Title of Invention	AN OPTICAL BODY
Abstract	The present invention relates to an optical body, comprising: a continuous phase and a disperse phase; wherein at least one of said continuous and disperse phases comprises a first copolymer made from a blend of PEN and PET homopolymers, said copolymer having a mole % NDC composition of between 75% and 50%, wherein the intrinsic viscosity of said copolymer is higher than that attainable from a second copolymer having the same monomers in the same ratio but not made from homopolymers.

Title of Invention

AN OPTICAL BODY

Abstract

The present invention relates to an optical body, comprising: a continuous phase and a disperse phase; wherein at least one of said continuous and disperse phases comprises a first copolymer made from a blend of PEN and PET homopolymers, said copolymer having a mole % NDC composition of between 75% and 50%, wherein the intrinsic viscosity of said copolymer is higher than that attainable from a second copolymer having the same monomers in the same ratio but not made from homopolymers.

Full Text	The present invention relates generally to an optical body and more particularly to improvements in the materials used to make such bodies. Various optical films and devices are known to the art which rely upon refractive index differentials, sometimes produced by strain-induced birefringence, to achieve certain optical effects, such as the polarization of randomly polarized light. Such films and devices may be in the form of a multilayer stack in which index differentials between adjacent layers in the stack give rise to certain optical properties, as in the films disclosed in U.S. Pat. No. 5,882,774 (Jonza et al). Other optical devices comprise a disperse phase which is disposed in a continuous matrix, and derive their optical properties from refractive index differentials between the continuous and disperse phases. The materials disclosed in U.S. Pat. No. 5,825,543 (Ouderkirk et al.) are representative of this type of a system. Various hybrids of the aforementioned systems are also known, such as the multilayer optical films disclosed in U.S. Pat. No. 5,867,316 (Carlson et al), wherein the film comprises a multilayer stack having a repeating layer sequence in which at least one of the layers has a continuous phase/disperse phase morphology. Various other optical films and devices are also known to the art, and are described in U.S. Pat. No. 5,831,375 (Benson, Jr.), U.S. Pat. No. 5,825,542 (Cobb, Jr. et al.), U.S. Pat. No. 5,808,794 (Weber et al.), U.S. Pat. No. 5,783,120 (Ouderkirk et al), U.S. Pat. No. 5,751,388 (Larson), U.S. Pat. No. 5,940,211 (Hikmet et al), U.S. Pat. No. 3,213,753 (Rogers), U.S. Pat. No. 2,604,817 (Schupp, Jr.), Aphonin, O. A., "Optical Properties of Stretched Polymer Dispersed Liquid Crystal Films: Angle-Dependent Polarized Light Scattering", Liquid Crystals, Vol. 19, No. 4, pp. 469-480 (1995), Land, E. H., "Some Aspects of the Development of Sheet Polarizers,.COPYRGT.1951 Optical Society of America, Reprinted from Journal of the Optical Society of America, Vol. 41(12), 957-963, (Dec. 1951), pp. 45-51 and 2244 Research Disclosure (1993), July, No. 351, Emsworth, GB, "Polarizer", pp. 452-453. In the past several years, a number of advances have been made in the materials sciences, especially in the area of block copolymers, which have resulted in the development of new and interesting materials and methods for making and using these materials to various ends. In some cases, these advances have led to applications in the field of optical films and devices. Thus, for example, Urbas et al., "One-Dimensional Peroidic Reflectors from Self-Assembly Block Copolymer-Homopolymer Blends," Macromolecules, Vol. 32, pages 4748-50 (1999), report the formation of well ordered photonic crystals similar to a: multilayer quarter wave stack comprising self assembling blends of block copolymers optionally containing homopolymers. One embodiment describes the formation of a narrow band reflector. Also summarized is the use of neat block copolymers as well as copolymers comprising Uquid crystalline materials as means of producing periodicities in block copolymer materials. U.S. Serial No. 08/904,325 (Weber et al.)(corresponding to WO 99u6203) discloses the transesterification or reaction of polyesters lying in adjacent layers of a multilayer optical stack for the express purpose of improving interlayer adhesion. It is assximed that the thickness of the interface comprising the reacted materials is sufficiently thin so as not to otherwise affect the optical properties of the optical stack except at the interface. U.S. Serial No. 09/006,455 (Merrill et al.)(coiTesponding to WO 9936812) discloses the use of transesterified blends of PEN and PET within a single layer in a multilayer optical stack for the purpose of producing optical devices such as polarizers and mirrors. U.S. 3,546,320 (Duling et al.) discloses transesterification methods for preparing a semicrystalluie composition comprising 94 to 60 weight percent polyalkylene terephthalates, 6 to 40 weight percent polyalkylene naphthalene-2,6-dicarboxylate, and at least 5 weight percent of a block copolymer comprising discrete polymer segments of the percent polyalkylene terephthalate and the polyalkylene naphthalene-2,6-dicarboxylate. The block copolymer is prepared by melt transesterification of the individual homopolymers, and the degree of transesterification is controlled by the mixing time. Duling demonstrates a total loss of crystallinity of the block copolymer after extensive transesterification, depending on the composition. U.S. 3,937,754 (Sagamihara et al.) discloses a biaxially oriented polyethylene-2,6-naphthalate (PEN) film containing a polyester resin other than PEN in an amount of 0.5 to 10 percent by weight based on the PEN, and a process for its proi^ictioii. The reference notes that when the PEN resin (1) is blended in the molten state with a polyester resin (2), the softening point of the blended mixture decreases gradually from the softening point of the PEN until it finally reaches a certain point, referred to as an equilibrium softening point The reference teaches that this softening point coincides with the softening point of a PEN copolymer obtained by copolymerising monomers of the same composition and proportion as the monomers which constitute the PEN resin (1) and the polyester resin (2). From this fact, the reference presumes that reaction occurs via a stage of forming a block copolymer, where given enough reaction time a copolymer will be obtained. Research Disclosures 28,340 and 29,410 disclose transesterified products of PEN, PET, and other polymers comprising dibasic acids. Typical dibasic acids include isophthahc, adipic, glutaric, azelaic, and sebacic acid and the like. The PEN based polymers are generally based on 2,6-naphthalene-dicarboxylic acid but may be based on 1,4-, 1,5-, or 2,7- isomers or mixtures of these isomers. These teachings primarily address the ability to control mechanical and physical properties such as modulus, gaseous permeabihties, and glass transition temperatures. WO 92/02584 (Cox et al.) disclose the use of phosphite materials to control the rate of transesterification during solid state polymerization, primarily for the intended use of improving physical and mechanical properties, such as gaseous diffusion, in the final product application. The reference discloses blends of PEN and PET homopolymer pellets, which are held at a temperature range between the higher glass transition temperature and the lower melting temperature. Despite the many advances noted above in the area of optical films and devices, a number of problems still persist in the art. For example, it is often desirable to rely on strain-induced birefiingence to achieve desirable optical properties in an optical film, since the film can be convraiently oriented in a controlled maimer on a laboratory stretcher in accordance with well established methodologies and principles. However, these methodologies do not work equally well for all materials selections. In particular, problems are frequently encountered with the use of thermodynamically immiscible polymers whose interfacial strength is not large, because the resulting film cannot always be stretched to a high enough draw ratio to achieve an optimal level of birefiingence. In the case of a continons/disperse phase system, for example, oriaiting such a film to the draw ratios required for optimal birefiingence may lead to voiding at the interface between the two phases, thereby compromising the desired optical properties (e.g., polarizing properties) of the system. Voiding of this type is described in U.S. 5,811,493 (Kent), where it is used to produce paper-like films which are difiusely reflective to both polarizations of light. Unfortunately, if lower draw ratios are used to prevent voiding, the resulting fihn may have a lower degree of birefiiugence arid less than optimal optical properties. There is thus a need in the art for a method for achieving a desired degree of birefiingeace in an optical fihn or device while reducing the draw ratio normally required to achieve the desired level of birefiingence. There is also a need in the art for a method formating optical films and devices from therinodynamically immiscible polymers whose int^dfecial straagth is not large, wherein the fihnsand devices are capable of being oriented to the higher draw ratios frequently required to achieve a higher degree of birefringence and optimal optical properties. These and dther needs are met by the present invention, as hereinafter described. Brief Description of the Drawings FIG. 1 is a plot of engineering stress as a fimction of apparent'draw ratio; FIG. 2 is a plot of refractive index in the principle draw direction, Nx, for a positively birefiingent material as a fimction of true draw ratio; FIG, 3 is a plot of % increase in on-axis gain as a fimction of % randomness; and FIG. 4 is a plot of engineering stress as a fimction of apparent draw ratio. Summary of the Invention In one aspect, the present invention relates to a method for making a continnous/disperse phase optical device, such as a mirror, polarizer, or diffiiser, and to optical devices so made. In accordance with the method, at least one of the continuous and disperse phases is fabricated from a blend of homopolymers under conditions that allow the homopolymers to inter-react (e.g., through transesterification or transamidization) to form a copolymer which can be used to make an optical device having improved physical and optical properties. In another aspect of the invention, the present invention relates to continuous/disperse phase optical devices made from a blend of homopolymers that are capable of inter-reacting, such devices having better physical and optical properties as compared to an analogous system in which the blend of homopolymers is replaced by a copolymer of the same monomers in the same ratios, but not made from homopolymers. Some of the improved physical and optical effects observed with such a system include increased gain, higher intrinsic viscosities, and an earlier onset of strain-hardening (that is, the optical devices of the present invention exhibit a higher level of birefringence for a given level of strain than their random copolymer coimterparts). The later property is especially advantageous in systems in which the materials of the continuous and disperse phases have poor adhesion, because it allows such systems to achieve a desired degree of birefringence at a lower draw ratio, thereby avoiding or minimizing voiding between the two phases. The degree of inter-reaction may be manipulated through control of processing conditions, such as residence time, so as to achieve desirable properties in the resulting optical device, but the degree of randomness will typically be less than 70%. The use of a blend of homopolymers in accordance with the method of the present invention allows for the attainment of higher molecular weights (and, therefore, higher intrinsic viscosities) than those achievable with the aforementioned statistically random copolymer analogs. Surprisingly, continuous/disperse phase optical devices which are made with such blends exhibit increased gain as compared to their statistically random analogs, even though the average particle size of the disperse phase in systems made with the blend materials was not observed to be smaller than the average particle size of the disperse phase in systems made with the random copolymer analogs, as might have been expected had there been a larger difference in intrinsic viscosities of the jBnal films. In another aspect, the present invention relates to a method for making an improved optical device, such as a mirror, polarizer, or diffaser, from a continuous/disperse phase system, and to the optical devices so produced. Surprisingly, applicants have discovered that, when at least one of the continuous and disperse phases comprises a block copolymer. the degree of randomness of the monomeric units of the copolymer can be manipulated to maximize the strain-induced birefiiagence achievable in the system. In particular, through prcq)erm2nqmlati La a related aspect, the present iuvention relates to a method for improving the physical and optical properties of a continuous/disperse phase optical body in which at least one of the phases comprises a statistically random copolymer of two or more monomers, incorporated into optical devices made according to the method. In accordance with the method, the statistically random copolymer is replaced with a blend of homc^IymeTS of the same monomers, such that the ratios of the monomers remains the same. Detailed Description of the Invention As used herein, the following abbreviations have the following meanings: "T" refers to dimethyl terephthalaie, 'TsP' refers to naphthalene dicarboxylate. "E" refers to ethylene glycol. . "coPEN" refers to a copolymer based on naphthalene dicarboxylate and dimethyl terephthalate and ethylene glycol. "PEN" refers to polyethylene naphthalate. "PET" refers to polyethylene terephthalate. "NDC" refers to naphthalene dicarboxylate. "DMT" refers to dimethyl terephthalate. "EG" refers to ethylene glycol. "LV." refers to intrinsic viscosity. "An" refers to bire&ingence, and is defined as the index of refiaction in the jMiodple draw direction minus the index of refi:action in a perpendicular direction. Where refeared to herein, indices of refraction are measured at 632.8 nm, as the index of re&action typically increases with decreasing wavelength due to dispersion. In addition to its use in creating block copolymers, solid state polymerization is a process commonly used to increase the molecular weight of polyesters including polyethylenenphthalate (PEN) and polyethyleneterephthalate (PET). As has been taught in prior cases describing continuous and disperse phase optical devices, such as, for example, U.S. Pat. Nos. 5,825,543 (Ouderkirk,et al.), 5,783,120 (Ouderkirk, et al.), and 5,867,316 (Carlson et al.), the particle size of the disperse phase is an important parameter to control in optimizing these devices. Matching the viscosities of the two phases is one method of minimizing and controlling the particle size of the disperse phase. During solid state polymerization, polymer pellets comprising polyesters of the type described are crystallized and then typically raised to a temperature of 235° to 255° C under vacuum of less than 5 torr to drive off the polycondensation by-product ethylene glycol and thus increase molecular weight. Below temperatures of 210° C, solid state polymerization of aromatic polyesters becomes impractical due to extremely slow reaction rates and thus long polymerization times. Long polymerization times can make the process and or materials cost prohibitive. Since the melting point of some random copolyesters are lower than 210° C, the use of higher temperatures will cause an agglomerate of the pellets into an undesirable solid mass. Thus, it is impractical and cost prohibitive to solid state polymerize random copolyethylenenaphthalates with less than about 75 mole percent naphthalate content. Copolymers of polyethylenenaphthalate haviag less than 75 mole percent naphthalate are desirable, however, for use ia optical devices such as polarizers and mirrors due to their improved color, lower dispersion, reduced degradation by light, including UV light, in the range of about 380 to 400 nm, and lower cost. Advantages of low naphthalate content resins are described in applicants copending U.S. Patent Application No. 09/416,462, filed on even date under attorney docket number 55028USA1A. High molecular.weight copolyethylenenaphthalates with less than about 75 mole percent naphthalate can be created by extrusion blending and transesterifyitig high molecular weight polyethylene terephthalate (PET) with high molecular weight polyethylene naphthalate (PEN). One can achieve higher viscosities of a copolymer of PET and PEN than can be obtained during polymerization in conventional reactor processes since solid state polymerized PET and PEN with higher viscosities can be used as starting homopolymers- In accordance with the present invention, the birefringence and ofeer c^cal and physical properties of a continuous/disperse phase syston comprising a statisicaDy random, or nearly random, copolymer of two or more monomers may be impioved by rrolacing the random or nearly random copolymer with a copolymer which comprises the same ratios of the individual monomers, but whose degree of randomness is less than that of a statistically random copolymer. Preferably, the replacement copolymer is a blend of condensation homopolymers of the individual monomers which are capable of inter-reacting with each other (e.g., by undergoing transesterification, transamidization, or similar reactions) to a degree that can be controlled so as to result in a copolymer whose degree of randonmess is less than that of a statistically random copolymer. Polarizers, mirrors, diflusers, and other optical elements made from the ccamnnous/disperse phase systems of the present invention have several advantages over analogous systems which utilize statistically random copolymers. In particular, the monomer ratios and the degree of transesterification or other inter-reaction can be conveniently controlled at the time of extrusion, thereby allowing one to optimize the amount of birefringence-achievable under a given set of stretching conditions. Moreover, the continuous/disperse phase systems of the present invention can be fabricated from homopolymers which are typically less expensive and more readily available in higher molecular weights than is typically the case with custom copolymers. Additionally, in contrast to a process that requires pre-made copolymer materials, the process of the present invention allows for greater compositional flexibility of the copolymer, in that the composition can be easily controlled or changed during extrusion. In an optical device comprising a continuous and disperse phase system, one of the methods of improving the optical performance of the device is to maximize the birefringence of at least one of the phases in at least one of three orthogonal directions while minimizing the refractive index mismatch between the two phases along at least another of the orthogonal directions. It has been found in the present invention that a given level of birefringence can be achieved sooner (e.g., at a lower draw ratio) for block copolymers and/or statistically non-random copolym^^ of the type described above than is the case with a statistically random copolymer analog. The ability to achieve a given degree of birefiitigence at a lower draw ratio is particularly advantageoxis when if is desirable to utilize for the continuous and disperse phases tiliermodynamically immiscible polymers whose interfacial strengths are not large, since the use of a lower draw ratio has less of a tendency to compromise the interfacial contact between the two phases (e.g., by inducing voiding). In the context of the present invention, transesterification, transesterifying and transesterifies are meant to include reaction of condensation polymers such as polyesters, polyamides, copolyesteramides, and certain methine moieties intended to provide color, UV stability, or other desirable properties. Materials useful in the present invention include polyesters, polyamides, copolyesteramides, as well as other materials, for example those mentioned in U.S. Patent No. 4,617,373 (Pniett et al.). In many embodiments of the present invention, the degree of transesterification is controlled in the thermoplastic component(s) of at least one phase of a continuous/disperse phase optical device such that a statistically non-random copolymer results which preferably inter-reacts to an extent such that the degree of randomness is less than about 70%, preferably less than about 50%, and more preferably about 40% or lower. Methods available to achieve the desired degree of randomness include melt processes, as well as solid state polymerization processes which can occur prior to melt processing. Various parameters may be used to control the rate of the inter-reaction, including, but not limited to, the molecular weight of the individual blocks and of the entire block copolymer, the temperature of reaction, the state of matter in which the reaction is perfonned (e.g., whether it is performed in the solid or molten state), and the time allowed for the reaction to complete. Optionally, any of the methods may use additives such as stabilizers and antioxidants to further accelerate or retard the rate of inter-reaction. For example, an optical device useful as a polarizer comprises a continuous phase and a disperse phase. The optical device operates by substantially matching the refractive index between the continuous and disperse phases along at least a first of three orthogonal directions and substantially mismatches the refractive index between the two phases alo;ig at least a second of three orthogonal directions. Mechanisms by which the index is substantially matched in at least a first direction and mismatched along at least a second direction are known to the art and are described, for example, in U.S. Patent No. 5,783,129 and in U.S. Serial Number 09/006,455 (MerriU et al.) (corresponding to WO 9936812), filed on Janoaiy 13,1998. in briet substantially matching the rejBractive index is largely accomplished by judicioiis selecti Howevea:, when at least one of the continuous or disperse phase materials comprises a copolymer — particularly when the copolymer is capable of strain induced and/OT qui^cent crystallization, it has been determiaed by the present inventors that in ad&dcHi to the degree, temperature, and rate of orientation, the amount of birefiingence that develops will also be dependent upon the degree of randomness of the individual monomer xmits comprising the copolymer or on the intrinsic viscosities of the homopolymers and the resulting copolymer. In one embodiment, miscible polymers comprising the individual monomers are envisioned as usefiil for the present invention. At least one of the polymers used should ideally be capable of developing a high degree of birefiingence. The differences in birefringence may be due to a wide variety of factors. Without wishing to be restrictive, at least some of these characteristics will include the amount of crystallinity that forms during orientation as weU as the intrinsic birefiingence of the random versus the block copolymer. For a given molecular weight and a copolymer comprising two monomers of equal amounts, the statistically random copolymer and a di-block copolymer define the extremes in attainable degree of randomness. In an illustrative embodiment, the continuous phase material is a polyester where the monomers comprise dimethyl terephthalate (T), naphthalene dicarboxylate (N)> and ethyiene glycol (E). Homopolymers of these monomers are commonly known as polyelhyiene terephthalate (PET) and polyethjdrae naphthalate (PEN). That is, PET co«ire^)onds to the sequence TE-TE-TE-... and PEN corresponds to the sequence NE-NE- NE-.... The degree of randomness of NE or TE blocks can be approximated by the ratio of the fraction of obsen'ed NET triads to the statistically random probability of an NET triad, assmning random placement. The procedure to determine triads has been described by Stewart and Cox in Polymer, Vol. 34, pp. 4060-67 (1993). fi can be shown that the statistically random probabihty of NET triads is given by the product: 2 x Wt x Wn, where Wt is the mole fraction of T monomer and Wn is the mole fraction of N monomer. The degree of randomness is defined as the ratio of the fraction of NET triads observed to the theoretical fraction of NET triads in a statistically random copolymer. For example, a high molecular weight block of a diblock copolymer of 50 mole percent T and 50 mole percent N would have a single NET triad ia each molecule, and hence would exhibit a virtually undetectable fraction of NET triads ia a high molecular weight polymer. The ratio defining the degree of randomness would be approximately zero. The theoretical probability of a NET triad for a random copolymer would be 0.5. The ratio defining the degree of randomness for such a truly raiidoiri copoloymer would be approximately 1.0 (100 percent). The degree of randomness of NE- or TE- sequences can be approximated using the following theoretical approach, assuming equivalent reaction ratios of the two monomer materials. A more sophisticated analysis can be performed for those cases where the reaction ratios of the monomer units are not equivalent. For the purposes of this discussion, let: , .,. Wn = mole fraction NE as charged or as measured by nuclear magnetic resonance spectroscopy (mnr); Wt = mole fraction TE as charged or as measured by nmr; Pnn = fraction of NEN sequences as measured by nmr; Pnt = fraction of NET sequences as measured by nmr; and Ptt = fraction of TET sequences as measured by nmr. It follows that Wt + Wn - 1 and Pnn-f-Pnt-f Ptt =1. Also, let P(jli) equal the conditional probability of finding a "j" monomer next on the polymer r^m^ given that the currently chosen monomer on the polymer chain is an "i" moasmier sequaice- There are four of these latter quantities, P(ntn), P(n\|t), Pt\|n) and P(t\|t). In the T^nTTt ofM^ molecular weight, the probabiUty of an end group is essentially zero and then ii follows that: P(n\|t) + P(tlt) = l and P(nin) + P(t\|n) = l. It also follows from the definition of conditional probabilities that Pnn = P(n\|n) * Wn, Ptt = P(t\|t) * Wt, and Pnt = P(n\|t)Wt + P(t\|n) Wn. The above equations thus define the conditional probabilities in terms of NMR measurable quantities. In the special case of a random copolymer, the probability of finding a "j" monomer next is independent of "i" and then P(j\|i) is merely Wj. Thus, for a random polymer: ■ Pnn=WnWn, Ptt=WtWt, and Pnt=2WnWt, as asserted previously, hi this high molecular weight limit, typically applicable in practice, the definition of % randomness now follows: % Randomness = Pnt / (2WnWt) = Pnt(observed)/Pnt(random) It should be noted that although the Wj's and Pij's are obtained from separate aspects of the nmr grq>hs, there is a further relationship between them. In general, hese relations should also hold: 0.5 * Pnt + Pnn = Wn, and 0.5*Pnt + Ptt = Wt Particularly in the case of low levels of randomness, experimental error tends to create small discrepancies in these relationships. Given th»e discrepancies, as a practical matter the best definition of percent randomness is based on the experimental (observed) value of Pnt as given above. The probability of a k length sequence of j-monomer units (only vahd when is not on the order of the number of monomers in a single chain, so this assumes the high molecular weight limit) is simply the probability of k-1 successive occurrences given a first occurrence of a "j" monomer times the probability that the k+l monomer is not a "j" monomer. Since every sequence must be some length it follows that: The more general case of a finite chain is presented by Frensdorff in , Macromolecules, 4, 369 (1971). The conditional probability is sUghtly reduced by the probability of the chain ending, e.g. (P(j \| j) is multiplied by an extent of rection near unity. An alternative "recursive" approach with similar results is given by Lopez-Serrano, et. Al. in Polymer, 21, 263 (1980). In any case, the characterization method as described here is appUcable to block copolymers comprising units "A" and "B", and are not limited to the example case where A==NE and B=TE. In the examples to follow, a random copolymer of 70% NE block monomer composition has a number average NE block sequence length of only about 3.. A random copolymer of 50% NE block composition has a number average NE block sequence length of only about 2. While not wishing to be bound by theory, it is believed that when the average sequence length is longer, various physical, optical or mechanical properties maybe improved. For example, the amount of crystallinitymay increase at a given drawing condition leading to higher birefiingence or dimensional stability. The melting point may also be increased leading to a more stable film than the random case at elevated temperatures. In that refi"active index is a key component to the pec&nnarKe of the c^cal device, then increasing block length should increase and/or mjimf^TTi nwlecuiar OTientadon during and following the drawing processes, pardcularly for optical devices thai are thennally stabilized by annealing or heat setting at elevated temperatures. One of the mechanisms that can stabihze or maintain the molecular orientation is the formation of crystalhtes during the dravraig process. The onset of crystallization during draw can often result in an increase in the drawing force. As a result, a block copolymer capable of crystallization during orientation may exhibit an increase in the stress above and beyond that of a statistically random copolymer cotnprising the same monomers at any given point of a similar drawing process; that is, the block a^x>lymer will tend to strain harden sooner than the statistically random, but otiifswise identical, .copolymer. Concomitant with the sooner strain hardening is a higher refeactive index for a positively birefiingent material in the draw direction and a higher birefringence for a given point in a given drawing process. Higher birefringence typically will result in higher gain when all other quantities are held constant. In practice, several factors can alter the stress versus draw behavior, which can thus cause a change in the onset of strain hardening. Besides the percent randomness, increasing the molecular weight or LV. of the continuous phase, increasing the relative composition of the block monomer unit with tiae higher glass transition temperature and/or more quickly crystallizing component (such as, for example, NE), and increasing the fraction of dispersed phase (such as, for example, syndiotactic polystyrene (sPS)) prior to a phase inversion, typically accelerate the onset of strain hardening. These factors are illustrative only, and should not be considered limiting. In general, each of these factors may also improve the birefringence and optical gain at noraial incidence for a given set of process conditions. In the following examples, the continuous phase comprises polyesters whose equihbrium state after transesterification is random or at least nearly random: the percent transesterification being 98% or higher. COMPARATIVE EXAMPLE 1 A polymeric blend was extruded and cast into a film, using extrusion techniques of the type described in U.S. Patent No. 5,783,120 (OudCTkiEk, et-aL). The blend comprised 57.6 % by weight coPEN (70 mole % PEN and 30 mole % PET) as the continuous phase, 40% by weight Questra MA 405 syndiotactic polystyrene (available commercially from the Dow Qiemical Co., Midland, Michigan) as the disperse phase, and 2.4% by weight Dylark 332 compatibilizer (available commercially from Nova Chemicals). The coPEN had an intrinsic viscosity (I.V.) of 0.57 (measured in 60% phenol, 40% dichlorobenzene). A sequence analysis was performed on the cast film using proton nuclear magnetic resonance according to the method described in Stewart et al., Polymer^ Vol. 34, pages 4060-4067 (1993). Three sharp resonances were observed corresponding to the ethylene glycol (E) protons in the NEN, NET, and TET triad sequences. The ratio of the observed probability of NET triad sequences to the theoretical probability of a NET triad sequence (expressed as a percentage) defines the degree of randomness. The measured degree of randomness was 98.1%, which implies that the-copolymer was virtually a random copolymer of PEN and PET. The cast film was oriented first in the machine direction to a draw ratio of about 1.3:1 using a conventional length orienter. The sheet was then oriented imiaxially in the transverse direction using a conventional tenter. The final transverse draw ratio was approximately 5.4:1 based on the rail settings at the entrance and exit of the tenter. The stretch temperature was 118°C (245""F). Following orientation, the film was heat set temperature at 163°C (325°F) The optical properties of the fihn were measured using a Perkin-Elmer Lambda-19 UV-visible spectrophotometer equipped with an integrating sphere and a Glans-Thompson cube polarizer. The average transmission was 83.5% for wavelengths of light between 400 and 700 nanometers whose polarisation orientation was aligned with the pass direction of the film. Light whose polarization orientation was aUgned with the block direction of the film had an average transmission of 16.3%. Gain was measured by placing the film into a C12P back light cavity. The on-axis luminance of the cavity with the film in place was 40.2% greater than the same apparatus without the film. The luminance at 40° to the normal axis with the film in place was 28.5% greater than the measured luminance of the apparatus without the film. CCMPARAUVE EXAMPLE 2 The coPEN from COMPARATIVE EXAMPLE 1 was extraded and cast into a transparoat film, and the degree of randomness was measured to be 99.1%. Hence, the presence of the Questra MA 405 resin in COMPARATIVE EXAMPLE 1 did not appear to alter the ability to measure the degree of randomness of the polyester. The intrinsic viscosity of the final copolymer was measured as 0.526. The cast sheet was uniaxially oriented to anominal stretch ratio of 6:1 in a laboratory batch stretcher at 115° C. The stress-strain relationship of the sheet was measured during orientation and is shown as Cur^e A in FIG. 1. The refiractive index along flie stretch direction at a wavelength of 632-8 nanometers was determined to be 1.766 for a true draw ratio of 5.30:1. In the other QOBi-stretcfa, in-plane direction, the index of refraction was determined to be 1.600. Differential scarming calorimetry was used to measure the crystallinity and an apparent heat of 25.0 J/g was measured with a peak melting temperature of 205^C. The cast sheet was further oriented to several different uniaxial draw ratios according to the conditions described above, with the exception that the draw temperature was 120"^ C. Using fiduciary marks scribed onto the cast sheet prior to orientation, the true draw ratios could be determined simply by taking the ratio of the distances between the marks following and prior to the orientation. The index of refraction in the principle draw direction was measured for various true draw ratios and are plotted as open circles in FIG. 2. As expected for this positively birefiingent material, an increase in refiractive index in the direction of draw as a fiinction of draw ratio is observed. EXAMPLES 1-2 A polymeric blend comprising 70 mole % PEN homopolymer and 30 mole % PET homopolymer was extruded and cast into a film. In EXAMPLE 1, the PEN had an LV. of 0-56, and the PET had an LV. of 0.60. The LV. of the final copolymer was measured as 0-535. The degree ofrandomness was 23.4%. In EXAMPLE 2, the PEN had an LV. of 0-36, and the PET had an LV. of 0.85. The LV. of the final copolymer was measured as 0.560. The degree of randomness was 30.9%. Sheets from both EXAMPLES 1 and 2 were transparent. The sheets of EXAMPLES 1-2 were oriented similarly to the film of COMPARATIVE EXAMPLE 2, and the corresponding stress-strain curves were determined. The stress-strain relationship for EXAMPLES 1 and 2 are shown as Curves B and C, respectively, in FIG. 1. The copolymer of EXAMPLE 1, which has a slightly lower intrinsic viscosity and a lower degree of randomness, shows a sUghtly earlier strain-hardening than the copolymer of EXAMPLE 2. The differences between Curves B and C are. likely not statistically significant. However, the strain-hardening behavior of these curves are significantly different from the corresponding behavior of the statistically random copolymer of COMPABATIVE EXAMPLE 1 (Curve A), where strain-hardening is meant to describe the dependence of stress on the imposed orientational strain. Cast sheets from EXAMPLES 1 and 2 were oriented to various true draw ratios as described in COMPARATIVE EXAMPLE 2. The refractive indices in the principle draw direction were measured and plotted in FIG. 2 as closed squares and open triangles, respectively. EXAMPLES 1 and 2 exhibit an increase in the refractive index along the direction of draw. Moreover in accordance with an earlier onset of strain-hardening, the refractive indices for EXAMPLES 1 and 2 are higher than the corresponding refractive index for COMPARATIVE EXAMPLE 2 for any given stretch condition. Differential scanning calorimetry was used to measure the crystallinity. In EXAMPLE 1, an apparent heat fusion equal to 35.9 J/g was measured along with a peak melting temperature of 251° C. In EXAMPLE 2, an apparent heat of fusion equal to 35.3 J/g was measured along with a peak melting temperature of 244° C. A similar series of stress strain experiments were performed at a draw temperature of 120° C. The strain-hardening appeared at a slightly higher draw ratio for EXAMPLES 1 and 2. The indices of all three were slightly reduced by about 0.01 in the stretch directions. Without wishing to be bound by any particular theory, it would appear that the increase in stress at apparent uniaxial draw ratios greater than about 3 will translate into improved optical properties. For example, a greater difference in the refractive index between the continuous and disperse phases may be achieved in a continuous phase matCTial exhibiting strain-hardening behavior relative to a continuous phase material that does not exhibit strain-hardening behavior at the same draw ratio. FOT an optical (tevice such as a reflective polarizer where the optical properties dq)ead in jxart on the r^'active index differential between the continuous phase and disperse jdiases along at least one axis, the block copolymers exemplified in EXAMPLES 1 and 2 should exhibit an increase in optical properties when used as part of a material combination described in COMPARATIVE EXAMPLE 1. EXAMPLE 3 A film was prepared ia accordance with the methodology of COMPARATIVE EXAMPLE 1, except that the blend of PEN and PET homopolymers fi-om EXAMPLE 2 was substituted for the coPEN copolymer. The cast film had a degree of randomness of S-7%. The cast film was first oriented to a stretch ratio of 1.25:1 using a conventional kagtii ori^iter, and then drawn to a stretch ratio of 5.1:1 in the transverse direction at 11S°C(245°F). The on-axis gain was 43.8%. The 40° gain was 20.1%. Relative to COMPARATIVE EXAMPLE 1, this example demonstrates that a mixture of homopolymers and/or a lower degree of randomness may be used to achieve an increase in on-axis gain, EXAMPLE 4 i' ^^ A film was made in accordance with the methodology of EXAMPLE 3, except .that the PEN and PET homopolymers were those used in EXAMPLE L This sample had a degree of randomness of 10.8%. The on-axis gain was. 42.8%. The 40^ gain was 19.2%. By comparing EXAMPLE 4 to EXAMPLE 3, it is seen that at a fixed degree of randomness, and nearly identical composition and process conditions, increasing the L V. increases the gain. EXAMPLES A film was prepared in accordance with the methodology of EXAMPLE 3, except that the residence time of the melt was substantially increased compared to EXAMPLE 3 by including an additional filtration device in the melt stream. EXAMPLE 5 used two filters in the melt stream, whereas EXAMPLE 3 used only one filter, so the residence time was approximately doubled. By increasing residence time, the degree of randomness is increased. Control of residence time can be used to control the degree of randonmess. The degree of randomness was 27.9%; the on-axis gain was 43 J2%; and the 40° gain was 18.1%. This example suggests that residence time associated with the melt affects the degree of randomness. This example also demonstrates that there need not be a linear dependence of optical performance with respect to the degree of randomness. FIG. 3, which is a plot of on-axis gain versus degree of randonmess for COMPARATIVE EXAMPLE 1 and EXAMPLES 3, 4, and 5, demonstrates the positive effect of blockiness in at least ono of the phases of the continuous/disperse phase reflective polarizing device. EXAMPLE 6 A film was prepared in accordance with the methodology of EXAMPLE 5 except that the tenter preheat temperature was 140'^ C (285° F) compared to 135° C (275° F) for Example 5. The sample had a degree of randomness of 28.5% and exhibited an on-axis gain of 41.9%. EXAMPLE? This example demonstrates yet another range of intrinsic viscosities useful in the present invention. A fikn was made in accordance with the methodology of EXAMPLE 6, except that the PEN had an intrinsic viscosity of 0.48 and the PET had an intrinsic viscosity of 0.72. The sample had a degree of randomness of 25.2% and exhibited an on-axis gain of 40.4%. By comparing EXAMPLE 7 to EXAMPLE 6, it is seen that at nearly identical degrees of randomness and processing conditions, increasing the viscosity of the blended homopolymers increases the gain. EXAMPLES 8-10 These examples demonstrate that varying degrees of randomness can be obtained for various compositions of PEN and PET. The films of EXAMPLES 8-10 were prepared in accordance with the methodology of EXAMPLE 4, except that the PEN to PET composition ratios were 65/35, 60/40, and 55/4^5, respectively. The degrees of randomness were 11.7%, 9.4%, and 10.1%, respectively, for EXAMPLES 8, 9, and 10. The on-axis gains were 40.2%, 44.2%, and 43.9%, respectively, for EXAMPLES 8, 9, and 10. It should be noted that the 65/35 sample wa$ stretched at about 10° C hotter than the 60/40 and 55/45 samples, resulting in a lower gain than would be expected and thus the gain values reported are not directly comparable. The 40° gains were 27.0%, 24.8%, and 28.7%, respectively, for EXAMPLES 8, 9, and 10. EXAMPLE 11 This example illustrates the effect of an increased degree of randomness on gain. A continuous/disperse phase blend was made in accordance with the methodology of Comparative EXAMPLE 1, except that the blend comprised 34.8% by weight of coPEN having a 70/30 mole percent ratio of PEN/PET, 22.8% by weight of 0.85 LV. PET, 40% by " weight of Questra MA 405, and 2.4% by weight of Dylark, resulting in an effective PEN to PEl' ratio of 55/45. The blend was then extruded and cast into a film using methodology similar to that of EXAMPLE 4. The degree of randomness was determined to be 71.0%. The on-axis gain was 37.9%. The 40° gain was 27.6%. In. comparison to- EXAMPLE 10, where the degree of randomness was 10.1%, the fihn of this example, which had a degree of randomnesstransesterification of 71.0%, exhibited a reduction in gain, both on-axis and at 40°. COMPARATIVE EXAMPLE 3 A sample of film was prepared from the cast fihn of COMPARATIVE EXAMPLE 1, except that the orientation process was performed on a laboratory batch stretcher where the orientation temperature was 115°C and the final nominal stretch ratio was 6.0:1. Engineering stress measurements were taken during the process of orientation, and are represented as Curve D in FIG. 4. By comparing Curve A from FIG. 1 with Curve D from FIG. 4, it is obvioiis that the addition of a disperse phase altered the strain-hardening behavior, irrespective of the degree of randomness of the continuous phase. EXAMPLE 12 A film was made in accordance with the methodology of COMPARATIVE EXAMPLE 3, except that it was prepared from cast sheet produced as part of EXAMPLE 3. The stress-strain measxirements are shown as Curve F in FIG. 4, EXAMPLE 13 A fihn was made in accordance with the methodology of COMPARATIVE EXAMPLE 3, using a cast web prepared similarly to that of EXAMPLE 3 except that the % randomness was 40%, The stress-strain measurements are shown as Curve E in FIG. 4, Comparison of the three curves in FIG. 4 demonstrate that while the strain-hardening behavior may be altered by the presence of a disperse phase, there is a consistent decrease in the apparent draw ratio at which strain-hardening is initiated as the degree of randomness is decreased. As discussed previously, the increase ia stress at apparent uniaxial draw ratios greater than about 3 would be expected to translate into improved optical properties by producing a greater difference in refractive index for those material combinations that strain-harden sooner rather than later as a function of draw ratio. The preceding description of the present invention is merely illustrative, and is not intended to be limiting. For example, reference is frequently made throughout the application to films. However, one skilled in the art will readily appreciate that the teachings set forth herein can be appHed to other optical elements besides optical fihns, such as non-planar optical lenses. Therefore, the scope of the present invention should be construed solely by reference to the appended claims. WE CLAIM: 1. An optical body, comprising: a continuous phase and a disperse phase; wherein at least one of said continuous and disperse phases comprises a first copolymer made from a blend of PEN and PET homopolymers, said copolymer having a mole % NDC composition of between 75% and 50%, wherein the intrinsic viscosity of said copolymer is higher than that attainable from a second copolymer having the same monomers in the same ratio but not made from homopolymers. 2. The optical body as claimed in claim 1, wherein said optical body is a polarizer. 3. The optical body as claimed in claim 1, wherein said optical body is a forward-scattering diffuser. 4. The optical body as claimed in claim 1, wherein said copolymer has a degree of randomness of less than about 70%. 5. The optical body as claimed in claim 1, wherein said copolymer has a degree of randomness of less than about 50%. 6. The optical body as claimed in claim 1, wherein said copolymer has a degree of randomness of less than about 40%. 7. An optical body, comprising: a continuous phase and a disperse phase; wherein at least one of said continuous and disperse phases comprises a first copolymer of at least first and second monomers, and wherein the number average sequence length of said first monomer in said first copolymer is greater than the number average sequence length of said first monomer in a second statistically random copolymer based on the same monomers and ratios of monomers as said first copolymer. 8. The optical body as claimed in claim 7, wherein the number average sequence lenth of said second monomer in said first copolymer is greater than the number average sequence length of said second monomer in said second copolymer. 9. The optical body as claimed in claim 7, wherein said first copolymer corresponds to said continuous phase. 10. The optical body as claimed in claim 7, wherein said first copolymer is synthesized independent of inter-reaction between two or more polymers. 11. The optical body as claimed in claim 7, wherein said first copolymer is the product of inter-reaction between two or more polymers. 12. The optical body as claimed in claim 11, wherein said polymers are homopolymers. 13. The optical body as claimed in claim 12, wherein at least one of said homopolymers comprises polyethylene terephthalate. 14. The optical body as claimed in claim 13, wherein the wt % of said polyethylene terephthalate ranges from 5-95 wt % of said copolymer. 15. The optical body as claimed in claim 12, wherein at least one of said homopolymers comprises polyethylene naphthalate. 16. The optical body as claimed in claim 15, wherein the wt % of said polyethylene naphthalate ranges from 5-95 wt% of said copolymer. 17. The optical body as claimed in claim 12, wherein said homopolymers comprise polyethylene terephthalate and polyethylene naphthalate. 18. The optical body as claimed in claim 11, wherein said inter-reation is a transesterification reaction. 19. The optical body as claimed in claim 18, wherein said inter-reaction achieves a degree of transesterification ranging from essentially 0% to 70%. 20. The optical body as claimed in claim 11, wherein said inter-reaction is a transamidization reaction. 21. The optical body as claimed in claim 7, wherein said optical body is a mirror. 22. The optical body as claimed in claim 7, wherein said optical body is a polarizer. 23. The optical body as claimed in claim 7, wherein said optical body is a diffliser. 24. The optical body as claimed in claim 7, wherein said intrinsic viscosity of said first copolymer is higher than that attainable from said second copolymer. 25. The optical body as claimed in claim 7, said optical body being mechanically oriented along at least a first axis to achieve a strain-induced birefringence. 26. The optical body as claimed in claim 7, said optical body exhibiting a given birefringence at a lower strain than a corresponding optical body containing said second copolymer. 27. The optical body as claimed in claim 7, said optical body exhibiting a birefringence that is higher for a given strain than a corresponding optical body containing said second copolymer. 28. The optical body as claimed in claim 7, wherein said first copolymer has a degree of randomness of less than about 70%. 29. The optical body as claimed in claim 7, wherein said first copolymer has a degree of randomness of less than about 50%. 30. The optical body as claimed in claim 7, wherein said first copolymer has a degree of randomness of less than about 40%.

Full Text

The present invention relates generally to an optical body and more particularly to improvements in the materials used to make such bodies.
Various optical films and devices are known to the art which rely upon refractive index differentials, sometimes produced by strain-induced birefringence, to achieve certain optical effects, such as the polarization of randomly polarized light. Such films and devices may be in the form of a multilayer stack in which index differentials between adjacent layers in the stack give rise to certain optical properties, as in the films disclosed in U.S. Pat. No. 5,882,774 (Jonza et al). Other optical devices comprise a disperse phase which is disposed in a continuous matrix, and derive their optical properties from refractive index differentials between the continuous and disperse phases. The materials disclosed in U.S. Pat. No. 5,825,543 (Ouderkirk et al.) are representative of this type of a system. Various hybrids of the aforementioned systems are also known, such as the multilayer optical films disclosed in U.S. Pat. No. 5,867,316 (Carlson et al), wherein the film comprises a multilayer stack having a repeating layer sequence in which at least one of the layers has a continuous phase/disperse phase morphology. Various other optical films and devices are also known to the art, and are described in U.S. Pat. No. 5,831,375 (Benson, Jr.), U.S. Pat. No. 5,825,542 (Cobb, Jr. et al.), U.S. Pat. No. 5,808,794 (Weber et al.), U.S. Pat. No. 5,783,120 (Ouderkirk et al), U.S. Pat. No. 5,751,388 (Larson), U.S. Pat. No. 5,940,211 (Hikmet et al), U.S. Pat. No. 3,213,753 (Rogers), U.S. Pat. No. 2,604,817 (Schupp, Jr.), Aphonin, O. A., "Optical Properties of Stretched Polymer Dispersed Liquid Crystal Films: Angle-Dependent Polarized Light Scattering", Liquid Crystals, Vol. 19, No. 4, pp. 469-480 (1995), Land, E. H., "Some Aspects of the Development of Sheet Polarizers,.COPYRGT.1951 Optical Society of America, Reprinted from Journal of the Optical Society of America, Vol. 41(12), 957-963, (Dec. 1951), pp. 45-51 and 2244 Research Disclosure (1993), July, No. 351, Emsworth, GB, "Polarizer", pp. 452-453.

In the past several years, a number of advances have been made in the materials sciences, especially in the area of block copolymers, which have resulted in the development of new and interesting materials and methods for making and using these materials to various ends. In some cases, these advances have led to applications in the field of optical films and devices. Thus, for example, Urbas et al., "One-Dimensional Peroidic Reflectors from Self-Assembly Block Copolymer-Homopolymer Blends," Macromolecules, Vol. 32, pages 4748-50 (1999), report the formation of well ordered photonic crystals similar to a: multilayer quarter wave stack comprising self assembling blends of block copolymers optionally containing homopolymers. One embodiment describes the formation of a narrow band reflector. Also summarized is the use of neat block copolymers as well as copolymers comprising Uquid crystalline materials as means of producing periodicities in block copolymer materials.
U.S. Serial No. 08/904,325 (Weber et al.)(corresponding to WO 99u6203) discloses the transesterification or reaction of polyesters lying in adjacent layers of a multilayer optical stack for the express purpose of improving interlayer adhesion. It is assximed that the thickness of the interface comprising the reacted materials is sufficiently thin so as not to otherwise affect the optical properties of the optical stack except at the interface.
U.S. Serial No. 09/006,455 (Merrill et al.)(coiTesponding to WO 9936812) discloses the use of transesterified blends of PEN and PET within a single layer in a multilayer optical stack for the purpose of producing optical devices such as polarizers and mirrors.
U.S. 3,546,320 (Duling et al.) discloses transesterification methods for preparing a semicrystalluie composition comprising 94 to 60 weight percent polyalkylene terephthalates, 6 to 40 weight percent polyalkylene naphthalene-2,6-dicarboxylate, and at least 5 weight percent of a block copolymer comprising discrete polymer segments of the percent polyalkylene terephthalate and the polyalkylene naphthalene-2,6-dicarboxylate. The block copolymer is prepared by melt transesterification of the individual homopolymers, and the degree of transesterification is controlled by the mixing time. Duling demonstrates a total loss of crystallinity of the block copolymer after extensive transesterification, depending on the composition.

U.S. 3,937,754 (Sagamihara et al.) discloses a biaxially oriented polyethylene-2,6-naphthalate (PEN) film containing a polyester resin other than PEN in an amount of 0.5 to 10 percent by weight based on the PEN, and a process for its proi^ictioii. The reference notes that when the PEN resin (1) is blended in the molten state with a polyester resin (2), the softening point of the blended mixture decreases gradually from the softening point of the PEN until it finally reaches a certain point, referred to as an equilibrium softening point The reference teaches that this softening point coincides with the softening point of a PEN copolymer obtained by copolymerising monomers of the same composition and proportion as the monomers which constitute the PEN resin (1) and the polyester resin (2). From this fact, the reference presumes that reaction occurs via a stage of forming a block copolymer, where given enough reaction time a copolymer will be obtained.
Research Disclosures 28,340 and 29,410 disclose transesterified products of PEN, PET, and other polymers comprising dibasic acids. Typical dibasic acids include isophthahc, adipic, glutaric, azelaic, and sebacic acid and the like. The PEN based polymers are generally based on 2,6-naphthalene-dicarboxylic acid but may be based on 1,4-, 1,5-, or 2,7- isomers or mixtures of these isomers. These teachings primarily address the ability to control mechanical and physical properties such as modulus, gaseous permeabihties, and glass transition temperatures.
WO 92/02584 (Cox et al.) disclose the use of phosphite materials to control the rate of transesterification during solid state polymerization, primarily for the intended use of improving physical and mechanical properties, such as gaseous diffusion, in the final product application. The reference discloses blends of PEN and PET homopolymer pellets, which are held at a temperature range between the higher glass transition temperature and the lower melting temperature.
Despite the many advances noted above in the area of optical films and devices, a number of problems still persist in the art. For example, it is often desirable to rely on strain-induced birefiingence to achieve desirable optical properties in an optical film, since the film can be convraiently oriented in a controlled maimer on a laboratory stretcher in accordance with well established methodologies and principles. However, these methodologies do not work equally well for all materials selections. In particular, problems are frequently encountered with the use of thermodynamically immiscible

polymers whose interfacial strength is not large, because the resulting film cannot always be stretched to a high enough draw ratio to achieve an optimal level of birefiingence. In the case of a continons/disperse phase system, for example, oriaiting such a film to the draw ratios required for optimal birefiingence may lead to voiding at the interface between the two phases, thereby compromising the desired optical properties (e.g., polarizing properties) of the system. Voiding of this type is described in U.S. 5,811,493 (Kent), where it is used to produce paper-like films which are difiusely reflective to both polarizations of light. Unfortunately, if lower draw ratios are used to prevent voiding, the resulting fihn may have a lower degree of birefiiugence arid less than optimal optical properties.
There is thus a need in the art for a method for achieving a desired degree of birefiingeace in an optical fihn or device while reducing the draw ratio normally required to achieve the desired level of birefiingence. There is also a need in the art for a method formating optical films and devices from therinodynamically immiscible polymers whose int^dfecial straagth is not large, wherein the fihnsand devices are capable of being oriented to the higher draw ratios frequently required to achieve a higher degree of birefringence and optimal optical properties. These and dther needs are met by the present invention, as hereinafter described.
Brief Description of the Drawings
FIG. 1 is a plot of engineering stress as a fimction of apparent'draw ratio; FIG. 2 is a plot of refractive index in the principle draw direction, Nx, for a positively birefiingent material as a fimction of true draw ratio;
FIG, 3 is a plot of % increase in on-axis gain as a fimction of % randomness; and FIG. 4 is a plot of engineering stress as a fimction of apparent draw ratio.
Summary of the Invention
In one aspect, the present invention relates to a method for making a continnous/disperse phase optical device, such as a mirror, polarizer, or diffiiser, and to optical devices so made. In accordance with the method, at least one of the continuous and disperse phases is fabricated from a blend of homopolymers under conditions that allow

the homopolymers to inter-react (e.g., through transesterification or transamidization) to form a copolymer which can be used to make an optical device having improved physical and optical properties.
In another aspect of the invention, the present invention relates to continuous/disperse phase optical devices made from a blend of homopolymers that are capable of inter-reacting, such devices having better physical and optical properties as compared to an analogous system in which the blend of homopolymers is replaced by a copolymer of the same monomers in the same ratios, but not made from homopolymers. Some of the improved physical and optical effects observed with such a system include increased gain, higher intrinsic viscosities, and an earlier onset of strain-hardening (that is, the optical devices of the present invention exhibit a higher level of birefringence for a given level of strain than their random copolymer coimterparts). The later property is especially advantageous in systems in which the materials of the continuous and disperse phases have poor adhesion, because it allows such systems to achieve a desired degree of birefringence at a lower draw ratio, thereby avoiding or minimizing voiding between the two phases. The degree of inter-reaction may be manipulated through control of processing conditions, such as residence time, so as to achieve desirable properties in the resulting optical device, but the degree of randomness will typically be less than 70%.
The use of a blend of homopolymers in accordance with the method of the present invention allows for the attainment of higher molecular weights (and, therefore, higher intrinsic viscosities) than those achievable with the aforementioned statistically random copolymer analogs. Surprisingly, continuous/disperse phase optical devices which are made with such blends exhibit increased gain as compared to their statistically random analogs, even though the average particle size of the disperse phase in systems made with the blend materials was not observed to be smaller than the average particle size of the disperse phase in systems made with the random copolymer analogs, as might have been expected had there been a larger difference in intrinsic viscosities of the jBnal films.
In another aspect, the present invention relates to a method for making an improved optical device, such as a mirror, polarizer, or diffaser, from a continuous/disperse phase system, and to the optical devices so produced. Surprisingly, applicants have discovered that, when at least one of the continuous and disperse phases comprises a block copolymer.

the degree of randomness of the monomeric units of the copolymer can be manipulated to maximize the strain-induced birefiiagence achievable in the system. In particular, through prcq)erm2nqmlati La a related aspect, the present iuvention relates to a method for improving the physical and optical properties of a continuous/disperse phase optical body in which at least one of the phases comprises a statistically random copolymer of two or more monomers, incorporated into optical devices made according to the method. In accordance with the method, the statistically random copolymer is replaced with a blend of homc^IymeTS of the same monomers, such that the ratios of the monomers remains the same.
Detailed Description of the Invention
As used herein, the following abbreviations have the following meanings: "T"
refers to dimethyl terephthalaie,
'TsP' refers to naphthalene dicarboxylate.
"E" refers to ethylene glycol. .
"coPEN" refers to a copolymer based on naphthalene dicarboxylate and dimethyl terephthalate and ethylene glycol.
"PEN" refers to polyethylene naphthalate.
"PET" refers to polyethylene terephthalate.
"NDC" refers to naphthalene dicarboxylate.
"DMT" refers to dimethyl terephthalate.
"EG" refers to ethylene glycol.
"LV." refers to intrinsic viscosity.
"An" refers to bire&ingence, and is defined as the index of refi*action in the jMiodple draw direction minus the index of refi:action in a perpendicular direction. Where refeared to herein, indices of refraction are measured at 632.8 nm, as the index of re&action typically increases with decreasing wavelength due to dispersion.

In addition to its use in creating block copolymers, solid state polymerization is a process commonly used to increase the molecular weight of polyesters including polyethylenenphthalate (PEN) and polyethyleneterephthalate (PET). As has been taught in prior cases describing continuous and disperse phase optical devices, such as, for example, U.S. Pat. Nos. 5,825,543 (Ouderkirk,et al.), 5,783,120 (Ouderkirk, et al.), and 5,867,316 (Carlson et al.), the particle size of the disperse phase is an important parameter to control in optimizing these devices. Matching the viscosities of the two phases is one method of minimizing and controlling the particle size of the disperse phase. During solid state polymerization, polymer pellets comprising polyesters of the type described are crystallized and then typically raised to a temperature of 235° to 255° C under vacuum of less than 5 torr to drive off the polycondensation by-product ethylene glycol and thus increase molecular weight. Below temperatures of 210° C, solid state polymerization of aromatic polyesters becomes impractical due to extremely slow reaction rates and thus long polymerization times. Long polymerization times can make the process and or materials cost prohibitive. Since the melting point of some random copolyesters are lower than 210° C, the use of higher temperatures will cause an agglomerate of the pellets into an undesirable solid mass. Thus, it is impractical and cost prohibitive to solid state polymerize random copolyethylenenaphthalates with less than about 75 mole percent naphthalate content. Copolymers of polyethylenenaphthalate haviag less than 75 mole percent naphthalate are desirable, however, for use ia optical devices such as polarizers and mirrors due to their improved color, lower dispersion, reduced degradation by light, including UV light, in the range of about 380 to 400 nm, and lower cost. Advantages of low naphthalate content resins are described in applicants copending U.S. Patent Application No. 09/416,462, filed on even date under attorney docket number 55028USA1A.
High molecular.weight copolyethylenenaphthalates with less than about 75 mole percent naphthalate can be created by extrusion blending and transesterifyitig high molecular weight polyethylene terephthalate (PET) with high molecular weight polyethylene naphthalate (PEN). One can achieve higher viscosities of a copolymer of PET and PEN than can be obtained during polymerization in conventional reactor

processes since solid state polymerized PET and PEN with higher viscosities can* be used as starting homopolymers- In accordance with the present invention, the birefringence and ofeer c^cal and physical properties of a continuous/disperse phase syston comprising a statisicaDy random, or nearly random, copolymer of two or more monomers may be impioved by rrolacing the random or nearly random copolymer with a copolymer which comprises the same ratios of the individual monomers, but whose degree of randomness is less than that of a statistically random copolymer. Preferably, the replacement copolymer is a blend of condensation homopolymers of the individual monomers which are capable of inter-reacting with each other (e.g., by undergoing transesterification, transamidization, or similar reactions) to a degree that can be controlled so as to result in a copolymer whose degree of randonmess is less than that of a statistically random copolymer.
Polarizers, mirrors, diflusers, and other optical elements made from the ccamnnous/disperse phase systems of the present invention have several advantages over analogous systems which utilize statistically random copolymers. In particular, the monomer ratios and the degree of transesterification or other inter-reaction can be conveniently controlled at the time of extrusion, thereby allowing one to optimize the amount of birefringence-achievable under a given set of stretching conditions. Moreover, the continuous/disperse phase systems of the present invention can be fabricated from homopolymers which are typically less expensive and more readily available in higher molecular weights than is typically the case with custom copolymers. Additionally, in contrast to a process that requires pre-made copolymer materials, the process of the present invention allows for greater compositional flexibility of the copolymer, in that the composition can be easily controlled or changed during extrusion.
In an optical device comprising a continuous and disperse phase system, one of the methods of improving the optical performance of the device is to maximize the birefringence of at least one of the phases in at least one of three orthogonal directions while minimizing the refractive index mismatch between the two phases along at least another of the orthogonal directions. It has been found in the present invention that a given level of birefringence can be achieved sooner (e.g., at a lower draw ratio) for block copolymers and/or statistically non-random copolym^^ of the type described above than is the case with a statistically random copolymer analog. The ability to achieve a given

degree of birefiitigence at a lower draw ratio is particularly advantageoxis when if is desirable to utilize for the continuous and disperse phases tiliermodynamically immiscible polymers whose interfacial strengths are not large, since the use of a lower draw ratio has less of a tendency to compromise the interfacial contact between the two phases (e.g., by inducing voiding).
In the context of the present invention, transesterification, transesterifying and transesterifies are meant to include reaction of condensation polymers such as polyesters, polyamides, copolyesteramides, and certain methine moieties intended to provide color, UV stability, or other desirable properties. Materials useful in the present invention include polyesters, polyamides, copolyesteramides, as well as other materials, for example those mentioned in U.S. Patent No. 4,617,373 (Pniett et al.).
In many embodiments of the present invention, the degree of transesterification is controlled in the thermoplastic component(s) of at least one phase of a continuous/disperse phase optical device such that a statistically non-random copolymer results which preferably inter-reacts to an extent such that the degree of randomness is less than about 70%, preferably less than about 50%, and more preferably about 40% or lower. Methods available to achieve the desired degree of randomness include melt processes, as well as solid state polymerization processes which can occur prior to melt processing. Various parameters may be used to control the rate of the inter-reaction, including, but not limited to, the molecular weight of the individual blocks and of the entire block copolymer, the temperature of reaction, the state of matter in which the reaction is perfonned (e.g., whether it is performed in the solid or molten state), and the time allowed for the reaction to complete. Optionally, any of the methods may use additives such as stabilizers and antioxidants to further accelerate or retard the rate of inter-reaction.
For example, an optical device useful as a polarizer comprises a continuous phase and a disperse phase. The optical device operates by substantially matching the refractive index between the continuous and disperse phases along at least a first of three orthogonal directions and substantially mismatches the refractive index between the two phases alo;ig at least a second of three orthogonal directions. Mechanisms by which the index is substantially matched in at least a first direction and mismatched along at least a second direction are known to the art and are described, for example, in U.S. Patent No. 5,783,129

and in U.S. Serial Number 09/006,455 (MerriU et al.) (corresponding to WO 9936812), filed on Janoaiy 13,1998.
in briet substantially matching the rejBractive index is largely accomplished by judicioiis selecti Howevea:, when at least one of the continuous or disperse phase materials comprises a copolymer — particularly when the copolymer is capable of strain induced and/OT qui^cent crystallization, it has been determiaed by the present inventors that in ad&dcHi to the degree, temperature, and rate of orientation, the amount of birefiingence that develops will also be dependent upon the degree of randomness of the individual monomer xmits comprising the copolymer or on the intrinsic viscosities of the homopolymers and the resulting copolymer.
In one embodiment, miscible polymers comprising the individual monomers are envisioned as usefiil for the present invention. At least one of the polymers used should ideally be capable of developing a high degree of birefiingence. The differences in birefringence may be due to a wide variety of factors. Without wishing to be restrictive, at least some of these characteristics will include the amount of crystallinity that forms during orientation as weU as the intrinsic birefiingence of the random versus the block copolymer. For a given molecular weight and a copolymer comprising two monomers of equal amounts, the statistically random copolymer and a di-block copolymer define the extremes in attainable degree of randomness.
In an illustrative embodiment, the continuous phase material is a polyester where the monomers comprise dimethyl terephthalate (T), naphthalene dicarboxylate (N)> and ethyiene glycol (E). Homopolymers of these monomers are commonly known as polyelhyiene terephthalate (PET) and polyethjdrae naphthalate (PEN). That is, PET co«ire^)onds to the sequence TE-TE-TE-... and PEN corresponds to the sequence NE-NE-

NE-.... The degree of randomness of NE or TE blocks can be approximated by the ratio of the fraction of obsen'ed NET triads to the statistically random probability of an NET triad, assmning random placement. The procedure to determine triads has been described by Stewart and Cox in Polymer, Vol. 34, pp. 4060-67 (1993). fi can be shown that the statistically random probabihty of NET triads is given by the product: 2 x Wt x Wn, where Wt is the mole fraction of T monomer and Wn is the mole fraction of N monomer. The degree of randomness is defined as the ratio of the fraction of NET triads observed to the theoretical fraction of NET triads in a statistically random copolymer.
For example, a high molecular weight block of a diblock copolymer of 50 mole percent T and 50 mole percent N would have a single NET triad ia each molecule, and hence would exhibit a virtually undetectable fraction of NET triads ia a high molecular weight polymer. The ratio defining the degree of randomness would be approximately zero. The theoretical probability of a NET triad for a random copolymer would be 0.5. The ratio defining the degree of randomness for such a truly raiidoiri copoloymer would be approximately 1.0 (100 percent).
The degree of randomness of NE- or TE- sequences can be approximated using the
following theoretical approach, assuming equivalent reaction ratios of the two monomer
materials. A more sophisticated analysis can be performed for those cases where the
reaction ratios of the monomer units are not equivalent. For the purposes of this
discussion, let: , .,.
Wn = mole fraction NE as charged or as measured by nuclear magnetic resonance spectroscopy (mnr);
Wt = mole fraction TE as charged or as measured by nmr;
Pnn = fraction of NEN sequences as measured by nmr;
Pnt = fraction of NET sequences as measured by nmr; and
Ptt = fraction of TET sequences as measured by nmr. It follows that
Wt + Wn - 1
and
Pnn-f-Pnt-f Ptt =1.

Also, let P(jli) equal the conditional probability of finding a "j" monomer next on the polymer r^m^ given that the currently chosen monomer on the polymer chain is an "i" moasmier sequaice- There are four of these latter quantities, P(ntn), P(n|t), Pt|n) and P(t|t). In the T^nTTt ofM^ molecular weight, the probabiUty of an end group is essentially zero and then ii follows that:
P(n|t) + P(tlt) = l
and
P(nin) + P(t|n) = l. It also follows from the definition of conditional probabilities that
Pnn = P(n|n) * Wn,
Ptt = P(t|t) * Wt, and
Pnt = P(n|t)*Wt + P(t|n)* Wn.
The above equations thus define the conditional probabilities in terms of NMR measurable quantities. In the special case of a random copolymer, the probability of finding a "j" monomer next is independent of "i" and then P(j|i) is merely Wj. Thus, for a random polymer:
■ Pnn=Wn*Wn,
Ptt=Wt*Wt, and
Pnt=2*Wn*Wt, as asserted previously, hi this high molecular weight limit, typically applicable in practice, the definition of % randomness now follows:
% Randomness = Pnt / (2*Wn*Wt) = Pnt(observed)/Pnt(random)
It should be noted that although the Wj's and Pij's are obtained from separate aspects of the nmr grq>hs, there is a further relationship between them. In general, hese relations should also hold:
0.5 * Pnt + Pnn = Wn, and
0.5*Pnt + Ptt = Wt

Particularly in the case of low levels of randomness, experimental error tends to create small discrepancies in these relationships. Given th»e discrepancies, as a practical matter the best definition of percent randomness is based on the experimental (observed) value of Pnt as given above. The probability of a k length sequence of j-monomer units (only vahd when is not on the order of the number of monomers in a single chain, so this assumes the high molecular weight limit) is simply the probability of k-1 successive occurrences given a first occurrence of a "j" monomer times the probability that the k+l monomer is not a "j" monomer. Since every sequence must be some length it follows that:

The more general case of a finite chain is presented by Frensdorff in , Macromolecules, 4, 369 (1971). The conditional probability is sUghtly reduced by the probability of the chain ending, e.g. (P(j | j) is multiplied by an extent of rection near unity. An alternative "recursive" approach with similar results is given by Lopez-Serrano, et. Al. in Polymer, 21, 263 (1980). In any case, the characterization method as described here is appUcable to block copolymers comprising units "A" and "B", and are not limited to the example case where A==NE and B=TE. In the examples to follow, a random copolymer of 70% NE block monomer composition has a number average NE block sequence length of only about 3.. A random copolymer of 50% NE block composition has a number average NE block sequence length of only about 2. While not wishing to be bound by theory, it is believed that when the average sequence length is longer, various physical, optical or mechanical properties maybe improved. For example, the amount of crystallinitymay increase at a given drawing condition leading to higher birefiingence or dimensional

stability. The melting point may also be increased leading to a more stable film than the random case at elevated temperatures. In that refi"active index is a key component to the pec&nnarKe of the c^cal device, then increasing block length should increase and/or mjimf^TTi nwlecuiar OTientadon during and following the drawing processes, pardcularly for optical devices thai are thennally stabilized by annealing or heat setting at elevated temperatures. One of the mechanisms that can stabihze or maintain the molecular orientation is the formation of crystalhtes during the dravraig process. The onset of crystallization during draw can often result in an increase in the drawing force. As a result, a block copolymer capable of crystallization during orientation may exhibit an increase in the stress above and beyond that of a statistically random copolymer cotnprising the same monomers at any given point of a similar drawing process; that is, the block a^x>lymer will tend to strain harden sooner than the statistically random, but otiifswise identical, .copolymer. Concomitant with the sooner strain hardening is a higher refeactive index for a positively birefiingent material in the draw direction and a higher birefringence for a given point in a given drawing process. Higher birefringence typically will result in higher gain when all other quantities are held constant.
In practice, several factors can alter the stress versus draw behavior, which can thus cause a change in the onset of strain hardening. Besides the percent randomness, increasing the molecular weight or LV. of the continuous phase, increasing the relative composition of the block monomer unit with tiae higher glass transition temperature and/or more quickly crystallizing component (such as, for example, NE), and increasing the fraction of dispersed phase (such as, for example, syndiotactic polystyrene (sPS)) prior to a phase inversion, typically accelerate the onset of strain hardening. These factors are illustrative only, and should not be considered limiting. In general, each of these factors may also improve the birefringence and optical gain at noraial incidence for a given set of process conditions.
In the following examples, the continuous phase comprises polyesters whose equihbrium state after transesterification is random or at least nearly random: the percent transesterification being 98% or higher.

COMPARATIVE EXAMPLE 1
A polymeric blend was extruded and cast into a film, using extrusion techniques of the type described in U.S. Patent No. 5,783,120 (OudCTkiEk, et-aL). The blend comprised 57.6 % by weight coPEN (70 mole % PEN and 30 mole % PET) as the continuous phase, 40% by weight Questra MA 405 syndiotactic polystyrene (available commercially from the Dow Qiemical Co., Midland, Michigan) as the disperse phase, and 2.4% by weight Dylark 332 compatibilizer (available commercially from Nova Chemicals). The coPEN had an intrinsic viscosity (I.V.) of 0.57 (measured in 60% phenol, 40% dichlorobenzene).
A sequence analysis was performed on the cast film using proton nuclear magnetic resonance according to the method described in Stewart et al., Polymer^ Vol. 34, pages 4060-4067 (1993). Three sharp resonances were observed corresponding to the ethylene glycol (E) protons in the NEN, NET, and TET triad sequences. The ratio of the observed probability of NET triad sequences to the theoretical probability of a NET triad sequence (expressed as a percentage) defines the degree of randomness. The measured degree of randomness was 98.1%, which implies that the-copolymer was virtually a random copolymer of PEN and PET.
The cast film was oriented first in the machine direction to a draw ratio of about 1.3:1 using a conventional length orienter. The sheet was then oriented imiaxially in the transverse direction using a conventional tenter. The final transverse draw ratio was approximately 5.4:1 based on the rail settings at the entrance and exit of the tenter. The stretch temperature was 118°C (245""F). Following orientation, the film was heat set temperature at 163°C (325°F)
The optical properties of the fihn were measured using a Perkin-Elmer Lambda-19 UV-visible spectrophotometer equipped with an integrating sphere and a Glans-Thompson cube polarizer. The average transmission was 83.5% for wavelengths of light between 400 and 700 nanometers whose polarisation orientation was aligned with the pass direction of the film. Light whose polarization orientation was aUgned with the block direction of the film had an average transmission of 16.3%. Gain was measured by placing the film into a C12P back light cavity. The on-axis luminance of the cavity with the film in place was 40.2% greater than the same apparatus without the film. The luminance at 40° to the

normal axis with the film in place was 28.5% greater than the measured luminance of the apparatus without the film.
CCMPARAUVE EXAMPLE 2
The coPEN from COMPARATIVE EXAMPLE 1 was extraded and cast into a transparoat film, and the degree of randomness was measured to be 99.1%. Hence, the presence of the Questra MA 405 resin in COMPARATIVE EXAMPLE 1 did not appear to alter the ability to measure the degree of randomness of the polyester. The intrinsic viscosity of the final copolymer was measured as 0.526. The cast sheet was uniaxially oriented to anominal stretch ratio of 6:1 in a laboratory batch stretcher at 115° C. The stress-strain relationship of the sheet was measured during orientation and is shown as Cur^e A in FIG. 1. The refiractive index along flie stretch direction at a wavelength of 632-8 nanometers was determined to be 1.766 for a true draw ratio of 5.30:1. In the other QOBi-stretcfa, in-plane direction, the index of refraction was determined to be 1.600. Differential scarming calorimetry was used to measure the crystallinity and an apparent heat of 25.0 J/g was measured with a peak melting temperature of 205^C.
The cast sheet was further oriented to several different uniaxial draw ratios according to the conditions described above, with the exception that the draw temperature was 120"^ C. Using fiduciary marks scribed onto the cast sheet prior to orientation, the true draw ratios could be determined simply by taking the ratio of the distances between the marks following and prior to the orientation. The index of refraction in the principle draw direction was measured for various true draw ratios and are plotted as open circles in FIG. 2. As expected for this positively birefiingent material, an increase in refiractive index in the direction of draw as a fiinction of draw ratio is observed.
EXAMPLES 1-2
A polymeric blend comprising 70 mole % PEN homopolymer and 30 mole % PET homopolymer was extruded and cast into a film. In EXAMPLE 1, the PEN had an LV. of 0-56, and the PET had an LV. of 0.60. The LV. of the final copolymer was measured as 0-535. The degree ofrandomness was 23.4%. In EXAMPLE 2, the PEN had an LV. of 0-36, and the PET had an LV. of 0.85. The LV. of the final copolymer was measured as

0.560. The degree of randomness was 30.9%. Sheets from both EXAMPLES 1 and 2 were transparent.
The sheets of EXAMPLES 1-2 were oriented similarly to the film of COMPARATIVE EXAMPLE 2, and the corresponding stress-strain curves were determined. The stress-strain relationship for EXAMPLES 1 and 2 are shown as Curves B and C, respectively, in FIG. 1. The copolymer of EXAMPLE 1, which has a slightly lower intrinsic viscosity and a lower degree of randomness, shows a sUghtly earlier strain-hardening than the copolymer of EXAMPLE 2. The differences between Curves B and C are. likely not statistically significant. However, the strain-hardening behavior of these curves are significantly different from the corresponding behavior of the statistically random copolymer of COMPABATIVE EXAMPLE 1 (Curve A), where strain-hardening is meant to describe the dependence of stress on the imposed orientational strain.
Cast sheets from EXAMPLES 1 and 2 were oriented to various true draw ratios as described in COMPARATIVE EXAMPLE 2. The refractive indices in the principle draw direction were measured and plotted in FIG. 2 as closed squares and open triangles, respectively. EXAMPLES 1 and 2 exhibit an increase in the refractive index along the direction of draw. Moreover in accordance with an earlier onset of strain-hardening, the refractive indices for EXAMPLES 1 and 2 are higher than the corresponding refractive index for COMPARATIVE EXAMPLE 2 for any given stretch condition.
Differential scanning calorimetry was used to measure the crystallinity. In EXAMPLE 1, an apparent heat fusion equal to 35.9 J/g was measured along with a peak melting temperature of 251° C. In EXAMPLE 2, an apparent heat of fusion equal to 35.3 J/g was measured along with a peak melting temperature of 244° C.
A similar series of stress strain experiments were performed at a draw temperature of 120° C. The strain-hardening appeared at a slightly higher draw ratio for EXAMPLES 1 and 2. The indices of all three were slightly reduced by about 0.01 in the stretch directions.
Without wishing to be bound by any particular theory, it would appear that the increase in stress at apparent uniaxial draw ratios greater than about 3 will translate into improved optical properties. For example, a greater difference in the refractive index between the continuous and disperse phases may be achieved in a continuous phase

matCTial exhibiting strain-hardening behavior relative to a continuous phase material that does not exhibit strain-hardening behavior at the same draw ratio.
FOT an optical (tevice such as a reflective polarizer where the optical properties dq)ead in jxart on the r^'active index differential between the continuous phase and disperse jdiases along at least one axis, the block copolymers exemplified in EXAMPLES 1 and 2 should exhibit an increase in optical properties when used as part of a material combination described in COMPARATIVE EXAMPLE 1.
EXAMPLE 3
A film was prepared ia accordance with the methodology of COMPARATIVE EXAMPLE 1, except that the blend of PEN and PET homopolymers fi-om EXAMPLE 2 was substituted for the coPEN copolymer. The cast film had a degree of randomness of S-7%. The cast film was first oriented to a stretch ratio of 1.25:1 using a conventional kagtii ori^iter, and then drawn to a stretch ratio of 5.1:1 in the transverse direction at 11S°C(245°F). The on-axis gain was 43.8%. The 40° gain was 20.1%.
Relative to COMPARATIVE EXAMPLE 1, this example demonstrates that a mixture of homopolymers and/or a lower degree of randomness may be used to achieve an increase in on-axis gain,
EXAMPLE 4
i' ^^
A film was made in accordance with the methodology of EXAMPLE 3, except .that the PEN and PET homopolymers were those used in EXAMPLE L This sample had a degree of randomness of 10.8%. The on-axis gain was. 42.8%. The 40^ gain was 19.2%.
By comparing EXAMPLE 4 to EXAMPLE 3, it is seen that at a fixed degree of randomness, and nearly identical composition and process conditions, increasing the L V. increases the gain.
EXAMPLES
A film was prepared in accordance with the methodology of EXAMPLE 3, except that the residence time of the melt was substantially increased compared to EXAMPLE 3 by including an additional filtration device in the melt stream. EXAMPLE 5 used two

filters in the melt stream, whereas EXAMPLE 3 used only one filter, so the residence time was approximately doubled. By increasing residence time, the degree of randomness is increased. Control of residence time can be used to control the degree of randonmess. The degree of randomness was 27.9%; the on-axis gain was 43 J2%; and the 40° gain was 18.1%.
This example suggests that residence time associated with the melt affects the degree of randomness. This example also demonstrates that there need not be a linear dependence of optical performance with respect to the degree of randomness.
FIG. 3, which is a plot of on-axis gain versus degree of randonmess for COMPARATIVE EXAMPLE 1 and EXAMPLES 3, 4, and 5, demonstrates the positive effect of blockiness in at least ono of the phases of the continuous/disperse phase reflective polarizing device.
EXAMPLE 6
A film was prepared in accordance with the methodology of EXAMPLE 5 except that the tenter preheat temperature was 140'^ C (285° F) compared to 135° C (275° F) for Example 5. The sample had a degree of randomness of 28.5% and exhibited an on-axis gain of 41.9%.
EXAMPLE?
This example demonstrates yet another range of intrinsic viscosities useful in the present invention. A fikn was made in accordance with the methodology of EXAMPLE 6, except that the PEN had an intrinsic viscosity of 0.48 and the PET had an intrinsic viscosity of 0.72. The sample had a degree of randomness of 25.2% and exhibited an on-axis gain of 40.4%. By comparing EXAMPLE 7 to EXAMPLE 6, it is seen that at nearly identical degrees of randomness and processing conditions, increasing the viscosity of the blended homopolymers increases the gain.
EXAMPLES 8-10
These examples demonstrate that varying degrees of randomness can be obtained for various compositions of PEN and PET.

The films of EXAMPLES 8-10 were prepared in accordance with the methodology of EXAMPLE 4, except that the PEN to PET composition ratios were 65/35, 60/40, and 55/4^5, respectively. The degrees of randomness were 11.7%, 9.4%, and 10.1%, respectively, for EXAMPLES 8, 9, and 10. The on-axis gains were 40.2%, 44.2%, and 43.9%, respectively, for EXAMPLES 8, 9, and 10. It should be noted that the 65/35 sample wa$ stretched at about 10° C hotter than the 60/40 and 55/45 samples, resulting in a lower gain than would be expected and thus the gain values reported are not directly comparable. The 40° gains were 27.0%, 24.8%, and 28.7%, respectively, for EXAMPLES 8, 9, and 10.
EXAMPLE 11
This example illustrates the effect of an increased degree of randomness on gain. A continuous/disperse phase blend was made in accordance with the methodology of Comparative EXAMPLE 1, except that the blend comprised 34.8% by weight of coPEN having a 70/30 mole percent ratio of PEN/PET, 22.8% by weight of 0.85 LV. PET, 40% by " weight of Questra MA 405, and 2.4% by weight of Dylark, resulting in an effective PEN to PEl' ratio of 55/45. The blend was then extruded and cast into a film using methodology similar to that of EXAMPLE 4. The degree of randomness was determined to be 71.0%. The on-axis gain was 37.9%. The 40° gain was 27.6%.
In. comparison to- EXAMPLE 10, where the degree of randomness was 10.1%, the fihn of this example, which had a degree of randomnesstransesterification of 71.0%, exhibited a reduction in gain, both on-axis and at 40°.
COMPARATIVE EXAMPLE 3
A sample of film was prepared from the cast fihn of COMPARATIVE EXAMPLE 1, except that the orientation process was performed on a laboratory batch stretcher where the orientation temperature was 115°C and the final nominal stretch ratio was 6.0:1. Engineering stress measurements were taken during the process of orientation, and are represented as Curve D in FIG. 4. By comparing Curve A from FIG. 1 with Curve D from FIG. 4, it is obvioiis that the addition of a disperse phase altered the strain-hardening behavior, irrespective of the degree of randomness of the continuous phase.

EXAMPLE 12
A film was made in accordance with the methodology of COMPARATIVE EXAMPLE 3, except that it was prepared from cast sheet produced as part of EXAMPLE 3. The stress-strain measxirements are shown as Curve F in FIG. 4,
EXAMPLE 13
A fihn was made in accordance with the methodology of COMPARATIVE EXAMPLE 3, using a cast web prepared similarly to that of EXAMPLE 3 except that the % randomness was 40%, The stress-strain measurements are shown as Curve E in FIG. 4,
Comparison of the three curves in FIG. 4 demonstrate that while the strain-hardening behavior may be altered by the presence of a disperse phase, there is a consistent decrease in the apparent draw ratio at which strain-hardening is initiated as the degree of randomness is decreased.
As discussed previously, the increase ia stress at apparent uniaxial draw ratios greater than about 3 would be expected to translate into improved optical properties by producing a greater difference in refractive index for those material combinations that strain-harden sooner rather than later as a function of draw ratio.
The preceding description of the present invention is merely illustrative, and is not intended to be limiting. For example, reference is frequently made throughout the application to films. However, one skilled in the art will readily appreciate that the teachings set forth herein can be appHed to other optical elements besides optical fihns, such as non-planar optical lenses. Therefore, the scope of the present invention should be construed solely by reference to the appended claims.

WE CLAIM:
1. An optical body, comprising: a continuous phase and a disperse phase; wherein at
least one of said continuous and disperse phases comprises a first copolymer made from a blend of PEN and PET homopolymers, said copolymer having a mole % NDC composition of between 75% and 50%, wherein the intrinsic viscosity of said copolymer is higher than that attainable from a second copolymer having the same monomers in the same ratio but not made from homopolymers.
2. The optical body as claimed in claim 1, wherein said optical body is a polarizer.
3. The optical body as claimed in claim 1, wherein said optical body is a forward-scattering diffuser.
4. The optical body as claimed in claim 1, wherein said copolymer has a degree of randomness of less than about 70%.
5. The optical body as claimed in claim 1, wherein said copolymer has a degree of randomness of less than about 50%.
6. The optical body as claimed in claim 1, wherein said copolymer has a degree of randomness of less than about 40%.
7. An optical body, comprising: a continuous phase and a disperse phase; wherein at least one of said continuous and disperse phases comprises a first copolymer of at least first and second monomers, and wherein the number average sequence length of said first monomer in said first copolymer is greater than the number average sequence length of said first monomer in a second statistically random copolymer based on the same monomers and ratios of monomers as said first copolymer.

8. The optical body as claimed in claim 7, wherein the number average sequence lenth of said second monomer in said first copolymer is greater than the number average sequence length of said second monomer in said second copolymer.
9. The optical body as claimed in claim 7, wherein said first copolymer corresponds to said continuous phase.
10. The optical body as claimed in claim 7, wherein said first copolymer is
synthesized independent of inter-reaction between two or more polymers.
11. The optical body as claimed in claim 7, wherein said first copolymer is the product
of inter-reaction between two or more polymers.
12. The optical body as claimed in claim 11, wherein said polymers are homopolymers.
13. The optical body as claimed in claim 12, wherein at least one of said homopolymers comprises polyethylene terephthalate.
14. The optical body as claimed in claim 13, wherein the wt % of said polyethylene
terephthalate ranges from 5-95 wt % of said copolymer.
15. The optical body as claimed in claim 12, wherein at least one of said
homopolymers comprises polyethylene naphthalate.
16. The optical body as claimed in claim 15, wherein the wt % of said polyethylene
naphthalate ranges from 5-95 wt% of said copolymer.

17. The optical body as claimed in claim 12, wherein said homopolymers comprise
polyethylene terephthalate and polyethylene naphthalate.
18. The optical body as claimed in claim 11, wherein said inter-reation is a transesterification reaction.
19. The optical body as claimed in claim 18, wherein said inter-reaction achieves a degree of transesterification ranging from essentially 0% to 70%.
20. The optical body as claimed in claim 11, wherein said inter-reaction is a transamidization reaction.
21. The optical body as claimed in claim 7, wherein said optical body is a mirror.
22. The optical body as claimed in claim 7, wherein said optical body is a polarizer.
23. The optical body as claimed in claim 7, wherein said optical body is a diffliser.
24. The optical body as claimed in claim 7, wherein said intrinsic viscosity of said first copolymer is higher than that attainable from said second copolymer.

25. The optical body as claimed in claim 7, said optical body being mechanically oriented along at least a first axis to achieve a strain-induced birefringence.
26. The optical body as claimed in claim 7, said optical body exhibiting a given birefringence at a lower strain than a corresponding optical body containing said second copolymer.

27. The optical body as claimed in claim 7, said optical body exhibiting a
birefringence that is higher for a given strain than a corresponding optical body
containing said second copolymer.
28. The optical body as claimed in claim 7, wherein said first copolymer has a degree
of randomness of less than about 70%.
29. The optical body as claimed in claim 7, wherein said first copolymer has a degree of randomness of less than about 50%.
30. The optical body as claimed in claim 7, wherein said first copolymer has a degree of randomness of less than about 40%.

Documents:

500-chenp-2003-abstract.pdf

500-chenp-2003-assignement.pdf

500-chenp-2003-claims duplicate.pdf

500-chenp-2003-claims original.pdf

500-chenp-2003-correspondnece-others.pdf

500-chenp-2003-correspondnece-po.pdf

500-chenp-2003-description(complete) duplicate.pdf

500-chenp-2003-description(complete) original.pdf

500-chenp-2003-drawings.pdf

500-chenp-2003-form 1.pdf

500-chenp-2003-form 18.pdf

500-chenp-2003-form 26.pdf

500-chenp-2003-form 3.pdf

500-chenp-2003-form 5.pdf

500-chenp-2003-pct.pdf

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Patent Number

209215

Indian Patent Application Number

500/CHENP/2003

PG Journal Number

04/2008

Publication Date

25-Jan-2008

Grant Date

22-Aug-2007

Date of Filing

09-Apr-2003

Name of Patentee

M/S. 3M INNOVATIVE PROPERTIES COMPANY

Applicant Address

3M Center, P.O. Box 33427, Saint Paul, Minnesota 55133-3427

Inventors:

#	Inventor's Name	Inventor's Address
1	MERRILL, William	P.O. Box 33427, Saint Paul, MN 55133-3427

PCT International Classification Number

G02B 5/30

PCT International Application Number

PCT/US2001/021355

PCT International Filing date

2001-07-02

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	09/686,460	2000-10-11	U.S.A.