# Patent

## Title
Multilayer optical films having side-by-side mirror/polarizer zones

## Abstract

A reflective film includes interior layers that selectively reflect light by constructive or destructive interference, the layers extending from a first to a second zone of the film. In the first zone, the layers operate substantially as a reflective polarizer; in the second zone they operate substantially as a mirror. The layers may thus provide a first reflective characteristic in the first zone wherein normally incident light of one polarization state is substantially reflected and normally incident light of an orthogonal polarization state is substantially transmitted, and a second reflective characteristic in the second zone wherein normally incident light of any polarization state is substantially reflected. The film may have a first thickness in the first zone that is substantially the same as a second thickness in the second zone. Alternatively, the second thickness may be substantially less than the first thickness. Related methods, articles, and systems are also disclosed.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional of U.S. application Ser. No. 13/139,838, filed Jun. 15, 2011, now allowed, which is a US 371 application based on PCT/US2009/069120, filed on Dec. 22, 2009, which claims the benefit of U.S. Provisional Application Nos. 61/139,736, filed Dec. 22, 2008; 61/157,996, filed Mar. 6, 2009; and 61/158,006, filed Mar. 6, 2009, the disclosures of which are incorporated by reference in their entirety herein.


FIELD OF THE INVENTION
This invention relates generally to optical films, with particular application to such films whose reflection characteristics are determined in large part by constructive and destructive interference of light reflected from interfaces between layers disposed within the film, i.e., internal to the film. The invention also relates to associated systems and methods.
BACKGROUND
Multilayer optical films, i.e., films that contain a multiplicity of distinct layers of different refractive index and of suitable thicknesses to selectively reflect and transmit light as a result of constructive and destructive interference of light reflected at the interfaces between the layers, are known. In some cases, such films are formed by vacuum depositing alternating layers of a high refractive index inorganic material, such as titanium dioxide, and a low refractive index inorganic material, such as silicon dioxide, onto a glass substrate or other rigid substrate.
In other cases, such films are formed by coextruding different organic polymer materials in an alternating layer arrangement through a die, cooling the extrudate to form a cast web, and stretching the cast web in order to thin the web to a suitable final thickness. In some cases the stretching may also be carried out in such a way as to cause one or both of the alternating polymer materials to become birefringent, i.e., wherein a given material has a refractive index for light polarized along one direction that differs from a refractive index for light polarized along a different direction.
This birefringence may result in the finished film having a large refractive index mismatch between adjacent layers along a first in-plane direction (sometimes referred to as an x-axis or block axis), and a substantial refractive index match between adjacent layers along a second in-plane direction (sometimes referred to as a y-axis or pass axis), whereupon normally incident light polarized along the first direction is highly reflected and normally incident light polarized along the second direction is highly transmitted. See, e.g., U.S. Pat. No. 3,610,729 (Rogers), U.S. Pat. No. 4,446,305 (Rogers et al.), and U.S. Pat. No. 5,486,949 (Schrenk et al.). Such a film is typically referred to as a reflective polarizer.
The birefringence may also result in a refractive index difference between adjacent layers along an out-of-plane direction (i.e., along an axis perpendicular to the film) that differs significantly from a refractive index difference between adjacent layers along one or both in-plane directions. An example of this latter situation is a film having substantially the same large refractive index mismatch between adjacent layers along both orthogonal in-plane directions (x and y), such that normally incident light of any polarization is highly reflected, but where the refractive indices of adjacent layers along the out-of-plane direction (z) are substantially matched, such that the reflectivity of the interfaces for so-called “p-polarized” light (light polarized in the plane of incidence) is substantially constant. See, e.g., U.S. Pat. No. 5,882,774 (Jonza et al.). Such a film may typically be referred to as a mirror or mirror-like film by virtue of its high reflectivity for normally incident light of any polarization. Jonza et al. teach, among other things, how a z-axis mismatch in refractive index between adjacent microlayers, more briefly termed the z-index mismatch or Δnz, can be tailored to allow the construction of multilayer stacks for which the Brewster angle—the angle at which reflectance of p-polarized light at an interface goes to zero—is very large or is nonexistent. This in turn allows for the construction of multilayer mirrors and polarizers whose interfacial reflectivity for p-polarized light decreases slowly with increasing angle of incidence, or is independent of angle of incidence, or increases with angle of incidence away from the normal direction. As a result, multilayer films having high reflectivity for both s-polarized light (light polarized perpendicular to the plane of incidence) and p-polarized light for any incident direction in the case of mirrors, and for the selected direction in the case of polarizers, over a wide bandwidth, can be achieved.
It is also known to impart a pattern to multilayer optical films to form indicia. See, e.g., U.S. Pat. No. 6,045,894 (Jonza et al.) “Clear to Colored Security Film”, U.S. Pat. No. 6,531,230 (Weber et al.) “Color Shifting Film”, and U.S. Pat. No. 6,788,463 (Merrill et al.) “Post-Formable Multilayer Optical Films and Methods of Forming”. Pressure is selectively applied to the film, such as with an embossing die, to thin the film in selected areas or zones to produce the desired pattern. The selective thinning, which may produce a thickness reduction greater than 5% or greater than approximately 10%, is effective throughout the thickness of the film in the selected areas, such that the stack of optically thin layers (“microlayers”) internal to the film, which microlayers are responsible for the observed reflective and transmissive characteristics, is also thinned in the selected areas relative to neighboring areas of the film. This thinning of the microlayers shifts any reflection bands associated with the microlayers to shorter wavelengths as a result of the shortened optical path length difference through the microlayers. The shift in the reflection band is manifested to the observer as a difference in reflected or transmitted color between the embossed and unembossed areas, so that the pattern is readily perceived.
For example, the '463 Merrill et al. patent describes an embossed color shifting security film in which a multilayer polymer film containing 418 internal microlayers (two packets of 209 microlayers each) was embossed in selected regions. Before embossing, and in unembossed areas after embossing, the microlayers had refractive indices and thicknesses that produced a reflection band whose short wavelength band edge shifted with incidence angle (viewing angle) from 720 nm at normal incidence, to 640 nm at 45 degree viewing, to an even shorter wavelength at 60 degree viewing, corresponding to a clear appearance at normal, to cyan at 45 degrees, to a brilliant cyan at 60 degrees. In these unembossed areas the film had a thickness of 3.4 mils, i.e., 0.0034 inches. The film was then embossed between a roll at 149 degrees C. and a pre-heated embossing plate to thin the film down to about 3.0 mils in the selected areas. The embossed areas exhibited a bright gold color at normal incidence, indicative of a band edge shift from 720 nm to shorter wavelengths. The observed color in the embossed areas changed to cyan or deeper blue at oblique viewing angles.
BRIEF SUMMARY
We describe herein, among other things, multilayer optical films that can incorporate both a polarizer and a mirror in a side-by-side arrangement in a film construction that is continuous or unitary at least in the in-plane direction from the polarizer to the mirror. Thus, the same microlayers that form all or a substantial part of the polarizer in one zone of the film may form all or a substantial portion of the mirror in another, e.g., neighboring or adjacent, zone of the film. The polarizer and mirror may both be broad-band, e.g., reflecting over an extended wavelength band that includes the visible spectrum, or may both be relatively narrow band, e.g. reflecting over only a portion of the visible spectrum so as to provide a colored appearance in reflected and/or transmitted light. For the polarizer, of course, such reflection in either case occurs predominantly or exclusively for light of a first polarization state (referred to as a block polarization state or simply a block state) rather than for light of a second polarization state (referred to as a pass polarization state or simply a pass state) perpendicular to the first polarization state. The polarizer and mirror may be arranged in zones having in-plane shapes that define a desired pattern, e.g., indicia. These zones may be complementary over at least some portions of the film such that the polarizer may, for example, form a background and the mirror may form a foreground of the indicia.
The unitary polarizer/mirror film may be fabricated using a process that includes coextruding a plurality of polymer layers, casting the layered extrudate, and stretching or otherwise orienting the cast film to induce birefringence in at least some layers that form a coherent stack or packet of optically thin layers. The stretched film may at this point be a narrow band or broad-band reflective polarizer over substantially its entire area, with high reflectivity for normally incident light of a selected wavelength of the block polarization state and low reflectivity for normally incident light of the selected wavelength of the pass polarization state. The difference in reflectivity of the pass and block polarization states is a consequence of the birefringence of the optically thin layers within the film. In a subsequent step, selected portions or zones of the film may be selectively heated so as to reduce or eliminate this birefringence in the selected zones without reducing the birefringence in the remaining portions of the film, and while maintaining the physical integrity of the layer structure within the film in the selected (or “treated”) zones. With appropriate materials selection, and with appropriate film design, e.g., a sufficient number of optically thin layers in the packet, the reduced birefringence may result in a modified layer packet in the selected or treated zones that substantially reflects light of any polarization, i.e., that acts as a narrow band or broad-band mirror.
In some cases, discussed extensively below, the selective heating that provides the reduced birefringence in the treated zones may be accomplished, at least in part, by illuminating the film in such zones with high intensity radiation which is then absorbed by the film or selected layers thereof to provide absorptive heating. This absorptive heating technique can be carried out without any selective application of external pressure or force to the treated zones, and in some cases without any significant thinning of the film in the treated zones. An alternative technique that one may wish to employ to selectively heat the treated zones so as to reduce the birefringence of constituent layers thereof, while maintaining the structural integrity (but not the thicknesses) of such layers, involves embossing the film with a heated embossing tool under carefully controlled conditions with appropriate embossing tool temperature, applied pressure, and dwell time. This possible alternative technique does, of course, involve the selective application of pressure and force to the treated zones, and does produce a thinning of the film (with a corresponding band shift to shorter wavelengths) in the treated zones. Still other techniques to selectively heat the treated zones may also be employed, including any suitable combination of convective heating, conductive heating, and radiative heating, with or without applied pressure.
With the absorptive heating technique, the selective birefringence reduction is accomplished by the judicious delivery of an appropriate amount of energy to a second zone (without the delivery of such energy to an untreated first zone) of the film so as to selectively heat at least some of the interior layers therein to a temperature high enough to produce a relaxation in the material that reduces or eliminates a preexisting optical birefringence, but low enough to maintain the physical integrity of the layer structure within the film. The reduction in birefringence may be partial or it may be complete, in which case interior layers that are birefringent in the first zone are rendered optically isotropic in the second zone. In exemplary embodiments, the selective heating is achieved at least in part by selective delivery of light or other radiant energy to the second zone of the film. The light may comprise ultraviolet, visible, or infrared wavelengths, or combinations thereof. At least some of the delivered light is absorbed by the film to provide the desired heating, with the amount of light absorbed being a function of the intensity, duration, and wavelength distribution of the delivered light, and the absorptive properties of the film. This absorptive heating technique for internally patterning a multilayer optical film is compatible with known high intensity light sources and electronically addressable beam steering systems, thus allowing for the creation of virtually any desired pattern or image in the film by simply steering the light beam appropriately, without the need for dedicated hardware such as image-specific embossing plates or photomasks.
We also describe a multilayer optical film that includes a plurality of interior layers arranged to selectively reflect light by constructive or destructive interference, the layers extending from a first zone to a second zone of the film. In the first zone, the plurality of layers provides a first reflective characteristic representative of a reflective polarizer, i.e., normally incident light of one polarization state is substantially reflected and normally incident light of an orthogonal polarization state is substantially transmitted. In the second zone, the plurality of layers provides a second reflective characteristic representative of a mirror, i.e., normally incident light of any polarization state is substantially reflected.
If the absorptive heating technique is used to convert the first reflective characteristic to the second reflective characteristic, the difference between these reflective characteristics is not substantially attributable to any difference between a first thickness of the film in the first zone and a second thickness of the film in the second zone, which difference in thickness may be zero. In one example, the film may exhibit a variability in thickness Δd over the first zone, such as may be expected from normal processing variability, and the second thickness may differ from the first thickness by no more than Δd, where the first and second thicknesses are taken to be spatial averages of the film thickness over the first and second zones, respectively. In some cases, the film may include one or more absorbing agents in one or more constituent layers thereof to promote heating during the patterning procedure.
The substantial reflection of the first reflective characteristic may be limited to a first spectral band, and the substantial reflection of the second reflective characteristic may be limited to a second spectral band. If the absorptive heating technique is used to pattern the film, and there is no substantial difference in film thickness between the first and second zones, the first and second spectral bands may also then be substantially the same. If instead an embossing technique is employed, such that there is a substantial difference in film thickness between the first and second zones, then the first and second spectral bands will be substantially different.
In some cases, the first reflective characteristic may be such that normally incident light of the one polarization state and of a first wavelength is reflected by at least 70%, or 80%, or 90%. The first reflective characteristic may also be such that normally incident light of the orthogonal polarization state and of the first wavelength is reflected by no more than 30%, or 20%, or 10%, for example. The second reflective characteristic may be such that normally incident light of any polarization state and of a first wavelength is reflected by at least 50%, or 70%, or 80%.
We also describe a method of making a patterned multilayer optical film, that includes providing a multilayer optical film that comprises a plurality of interior layers arranged to provide a first reflective characteristic associated with constructive or destructive interference of light and characterized by a high reflectivity for normally incident light of one polarization and a low reflectivity for normally incident light of an orthogonal polarization, the interior layers extending from a first zone to a second zone of the film, and the first and second zones each exhibiting the first reflective characteristic. The method also includes selectively heating the film in the second zone in an amount sufficient to cause the second zone to exhibit a second reflective characteristic that is also associated with constructive or destructive interference of light, but that is characterized by a high reflectivity for normally incident light of any polarization. The selective heating may be carried out without any substantial reduction in thickness of the film in the second zone, and without any selective application of pressure to the film. Alternatively, the selective heating may be carried out with selective application of pressure to the film.
The first reflective characteristic may have a first reflectivity for normally incident light of the one polarization and of a first wavelength, and may have a second reflectivity for normally incident light of the orthogonal polarization and of the first wavelength. The second reflective characteristic may have a third reflectivity for normally incident light of the one polarization and of the first wavelength, and may have a fourth reflectivity for normally incident light of the orthogonal polarization and of the first wavelength. In exemplary embodiments, the third reflectivity is less than the first reflectivity, and the fourth reflectivity is greater than the third reflectivity.
Related methods, systems, and articles are also discussed.
These and other aspects of the present application will be apparent from the detailed description below. In no event, however, should the above summaries be construed as limitations on the claimed subject matter, which subject matter is defined solely by the attached claims, as may be amended during prosecution.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a roll of multilayer optical film having reflective polarizer characteristics that has been internally patterned to provide reflective mirror characteristics in different portions or zones of the film so as to form indicia;
FIG. 2 is a schematic side view of a portion of a multilayer optical film;
FIG. 3 is a schematic sectional view of a portion of the multilayer optical film of FIG. 1;
FIG. 4 is a schematic sectional view of a portion of another multilayer optical film with internal patterning;
FIGS. 5A-G are idealized plots showing each refractive index (nx, ny, nz) of each layer of a 2-layer optical repeat unit, for different states of manufacture of various internally patterned unitary polarizer/mirror films;
FIG. 6 is a schematic side view of an arrangement for selectively heating a multilayer optical film to accomplish internal patterning;
FIGS. 7A-C are schematic top views of different second zones of a patterned multilayer film, and superimposed thereon possible paths of a light beam relative to the film capable of forming the depicted zones;
FIG. 8A is an idealized plot showing the relative intensity of a beam of light as a function of the depth the light beam propagates into the film, with three curves provided for three different multilayer optical films;
FIG. 8B is an idealized plot showing the local absorption coefficient as a function of the depth or axial position within the film, with three curves corresponding to the three curves of FIG. 8A;
FIG. 9 is a graph of percent transmission versus wavelength for different cast multilayer webs that were fabricated;
FIG. 10 is a graph of percent transmission versus wavelength for a multilayer optical film made using one of the cast webs of FIG. 9;
FIG. 11 is a graph of percent transmission versus wavelength for a treated and untreated zone of a composite multilayer optical film that includes an internally patterned polarizer/mirror multilayer optical film made using one of the cast webs of FIG. 9, where the percent transmission is measured for light of a first or block polarization state; and
FIG. 12 is a graph of percent transmission versus wavelength for the same treated and untreated zone of the same composite multilayer optical film as that of FIG. 11, but where the percent transmission is measured for light of a second or pass polarization state.



In the figures, like reference numerals designate like elements.
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
In at least some embodiments, the disclosed unitary polarizer/mirror multilayer optical films can be made using patterning techniques that do not rely on a selective thinning of the film to accomplish the patterning. For example, one or more mirror zones may be formed in an initially spatially uniform reflective polarizing film using the absorptive heating technique mentioned above, in which a multilayer optical film is selectively heated in at least one zone by exposing the film to suitable directed radiation, without any selective application of pressure, in such a way that birefringence of at least some interior layers is reduced or eliminated in the selected zone but not in a neighboring zone, while substantially maintaining the physical integrity of the layer structure in the selected (treated) zone, so as to change the reflective properties of the film in the selected zone relative to the neighboring zone. The various treated and untreated zones of the film may have substantially the same overall film thickness, or at any rate the difference in reflective characteristics between the different zones may not be substantially attributable to any differences in film thickness between the zones. Reference is made to U.S. Patent Application 61/139,736, “Internally Patterned Multilayer Optical Films Using Spatially Selective Birefringence Reduction”, filed Dec. 22, 2008, and International Application No. PCT/US2009/069153, “Internally Patterned Multilayer Optical Films Using Spatially Selective Birefringence Reduction”, filed on even date herewith, each of which is incorporated herein by reference. The reader should keep in mind, however, that the described unitary polarizer/mirror multilayer optical films are not intended to be limited to those made with the absorptive heating fabrication technique, and encompass embodiments made by other suitable techniques, such as for example a suitably implemented embossing technique.
FIG. 1 depicts a multilayer optical film 110 that has been internally patterned or spatially tailored using spatially selective birefringence reduction of at least some of the internal layers (not shown in FIG. 1). The internal patterning defines distinct zones 112, 114, 116 that are shaped so as to form the indicia “3M” as shown. The film 110 is shown as a long flexible material wound into a roll because the methodology described herein is advantageously compatible with high volume roll-to-roll processes. However, the methodology is not limited to flexible roll goods and can be practiced on small piece parts or samples as well as non-flexible films and articles.
The “3M” indicia is visible because the different zones 112, 114, 116 have different reflective characteristics. In the depicted embodiment, zone 112 has a first reflective characteristic representative of a reflective polarizer, and zones 114, 116 have a second reflective characteristic different from the first reflective characteristic, the second characteristic being representative of a mirror. In this regard, a reflective polarizer may be considered for purposes of this application to be an optical body that strongly reflects normally incident light that is polarized along one in-plane axis (referred to as the “block axis”) if the wavelength is within the reflection band of the packet, and strongly transmits such light that is polarized along an orthogonal in-plane axis (referred to as the “pass axis”). “Strongly reflects” and “strongly transmits” may have different meanings depending on the intended application or field of use, but in many cases a reflective polarizer will have at least 70, 80, or 90% reflectivity for the block axis, and at least 70, 80, or 90% transmission (less than 30, 20, or 10% reflection) for the pass axis. Similarly, a mirror or mirror-like film may be considered for purposes of this application to be an optical body that strongly reflects normally incident light of any polarization if the wavelength is within the reflection band of the packet. Again, “strongly reflecting” may have different meanings depending on the intended application or field of use, but in many cases a mirror will have at least 50, 60, 70, 80, or 90% reflectivity for normally incident light of any polarization at the wavelength of interest. The mirror need not have the same reflectivity for all polarizations at normal incidence, i.e., it may be asymmetric in the sense that one polarization state may be reflected somewhat more or less than an orthogonal polarization state, but the difference in reflectivities of the orthogonal polarization states is generally smaller for the mirror than for the polarizer.
Typically, but not necessarily, the film 110 will be at least partially light transmissive, in which case the zones 112, 114, 116 will also have different transmissive characteristics that correspond to their respective reflective characteristics. In general, of course, transmission (T) plus reflection (R) plus absorption (A)=100%, or T+R+A=100%. In some embodiments the film is composed entirely of materials that have low absorption over at least a portion of the wavelength spectrum. This may be the case even for films that incorporate an absorbing dye or pigment to promote heat delivery, since some absorbing materials are wavelength-specific in their absorptivity. For example, infrared dyes are available that selectively absorb in the near-infrared wavelength region but that have very little absorption in the visible spectrum. At the other end of the spectrum, many polymer materials that are considered to be low loss in the multilayer optical film literature do have low loss over the visible spectrum but also have significant absorption at certain ultraviolet wavelengths. Thus, in many cases the multilayer optical film 110 may have an absorption that is small or negligible over at least a limited portion of the wavelength spectrum, such as the visible spectrum, in which case the reflection and transmission over that limited range take on a complementary relationship because T+R=100%−A, and since A is small,

T+R≈100%.

As will be explained further below, the first and second reflective characteristics are each the result of structural features that are internal to the film 110, rather than the result of coatings applied to the surface of the film or other surface features. This aspect of the disclosed films makes them advantageous for security applications (e.g. where the film is intended for application to a product, package, or document as an indicator of authenticity) because the interior features are difficult to copy or counterfeit.
The first and second reflective characteristics differ in a way that is perceptible under at least some viewing conditions to permit detection of the pattern by an observer or by a machine. In some cases it may be desirable to maximize the difference between the first and second reflective characteristics at visible wavelengths so that the pattern is conspicuous to human observers under most viewing and lighting conditions. In other cases it may be desirable to provide only a subtle difference between the first and second reflective characteristics, or to provide a difference that is conspicuous only under certain viewing conditions. The difference between the first and second reflective characteristics may in some cases be attributable primarily to a difference in the refractive index properties of interior layers of the multilayer optical film in the different neighboring zones of the film, and not primarily attributable to differences in thickness between the neighboring zones.
The human observer or other observation system may employ a separate polarizer, referred to as an analyzing polarizer or simply an analyzer, to help distinguish the first and second reflective characteristics, i.e., to help distinguish the polarizer portion of film 110 from the mirror portion. The analyzer may be rotated from a first orientation, at which its pass axis is aligned with or parallel to the pass axis of the polarizer portion of the film (zone 112), to a second orientation at which its pass axis is aligned with or parallel to the block axis of the polarizer portion of the film. In cases where the first and second reflective characteristics of the film 110 are limited to narrow bands of the electromagnetic spectrum, such that the zones 112, 114, 116 appear colored, observing the film 110 through the analyzer in the second orientation can help increase the apparent color saturation of the polarizer (zone 112) by viewing only the polarization component that is being partially blocked in the visible region. These observation conditions may also increase the contrast between the polarizer portion of film 110 (zone 112) and the mirror portions of film 110 (zones 114, 116). Rotating the analyzer 90 degrees, i.e., back to the first orientation, allows viewing of the polarization component that is being passed (transmitted) by the polarizer of zone 112, which, in an exemplary embodiment, may result in no observed color. Removing the analyzer and observing all polarizations of light transmitted or reflected by the film 110 results in an observed color saturation and color contrast that lie between the two extremes that are observed when using the analyzer.
In general, zone-to-zone differences in refractive index can produce various differences between the first and second reflective characteristics depending on the design of the multilayer optical film. In some cases the first reflective characteristic may include a first reflection band with a given center wavelength, band edge, and maximum reflectivity, and the second reflective characteristic may differ from the first by having a second reflection band that is similar in center wavelength and/or band edge to the first reflection band, but that has a substantially different maximum reflectivity (whether greater or lesser) than the first reflection band, or the second reflection band may be substantially absent from the second reflection characteristic. These first and second reflection bands may be associated with light of only one polarization state, or with light of any polarization state depending on the design of the film.
In some cases the first and second reflective characteristics may differ in their dependence with viewing angle. For example, the first reflective characteristic may include a first reflection band that has a given center wavelength, band edge, and maximum reflectivity at normal incidence, and the second reflective characteristic may include a second reflection band that is very similar to these aspects of the first reflection band at normal incidence. With increasing incidence angle, however, although both the first and second reflection bands may shift to shorter wavelengths, their respective maximum reflectivities may deviate from each other greatly. For example, the maximum reflectivity of the first reflection band may remain constant or increase with increasing incidence angle, while the maximum reflectivity of the second reflection band, or at least the p-polarized component thereof, may decrease with increasing incidence angle.
In cases where the differences discussed above between the first and second reflective characteristics relate to reflection bands that cover a portion of the visible spectrum, the differences may be perceived as differences in color between the first and second zones of the film.
Turning now to FIG. 2, we see there a portion of a multilayer film 210 in schematic side view to reveal the structure of the film including its interior layers. The film is shown in relation to a local x-y-z Cartesian coordinate system, where the film extends parallel to the x- and y-axes, and the z-axis is perpendicular to the film and its constituent layers and parallel to a thickness axis of the film. Note that the film 210 need not be entirely flat, but may be curved or otherwise shaped to deviate from a plane, and even in those cases arbitrarily small portions or regions of the film can be associated with a local Cartesian coordinate system as shown. The film 210 may in general be considered to represent the film 110 of FIG. 1 in any of its zones 112, 114, 116, since the individual layers of the film 110 preferably extend continuously from each such zone to the next.
Multilayer optical films include individual layers having different refractive indices so that some light is reflected at interfaces between adjacent layers. These layers, sometimes referred to as “microlayers”, are sufficiently thin so that light reflected at a plurality of the interfaces undergoes constructive or destructive interference to give the multilayer optical film the desired reflective or transmissive properties. For multilayer optical films designed to reflect light at ultraviolet, visible, or near-infrared wavelengths, each microlayer generally has an optical thickness (a physical thickness multiplied by refractive index) of less than about 1 μm. However, thicker layers can also be included, such as skin layers at the outer surfaces of the multilayer optical film, or protective boundary layers (PBLs) disposed within the multilayer optical film to separate coherent groupings (known as “stacks” or “packets”) of microlayers. In FIG. 2, the microlayers are labeled “A” or “B”, the “A” layers being composed of one material and the “B” layers being composed of a different material, these layers being stacked in an alternating arrangement to form optical repeat units or unit cells ORU 1, ORU 2, . . . ORU 6 as shown. Typically, a multilayer optical film composed entirely of polymeric materials would include many more than 6 optical repeat units if high reflectivities are desired. Note that all of the “A” and “B” microlayers shown in FIG. 2 are interior layers of film 210, except for the uppermost “A” layer whose upper surface in this illustrative example coincides with the outer surface 210a of the film 210. The substantially thicker layer 212 at the bottom of the figure can represent an outer skin layer, or a PBL that separates the stack of microlayers shown in the figure from another stack or packet of microlayers (not shown). If desired, two or more separate multilayer optical films can be laminated together, e.g. with one or more thick adhesive layers, or using pressure, heat, or other methods to form a laminate or composite film.
In some cases, the microlayers can have thicknesses and refractive index values corresponding to a 1⁄4-wave stack, i.e., arranged in optical repeat units each having two adjacent microlayers of equal optical thickness (f-ratio=50%, the f-ratio being the ratio of the optical thickness of a constituent layer “A” to the optical thickness of the complete optical repeat unit), such optical repeat unit being effective to reflect by constructive interference light whose wavelength λ is twice the overall optical thickness of the optical repeat unit, where the “optical thickness” of a body refers to its physical thickness multiplied by its refractive index. In other cases, the optical thickness of the microlayers in an optical repeat unit may be different from each other, whereby the f-ratio is greater than or less than 50%. In the embodiment of FIG. 2, the “A” layers are depicted for generality as being thinner than the “B” layers. Each depicted optical repeat unit (ORU 1, ORU 2, etc.) has an optical thickness (OT1, OT2, etc.) equal to the sum of the optical thicknesses of its constituent “A” and “B” layer, and each optical repeat unit reflects light whose wavelength λ is twice its overall optical thickness. The reflectivity provided by microlayer stacks or packets used in multilayer optical films in general, and in the internally patterned multilayer films discussed herein in particular, is typically substantially specular in nature, rather than diffuse, as a result of the generally smooth well-defined interfaces between microlayers, and the low haze materials that are used in a typical construction. In some cases, however, the finished article may be tailored to incorporate any desired degree of scattering, e.g., using a diffuse material in skin layer(s) and/or PBL layer(s), and/or using one or more surface diffusive structures or textured surfaces, for example.
In some embodiments, the optical thicknesses of the optical repeat units in a layer stack may all be equal to each other, to provide a narrow reflection band of high reflectivity centered at a wavelength equal to twice the optical thickness of each optical repeat unit. In other embodiments, the optical thicknesses of the optical repeat units may differ according to a thickness gradient along the z-axis or thickness direction of the film, whereby the optical thickness of the optical repeat units increases, decreases, or follows some other functional relationship as one progresses from one side of the stack (e.g. the top) to the other side of the stack (e.g. the bottom). Such thickness gradients can be used to provide a widened reflection band to provide substantially spectrally flat transmission and reflection of light over the extended wavelength band of interest, and also over all angles of interest. Thickness gradients tailored to sharpen the band edges at the wavelength transition between high reflection and high transmission can also be used, as discussed in U.S. Pat. No. 6,157,490 (Wheatley et al.) “Optical Film With Sharpened Bandedge”. For polymeric multilayer optical films, reflection bands can be designed to have sharpened band edges as well as “flat top” reflection bands, in which the reflection properties are essentially constant across the wavelength range of application. Other layer arrangements, such as multilayer optical films having 2-microlayer optical repeat units whose f-ratio is different from 50%, or films whose optical repeat units include more than two microlayers, are also contemplated. These alternative optical repeat unit designs can be configured to reduce or to excite certain higher-order reflections, which may be useful if the desired reflection band resides in or extends to near infrared wavelengths. See, e.g., U.S. Pat. No. 5,103,337 (Schrenk et al.) “Infrared Reflective Optical Interference Film”, U.S. Pat. No. 5,360,659 (Arends et al.) “Two Component Infrared Reflecting Film”, U.S. Pat. No. 6,207,260 (Wheatley et al.) “Multicomponent Optical Body”, and U.S. Pat. No. 7,019,905 (Weber) “Multi-layer Reflector With Suppression of High Order Reflections”.
The thickness gradient and optical repeat unit design may thus be tailored as desired to provide the mirror and polarizer of the disclosed embodiments with a substantial reflectivity (for the block polarization state in the case of the polarizer, and for two orthogonal polarization states in the case of the mirror) in a limited spectral band. For example, the substantial reflectivity may be at least 50%, or at least 60, 70, 80, or 90% or more, over only substantially one spectral band, the band being disposed in the visible or in any other desired portion of the spectrum. The band may have a bandwidth of less than 200, or 150, or 100, or 50 nm or less, for example, which may be measured as a full-width at half-maximum (FWHM) reflectivity. As noted above, the band may be associated with zero-order reflection, or with a desired higher order reflection if the optical repeat unit is suitably designed.
As mentioned above, adjacent microlayers of the multilayer optical film have different refractive indices so that some light is reflected at interfaces between adjacent layers. We refer to the refractive indices of one of the microlayers (e.g. the “A” layers in FIG. 2) for light polarized along principal x-, y-, and z-axes as n1x, n1y, and n1z, respectively. We refer to the refractive indices of the adjacent microlayer (e.g. the “B” layers in FIG. 2) along the same axes as n2x, n2y, n2z, respectively. The x-, y-, and z-axes may, for example, correspond to the principal directions of the dielectric tensor of the material. Typically, and for discussion purposes, the principle directions of the different materials are coincident, but this need not be the case in general. We refer to the differences in refractive index between these layers as Δnx (=n1x−n2x) along the x-direction, Δny (=n1y−n2y) along the y-direction, and Δnz (=n1z−n2z) along the z-direction. The nature of these refractive index differences, in combination with the number of microlayers in the film (or in a given stack of the film) and their thickness distribution, controls the reflective and transmissive characteristics of the film (or of the given stack of the film) in a given zone. For example, if adjacent microlayers have a large refractive index mismatch along one in-plane direction (Δnx large) and a small refractive index mismatch along the orthogonal in-plane direction (Δny≈0), the film or packet may behave as a reflective polarizer for normally incident light.
For purposes of the present application, a material is considered to be “birefringent” if the material has an anisotropic dielectric tensor over a wavelength range of interest, e.g., a selected wavelength or band in the UV, visible, and/or infrared portions of the spectrum. Stated differently, a material is considered to be “birefringent” if the principal refractive indices of the material (e.g., n1x, n1y, n1z) are not all the same.
In another example, adjacent microlayers may have a large refractive index mismatch along both in-plane axes (Δnx large and Δny large), in which case the film or packet may behave as an on-axis mirror.
In variations of the foregoing embodiments, the adjacent microlayers may exhibit a refractive index match or mismatch along the z-axis (Δnz≈0 or Δnz large), and the mismatch may be of the same or opposite polarity or sign as the in-plane refractive index mismatch(es). Such tailoring of Δnz plays a key role in whether the reflectivity of the p-polarized component of obliquely incident light increases, decreases, or remains the same with increasing incidence angle.
In view of the large number of permutations of possible refractive index differences along the different axes, the total number of layers and their thickness distribution(s), and the number and type of microlayer packets included in the multilayer optical film, the variety of possible multilayer optical films 210 and packets thereof is vast. We refer to multilayer optical films disclosed in any of the patent documents cited herein (whether or not patented, and whether published by the U.S. Patent Office or by any another country or patent authority), as well as the following documents, all of which are incorporated herein by reference: U.S. Pat. No. 5,486,949 (Schrenk et al.) “Birefringent Interference Polarizer”; U.S. Pat. No. 5,882,774 (Jonza et al.) “Optical Film”; U.S. Pat. No. 6,045,894 (Jonza et al.) “Clear to Colored Security Film”; U.S. Pat. No. 6,179,949 (Merrill et al.) “Optical Film and Process for Manufacture Thereof”; U.S. Pat. No. 6,531,230 (Weber et al.) “Color Shifting Film”; U.S. Pat. No. 6,939,499 (Merrill et al.) “Processes and Apparatus for Making Transversely Drawn Films with Substantially Uniaxial Character”; U.S. Pat. No. 7,256,936 (Hebrink et al.) “Optical Polarizing Films with Designed Color Shifts”; U.S. Pat. No. 7,316,558 (Merrill et al.) “Devices for Stretching Polymer Films”; PCT Publication WO 2008/144136 A1 (Nevitt et al.) “Lamp-Hiding Assembly for a Direct Lit Backlight”; PCT Publication WO 2008/144656 A2 (Weber et al.) “Backlight and Display System Using Same”.
We note that at least some of the microlayers in at least one packet of the multilayer optical film are birefringent in at least one zone of the film (e.g., zone 112 of FIG. 1). Thus, a first layer in the optical repeat units may be birefringent (i.e., n1x≠n1y, or n1x≠n1z, or n1y≠n1z), or a second layer in the optical repeat units may be birefringent (i.e., n2x≠n2y, or n2x≠n2z, or n2y≠n2z), or both the first and second layers may be birefringent. Moreover, the birefringence of one or more such layers is diminished in at least one zone relative to a neighboring zone. In some cases, the birefringence of these layers may be diminished to zero, such that they are optically isotropic (i.e., n1x=n1y=n1z, or n2x=n2y=n2z) in one of the zones but birefringent in a neighboring zone. In cases where both layers are initially birefringent, depending on materials selection and processing conditions, they can be processed in such a way that the birefringence of only one of the layers is substantially diminished, or the birefringence of both layers may be diminished.
Exemplary multilayer optical films are composed of polymer materials and may be fabricated using coextruding, casting, and orienting processes. Reference is made to U.S. Pat. No. 5,882,774 (Jonza et al.) “Optical Film”, U.S. Pat. No. 6,179,949 (Merrill et al.) “Optical Film and Process for Manufacture Thereof”, and U.S. Pat. No. 6,783,349 (Neavin et al.) “Apparatus for Making Multilayer Optical Films”. The multilayer optical film may be formed by coextrusion of the polymers as described in any of the aforementioned references. The polymers of the various layers are preferably chosen to have similar rheological properties, e.g., melt viscosities, so that they can be co-extruded without significant flow disturbances. Extrusion conditions are chosen to adequately feed, melt, mix, and pump the respective polymers as feed streams or melt streams in a continuous and stable manner. Temperatures used to form and maintain each of the melt streams may be chosen to be within a range that avoids freezing, crystallization, or unduly high pressure drops at the low end of the temperature range, and that avoids material degradation at the high end of the range.
In brief summary, the fabrication method may comprise: (a) providing at least a first and a second stream of resin corresponding to the first and second polymers to be used in the finished film; (b) dividing the first and the second streams into a plurality of layers using a suitable feedblock, such as one that comprises: (i) a gradient plate comprising first and second flow channels, where the first channel has a cross-sectional area that changes from a first position to a second position along the flow channel, (ii) a feeder tube plate having a first plurality of conduits in fluid communication with the first flow channel and a second plurality of conduits in fluid communication with the second flow channel, each conduit feeding its own respective slot die, each conduit having a first end and a second end, the first end of the conduits being in fluid communication with the flow channels, and the second end of the conduits being in fluid communication with the slot die, and (iii) optionally, an axial rod heater located proximal to said conduits; (c) passing the composite stream through an extrusion die to form a multilayer web in which each layer is generally parallel to the major surface of adjacent layers; and (d) casting the multilayer web onto a chill roll, sometimes referred to as a casting wheel or casting drum, to form a cast multilayer film. This cast film may have the same number of layers as the finished film, but the layers of the cast film are typically much thicker than those of the finished film. Furthermore, the layers of the cast film are typically all isotropic.
Many alternative methods of fabricating the cast multilayer web can also be used. One such alternative method that also utilizes polymer coextrusion is described in U.S. Pat. No. 5,389,324 (Lewis et al.).
After cooling, the multilayer web can be drawn or stretched to produce the near-finished multilayer optical film, details of which can be found in the references cited above. The drawing or stretching accomplishes two goals: it thins the layers to their desired final thicknesses, and it orients the layers such that at least some of the layers become birefringent. The orientation or stretching can be accomplished along the crossweb direction (e.g. via a tenter), along the down-web direction (e.g. via a length orienter), or any combination thereof, whether simultaneously or sequentially. If stretched along only one direction, the stretch can be “unconstrained” (wherein the film is allowed to dimensionally relax in the in-plane direction perpendicular to the stretch direction) or “constrained” (wherein the film is constrained and thus not allowed to dimensionally relax in the in-plane direction perpendicular to the stretch direction). If stretched along both in-plane directions, the stretch can be symmetric, i.e., equal along the orthogonal in-plane directions, or asymmetric, although symmetric stretching is normally not employed to fabricate a reflective polarizing film. Alternatively, the film may be stretched in a batch process. In any case, subsequent or concurrent draw reduction, stress or strain equilibration, heat setting, and other processing operations can also be applied to the film.
The multilayer optical films and film bodies can also include additional layers and coatings selected for their optical, mechanical, and/or chemical properties. For example, a UV absorbing layer can be added at one or both major outer surfaces of the film to protect the film from long-term degradation caused by UV light. Additional layers and coatings can also include scratch resistant layers, tear resistant layers, and stiffening agents. See, e.g., U.S. Pat. No. 6,368,699 (Gilbert et al.).
In some cases, the natural or inherent absorptivity of one, some, or all of the constituent polymer materials that make up the multilayer optical film may be utilized for the absorptive heating procedure. For example, many polymers that are low loss over the visible region have substantially higher absorptivity at certain ultraviolet and/or infrared wavelengths. Exposing portions of the film to light of such wavelengths may be used to selectively heat such portions of the film.
In other cases, absorbing dyes, pigments, or other agents can be incorporated into some or all of the individual layers of the multilayer optical film to promote absorptive heating as mentioned above. In some cases, such absorbing agents are spectrally selective, whereby they absorb in one wavelength region but not in another. For example, some of the disclosed films may be intended for use in the visible region, such as with anti-counterfeiting security labels or as a component of a liquid crystal display (LCD) device or other display device, in which case an absorbing agent that absorbs at infrared or ultraviolet wavelengths but not substantially at visible wavelengths may be used. Further, an absorbing agent may be incorporated into one or more selected layers of a film. For example, the film may comprise two distinct microlayer packets separated by an optically thick layer such as a protective boundary layer (PBL), a laminating adhesive layer, one or more skin layers, or the like, and an absorbing agent may be incorporated into one of the packets and not the other, or may be incorporated into both packets but at a higher concentration in one relative to the other.
A variety of absorbing agents can be used. For optical films operating in the visible spectrum, dyes, pigments, or other additives that absorb in the ultraviolet and infrared (including near infrared) regions may be used. In some cases it may be advantageous to select an agent that absorbs in a spectral range for which the polymer materials of the film have a substantially lower absorption. By incorporating such an absorbing agent into selected layers of a multilayer optical film, directed radiation can preferentially deliver heat to the selected layers rather than throughout the entire thickness of the film. Exemplary absorbing agents may be melt extrudable so that they can be embedded into a selected layer set of interest. To this end, the absorbers are preferably reasonably stable at the processing temperatures and residence times required for extrusion. Some potential IR dyes include any of the Nickel, Palladium, and Platinum-based dyes available from Epolin, Inc. under the tradename EpolightTM. Other suitable candidates include AmaplastTM-brand dyes, available from ColorChem International Corp., Atlanta, Ga. For further information on suitable absorbing agents, reference is made to U.S. Pat. No. 6,207,260 (Wheatley et al.) “Multicomponent Optical Body”.
In some cases the absorbing agent may be a non-linear absorber, i.e., it may be or comprise a composition in which the light energy absorption coefficient is intensity or fluence dependent, where intensity refers to energy per unit area per unit time, and fluence refers to energy density or energy per unit area. Nonlinear light absorbers may be of the two-photon absorption type or the reverse saturable absorption type, for example.
The two-photon absorption process is a nonlinear light absorption process in which the photon energy is approximately equal to half the energy required for linear excitation of the material. Excitation of the absorbing material therefore requires the simultaneous absorption of two of the lower energy photons. Examples of useful two-photon absorbers include those exhibiting large multiphoton absorption cross-sections, such as Rhodamine B (that is, N-[9-(2-carboxyphenyl)-6-(diethylamino)-3H-xanthen-3-ylidene]-N-ethylethanaminium chloride and the hexafluoroantimonate salt of Rhodamine B) and the four classes of photosensitizers described, for example, in PCT Publications WO 98/21521 (Marder et al.) and WO 99/53242 (Cumptson et al.).
The reverse saturable absorption process is also sometimes referred to as excited state absorption, and is characterized by the absorption cross section for the excited state involved in the absorption process being much larger than the cross section for excitation from the ground state to the excited state. The total light absorption involves both ground state absorption and excited state absorption. Examples of reverse saturable absorption materials include, for example, metallophthalocyanines, naphthalocyanines, cyanines, fullerenes, metal nanoparticles, metal oxide nanoparticles, metal cluster compounds, porphyrins, indanthrone derivatives and oligomers or combinations thereof. Examples of metallophthalocyanines include, for example, copper phthalocyanine (CuPC), and phthalocyanines containing metal or metalloids from group IIIA (Al, Ga, In) and IVA (Si, Ge, Sn, Pb). Examples of naphthalocyanines include, for example, the phthalocyanine derivatives of silicon (SiNC), tin (SnNC), and lead (PbNC). Examples of cyanines include, for example, 1,3,3,1′,3′,3′-hexamethylindotricarbocyanine iodide (HITCI). Examples of fullerenes include C60 and C70 fullerenes. Examples of metal nanoparticles include gold, silver, aluminum, and zinc nanoparticles. Examples of metal oxide nanoparticles include titanium dioxide, antimony tin oxide, and zirconium dioxide nanoparticles. Examples of metal clusters include iron tricobalt metal clusters such as HFeCo3(CO)12 and NEt4FeCO3(CO)12. Examples of porphyrins include tetraphenylporphyrin (H2TPP), zinc tetraphenylporphyrin (ZnTPP), and cobalt tetraphenylporphyrin (CoTPP). Examples of indanthrone derivatives include unsubstituted indanthrone, oxidized indanthrone, chloroindanthrone, and an indanthrone oligomer.
We turn now to FIG. 3, which shows a schematic sectional view of a portion of the multilayer optical film 110 of FIG. 1 in the vicinity of area 118 at a boundary of zone 112 and zone 116, and which assumes that the absorptive heating technique rather than an embossing technique has been used to form the zone 116. In this expanded view of the film 110, a narrow transition zone 115 can be seen separating the zone 112 from the neighboring zone 116. Such a transition zone may or may not be present depending on processing details, and if it is not present then zone 116 may be immediately adjacent to zone 112 with no significant intervening features. Construction details of film 110 can also be seen: the film includes optically thick skin layers 310, 312 on opposite sides thereof, with a plurality of microlayers 314 and another plurality of microlayers 316 disposed between the skin layers 310, 312. All of the microlayers 314, 316 are interior to the film 110 by virtue of the outer skin layers. The space between microlayers 314 and 316 is left open in the drawing, to allow for the case where the microlayers 314, 316 are portions of a single microlayer packet that begins at one skin layer 310 and ends at the opposite skin layer 312, and also the case where the microlayers 314, 316 are portions of two or more distinct microlayer packets that are separated from each other by one or more optically thick protective boundary layers (PBLs) or another optically thick interior layer(s). In either case, the microlayers 314, 316 preferably each comprise two alternating polymer materials arranged into optical repeat units, each of the microlayers 314, 316 extending continuously in a lateral or transverse fashion from the zone 112 to the neighboring zone 116 as shown. The microlayers 314, 316 provide a first reflective characteristic in the zone 112 by constructive or destructive interference, and at least some of the microlayers 314, 316 are birefringent. The zones 115, 116 previously had the same characteristics as zone 112, but have been processed by the selective application of heat thereto in an amount sufficient to reduce or eliminate the birefringence of some of the microlayers 314, 316 in the zone 116 while maintaining the birefringence of the microlayers in zone 112, the heat also being low enough to maintain the structural integrity of the microlayers 314, 316 in the treated zone 116. The reduced birefringence of the microlayers 314, 316 in the zone 116 is primarily responsible for a second reflective characteristic for the zone 116 that is different from the first reflective characteristic for the zone 112.
The film 110 has characteristic thicknesses d1, d2 in zone 112, and characteristic thicknesses d1′, d2′ in zone 116, as shown in the figure. The thicknesses d1, d1′ are physical thicknesses measured from a front outer surface of the film to a rear outer surface of the film in the respective zones. The thicknesses d2, d2′ are physical thicknesses measured from the microlayer (at one end of a microlayer packet) that is disposed nearest the front surface of the film to the microlayer (at an end of the same or a different microlayer packet) that is disposed nearest the rear surface of the film. Thus, if one wishes to compare the thickness of the film 110 in zone 112 with the thickness of the film in zone 116, one may choose to compare d1 to d1′, or d2 to d2′, depending on which measurement is more convenient. In most cases the comparison between d1 and d1′ may well yield substantially the same result (proportionally) as the comparison between d2 and d2′. (Of course, in cases where the film contains no outer skin layers, and where microlayer packets terminate at both outer surfaces of the film, d1 and d2 become the same.) However, where a significant discrepancy exists, such as where a skin layer experiences a significant thickness change from one place to another but no corresponding thickness change exists in the underlying microlayers, or vice versa, then it may be desirable to use the d2 and d2′ parameters as being more representative of the overall film thickness in the different zones, in view of the fact that the skin layers typically have a minor effect on the reflective characteristics of the film compared to the microlayer packet(s).
Of course, for multilayer optical films containing two or more distinct microlayer packets separated from each other by optically thick layers, the thickness of any given microlayer packet can also be measured and characterized as the distance along the z-axis from the first to the last microlayer in the packet. This information may become significant in a more in-depth analysis that compares the physical characteristics of the film 110 in the different zones 112, 116.
As mentioned, FIG. 3 assumes that the zone 116 has been treated with the selective application of heat to cause at least some of the microlayers 314, 316 to lose some or all of their birefringence relative to their birefringence in neighboring zone 112, such that zone 116 exhibits a reflective characteristic, resulting from constructive or destructive interference of light from the microlayers, that differs from a reflective characteristic of zone 112. The selective heating process may involve no selective application of pressure to zone 116, and it may result in substantially no thickness change (whether using the parameters d1/d1′ or the parameters d2/d2′) to the film. For example, the film 110 may exhibit an average thickness in zone 116 that deviates from an average thickness in zone 112 by no more than the normal variability in thickness that one observes in the zone 112, or in the untreated film. Thus, the film 110 may exhibit in zone 112, or over an area of the film encompassing a portion of zone 112 and zone 116 before the heat treatment of zone 116, a variability in thickness (whether d1 or d2) of Δd, and the zone 116 may have spatially averaged thicknesses d1′, d2′ which differ from spatially averaged thicknesses d1, d2 (respectively) in zone 112 by no more than Δd. The parameter Δd may represent, for example, one, two, or three standard deviations in the spatial distribution of the thickness d1 or d2.
In some cases, the heat treatment of zone 116 may give rise to certain changes to the thickness of the film in zone 116. These thickness changes may result from, for example, local shrinkage and/or expansion of the different materials that constitute the multilayer optical film, or may result from some other thermally-induced phenomenon. However, such thickness changes, if they occur, play only a secondary role in their effect on the reflective characteristic of the treated zone 116 compared to the primary role played by the reduction or elimination of birefringence in the treated zone. Note also that in many cases it may be desirable to hold the film by its edges under tension during the selective heat treatment that accomplishes the internal patterning, in order to avoid wrinkling of the film, or for other reasons. The amount of tension applied and details of the heat treatment may also result in some amount of thickness change in the treated zones.
Of course, if an embossing technique is used rather than the absorptive heating technique, significant thinning of zone 116 relative to zone 112 may occur, with a concomitant shift in spectral features to shorter wavelengths.
In some cases it is possible to distinguish the effect of a thickness change from a change in birefringence by analyzing the reflective properties of the film. For example, if the microlayers in an untreated zone (e.g. zone 112) provide a reflection band characterized by a left band edge (LBE), right band edge (RBE), center wavelength λc, and peak reflectivity R1, a given thickness change for those microlayers (with no change in the refractive indices of the microlayers) will produce a reflection band for the treated zone having a peak reflectivity R2 about the same as R1, but having an LBE, RBE, and center wavelength that are proportionally shifted in wavelength relative to those features of the reflection band of the untreated zone, and this shift can be measured. On the other hand, a change in birefringence will typically produce only a very minor shift in wavelength of the LBE, RBE, and center wavelengths, as a result of the (usually very small) change in optical thickness caused by the change in birefringence. (Recall that optical thickness equals physical thickness multiplied by refractive index. Also keep in mind that a reflective polarizing film may exhibit a reflection band not only for light of the block state, but may also have a relatively weak reflection band for light of the pass state.) The change in birefringence can, however, have a large or at least a significant effect on the peak reflectivity of the reflection band, depending on the design of the microlayer stack. Thus, in some cases, the change in birefringence may provide a peak reflectivity R2 for the reflection band in the modified zone that differs substantially from R1, where of course R1 and R2 are compared under the same illumination and observation conditions. If R1 and R2 are expressed in percentages, R2 may differ from R1 by at least 10%, or by at least 20%, or by at least 30%. As a clarifying example, R1 may be 70%, and R2 may be 60%, 50%, 40%, or less. Alternatively, R1 may be 10%, and R2 may be 20%, 30%, 40%, or more. R1 and R2 may also be compared by taking their ratio. For example, R2/R1 or its reciprocal may be at least 2, or at least 3.
A significant change in peak reflectivity, to the extent it is indicative of a change in the interfacial reflectivity (sometimes referred to as optical power) resulting from a change in refractive index difference between adjacent layers due to a change in birefringence, is also typically accompanied by at least some change in the bandwidth of the reflection band, where the bandwidth refers to the separation between the LBE and RBE.
As we have discussed, in some cases the thickness of the film 110 in the treated zone 116, i.e., d1′ or d2′, may differ somewhat from the thickness of the film in the untreated zone 112, even if no selective pressure was in fact applied to the zone 116 during heat treatment. For this reason, FIG. 3 depicts d1′ as being slightly different from d1, and d2′ as being slightly different from d2. A transition zone 115 is also shown for generality, to show that a “bump” or other detectable artifact may exist on the outer surface of the film as a consequence of the selective heat treatment. In some cases, however, the treatment may result in no detectable artifact between the neighboring treated and untreated zones. For example, in some cases an observer who slides his or her finger across the boundary between the zones may detect no bump, ridge, or other physical artifact between the zones.
Under some circumstances it is possible for thickness differences between treated and untreated zones to be non-proportional through the thickness of the film. For example, in some cases it is possible for an outer skin layer to have a relatively small thickness difference, expressed as a percentage change, between the treated and untreated zones, while one or more internal microlayer packets may have a larger thickness difference, also expressed as a percentage change, between the same zones.
FIG. 4 shows a schematic sectional view of a portion of another multilayer optical film 410 that incorporates internal patterning. Film 410 comprises outer optically thick skin layers 412, 414, and a packet of microlayers that reside in a stratum or layer 416 sandwiched between the skin layers. All of the microlayers are internal to the film 410. (In alternative embodiments, one or both skin layers may be omitted, in which case one or both PBLs or outermost microlayers in the packet may become external layers.) The microlayers include at least some microlayers that are birefringent in at least some zones or areas of the film and that extend in a lateral or transverse fashion at least between neighboring zones of the film. The microlayers provide a first reflective characteristic associated with constructive or destructive interference of light at least in a first untreated zone 422 of the film. The film 410 has been selectively heated in the neighboring zones 420, 424, in some cases without applying any pressure selectively to these zones, so as to provide a second reflective characteristic also associated with constructive or destructive interference of light, but that differs from the first reflective characteristic. These differences in reflective characteristics may be manifested to an observer as differences in color between the treated and untreated zones in reflected or transmitted light. The respective colors and the differences therebetween also typically change or shift with angle of incidence. The film 410 may have substantially the same film thickness in the zones 420, 422, 424, or the film thickness may vary somewhat between these zones, but in at least some cases any difference in film thickness between the zones is not primarily responsible for the differences between the first and second reflective characteristics. The zones 420, 422, 424 form a pattern that is internal or interior to the film, as indicated by the crosshatching in the stratum or layer 416. The crosshatching indicates that at least some of the microlayers in the crosshatched region have a reduced birefringence (including zero birefringence) compared to their birefringence in the zone 422 or in other untreated zones.
We now turn our attention to the idealized graphs of FIGS. 5A-G. These graphs help to explain the process of patterning the multilayer optical films. They also help explain some of the different possible combinations of first and second reflective characteristics in the untreated and treated zones, respectively, and how they are achieved. For descriptive purposes, the reflective characteristics of both the untreated and treated zones of an optical film may be categorized into one of following three types: mirror-like reflective characteristics, window-like reflective characteristics, and polarizer-like reflective characteristics. A mirror-like reflective characteristic exhibits high reflectivity (e.g., in some cases greater than 50%, 60%, 70%, 80%, 90%, 95%, or 99%) for all polarization states of normally incident light, a window-like reflective characteristic exhibits low reflectivity (e.g., in some cases less than 20%, 10%, 5%, 3%, or 1%) for all polarization states of normally incident light, and a polarizer-like reflective characteristic exhibits high reflectivity (e.g., in some cases greater than 50%, 60%, 70%, 80%, 90%, 95%, or 99%) for normally incident light of one polarization state and low reflectivity (e.g., in some cases less than 30%, 20%, 10%, 5%, 3%, or 1%) for normally incident light of a different polarization state. (The reflective polarizer-like characteristic may alternatively be expressed in terms of the difference in reflectivity of one polarization state relative to the other polarization state.) The reader will keep in mind that reflectivity values discussed herein that are associated with multilayer optical films or stacks should be considered to not include the Fresnel reflections at the outer air/polymer interfaces, unless otherwise indicated.
The boundaries or limits of these different characteristics—e.g., what is considered to be “high” reflectivity and what is considered to be “low” reflectivity—and the distinctions therebetween may depend on the end-use application and/or on system requirements. For example, a multilayer optical film, or a microlayer packet thereof, that exhibits moderate levels of reflectivity for all polarization states may be considered to be a mirror for purposes of some applications and a window for purposes of other applications. Similarly, a multilayer optical film, or a microlayer packet thereof, that provides moderately different levels of reflectivity for different polarization states of normally incident light may be considered to be a polarizer for some applications, a mirror for other applications, and a window for still other applications, depending on the exact reflectivity values and on the sensitivity of a given end-use application to differences in reflectivity for different polarization states. Unless otherwise indicated, the mirror, window, and polarizer categories are specified for normally incident light. The reader will understand that oblique-angle characteristics may in some cases be the same as or similar to, and in other cases may be drastically different from, the characteristics of an optical film at normal incidence.
FIGS. 5A-G are representative of unitary polarizer/mirror multilayer optical films as described above. Multilayer optical films having other combinations of reflective characteristics, e.g., unitary mirror/window films, unitary polarizer/window films, unitary mirror/mirror films, unitary polarizer/polarizer films, and so forth, are discussed more fully in one or more of the following applications, incorporated herein by reference: International Application No. PCT/US2009/069153, “Internally Patterned Multilayer Optical Films Using Spatially Selective Birefringence Reduction”; International Application No. PCT/US2009/069160, “Internally Patterned Multilayer Optical Films With Multiple Birefringent Layers”; and International Application No. PCT/US2009/069192, “Multilayer Optical Films Having Side-by-Side Polarizer/Polarizer Zones”.
In each of the graphs of FIGS. 5A-G, relative refractive index “n” is plotted on the vertical axis. On the horizontal axis, a position or mark is provided for each of the six refractive indices that characterize a two-layer optical repeat unit: “1x”, “1y”, and “1z” represent the refractive indices of the first layer along the x-, y-, and z-axes, which were referred to above as n1x, n1y, and n1z. Likewise, “2x”, “2y”, and “2z” represent the refractive indices of the second layer along the x-, y-, and z-axes, which were referred to above as n2x, n2y, and n2z. Diamond-shaped symbols (⋄) in the figures represent refractive indices of the materials in a first processing stage. This first stage may correspond to polymer layers that have been extruded and quenched or cast onto a casting wheel, for example, but that have not yet been stretched or otherwise oriented. Open (unfilled) circle-shaped symbols (◯) in the figures represent refractive indices of materials in a second stage of processing, later than the first stage. The second stage may correspond to polymer layers that have been stretched or otherwise oriented into a multilayer optical film that reflects light by constructive or destructive interference from interfaces between microlayers within the film. Small filled circle-shaped symbols or dots (●) in the figures represent refractive indices of the materials in a third stage of processing, later than the first and second stages. The third stage may correspond to polymer layers that, after being extruded and oriented, have been selectively heat treated, as discussed further below. Such heat treatment is typically limited to one or more particular portions or zones of a film, referred to as treated zones.
By comparing the vertical coordinates of the various symbols in a given figure, the reader can readily ascertain a great deal of information about the optical film, its method of manufacture, and the optical properties of its treated and untreated portions. For example, the reader can ascertain: if one or both material layers are or were birefringent before or after the selective heat treatment, and whether the birefringence is uniaxial or biaxial, and whether the birefringence is large or small. The reader can also ascertain from FIGS. 5A-G relative magnitudes of each of the refractive index differences Δnx, Δny, Δnz between the two layers, for each of the three processing stages (the cast state, stretched state, and the treated state).
As discussed above, a precursor article to the finished, internally patterned multilayer optical film can be a cast web of polymer material. The cast web may have the same number of layers as the finished film, and the layers may be composed of the same polymer materials as those used in the finished film, but the cast web is thicker and its layers are usually all isotropic. In some cases, however, not depicted in the figures, the casting process may itself impart a level of orientation and birefringence in one or more of the materials. The diamond-shaped symbols in FIGS. 5A-G represent the refractive indices of the two polymer layers in the cast web that, after a subsequent stretching procedure, become the microlayers in the optical repeat units of the multilayer optical film. After stretching, at least some of the layers become oriented and birefringent, and an oriented (but still unpatterned) multilayer optical film is formed. This is exemplified in FIGS. 5A-G by open circles that may be vertically displaced from their respective original values represented by the diamond-shaped symbols. For example, in FIG. 5A, the stretching procedure raises the refractive index of the second layer along the x-axis, but lowers its refractive index along the y- and z-axis. Such a refractive index shift may be obtained by suitably uniaxially stretching a positively birefringent polymer layer along the x-axis while allowing the film to dimensionally relax along the y- and z-axes. In FIGS. 5C-G, the stretching procedure raises the refractive index of the first layer along the x- and y-axes, but lowers its refractive index along the z-axis. Such a refractive index shift may be obtained by suitably biaxially stretching a positively birefringent polymer layer along the x- and y-axes. (In these figures, the stretching operation causes the refractive indices of the second material to shift in a different way than the first material, and techniques for accomplishing this are discussed further below.) In FIG. 5B, the stretching procedure raises the refractive index of the first layer along the x-axis, lowers its refractive index along the z-axis, and maintains about the same refractive index along the y-axis. In some cases, this refractive index shift may be obtained by biaxially stretching a positively birefringent polymer layer asymmetrically along the x- and y-axes, using a higher degree of stretch along the x-axis compared to the y-axis. In other cases, this may be approximately obtained by uniaxially stretching along an x-axis while constraining the film in the y-axis (constrained uniaxial stretching). Note that in each of FIGS. 5B-G, the first layer in the oriented but untreated state (open circles) is birefringent because at least two of the open circles for n1x, n1y, and n1z have different values of refractive index n. In FIG. 5B, the second polymer layer remains isotropic after stretching as indicated by the same refractive index values (n2x=n2y=n2z) for the cast state and for the oriented but untreated state.
After formation of the at least partially birefringent multilayer optical film having the microlayers arranged into optical repeat units to provide the first reflective characteristic, the film is ready for the selective heating discussed above. The heating is carried out selectively in a second zone which neighbors a first zone of the multilayer optical film, and is tailored to selectively melt and disorient in part or in whole at least one birefringent material in the microlayer packet in order to reduce or eliminate the birefringence in at least some of the microlayers while leaving their birefringence unchanged in the first (untreated) zone. The selective heating is also carried out to maintain the structural integrity of the layers in the second zone. If the birefringent material in the treated second zone is disoriented in whole, i.e., completely, then the birefringent microlayers return to the isotropic state (e.g. of the cast web), while remaining optically thin. This can be seen in FIG. 5A, for example, where heat treatment causes the refractive indices of the second layer (see the small dark dots associated with n2x, n2y, and n2z) to revert to their values in the cast web state (see the diamond-shaped symbols for the refractive indices n2x, n2y, n2z). Recall that the diamond-shaped symbols represent the refractive indices of layers in the isotropic state (e.g., the cast web), the small dark dots represent the refractive indices of microlayers in the treated or selectively heated zones in the finished, internally patterned film, and the open circles represent the refractive indices of microlayers in untreated zones of the finished, internally patterned film.
If the birefringent material in the treated second zone is disoriented only in part, i.e., incompletely, then the birefringent microlayers relax to a state of birefringence that is less than the birefringent state before heating but is not isotropic. In this case, the refractive indices of the birefringent material in the treated second zone acquire values somewhere between the diamond-shaped symbols and the open circles shown in FIGS. 5A-G. Some examples of such incomplete birefringent relaxation are explained in more detail in commonly assigned International Application No. PCT/US2009/069160, “Internally Patterned Multilayer Optical Films With Multiple Birefringent Layers”, filed on even date herewith and incorporated herein by reference.
In FIG. 5A, a first polymer material is selected that has a relatively low refractive index, and a second polymer material is selected that has a higher refractive index and that has a positive stress-optic coefficient. The materials are coextruded in an alternating layer arrangement with a suitable number of layers to form a multilayer cast web, having indices shown by the diamond-shaped symbols. The cast web is then uniaxially stretched along the x-axis under suitable conditions to induce birefringence in the second polymer material while the first polymer material remains isotropic. The refractive index value n2x increases further to form a large index difference Δnx with n1x. The refractive index values n2y and n2z decrease to form small index differences Δny and Δnz with n1y and n1z respectively. The values Δny and Δnz may be zero, for example. This set of refractive indices, when implemented in a microlayer packet with an adequate number of layers, can provide a reflective polarizer with the x-axis being a block axis and the y-axis being a pass axis. The reflective polarizer may be broad band or narrow band, depending on the layer thickness distribution of the microlayers.
This reflective polarizing film can then be internally patterned in a second zone as described above, while leaving the reflective polarizing film intact in a first zone. Selective heating by selective delivery of radiant energy to the second zone causes the birefringent layers to relax to their original isotropic states, or to an intermediate birefringent state if the disorientation is incomplete. If relaxation is complete, the second zone can become a mirror-like film (if the microlayer packet has an adequate number of layers) with Δnx≈Δny≈Δnz. The finished film thus combines in a unitary film a reflective polarizer in one zone and a mirror-like film in a neighboring zone, with microlayers that extend continuously from one zone to the next. For this FIG. 5A, the selective heat treatment process is able to change a multilayer reflective polarizer film to a multilayer reflective mirror film, i.e.: polarizer→mirror.
A patterned multilayer optical film similar to that of FIG. 5A can be made through a variety of methods. A reflective polarizer film with substantially truly uniaxial character can be made, for example, using the stretching methods described in U.S. Patent Application Publication US 2004/0227994 (Ma et al.) or U.S. Pat. No. 6,949,212 (Merrill et al.). For example, a film comprising PEN and an EastarTM co-polyester, so-called “PETG” (available from Eastman Chemical, Kingsport, Tenn.), can be made via co-extrusion. A masterbatch comprising a selected absorbing dye can be introduced into one of the resin streams during co-extrusion, in accord with the methods described in the examples below for Cast Webs 2 and 3, to make the film susceptible to the laser heating method described herein. Alternatively, the isotropic refractive indices of the first material of FIG. 5A can be lower than the n2y and n2z refractive indices of the second material of FIG. 5A in the stretched (oriented) state. For example, a coPET (see e.g. paragraph 0076 of the above-referenced '994 Ma et al. reference), or other lower refractive index non-orienting (isotropic) materials such as PMMA or a coPMMA, can be substituted for the low refractive index EastarTM material mentioned above. The result in these cases is a stronger reflectivity mirror characteristic in the treated zone, and a so-called partial polarizer (having a pass state with reduced transmission and increased reflectivity, see the discussion of partial polarizers below) characteristic in the untreated zone.
In FIG. 5B, first and second polymer materials are again selected that have substantially different refractive indices, the first material again having a lower refractive index than the second material. Here, however, the first polymer material has a positive stress-optic coefficient. The materials are coextruded in an alternating layer arrangement with a suitable number of layers to form a multilayer cast web, having indices shown by the diamond-shaped symbols. The cast web is then oriented with a constrained uniaxial stretch—stretched along the x-axis, constrained along the y-axis—under suitable conditions to induce birefringence in the first polymer material while the second polymer material remains isotropic. The constrained uniaxial stretch causes the refractive index n1x to increase to substantially match refractive index n2x, while refractive index n1z decreases substantially and Δny may experience little or no change (shown in FIG. 5B as decreasing slightly). This yields a very small refractive index difference Δnx, a much larger index difference Δny, and an even larger refractive index difference Δnz that has the same polarity or sign as Δny. This set of refractive indices, when implemented in a microlayer packet with an adequate number of layers, can provide a reflective polarizer film having a pass axis in the x-direction and a block axis in the y-direction. The reflection provided by the film (for light in the block state of polarization) may be broad band or narrow band, depending on the layer thickness distribution of the microlayers. For obliquely incident light, the reflectivity of the microlayer interfaces for p-polarized light will decrease with increasing incidence angle until the Brewster angle is reached, and will then increase as the incidence angle becomes greater than the Brewster angle.
This reflective polarizer film can then be internally patterned in a second zone as described above, while leaving the polarizer film intact in a first zone. Selective heating by selective delivery of radiant energy to the second zone causes the birefringent layers to relax to their original isotropic states, or to an intermediate birefringent state if the disorientation is incomplete. If relaxation is complete, the second zone becomes a multilayer mirror-like film with Δnx≈Δny≈Δnz≠0. The finished film thus combines in a unitary film a multilayer reflective polarizer film in one zone and a multilayer mirror film in a neighboring zone, with microlayers that extend continuously from one zone to the next. For this FIG. 5B, the selective heat treatment process is able to change a multilayer reflective polarizer film to a multilayer reflective mirror film (polarizer→mirror).
In each of FIGS. 5A and 5B, one of the optical materials remains isotropic after stretching (and after the selective heat treatment). This, however, need not be the case in general, and many interesting and useful multilayer optical film designs that can be converted into unitary mirror/polarizer films using selective heat treatment techniques comprise two different optical materials for the constituent layers of the optical repeat unit, and both (rather than only one) of these constituent material layers become birefringent when the cast web is stretched or otherwise oriented. Such multilayer optical films are referred to herein as “doubly birefringent” optical films, since optical repeat units in such a film each include at least two constituent microlayers that are birefringent after stretching. When such a doubly birefringent multilayer optical film is exposed to the selective heat treatment, a number of different responses are possible in the treated zone depending on the material properties and the heating conditions: both material layers may completely relax to become isotropic, or one material layer may relax completely or partially while the other material layer maintains its birefringence, or both material layers may relax by different amounts (e.g., one material layer may relax completely to become isotropic, while the other material relaxes partially so as to maintain only a portion of its birefringence), for example. In any case, the change in birefringence of one or both material layers results in a reflective characteristic in the second (treated) zone of the optical film that differs substantially from a reflective characteristic in the first (untreated) zone of the film. Further details of doubly birefringent multilayer optical films, and selective heating techniques used to internally pattern them, are provided in the following commonly assigned international applications, which are filed on even date herewith and incorporated herein by reference: PCT/US2009/069160, “Internally Patterned Multilayer Optical Films With Multiple Birefringent Layers”; and International Application No. PCT/US2009/069192, “Multilayer Optical Films Having Side-by-Side Polarizer/Polarizer Zones”. Some examples of doubly birefringent multilayer optical films suitable for internal patterning by selective heat treatment to provide unitary mirror/polarizer films are shown in the present application in FIGS. 5C-G.
The embodiments of FIGS. 5C-G also make use of a two-step drawing process that is described in U.S. Pat. No. 6,179,948 (Merrill et al.). In this process, the stretching or orientation of the cast film is carried out using a two-step drawing process that is carefully controlled so that one set of layers (e.g., the first material layer of each optical repeat unit) substantially orients during both drawing steps, while the other set of layers (e.g., the second material layer of each optical repeat unit) only substantially orients during one drawing step. The result is a multilayer optical film having one set of material layers that are substantially biaxially oriented after drawing, and having another set of material layers that are substantially uniaxially oriented after drawing. The differentiation is accomplished by leveraging the different visco-elastic and crystallization characteristics of the two materials by using one or more suitably different process conditions such as temperature, strain rate, and strain extent for the two process drawing steps. Thus, for example, a first drawing step may substantially orient the first material along a first direction while at most only slightly orienting the second material along this direction. After the first drawing step, one or more process conditions are suitably changed such that in a second drawing step, both the first and the second materials are substantially oriented along a second direction. Through this method, the first material layers can assume an essentially biaxially-oriented character (for example, the refractive indices may satisfy the relationship n1x≈n1y≠n1z, sometimes referred to as a uniaxially birefringent material), while the second material layers in the very same multilayer film can assume an essentially uniaxially-oriented character (for example, the refractive indices may satisfy the relationship n2x≠n2y≠n2z≠n2x, sometimes referred to as a biaxially birefringent material).
With this background, FIG. 5C depicts an embodiment in which the first and second polymer materials are selected to have the same or similar isotropic refractive indices, and to both become birefringent after drawing, and to have the same polarity of stress-optic coefficient (in the drawing they are both depicted as positive, but they can instead both be negative). The first and second materials have different melting or softening temperatures, and have different visco-elastic and/or crystallization characteristics such that the two-step drawing process discussed above can be implemented. The materials are coextruded in an alternating layer arrangement with a suitable number of layers to form a multilayer cast web, having indices shown by the diamond-shaped symbols. The cast web is then biaxially stretched along the x- and y-axes using the above-described two-step process, such that the first material is oriented comparably along both the x- and y-axes, whereas the second material is oriented preferentially along the y-axis, with lesser orientation (including in some cases no orientation) along the x-axis. The net result is a multilayer optical film whose first and second microlayers are both birefringent, but the first material layers have a substantially biaxially-oriented character, whereas the second material layers have an asymmetric biaxially-oriented character, or even a substantially uniaxially-oriented character. As shown, the materials and process conditions are selected so that the stretching causes the refractive index values n1x and n1y to increase by similar amounts, while causing n1z to decrease by a larger amount. The stretching also causes the refractive index value n2y to increase to a value equal to or close to that of n1x and n1y, and causes the refractive index n2z to decrease, and causes the refractive index n2x to remain about the same (if the second material orients to a small degree during the x-axis orientation step, then n2x may increase slightly as shown in the figure). This results in refractive indices of the two material layers that have one large in-plane refractive index mismatch (Δnx), one significantly smaller in-plane refractive index mismatch (Δny≈0), and an intermediate out-of-plane refractive index mismatch (Δnz) of opposite polarity from Δnx. When the second material orients more biaxially, index matching in the x-direction after treatment may be achieved by pairing with a first material whose isotropic index is higher than the second. This set of refractive indices, when implemented in a microlayer packet with an adequate number of layers, can provide a reflective polarizer film with a block axis along the x-direction and a pass axis along the y-direction. The reflection provided by the film (for light polarized parallel to the block axis) may be broad band or narrow band, depending on the layer thickness distribution of the microlayers. This reflective polarizer film maintains high reflectivity with increasing incidence angle due to the z-index mismatch of opposite polarity.
This multilayer polarizer film can then be internally patterned in a second zone as described above, while leaving the reflective polarizer film intact in a first zone. Selective heating by selective delivery of radiant energy to the second zone causes at least some of the birefringent layers to relax, becoming less birefringent. In the present case, the heating is carefully controlled to a temperature that is above the melting or softening point of the second material layers, but below the melting or softening point of the first material layers. In this way, the selective heating causes the second birefringent layers in the second zone to relax to their original isotropic states, or to an intermediate birefringent state if the disorientation is incomplete, while causing the first birefringent layers in the second zone to substantially maintain their birefringence. If relaxation of the second material is complete, the second zone is characterized by relatively large in-plane refractive index mismatches (Δnx and Δny), and a large out-of-plane refractive index difference (Δnz) of opposite polarity or sign compared to Δnx and Δny. These refractive index relationships, when implemented in a microlayer packet with an adequate number of layers, can provide a multilayer mirror film in the second zone. The mirror film provides increased reflectivity with increasing incidence angle due to the opposite polarity of the z-index mismatch Δnz. The finished film thus combines in a unitary film a multilayer reflective polarizer film in one zone and a multilayer mirror film in a neighboring zone, with microlayers that extend continuously from one zone to the next. For this FIG. 5C, the selective heat treatment process is able to change a multilayer reflective polarizer film to a multilayer reflective mirror film (polarizer→mirror).
FIG. 5D depicts an alternative embodiment to that of FIG. 5C, where the same first polymer material as that of FIG. 5C may be used, but a slightly different second polymer material is used. Specifically, the second material of FIG. 5D has refractive indices in the cast web, drawn film, and heat-treated film that are all somewhat lower than those of the second material of FIG. 5C in the corresponding cast, drawn, and heat-treated states. This shift in refractive index of the second material produces larger values for Δnx and Δny in the drawn (stretched) film, and a smaller value for Δnz, but Δnx remains significantly larger than Δny. If these refractive index relationships are implemented in a microlayer packet with an adequate number of layers, the result may be an asymmetric reflecting film referred to herein as a partial polarizer. Such a film provides a high degree of reflectivity for normally incident light of one polarization, and a much smaller, yet substantial, degree of reflectivity for normally incident light of the opposite polarization. Such polarizing films can be particularly useful in certain high efficiency, low loss display applications, for example, and in light recycling and spatial homogenization systems, and in other applications. Reference is made to PCT Publication WO 2008/144656 (Weber et al.), “Backlight and Display System Using Same” for further disclosure of such films, which are referred to in that publication as Asymmetric Reflecting Films (ARF), and applications for such films. In FIG. 5D, the block axis of this polarizer film is parallel to the x-axis, and the pass axis (which may exhibit a moderate amount of on-axis reflectivity) is parallel to the y-axis.
The internal patterning of the multilayer film of FIG. 5D in a second zone is carried out in the same way as in FIG. 5C, i.e., selective delivery of radiant energy to the second zone is carefully controlled to heat the microlayers to a temperature that is above the melting or softening point of the second material layers, but below the melting or softening point of the first material layers. The selective heating thus again causes the second birefringent layers in the second zone to relax to their original isotropic states, or to an intermediate birefringent state if the disorientation is incomplete, while causing the first birefringent layers in the second zone to substantially maintain their birefringence. If relaxation of the second material is complete, the second zone is characterized by relatively large in-plane refractive index mismatches (Δnx and Δny), and a substantial out-of-plane refractive index difference (Δnz) of opposite polarity or sign compared to Δnx and Δny. These refractive index relationships, when implemented in a microlayer packet with an adequate number of layers, can provide a multilayer mirror film in the second zone. The mirror film provides increased reflectivity with increasing incidence angle due to the opposite polarity of the z-index mismatch Δnz. The finished film thus combines in a unitary film a multilayer reflective polarizer film in one zone and a multilayer mirror film in a neighboring zone, with microlayers that extend continuously from one zone to the next. For this FIG. 5D, the selective heat treatment process is able to change a multilayer reflective polarizer film to a multilayer reflective mirror film (polarizer→mirror).
FIG. 5E depicts an embodiment very similar to that of FIG. 5D. For example, the same two-step orientation process is used to provide the first material layers with a substantially biaxially-oriented character, and the second material layers with a substantially uniaxially-oriented character. The first and second polymer materials used for FIG. 5E may be nearly identical to those of FIG. 5D, for example, they may have the same refractive indices and the same stress-optic coefficients as the materials of FIG. 5D. Thus, after the stretching process, a multilayer optical film is again formed having a relatively large value of Δnx, a smaller but substantial value for Δny, and an even smaller value for Δnz. If an adequate number of layers is used, the microlayer film or packet may be an asymmetric reflecting film referred to here as a partial polarizer, as discussed above. The block axis of this polarizer film is again parallel to the x-axis, and the pass axis (which may exhibit a moderate amount of on-axis reflectivity) is again parallel to the y-axis.
The materials used in FIG. 5E differ from those of FIG. 5D in one significant respect: the first and second materials of FIG. 5E have relative melting or softening temperatures that are interchanged relative to the first and second materials of FIG. 5D. Thus, in FIG. 5E, the melting or softening temperature of the first material is lower than the corresponding temperature of the second material. This change in material properties allows the selective heating used in the internal patterning operation (in a second zone of the multilayer optical film) to be carefully controlled to a temperature that is above the melting or softening point of the first material layers, but below the melting or softening point of the second material layers. Thus, in this case, the selective heating causes the first birefringent layers in the second zone to relax to their original isotropic states, or to an intermediate birefringent state if the disorientation is incomplete, while causing the second birefringent layers in the second zone to substantially maintain their birefringence. If relaxation of the first material is complete, the second zone is characterized by moderate in-plane refractive index mismatches (Δnx and Δny), and a smaller out-of-plane refractive index difference (Δnz) Note that in-plane mismatches Δnx and Δny have similar magnitudes but opposite polarities. Although the in-plane mismatches are smaller than the block-axis mismatch for the polarizer film in the first (untreated) zone of the film, they may nevertheless be able to provide a substantial multilayer mirror film in the second zone if the microlayer packet or film has an adequate number of microlayers. The finished film thus combines in a unitary film a multilayer reflective polarizer film in one zone and a multilayer mirror film in a neighboring zone, with microlayers that extend continuously from one zone to the next. For this FIG. 5E, the selective heat treatment process is able to change a multilayer reflective polarizer film to a multilayer reflective mirror film (polarizer→mirror).
The multilayer mirror film characterized by the second (processed) zone of FIG. 5E, in which the in-plane mismatches Δnx and Δny are of similar magnitude (including the same or substantially the same magnitude) but opposite sign, and the out-of-plane mismatch Δnz is non-zero and has the same polarity as only one of the in-plane mismatches, has unique optical properties. Such a mirror film can have as high or as low a reflectivity as desired (depending on the number of layers used in the stack) for all polarization states of normally incident light in the reflection band of the stack. For obliquely incident light, however, the mirror film behaves very differently depending on the plane of incidence of the light. For light incident in the plane having the same polarity of in-plane mismatch and out-of-plane mismatch (for the mirror film of FIG. 5E, this would be the x-z plane), the reflectivity of the s-polarized component of the light increases with increasing incidence angle, but the reflectivity of the p-polarized component of the light decreases with increasing incidence angle. In fact, this p-pol reflectivity decreases to a value of zero at the Brewster angle, assuming the Brewster angle is accessible to light incident on the film from air (or from other medium in which the multilayer optical film is immersed), and then rapidly increases for even higher angles of incidence. For light incident in the plane having opposite polarities of in-plane mismatch and out-of-plane mismatch (for the mirror film of FIG. 5E, this would be the y-z plane), the reflectivity of the s-polarized component of the light increases with increasing incidence angle, and the reflectivity of the p-polarized component of the light also increases with increasing incidence angle. The very different reflectivity for p-polarized light at oblique angles for different directions of incidence, combined with the uniform or symmetric reflectivity of all polarization states for normal- and near-normally-incident light, may be advantageously exploited in a variety of systems and applications.
FIG. 5F shows yet another set of material properties that can be used to make a unitary mirror/polarizer multilayer film. This embodiment is again quite similar to that of FIG. 5D, but in a different way from FIG. 5E. In FIG. 5F, the first material has a higher melting or softening temperature than the corresponding temperature of the second material, just as in FIG. 5D. Further, the first and second materials may have the same isotropic refractive indices as in FIG. 5D when the materials are coextruded and quenched to form the cast web. Still further, the first and second materials have different visco-elastic and/or crystallization characteristics such that the two-step drawing process discussed above can again be implemented, just as in FIG. 5D, whereby the first material layers have a substantially biaxially-oriented character, and the second material layers have a more uniaxially-oriented character. The materials used in FIG. 5F differ from those of FIG. 5D in one significant respect: the second material of FIG. 5F has a negative stress-optic coefficient rather than a positive one. (More generally, we may say that the second material of FIG. 5F has a stress-optic coefficient of opposite polarity from that of the first material.) This difference produces corresponding differences in the oriented multilayer optical film. Thus, in FIG. 5F, after orientation, the drawn multilayer film is characterized by a large in-plane refractive index mismatch Δny, and smaller but substantial refractive index mismatches Δny and Δnz. If an adequate number of layers is used, the microlayer film or packet may be an asymmetric reflecting film referred to here as a partial polarizer, as discussed above. Unlike FIG. 5D, the block axis of the FIG. 5F polarizer film is again parallel to the y-axis, and the pass axis (which may exhibit a moderate amount of on-axis reflectivity) is parallel to the x-axis.
The internal patterning of the multilayer film of FIG. 5F in a second zone is carried out in the same way as in FIG. 5D, i.e., selective delivery of radiant energy to the second zone is carefully controlled to heat the microlayers to a temperature that is above the melting or softening point of the second material layers, but below the melting or softening point of the first material layers. The selective heating thus again causes the second birefringent layers in the second zone to relax to their original isotropic states, or to an intermediate birefringent state if the disorientation is incomplete, while causing the first birefringent layers in the second zone to substantially maintain their birefringence. If relaxation of the second material is complete, the second zone is characterized by relatively large in-plane refractive index mismatches (Δnx and Δny), and a substantial out-of-plane refractive index difference (Δnz) of opposite polarity or sign compared to Δnx and Δny. These refractive index relationships, when implemented in a microlayer packet with an adequate number of layers, can provide a multilayer mirror film in the second zone. The mirror film provides increased reflectivity with increasing incidence angle due to the opposite polarity of the z-index mismatch Δnz. The finished film thus combines in a unitary film a multilayer reflective polarizer film in one zone and a multilayer mirror film in a neighboring zone, with microlayers that extend continuously from one zone to the next. For this FIG. 5F, the selective heat treatment process is able to change a multilayer reflective polarizer film to a multilayer reflective mirror film (polarizer→mirror).
FIG. 5G shows yet another set of material properties that can be used to make a unitary mirror/polarizer multilayer film. In this case, the unprocessed film is a mirror-like multilayer film, and the processed film is a polarizer film. The first and second polymer materials are selected to have similar isotropic refractive indices, but the second material's index is slightly lower than that of the first material. Both materials become birefringent after drawing, and both have the same polarity of stress-optic coefficient (in the drawing they are both depicted as positive, but they can instead both be negative). The first and second materials have different melting or softening temperatures, and have different visco-elastic and/or crystallization characteristics, so that the two-step drawing process can be implemented. The materials are coextruded in an alternating layer arrangement with a suitable number of layers to form a multilayer cast web, having indices shown by the diamond-shaped symbols. The cast web is then biaxially stretched along the x- and y-axes using the two-step process, such that the first material is oriented comparably along both the x- and y-axes, whereas the second material is oriented preferentially along the y-axis, with a small amount of orientation along the x-axis. The net result is a multilayer optical film whose first and second microlayers are both birefringent, but the first material layers have a substantially biaxially-oriented character, while the second material layers have a more uniaxially-oriented character. The materials and process conditions are selected so that the stretching causes the refractive index values n1x and n1y to increase by similar amounts, while causing n1z to decrease by a larger amount. The stretching also causes the refractive index value n2y to increase to a value above that of n1y, and causes n2x to increase to a value below that of n1x, and causes n2z to decrease to a value near that of n1z. This results in refractive indices for the two material layers characterized by two substantial in-plane refractive index mismatches (Δnx and Δny, which are of opposite polarity or sign), and a smaller out-of-plane refractive index mismatch (Δnz) having the same polarity as Δny. This set of refractive indices, when implemented in a microlayer packet with an adequate number of layers, can provide a reflective mirror film. The reflection provided by this film may be broad band or narrow band, depending on the layer thickness distribution of the microlayers. This reflective mirror film maintains high reflectivity with increasing incidence angle for oblique light incident in the x-z plane due to Δnz being opposite polarity relative to Δnx. Reflectivity of p-polarized light in the orthogonal y-z plane of incidence may decrease slowly with increasing incidence angle due to Δnz being small but of the same polarity as Δny
The internal patterning of the multilayer film of FIG. 5G in a second zone is carried out in the same way as in FIG. 5E, i.e., selective delivery of radiant energy to the second zone is carefully controlled to heat the microlayers to a temperature that is above the melting or softening point of the first material layers, but below the melting or softening point of the second material layers. The selective heating thus causes the first birefringent layers in the second zone to relax to their original isotropic states, or to an intermediate birefringent state if the disorientation is incomplete, while causing the second birefringent layers in the second zone to substantially maintain their birefringence. If relaxation of the first material is complete, the second zone is characterized by one relatively large in-plane refractive index mismatch (Δny), one small or zero in-plane refractive index mismatch (Δnx), and a substantial out-of-plane refractive index difference (Δnz) of opposite polarity or sign compared to Δny. These refractive index relationships, when implemented in a microlayer packet with an adequate number of layers, can provide a multilayer polarizer film in the second zone, whose pass axis is parallel to the x-axis, and whose block axis is parallel to the y-axis. The polarizer film provides increased reflectivity with increasing incidence angle due to the opposite polarity of Δnz compared to Δny. The finished film thus combines in a unitary film a multilayer mirror film in one zone and a multilayer reflective polarizer film in a neighboring zone, with microlayers that extend continuously from one zone to the next. For this FIG. 5G, the selective heat treatment process is able to change a multilayer mirror film to a multilayer reflective polarizer film (mirror→polarizer).
The scenarios discussed above involve only some of a multitude of possible combinations of material characteristics and processing parameters that can be used to produce unitary mirror/polarizer multilayer optical films, and should not be considered to be limiting. Note that not just positively birefringent but also negatively birefringent materials, and combinations thereof, can be used. Note also that in cases where the combination of a birefringent and isotropic polymer is used, the birefringent polymer may have a pre-stretch isotropic index that is less than, greater than, or equal to the refractive index of the isotropic polymer. Although the above-described scenarios (in connection with FIGS. 5A-G) can be achieved with selective heat treatment in the second zone that utilizes a laser or similar radiation source, with little or no application of force or pressure to the second zone (see e.g. the discussion below in connection with FIGS. 6, 7A-C, and 8A-B), and thus with little or no difference in thickness between the first and second zones of the film, the reader should also understand that other techniques can be used that do involve the selective application of force or pressure to the second zone, and that do result in substantial thickness differences between the first and second zones. In a hot-tool embossing approach, for example, heat can be selectively applied to the second zone of the film so as to bring about the refractive index relationships discussed above, while pressure is also applied to the same second zone. In such an approach, the portions of the microlayers in the second zone are thinned relative to the portions in the first zone, resulting in a spectral shift to shorter wavelengths for the second zone in addition to the change in reflective characteristics discussed above.
In FIG. 6, we show one arrangement 600 that can be used to selectively heat the second zone of the multilayer optical films to provide the disclosed internally patterned films. Briefly, a multilayer optical film 610 is provided that comprises at least one microlayer packet that extends throughout the film, or at least from a first to a second zone thereof. The microlayers are internal to the film and provide the film with a first reflective characteristic. A high radiance light source 620 provides a directed beam 622 of suitable wavelength, intensity, and beam size to selectively heat an illuminated portion 624 of the film by converting some of the incident light to heat by absorption. Preferably, the absorption of the film is great enough to provide sufficient heating with a reasonably-powered light source, but not so high that an excessive amount of light is absorbed at the initial surface of the film, which may cause surface damage. This is discussed further below. In some cases it may be desirable to orient the light source at an oblique angle θ, as shown by the obliquely positioned light source 620a, directed beam 622a, and illuminated portion 624a. Such oblique illumination may be desirable where the multilayer optical film 610 contains a microlayer packet having a reflection band at normal incidence that substantially reflects the directed beam 622 in a way that prevents the desired amount of absorption and concomitant heating. Thus, taking advantage of the shift of the reflection band to shorter wavelengths with increasing incidence angle, the directed beam 622a can be delivered at an oblique angle θ that avoids the (now shifted) reflection band to allow the desired absorption and heating.
In some cases, the directed beam 622 or 622a may be shaped in such a way that the illuminated portion 624 or 624a has the desired shape of the finished second zone. In other cases, the directed beam may have a shape that is smaller in size than the desired second zone. In the latter situation, beam steering equipment can be used to scan the directed beam over the surface of the multilayer optical film so as to trace out the desired shape of the zone to be treated. Spatial and temporal modulation of the directed beam can also be utilized with devices such as beam splitters, lens arrays, pockels cells, acousto-optic modulators, and other techniques and devices known to those of ordinary skill in the art.
FIGS. 7A-C provide schematic top views of different second zones of a patterned multilayer film, and superimposed thereon possible paths of a directed light beam relative to the film capable of forming the depicted zones. In FIG. 7A, a light beam is directed at a multilayer optical film 710 and scanned at a controlled speed from a starting point 716a to an ending point 716b along a path 716 to selectively heat the film in an arbitrarily-shaped zone 714 to distinguish it from a first zone 712. FIGS. 7B and 7C are similar. In FIG. 7B, a light beam is directed at a multilayer optical film 720 and scanned at a controlled speed from a starting point 726a along a path 726 to selectively heat the film in a rectangular-shaped zone 724 to distinguish it from a neighboring first zone 722. In FIG. 7C, a light beam is directed at a multilayer optical film 730 and scanned at controlled speeds along the discontinuous paths 736-742, and so on, to selectively heat the film in a rectangular-shaped zone 734 to distinguish it from a neighboring first zone 732. In each of FIGS. 7A-C, the heating is sufficient to reduce or eliminate birefringence of at least some interior microlayers in the second zone while maintaining the birefringence of those layers in the first zone, and is accomplished while maintaining the structural integrity of the microlayers in the second zone and without any selective application of pressure to the second zone.
The directed light beam may also be modulated to create paths that are dashed, dotted, or otherwise broken or discontinuous. The modulation may be complete, wherein the light beam intensity changes from 100% or “full on” to 0% or “full off”. Alternatively, the modulation may be partial. Further, the modulation may include abrupt (e.g. stepwise) changes in beam intensity, and/or it may include more gradual changes in beam intensity.
FIGS. 8A and 8B address the topic of how the absorption of the multilayer optical film can or should be tailored to provide optimal localized heating. The graphs of FIGS. 8A and 8B are plotted on the same horizontal scale, which represents the depth or position of the radiant light beam as it propagates through the film. A depth of 0% corresponds to the front surface of the film, and a depth of 100% corresponds to the rear surface of the film. FIG. 8A plots along the vertical axis the relative intensity I/I0 of the radiant beam. FIG. 8B plots the local absorption coefficient (at the selected wavelength or wavelength band of the radiant beam) at each depth within the film.
Three curves are plotted in each figure, for three different multilayer optical film embodiments. In a first embodiment, the film has a substantially uniform and low absorption throughout its thickness at the wavelength of the directed light beam. This embodiment is plotted as curve 810 in FIG. 8A and curve 820 in FIG. 8B. In a second embodiment, the film has a substantially uniform and high absorption throughout its thickness. This embodiment is plotted as curve 812 in FIG. 8A and curve 822 in FIG. 8B. In a third embodiment, the film has a relatively low absorption throughout regions 815a and 815c of its thickness, but has a higher, intermediate absorption in region 815b of its thickness.
The first embodiment has an absorption coefficient that is too low for many situations. Although the directed light beam is absorbed uniformly as a function of depth as indicated by the constant slope of the curve 810, which may be desirable in some cases, very little of the light is actually absorbed as shown by the high value of the curve 810 at a depth of 100%, meaning that a high percentage of the directed light beam is wasted. Nevertheless, in some cases this first embodiment may still be quite useful in the treatment of some films. The second embodiment has an absorption coefficient that is too high for many situations. Although substantially all of the directed light beam is absorbed, and none is wasted, the high absorption causes an excessive amount of light to be absorbed at the front surface of the film, which may cause surface damage to the film. If the absorption is too high, an adequate amount of heat cannot be delivered to interior layers of interest without damaging layers at or near the front surface of the film. The third embodiment utilizes a non-uniform absorption profile that may be achieved, for example, by incorporating an absorbing agent into selected interior layers of the film. The level of absorptivity (controlled by the local absorption coefficient) is desirably set to an intermediate level so that an adequate portion of the directed light beam is absorbed in the tailored absorbing region 815b of the film, but the absorptivity is not so high that an excessive amount of heat is delivered to the incident end of the region 815b relative to the opposite end. In many instances, the absorptivity in absorbing region 815b is still reasonably weak, e.g. the relative intensity profile 814 over that region may appear more as a straight line with merely a steeper slope than the other regions, e.g. 815a and 815c. As further described later, the adequacy of the absorption is determined by balancing that absorptivity against the power and duration of the incoming directed light beam to achieve the desired effect.
In an elementary example of the third embodiment, the multilayer film may have a construction of two thick skin layers with one or more packets of microlayers therebetween (separated by protective boundary layers if two or more microlayer packets are included), and the film may be composed of only two polymer materials A and B. An absorbing agent is incorporated into polymer material A to increase its absorptivity to a moderate level but no absorbing agent is incorporated into polymer B. Both materials A and B are provided in alternating layers of the microlayer packet(s), but the skin layers and the protective boundary layers, if present, are composed only of polymer B. Such a construction will have a low absorptivity at the outer surfaces, i.e. the skin layers, of the film, due to the use of the weakly absorbing material B, and will also have a low absorptivity at the optically thick PBLs if they are present. The construction will have a higher absorptivity in the microlayer packet(s) due to the use of the more strongly absorbing material A in alternating microlayers (along with alternating microlayers of the more weakly absorbing material B). Such an arrangement can be used to preferentially deliver heat to interior layers of the film, in particular to the interior microlayer packet(s), rather than to outer surface layers. Note that with an appropriately designed feedblock the multilayer optical film can comprise three or more different types of polymer materials (A, B, C, . . . ), and an absorptive agent may be incorporated into one, some, or all of the materials in order to provide a wide variety of different absorption profiles so as to deliver heat to selected interior layers, packets, or regions of the film. In other cases, it may be useful to include an absorbing agent in the PBL(s) or even in the skin layer, if present. In either case, the loading or concentration may be same or different, either higher or lower, than in the microlayers.
Similar absorption profiles as those of the foregoing embodiments may be obtained using the inherent absorption characteristics of the various native materials used in the multilayer optical film. Thus, the multilayer film construction may comprise different materials having different absorption characteristics among the various layers or packets of the film, and those various layers or packets may have been formed together during film formation (e.g. by coextrusion), or may have been formed as separate precursor films which were later combined e.g. by lamination.
We now reiterate and embellish upon aspects of some of the foregoing teachings and disclosure.
The foregoing disclosure may be considered to describe, among other things, “write-able” multilayer optical films that can be altered by noncontact, radiative means after its initial manufacture. The multilayer optical film (MOF) may comprise at least two materials of alternating layers and at least one optical packet of such layers tuned to reflect a selected portion of the spectrum, such as a visible spectral band, at a first selected angle of incidence, furthermore optionally comprising an absorbing agent which may for purposes of the present discussion be referred to as a third material, dispersed in either or both layers of a selected optical packet, that preferentially absorbs electro-magnetic radiation not principally reflected by the MOF reflective band at a second selected angle of incidence nor significantly absorbed by the other materials of the MOF. We also disclose a process using a directed radiant energy treatment of a specified spectral band to selectively melt and disorient in part or in whole, at least one birefringent material in the optical packet containing the absorbing material in order to reduce or eliminate the birefringence in these layers. The treatment is applied to chosen spatial locations across the film plane. Also disclosed is the finished optical film itself with the spatially tailored optical variations after treatment. The disclosed films can be used in business processes in which an originally uniformly cast and drawn optical body is spatially tailored to conform to the individual requirements of a given application.
One aspect of particular interest is the controlled spatial patterning of multilayer optical films containing, for example, near-IR absorbing dyes or other absorbing agents by selectively removing the birefringence of chosen interior optical layers while leaving other interior or surface layers relatively unchanged by subsequent treating with pulsed IR laser sources or other suitable high radiance light sources.
The films disclosed herein (both prior to selective heat treatment and after selective heat treatment), in which the birefringence of at least some of its internal microlayers can be reduced in one or more zones of the film to provide a second reflective characteristic, different from the initial or first reflective characteristic, may be referred to as STOF: Spatially Tailored Optical Films.
The films, methods, and business processes may be generally useful in any application in which a spatially controlled level of orientation is desired. Fields of interest may include, for example, display, decorative, and security applications. Some applications may overlap multiple fields. For example, some articles may incorporate the internally patterned films disclosed herein in combination with a film, substrate, or other layer that includes conventional patterning in the form of indicia, for example. The resulting article may be useful in security applications, but versions of it may also be considered decorative. Selectively heat treating such an article may produce zones in the internally patterned film that selectively obstruct (by increasing reflectivity) or reveal (by decreasing reflectivity) portions of the conventional patterning of the other film, depending on the design of the internally patterned film. Color shifting characteristics of the disclosed internally patterned films may also be exploited in combination with colored or black-and-white background indicia as disclosed for example in U.S. Pat. No. 6,045,894 (Jonza et al.) “Clear to Colored Security Film”, and U.S. Pat. No. 6,531,230 (Weber et al.) “Color Shifting Film”.
Further in regard to security applications, the disclosed films may be used in a variety of security constructions including identification cards, driver's licenses, passports, access control passes, financial transaction cards (credit, debit, pre-pay, or other), brand protection or identification labels, and the like. The film may be laminated or otherwise adhered as interior or exterior layers to other layers or portions of the security construction. When the film is included as a patch, it may cover only a portion of the major surface of the card, page or label. In some cases, it may be possible to use the film as the base substrate or the only element of the security construction. The film may be included as one of many features in the security construction such as holograms, printed images (intaglio, offset, barcode, etc.), retroreflective features, UV or IR activated images and the like. In some instances, the disclosed films may be layered in combination with these other security features. The film may be used to provide a personalizable feature to the security construction, for example, a signature, an image, an individual coded number, etc. The personalizable feature may be in reference to the individual document holder or a specific product entity, such as in the case of a manufacturer tag, a lot verification tag, a tamper-proof coding, or the like. The personalizable feature can be made with a variety of scanning patterns including lines and dot patterns. Patterns can be the same or different among writable packets, depending on the film construction.
Consider, for example, the case of a first writable packet that initially exhibits a perceptible color but then becomes clear upon treatment or patterning. One or more such color packets can be used. Consider the addition of a second multilayer optical film packet to form the film construction to be included in the security construction. Patterning or writing the first packet will create a design or image in the color of the second packet in a background representing the color characteristics of the two packets combined. When the spectral bands are sufficiently narrow, both the foreground (patterned area) and background can color shift with viewing angle. The variation of the perceived color with background, e.g. white or black backgrounds, to favor transmitted or reflected light viewing can be used as a security feature. For example, a page or leaf of the film in a document, such as a passport, can be flipped to view the film against different backgrounds or portions of the document.
The film may provide both overt (e.g. clearly visible to an ordinary observer) and covert security features to the security construction. For example, a writable (color) reflective polarizer layer can provide a covert feature viewable with a polarizing analyzer, e.g. a feature that changes color or disappears depending on the polarization state of the analyzer. An infrared reflecting packet can be patterned to make an IR detectable, e.g. machine readable, personalized coding feature.
In this regard, any of the disclosed unitary mirror/polarizer multilayer optical films may also be used in any of these security applications.
Multilayer optical films may include at least one selected reflection band for at least one state of linear polarization formed by at least one selected packet of optical interference layers, which may comprise a radiatively absorbing material. The patterning method allows the removal or reduction of the birefringence among a selected set of material layers thus altering the interference characteristics of the optical stack over a selected spectral band. In this manner, the film may be spatially tailored for a desired application, e.g. a pixilated display. The optical film can thus be made to be spatially changing color filters, or can be made to vary between transmissive, reflective mirror and/or reflective polarizers, or in combination of color filtering and these reflective states, or strengths or quality of these states (e.g. from a strong to weak mirror, or from a polarizer or partial polarizer to a mirror). One useful application may be color filters used in liquid crystal display (LCD) devices. Another application may be to use the disclosed materials and techniques to create or “write” structures in the interior or inside of films and similar optical bodies for purposes besides or in addition to wavelength-selective transmission or reflection. The spatial tailoring of optical properties and materials described herein may be used to effect a light guiding structure inside film, for instance bringing the guide through the film and intermittently drawing to the surface. The combination of anisotropic and selectively absorbing materials and laser writing process can produce highly functioning optical structures with the added processing advantage of using longer laser pulse widths, reduced numeric aperture, and potentially greater speed of writing.
A particularly useful class of constructions is a polymeric optical body comprising two or more sets of optically functional layers, each set having a similar function (e.g. optical transform, whether it be reflection or transmission, for example) but wherein each particular set is included to act on a particular portion of the spectral band. At least one set may comprise radiant absorbers, and at least one other set does not. In some cases, more than one set may comprise radiant absorbers. For example, a multilayer optical film may comprise two or more optical interference packets. These packets (sets of optically functional layers) may comprise many layers of alternating materials. One optical packet may contain radiant absorbers and another may not.
A variety of optical absorbers can be used. For optical films operating in the visible spectrum, ultraviolet and infrared absorbing dyes, pigments, or other additives may be useful. It may be desirable to choose a spectral range for absorption that is not highly absorbed by the polymers of the construction. In this manner, the directed radiation can be concentrated in the selected regions of interest throughout the thickness of the optical body. The absorbers are desirably melt extrudable so that they can be embedded in the selected layer set of interest. To this end, the absorbers should be reasonably stable at the processing temperatures and residence times required for extrusion.
The disclosed films and optical bodies can be radiatively treated in a chosen spectral range that is outside the spectral band normally transformed by the optical body for a chosen application of interest. The radiative treatment may be achieved by any variety of means which can focus light of the selected spectral band at a sufficient intensity on a chosen location of the film. A particularly suitable means for the radiative treatment is a pulsed laser. This may be an amplified pulsed laser. In some circumstances, the laser may be tunable. For example, an optical film operationally reflective in the visible band may have an absorber in the near IR, or the near UV if the polymer is not particularly absorptive there. For a multilayer optical film, the selection of the absorption band for treatment may be chosen with regard to the optical band of the film. Preferably, the film should not reflect the directed radiant energy for the angle of incidence chosen for this directed radiant energy, although treatment may still be possible if the reflection is sufficiently low. Radiant energy from lasers is frequently substantially polarized. It can be useful to orient the impinging beam at an angle coincident with the Brewster's angle at the outer surface to minimize energy loss. Because the MOF reflection band also shifts to shorter wavelengths with higher incident angles, shorter absorption wavelengths can be used than would be expected solely by the band placement at the normal incident angle.
For example, an MOF mirror film with a biaxially oriented skin layer of index 1.75 (at a wavelength of 632 nm) and corresponding Brewster's angle of about 60 degrees and a sharp normal incident right band edge at about 800 nm can accept a directed light beam above about 700 nm at the Brewster's angle, allowing for processing using this wavelength even though it is reflected at normal incidence. The right band edge is chosen in part to ensure reflection at all angles of interest. At 880 nm, the reflection band still covers to about 700 nm at grazing incidence. At this band position, the band covers up to 750 nm near the Brewster's angle of this case. Some headroom may be desirable between the band edge and the wavelength of the directed radiation. If it is desired that the beam be directed through any of the potential layers, then this puts a practical lower limit in this case of about 750 to 800 nm (vacuum) for the directed energy above the optical band. Alternatively, one may choose to direct the radiant energy through a preferred side of the film so that the intervening wavelength bands in the film do not block the particular energy of interest. For example, a green laser at 532 nm may be used to process a blue packet as long as it does not need to pass at normal incidence through a green reflecting packet, or if the beam could pass through it at sufficiently oblique angle to no longer be reflected by that packet due to the band shift.
If near UV radiation is used for patterning (which again depends on the material absorption characteristics), the band shifting of packets with a longer wavelength reflection band may obstruct the beam. Normally incident directed radiation can then have the highest wavelength relative to the fixed left band edge of the film, whereas oblique angle processing could be obstructed by band shifting. Left band edge shifting is also relevant for other visible or IR beams used with constructions that have band shifting reflection bands higher than the beam vacuum wavelength.
Management of the absorbed radiant energy through the thickness of the film and the resulting thermal pulse through the thickness, is one aspect of the present disclosure. Controlled melting resulting in reduced or eliminated birefringence of materials in the selective layers spanning a selected portion of the film thickness calls for a reasonably low level of absorption of the directed radiation to ensure uniform effect. The materials in the selected layers(s) should not over-heat either from a time pulse or thermal standpoint resulting in either excessive ionization or thermal decomposition. For example, if one considers a purely heat capacity driven situation, a material brought from 25 degrees C. to a desired 300 degrees C. heats up 275 degrees C. If the selected layer absorbs 10% of the directed radiation, then the front portion closest to the source of the directed radiation needs to heat up to about 330 degrees C. in order for the back portion to heat up to the desired 300 degrees C. Sufficient headroom between the hottest portion of the film and deleterious temperatures or ionizing conditions should be maintained. Through-thickness temperature control may be important to selectively remove birefringence from only one material, e.g., to prevent overheating. In some cases, preheating may be desired. Efficiency of the process, from a laser energy perspective, can be increased by preheating the film before and during laser exposure. The preheat temperature of the film should be above room temperature but below the melting temperature for the polymers used in the optical packet. Typically, when the film is pre-heated throughout its thickness, then a larger amount of the directed radiation may be absorbed for the same level of thermal headroom. For example, when a back portion of a selected film region at 200 degrees C. is heated to 300 degrees C. for a difference of 100 degrees C., the front portion will only be overheated to 310 degrees C. when about 10% of the incident energy of the beam is absorbed. In this case, the selected region could absorb up to about 23% of the directed radiation, to again result in heating up to about 330 degrees C. with a temperature rise of 130 degrees C. for the front portion and a 100 degree C. rise for the back portion to again reach the desired 300 degrees C. The amount of preheating may need to be controlled to prevent wash-out of the thermal pulse during cooling resulting in significant melting beyond the selected region. Generally, the higher the pre-heating, the closer the remainder of the film thickness is to melting. These non-selected portions can become liable to melting as the thermal pulse spreads. The maximum temperatures induced by the directed radiation, the sidedness of the film construction with its various layer thicknesses, the pre-heating gradient through the film, and the path of the directed radiation, all may need to be considered together to optimize the film and process. In fact, the thermal management is even more complicated, because sufficient energy is preferably absorbed not only to raise the material into its melting range but also to actually cause the melting. The management of the energy pulse(s) of the directed radiation should include the time factor to ensure that melting can in fact occur and that the thermal wave is adequately contained along the thickness- or z-axis to prevent undesired melting, such as to melt birefringent layers in one microlayer packet without melting birefringent layers in another microlayer packet. In particular, the sequence and duration of the pulses may need to be carefully controlled.
The power, scan speed, and beam shape of a laser source (if a laser source is used for the selective heating) and the dye loading (or loading of another absorbing agent, if in fact any absorbing agent is used) combine to provide an effective energy transmitted to the processed region of the film under adiabatic conditions. Although thermal conditions are not generally adiabatic in practice, approximate laser processing conditions can be estimated by determining the required energy for conversion assuming adiabatic conditions with a specification of the film construction, background temperature, and knowledge of the various heat capacities, heats of fusion, and melting points of the pertinent materials. Dispersion of the IR absorber or other absorbing agent may be an important consideration, including dye solubility limits and dissolution mechanics. For undissolved dyes and pigments, particle size and shape distributions may be important. For example, excessively large absorbing particles can over-heat relative to their surrounding film matrix, causing film defects such as degradation, wrinkling, blistering, layer delamination, or other damage. Film cleanliness may also be important, since surface and embedded dust and similar particulate matter may also cause random or unanticipated defects. Other considerations include the beam shape and frequency (if a pulsed source is used) of the laser source, the scanning pattern, the mounting of the film (e.g. onto a card or other substrate by lamination such as with an adhesive or by other means), and the heat transfer, e.g. as controlled by the various thermal conductivities within and heat transfer coefficients from the film.
Management of the absorbed radiant energy across the film plane may also be important to ensure the desired spatial feature. Beam size and focus can also be important process controls. In some cases, it may be desirable to place the film at a location where the beam is focused to its smallest size, while in other cases the film may be deliberately placed at a location where the beam is defocused by a desired amount. The manner of scanning the film and how quickly the directed light beam path can overlap or turn on itself during processing of an area can alter surface roughness, smoothness, haze, wrinkling and other phenomena. With regard to the film preheating discussion above, the beam may be controlled in such a way that a portion of the film currently being irradiated is close to a portion of the film that was recently irradiated, so that the heat provided by the laser itself can be considered to preheat the portion of the film currently being irradiated. This may occur, for example, where the beam is scanned along a first path, and soon thereafter (while the portion of the film along and close to the first path is still at an elevated temperature) scanned along a second path that is adjacent to, or even somewhat overlapping with, the first path.
Time-related aspects such as the duration of the directed radiation may also be important. We have found that relatively short, pulsed operation is often advantageous. For example, in some typical cases we have found that the heating time, as determined by the duration of the laser exposure, is preferably in the range of 10 nanoseconds to 10 milliseconds. The upper exposure duration is a function of the amount of thermal diffusion into other portions of the film through the thickness that can be tolerated for the given application. The shorter the duration, the more compact the delivery of the energy into the desired film region of interest; for example, it may be possible to establish a momentary heat pulse mostly contained within the desired packet. The details of the thermal diffusion are a function of the materials, the anisotropic thermal conductivities at the particular material orientation conditions, the densities, the heat capacities, the thickness of the regions of interest, the beam durations, and the like. In exemplary embodiments, the energy absorbed by the optical packet is of sufficient intensity and duration to melt the optical repeat units in the optical packet but of insufficient intensity and duration to evaporate, significantly chemically modify, or ablate components of the film.
In order for the laser exposure to modify the packet birefringence in the second zone, both high intensity (high power/unit area) and high energy density are desirable, but not necessary. These characteristics help to ensure that a substantial amount of heat generated by absorption of the directed radiation by the materials in the packet stays in the packet, by reducing the time needed for treatment. Thermal diffusion reduces the concentration of energy in the packet and therefore may reduce the efficiency of the process. In this regard, it is often desirable for only a small amount of heat to be dissipated outside of the packet, either laterally into the first (untreated) zone or within the (treated) second zone to other layers of the film. The more heat dissipated outside of the absorbing packet or packets in the second zone, the less efficient the process in those cases where it is desired to heat only a portion of the thickness of the film in the second zone.
The manner of cooling may also need to be carefully considered. Rapid cooling may be useful in some instances. Cooling from one or both sides of the film may be desirable.
Reasonably low levels of absorption of the directed radiation may also be important for end-use applications. It is desirable that environmental exposure not unduly overheat the film. In particular, near IR absorption may result in film heating when exposed to direct sunlight. Preferably, the expected flux does not raise the film temperature unduly. For example, it may be desirable to maintain the temperature of the system below the glass transition temperature of the film under normal use. The amount of energy absorption is in part related to the amount of energy that must be captured from the pulses to achieve the needed temperature difference from the given level of pre-heat.
The desired absorption in the system may thus be optimized, balancing the flux levels, thermal diffusion (wash-out), preheating, and cooling to achieve the desired uniformity and extent of treatment while minimizing end-use concerns, such as color, grayness, or environmental radiant absorption.
It may be useful to incorporate energy absorbing buffer layers or regions between the functional layers or regions of the film. These buffer regions can heat up and even partially or totally melt while protecting another functional region of the film from heating via thermal diffusion (wash-out). In one example, this buffer region could be layers (e.g. PBLs) between packets of a similar or different material than that used in the optical layers. In another example, a lower melting temperature material can be used as “thermal speed bump” between functional layers of higher melting temperature materials. In a multilayer optical film, one simple example is a PEN:PMMA or PEN:isotropic coPEN mirror construction comprising optical packets separated by a lower melting and oriented coPEN protective boundary layer (PBL) such as a so-called low-melt PEN (LmPEN) which e.g. may comprise 90%/10% naphthalate/terephthalate carboxalate subunits.
The melting point and/or softening point (e.g., the glass transition temperature) of a material layer in a polymer film can be measured and analyzed using differential scanning calorimeter (DSC) techniques. In such techniques, the film sample may first be suitably dried, e.g. under vacuum of less than 200 mTorr for about 48 hours at 60 degrees C. before testing. A sample of about 5 mg may then be weighed and sealed in a hermetically sealed aluminum Tzero pan. A heating-cooling-heating ramp may then be conducted over a suitable temperature range, e.g., 30-290 degrees C. A constant heating rate of 20 degrees C./min, or other suitable heating rate, can be used for the ramp. After the scan, the first heating thermal trace may be analyzed for softening step changes and melting peaks. The analysis may reveal both the melting temperature and the characteristic bandwidth associated with the melting temperature, the bandwidth referred to as the peak width at half height (PWHH). Finite values of PWHH reflect the fact that a material can melt over a finite range of the temperatures rather than at a single precise temperature. The PWHH may become important for articles whose different materials have (peak) melting temperatures that are close to each other. The DSC technique was used to measure the melting temperature and PWHH for three exemplary materials suitable for use in multilayer optical films: polyethylene naphthalate (PEN); a naphthalate-based copolymer of PEN, described in Example 7, so-called PEN-CHDM10 of U.S. Patent Application Publication US 2009/0273836 (Yust et al.), referred to herein as “PEN-Gb”; and a PEN-based polymer in which 20% of the dimethyl 2,6-naphthalene dicarboxylate (NDC) is substituted with 4,4′Biphenyldicarboxylic acid dimethyl ester, referred to herein as “PENBB20”. Samples of these materials were measured, and exhibited melting points of 261, 248, and 239 degrees C. for the PEN, PEN-Gb, and PENBB20 samples respectively. The PWHH of the samples were also measured. The PWHH of the PEN sample was 7 degrees C., but depending on processing conditions of the polymer this may range from 5 to 10 degrees C. The PWHH of the PEN-Gb sample was 6 degrees C., but depending on processing conditions this may range from 5 to 15 degrees C. The PWHH of the PENBB20 sample was 10.4 degrees C., but depending on processing conditions this may range from 5 to 15 degrees C. In general, the PWHH of a polymer film may be decreased by heat setting the film at a suitable temperature below the melting point for a suitable time.
In general, for any particular wavelength band for the directed radiation, the absorptive power of the remainder of the film along the thickness direction may be tailored to be sufficiently low, relative to the selected portion of the film for this radiation, to prevent undesired over-heating and undesired alteration of these non-selected portions. The film extrusion process may be designed to ensure that migration of the actively absorbing material of a selected portion of the film from that portion to another functional portion of the film does not happen to a significant degree. Again, a buffer layer that blocks such migration, e.g. through chemical nonaffinity, can be used. Processing methods, including residence times for layer contact and the like, can also be used.
The directed radiant treatment may be achieved directly after or even during film manufacture, separately but still in roll form, after sheeting, or after mounting to another substrate such as a glass plate, or plastic or paper cardstock. The level of precision should be balanced against the process variations. For example, web flutter should be sufficiently handled for a roll process. The directed radiant treatment could be achieved as the film moves over a roller while the film is under tension, perhaps between nips. A protective film can be placed between the film and the rollers to continuously clean the rollers and otherwise prevent cosmetic defects such as scratches. In another example, the film can be mounted on a fixed substrate after sheeting, or mounted or fixed over a temporary backing in a semibatch manner. For example, portions of the film roll can successively contact a protective film and slide over a plate. The film roll conveyance could stop, the designated portion over the plate could be slightly tensioned as desired, and then the directed radiant treatment applied over the designated portion backed by the plate. The finished roll portion may then be moved off the plate treatment zone by a successive conveyance by which the successive portion of the roll may be treated, and so on until the entire roll is treated.
The interior patterning method described herein may also be combined with known techniques, e.g. ablative, surface amorphization techniques, focusing methods, embossing, thermoforming, etc.
A variety of melt-extrudable absorbing additives are available from a variety of sources. The additives may be organic, inorganic, or a hybrid. They may be dyes, pigments, nano-particles, or the like. Some potential IR dyes include any of the Nickel, Palladium, and Platinum-based dyes available from Epolin, Inc. under the tradename EpolightTM. Other suitable candidates include AmaplastTM-brand dyes, available from ColorChem International Corp., Atlanta, Ga. Both linear and non-linear absorbing additives may be considered.
Several factors in combination may make a dye particularly suitable for the present application. Thermal stability through the extrusion process is particularly desirable. In general, the extrusion process is desirably hot enough to both melt and allow the conveyance of the melt streams at suitably manageable pressure drops. For example, polyester based systems may require very high stability up to about 280 degrees C. These requirements can be reduced by using co-polymers of various polymers, such as coPENs, e.g. with processing around 250 degrees C. Olefinic systems like polypropylene, and polystyrene, are typically less demanding. The choice of resins in a particular multilayer optical film construction can narrow the choices of potential absorbing material candidates, as can dye migration tendencies, the ability to be uniformly dispersed in the desired materials layers, the chemical affinities of the dye to the various materials, and so forth.
EXAMPLES
Cast Webs 1, 2, and 3
The term “cast web” refers to a cast and formed multilayer body prior to subsequent drawing and orientation but after the initial casting process. A first multilayer polymer web, or cast web, was constructed using naphthalate-based co-polymers. The first such co-polymer is referred to as PEN-Gb and the second such co-polymer is referred to as coPEN 55/45 HD. The first co-polymer, PEN-Gb, is described in Example 7, so-called PEN-CHDM10, of U.S. Patent Application Publication US 2009/0273836 (Yust et al.). PEN-Gb is thus a co-polymer made with initial monomer charges in the proportion of 38.9 lbs NDC (dimethyl 2,6-naphthalene dicarboxylic acid—e.g. as available from BP Amoco, Naperville, Ill.) to 20.8 lbs of EG (ethylene glycol—e.g. as available from ME Global, Midland, Mich.) and 2.23 lbs of CHDM (cyclohexane dimethanol—e.g. as available from Eastman Chemical, Kingsport, Tenn.), according to Table 1 of the referenced U.S. patent application. The second co-polymer, coPEN 55/45 HD, is the copolyethylenenaphthlate, comprising 55 mol % naphthalene dicarboxylate, 45 mol % terephthalate as carboxylates and 95.8 mol % ethylene glycol, 4 mol % hexane diol and 0.2% trimethylol propane as glycols, as described in Example 10 of U.S. Pat. No. 6,352,761 (Hebrink et al.).
The multilayer polymer web was formed using a coextrusion process as generally described in U.S. Pat. No. 6,830,713 (Hebrink et al). The various polymers were generally dried, e.g. at 85 degrees C. for 60 hours, and then fed into separate extruders of either a single screw or twin screw configuration. The first and second polymers forming the optical layers were co-extruded, each with its own extruder with a final extruder zone temperature, and fed through a melt train including a 151 alternating layer feedblock using a gradient feed plate that provides a layer thickness gradient through the film thickness. These layers form the so-called optical stack or microlayer packet of the finished multilayer film. To improve flow quality of the layers, two thicker, so-called protective boundary layers (PBLs) adjoin the outermost layers of the optical stack and protect the optical stack from the highest shear rates at the feedblock walls. The PBLs are also fed by the one of the extruders. For purposes of these examples, the material feeding the PBLs will be referred to as material 1, the other as material 2, and likewise for the extruders. Each PBL is about 4% of the thickness of the optical stack. Prior to spreading in the die at a die set point temperature, an additional skin layer fed by extruder 3, with a material 3, is joined to the coextruding multilayer flow, top and bottom, for additional layer stability during flow in the die. In these described examples, material 3 may be the same as material 1 or 2. (The terminology “material 1”, “material 2”, and “material 3” used in connection with the examples should not be construed in any predetermined fashion with respect to the “first material” and “second material” terminology used elsewhere in this document, e.g. in connection with FIGS. 5A-G. For example, the “material 1” of the present examples may correspond to the “first material” of FIGS. 5A-G, or alternatively the “material 2” of the present examples may correspond to such “first material”.) In the case of this first cast multilayer web, material 1 was the first co-polymer, so called PEN-Gb, material 2 was the second co-polymer, so-called coPEN 55/45 HD, and material 3 was again PEN-Gb. The multilayer construction was cast from a die, quenched and electro-statically pinned to a casting wheel to form rolls of the first cast multilayer optical web. This first cast web was wound upon disposable cores having widths of at least 10 cm with a desired approximate thickness (or caliper) over a central portion in width dimension. Other details of construction of the first cast web are provided in Table A below.







TABLE A







Processing Conditions for Cast Web 1










Conditions
Cast Web 1







Material 1
PENGb



Material 2
coPEN 55/45 HD



Material 3
PENGb



Extruder 1 Final Temperature
254 degrees C.



Extruder 2 Final Temperature
249 degrees C.



Extruder 3 Final Temperature
254 degrees C.



Melt Train Temperature
260 degrees C.



Die Temperature
249 degrees C.



Material 1 relative weight fed
8



Material 2 relative weight fed
9



Material 3 relative weight fed
15



Stream fed Masterbatch
none



weight % dye in Master batch
NA



Masterbatch fraction of stream
NA



Cast thickness, center (microns)
420










Cast webs 2 and 3 were made in like fashion to Cast Web 1, except that an absorbing agent was added to the extruder feed of material 2, and the casting wheel speed was adjusted to adjust the overall thickness of the cast webs. The absorbing agent was an IR dye used to capture radiant energy in the subsequent writing process. The IR dye was compounded into material 2 in a so-called “masterbatch,” and this masterbatch was then introduced into the extruder feed stream in a prescribed proportion to virgin material 2. For Cast Webs 2 and 3, the prescribed proportion was 1:13 (1 part master batch to 13 parts virgin material). Just as with Cast Web 1, material 1 was the so-called PEN-G, material 2 the so-called coPEN 55/45 HD and material 3 was also the PEN-G for the Cast Webs 2 and 3.
Masterbatches were made prior to the multi-layer co-extrusion by feeding the dye and polymer resin in prescribed weight ratios into a twin screw extruder with or without an additional vacuum applied as needed to ensure minimal degradation of the resin. The extrudate was then chopped into pellets for feeding. The dye used in these example Cast Webs 2 and 3 was a platinum-based dye, EpoliteTM 4121 available from Epolin, Inc., Newark, N.J. The peak absorption wavelength for this dye is around 800 nm. For the masterbatch compounding with the EpoliteTM 4121 dye, nominal final zone extrusion temperatures were between 240 degrees C. and 260 degrees C. A typical masterbatch nominal dye concentration was 1.0 wt % dye in polymer.
Extrusion and process details for the Cast Webs 2 and 3 are provided in Table B below. Note that the difference in thickness between Cast Web 2 and Cast Web 3 was achieved by simply changing the speed of the casting wheel.







TABLE B







Processing Conditions for Cast Webs 2 and 3









Conditions
Cast Web 2
Cast Web 3





Material 1
PENGb
PENGb


Material 2
coPEN 55/45 HD
coPEN 55/45 HD


Material 3
PENGb
PENGb


Extruder 1 Final Temperature
254 degrees C.
254 degrees C.


Extruder 2 Final Temperature
249 degrees C.
249 degrees C.


Extruder 3 Final Temperature
254 degrees C.
254 degrees C.


Melt Train Temperature
260 degrees C.
260 degrees C.


Die Temperature
249 degrees C.
249 degrees C.


Material 1 relative weight fed
8
8


Material 2 relative weight fed
7
7


Material 3 relative weight fed
15
15


Stream fed Masterbatch
Material 2
Material 2


weight % dye in Master batch
1
1


Masterbatch fraction of stream
0.07
0.07


Cast thickness, center (microns)
365
115









The surface indices of refraction (of the PEN Gb material at the outside of the cast webs) were measured using a Metricon Prism Coupler. The index of refraction was essentially isotropic, with values of 1.638, 1.639, and 1.634 in the casting (MD), width (TD), and thickness directions respectively. The refractive index of the coPEN 55/45 HD layers was nominally 1.610 in all directions The transmission characteristics of Cast Webs 1, 2, and 3 were also measured, using a Perkin-Elmer Lambda 950 spectrophotometer. The results are provided in FIG. 9, where percent transmission is plotted against wavelength, and where curve 910 is for Cast Web 1, curve 912 is for Cast Web 2, and curve 914 is for cast web 3. The infrared absorption provided by the absorbing agent in Cast Webs 2 and 3 is readily apparent at about 800 nm, with the absorption of Cast Web 2 being stronger than Cast Web 3 due to the greater thickness of cast web 2 compared to Cast Web 3. Note also that the IR dye has a secondary absorption peak around 530 nm, which gives Cast Webs 2 and 3 a rosy hue.
Birefringent Multilayer Films Made Using Cast Webs 1, 2, and 3
The multilayer cast webs were then drawn or stretched so as to form multilayer optical films containing birefringent microlayers. A laboratory stretcher such as the KARO IV (available from Bruekner) was used for the present examples. The cast webs were generally pre-heated (with a pre-heat time and temperature) and then stretched at a uniform separation speed of the grippers corresponding to an initial strain rate (given by a % strain rate) to nominal draw ratios (the ratio of initial to final gripper separation) in two in-plane orthogonal directions (referred to as “x” and “y” directions). Some of the films were subsequently heat set after drawing at elevated temperature (heat set temperature) over a prescribed duration (heat set time). The processing conditions used for stretching the Cast Webs 1, 2, and 3 were selected such that, in the resulting multilayer optical films (referred to below as Multilayer Optical Films 1, 2, 3, 4, 5, 6, and 7), the PEN Gb microlayers were positively birefringent, and the coPEN 55/45 HD microlayers remained substantially isotropic with a refractive index of about 1.610.
Multilayer films 1 and 2 were made in this fashion from Cast Web 1 under the following conditions:







TABLE C







Multilayer Optical Films 1 and 2











Conditions
Film 1
Film 2















Cast Web
1
1



Preheat time (seconds)
60
60



Pre-heat temperature (degrees C.)
125
125



Draw temperature (degrees C.)
125
125



Initial strain rate along x per second
10%
10%



Initial strain rate along y per second
10%
10%



Final Nominal x Draw Ratio
4
3.2



Final Nominal y Draw Ratio
4
3.2



Heat set time (seconds)
30
30



Heat set temperature (degrees C.)
180
160



Visible Appearance of transmitted light
cyan
white/clear



Visible Appearance of reflected light
pink
white/clear










The final films could then be analyzed, before and/or after radiant energy processing, using a variety of physical and optical methods. The refractive indices of the outside of the skin layer (composed of the oriented PEN Gb material), where indicated, were measured at 632.8 nm using a Prism Coupler available from Metricon (Piscataway, N.J.). In summary, these values were measured as: nx and ny in a range from 1.69 to 1.75 and nz in a range from 1.50 to 1.52 (for all of Multilayer Optical Films 3 through 6, discussed below); nx=1.723, ny=1.733, nz=1.507 for Multilayer Optical Film 6, discussed below); and nx=1.841, ny=1.602, nz=1.518 for Multilayer Optical Film 7, discussed below).
The transmission band characteristics of the various cast webs and final films were measured with a Perkin-Elmer Lambda 950 spectrophotometer. Color characteristics were also observed visually under conditions that favored perception of transmitted and/or reflected light.
FIG. 10 illustrates typical spectra for Film 1 of this Example 1, where curves 1010 and 1012 were taken at different positions on the film. Both curves are fairly representative of Film 1. Differences between the curves may be the result of thickness variations as well as layer profile variations due to flow variations down and crossweb during extrusion, film casting, and drawing. The major portion of the reflection band, defined by left and right band edges at 50% of the half minimum relative to the baseline transmission of around 85%, generally lie between 560 nm and 670 nm. The baseline transmission drop from 100% is the result of surface reflection from the two major surfaces of the constructions (front and back).
Cast webs 2 and 3 were then also drawn or stretched to form other multilayer optical films containing birefringent microlayers. The resulting multilayer optical films, referred to as Films 3-7, and their processing conditions are as described in Table D:







TABLE D







Multilayer Optical Films 3 through 7












Conditions
Film 3
Film 4
Film 5
Film 6
Film 7















Cast Web
2
2
2
2
3


Preheat time (seconds)
60
60
60
60
60


Pre-heat temperature (degrees C.)
125
125
125
125
125


Draw temperature (degrees C.)
125
125
125
125
125


Initial strain rate along x per second
20%
10%
10%
10%
10%


Initial strain rate along y per second
20%
10%
10%
10%
 1%


Final Nominal x Draw Ratio
4
4.25
4
4.25
6


Final Nominal y Draw Ratio
4
4.25
4
4.25
1.1


Heat set time (seconds)
none
None
30
30
none


Heat set temperature (degrees C.)
NA
NA
180
180
NA


Visible Appearance of transmitted
magenta
yellow
magenta
yellow
yellow


light


Visible Appearance of reflected
green
purple/blue
green
purple/blue
purple/blue


light









Multilayer Films with Internal Patterning
Polarizer/Mirror Film 1
A crude unitary polarizer/mirror multilayer optical film was made by combining Film 7 (which was a narrow band reflective polarizing film having a pass axis and an orthogonal block axis) with two pieces of Film 1 (which was a narrow band mirror film), to produce a composite multilayer optical film with Film 7 sandwiched between the pieces of Film 1, and then selectively heating interior layers of the Film 7 in a zone using the absorptive heating technique discussed above to change the reflective polarizing characteristic of Film 7 to a reflective characteristic more representative of a mirror in the treated zone. The addition of the pieces of the mirror-like Film 1 was not necessary to demonstrate the patterned polarizer/mirror film, but was included to provide visually interesting color combinations as described below.
In particular, a composite multilayer optical film, in the form of a three film laminated stack, was formed by successively hand laminating a piece of Film 1 to a piece of Film 7, and then laminating the exposed side of Film 7 to another piece of Film 1, where each lamination used 3MTM 8141 Optically Clear Adhesive available from 3M Company, St. Paul, Minn. The resulting composite film appeared green in unpolarized light. It was particularly advantageous to view the film on a light box which highlighted the light transmitted through the film.
A separate polarizer, i.e. an analyzer, whether of the reflective or absorptive type, could be used to visually or spectrally analyze the film. A broadband analyzer was obtained, and the composite film resting on the light box was viewed through the analyzer. When the analyzer was oriented such that its block axis was aligned with the pass axis of the Film 7 (and the pass axis of the analyzer was aligned with the block axis of the Film 7), the light transmitted by the composite film appeared deeper green than without the analyzer. When the analyzer was oriented such that its block axis was aligned with the block axis of the Film 7 (and the pass axis of the analyzer was aligned with the pass axis of the Film 7), the color contribution of the polarizing Film 7 was essentially removed and the composite film assumed a cyan color.
The composite film was then treated in selected portions or zones with a Coherent Micra ultrafast oscillator laser (wavelength=800 nm, pulse rate=70 MHz) at a scanning speed of 20 mm/sec and with an average laser power of 250 mW. In this manner, the birefringence of interior layers of Film 7 was partially removed in the treated zone to produce a patterned composite film referred to as Polarizer/Mirror Film 1. The composite film thus assumed a more cyan appearance in the treated zone without using any analyzer to view the film. Then, the broadband analyzer was again used to visually and spectrally analyze the film. When the block axis of the analyzer was aligned with the pass axis of the polarizing Film 7, the composite film in the treated zone remained cyan while the background untreated zone had the deeper green appearance observed previously. When the block axis of the analyzer was aligned with the block axis of the polarizing Film 7, the color contribution of the polarizing Film 7 was again essentially removed and the treated and untreated zones both assumed the same basic cyan color. Under these viewing conditions, the color of the treated zone blended into that of the untreated background zone.
The visual appearance changes have concomitant changes in the transmission spectra of the treated and untreated portions of the composite film. FIG. 11 shows the measured normal angle spectral transmission through the Polarizer/Mirror Film 1 for light polarized parallel to the block axis of the Film 7 (i.e., where the spectrophotometer used a broadband analyzer whose pass axis was aligned with the block axis of Film 7). Curve 1110 was obtained on the Polarizer/Mirror Film 1 prior to laser treatment (thus also being representative of untreated zones of the Polarizer/Mirror Film 1 after laser treatment), and curve 1112 was obtained on a treated zone of the Polarizer/Mirror Film 1. FIG. 12 shows the measured normal angle spectral transmission through the Polarizer/Mirror Film 1 for light polarized parallel to the pass axis of the Film 7 (i.e., where the spectrophotometer used a broadband analyzer whose pass axis was aligned with the pass axis of Film 7). Curve 1210 was obtained on the Polarizer/Mirror Film 1 prior to laser treatment (thus also being representative of untreated zones of the Polarizer/Mirror Film 1 after laser treatment), and curve 1212 was obtained on a treated zone of the Polarizer/Mirror Film 1. Note that in FIGS. 11 and 12, the reflection band disposed between about 550 and 725 nm is predominantly due to the two pieces of Film 1 of the composite film, and the reflection band disposed between about 400 and 550 nm (which is stronger in FIG. 11 than in FIG. 12) is predominantly due to the single piece of Film 7 of the composite film. Inspection of the figures shows that polarizing strength of Film 7, i.e., the difference between the maximum transmission for the block state and the maximum transmission for the pass state in the spectral band from 400-550 nm, or the difference between the maximum reflectivity for the block state and the maximum reflectivity for the pass state in the spectral band from 400-550 nm, is reduced in the treated zone, with the pass state of the treated zone reflecting more and the block state of the treated zone reflecting less than the untreated zone. The person of ordinary skill will understand that further optimization of processing conditions can be readily carried out to provide a more balanced mirror characteristic in the treated zone. The person of ordinary skill will also understand that a unitary polarizer/mirror multilayer optical film similar to Polarizer/Mirror Film 1 can be made, but where the outer pieces of Film 1 are omitted.
Additional Embodiment (Prophetic)
Multilayer Optical Film 8, and Polarizer/Mirror Film 2
Another unitary polarizer/mirror multilayer optical film can be made in similar fashion to Polarizer/Mirror Film 1, using a multilayer optical film similar to Multilayer Optical Film 7. The new multilayer optical film is referred to herein as Multilayer Optical Film 8 (or simply Film 8), and after patterning by selective heat treatment the film is referred to as Polarizer/Mirror Film 2.
The new film can be made from a cast web similar to Cast Webs 1-3 described above, except that the new cast web can use PEN for materials 1 and 3, and PET BB for material 2. PET BB refers to a copolyester of PET comprising a carboxylate sub-unit substitution. That is, some of the di-methyl terephthalate (DMT) is substituted with 4,4′Biphenyldicarboxylic acid dimethyl ester. In determining a suitable substitution percentage, the skilled person may wish to consider the effect that increasing BB content has on increasing the glass transition temperature of the polymer (which could make the first processing step window more narrow), increasing the refractive index, and reducing the melting point. A masterbatch of PET BB and an absorbing agent, e.g., an IR dye such as EpoliteTM 4121, or AmaplastTM IR 1050, can be fed into material stream 2. The PEN and PET BB materials can be coextruded using a suitable feedblock to form a cast polymer web having a suitable number of alternating layers. The first and second layers of the cast web, composed respectively of the PEN and PET BB polymer materials, will have different isotropic refractive indices similar to the diamond-shaped symbols shown in FIG. 5D.
This cast web can then be processed substantially as described above in connection with FIG. 5D. With regard to the two-step drawing process to be used, the conditions set forth in examples 1-3 of U.S. Pat. No. 6,179,948 (Merrill et al.) are of particular interest. The drawing process produces Multilayer Optical Film 8, which may exhibit refractive indices similar to the open-circle shaped symbols in FIG. 5D, thus providing a reflective polarizer film having a block axis parallel to the x-axis, a pass state parallel to the y-axis, and having substantial reflectivity of the pass-state polarized light due to the residual mismatch Δny. This partial polarizer Film 8 can then be selectively heated in one or more second zones thereof using a technique such as that used to fabricate Polarizer/Mirror Film 1, or by any other suitable technique discussed herein, to substantially relax the birefringence in one set of polymer material layers while maintaining birefringence in the other set of layers (see FIG. 5D). Such heat treatment provides a high reflectivity multilayer mirror in the second (processed) zones of the film. The resulting patterned film is a unitary polarizer/mirror film, and is referred to herein as Polarizer/Mirror Film 2.
The teachings of the present application can be used in combination with the teachings of any or all of the following commonly assigned applications, which are incorporated herein by reference: U.S. Provisional Application No. 61/139,736, “Internally Patterned Multilayer Optical Films Using Spatially Selective Birefringence Reduction”, filed Dec. 22, 2008; U.S. Provisional Application No. 61/157,996, “Multilayer Optical Films Having Side-by-Side Mirror/Polarizer Zones”, filed Mar. 6, 2009; and U.S. Provisional Application No. 61/158,006, “Multilayer Optical Films Suitable for Bi-Level Internal Patterning”, filed Mar. 6, 2009.
The teachings of this application can be used in combination with the teachings of any or all of the following commonly assigned applications being filed on even date herewith, which are incorporated herein by reference: International Application No. PCT/US2009/069153, “Internally Patterned Multilayer Optical Films Using Spatially Selective Birefringence Reduction”; International Application No. PCT/US2009/069173, “Multilayer Optical Films Suitable for Bi-Level Internal Patterning”; International Application No. PCT/US2009/069160, “Internally Patterned Multilayer Optical Films With Multiple Birefringent Layers”; and International Application No. PCT/US2009/069192,“Multilayer Optical Films Having Side-by-Side Polarizer/Polarizer Zones”.
Unless otherwise indicated, all numbers expressing quantities, measurement of properties and so forth used in the specification and claims are to be understood as being modified by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that can vary depending on the desired properties sought to be obtained by those skilled in the art utilizing the teachings of the present application. Not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, to the extent any numerical values are set forth in specific examples described herein, they are reported as precisely as reasonably possible. Any numerical value, however, may well contain errors associated with testing or measurement limitations.
Various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention, and it should be understood that this invention is not limited to the illustrative embodiments set forth herein. All U.S. patents, patent application publications, and other patent and non-patent documents referred to herein are incorporated by reference, to the extent they are not inconsistent with the foregoing disclosure.

## Claims

1. A multilayer optical film, comprising:
a plurality of interior layers arranged to selectively reflect light by constructive or destructive interference to provide a first reflective characteristic, the layers extending from a first zone to a second zone of the film;
wherein the plurality of interior layers comprises a first set of layers composed of a first material and a second set of layers composed of a second material different from the first material, at least one of the first and second sets of layers being birefringent;
wherein the film has an absorption characteristic tailored to heat the interior layers, in response to the film being illuminated with a light beam in the second zone of the film, sufficiently to change a birefringence of at least some of the interior layers in the second zone while maintaining a structural integrity of the plurality of interior layers, such change in birefringence being sufficient to change the first reflective characteristic to a different second reflective characteristic in the second zone of the film;
wherein the first reflective characteristic is substantially a polarizer characteristic and the second reflective characteristic is substantially a mirror characteristic, or the first reflective characteristic is substantially a mirror characteristic and the second reflective characteristic is substantially a polarizer characteristic, and
wherein the plurality of interior layers has a first thickness in the first zone and a second thickness in the second zone, and the first thickness is substantially the same as the second thickness.

2. The film of claim 1, wherein the first material comprises a first polymer and an absorbing dye or pigment.

3. The film of claim 2, wherein the absorbing dye or pigment preferentially absorbs light in a near-infrared or infrared wavelength region.

4. The film of claim 1, wherein the first reflective characteristic is substantially a polarizer characteristic and the second reflective characteristic is substantially a mirror characteristic.

5. A method of making a multilayer optical film, comprising:
providing a plurality of interior layers arranged to selectively reflect light by constructive or destructive interference to provide a first reflective characteristic, the layers extending from a first zone to a second zone of the film, wherein the plurality of interior layers comprises a first set of layers composed of a first material and a second set of layers composed of a second material different from the first material, at least one of the first and second sets of layers being birefringent; and
selectively heating the interior layers by illuminating the film with a light beam in the second zone of the film, sufficiently to change a birefringence of at least some of the interior layers in the second zone while maintaining a structural integrity of the plurality of interior layers, such change in birefringence being sufficient to change the first reflective characteristic to a different second reflective characteristic in the second zone,
wherein the first reflective characteristic is substantially a polarizer characteristic and the second reflective characteristic is substantially a mirror characteristic, or the first reflective characteristic is substantially a mirror characteristic and the second reflective characteristic is substantially a polarizer characteristic, and
wherein the plurality of interior layers has a first thickness in the first zone and a second thickness in the second zone, and the first thickness is substantially the same as the second thickness.

6. The method of claim 5, wherein the first material comprises a first polymer and an absorbing dye or pigment.

7. The method of claim 6, wherein the absorbing dye or pigment preferentially absorbs light in a near-infrared or infrared wavelength region.

8. The method of claim 5, wherein the first reflective characteristic is substantially a polarizer characteristic and the second reflective characteristic is substantially a mirror characteristic.

9. The multilayer optical film of claim 1, wherein the plurality of interior layers comprises one or more coextrudable materials.

10. The multilayer optical film of claim 1, wherein in response to the film being illuminated with the light beam in the second zone of the film, at least a portion of materials in the second zone is changed to be less birefringent.

11. The multilayer optical film of claim 1, wherein the polarizer or mirror characteristic is for an incident light having a selected wavelength or band in ultraviolet, visible, or infrared portions of a spectrum.

12. The method of claim 5, wherein the plurality of interior layers comprises one or more coextrudable materials.

13. The method of claim 5, wherein the selectively heating in the second zone of the film changes at least a portion of materials in the second zone to be less birefringent.

14. The method of claim 5, wherein the polarizer or mirror characteristic is for an incident light having a selected wavelength or band in ultraviolet, visible, or infrared portions of a spectrum.