (i.e., differ by less than about 0.05) along a first of three CA 022482l4 l998-08-28 W O 97/32224 PCTAJS97tO0981 mutually orthogonal axes, and are substantially mi.~m~tched (i.e., differ by more than about 0.05) along a second of three mutually orthogonal axes. Preferably, the indices of refraction of the continuous and disperse phases differ by less than about 0.03 in the match direction, more preferably, less than about 0.02, and most 5 preferably, less than about 0.01. The indices of refraction of the continuous and disperse phases preferably differ in the mi~m~tch direction by at least about 0.07, more preferably, by at least about 0.1, and most preferably, by at least about 0.2.
The mi~m~tch in refractive indices along a particular axis has the effect that incident light polarized along that axis will be substantially scattered, resulting in a o significant amount of reflection. By contrast, incident light polarized along an axis in which the refractive indices are matched will be spectrally transmitted or reflected with a much lesser degree of scattering. This effect can be utilized to make a variety of optical devices, including reflective polarizers and mirrors.
The present invention provides a practical and simple optical body and s method for making a reflective polarizer, and also provides a means of obtaining a continuous range of optical properties according to the principles described herein.
Also, very efficient low loss polarizers can be obtained with high e~tinction ratios.
Other advantages are a wide range of practical materials for the disperse phase and the continuous phase, and a high degree of control in providing optical bodies of 20 consistent and predictable high quality performance.
Effect of Index Match/Mismatch In the preferred embodiment, the materials of at least one of the continuous and disperse phases are of a type that undergoes a change in refractive index upon 25 orientation. Consequently, as the film is oriented in one or more directions,refractive index m~tch~s or mi~m~tches are produced along one or more axes. By careful manipulation of orientation parameters and other proces~ing conditions, the positive or negative birefringence of the matrix can be used to induce diffuse reflection or tr~n.~mi.csion of one or both polarizations of light along a given axis.
30 The relative ratio between tr~n~mi~ion and diffuse reflection is dependent on the concentration of the disperse phase inclusions, the thickness of the film, the square W O 97/32224 PCTnJS97/00981 of the difference in the index of refraction between the continuous and dispersephases, the size and geometry of the disperse phase inclusions, and the wavelength or wavelength band of the incident radiation.
The magnitude of the index match or mi.cm~tch along a particular axis directly affects the degree of scattering of light polarized along that axis. Ingeneral, scattering power varies as the square of the index mi~m~tch Thus, the larger the index mi~m~tch along a particular axis, the stronger the scattering of light polarized along that axis. Conversely, when the mi.~m~tch along a particular axis is small, light polarized along that axis is scattered to a lesser extent and is 0 thereby transmitted specularly through the volume of the body.
FIGS. 4a-b demonstrate this effect in oriented films made in accordance with the present invention. There, a typical Bidirectional Scatter Distribution Function (BSDF) measurement is shown for normally incident light at 632.8 mn.
The BSDF is described in J. Stover, "Optical Scattering Measurement and Analysis" (1990). The BSDF is shown as a function of scattered angle for polarizations of light both perpendicular and parallel to the axis of orientation. A
scattered angle of zero corresponds to lm~c~ttçred (specularly transmitted) light.
For light polarized in the index match direction (that is, perpendicular to the orientation direction) as in FIG. 4a, there is a significant specularly transmitted peak with a sizable component of diffusely transmitted light (scattering angle between 8 and 80 degrees), and a small component of diffusely reflected light (scattering angle larger than 100 degrees). For light polarized in the index micm~tch direction (that is, parallel to the orientation direction) as in FIG. 4b, there is negligible specularly tr~n~mitted light and a greatly reduced component of 2s diffusely Lldn~ iLLed light, and a sizable diffusely reflected component. It should be noted that the plane of scattering shown by these graphs is the plane perpendicular to the orientation direction where most of the scattered light exists for these elongated inclusions. Scattered light contributions outside of this plane are greatly reduced.
If the index of refraction of the inclusions (i.e., the disperse phase) m~tches that of the continuous host media along some axis, then incident light polarized W O 97132224 PCTrUS97/00981 with electric fields parallel to this axis will pass through lln~c~ttered regardless of the size, shape, and density of inclusions. If the indices are not matched alongsome axis, then the inclusions will scatter light polarized along this axis. Forscatterers of a given cross-sectional area with dimensions larger than 5 approximately ~/30 ( where ~ is the wavelength of light in the media), the strength of the scattering is largely determined by the index mi~m~tch The exact size, shape and alignment of a mism~tched inclusion play a role in determining how much light will be scattered into various directions from that inclusion. If thedensity and thickness of the scattering layer is sufficient, according to multiple o scattering theory, incident light will be either reflected or absorbed, but not transmitted, regardless of the details of the scatterer size and shape.
When the material is to be used as a polarizer, it is preferably processed, as by stretching and allowing some dimensional relaxation in the cross stretch in-plane direction, so that the index of refraction difference between the continuous 1S and disperse phases is large along a first axis in a plane parallel to a surface of the material and small along the other two orthogonal axes. This results in a large optical anisotropy for electromagnetic radiation of dirrelent polarizations.
Some of the polarizers within the scope of the present invention are elliptical polarizers. In general, elliptical polarizers will have a difference in index 20 of refraction between the disperse phase and the continuous phase for both the stretch and cross-stretch directions. The ratio of forward to back scattering isdependent on the difference in refractive index between the disperse and continuous phases, the concentration of the disperse phase, the size and shape of the disperse phase, and the overall thickness of the film. In general, elliptical 25 diffusers have a relatively small difference in index of refraction between the particles of the disperse and continuous phases. By using a birefringent polymer-based diffuser, highly elliptical polarization sensitivity (i.e., diffuse reflectivity depending on the polarization of light) can be achieved. At an extreme, where the index of refraction of the polymers match on one axis, the elliptical polarizer will 30 be a diffuse reflecting polarizer.
W O 97/32224 PCT~US97/00981 Methods of Obl~inin~ Index Match/Mismatch The materials selected for use in a polarizer in accordance with the present invention, and the degree of orientation of these materials, are preferably chosen so that the phases in the finished polarizer have at least one axis for which the associated indices of refraction are substantially equal. The match of refractive indices associated with that axis, which typically, but not necessarily, is an axis transverse to the direction of orientation, results in substantially no reflection of light in that plane of polarization.
The disperse phase may also exhibit a decrease in the refractive index lo associated with the direction of orientation after stretching. If the birefringence of the host is positive, a negative strain ind~1ced birefringence of the disperse phase has the advantage of increasing the difference between indices of refraction of the adjoining phases associated with the orientation axis while the reflection of light with its plane of polarization perpendicular to the orientation direction is still negligible. Differences between the indices of refraction of adjoining phases in the direction orthogonal to the orientation direction should be less than about 0.05 after orientation, and preferably, less than about 0.02.
The disperse phase may also exhibit a positive strain in~ ced birefringence.
However, this can be altered by means of heat treatment to match the refractive index of the axis perpendicular to the orientation direction of the continuous phase.
The temperature of the heat treatment should not be so high as to relax the birefringence in the continuous phase.
Size of Disperse Phase The size of the disperse phase also can have a signific~nt effect on scattering. If the disperse phase particles are too small (i.e., less than about 1/30 the wavelength of light in the medium of interest) and if there are many particles pér cubic wavelength, the optical body behaves as a medium with an effective index of refraction somewhat between the indices of the two phases along any given axis. In such a case, very little light is scattered. If the particles are too large, the light is specularly reflected from the surface of the particle, with very W O 97/32224 PCTrUS97/00981 little diffusion into other directions. When the particles are too large in at least two orthogonal directions, undesirable iridescence effects can also occur. Practical limits may also be reached when particles become large in that the thickness of the optical body becomes greater and desirable mechanical properties are colllplolllised.
The dimensions of the particles of the disperse phase after alignment can vary depending on the desired use of the optical material. Thus, for example, the ~1imçn~ions of the particles may var,v depending on the wavelength of electromagnetic radiation that is of interest in a particular application, with o different ~limen~ions required for reflecting or transmitting visible, ultraviolet, infrared, and microwave radiation. Generally, however, the length of the particles should be such that they are approximately greater than the wavelength of electromagnetic radiation of interest in the medium, divided by 30.
Preferably, in applications where the optical body is to be used as a low loss reflective polarizer, the particles will have a length that is greater than about 2 times the wavelength of the electromagnetic radiation over the wavelength range of interest, and preferably over 4 times the wavelength. The average diameter of the particles is preferably equal or less than the wavelength of the electromagneticradiation over the wavelength range of interest, and preferably less than 0.5 of the desired wavelength. While the llimen~ions of the disperse phase are a secondary consideration in most applications, they become of greater hll~ol~lce in thin film applications, where there is comparatively little diffuse reflection.
Geometry of Disperse Phase While the index mi~m~t~.h is the predominant factor relied upon to promote scattering in the films of the present invention (i.e., a diffuse mirror or polarizer made in accordance with the present invention has a substantial mi~m~tch in the indices of refraction of the continuous and disperse phases along at least one axis), the geometry of the particles of the disperse phase can have a secondary effect on scattering. Thus, the depolarization factors of the particles for the electric field in the index of refraction match and mi~m~t~h directions can reduce or enhance the W O 97132224 PCT~US97/00981 amount of sc~ ring in a given direction. For example, when the disperse phase iselliptical in a cross-section taken along a plane perpendicular to the axis of orientation, the elliptical cross-sectional shape of the disperse phase contributes to the asymmetric diffusion in both back scattered light and forward scattered light.
5 The effect can either add or detract from the amount of scattering from the index mi.cm~tch, but generally has a small influence on scattering in the preferred range of properties in the present invention.
The shape of the disperse phase particles can also influence the degree of diffusion of light scattered from the particles. This shape effect is generally small o but increases as the aspect ratio of the geometrical cross-section of the particle in the plane perpendicular to the direction of incidence of the light increases and as the particles get relatively larger. In general, in the operation of this invention, the disperse phase particles should be sized less than several wavelengths of light in one or two mutually orthogonal tlimen~ions if diffuse, rather than specular, 5 reflection is preferred.
Preferably, for a low loss reflective polarizer, the plef~,.. d embodiment consists of a disperse phase disposed within the continuous phase as a series ofrod-like structures which, as a consequence of orientation, have a high aspect ratio which can enhance reflection for polarizations parallel to the orientation direction by increasing the scattering strength and dispersion for that polarization relative to polarizations perpendicular to the orientation direction. However, as indicated in FIGS. 3a-e, the disperse phase may be provided with many dirre.~l~l geometries.
Thus, the disperse phase may be disk-shaped or elongated disk-shaped, as in FIGS.
3a-c, rod-shaped, as in FIG. 3d-e, or spherical. Other embodiments are 2s contemplated wherein the disperse phase has cross sections which are approximately elliptical (including circular), polygonal, irregular, or a combination of one or more of these shapes. The cross-sectional shape and size of the particles of the disperse phase may also vary from one particle to another, or from one region of the film to another (i.e., from the surface to the core).
In some embodiments, the disperse phase may have a core and shell construction, wherein the core and shell are made out of the same or different W O 97132224 PCT~US97/00981 materials, or wherein the core is hollow. Thus, for example, the disperse phase may consist of hollow fibers of equal or random lengths, and of uniform or non-uniform cross section. The interior space of the fibers may be empty, or may be occupied by a suitable medium which may be a solid, liquid, or gas, and may be organic or inorganic. The refractive index of the medium may be chosen in consideration of the refractive indices of the disperse phase and the continuousphase so as to achieve a desired optical effect (i.e., reflection or polarization along a given ax1s).
The geometry of the disperse phase may be arrived at through suitable o orientation or processing of the optical material, through the use of particles having a particular geometry, or through a combination of the two. Thus, for example, adisperse phase having a substantially rod-like structure can be produced by orienting a film con.~isting of approximately spherical disperse phase particlesalong a single axis. The rod-like structures can be given an elliptical cross-section by orienting the film in a second direction perpendicular to the first. As a further example, a disperse phase having a substantially rod-like structure in which therods are rectangular in cross-section can be produced by orienting in a single direction a film having a disperse phase con~i~ting of a series of essPnti~lly rectangular flakes.
Stretching is one convenient manner for arriving at a desired geometry, since stretching can also be used to induce a difference in indices of refraction within the material. As indicated above, the orientation of films in accordance with the invention may be in more than one direction, and may be sequential or simultaneous.
In another example, the components of the continuous and disperse phases may be extruded such that the disperse phase is rod-like in one axis in the unoriented film. Rods with a high aspect ratio may be generated by orienting in the direction of the major axis of the rods in the extruded film. Plate-like structures may be generated by orienting in an orthogonal direction to the major axis of the rods in the extruded film.
W O 97/32224 PCTrUS97/00981 The structure in FIG. 2 can be produced by asymmetric biaxial orientation of a blend of es~enti~lly spherical particles within a continuous matrix.
Alternatively, the structure may be obtained by incorporating a plurality of fibrous structures into the matrix material, aligning the structures along a single axis, and 5 orienting the mixture in a direction transverse to that axis. Still another method for obtaining this structure is by controlling the relative viscosities, shear, or surface tension of the components of a polymer blend so as to give rise to a fibrous disperse phase when the blend is extruded into a film. In general, it is found that the best results are obtained when the shear is applied in the direction of extrusion.
Dimensional Alignment of Disperse Phase Dimensional alignment is also found to have an effect on the sc~ttering behavior of the disperse phase. In particular, it has been observed in optical bodies made in accordance with the present invention that aligned scatterers will not 5 scatter light symmetrically about the directions of specular tr~n~mi~ion or reflection as randomly aligned sc~ cl~ would. In particular, inclusions that have been elongated through orientation to resemble rods scatter light primarily along (or near) the surface of a cone centered on the orientation direction and along the specularly transmitted direction. This may result in an anisotropic distribution of 20 scattered light about the specular reflection and specular tr~n~mi.c~ion directions.
For example, for light incident on such an elongated rod in a direction perpendicular to the orientation direction, the scattered light appears as a band of light in the plane perpendicular to the orientation direction with an intensity that decreases with increasing angle away from the specular directions. By tailoring the 25 geometry of the inclusions, some control over the distribution of scattered light can be achieved both in the tr~n~mi~sive hemisphere and in the reflective hemisphere.
Dimensions of D;;,~ sc Phase In applications where the optical body is to be used as a low loss reflective 30 polarizer, the structures of the disperse phase preferably have a high aspect ratio, i.e., the structures are substantially larger in one dimension than in any other dimension. The aspect ratio is preferably at least 2, and more preferably at least 5.
The largest ~limencion (i.e., the length) is preferably at least 2 times the wavelength of the electromagnetic radiation over the wavelength range of interest, and morepreferably at least 4 times the desired wavelength. On the other hand, the smaller (i.e., cross-sectional) dimensions of the structures of the disperse phase are preferably less than or equal to the wavelength of interest, and more preferably less than 0.5 times the wavelength of interest.
Volume Fraction of Di~l.c. ~e Phase 0 The volume fraction of the disperse phase also affects the scattering of light in the optical bodies of the present invention. Within certain limits, increasing the volume fraction of the disperse phase tends to increase the amount of scatteringthat a light ray experiences after entering the body for both the match and mi~m~tch directions of polarized light. This factor is important for controlling the reflection and tr~mi~.cion properties for a given application. However, if the volume fraction of the disperse phase becomes too large, light scattering can ~limini~h Without wishing to be bound by theory, this appears to be due to the fact that the disperse phase particles are closer together, in terrns of the wavelength of light, so that the particles tend to act together as a smaller number of large effective particles.
The desired volume fraction of the disperse phase will depend on many factors, including the specific choice of materials for the continuous and disperse phase. However, the volume fraction of the disperse phase will typically be at least about 1% by volume relative to the continuous phase, more preferably within the range of about 5 to about 15%, and most preferably within the range of about l S to about 30%.
Thickness of Optical Body The thickness of the optical body is also an important parameter which can be manipulated to affect reflection and tr~n~mi~sion properties in the present invention. As the thickness of the optical body increases, diffuse reflection also W O 97/32224 PCTrUS97/00981 increases, and tr~n.smi.ssion, both specular and diffuse, decreases. Thus, while the thickness of the optical body will typically be chosen to achieve a desired degree of mechanical strength in the finished product, it can also be used to directly to control reflection and tr~n.smission properties.
Thickness can also be utilized to make final adjustments in reflection and tr~n~mi~sion properties of the optical body. Thus, for example, in film applications, the device used to extrude the film can be controlled by a downstream optical device which measures transmission and reflection values in the extrudedfilm, and which varies the thickness of the film (i.e., by adjusting extrusion rates or 0 ch~nging casting wheel speeds) so as to m~int:~in the reflection and tr~nsmiqsion values within a predet~ ed range.
Materials for Continuous/Di~ ,e Phases Many different materials may be used as the continuous or disperse phases in the optical bodies of the present invention, depending on the specific application to which the optical body is directed. Such materials include inorganic materials such as silica-based polymers, organic m~teri~ls such as liquid crystals, and polymeric materials, including monomers, copolymers, grafted polymers, and mixtures or blends thereof. The exact choice of materials for a given application will be driven by the desired match and mi.sm~tch obtainable in the refractive indices of the continuous and disperse phases along a particular axis, as well as the desired physical properties in the resulting product. However, the materials of the continuous phase will generally be characterized by being substantially transparent in the region of the spectrum desired.
A further consideration in the choice of materials is that the resulting product must contain at least two distinct phases. This may be accomplished by casting the optical material from two or more materials which are immiscible with each other. Alternatively, if it is desired to make an optical material with a first and second material which are not immiscible with each other, and if the first material has a higher melting point than the second material, in some cases it may - be possible to embed particles of applopliate dimensions of the first material W O 97132224 rCTrUS97/00981 within a molten matrix of the second material at a temperature below the meltingpoint of the first material. The resulting mixture can then be cast into a film, with or without subsequent orientation, to produce an optical device.
Suitable polymeric materials for use as the continuous or disperse phase in the present invention may be amorphous, semicrystalline, or crystalline polymeric materials, including materials made from monomers based on carboxylic acids such as isophthalic, azelaic, adipic, sebacic, dibenzoic, terephthalic, 2,7-naphthalene dicarboxylic, 2,6-naphthalene dicarboxylic, cyclohexanedicarboxylic,and bibenzoic acids (including 4,4t-bibenzoic acid), or materials made from the o corresponding esters of the aforementioned acids (i.e., dimethylterephth~l~tP). Of these, 2,6-polyethylene naphth~l~te (PEN) is especially preferred because of itsstrain induced birefringence, and because of its ability to remain permanently birefringent after stretching. PEN has a refractive index for polarized incident light of 550 nm wavelength which increases after stretching when the plane of polarization is parallel to the axis of stretch from about 1.64 to as high as about 1.9, while the refractive index decreases for light polarized perpendicular to the axis of stretch. PEN exhibits a birefringence (in this case, the difference between the index of refraction along the stretch direction and the index perpendicular to the stretch direction) of 0.25 to 0.40 in the visible spectrum. The birefringence can be increased by increasing the molecular orientation. PEN may be substantially heatstable from about 155~C up to about 230~C, depending upon the processing conditions utilized during the m~mlf~ture of the film.
Polybutylene naphth~l~te is also a suitable material as well as other crystalline naphthalene dicarboxylic polyesters. The crystalline naphthalene dicarboxylic polyesters exhibit a difference in refractive indices associated with different in-plane axes of at least 0.05 and preferably above 0.20.
When PEN is used as one phase in the optical material of the present invention, the other phase is preferably polymethylmethacrylate (PMMA) or a syndiotactic vinyl aromatic polymer such as polystyrene (sPS). Other preferred polymers for use with PEN are based on terephthalic, isophthalic, sebacic, azelaic or cyclohexanedicarboxylic acid or the related alkyl esters of these materials.
Naphthalene dicarboxylic acid may also be employed in minor amounts to improve adhesion between the phases. The diol component may be ethylene glycol or a related diol. Preferably, the index of refraction of the selected polymer is less than about 1.65, and more preferably, less than about 1.55, although a similar result may 5 be obtainable by using a polymer having a higher index of refraction if the same index difference is achieved.
Syndiotactic-vinyl aromatic polymers useful in the current invention include poly(styrene), poly(alkyl styrene), poly(styrene halide), poly(alkyl styrene), poly(vinyl ester benzoate), and these hydrogenated polymers and ~ es, or o copolymers co.~ g these structural units. Exarnples of poly(alkyl styrenes) include: poly(methyl styrene), poly(ethyl styrene), poly(propyl styrene), poly(butyl styrene), poly(phenyl styrene), poly(vinyl naphthalene), poly(vinylstyrene), and poly(acenaphthalene) may be mentioned. As for the poly(styrene halides), examples include: poly(chlorostyrene), poly(bromostyrene), 5 and poly(fluorostyrene). Examples of poly(alkoxy styrene) include: poly(methoxy styrene), and poly(ethoxy styrene). Among these exarnples, as particularly preferable styrene group polymers, are: polystyrene, poly(p-methyl styrene), poly(m-methyl styrene), poly(p-tertiary butyl styrene), poly(p-chlorostyrene), poly(m-chloro styrene), poly(p-fluoro styrene), and copolymers of styrene and p-20 methyl styrene may be mentioned.
Furthermore, as comonomers of syndiotactic vinyl-aromatic group copolymers, besides monomers of above explained styrene group polymer, olefin monomers such as ethylene, propylene, butene, hexene, or octene; diene monomers such as butadiene, isoprene; polar vinyl monomers such as cyclic diene monomer, 25 methyl methacrylate, maleic acid anhydride, or acrylonitrile may be mentioned.
The syndiotactic-vinyl aromatic polymers of the present invention may be block copolymers, random copolymers, or alternating copolymers.
The vinyl aromatic polymer having high level syndiotactic structure referred to in this invention generally includes polystyrene having syndiotacticity 30 of higher than 75% or more, as determined by carbon-13 nuclear magnetic W O 97/32224 PCTrUS97/00981 resonance. Preferably, the degree of syndiotacticity is higher than 85% racemic diad, or higher than 30%, or more preferably, higher than 50%, racemic pentad.
In addition, although there are no particular restrictions regarding the molecular weight of this syndiotactic-vinyl aromatic group polymer, preferably, the s weight average molecular weight is greater than 10,000 and less than 1,000,000, and more preferably, greater than 50,000 and less than 800,000.
As for said other resins, various types may be mentioned, including, for instance, vinyl aromatic group polymers with atactic structures, vinyl aromatic group polymers with isotactic structures, and all polymers that are miscible. For o example, polyphenylene ethers show good miscibility with the previous explained vinyl aromatic group polymers. Furthermore, the composition of these miscible resin components is preferably between 70 to 1 weight %, or more preferably, 50 to 2 weight %. When composition of miscible resin component exceeds 70 weight %, degradation on the heat resistance may occur, and is usually not 1 5 desirable.
It is not required that the selected polymer for a particular phase be a copolyester or copolycarbonate. Vinyl polymers and copolymers made from monomers such as vinyl n~phth~lenes, styrenes, ethylene, maleic anhydride, acrylates, and methacrylates may also be employed. Cond~n.c~tion polymers, otherthan polyesters and polycarbonates, can also be lltili7f?cl Suitable contlenc~tion polymers include polysulfones, polyamides, polyureth~nes, polyamic acids, and polyimides. Naphthalene groups and halogens such as chlorine, bromine and iodine are useful in increasing the refractive index of the selected polymer to the desired level (1.59 to 1.69) if needed to substantially match the refractive index if 2s PEN is the host. Acrylate groups and fluorine are particularly useful in decreasing the refractive index.
Minor amounts of comonomers may be substituted into the n~phth~lene dicarboxylic acid polyester so long as the large refractive index difference in the orientation direction(s) is not substantially compromised. A smaller index difference (and therefore decreased reflectivity) may be counterbalanced by advantages in any of the following: improved adhesion between the continuous W O 97/322Z4 PCTrUS97/00981 and disperse phase, lowered temperature of extrusion, and better match of melt viscosities.
Region of Spectrum s While the present invention is frequently described herein with reference to the visible region of the spectrum, various embo~limentc of the present invention can be used to operate at different wavelengths ~and thus frequencies) of electromagnetic radiation through a~lopliate scaling of the components of the optical body. Thus, as the wavelength increases, the linear size of the components o of the optical body may be increased so that the dimensions of these components, measured in units of wavelength, remain approximately constant.
Of course, one major effect of ch~nging wavelength is that, for most materials of interest, the index of refraction and the absorption coefficient change.
However, the principles of index match and mi~m~tch still apply at each 1S wavelength of interest, and may be utilized in the selection of materials for an optical device that will operate over a specific region of the spectrum. Thus, for example, proper scaling of ~iime~jons will allow operation in the infrared, near-ultraviolet, and ultra-violet regions of the spectrum. In these cases, the indices of refraction refer to the values at these wavelengths of operation, and the body thickness and size of the disperse phase scattering components should also be approximately scaled with wavelength. Even more of the electrom~gnetic spectrum can be used, including very high, ultrahigh, microwave and millimeter wave frequencies. Polarizing and diffusing effects will be present with proper scaling to wavelength and the indices of refraction can be obtained from the square 2s root of the dielectric function (including real and im~gin~ry parts). Useful products in these longer wavelength bands can be diffuse reflective polarizers and partial polarizers.
In some embodiments of the present invention, the optical pl~pCl lies of the optical body vary across the wavelength band of interest. In these embodiments, materials may be utilized for the continuous and/or disperse phases whose indices of refraction, along one or more axes, varies from one wavelength region to W O 97/32224 PCT~US97/00981 another. The choice of continuous and disperse phase materials, and the optical properties (i.e., diffuse and disperse reflection or specular tr~n~mi.csion) resulting from a specific choice of materials, will depend on the wavelength band of interest.
Skin Layers A layer of material which is substantially free of a disperse phase may be coextensively disposed on one or both major surfaces of the film, i.e., the extruded blend of the disperse phase and the continuous phase. The composition of the layer, also called a skin layer, may be chosen, for example, to protect the integrity o of the disperse phase within the extruded blend, to add mechanical or physical properties to the final film or to add optical functionality to the fina} film. Suitable materials of choice may include the material of the continuous phase or the material of the disperse phase. Other materials with a melt viscosity similar to the extruded blend may also be useful.
s A skin layer or layers may reduce the wide range of shear intensities the extruded blend might experience within the extrusion process, particularly at the die. A high shear environment may cause undesirable surface voiding and may result in a textured surface. A broad range of shear values throughout the thickness of the film may also prevent the disperse phase from forming the desired particle size in the blend.
A skin layer or layers may also add physical strength to the resulting composite or reduce problems during processing, such as, for example, reducing the tendency for the film to split during the orientation process. Skin layer materials which remain amorphous may tend to make films with a higher toughness, while skin layer materials which are semicrystalline may tend to makefilms with a higher tensile modulus. Other functional components such as ~nti~t~tic additives, UV absorbers, dyes, antioxidants, and pigments, may be added to the skin layer, provided they do not substantially interfere with the desiredoptical properties of the resulting product.
The skin layers may be applied to one or two sides of the extruded blend at some point during the extrusion process, i.e., before the extruded blend and skin W O 97132224 PCTrUS97100981 layer(s) exit the extrusion die. This may be accomplished using conventional coextrusion technology, which may include using a three-layer coextrusion die.
T ~min~tion of skin layer(s) to a previously formed film of an extruded blend is also possible. Total skin layer thicknesses may range from about 2% to about 50% of the total blend/skin layer thickness.
A wide range of polymers are suitable for skin layers. Predomin~ntly arnorphous polymers include copolyesters based on one or more of terephthalic acid, 2,6-naphthalene dicarboxylic acid, isophthalic acid phthalic acid, or their alkyl ester counterparts, and alkylene diols, such as ethylene glycol. Exarnples of o semicrystalline polymers are 2,6-polyethylene n~phth~l~te, polyethylene terephth~l~te, and nylon materials.
Antireflection Layers The films and other optical devices made in accordance with the invention may also include one or more anti-reflective layers. Such layers, which may or may not be polari_ation sensitive, serve to increase tr~n.cmi~sion and to reducereflective glare. An anti-reflective layer may be imparted to the films and optical devices of the present invention through ~propllate surface treatment, such as coating or sputter etching.
In some embodiments of the present invention, it is desired to maximize the tr~n~mi~sion and/or minimi7~ the specular reflection for certain polarizations of light. In these embodiments, the optical body may comprise two or more layers inwhich at least one layer comprises an anti-reflection system in close contact with a layer providing the continuous and disperse phases. Such an anti-reflection system acts to reduce the specular reflection of the incident light and to increase theamount of incident light that enters the portion of the body comprising the continuous and disperse layers. Such a function can be accomplished by a varietyof means well known in the art. Examples are ~uarter wave anti-reflection layers, two or more layer anti-reflective stack, graded index layers, and graded densitylayers. Such anti-reflection functions can also be used on the transmitted lightside of the body to increase transmitted light if desired.
W 097/32224 PCTrUS97/00981 Microvoiding In some embodiments, the materials of the continuous and disperse phases may be chosen so that the interface between the two phases will be sufficiently 5 weak to result in voiding when the film is oriented. The average dimensions of the voids may be controlled through careful manipulation of processing parameters and stretch ratios, or through selective use of compatibilizers. The voids may be back-filled in the finiched product with a liquid, gas, or solid. Voiding may beused in conjunction with the aspect ratios and refractive indices of the disperse and 0 continuous phases to produce desirable optical properties in the resulting film.
More Than Two Phases The optical bodies made in accordance with the present invention may also consist of more than two phases. Thus, for example, an optical material made in 5 accordance with the present invention can consist of two dirr~ disperse phaseswithin the continuous phase. The second disperse phase could be randomly or non-randomly dispersed throughout the continuous phase, and can be randomly aligned or aligned along a common axis.
Optical bodies made in accordance with the present invention may also 20 consist of more than one continuous phase. Thus, in some embodimentc, the optical body may include, in addition to a first continuous phase and a dispersephase, a second phase which is co-continuous in at least one ~iimencion with thefirst continuous phase. In one particular embodiment, the second continuous phase is a porous, sponge-like material which is coextensive with the first continuous25 phase (i.e., the first continuous phase extends through a network of channels or spaces exten~ling through the second continuous phase, much as water extends through a network of channels in a wet sponge). In a related embodiment, the second continuous phase is in the forrn of a dendritic structure which is coextensive in at least one dimension with the first continuous phase.
CA 022482l4 l998-08-28 W O 97132224 PCTrUS97/00981 Multilayer Combinations If desired, one or more sheets of a continuous/disperse phase film made in accordance with the present invention may be used in combination with, or as a component in, a multilayered film (i.e., to increase reflectivity). Suitable multilayered films include those of the type described in WO 95/17303 (Ouderkirket al.). In such a construction, the individual sheets may be l~min~ted or otherwise adhered together or may be spaced apart. If the optical thicknesses of the phases within the sheets are substantially equal (that is, if the two sheets present a substantially equal and large number of scatterers to incident light along a given axis), the composite will reflect, at somewhat greater efficiency, substantially the same band width and spectral range of reflectivity (i.e., "band") as the individual sheets. If the optical thickn~.ces of phases within the sheets are not substantially equal, the composite will reflect across a broader band width than the individual phases. A composite combining mirror sheets with polarizer sheets is useful for increasing total reflectance while still polarizing transmitted light. Alternatively, a single sheet may be asymmetrically and biaxially oriented to produce a film having selective reflective and polarizing plope, lies.
FIG. 5 illustrates one example of this embodiment of the present invention.
There, the optical body consists of a multilayer film 20 in which the layers alternate between layers of PEN 22 and layers of co-PEN 24. Each PEN layer includes a disperse phase of syndiotactic polystyrene (sPS) within a matrix of PEN.
This type of construction is desirable in that it promotes lower off-angle color.
Furthermore, since the layering or inclusion of scatterers averages out light leakage, control over layer thickness is less critical, allowing the film to be more tolerable of variations in processing parameters.
Any of the materials previously noted may be used as any of the layers in this embolliment, or as the continuous or disperse phase within a particular layer.
However, PEN and co-PEN are particularly desirable as the major components of adjacent layers, since these materials promote good laminar adhesion.
Also, a number of variations are possible in the arrangement of the layers.
Thus, for example, the layers can be made to follow a repeating sequence through W O 97/32224 PCTrUS97/0098 part or all of the structure. One example of this is a construction having the layer pattern ... ABCABC ..., wherein A, B, and C are distinct materials or distinct blends or mixtures of the same or different materials, and wherein one or more of A, B, or C contains at least one disperse phase and at least one continuous phase.
5 The skin layers are preferably the same or chemically similar materials.
Additives The optical materials of the present invention may also comprise other materials or additives as are known to the art. Such materials include pigments,o dyes, binders, coatings, fillers, compatibilizers, antioxidants (including sterically hindered phenols), surfactants, antimicrobial agents, zlnti~t~tic agents, flarneretardants, foaming agents, lubricants, reinforcers, light stabilizers (including UV
stabilizers or blockers), heat stabilizers, impact modifiers, plasticizers, viscosity modifiers, and other such materials. Furthermore, the films and other optical 5 devices made in accordance with the present invention may include one or more outer layers which serve to protect the device from abrasion, impact, or other damage, or which enhance the processability or durability of the device.
Suitable lubricants for use in the present invention include calcium sterate, zinc sterate, copper sterate, cobalt sterate, molybdenum neodocanoate, and 20 ruthenium (III) acetylacetonate.
Antioxidants useful in the present invention include 4,4'-thiobis-(6-t-butyl-m-cresol), 2,2'-methylenebis-(4-methyl-6-t-butyl-butylphenol), octadecyl-3,5-di-t-butyl-4-hydroxyhydrocinn~m:~te, bis-(2,4-di-t-butylphenyl) pentaerythritol diphosphite, IrganoxTM 1093 (1979)(((3,5-bis(1,1 -dimethylethyl)-4-25 hydroxyphenyl~methyl)-dioctadecyl ester phosphonic acid), IrganoxTM 1098 (N,N'-1,6-hexanediylbis(3,5-bis(1, I -dimethyl)-4-hydroxy-benzenepl opal1amide), NaugaardTM 445 (aryl arnine), IrganoxTM L 57 (alkylated diphenylarnine), IrganoxTM
L 115 (sulfur cont~ining bisphenol), IrganoxTM LO 6 (alkylated phenyl-delta-napthylamine), Ethanox 398 (flourophosphonite), and 2,2'-ethylidenebis(4,6-di-t-30 butylphenyl)fluorophosnite.
W O 97/32224 PCTrUS97100981 A group of antioxidants that are especially prefe,l~d are sterically hindered phenols, including butylated hydroxytoluene (BHT), Vitamin E (di-alpha-tocopherol), IrganoxTM 1425WL(calcium bis-(O-ethyl(3,5-di-t-butyl-4-hydroxybenzyl))phosphonate), IrganoxTM 1010 (tetrakis(methylene(3,5,di-t-butyl-4-hydroxyhydrocinn~m~te))methane), IrganoxTM 1076 (octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinn~m~te), EthanoxTM 702 (hindered bis phenolic), Etanox 330 (high molecular weight hindered phenolic), and EthanoxTM 703 (hindered phenolic amine).
Dichroic dyes are a particularly useful additive in some applications to o which the optical m~t~ri~ls of the present invention may be directed, due to their ability to absorb light of a particular polarization when they are molecularly aligned within the m~t~ri~l. When used in a film or other material which predomin~ntly scatters only one polarization of light, the dichroic dye causes the material to absorb one polarization of light more than another. Suitable dichroic dyes for use in the present invention include Congo Red (sodium diphenyl-bis-a-aphlhylamine sulfonate), methylene blue, stilbene dye (Color Index (CI) = 620), and 1,1 '-diethyl-2,2'-cyanine chloride (CI = 374 (orange) or CI = 518 (blue)). The properties of these dyes, and methods of m~king them, are described in E.H. Land, Colloid Chemistry (1946). These dyes have noticeable dichroism in polyvinyl alcohol and a lesser dichroism in cellulose. A slight dichroism is observed withCongo Red in PEN.
W O 97/32224 rCT~US97/00981 Other suitable dyes include the following materials:
(1) R~ R
where R is ~ CH=N~
,~ ,~i ~ ~ ~ O--C9HI9 O OH
J~ _ ~ OR
O NH2 o N--CH
O NH2 ~
The properties of these dyes, and methods of making them, are discussed in the Kirk Othmer Encyclopedia of Chemical Technology, Vol. 8, pp. 652-661 (4th Ed.
5 1993), and in the references cited therein.
When a dichroic dye is used in the optical bodies of the present invention, it may be incorporated into either the continuous or disperse phase. However, it is- preferred that the dichroic dye is incorporated into the disperse phase.
W O 97/32224 PCT~US97/00981 Dychroic dyes in combination with certain polymer systems exhibit the ability to polarize light to varying degrees. Polyvinyl alcohol and certain dichroic dyes may be used to make films with the ability to polarize light. Other polymers, such as polyethylene terephth~1~te or polyamides, such as nylon-6, do not exhibit s as strong an ability to polarize light when combined with a dichroic dye. The polyvinyl alcohol and dichroic dye combination is said to have a higher dichroism ratio than, for example, the same dye in other film forming polymer systems. A
higher dichroism ratio indicates a higher ability to polarize light.
Molecular alignment of a dichroic dye within an optical body made in 0 accordance with the present invention is preferably accomplished by stretching the optical body after the dye has been incorporated into it. However, other methodsmay also be used to achieve molecular ~lignment Thus, in one method, the dichroic dye is cryst~lli7~.1, as through sublimation or by cryst~11i7~tion fromsolution, into a series of elongated notches that are cut, etched, or otherwise formed 5 in the surface of a film or other optical body, either before or after the optical body has been oriented. The treated surface may then be coated with one or more surface layers, may be incorporated into a polymer matrix or used in a multilayer structure, or may be utilized as a component of another optical body. The notches may be created in accordance with a predetermined pattern or diagram, and with a20 predetermined amount of spacing between the notches, so as to achieve desirable optical properties.
In a related embodiment, the dichroic dye may be disposed within one or more hollow fibers or other conduits, either before or after the hollow fibers or conduits are disposed within the optical body. The hollow fibers or conduits may2s be constructed out of a m~t~ri~1 that is the same or different from the surrounding material of the optical body.
In yet another embodiment, the dichroic dye is disposed along the layer interface of a multilayer construction, as by sublimation onto the surface of a layer before it is incorporated into the multilayer construction. In still other 30 embo~iment~, the dichroic dye is used to at least partially backfill the voids in a microvoided film made in accordance with the present invention.
W O 97/32224 PCT~US97/00981 Applications of Present Invention The optical bodies of the present invention are particularly useful as diffuse polarizers. However, optical bodies may also be made in accordance with the 5 invention which operate as reflective polarizers or diffuse mirrors. In these applications, the construction of the optical material is similar to that in the diffuser applications described above. However, these reflectors will generally have a much larger difference in the index of refraction along at least one axis. This index difference is typically at least about 0.1, more preferably about 0.15, and mosto preferably about 0.2.
Reflective polarizers have a refractive index difference along one axis, and substantially m~t~h~cl indices along another. Reflective films, on the other hand, differ in refractive index along at least two in-film plane orthogonal axes.
However, the reflective properties of these embo-liment~ need not be ~ in~d 15 solely by reliance on refractive index mi~m~tches. Thus, for example, the thickness of the films could be adjusted to attain a desired degree of reflection. In some cases, adjustment of the thickness of the film may cause the film to go from being a tr~n~mi~ive diffuser to a diffuse reflector.
The reflective polarizer of the present invention has many different 20 applications, and is particularly useful in liquid crystal display panels. In addition, the polarizer can be constructed out of PEN or similar materials which are good ultraviolet filters and which absorb ultraviolet light efficiently up to the edge of the visible spectrum. The reflective polarizer can also be used as a thin infrared sheet polarizer.
2s Overview of Examples The following Examples illustrate the production of various optical materials in accordance with the present invention, as well as the spectral properties of these materials. Unless otherwise indicated, percent composition 30 refers to percent composition by weight. The polyethylene naphth~l~te resin used was produced for these samples using ethylene glycol and dimethyl-2,6-naphthalenedicarboxylate, available from Amoco Corp., Chicago, Illinois. These reagents were polymerized to various intrinsic viscosities (IV) using conventional polyester resin polymerization techniques. Syndiotactic polystyrene (sPS) may beproduced in accordance with the method disclosed in U. S. Patent 4,680,353 s (Ishihara et al). The examples includes various polymer pairs, various fractions of continuous and disperse phases and other additives or process changes as ~ cl-sse~
below.
Stretching or orienting of the samples was provided using either conventional orientation equipment used for making polyester film or a laboratory o batch orienter. The laboratory batch orienter used was designed to use a small piece of cast material (7.5cm by 7.5cm) cut from the extruded cast web and held by a square array of 24 ~,li~el~ (6 on each side). The orientation temp~ldlule ofthe sample was controlled a hot air blower and the film sample was oriented through a mechanical system that increased the distance between the gli~JpC;I~ in one or both directions at a controlled rate. Samples stretched in both directions could be oriented sequentially or simultaneously. For samples that were oriented in the constrained mode (C), all g~i~e-~ hold the web and the gli~)~Cl:i move only in one dimension. Whereas, in the unconslldined mode (U), the ~ri~ that hold the film at a fixed dimension perpendicular to the direction of stretch are not engaged and the film is allowed to relax or neckdown in that ~imçn.~ion.
Polarized diffuse tran~mi~ion and reflection were measured using a Perkin Elmer Lambda 19 ultravioletlvisible/near infrared spectrophotometer equipped with a Perkin Elmer Labsphere S900-1000 150 millimeter integrating sphere accessory and a Glan-Thompson cube polarizer. Parallel and crossed tran~mi~sion and reflection values were measured with the e-vector of the polarized light parallel or perpendicular, respectively, to the stretch direction of the film. All scans were continuous and were conducted with a scan rate of 480 nanometers per minute and a slit width of 2 nanometers. Reflection was performed in the "V-reflection"
mode. Tr~n~mi~.sion and reflectance values are averages of all wavelengths from 400 to 700 nanometers.
WO 97t32224 PCTtUS97/00981 EXAMPLE I
In Example 1, an optical film was made in accordance with the invention by extruding a blend of 75% polyethylene naphth~ te (PEN) as the continuous or major phase and 25% of polymethylmethacrylate (PMMA) as the disperse or minor s phase into a cast film or sheet about 380 microns thick using conventional extrusion and casting techniques. The PEN had an intrinsic viscosity (IV) of 0.52 (measured in 60% phenol, 40% dichlorobenzene). The PMMA was obtained from ICI Americas, Inc., Wilmington, Delaware, under the product designation CP82.
The extruder used was a 3.15 cm (1.24") Brabender with a 1 tube 60 ,~m Tegra o filter. The die was a 30.4 cm (12") EDI UltraflexTM 40.
About 24 hours after the film was extruded, the cast film was oriented in the width or transverse direction (TD) on a polyester film tentering device. Thestretching was accomplished at about 9.1 meters per minute (30 ft/min) with an output width of about 140 cm (55 inches) and a stretching temperature of about 160~C (320~F). The total reflectivity ofthe stretched sample was measured with an integrating sphere ~ chm~nt on a Lambda 19 spectrophotometer with the sarnple beam polarized with a Glan-Thompson cube polarizer. The sample had a 75% parallel reflectivity (i.e., reflectivity was measured with the stretch direction of the film parallel to the e-vector of the polarized light), and 52% crossed reflectivity (i.e., reflectivity was measured with the e-vector of the polarized light perpendicular to the stretch direction).
In Example 2, an optical film was made and evaluated in a manner similar to Example I except using a blend of 75% PEN, 25% syndiotactic polystyrene (sPS), 0.2% of a polystyrene glycidyl methacrylate compatibilizer, and 0.25% each of IrganoxTM 1010 and UltranoxTM 626. The synthesis of polystyrene glycidyl methacrylate is described in Polymer Processes, "Chemical Technology of Plastics, Resins, Rubbers, Adhesives and Fibers", Vol. 10, Chap. 3, pp. 69-109 (1956)(Ed.
by Calvin E. Schildknecht).
W O 97/32224 PCTrUS97/00981 The PEN had an intrinsic viscosity of 0.52 measured in 60% phenol, 40%
dichlorobenzene. The sPS was obtained from Dow Chemical Co. and had a weight average molecular weight of about 200,000, designated subsequently as sPS-200-0.The parallel reflectivity on the stretched film sample was determined to be 73.3%, s and the crossed reflectivity was determined to be 35%.
In Example 3, an optical film was made and evaluated in a manner similar to Example 2 except the compatibilizer level was raised to 0.6%. The resulting o parallel reflectivity was deterrnined to be 81 % and the crossed reflectivity was determined to be 35.6%.
In Example 4, an three layer optical film was made in accordance with the present invention ~ltili7ing conventional three layer coextrusion techniques. The film had a core layer and a skin layer on each side of the core layer. The core layer consisted of a blend of 75% PEN and 25% sPS 200-4 (the deci&n~tion sPS-200-4 refers to a copolymer of syndiotactic-polystyrene co~ g 4 mole % of para-methyl styrene), and each skin layer consisted of 100% PEN having an intrinsic viscosity of 0.56 measured in 60% phenol, 40% dichlorobenzene.
The resulting three-layer cast film had a core layer thickness of about 415 microns, and each skin layer was about 110 microns thick for a total thickness of about 635 microns. A laboratory batch stretcher was used to stretch the resulting three-layer cast film about 6 to 1 in the m~ehine direction (MD) at a tel,lpeldlllre of 2s about 129~C. Because the edges of the film sample parallel to the stretch direction were not gripped by the lab stretcher, the sample was unconstrained in the transverse direction (TD) and the sample necked-down in the TD about 50% as a result of the stretch procedure.
Optical performance was evaluated in a manner similar to Example l. The parallel reflectivity was deterrnined to be 80.1 %, and the crossed reflectivity was W O 97/32224 PCTrUS97/00981 determined to be 15%. These results demonstrate that the film perforrns as a lowabsorbing, energy conserving system.
In Examples 5-29, a series of optical films were produced and evaluated in a manner similar to Example 4, except the sPS fraction in the core layer and the IV
of the PEN resin used were varied as shown in Table 1. The IV of the PEN resin in the core layer and that in the skin layers was the same for a given sample. The total thickness of the cast sheet was about 625 microns with about two-thirds ofo this total in the core layer and the balance in the skin layers which were approximately equal in thickness. Various blends of PEN and sPS in the core layer were produced, as indicated in Table 1. The f1lms were stretched to a stretch ratio of about 6:1 in either the m~hine direction (MD) or in the transverse direction (TD) at various telllpe,~l lres as indicated in Table 1. Some of the samples were constrained (C) in the direction perpendicular to the stretch direction to prevent the sample from n~c~ing down during stretching. The samples labeled "U'~ in Table 1 were uncon~ hled and permitted to neckdown in the unconstrained dimension.
Certain optical properties of the stretched samples, including percent tr~n~mi~ion, reflection, and absorption, were measured along axes both parallel and crossed or perpendicular to the direction of stretch. The results are summarized in Table 1.
Heat setting, as indicated for Examples 24-27, was accomplished by manually constraining the two edges of the stretched sarnple which were perpendicular to the direction of stretch by clamping to an apl)lopliately sized rigid frame and placing the clamped sarnple in an oven at the indicated temperature for 1 minute. The two sides of the sample parallel to the direction of stretch were unconstrained (U) or not clamped and allowed to neckdown. The h~tsetting of Example 29 was similar except all four of the edges of the stretched sarnple were constrained (C) or clamped. Example 28 was not heat set.
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All of the above samples were observed to contain varying shapes of the disperse phase depending on the location of the disperse phase within the body of the film sarnple. The disperse phase inclusions located nearer the surfaces of the samples were observed to be of an elongated shape rather than more nearly spherical. The inclusions which are more nearly centered between the surfaces ofthe samples may be more nearly spherical. This is true even for the samples withthe skin layers, but the magnitude of the effect is reduced with the skin layers. The addition of the skin layers improves the processing of the films by reducing thetendency for splitting during the stretching operation.
o Without wishing to be bound by theory, the elongation of the inclusions(disperse phase) in the core layer of the cast film is thought to be the result of shear on the blend as it is transported through the die. This elongation feature may be altered by varying physical dimensions of the die, extrusion temperatures, flow rate of the extrudate, as well as chemical aspects of the continuous and disperse phase 1S materials which would alter their relative melt viscosities. Certain applications or uses may benefit from providing some elongation to the disperse phase during extrusion. For those applications which are subsequently stretched in the machine direction, starting with a disperse phase elongated during extrusion may allow ahigher aspect ratio to be reached in the resulting disperse phase.
Another notable feature is the fact that a noticeable improvement in performance is observed when the same sample is stretched unconstrained. Thus, in Exarnple 9, the % tr~n.cmi~ion was 79.5% and 20.3% in the parallel and perpendicular directions, respectively. By contrast, the tr~n~mi~.~ion in Exarnple 16 was only 75.8% and 28.7% in the parallel and perpendicular directions, respectively. There is a thickness increase relative to constrained stretching when samples are stretched unconstrained, but since both tr~n~mi~sion and extinction improve, the index match is probably being improved.
An alternative way to provide refractive index control is to modify the chemistry of the materials. For example, a copolymer of 30 wt % of interpolymerized units derived from terephthalic acid and 70 wt % of units derived from 2,6-naphthalic acid has a refractive index 0.02 units lower than a 100% PEN
W O 97/32224 PCTrUS97100981 polymer. Other monomers or ratios may have slightly different results. This typeof change may be used to more closely match the refractive indices in one axis while only causing a slight reduction in the axis which desires a large difference.
In other words, the benefits attained by more closely matching the index values in 5 one axis more than compensate for the reduction in an orthogonal axis in which a large difference is desired. Secondly, a chemical change may be desirable to alter the temperature range in which stretching occurs. A copolymer of sPS and varyingratios of para methyl styrene monomer will alter the optimum stretch-temperaturerange. A combination of these techniques may be necessary to most effectively 0 optimize the total system for processing and resulting refractive index matches and differences. Thus, an improved control of the final performance may be ~tt:~in~od by optimi7ing the process and chemistry in terms of stretching conditions and further adjusting the chemistry of the materials to maximize the difference in refractive index in at least one axis and minimi7ing the difference at least one15 orthogonal axis.
These samples displayed better optical performance if oriented in the MD
rather than TD direction (compare Examples 14-15). Without wishing to be bound by theory, it is believed that different geometry inclusions are developed with an MD orientation than with a TD orientation and that these inclusions have higher 20 aspect ratios, making non-ideal end effects less important. The non-ideal endeffects refers to the complex geometry/index of refraction relationship at the tip of each end of the elongated particles. The interior or non-end of the particles are thought to have a uniform geometry and refractive index which is thought to be desirable. Thus, the higher the percentage of the elongated particle that is uniform, 25 the better the optical performance.
The extinction ratio of these materials is the ratio of the tr~n~mi~.cion for polarizations perpendicular to the stretch direction to that parallel to the stretch direction. For the examples cited in Table 1, the extinction ratio ranges between about 2 and about 5, although extinction ratios up to 7 have been observed in 30 optical bodies made in accordance with the present invention. It is expected that W O 97/32224 PCTrUS97100981 even higher extinction ratios can be achieved by adjusting film thickness, inclusion volume fraction, particle size, and the degree of index match and mi~m~tr.1 In Examples 30-100, samples of the invention were made using various materials as listed in Table 2. PEN 42, PEN 47, PEN 53, PEN 56, and PEN 60 refer to polyethylene naphth~l~te having an intrinsic viscosity (IV) of 0.42, 0.47, 0.53, 0.56, and 0.60, respectively, measured in 60% phenol, 40% dichlorobenzene.The particular sPS-200-4 used was obtained from Dow Chemical Co. EcdelTM
o 9967 and EastarTM are copolyesters which are available commercially from F~tm~n Chemical Co., Rochester, New York. SurlynTM 1706 is an ionomer resin available from E.I. du Pont de Nemours & Co., Wilmington, Delaware. The materials listed as Additive 1 or 2 include polystyrene glycidyl methacrylate. The ~e~i~n~tions GMAPS2, GMAPS5, and GMAPS8 refer to glycidyl methacrylate having 2, 5, and 8% by weight, respectively, of glycidyl methacrylate in the total copolymer. ETPB refers to the cros~linkin~ agent ethyltriphenylphosphonium bromide. PMMA V044 refers to a polymethylmethacrylate available commercially from Atohaas North America, Inc.
The optical film samples were produced in a manner similar to Exarnple 4 except for the differences noted in Table 2 and discussed below. The continuous phase and its ratio of the total is reported as major phase. The disperse phase and its ratio of the total is reported as minor phase. The value reported for blend thickness represents the approximate thickness of the core layer in microns. Thethickness of the skin layers varied when the core layer thickness varied, but was kept to a constant ratio, i.e., the skin layers were approximately equal and the total of the two skin layers was about one-third of the total thickness. The size of the disperse phase was determined for some samples by either sc~nnincg electron microscope (SEM) or tr~n~mi.~ion electron microscope (TEM). Those examples which were subsequently stretched using the laboratory batch orienter are shown by an "X" in the column labeled Batch Stretched.
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s EXAMPLE 101 In Example 101, an optical film was made in a manner similar to Example 4 except the resulting core thickness was about 420 microns thick, and each skinlayer was about 105 microns thick. The PEN had a 0.56 IV. The cast film was oriented as in Example 1, except the temperature of stretch was 165~C and there o was a 15 day delay between casting and stretching. The tr~n~mi~ion was 87.1%and 39.7% for parallel and perpendicularly polarized light, respectively.
In Examples 102 - 121, optical films were made as in Example 101, except that orientation conditions were varied and/or the sPS-200-0 was replaced with either copolymers of sPS cont~ining either 4 or 8 mole % of para-methyl styrene or with an atactic-form of styrene, Styron 663 (available from Dow Chemical Company, Midland, Michigan) as listed in Table 3. Evaluations of tr~n~mi~ion properties are also reported. Tr~n~mi~ion values are averaged over all wavelengths between 450-700 nm.
Ex. % PS PEN Temper Rail Perpendicular Parallel sPS IV -ature Settin Tr~n~mi.csion Transmission of g (%) (%) Draw (cm) (~C) 101 25 200-0 0.56 165 152 87.1 39.7 102 35 200-0 0.56 165 152 87.8 44.4 103 15 200-4 0.56 165 152 86.1 43.5 104 25 200-4 0.56 165 152 86.5 43.6 105 35 200-4 0.56 165 152 88.2 50.7 W 097/32224 PCT~US97/00981 Ex. %PS PEN Temper Rail Perpendicular Parallel sPS IV -atureSettinTr~ncmic~cion Transmission of g (%) (%) Draw (cm) (~C) 106 l S200-8 0.56 165 152 89.3 40.7 107 25200-8 0.56 165 152 88.5 42.8 108 35200-8 0.56 165 152 88.6 43.3 109 15Styron0.56 165 152 89.3 45.7 110 25Styron 0.56 165 152 87.8 41.6 111 35Styron 0.56 165 152 88.8 48.2 112 15Styron 0.48 165 152 88.5 62.8 113 25Styron 0.48 165 152 87.1 59.6 114 35Styron 0.48 165 152 86.8 59.6 115 15 200-0 0.48 165 152 88.0 58.3 116 25 200-0 0.48 165 152 88.0 58.7 117 35 200-0 0.48 165 152 88.5 60.6 118 15 200-4 0.48 165 152 89.0 57.4 119 35 200-4 0.48 165 152 87.3 64.0 120 35 200-0 0.56 171 127 86.5 65.1 121 35 200-0 0.56 171 152 88.1 61.5 These examples indicate that the particles of the included phase are elongated more in the m~chine direction in high IV PEN than in low IV PEN. This is con.cictPnt with the observation that, in low IV PEN, elongation occurs to a 5 greater extent near the surface of the film than at points interior to the film, with s2 W O 97/32224 PCTrUS97/00981 the result that fibrillar structures are formed near the surface and spherical structures are formed towards the center.
Some of these Examples suggest that the orientation temperatures and degree of orientation are important variables in achieving the desired effect.
Examples 109 to 114 suggest that quiescent crystallization need not be the only reason for the lack of tr~n~mi~ion of a preferred polarization of light.
In Examplel 22, a multilayer optical film was made in accordance with the o invention by means of a 209 layer feedblock. The feedblock was fed with twomaterials: (1) PEN at 38.6 kg per hour (intrinsic viscosity of 0.48); and (2) a blend of 95% CoPEN and 5% by weight of sPS homopolymer (200,000 molecular weight). The CoPEN was a copolymer based on 70 mole % naphthalene dicarboxylate and 30 mole % dimethyl isophth~l~te polymerized with ethylene glycol to an intrinsic viscosity of 0.59. The CoPEN/sPS blend was fed into the feedblock at a rate of 34.1 kg per hour.
The CoPEN blend material was on the outside of the extrudate, and the layer composition of the resulting stack of layers alternated between the two materials. The thicknesses of the layers was designed to result in a one-quarterwavelength stack with a linear gradient of thicknesses, and having a 1.3 ratio from the thinnest to the thickest layer. Then, a thicker skin layer of CoPEN (made inaccordance with the method described above to make the CoPEN/sPS blend, except the molar ratios were 70/15/15 naphthalene dicarboxylate /dimethyl terephth~l~te/dimethyl isophth~l~te) devoid of sPS was added to each side of the209 layer composite. The total skin layer was added at a rate of 29.5 kg per hour, with about one-half of this quantity on each side or surface of the stack.
The resulting skin layer clad multilayer composite was extruded through a 1.2 ratio asymmetric multiplier to achieve a multilayer composite of 421 layers.The resulting multilayer composite was then clad with another skin layer of the 70/15/15 CoPEN on each surface at a total rate of 29.5 kg per hour with about one-half of this quantity on each side. Since this second skin layer may not be separately detectable from the existing skin layer (as the material is the same), for the purposes of this discussion, the resulting extra thick skin layer will be counted as only one layer.
The resulting 421 layer composite was again extruded through a 1.40 ratio asymmetric multiplier to achieve a 841 layer film which was then cast into a sheet by extruding through a die and quenching into a sheet about 30 mils thick. The resulting cast sheet was then oriented in the width direction using a conventional film making tentering device. The sheet was stretched at a temperature of about 300~F (149~C) to a stretch ratio of about 6: 1 and at a stretch rate of about 20% per o second. The resulting stretched film was about 5 mils thick.
In Exa~nple 123, a multilayer optical film was made as in Example 122, except that the amount of sPS in the CoPEN/sPS blend was 20% instead of 5%.
In Example 124, a multilayer optical film was made as in Example 122, except that no sPS was added to the film.
s The results reported in Table 4 include a measure of the optical gain of the film. The optical gain of a film is the ratio of light transmitted through an LCD
panel from a b~ light with the film inserted between the two to the light transmitted without the film in place. The significance of optical gain in the context of optical films is described in WO 95/17692 in relation to Figure 2 of that reference. A higher gain value is generally desirable. The tr~n~mi.csion values include values obtained when the light source was polarized parallel to the stretch direction (Tll) and light polarized perpendicular to the stretch direction (Tl). Off-angle-color (OAC) was measured using an Oriel spectrophotometer as the root mean square deviation of p-polarized tr~n~mi.~sion at 50 degree incident light of wavelength between 400 and 700 nm.
Ex.mole% sPS Gain Tl(%) Tll (%) OAC (%) 122 5 1.5 83 2 1.5 123 20 1.45 81 1.5 1.2 124 0 1.6 87 5 3.5 W O 97/32224 PCTrUS97/00981 The value of off-angle-color (OAC) demonstrates the advantage of using a multilayer construction within the context of the present invention. In particular, such a construction can be used to substantially reduce OAC with only a modest reduction in gain. This tradeoff may have advantages in some applications. The s values of Tll for the examples of the invention may be lower than expected because light scattered by the sPS dispersed phase may not be received by the detector.
The prece(ling description of the present invention is merely illustrative, and is not intendcd to be limiting. Therefore, the scope of the present invention should be construed solely by reference to the appended claims.
Claims (65)
1. An optical body, comprising:
a first phase having a birefringence of at least about 0.05; and a second phase, disposed within said first phase, whose index of refraction differs from said first phase by greater than about 0.05 along a first axis and by less than about 0.05 along a second axis orthogonal to said first axis;
wherein the diffuse reflectivity of said first and second phases taken together along at least one axis for at least one polarization of electromagnetic radiation is at least about 30%.
a first phase having a birefringence of at least about 0.05; and a second phase, disposed within said first phase, whose index of refraction differs from said first phase by greater than about 0.05 along a first axis and by less than about 0.05 along a second axis orthogonal to said first axis;
wherein the diffuse reflectivity of said first and second phases taken together along at least one axis for at least one polarization of electromagnetic radiation is at least about 30%.
2. The optical body of claim 1, wherein said first phase has a birefringence of at least about 0.1.
3. The optical body of claim 1, wherein said first phase has a birefringence of at least about 0.15.
4. The optical body of claim 1, wherein said first phase has a birefringence of at least about 0.2.
5. The optical body of claim 1, wherein said second phase has a birefringence of less than about 0.02.
6. The optical body of claim 1, wherein said second phase has a birefringence of less than about 0.01.
7. The optical body of claim 1, wherein said second phase has an index of refraction which differs from said first phase by more than about 0.1 along saidfirst axis.
8. The optical body of claim 1, wherein said second phase has an index of refraction which differs from said first phase by more than about 0.15 along said first axis.
9. The optical body of claim 1, wherein said second phase has an index of refraction which differs from said first phase by more than about 0.2 along saidfirst axis.
10. The optical body of claim 1, wherein said second phase has an index of refraction which differs from said first phase by less than about 0.03 along said second axis.
11. The optical body of claim 1, wherein said second phase has an index of refraction which differs from said first phase by less than about 0.01 along said second axis.
12. The optical body of claim 1, wherein said optical body has a total diffuse reflectivity of greater than about 50% for light polarized along a first axis and a total reflectivity of greater than about 50% for light polarized along a second axis perpendicular to said first axis.
13. The optical body of claim 1, wherein said optical body has a total reflectivity of greater than about 50% for a first polarization of electromagnetic radiation and a total transmission of greater than about 50% for a second polarization of electromagnetic radiation orthogonal to said first polarization.
14. The optical body of claim 13 wherein said optical body has a total reflectivity of greater than about 60% for said first polarization of electromagnetic radiation.
15. The optical body of claim 13, wherein said optical body has a total reflectivity of greater than about 70% for said first polarization of electromagnetic radiation.
16. The optical body of claim 13, wherein said optical body has a total transmission of greater than about 60% for said second polarization of electromagnetic radiation.
17. The optical body of claim 13, wherein said optical body has a total transmission of greater than about 70% for said second polarization of electromagnetic radiation.
18. The optical body of claim 13 wherein at least about 40% of light polarized orthogonal to a first polarization of light is transmitted through said optical body with an angle of deflection of less than about 8°.
19. The optical body of claim 13 wherein at least about 60% of light polarized orthogonal to a first polarization of light is transmitted through said optical body with an angle of deflection of less than about 8°.
20. The optical body of claim 13 wherein at least about 70% of light polarized orthogonal to a first polarization of light is transmitted through said optical body with an angle of deflection of less than about 8°.
21. The optical body of claim 1, wherein said first phase comprises a thermoplastic resin.
22. The optical body of claim 21, wherein said thermoplastic resin is a syndiotactic vinyl aromatic polymer derived from a vinyl aromatic monomer.
23. The optical body of claim 21, wherein said thermoplastic resin comprises interpolymerized units of syndiotactic polystyrene.
24. The optical body of claim 21, wherein said thermoplastic resin comprises polyethylene naphthalate.
25. The optical body of claim 24, wherein said second phase comprises syndiotactic polystyrene.
26. The optical body of claim 21, wherein said second phase also comprises at least one thermoplastic polymer.
27. The optical body of claim 1, wherein said optical body is stretched to a stretch ratio of at least about 2.
28. The optical body of claim 1, wherein said optical body is stretched to a stretch ratio of at least about 4.
29. The optical body of claim 1, wherein said optical body is stretched to a stretch ratio of at least about 6.
30. The optical body of claim 1, wherein said first and second phases are immiscible.
31. The optical body of claim 1, wherein said second phase comprises a plurality of elongated masses whose major axes are substantially aligned along acommon axis.
32. The optical body of claim 31 wherein said elongated masses have an aspect ratio of at least about 2.
33. The optical body of claim 31 wherein said elongated masses have an aspect ratio of at least about 5.
34. The optical body of claim 1, wherein said second phase comprises a plurality of rod-like structures.
35. The optical body of claim 1, wherein said optical body is stretched in at least two directions.
36. The optical body of claim 1, wherein said second phase is present in an amount of at least about 1% by volume relative to said first phase.
37. The optical body of claim 1, wherein said second phase is present in an amount of about 5% to about 50% by volume relative to said first phase.
38. The optical body of claim 1, wherein said second phase is present in an amount of about 15% to about 30% by volume relative to said first phase.
39. The optical body of claim 1, wherein said optical body contains a plurality of layers.
40. The optical body of claim 39, wherein at least one of said plurality of layers does not contain a disperse phase.
41. The optical body of claim 1, wherein said second phase is discontinuous along at least two of any three mutually perpendicular axes.
42. The optical body of claim 1, wherein said disperse phase is discontinuous along any three mutually perpendicular axes.
43. The optical body of claim 1, wherein the diffuse reflectivity of said first and second phases taken together along at least one axis for at least one polarization of visible, ultraviolet, or infrared electromagnetic radiation is at least about 30%.
44. The optical body of claim 1, wherein the extinction ratio of said optical body is greater than about 3.
45. The optical body of claim 1, wherein the extinction ratio of said optical body is greater than about 5.
46. The optical body of claim 1, wherein the extinction ratio of said optical body is greater than about 10.
47. The optical body of claim 1, wherein the optical body is a film, and whereinthe index difference between said first and second phases is less than about 0.05 along an axis perpendicular to the surface of said film.
48. The optical body of claim 47, wherein the electromagnetic radiation is distributed anisotropically about the axis of specular reflection.
49. The optical body of claim 48, wherein said optical body is stretched in at least one direction, and wherein the diffusely reflected portion of said at least one polarization of electromagnetic radiation is distributed primarily along or near the surface of a cone whose axis is centered on the stretch direction and whose surface contains the specularly reflected direction.
50. The optical body of claim 48, wherein said second phase comprises elongated inclusions whose axes of elongation are aligned in a common direction.wherein said optical body is stretched in at least one direction, and wherein the diffusely reflected portion of said at least one polarization of electromagneticradiation is distributed primarily along or near the surface of a cone whose axis is centered on the axis of elongation direction and whose surface contains the specularly reflected direction
51. The optical body of claim 47, wherein the electromagnetic radiation is distributed anisotropically about the axis of specular transmission.
52. The optical body of claim 13 wherein said optical body is stretched in at least one direction, wherein at least about 40% of light polarized orthogonal to a first polarization of light is diffusely transmitted through said optical body, and wherein said diffusely transmitted rays are distributed primarily along or near the surface of a cone whose surface contains the spectrally transmitted direction and whose axis is centered on the stretch direction.
53. The optical body of claim 1, wherein said second phase comprises elongated inclusions whose axes of elongation are aligned in a common direction,wherein said optical body is stretched in at least one direction, and wherein the diffusely transmitted portion of said at least one polarization of electromagnetic radiation is distributed primarily along or near the surface of a cone whose axis is centered on the axis of elongation direction and whose surface contains the diffusely transmitted direction.
54. The optical body of claim 1, wherein the optical body is a film, and whereinthe index difference between said first and second phases is less than about 0.02 along an axis perpendicular to the surface of said film.
55. An optical body, comprising:
a continuous phase;
a disperse phase whose index of refraction differs from said continuous phase by greater than about 0.05 along a first axis; and a dichroic dye.
a continuous phase;
a disperse phase whose index of refraction differs from said continuous phase by greater than about 0.05 along a first axis; and a dichroic dye.
56. The optical body of claim 55, wherein the disperse phase has an index of refraction that differs from said continuous phase by less than about 0.05 along a second axis orthogonal to said first axis.
57. The optical body of claim 55, wherein said dichroic dye is disposed within said disperse phase.
58. An optical body, comprising:
a first phase having a birefringence of at least about 0.05; and a second phase, disposed within said first phase;
wherein the absolute value of the difference in index of refraction of said first and second phases is .DELTA.n1 along a first axis and .DELTA.n2 along a second axis orthogonal to said first axis, wherein the absolute value of the difference between .DELTA.n1 and .DELTA.n2 is at least about 0.05, and wherein the diffuse reflectivity of said first and second phases taken together along at least one axis for at least one polarization of electromagnetic radiation is at least about 30%.
a first phase having a birefringence of at least about 0.05; and a second phase, disposed within said first phase;
wherein the absolute value of the difference in index of refraction of said first and second phases is .DELTA.n1 along a first axis and .DELTA.n2 along a second axis orthogonal to said first axis, wherein the absolute value of the difference between .DELTA.n1 and .DELTA.n2 is at least about 0.05, and wherein the diffuse reflectivity of said first and second phases taken together along at least one axis for at least one polarization of electromagnetic radiation is at least about 30%.
59. The optical body of claim 58, wherein wherein the absolute value of the difference between .DELTA.n1 and .DELTA.n2 is at least about 0.1.
60. The optical body of claim 58, wherein said first phase has a larger birefringence than said second phase.
61. The optical body of claim 60, wherein the birefringence of said first phase is at least 0.02 greater than the birefringence of said second phase.
62. The optical body of claim 60, wherein the birefringence of said first phase is at least 0.05 greater than the birefringence of said second phase.
63. An optical body of claim 58, wherein said second phase is discontinuous along at least two of any three mutually orthogonal axes.
64. A polarizer, comprising:
a first phase having a birefringence of at least about 0.05 and comprising a first polymer; and a second phase, disposed within said first phase, comprising a second polymer;
wherein the index of refraction of said second phase differs from the index of refraction of said first phase by greater than about 0.05 for visible light polarized along a first axis and by less than about 0.05 for visible light polarized along a second axis orthogonal to said first axis, and wherein the diffuse reflectivity of said first and second phases taken together along at least one axis for at least one polarization of visible light is at least about 30%.
a first phase having a birefringence of at least about 0.05 and comprising a first polymer; and a second phase, disposed within said first phase, comprising a second polymer;
wherein the index of refraction of said second phase differs from the index of refraction of said first phase by greater than about 0.05 for visible light polarized along a first axis and by less than about 0.05 for visible light polarized along a second axis orthogonal to said first axis, and wherein the diffuse reflectivity of said first and second phases taken together along at least one axis for at least one polarization of visible light is at least about 30%.
65. The polarizer of claim 64, further comprising a dichroic dye.
Applications Claiming Priority (2)
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US08/610092 | 1996-02-29 | ||
US08/610,092 US5825543A (en) | 1996-02-29 | 1996-02-29 | Diffusely reflecting polarizing element including a first birefringent phase and a second phase |
Publications (1)
Publication Number | Publication Date |
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CA2248214A1 true CA2248214A1 (en) | 1997-09-04 |
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CA002248214A Abandoned CA2248214A1 (en) | 1996-02-29 | 1997-01-17 | An optical film |
CA002248237A Abandoned CA2248237A1 (en) | 1996-02-29 | 1997-02-28 | Light fixture containing optical film |
CA002246545A Abandoned CA2246545A1 (en) | 1996-02-29 | 1997-02-28 | Optical fiber with light extractor |
CA002246449A Abandoned CA2246449A1 (en) | 1996-02-29 | 1997-02-28 | Optical film with increased gain at non-normal angles of incidence |
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Application Number | Title | Priority Date | Filing Date |
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CA002248237A Abandoned CA2248237A1 (en) | 1996-02-29 | 1997-02-28 | Light fixture containing optical film |
CA002246545A Abandoned CA2246545A1 (en) | 1996-02-29 | 1997-02-28 | Optical fiber with light extractor |
CA002246449A Abandoned CA2246449A1 (en) | 1996-02-29 | 1997-02-28 | Optical film with increased gain at non-normal angles of incidence |
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US (4) | US5825543A (en) |
EP (4) | EP0883821B1 (en) |
JP (4) | JP4336840B2 (en) |
KR (5) | KR100455987B1 (en) |
CN (4) | CN1117995C (en) |
AU (4) | AU714738B2 (en) |
BR (4) | BR9707791A (en) |
CA (4) | CA2248214A1 (en) |
DE (3) | DE69722386T2 (en) |
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1996
- 1996-02-29 US US08/610,092 patent/US5825543A/en not_active Expired - Lifetime
-
1997
- 1997-01-17 DE DE69722386T patent/DE69722386T2/en not_active Expired - Lifetime
- 1997-01-17 JP JP53094297A patent/JP4336840B2/en not_active Expired - Lifetime
- 1997-01-17 KR KR10-1998-0706720A patent/KR100455987B1/en not_active IP Right Cessation
- 1997-01-17 BR BR9707791A patent/BR9707791A/en not_active IP Right Cessation
- 1997-01-17 WO PCT/US1997/000981 patent/WO1997032224A1/en active IP Right Grant
- 1997-01-17 EP EP97904835A patent/EP0883821B1/en not_active Expired - Lifetime
- 1997-01-17 CN CN97192660A patent/CN1117995C/en not_active Expired - Lifetime
- 1997-01-17 AU AU17523/97A patent/AU714738B2/en not_active Ceased
- 1997-01-17 CA CA002248214A patent/CA2248214A1/en not_active Abandoned
- 1997-02-25 MY MYPI97000710A patent/MY133809A/en unknown
- 1997-02-28 AU AU22097/97A patent/AU2209797A/en not_active Abandoned
- 1997-02-28 AU AU19764/97A patent/AU1976497A/en not_active Abandoned
- 1997-02-28 JP JP9531076A patent/JP2000506992A/en not_active Ceased
- 1997-02-28 EP EP97907932A patent/EP0883826B1/en not_active Expired - Lifetime
- 1997-02-28 AU AU19804/97A patent/AU1980497A/en not_active Abandoned
- 1997-02-28 WO PCT/US1997/002995 patent/WO1997032225A1/en active IP Right Grant
- 1997-02-28 US US08/807,270 patent/US6297906B1/en not_active Expired - Lifetime
- 1997-02-28 EP EP97915054A patent/EP0883823A1/en not_active Withdrawn
- 1997-02-28 KR KR10-1998-0706722A patent/KR100424519B1/en active IP Right Review Request
- 1997-02-28 KR KR1019980706777A patent/KR19990087367A/en not_active Application Discontinuation
- 1997-02-28 US US08/807,930 patent/US6057961A/en not_active Expired - Lifetime
- 1997-02-28 US US08/807,262 patent/US6111696A/en not_active Expired - Lifetime
- 1997-02-28 JP JP9531138A patent/JP2000506993A/en not_active Ceased
- 1997-02-28 BR BR9707714A patent/BR9707714A/en not_active Application Discontinuation
- 1997-02-28 CN CN97192655A patent/CN1212764A/en active Pending
- 1997-02-28 CA CA002248237A patent/CA2248237A1/en not_active Abandoned
- 1997-02-28 KR KR10-1998-0706717A patent/KR100457447B1/en active IP Right Grant
- 1997-02-28 BR BR9707763A patent/BR9707763A/en not_active Application Discontinuation
- 1997-02-28 BR BR9707758A patent/BR9707758A/en not_active Application Discontinuation
- 1997-02-28 WO PCT/US1997/003955 patent/WO1997032227A1/en active IP Right Grant
- 1997-02-28 DE DE69722186T patent/DE69722186T2/en not_active Expired - Lifetime
- 1997-02-28 DE DE69709546T patent/DE69709546T2/en not_active Expired - Lifetime
- 1997-02-28 CN CN97192652A patent/CN1212762A/en active Pending
- 1997-02-28 EP EP97907875A patent/EP0883822B1/en not_active Expired - Lifetime
- 1997-02-28 KR KR10-1998-0706718A patent/KR100409062B1/en active IP Right Grant
- 1997-02-28 CA CA002246545A patent/CA2246545A1/en not_active Abandoned
- 1997-02-28 CN CN97194162A patent/CN1217068A/en active Pending
- 1997-02-28 JP JP9531225A patent/JP2000506994A/en not_active Ceased
- 1997-02-28 CA CA002246449A patent/CA2246449A1/en not_active Abandoned
- 1997-02-28 WO PCT/US1997/003130 patent/WO1997032230A1/en active IP Right Grant
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US7289266B1 (en) | 2002-10-08 | 2007-10-30 | Nitto Denko Corporation | Polarizer, optical film, and image display |
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