WO2002031540A1 - Optical device containing polymeric material domains having different degrees of randomness - Google Patents
Optical device containing polymeric material domains having different degrees of randomness Download PDFInfo
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- WO2002031540A1 WO2002031540A1 PCT/US2001/020998 US0120998W WO0231540A1 WO 2002031540 A1 WO2002031540 A1 WO 2002031540A1 US 0120998 W US0120998 W US 0120998W WO 0231540 A1 WO0231540 A1 WO 0231540A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
- G02B5/0825—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only
- G02B5/0841—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only comprising organic materials, e.g. polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0808—Mirrors having a single reflecting layer
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates generally to optical devices such as polarizers, diffusers, and mirrors, and more particularly to improvements in the materials used to make such devices.
- Narious 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. 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. 5,825,543 (Ouderkirk et al.) are representative of this type of a system.
- Narious hybrids of the aforementioned systems are also known, such as the multilayer optical films disclosed in U.S. 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.
- Narious other optical films and devices are also known to the art, and are described in U.S. 5,831,375 (Benson, Jr.), U.S. 5,825,542 (Cobb, Jr. et al.), U.S.
- U.S. Serial No. 09/006,455 (Merrill et al.)(corresponding 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. Serial No. 09/006,455 (Merrill et al.)(corresponding 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.
- 3,546,320 discloses transesterification methods for preparing a semicrystalline 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 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 production.
- PEN polyethylene-2,6- naphthalate
- 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.
- 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.
- PEN poly(ethylene glycol)
- PET poly(ethylene glycol)
- Typical dibasic acids include isophthalic, 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 permeabilities, and glass transition temperatures.
- WO 92/02584 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.
- FIG. 1 is a plot of engineering stress as a function of apparent draw ratio
- FIG. 2 is a plot of refractive index in the principle draw direction, Nx, for a positively birefringent material as a function of true draw ratio
- FIG. 3 is a plot of % increase in on-axis gain as a function of % randomness
- FIG. 4 is a plot of engineering stress as a function of apparent draw ratio
- FIG. 5 is a plot of refractive index in the principle draw direction, Nx, for several positively birefringent materials as a function of true draw ratio
- FIG. 6 is a plot of refractive index in the direction Ny transverse to the principle draw direction, for several positively birefringent materials as a function of true draw ratio
- FIG. 7 is a plot of refractive index in the direction Nx perpendicular to the plane of the film for several positively birefringent materials as a function of true draw ratio
- FIG. 8 is a plot of engineering stress as a function of nominal draw ratio.
- the present invention relates to a method for making a continuous/disperse phase optical device, such as a mirror, polarizer, or diffuser, and to optical devices so made.
- a continuous/disperse phase optical device such as a mirror, polarizer, or diffuser
- 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.
- 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 counterparts).
- 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%.
- 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.
- 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 final films.
- the present invention relates to a method for making an improved optical device, such as a mirror, polarizer, or diffuser, from a continuous/disperse phase system, and to the optical devices so produced.
- an improved optical device such as a mirror, polarizer, or diffuser
- the degree of randomness of the monomeric units of the copolymer can be manipulated to maximize the strain-induced birefringence achievable in the system.
- a higher degree of birefringence can be obtained under the same stretching conditions than is achievable for a similar system in which the sequence lengths of the monomeric units are statistically random.
- the present invention 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.
- the statistically random copolymer is replaced with a blend of homopolymers of the same monomers, such that the ratios of the monomers remains the same.
- the present invention relates to optical devices, such as mirrors, polarizers, or diffusers, which have a first material domain of copolymer P r and a second material domain of copolymer P n , and to methods for making the same.
- Copolymers P r and P n are chemically identical in that they are derived from the same monomers and in that the constituent monomers are present in each copolymer in the same ratios.
- copolymer P r possesses a higher degree of randomness than copolymer P n .
- the difference in randomness between the two copolymers may be advantageously utilized to obtain refractive index differentials between the material domains, thereby giving rise to desirable optical properties. In some cases, these differentials may be achieved simply by coextruding the two polymers or by mixing them together; however, in the preferred embodiment, the differentials are achieved through strain-induced birefringence, e.g., by stretching the first and/or second material domains.
- the material domains may be present in a variety of morphologies, but are preferably present as the phases in a continuous/disperse phase film or device or as the layers in a multilayer film or device.
- Such devices may be obtained, for example, by blending or multilayer co- extruding two copolymers under conditions that minimize interdiffusion and chemical reactions such as transesterification between the two phases, and then drawing under conditions (e.g., temperatures) at which only one of the copolymers orients or crystallizes. Adjustment of the molecular weight may also be used between the two phases. For example, a less random copolymer may be chosen as the material of high birefringence.
- the blend or multilayer might then be drawn at a temperature at which the less random copolymer more strongly orients and more quickly crystallizes than the more random copolymer.
- a temperature for draw can be chosen above the melting point of the more random copolymer but below the melting point of the less random copolymer.
- This methodology of obtaining index differentials is applicable to a wide variety of optical devices, but is particularly useful for producing forward-scattering diffusers. Moreover, since the domains are chemically identical, many of the problems that are often encountered with systems based on diverse polymeric materials (e.g., voiding or delamination) are avoided. Devices of this type may be advantageously produced by manipulating the differences in physical properties, such as crystallinity and melting point, which arise from the difference in degree of randomness between the two polymers. Thus, for example, a continuous/disperse phase device may be obtained by blending the two copolymers at a temperature at which only one of the copolymers is molten.
- the present invention relates to optical devices, such as mirrors, polarizers, or diffusers, which have a first material domain of copolymer P r and a second material domain of copolymer P n , and to methods for making the same.
- the copolymers P r and P n need not be identical.
- the degree of randomness of at least one of P r and P n is manipulated to increase or decrease the refractive index differentials between the two domains along at least one axis.
- the degree of randomness of at least one of the copolymers maybe decreased to produce a larger refractive index differential between the two material domains along at least one axis.
- the present invention relates to a method for making an optical device, and to an optical device so made.
- at least two copolymers P r and P n are provided, wherein each of P r and P n are polyesters, wherein P r and P n are derived from monomers selected from the group consisting of monomers m ls ..., ⁇ i k , wherein the % by weight of each of monomers mi, ..., m k present in P r , based on the total weight of P r , is w rl , ..., w rk , respectively, wherein the % by weight of each of monomers m s ..., m present in P n , based on the total weight of P n , is w nl , ..., w nk , respectively, wherein the magnitude of the vector I w r - w n
- the difference in degree of randomness may be obtained, for example, by controlling the degree of inter- polymerization or blockiness within the copolymers P r and P n such that P r is more extensively trans-polymerized than P n .
- k will be at least about 30%, more preferably at least about 50%, and most preferably at least about 60%.
- a similar relationship may be employed using % molar volumes in place of weight %.
- An article such as a film is then created from the copolymers P r and P n such that the copolymers are present as first and second material domains within the article, and such that the absolute value of the difference in refractive indices between the first and second material domains is at least 0.02, more preferably at least 0.03, and most preferably at least 0.05 along a first axis, and is less than 0.01, and preferably essentially zero, along a second axis.
- the material domains may be present, for example, as the phases in a continuous/disperse phase film, or as distinct layers in a multilayer film.
- the index differentials may be advantageously obtained by stretching the film in at least one direction, although the present invention also contemplates other known methods of obtaining the desired refractive index differentials. Because of the chemical similarity of the first and second material domains, optical devices made in accordance with this methodology exhibit superior physical properties (e.g., improved resistance to delamination or voiding), while the difference in degree of randomness or blockiness in the copolymers gives rise to desirable optical properties.
- T refers to dimethyl terephthalate
- N 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 dimethyl terephthalate
- EG ethylene glycol
- ⁇ n refers to birefringence, and is defined as the index of refraction in the principle draw direction minus the index of refraction in a perpendicular direction. Where referred to herein, indices of refraction are measured at 632.8 nm, as the index of refraction typically increases with decreasing wavelength due to dispersion.
- solid state polymerization is a process commonly used to increase the molecular weight of polyesters including polyethylenenphthalate (PEN) and polyethyleneterephthalate (PET).
- PEN polyethylenenphthalate
- PET polyethyleneterephthalate
- 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.
- 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.
- 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.
- 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.
- Copolymers of polyethylenenaphthalate having less than 75 mole percent naphthalate are desirable, however, for use in optical devices such as polarizers and mirrors due to their improved color, lower dispersion, reduced degradation by light, including UN 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. 09/416462 filed on even date herewith under attorney docket number 55028USA1A.
- High molecular weight copolyethylenenaphthalates with less than about 75 mole percent naphthalate can be created by extrusion blending and transesterifying high molecular weight polyethylene terephthalate (PET) with high molecular weight polyethylene naphthalate (PEN).
- PET high molecular weight polyethylene terephthalate
- PEN high molecular weight polyethylene naphthalate
- the birefringence and other optical and physical properties of a continuous/disperse phase system comprising a statistically random, or nearly random, copolymer of two or more monomers may be improved by replacing 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.
- 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 randomness is less than that of a statistically random copolymer.
- Polarizers, mirrors, diffusers, and other optical elements made from the continuous/disperse phase systems of the present invention have several advantages over analogous systems which utilize statistically random copolymers.
- 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.
- 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.
- 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.
- 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 copolymers of the type described above than is the case with a statistically random copolymer analog.
- 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, UN stability, or other desirable properties.
- 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.
- Narious 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 performed (e.g., whether it is performed in the solid or molten state), and the time allowed for the reaction to complete.
- any of the methods may use additives such as stabilizers and antioxidants to further accelerate or retard the rate of inter-reaction.
- 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 along 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 (Merrill et al.) (corresponding to WO 9936812), filed on January 13, 1998.
- substantially matching the refractive index is largely accomplished by judicious selection of materials and processing techniques. For example, orientation of a material along a first direction may alter the refractive index in that and other directions by an amount that depends upon the temperature and rate of orientation. Therefore, in order to match the refractive index of the continuous phase with that of the disperse phase, one must start with materials whose nominal refractive indices are appropriately different from one another, such that the birefringence that develops during orientation in one or both phases produces the substantial match.
- the continuous or disperse phase materials comprises a copolymer — particularly when the copolymer is capable of strain induced and/or quiescent crystallization, it has been determined by the present inventors that in addition to the degree, temperature, and rate of orientation, the amount of birefringence that develops will also be dependent upon the degree of randomness of the individual monomer units comprising the copolymer or on the intrinsic viscosities of the homopolymers and the resulting copolymer.
- miscible polymers comprising the individual monomers are envisioned as useful for the present invention.
- At least one of the polymers used should ideally be capable of developing a high degree of birefringence.
- 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 well as the intrinsic birefringence of the random versus the block copolymer.
- the statistically random copolymer and a di-block copolymer define the extremes in attainable degree of randomness.
- the continuous phase material is a polyester where the monomers comprise dimethyl terephthalate (T), naphthalene dicarboxylate (N), and ethylene glycol (E). Homopolymers of these monomers are commonly known as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). That is, PET corresponds 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 observed NET triads to the statistically random probability of an NET triad, assuming random placement.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- 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 in each molecule, and hence would exhibit a virtually undetectable fraction of NET triads in 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 random copoloymer would be approximately 1.0 (100 percent).
- Wn mole fraction NE as charged or as measured by nuclear magnetic resonance spectroscopy (nmr);
- 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
- Ptt fraction of TET sequences as measured by nmr.
- i) the conditional probability of finding a "j" monomer next on the polymer chain given that the currently chosen monomer on the polymer chain is an "i" monomer sequence.
- P(n)n) the probability of finding a "j" monomer next on the polymer chain
- t) the probability of finding a "j" monomer next on the polymer chain
- Ptt P(t
- Pnt P(n
- the probability of a k length sequence of j -monomer units (only valid when ⁇ k> 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+1 monomer is not a "j" monomer. Since every sequence must be some length it follows that:
- the amount of crystallinity may increase at a given drawing condition leading to higher birefringence or dimensional stability.
- the melting point may also be increased leading to a more stable film than the random case at elevated temperatures.
- refractive index is a key component to the performance of the optical device
- increasing block length should increase and/or maintain molecular orientation during and following the drawing processes, particularly for optical devices that are thermally stabilized by annealing or heat setting at elevated temperatures.
- One of the mechanisms that can stabilize or maintain the molecular orientation is the formation of crystallites during the drawing process. The onset of crystallization during draw can often result in an increase in the drawing force.
- a block copolymer capable of crystallization during orientation may exhibit an increase in the stress above and beyond that of a statistically random copolymer comprising the same monomers at any given point of a similar drawing process; that is, the block copolymer will tend to strain harden sooner than the statistically random, but otherwise identical, copolymer.
- Concomitant with the sooner strain hardening is a higher refractive index for a positively birefringent 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.
- the continuous phase comprises polyesters whose equilibrium state after transesterification is random or at least nearly random: the percent transesterification being 98% or higher.
- 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 (Ouderkirk, 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
- the coPEN had an intrinsic viscosity (IN.) of 0.57 (measured in 60% phenol, 40% dichlorobenzene).
- 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 uniaxially 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 film were measured using a Perkin-Elmer Lambda- 19 UN- 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 polarization orientation was aligned with the pass direction of the film.
- Light whose polarization orientation was aligned 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.
- the coPE ⁇ from COMPARATIVE EXAMPLE 1 was extruded and cast into a transparent 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 a nominal 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
- Curve A in FIG. 1 The refractive index along the stretch direction at a wavelength of 632.8 nanometers was determined to be 1.766 for a true draw ratio of 5.30:1. h the other non-stretch, in-plane direction, the index of refraction was determined to be 1.600. Differential scanning 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.
- 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.
- EXAMPLES 1-2 A polymeric blend comprising 70 mole % PEN homopolymer and 30 mole % PET homopolymer was extruded and cast into a film.
- the PEN had an IN. of 0.56
- the PET had an IN. of 0.60.
- the IN. of the final copolymer was measured as 0.535.
- the degree of randomness was 23.4%.
- the PEN had an IN. of 0.56, and the PET had an IN. of 0.85.
- the IN. 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 slightly earlier strain- hardening than the copolymer of EXAMPLE 2.
- the differences between Curves B and C are likely not statistically significant.
- 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.
- a film was prepared in accordance with the methodology of COMPARATIVE EXAMPLE 1 , except that the blend of PEN and PET homopolymers from EXAMPLE 2 was substituted for the coPEN copolymer.
- the cast film had a degree of randomness of 8.7%.
- the cast film was first oriented to a stretch ratio of 1.25:1 using a conventional length orienter, and then drawn to a stretch ratio of 5.1 : 1 in the transverse direction at 118°C (245°F).
- the on-axis gain was 43.8%.
- the 40° gain was 20.1%.
- 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.
- a film was made in accordance with the methodology of EXAMPLE 3, except that the PEN and PET homopolymers were those used in EXAMPLE 1. This sample had a degree of randomness of 10.8%. The on-axis gain was 42.8%. The 40° gain was 19.2%.
- EXAMPLE 4 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 IN. increases the gain.
- 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.
- the degree of randomness is increased. Control of residence time can be used to control the degree of randomness.
- the degree of randomness was 27.9%; the on-axis gain was 43.2%; and the 40° gain was
- FIG. 3 is a plot of on-axis gain versus degree of randomness for
- COMPARATIVE EXAMPLE 1 and EXAMPLES 3, 4, and 5 demonstrates the positive effect of blockiness in at least one of the phases of the continuous/disperse phase reflective polarizing device.
- 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 7 This example demonstrates yet another range of intrinsic viscosities useful in the present invention.
- a film 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%.
- EXAMPLE 7 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.
- 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 55/45, 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.
- the 40° gains were 27.0%, 24.8%, and 28.7%, respectively, for EXAMPLES 8, 9, and 10.
- 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 IN. PET, 40% by weight of Questra MA 405, and 2.4% by weight of Dylark, resulting in an effective PEN to PET 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%.
- the degree of randomness was 10.1%
- the film of this example which had a degree of randomness 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 film of COMPARATIVE EXAMPLE
- 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
- a film 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 in 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.
- EXAMPLES 14-16 were made in accordance with the methodology of EXAMPLES 1-2.
- EXAMPLE 14 (depicted as Ul in FIGS. 5-7), the material was a statistically random coPEN with an intrinsic viscosity of 0.57 and was 99.1% transesterified.
- EXAMPLE 15 (depicted as U3 in FIGS. 5-7), the material was a 70%/30% blend of PEN and PET. The PEN had an intrinsic viscosity of 0.56 and the PET had an intrinsic viscosity of 0.58. The material was 23.4% transesterified.
- EXAMPLE 16 (depicted as U7 in FIGS. 5-7), the material was a 70%/30% blend of PEN and PET.
- the PEN had an intrinsic viscosity of 0.56 and the PET had an intrinsic viscosity of 0.85.
- the material was 30.9% transesterified.
- the melting points of Ul, U3 and U7 were found to be 205°C, 251°C, and 244°C, respectively.
- the glass transition temperatures of Ul, U3 and U7 were found to be 104.7°C, 111.9°C, and 105.4°C, respectively.
- the refractive indices of all three materials were measured as a function of true draw ratio at both 115°C and 120°C. The results are depicted in FIGS. 5-7.
- the engineering stress as a function of nominal draw ratio was determined for each of these materials at both 115°C and 120°C.
- the results are depicted in FIG. 8.
Abstract
Description
Claims
Priority Applications (4)
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EP01948859A EP1325359A1 (en) | 2000-10-11 | 2001-07-02 | Optical device containing polymeric material domains having different degrees of randomness |
AU2001270285A AU2001270285A1 (en) | 2000-10-11 | 2001-07-02 | Optical device containing polymeric material domains having different degrees ofrandomness |
KR10-2003-7005052A KR20030038809A (en) | 2000-10-11 | 2001-07-02 | Optical device containing polymeric material domains having different degrees of randomness |
JP2002534872A JP2004511627A (en) | 2000-10-11 | 2001-07-02 | Optical element including polymer material regions with different degrees of randomness |
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US09/686,519 US6627300B1 (en) | 1997-10-12 | 2000-10-11 | Optical device containing polymeric material domains having different degrees of randomness |
US09/686,519 | 2000-10-11 |
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PCT/US2001/020998 WO2002031540A1 (en) | 2000-10-11 | 2001-07-02 | Optical device containing polymeric material domains having different degrees of randomness |
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US (1) | US6627300B1 (en) |
EP (1) | EP1325359A1 (en) |
JP (1) | JP2004511627A (en) |
KR (1) | KR20030038809A (en) |
CN (1) | CN1470001A (en) |
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WO2012099794A3 (en) * | 2011-01-18 | 2012-10-04 | 3M Innovative Properties Company | Optical film stack |
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US6834956B2 (en) * | 2002-12-27 | 2004-12-28 | International Polarizer, Inc. | Thermoformable polarized lens with substrate having adjusted glass transition temperature |
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US9046656B2 (en) * | 2008-11-18 | 2015-06-02 | 3M Innovative Properties Company | Isotropic layer of multilayer optical film comprising birefringent thermoplastic polymer |
CN109385110A (en) * | 2018-10-08 | 2019-02-26 | 安徽大学 | A kind of anti-mildew halogen-free flameproof bamboo-plastic composite material and preparation method thereof |
US11628656B2 (en) | 2021-01-29 | 2023-04-18 | Meta Platforms Technologies, Llc | Birefringent polymer having bimodal molecular weight |
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Also Published As
Publication number | Publication date |
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US6627300B1 (en) | 2003-09-30 |
EP1325359A1 (en) | 2003-07-09 |
KR20030038809A (en) | 2003-05-16 |
JP2004511627A (en) | 2004-04-15 |
CN1470001A (en) | 2004-01-21 |
AU2001270285A1 (en) | 2002-04-22 |
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