OPTICAL DEVICE WITH REFLECTIVE MULTICOLORED AND EMISSIVE IMAGES
20200049871 ยท 2020-02-13
Inventors
Cpc classification
B42D25/387
PERFORMING OPERATIONS; TRANSPORTING
International classification
B42D25/387
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The current invention relates to a patterned optical device comprises a patterned cholesteric liquid crystal polymer layer where different domains of the pattern reflect different colors and where luminescent molecules are embedded in a subset of said reflective domains or in a separate layer. The current invention also relates to an optical security device comprises overt reflective OVD images and covert luminescent images with multiple authentication levels including detection of polarized reflections and emissions.
Claims
1. A patterned OVD and luminescent device comprises a substrate, a CLCP layer and an optional transparent top layer. Where the patterned CLCP layer reflects one circular polarization, and where its background domains reflect a first color and its image domains reflect a second color or multiple colors; and where a subset of the pattern's domains is embedded with one or more invisible luminescent dyes or pigments, part of which emit one or more partially polarized emission colors when illuminated with UV radiation.
2. A device as in claim 1 where the reflected polarization is essentially left-handed or right-handed.
3. A device as in claim 1 where the luminescent materials are fluorescent.
4. A device as in claim 1 where part of the luminescent materials comprises fluorescent dichroic molecules.
5. A device as in claim 1 where the luminescent materials are embedded in the CLCP layer over the entire device area.
6. A device as in claim 1 comprises one or more distinct fluorescent materials, part of which have their emission peaks within the reflection bands of one or more domains in said CLCP.
7. An authentication or security label or laminate device as in claim 1.
8. An authentication method of a patterned device as in claim 1 comprises of illuminating said device by UV radiation and detecting brightness or color variations of the covert luminescent images by a circular polarizer or by interchanging two distinct circular polarizers or by varying the viewing angle.
9. An authentication method of a patterned device as in claim 1 comprises naked-eye detection of a simultaneous OVD effects in multiple colored domains by varying the viewing angle or by observing changes in the reflected brightness or colors from said device when viewed through one or two interchanging distinct circular polarizers.
10. A patterned OVD and luminescent device comprises a substrate, a first luminescent print or a patterned luminescent layer and a second patterned CLCP layer. Said luminescent component comprises a covert pattern of one or more invisible luminescent dyes or pigments and said second CLCP layer, reflecting one circular polarization, comprises an overt pattern of background domains reflecting a first color and image domains reflecting a second color or multiple colors; and said device emits partially polarized luminescent colors when illuminated with UV radiation.
11. A device as in claim 10 where the first luminescent layer and the second CLCP layer are on opposite sides of a transparent substrate.
12. A device as in claim 10 where the reflected polarization is essentially left-handed or right-handed.
13. A device as in claim 10 where the luminescent materials are fluorescent.
14. A device as in claim 10 where the luminescent materials are uniformly embedded in said first layer.
15. A device as in claim 10 comprises one or more distinct fluorescent materials, part of which have their emission peaks within the reflection bands of one or more domains in said CLCP layer.
16. An authentication or security label or laminate device as in claim 10.
17. An authentication method of the patterned device as in claim 10 comprises of illuminating said device by UV radiation and detecting brightness variations of the covert luminescent images by a circular polarizer or by interchanging two distinct circular polarizers or by varying the viewing angle.
18. An authentication method of a patterned device as in claim 10 comprises naked-eye detection of a simultaneous OVD effects in multiple colored domains by varying the viewing angle or by observing changes in the reflected brightness or colors from said device when viewed through one or two interchanging distinct circular polarizers.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0021]
[0022]
[0023]
[0024]
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0025] Cholesteric liquid crystals (CLC) constitute a LC phase where elongated shape molecules are, on the average, parallel one to the other except for a small, consistent twist around a direction that is perpendicular to the molecular long axis. The twisting of the molecular orientation results from the molecular chiral structure, one where a molecule's structure cannot be superimposed on its mirror image. The axis of twist is the optical axis of the system. The fixed rate rotation builds up to a 1D periodic structure along the optical axis. The distance required for a 360-degree rotation, the pitch (P), is the structure's period.
[0026] In practice, CLC liquids are a mixture of a nematic LC (NLC) component, which lacks any twist, with a chiral dopant and, therefore, it is known also as a chiral nematic. One important advantage of a chiral nematic mixture is that the pitch can be modified continuously by adjusting the concentration of the chiral component.
[0027] Since the constituting molecules are anisotropic, the index of refraction of the NLC and CLC phases is anisotropic as light propagates faster along the molecular axis than perpendicular to it. Such a uniaxial medium has two different refraction indices: n.sub.e and n.sub.0. The optical properties of CLC are expressed in terms of an average index n=(n.sub.e+n.sub.0)/2 and the birefringence n=n.sub.en.sub.0.
[0028] The periodic twisted structure of a uniform pitch is the lowest energy configuration of a liquid CLC layer. However, unless planar surface conditions are provided, a short pitch CLC layer is likely to adopt a metastable, multi-domain structure, where the domains have the same pitch, but each orients its optical axis in a random direction. The multi-domain state, known as a focal conics texture, is associated with a strong light scattering. However, if a CLC layer has one or two confining substrates that are treated to force the adjacent molecules to align along a single direction in the substrates' plane, the CLC will adopt a uniform planar configuration where its optical axis is perpendicular everywhere to the substrates. Only the planar configuration is of interest herein. In few cases it is possible to achieve a planar configuration on a single aligning substrate, where one CLC surface interfaces air. A liquid CLC monomer can be aligned in its liquid phase in a planar configuration and then be UV polymerized into a solid polymer (CLCP), essentially freezing its previous configuration. As a result, CLC and their polymeric analogue, CLCP, have identical structures and, hence, also exhibit identical optical properties.
[0029] The main manifestation of the periodic chiral structure in a planar configuration, is the appearance of a reflection band of circularly polarized light, of the same handedness as the chirality of the cholesteric structure. The center wavelength of the reflection band, .sub.0, is related to the pitch by: .sub.0=nP, where n is the average index-of-refraction of the CLCP. The width of the reflection band, , is related to the birefringence: =nP. Typical reflection bands in the visible range are 30-60 nm wide. A right handed (RH) CLCP, for example, reflects completely the RH circular polarization component of unpolarized radiation within the reflection band. It fully transmits the LH polarization component within the reflection band. A CLCP is essentially transparent to both polarizations at all wavelengths outside the reflection band. CLCP layers, particularly on a black background, exhibit bright reflection colors. Their circularly polarized reflection can be extinguished when viewed through a circular polarizer of the opposite handedness.
[0030] The intrinsic reflection color of a planar CLCP layer, customarily characterized by .sub.0, is the color seen for light incidence normal to the CLCP plane (along the optical axis). For light incidence at an angle to the optical axis, the reflected color is shorter than the intrinsic color .sub.0, and is given approximately by: =.sub.0 cos(). This effect, where the perceived color is of shorter wavelength with increasing viewing angle, is known as the blue shift, or color shift, or color travel, or OVD effect of the CLCP color. The blue-shift effect is very important in optical security applications since it cannot be replicated by any known reprographic counterfeiting method. At the same time, the effect is readily observable and verifiable by the naked eye. Other 1D periodic structures (e.g., periodic thin film structures) also possess this useful feature and are known collectively as Optical Variable Devices (OVD).
[0031] The CLCP circularly polarized reflection is unique among OVD devices. It is useful for optical security applications as it can be easily detected with a circular polarizer, having an opposite circular sense to the CLCP, by extinguishing the polarized reflection and, therefore, authenticating the CLCP device. A CLCP layer has also a forensic security level where the details of its reflection band, which can be customized, are verified using a spectrometer.
[0032] Since the reflection from a CLCP planar layer is specular (it follows Snell's reflection law), the blue-shift effect is observed only in specular configurations where the light source, the detector and the optical axis at the incidence point, are in the same plane and the incidence angle is equal the reflection angle. In practice, many environments frequently have a dominant light source, usually the closest illumination source to the CLCP. An observer can always create a specular configuration, by adjusting the tilt of the CLCP plane with respect to the eye and the dominant light source, to observe the strong (50%) polarized color reflection. By varying the observation angle, the observer can follow the color shift effect.
[0033] For non-specular observational configurations, the CLCP is essentially transparent. This feature is also useful as it allows overlaying a CLCP layer on top of standard printed information without obscuring it for most observational configurations. The CLCP's reflective image is dominant and visible only at or near the specular angles.
[0034] In NLC and CLC phases, the molecules are oriented, on the average only, along a single direction: the director vector n. In NLC the director field is uniform: n.sub.0. In a chiral CLC the director n rotates in a helical fashion around an axis perpendicular to n. On a molecular scale the twisting effect is negligible and the local environment of a CLC molecule is essentially the same as in a NLC phase.
[0035] An important concept for describing properties of anisotropic liquids, such as NLC or CLC, is the order parameter S. S describes how well the thermally fluctuating molecules align along the local n. In regular (isotropic) liquids even anisotropic molecules have no preferred direction. The order parameter for isotropic liquids is S=0. In the LC phases the anisotropic molecules tend to be mutually parallel and possess a typical order parameter in the range S=0.5-0.75. S=1 corresponds to an ideal LC phase where all the molecules are oriented along n with no fluctuations. LC phases with a positive S but less than about 0.4 do not exist.
[0036] CLC in general are not absorptive materials unless they host guest dyes or pigments which absorb visible light. When a dopant molecule is dissolved in a LC host, its orientational properties depend to a large degree on its shape anisotropy and its interaction with the LC molecules. In many cases the orientational distribution of a dopant molecules is isotropic even though their host LC material has S>0. However, dopant molecules with significant shape anisotropy and/or favorable interaction with the LC host can become oriented and possess an order parameter S>0. Dye molecules that are aligned by their LC host, are known as dichroic dyes. Once aligned, they exhibit an anisotropic absorption property. Dichroic dyes have significantly higher absorption of light polarized linearly along n than of light polarized perpendicular to n. As a result, a planar NLC layer doped with a dichroic dye acts like a linear polarizer: transmitting linear polarization perpendicular to n while significantly attenuating the polarization parallel to n. If the dichroic dye is fluorescent, its emission will, in general, also be polarized: the fluorescence emission that is parallel to n is stronger than emission perpendicular to n. If the order parameter of a fluorescent dye in a nematic host is S=0, the fluorescent emission is unpolarized.
[0037] The optical properties of a CLC material within its reflection band are those of a one dimensional photonic gap material. The existence of a high reflection band demonstrates that circularly polarized light, of the same handedness as the chirality of the CLC, is forbidden from propagating through a thick CLC layer. When a luminescent guest in a planar CLC host layer, said guest has its emission peak substantially inside the CLC's reflection band, is excited by UV light, its emission perpendicular to the layer is essentially circularly polarized in the opposite handedness to the CLC chirality. This is true even for fluorescent dyes having S=0. The polarized emission from a CLC is characterized by the intensity ratio of the transmitted left-handed (LH) to the right-handed (RH) polarizations: r=I.sub.LH/I.sub.RH and by the dissymmetry factor g=(2 I.sub.LH2I.sub.RH)/ (I.sub.LH+I.sub.RH). For a LH CLC, typical values within the reflection band are: r=0.15 and g1.5. Circularly polarized emission is unique to the CLC medium and its color is an indication of where is the CLC's reflection band.
[0038] The emission spectrum of fluorescent dyes in isotropic hosts is not polarized and has essentially the same shape (except for possible shifts of the peak emission) in most host media. In contrast, the shape of the emission spectrum changes drastically for the forbidden polarization in CLC hosts. A unique property of dye fluorescence in a CLC medium is a sharp increase in the density of states of the non-propagating polarization, typically at the long-wavelength edge of the reflection band. The fluorescence of the nominally forbidden polarization, which is very weak throughout the reflection band, exhibits a prominent intensity spike near the long edge of the band. The emission spectrum of the propagating polarization is not affected by the reflection band: it has the same shape as if the fluorescent dye was embedded in the isotropic phase of the CLC material. These unique features of the fluorescence emission from a CLC host are displayed by fluorescent molecules having S>0 as well as by molecules having S=0.
[0039] The polarization of the emission within the reflection band and the presence of a spike of the polarized fluorescence near the reflection-band's edge can be detected by comparing the emission when viewing the CLC through a LH or a RH polarizer. The two views will differ in the intensity of the emission as well as in its color.
[0040] In some implementations the fluorescent dye is embedded in a separate isotropic host resulting an isotropic emission. It is assumed, however, that the emission peak is within one the reflection bands of an adjacent CLCP layer. When this emission is viewed through the CLC, it becomes polarized in the opposite sense to the CLC chirality.
[0041] In the following discussion, in instances where particular chirality or circularities are assigned, it will be understood that all conclusions remain essentially the same in different instances where the chirality or circularities are simultaneously reversed. Namely, LH chirality or circularities are replaced by RH chirality or circularities and RH by LH.
[0042] The current invention discloses optical device structures that comprise an overt pattern of multiple reflective colors from a single CLCP layer and a covert luminescent pattern. The single CLCP layer is in a continuous, solid film format. In embodiments where the luminescent materials are embedded in the CLCP layer, the covert luminescent pattern registers with at least part of the overt pattern or may comprise the background. In embodiments where the luminescent materials are embedded in a separate layer, the overt and covert patterns may fully register, partially register, complement or be entirely separate. A typical device will include a substrate which may be transparent or opaque, having low or high reflection, having a glossy or diffusive surface, reflecting colors or being substantially white or black. In addition, the device may include an optional transparent top-coating layer, on the opposite side from the substrate, which serves as a protection layer for said device.
[0043] Luminescent materials are defined herein as fluorescent or phosphorescent molecules. Such molecules can be excited by UV or visible radiation to emit radiation at wavelengths longer than the excitation. In most circumstances the emission is unpolarized unless special measures are taken, such as stretching a polymer film in which the dyes are embedded, or employing special host materials such as CLCPs. The term luminescent dye or fluorescent dye is used herein to mean: molecules that absorb only UV radiation and are invisible under ambient illumination. The excitation illumination can be applied from either side of the device that does not have an opaque layer. Where one luminescent material is mentioned in the embodiments, it is understood that multiple luminescent materials may be deployed as well.
[0044] The CLCP pattern comprise of background domains with a first reflection band corresponding to a first color and image domains comprise a distinct second reflection band corresponding to a second color. The distinction between background domains and image domains is arbitrary in general. In informative patterns the image comprises of domains that convey information while the rest of the domains constitute the background. Both background and image comprise, in general, domains with multiple reflective and emissive colors.
[0045] The images in CLCP labels are fixed images or serialized images, where the image or information therein varies from one label to the next. The ability to serialize the information on label is an important functionality.
[0046] It is understood herein that the following embodiments can be extended to include images comprise of multiple domain of distinct reflection bands and the corresponding multiple distinct colors. The patterns in the CLCP or of the luminescent material comprise general images that can be classified, without limitations, as a mark, text, a logo, a photo, a barcode or a 2D code such as QR code.
[0047] In the following embodiments, all references to reflected colors assume a specular reflection configuration where the angle between the dominant ambient light source and the normal to the optical device is substantially equal to the angle between the observer and said normal. The specular angle coincides with the normal if the light source is essentially above the device. If an incidence angle is not specified or implied, the reflective or emissive colors assume normal incidence or propagation. At non-specular viewing configurations, the CLCP is essentially transparent, except for a weak tint, in which case the observed colors are essentially those of the substrate. The emission light is assumed to be observed at normal to the device unless stated otherwise.
[0048] One aspect of the present invention is the deliberate choice of the luminescent materials, or the reflection colors, such that in some domains the emission peaks are substantially within the reflection bands. The more the emission spectrum overlaps the reflection band in one domain, the stronger will be the observed polarization dependence effects of the covert image in this domain. The width of a reflection band is given approximately by: =nP=.sub.0n/n, and depends strongly on the CLCP's birefringence. Birefringence is a material parameter that is difficult to modify. However, it is well known to those skilled in the art, that broadening of the reflection band can be achieved by a process step that generates a pitch-gradient structure. The pitch in a pitch-gradient CLCP, rather than be a constant throughout the layer, is increasing in value from one surface of the layer to the other such that the reflection bandwidth is given approximately by: =nP. The reflection bandwidth of a pitch-gradient CLCP can be substantially wider than the bandwidth of a constant pitch CLCP and thus can provide more overlap with broad emission spectra of embedded luminescent dyes.
[0049] Another aspect of the current invention is to provide a single device with multiple optical effects: overt images exhibiting a color shift effect and polarized reflections as well as covert images based on luminescent materials that also exhibit partially polarized emissions. The polarization aspects of the reflection or emission can be observed by using circular polarizers.
[0050] Yet another important aspect of the present invention is to provide a single optical security device that can provide multiple authentication levels from simple visual inspection to forensic authentication. The forensic authentication is achieved by measuring the spectra details of the various CLCP's reflection bands or the emission spectra corresponding to different luminescent materials or by measuring their luminescent lifetime. This aspect permits the production of highly counterfeit-resistant labels, laminates and general optical security devices.
[0051] In a first embodiment, the optical device structure, illustrated in
[0052] In a non-limiting example of
[0053] If the CLCP in
[0054] Illuminating the device with an excitation beam 71, as shown in
[0055] When sources 4 and 7 illuminate the device simultaneously and the device is viewed at a specular angle, the luminescent background modifies the perceived domains colors compared to just ambient illumination. In this configuration both the overt reflection image from layer 2 and the covert emission from layer 1 are visible. However, when the CLCP is LH, introducing a RH polarizer 100 into the viewing path will, as discussed above, block the reflective image while transmitting only said emission.
[0056] In a second embodiment, the device structure is the same as in the first embodiment except that layer 1 comprises a print of luminescent material or patterned luminescent domains 11, as shown in
[0057] In a non-limiting example of the second embodiment,
[0058] In a third embodiment, the optical device structure,
[0059] In a non-limiting example of the third embodiment,
[0060] In a fourth embodiment, the optical device structure,
[0061] In a non-limiting example of the fourth embodiment,
[0062] When the device is viewed along its normal through a RH polarizer, the text appears bright Red. When viewed through a LH polarizer the text becomes darker and its color shifts towards the NIR. When viewed at large angle to the device' normal, 43 in
[0063] In a fifth embodiment, the optical device structure,
[0064] In a non-limiting example of the fifth embodiment,