WO2002066266A1 - Color shifting film with patterned fluorescent and non-fluorescent colorants - Google Patents

Color shifting film with patterned fluorescent and non-fluorescent colorants Download PDF

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Publication number
WO2002066266A1
WO2002066266A1 PCT/US2001/021288 US0121288W WO02066266A1 WO 2002066266 A1 WO2002066266 A1 WO 2002066266A1 US 0121288 W US0121288 W US 0121288W WO 02066266 A1 WO02066266 A1 WO 02066266A1
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WO
WIPO (PCT)
Prior art keywords
article
color shifting
shifting film
colored portion
fluorescent
Prior art date
Application number
PCT/US2001/021288
Other languages
French (fr)
Other versions
WO2002066266A8 (en
Inventor
Peng Huang
Hong Ji
Yaoqi J. Liu
Original Assignee
3M Innovative Properties Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Priority to DE60108531T priority Critical patent/DE60108531T2/en
Priority to JP2002565805A priority patent/JP4643123B2/en
Priority to AT01954621T priority patent/ATE287336T1/en
Priority to CA002438059A priority patent/CA2438059A1/en
Priority to EP01954621A priority patent/EP1361962B1/en
Priority to BR0116877-0A priority patent/BR0116877A/en
Publication of WO2002066266A1 publication Critical patent/WO2002066266A1/en
Publication of WO2002066266A8 publication Critical patent/WO2002066266A8/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44FSPECIAL DESIGNS OR PICTURES
    • B44F1/00Designs or pictures characterised by special or unusual light effects
    • B44F1/08Designs or pictures characterised by special or unusual light effects characterised by colour effects
    • B44F1/10Changing, amusing, or secret pictures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B42BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42DBOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29Securities; Bank notes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44FSPECIAL DESIGNS OR PICTURES
    • B44F1/00Designs or pictures characterised by special or unusual light effects
    • B44F1/08Designs or pictures characterised by special or unusual light effects characterised by colour effects
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/916Fraud or tamper detecting
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851Intermediate layer is discontinuous or differential
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851Intermediate layer is discontinuous or differential
    • Y10T428/24868Translucent outer layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851Intermediate layer is discontinuous or differential
    • Y10T428/24868Translucent outer layer
    • Y10T428/24876Intermediate layer contains particulate material [e.g., pigment, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24901Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree

Definitions

  • the present invention relates generally to films and other articles that incorporate information whose appearance is highly dependent upon viewing angle.
  • PCT Publication WO 99/36258 discloses, among other things, color shifting films with printed indicia, and optical brighteners such as dyes that absorb in the UN and fluoresce in the visible region of the color spectrum.
  • Such articles can also provide images whose appearance changes with viewing geometry, particularly where the printed indicia is provided on a back side of the color shifting film with respect to an observer.
  • Such articles can be viewed under ordinary diffuse lighting conditions, such as in a typical office environment.
  • the article includes a color shifting film and indicia disposed behind the color shifting film from the point of view of an ordinary observer of the article.
  • the indicia include a first and second colored portion arranged as a foreground and a background of the indicia.
  • the first colored portion comprises a fluorescent colorant
  • the second colored portion is substantially non-fluorescent.
  • the second colored portion is selected to have substantially the same color as the first colored portion to enhance concealment of the indicia.
  • the first and second colored portions have the same color when viewed by themselves apart from the color shifting film, and also have the same apparent color when viewed through the color shifting film at an angle at which the color shifting film substantially blocks transmission of an emission band of the fluorescent colorant. In this way, the contrast between foreground and background is substantially reduced, and the indicia become less noticeable at such a viewing angle.
  • FIG. 1 is a sectional view of an article having a color shifting film and a first and second colored portion disposed behind the film which form indicia, the article being adhered to a substrate;
  • FIG. 2 is a front view of the article of FIG. 1 from one viewing angle;
  • FIG. 3 is a front view of the article of FIG. 1 from another viewing angle;
  • FIG. 4 is an idealized and simplified composite graph depicting spectral properties of the first and second colored portions, and of the color shifting film at one viewing angle;
  • FIG. 5 is an idealized and simplified composite graph depicting spectral properties of the first and second colored portions, and of the color shifting film at another viewing angle;
  • FIG. 6 is an idealized and simplified composite graph depicting, for another embodiment, spectral properties of the first and second colored portions, and of the color shifting film at one viewing angle
  • FIG. 7 is an idealized and simplified composite graph depicting, for still another embodiment, spectral properties of the first and second colored portions, and of the color shifting film at one viewing angle
  • FIG. 8 is a graph of measured spectral transmission of a particular color shifting film at normal (0 degree) incidence and at 60 degrees incidence;
  • FIG. 9 is a graph of measured spectral properties of a particular orange fluorescent dye.
  • FIG. 10 is a graph of measured spectral reflectivity of a particular orange non-fluorescent colorant.
  • like reference numerals indicate like elements.
  • an article 10 includes a color shifting film 12 and indicia 14 (see FIG. 2) disposed behind the film 12 and viewable through the film 12 for at least some viewing and/or illumination geometries.
  • the indicia 14 is made up of or defined by at least a first colored portion 16 and a second colored portion 18.
  • portions 16,18 are patterned in complementary fashion so as to define the indicia 14, which in this embodiment is a single letter "W".
  • FIG. 1 corresponds roughly to a sectional view taken along axis 1- 1 in FIG. 2, which is drawn to a somewhat smaller scale than FIG. 1.
  • Article 10 also includes an optional adhesive layer 20, which preferably comprises a conventional pressure-sensitive adhesive (PSA), but alternatively can comprise a heat-activated adhesive or other suitable adhesive.
  • Adhesive layer 20 secures the article 10 to an optional substrate 22.
  • substrate 22 can form part of the article 10.
  • substrate 22 can itself comprise a wide variety of different articles, such as a document, sheet of paper, rigid or flexible sign backing, or rigid or flexible window material if some illumination is desired from the back of article 10. To the extent any light is transmitted through the combination of color shifting film 12 and indicia 14, such light can be absorbed, reflected diffusely or specularly, or transmitted by substrate
  • the color shifting film 12 has the property of transmitting different wavelengths of light as a function of the angle such light impinges on the film.
  • the transmission properties may also be polarization dependent, even at normal incidence.
  • film 12 can be a polarizer, a mirror, or a mirror having substantial polarizing properties.
  • Preferred films 12 have a multitude of alternating polymer layers arranged into a multitude of unit cells, each unit cell effective to reflect light at a wavelength twice the optical thickness of such unit cell. Such films can be made by co-extrusion of two or more polymers forming an interleaved stream of materials.
  • the cast coextruded film can be subsequently thinned and oriented by stretching uniaxially or biaxially to form a finished reflective polarizer or mirror.
  • at least one of the polymers is capable of strain-induced birefringence so that the indices of refraction change on stretching.
  • the unit cells which can each include two, three, or more individual polymer layers, are typically also arranged to have an optical thickness gradient across the thickness of the film 12 so that a relatively wide spectral band ("reflection band”) is reflected by the . film. Boundaries of the reflection band are referred to herein as band edges — spectral transitions from high reflectivity (low transmission) to low reflectivity (high transmission) or vice versa.
  • inorganic multilayer films made for example by vacuum deposition of two inorganic dielectric materials sequentially in a multitude of layers on a glass or other suitable substrate, or alternating layers of inorganic materials and organic polymers (see, e.g., U.S. Patent Nos. 5,440,446 (Shaw et al.), 5,877,895 (Shaw et al.), and 6,010,751 (Shaw et al.))— can also be used as the color shifting film 12.
  • preferred polymeric films described in the preceding paragraph have the added benefit of being able to maintain the integrity of their band edges over substantially all incidence angles and regardless of polarization of light, by controlling the out-of- plane (z-index) index of refraction of adjacent layers within the film.
  • the difference ⁇ n z in index of refraction along the z-axis of adjacent polymer layers within a unit cell is less than the maximum index difference in the plane of the film
  • Suitable films are available from 3M Company (St. Paul, Minnesota, USA) under the designation 3MTM Radiant Light Film.
  • Coextruded polymeric films whose layers are not oriented, and thus are substantially isotropic in refractive index, can also be used for the color shifting film. Such films are described, for example, in U.S. Patent Nos. 3,801,429
  • the first colored portion 16 is patterned to form the foreground of a letter "W", and is disposed behind color shifting film 12. Other letters, symbols, or shapes which convey information are also contemplated.
  • portion 16 includes a fluorescent colorant.
  • colorant as used herein means any pigment, dye, or other substance or combination of substances used to impart hue or chroma to an article.
  • fluorescent refers to the property of emitting light at one wavelength (or band of wavelengths) as a result of the absorption of light at a different (and typically shorter) wavelength (or band of wavelengths).
  • the wavelength range of emitted fluorescent light is referred to as an emission band; that of the absorbed light is referred to as an excitation band.
  • light in the emission band can be substantially transmitted through the color shifting film at some angles, but substantially reflected by the color shifting film (and therefore blocked from reaching the eye of an observer) at other angles. Additionally or alternatively, if a highly directional light source is used, light in the excitation band can be blocked from reaching the fluorescent colorant at some angles but transmitted to the fluorescent colorant at other angles.
  • Arrows 24,26 shown in FIG. 1 represent a normal-incidence viewing angle and an oblique viewing angle respectively. At one of these angles, color shifting film 12 transmits the fluorescent emission of first colored portion 16, yielding a bright "W" (FIG. 2). At the other angle, color shifting film 12 substantially blocks light in the emission band so that the "W" is relatively dark (FIG. 3).
  • excitation light passes through the color shifting film 12 before reaching first colored portion 16.
  • Some color shifting films 12 can effectively transmit the excitation light only for some directions of incidence and/or only for some polarizations.
  • Such selective transmission of excitation light can be used in a specialized procedure to interrogate the article: one light beam having the appropriate angular and/or polarization properties is alternated with another light beam not having those properties, and the visual response (fluorescent emission or lack thereof at a suitable observation angle) is monitored.
  • the application may be one in which the article 10 is exposed to light impinging on its front surface from substantially all angles and polarizations — such as is found in typical office environments — in which case a sufficient amount of light in the excitation band, and having the appropriate angular and/or polarization properties, will be present to produce fluorescence in the portion 16.
  • Other color shifting films 12 can effectively transmit excitation light for substantially all or at least a wide range of incidence angles and/or polarizations. For those films, a comparatively greater amount of ambient light will pass through the color shifting film to produce a brighter fluorescent emission.
  • a source of light such as a backlight or other lamp, is employed behind the article 10. In those cases any materials or elements disposed behind portion 16 are simply selected to have an aggregate transmission for light in the excitation band sufficient to produce the desired fluorescent effect in portion 16.
  • Article 10 also includes second colored portion 18 disposed behind color shifting film 12.
  • portion 18 can be patterned in a complementary fashion to portion 16.
  • the unpattemed portion can for instance be printed in a continuous layer to cover the patterned portion in some places and to extend between parts of the patterned portion in other places.
  • the patterned portion can be printed on top of the continuous unpattemed portion and the resulting combination laminated to or otherwise placed behind color shifting film 12.
  • the patterned portion can be printed to the back side of the color shifting film, and the unpattemed portion can simply be positioned behind that combination.
  • Conventional coating processes can be used to apply the colored portion(s) to the film 12, including without limitation flexographic printing techniques.
  • the article includes an unpattemed adhesive layer 20, such layer can replace the first or second colored portions 16,18 by inclusion of fluorescent and/or non-fluorescent colorants as appropriate. As shown in FIGS. 1 and 2, portion 18 forms a background for the indicia.
  • portion 18 is substantially non- fluorescent. That is, portion 18 does not produce fluorescent emission noticeable to an ordinary observer when exposed to expected light levels for the particular application.
  • the pigments, dyes, inks, or other colorants within portion 18 are selected to yield a perceived color that is substantially the same as the color of colored portion 16. Such selection helps reduce the contrast between the foreground and background of the indicia at some viewing angles, thus helping conceal the indicia (see FIG. 3) at such angles compared to constructions having no colored portion 18 or having fluorescent indicia printed onto a white surface or a surface of a different color.
  • the color of portions 16,18 are substantially the same when viewed from the front side of color shifting film 12 at an angle at which the color shifting film 12 blocks fluorescent emission from reaching the eye of the observer. Under those conditions, portion 16 will appear relatively dark compared to viewing angles where the bright fluorescent emission is visible. To the extent non- fluorescent colorants are also present in portion 16, they may contribute to its appearance or color under the stated conditions. If both portions 16, 18 are disposed behind color shifting film 12, it is preferred to select colors for portions 16,18 that are also substantially the same (even though their relative brightness may differ substantially) if viewed through a clear transparent medium (such color referred to as "inherent color”), e.g.
  • both portions can be essentially orange and portion 16 can include an orange fluorescent colorant.
  • both portions can be essentially green and portion 16 can include a green fluorescent colorant. If the portions are colored in this way, their appearance will typically also be very similar when viewed through the color shifting film at an angle at which the color shifting film blocks the fluorescent emission, to help conceal the indicia at such angles.
  • portion 16 can form the background and portion 18 can form the foreground of the indicia. Since fluorescent colorants tend to be more expensive than non-fluorescent colorants, it is desirable to use a smaller quantity of portion 16 than of portion 18. In many cases the foreground of particular indicia takes up less area than the background. Thus, in many cases it is preferred that portion 16 be used as the foreground of the indicia. Portion 16, even if it includes a brightly colored fluorescent pigment, will in many cases appear relatively dark in certain geometries — such as an observation angle at which the color shifting film 12 substantially blocks the fluorescent emission, or where the color shifting film substantially blocks light in the excitation band from a directional light source.
  • portion 18 may well be designed to have an inherent color such as dark brown or black that is substantially different than the inherent color of portion 16, which may for example be green, orange, or red. Yet, the portions 16, 18 can still have a similar apparent color when viewed from the front of film 12 at the certain geometries referred to, thus helping conceal the indicia. Indeed, portion 18 may then be positioned either behind or in front of film 12. In each case the indicia 14 would still be considered to be behind film 12 since at least one of the portions making it up is behind film 12.
  • FIGS. 4 & 5 are idealized, simplified composite graphs that depict spectral properties of the first and second colored portions, and of the color shifting film for a particular embodiment.
  • the x-axis represents the wavelength of light ⁇ in nanometers (nm), with the visible region extending , roughly from 400 to 700 nm.
  • Curve 50 (FIG. 4) represents the spectral transmission of color shifting film 12 at normal incidence, and curve 50' (FIG. 5) represents its transmission at an oblique angle of incidence.
  • curves maybe for a particular polarization of light, or instead an average over all polarizations.
  • the y-axis represents percent transmission, from 0% to 100%.
  • the specular reflectivity at a particular wavelength is substantially 100% minus the percent transmission, since absorption in the films is typically much less than 1% for most wavelengths of interest.
  • Curves 52 and 54 represent the effective reflectivity (reflectivity plus fluorescent intensity, if any) of colored portions 16, 18 respectively, measured by themselves in the absence of any color shifting film.
  • the y-axis represents effective reflectivity in arbitrary units. Curves 52,54 are roughly to scale with respect to each other, insofar as the portion 16 having the fluorescent colorant is much brighter at certain wavelengths than the other portion 18. However, the relative heights of the curves are not intended to be exact, and all curves are idealized for ease of discussion.
  • the color shifting film 12 has a low transmission in a reflectance band bounded by band edges 50a, 50b as shown. Outside the reflectance band, the film has high transmission. At this geometry, film 12 substantially blocks light associated with colored portions 16,18, except near one side of curves 52,54. The small amount of light that is transmitted has a similar apparent color and intensity, and the result is a low contrast appearance as depicted in FIG. 3.
  • the reflectance band and associated band edges now labeled 50a' and 50b', have shifted to shorter wavelengths — hence the term color shifting film to describe the accompanying shift in transmitted light.
  • light from both colored portions 16,18 is substantially transmitted by the film 12.
  • the high brightness of the fluorescent colorant in portion 16 however overpowers any reflectance from portion 18, which thus appears dark in comparison. The result is a high contrast appearance as depicted in FIG. 2.
  • FIG. 6 is an idealized, simplified composite graph for normal incidence similar to FIG. 4, but for a different embodiment having different first and second colored portions 16,18, and a different color shifting film 12.
  • Curve 60 represents the spectral transmission of color shifting film 12 at normal incidence.
  • Curve 60 includes band edge 60a.
  • Curves 62,64 represent the effective reflectivity (as discussed above) of colored portions 16, 18 respectively.
  • the overall spectral distributions of curves 62,64 represent similar colors.
  • the film 12 substantially blocks light associated with colored portions 16,18, except near one side of curves 62,64.
  • the small amount of light that is transmitted has a similar apparent color and intensity, and the result is a low contrast appearance as depicted in FIG. 3.
  • curve 60 with band edge 60a is replaced with a similar curve (not shown) shifted to shorter wavelengths by an amount dictated by the angle of observation.
  • the shifted transmission curve substantially transmits light from curves 62,64 to yield a high contrast appearance with a bright foreground colored portion 16 as depicted in FIG. 2.
  • FIG. 7 is an idealized, simplified composite graph for normal incidence similar to FIG. 6, but for still another embodiment having different first and second colored portions 16,18, and a different color shifting film 12.
  • Curve 70 represents the spectral transmission of color shifting film 12 at normal incidence.
  • Curve 70 includes band edge 70a.
  • Curves 72,74 represent the effective reflectivity (as discussed above) of colored portions 16, 18 respectively.
  • the overall spectral distributions of curves 72,74 represent similar colors.
  • the film 12 substantially transmits light from curves 72,74 to yield a high contrast appearance with a bright foreground colored portion 16 as depicted in FIG. 2.
  • the film 12 has the appearance of a substantially clear film, because it has high transmission throughout the visible spectrum.
  • curve 70 with band edge 70a is replaced with a similar curve (not shown) shifted to shorter wavelengths by an amount dictated by the angle of observation.
  • the shifted transmission curve substantially blocks light associated with colored portions 16,18, except near one side of curves 72,74.
  • the small amount of light that is transmitted has a similar apparent color and intensity, and the result is a low contrast appearance as depicted in FIG. 3.
  • suitable articles 10 can include additional layers and features.
  • color shifting film 12 can include one or more regions that have been embossed with heat and/or pressure.
  • the embossed regions are thinner than non- embossed neighboring regions and therefore have spectral transmission and reflection features that are blue-shifted relative to corresponding features of the non-embossed regions.
  • the embossed regions can take the form of indicia in addition to the indicia 14 discussed above.
  • the color shifting film 12 can contain or carry a microstructured relief pattern suitable for producing conventional holographic images. Such images can be used to further obscure the indicia 14 at selected geometries.
  • the relief pattern can be formed using known holographic embossing techniques into a suitable skin layer or coating on top of the color shifting film.
  • the relief pattern can alternately be incorporated into a separate transparent sheet that is laminated to the color shifting film.
  • a separate transparent sheet is preferably polymeric for ease of manufacture and for article integrity over operating temperature ranges.
  • additional graphics, symbols, or other indicia in addition to indicia 14 discussed above can be applied to the article 10 by conventional printing onto color shifting film 12 or onto additional layer(s) laminated to film 12.
  • a representative article was constructed using the following component materials: 3M brand Radiant Color Film CM590 for color shifting film 12; Seiko brand fluorescent orange dye (dye No. 503, made in Japan) for colored portion 16; and a conventional non-fluorescent orange/red dye (orange ink, made in Malaysia, available from BASF) for colored portion 18.
  • the different dyes were applied by hand to one side (designated the "back" side) of the color shifting film in complementary fashion to form a foreground and background of a single letter "W", substantially as depicted in FIGS. 1 and 2 except that: (a) no adhesive layer 20 was used, and (b) portion 16 formed the background and portion 18 formed the foreground of the "W".
  • the dyes were then allowed to dry.
  • the resulting coated film was flexible and had an overall thickness of about: 1.8 mils (45 ⁇ m) for the film 12 by itself; 2.0 mils (50 ⁇ m) on average for the film plus dye in the foreground regions; and 2.4 mils (60 ⁇ m) on average for the film plus dye in the background regions.
  • the thickness of the dried dyes was sufficient to render them substantially opaque if viewed against standard office lighting fixtures.
  • the article was placed back side down onto a sheet of white paper under ordinary office illumination. When viewed from the front at normal incidence, no fluorescence was detectable. Instead, the color seen was a blend of the reflected color of the color shifting film itself and the color of light transmitted by the color shifting film and reflected back through the film by the colored portions 16, 18. Since the fluorescent dye and non-fluorescent dye have substantially similar base colors, one sees only a slight contrast between the foreground letter "W" and the background. At highly oblique observation angles (about 60 degrees or higher from the normal), the reflection band of the film 12 shifts sufficiently to make the background (colored portion 16) appear very bright orange. Under these conditions the foreground (colored portion 18) remained relatively dark in comparison to the fluorescent background.
  • FIG. 8 plots the measured percent transmission versus wavelength.
  • Curve 80 was measured with unpolarized light at normal incidence to the film.
  • Curve 82 is an average of p- polarized light and s-polarized light (i.e., light linearly polarized in the plane of incidence and pe ⁇ endicular to the plane of incidence respectively) for an angle of 60 degrees from the normal direction. Note the wavelength shift of the reflection band and the good maintenance of the sharp band edges.
  • FIG. 9 is data measured using a Perkin Elmer Model LSB50 Luminescence Spectrophotometer for the orange fluorescent dye.
  • Curve 90 is the emission band and curve 92 is the excitation band for the dye. The two curves are plotted against relative response (in arbitrary units). Note that the excitation band 92 exists not only in the ultraviolet region but extends well into the visible region. In comparing FIGS. 8 and 9 note also that the CM590 film substantially transmits light in the excitation band 92 at normal angles and at oblique angles.
  • FIG. 10 plots reflectivity of the non-fluorescent orange/red dye used in the example, as measured using an Ocean Optics Model SD2000 Spectrometer with a reflection probe. The y-axis plots reflectivity in arbitrary units which are not to scale compared to the arbitrary units used in FIG. 9.

Abstract

Disclosed are articles (10) having a color shifting film (12) and indicia (14) located behind the color shifting film. The indicia include at least a first and second colored portion, the first portion (16) including a first fluorescent colorant. The second colored portion (18) is non-fluorescent but has a color similar to that of the first portion to enhance concealment of the indicia under certain viewing conditions. At least one of the colored portions is patterned.

Description

COLOR SHIFTING FILM WITH PATTERNED FLUORESCENT AND NON-FLUORESCENT COLORANTS
Field of the Invention The present invention relates generally to films and other articles that incorporate information whose appearance is highly dependent upon viewing angle.
Background of the Invention Films that incorporate directional images — images that are viewable at some viewing geometries and not others — are generally known. U.S. Patent 6,024,455 (O'Neill et al.), for example, discloses reflective articles in which a multilayer film covers a patterned retroreflective layer. The patterned retroreflective layer can include an indicia layer having patterned regions comprising conventional inks, dyes, or other substances which are substantially opaque to some wavelengths but transparent to others. Such films, however, require specialized lighting arrangements for optimal viewing.
PCT Publication WO 99/36258 (Weber et al.) discloses, among other things, color shifting films with printed indicia, and optical brighteners such as dyes that absorb in the UN and fluoresce in the visible region of the color spectrum. Such articles can also provide images whose appearance changes with viewing geometry, particularly where the printed indicia is provided on a back side of the color shifting film with respect to an observer. Advantageously, such articles can be viewed under ordinary diffuse lighting conditions, such as in a typical office environment.
Brief Summary
Close inspection of articles incorporating color shifting film and fluorescent indicia as described above has revealed a difficulty in satisfactorily concealing the fluorescent indicia from view. Articles having improved concealment of the fluorescent indicia are disclosed herein. In disclosed embodiments, the article includes a color shifting film and indicia disposed behind the color shifting film from the point of view of an ordinary observer of the article. The indicia include a first and second colored portion arranged as a foreground and a background of the indicia. The first colored portion comprises a fluorescent colorant, and the second colored portion is substantially non-fluorescent. The second colored portion is selected to have substantially the same color as the first colored portion to enhance concealment of the indicia. Preferably, the first and second colored portions have the same color when viewed by themselves apart from the color shifting film, and also have the same apparent color when viewed through the color shifting film at an angle at which the color shifting film substantially blocks transmission of an emission band of the fluorescent colorant. In this way, the contrast between foreground and background is substantially reduced, and the indicia become less noticeable at such a viewing angle.
Brief Description of the Drawings Fig. 1 is a sectional view of an article having a color shifting film and a first and second colored portion disposed behind the film which form indicia, the article being adhered to a substrate; FIG. 2 is a front view of the article of FIG. 1 from one viewing angle;
FIG. 3 is a front view of the article of FIG. 1 from another viewing angle; FIG. 4 is an idealized and simplified composite graph depicting spectral properties of the first and second colored portions, and of the color shifting film at one viewing angle; FIG. 5 is an idealized and simplified composite graph depicting spectral properties of the first and second colored portions, and of the color shifting film at another viewing angle;
FIG. 6 is an idealized and simplified composite graph depicting, for another embodiment, spectral properties of the first and second colored portions, and of the color shifting film at one viewing angle; FIG. 7 is an idealized and simplified composite graph depicting, for still another embodiment, spectral properties of the first and second colored portions, and of the color shifting film at one viewing angle;
FIG. 8 is a graph of measured spectral transmission of a particular color shifting film at normal (0 degree) incidence and at 60 degrees incidence;
FIG. 9 is a graph of measured spectral properties of a particular orange fluorescent dye; and
FIG. 10 is a graph of measured spectral reflectivity of a particular orange non-fluorescent colorant. In the figures, like reference numerals indicate like elements.
Detailed Description of the Illustrative Embodiments In FIG. 1, an article 10 includes a color shifting film 12 and indicia 14 (see FIG. 2) disposed behind the film 12 and viewable through the film 12 for at least some viewing and/or illumination geometries. The indicia 14 is made up of or defined by at least a first colored portion 16 and a second colored portion 18. As shown best in FIGS. 1 and 2, portions 16,18 are patterned in complementary fashion so as to define the indicia 14, which in this embodiment is a single letter "W". Note that FIG. 1 corresponds roughly to a sectional view taken along axis 1- 1 in FIG. 2, which is drawn to a somewhat smaller scale than FIG. 1. Article 10 also includes an optional adhesive layer 20, which preferably comprises a conventional pressure-sensitive adhesive (PSA), but alternatively can comprise a heat-activated adhesive or other suitable adhesive. Adhesive layer 20 secures the article 10 to an optional substrate 22. If desired, substrate 22 can form part of the article 10. Depending upon the intended use of the article 10, substrate 22 can itself comprise a wide variety of different articles, such as a document, sheet of paper, rigid or flexible sign backing, or rigid or flexible window material if some illumination is desired from the back of article 10. To the extent any light is transmitted through the combination of color shifting film 12 and indicia 14, such light can be absorbed, reflected diffusely or specularly, or transmitted by substrate
22. The color shifting film 12 has the property of transmitting different wavelengths of light as a function of the angle such light impinges on the film. The transmission properties may also be polarization dependent, even at normal incidence. In this regard, film 12 can be a polarizer, a mirror, or a mirror having substantial polarizing properties. Preferred films 12 have a multitude of alternating polymer layers arranged into a multitude of unit cells, each unit cell effective to reflect light at a wavelength twice the optical thickness of such unit cell. Such films can be made by co-extrusion of two or more polymers forming an interleaved stream of materials. The cast coextruded film can be subsequently thinned and oriented by stretching uniaxially or biaxially to form a finished reflective polarizer or mirror. Preferably, at least one of the polymers is capable of strain-induced birefringence so that the indices of refraction change on stretching. The unit cells, which can each include two, three, or more individual polymer layers, are typically also arranged to have an optical thickness gradient across the thickness of the film 12 so that a relatively wide spectral band ("reflection band") is reflected by the . film. Boundaries of the reflection band are referred to herein as band edges — spectral transitions from high reflectivity (low transmission) to low reflectivity (high transmission) or vice versa. It is also known to tailor the thickness profile of the unit cells to sharpen the band edges. These and other aspects of suitable color shifting films are described in one or more of U.S. Patent Nos. 5,882,774 (Jonza et al.); 6,024,455 (O'Neill et al.); and U.S. Patent Application No. 09/006,591 entitled "Color Shifting Film" (Weber et al.), filed Jan. 13, 1998. Reference is also made to U.S. Patent Nos. 5,103,337 (Schrenk et al.) (reissued as Re. 34,605) and 5,360,659 (Arends et al.) for discussions of unit cells having more than two individual layers and/or more than two unique polymer materials.
Conventional inorganic multilayer films — made for example by vacuum deposition of two inorganic dielectric materials sequentially in a multitude of layers on a glass or other suitable substrate, or alternating layers of inorganic materials and organic polymers (see, e.g., U.S. Patent Nos. 5,440,446 (Shaw et al.), 5,877,895 (Shaw et al.), and 6,010,751 (Shaw et al.))— can also be used as the color shifting film 12. Compared to these alternative multilayer films, preferred polymeric films described in the preceding paragraph have the added benefit of being able to maintain the integrity of their band edges over substantially all incidence angles and regardless of polarization of light, by controlling the out-of- plane (z-index) index of refraction of adjacent layers within the film. Preferably, the difference Δnz in index of refraction along the z-axis of adjacent polymer layers within a unit cell is less than the maximum index difference in the plane of the film
(i.e., Δnx or Δny ) between such adjacent layers, more preferably less than 0.5 or 0.2 times such maximum in-plane index difference, and can also preferably be substantially zero. These conditions help maintain the shape of the band edge even as the reflection band shifts in wavelength or color with changing incidence angle, which corresponds visually to high color saturation over a wide range of incidence angles. Suitable films are available from 3M Company (St. Paul, Minnesota, USA) under the designation 3M™ Radiant Light Film.
Coextruded polymeric films whose layers are not oriented, and thus are substantially isotropic in refractive index, can also be used for the color shifting film. Such films are described, for example, in U.S. Patent Nos. 3,801,429
(Schrenk et al.), 4,162,343 (Wilcox et al), and 4,310,584 (Cooper et al).
The first colored portion 16 is patterned to form the foreground of a letter "W", and is disposed behind color shifting film 12. Other letters, symbols, or shapes which convey information are also contemplated. Importantly, portion 16 includes a fluorescent colorant. The term "colorant" as used herein means any pigment, dye, or other substance or combination of substances used to impart hue or chroma to an article. The term "fluorescent" refers to the property of emitting light at one wavelength (or band of wavelengths) as a result of the absorption of light at a different (and typically shorter) wavelength (or band of wavelengths). The wavelength range of emitted fluorescent light is referred to as an emission band; that of the absorbed light is referred to as an excitation band. By proper selection of fluorescent colorant and color shifting film, light in the emission band can be substantially transmitted through the color shifting film at some angles, but substantially reflected by the color shifting film (and therefore blocked from reaching the eye of an observer) at other angles. Additionally or alternatively, if a highly directional light source is used, light in the excitation band can be blocked from reaching the fluorescent colorant at some angles but transmitted to the fluorescent colorant at other angles. Arrows 24,26 shown in FIG. 1 represent a normal-incidence viewing angle and an oblique viewing angle respectively. At one of these angles, color shifting film 12 transmits the fluorescent emission of first colored portion 16, yielding a bright "W" (FIG. 2). At the other angle, color shifting film 12 substantially blocks light in the emission band so that the "W" is relatively dark (FIG. 3).
The preceding discussion of course assumes that the fluorescent colorant in colored portion 16 is able to be excited by absorption of light in the excitation band. Such excitation can be achieved in a number of ways depending upon the intended application.
In some applications no significant amount of light is generated from behind the article 10. In those cases excitation light passes through the color shifting film 12 before reaching first colored portion 16. Some color shifting films 12 can effectively transmit the excitation light only for some directions of incidence and/or only for some polarizations. Such selective transmission of excitation light can be used in a specialized procedure to interrogate the article: one light beam having the appropriate angular and/or polarization properties is alternated with another light beam not having those properties, and the visual response (fluorescent emission or lack thereof at a suitable observation angle) is monitored. Alternatively, the application may be one in which the article 10 is exposed to light impinging on its front surface from substantially all angles and polarizations — such as is found in typical office environments — in which case a sufficient amount of light in the excitation band, and having the appropriate angular and/or polarization properties, will be present to produce fluorescence in the portion 16. Other color shifting films 12 can effectively transmit excitation light for substantially all or at least a wide range of incidence angles and/or polarizations. For those films, a comparatively greater amount of ambient light will pass through the color shifting film to produce a brighter fluorescent emission. In some applications a source of light, such as a backlight or other lamp, is employed behind the article 10. In those cases any materials or elements disposed behind portion 16 are simply selected to have an aggregate transmission for light in the excitation band sufficient to produce the desired fluorescent effect in portion 16.
Article 10 also includes second colored portion 18 disposed behind color shifting film 12. As shown in FIG. 1, portion 18 can be patterned in a complementary fashion to portion 16. Alternatively, for simplicity of manufacturing, only one of portions 16,18 can be patterned, and the other portion can be unpattemed. In that case the unpattemed portion can for instance be printed in a continuous layer to cover the patterned portion in some places and to extend between parts of the patterned portion in other places. In another manufacturing approach, the patterned portion can be printed on top of the continuous unpattemed portion and the resulting combination laminated to or otherwise placed behind color shifting film 12. In still another approach the patterned portion can be printed to the back side of the color shifting film, and the unpattemed portion can simply be positioned behind that combination. Conventional coating processes can be used to apply the colored portion(s) to the film 12, including without limitation flexographic printing techniques.
If the article includes an unpattemed adhesive layer 20, such layer can replace the first or second colored portions 16,18 by inclusion of fluorescent and/or non-fluorescent colorants as appropriate. As shown in FIGS. 1 and 2, portion 18 forms a background for the indicia.
Importantly, portion 18 is substantially non- fluorescent. That is, portion 18 does not produce fluorescent emission noticeable to an ordinary observer when exposed to expected light levels for the particular application. Furthermore, the pigments, dyes, inks, or other colorants within portion 18 are selected to yield a perceived color that is substantially the same as the color of colored portion 16. Such selection helps reduce the contrast between the foreground and background of the indicia at some viewing angles, thus helping conceal the indicia (see FIG. 3) at such angles compared to constructions having no colored portion 18 or having fluorescent indicia printed onto a white surface or a surface of a different color. Preferably, the color of portions 16,18 are substantially the same when viewed from the front side of color shifting film 12 at an angle at which the color shifting film 12 blocks fluorescent emission from reaching the eye of the observer. Under those conditions, portion 16 will appear relatively dark compared to viewing angles where the bright fluorescent emission is visible. To the extent non- fluorescent colorants are also present in portion 16, they may contribute to its appearance or color under the stated conditions. If both portions 16, 18 are disposed behind color shifting film 12, it is preferred to select colors for portions 16,18 that are also substantially the same (even though their relative brightness may differ substantially) if viewed through a clear transparent medium (such color referred to as "inherent color"), e.g. if viewed from behind color shifting film 12, or if viewed through a clear film substituted for the color shifting film 12, or if viewed from above after coating the portions side by side onto a different substrate. For example, both portions can be essentially orange and portion 16 can include an orange fluorescent colorant. As another example, both portions can be essentially green and portion 16 can include a green fluorescent colorant. If the portions are colored in this way, their appearance will typically also be very similar when viewed through the color shifting film at an angle at which the color shifting film blocks the fluorescent emission, to help conceal the indicia at such angles.
If desired, the role of foreground and background can be reversed: portion 16 can form the background and portion 18 can form the foreground of the indicia. Since fluorescent colorants tend to be more expensive than non-fluorescent colorants, it is desirable to use a smaller quantity of portion 16 than of portion 18. In many cases the foreground of particular indicia takes up less area than the background. Thus, in many cases it is preferred that portion 16 be used as the foreground of the indicia. Portion 16, even if it includes a brightly colored fluorescent pigment, will in many cases appear relatively dark in certain geometries — such as an observation angle at which the color shifting film 12 substantially blocks the fluorescent emission, or where the color shifting film substantially blocks light in the excitation band from a directional light source. In such cases portion 18 may well be designed to have an inherent color such as dark brown or black that is substantially different than the inherent color of portion 16, which may for example be green, orange, or red. Yet, the portions 16, 18 can still have a similar apparent color when viewed from the front of film 12 at the certain geometries referred to, thus helping conceal the indicia. Indeed, portion 18 may then be positioned either behind or in front of film 12. In each case the indicia 14 would still be considered to be behind film 12 since at least one of the portions making it up is behind film 12.
FIGS. 4 & 5 are idealized, simplified composite graphs that depict spectral properties of the first and second colored portions, and of the color shifting film for a particular embodiment. For all curves shown, the x-axis represents the wavelength of light λ in nanometers (nm), with the visible region extending , roughly from 400 to 700 nm. Curve 50 (FIG. 4) represents the spectral transmission of color shifting film 12 at normal incidence, and curve 50' (FIG. 5) represents its transmission at an oblique angle of incidence. These curves maybe for a particular polarization of light, or instead an average over all polarizations. For these curves, the y-axis represents percent transmission, from 0% to 100%. If the color shifting film 12 comprises the preferred polymeric multilayer films described above, then the specular reflectivity at a particular wavelength is substantially 100% minus the percent transmission, since absorption in the films is typically much less than 1% for most wavelengths of interest. Curves 52 and 54 represent the effective reflectivity (reflectivity plus fluorescent intensity, if any) of colored portions 16, 18 respectively, measured by themselves in the absence of any color shifting film. For curves 52,54, the y-axis represents effective reflectivity in arbitrary units. Curves 52,54 are roughly to scale with respect to each other, insofar as the portion 16 having the fluorescent colorant is much brighter at certain wavelengths than the other portion 18. However, the relative heights of the curves are not intended to be exact, and all curves are idealized for ease of discussion.
At normal incidence (FIG. 4), the color shifting film 12 has a low transmission in a reflectance band bounded by band edges 50a, 50b as shown. Outside the reflectance band, the film has high transmission. At this geometry, film 12 substantially blocks light associated with colored portions 16,18, except near one side of curves 52,54. The small amount of light that is transmitted has a similar apparent color and intensity, and the result is a low contrast appearance as depicted in FIG. 3. At a high angle of incidence (FIG. 5), the reflectance band and associated band edges, now labeled 50a' and 50b', have shifted to shorter wavelengths — hence the term color shifting film to describe the accompanying shift in transmitted light. At this geometry, light from both colored portions 16,18 is substantially transmitted by the film 12. The high brightness of the fluorescent colorant in portion 16 however overpowers any reflectance from portion 18, which thus appears dark in comparison. The result is a high contrast appearance as depicted in FIG. 2.
FIG. 6 is an idealized, simplified composite graph for normal incidence similar to FIG. 4, but for a different embodiment having different first and second colored portions 16,18, and a different color shifting film 12. Curve 60 represents the spectral transmission of color shifting film 12 at normal incidence. Curve 60 includes band edge 60a. Curves 62,64 represent the effective reflectivity (as discussed above) of colored portions 16, 18 respectively. The overall spectral distributions of curves 62,64 represent similar colors. Furthermore, at normal incidence the film 12 substantially blocks light associated with colored portions 16,18, except near one side of curves 62,64. The small amount of light that is transmitted has a similar apparent color and intensity, and the result is a low contrast appearance as depicted in FIG. 3. For oblique angle observation, curve 60 with band edge 60a is replaced with a similar curve (not shown) shifted to shorter wavelengths by an amount dictated by the angle of observation. At at least some angles, the shifted transmission curve substantially transmits light from curves 62,64 to yield a high contrast appearance with a bright foreground colored portion 16 as depicted in FIG. 2.
FIG. 7 is an idealized, simplified composite graph for normal incidence similar to FIG. 6, but for still another embodiment having different first and second colored portions 16,18, and a different color shifting film 12. Curve 70 represents the spectral transmission of color shifting film 12 at normal incidence. Curve 70 includes band edge 70a. Curves 72,74 represent the effective reflectivity (as discussed above) of colored portions 16, 18 respectively. The overall spectral distributions of curves 72,74 represent similar colors. In this embodiment, at normal incidence the film 12 substantially transmits light from curves 72,74 to yield a high contrast appearance with a bright foreground colored portion 16 as depicted in FIG. 2. Indeed, at normal incidence the film 12 has the appearance of a substantially clear film, because it has high transmission throughout the visible spectrum.
For oblique angle observation, curve 70 with band edge 70a is replaced with a similar curve (not shown) shifted to shorter wavelengths by an amount dictated by the angle of observation. At at least some angles, the shifted transmission curve substantially blocks light associated with colored portions 16,18, except near one side of curves 72,74. The small amount of light that is transmitted has a similar apparent color and intensity, and the result is a low contrast appearance as depicted in FIG. 3.
In general, suitable articles 10 can include additional layers and features. For example, color shifting film 12 can include one or more regions that have been embossed with heat and/or pressure. The embossed regions are thinner than non- embossed neighboring regions and therefore have spectral transmission and reflection features that are blue-shifted relative to corresponding features of the non-embossed regions. The embossed regions can take the form of indicia in addition to the indicia 14 discussed above. As another example, the color shifting film 12 can contain or carry a microstructured relief pattern suitable for producing conventional holographic images. Such images can be used to further obscure the indicia 14 at selected geometries. The relief pattern can be formed using known holographic embossing techniques into a suitable skin layer or coating on top of the color shifting film. The relief pattern can alternately be incorporated into a separate transparent sheet that is laminated to the color shifting film. Reference is made generally to U.S. Pat. 5,656,360 (Faykish et al.). Such a separate transparent sheet is preferably polymeric for ease of manufacture and for article integrity over operating temperature ranges. As yet another example, additional graphics, symbols, or other indicia in addition to indicia 14 discussed above can be applied to the article 10 by conventional printing onto color shifting film 12 or onto additional layer(s) laminated to film 12. Example
A representative article was constructed using the following component materials: 3M brand Radiant Color Film CM590 for color shifting film 12; Seiko brand fluorescent orange dye (dye No. 503, made in Japan) for colored portion 16; and a conventional non-fluorescent orange/red dye (orange ink, made in Malaysia, available from BASF) for colored portion 18. The different dyes were applied by hand to one side (designated the "back" side) of the color shifting film in complementary fashion to form a foreground and background of a single letter "W", substantially as depicted in FIGS. 1 and 2 except that: (a) no adhesive layer 20 was used, and (b) portion 16 formed the background and portion 18 formed the foreground of the "W". The dyes were then allowed to dry. The resulting coated film was flexible and had an overall thickness of about: 1.8 mils (45 μm) for the film 12 by itself; 2.0 mils (50 μm) on average for the film plus dye in the foreground regions; and 2.4 mils (60 μm) on average for the film plus dye in the background regions. The thickness of the dried dyes was sufficient to render them substantially opaque if viewed against standard office lighting fixtures.
The article was placed back side down onto a sheet of white paper under ordinary office illumination. When viewed from the front at normal incidence, no fluorescence was detectable. Instead, the color seen was a blend of the reflected color of the color shifting film itself and the color of light transmitted by the color shifting film and reflected back through the film by the colored portions 16, 18. Since the fluorescent dye and non-fluorescent dye have substantially similar base colors, one sees only a slight contrast between the foreground letter "W" and the background. At highly oblique observation angles (about 60 degrees or higher from the normal), the reflection band of the film 12 shifts sufficiently to make the background (colored portion 16) appear very bright orange. Under these conditions the foreground (colored portion 18) remained relatively dark in comparison to the fluorescent background. The transmission of a spare (uncoated) piece of the CM590 film was measured using a Perkin Elmer Lambda 19 RSA-PE19S spectrometer. FIG. 8 plots the measured percent transmission versus wavelength. Curve 80 was measured with unpolarized light at normal incidence to the film. Curve 82 is an average of p- polarized light and s-polarized light (i.e., light linearly polarized in the plane of incidence and peφendicular to the plane of incidence respectively) for an angle of 60 degrees from the normal direction. Note the wavelength shift of the reflection band and the good maintenance of the sharp band edges. FIG. 9 is data measured using a Perkin Elmer Model LSB50 Luminescence Spectrophotometer for the orange fluorescent dye. Curve 90 is the emission band and curve 92 is the excitation band for the dye. The two curves are plotted against relative response (in arbitrary units). Note that the excitation band 92 exists not only in the ultraviolet region but extends well into the visible region. In comparing FIGS. 8 and 9 note also that the CM590 film substantially transmits light in the excitation band 92 at normal angles and at oblique angles. FIG. 10 plots reflectivity of the non-fluorescent orange/red dye used in the example, as measured using an Ocean Optics Model SD2000 Spectrometer with a reflection probe. The y-axis plots reflectivity in arbitrary units which are not to scale compared to the arbitrary units used in FIG. 9.
The present invention has now been described with reference to several embodiments thereof. It will be apparent to those skilled in the art that many changes can be made in the embodiments described without departing from the scope of the invention. Thus, the scope of the present invention should not be limited to the preferred structures and methods described herein, but rather by the broad scope of the claims which follow.

Claims

What is claimed is:
1. An article, comprising: a color shifting film; and indicia disposed behind the color shifting film; ) wherein the indicia includes at least a first and second colored portion of substantially the same color and arranged as a foreground and a background of the indicia, wherein the first colored portion includes a first fluorescent colorant and the second colored portion is substantially non-fluorescent.
2. The article of claim 1, wherein the first fluorescent colorant has an emission band, and wherein the color shifting film substantially blocks transmission of light in the emission band at a first angle and substantially transmits light in the emission band at a second angle.
3. The article of claim 2, wherein the first and second colored portion have substantially the same color when viewed from a front surface of the color shifting film at the first angle.
4. The article of claim 1, wherein the first and second colored portion have substantially the same color when viewed through a substantially clear medium.
5. The article of claim 1, wherein at least the first colored portion is printed on the color shifting film.
6. The article of claim 1, wherein at least the second colored portion is printed on the color shifting film.
7. The article of claim 6, wherein the first colored portion is also printed on the color shifting film, and the second colored portion is printed substantially continuously to extend over the first colored portion.
8. The article of claim 1, further comprising an adhesive layer.
9. The article of claim 8, wherein the adhesive layer is disposed to permit attachment of the article to a substrate.
10. The article of claim 8, wherein the adhesive layer comprises one of the first and second colored portions.
11. The article of claim 1, wherein the foreground comprises the first colored portion and the background comprises the second colored portion.
12. The article of claim 1, wherein the background comprises the first colored portion and the foreground comprises the second colored portion.
13. The article of claim 1, wherein the color shifting film is selected from the group consisting of a polarizer and a mirror.
14. The article of claim 1, further comprising a substantially white diffuse surface disposed behind the indicia.
15. The article of claim 1, wherein the first fluorescent colorant has an excitation band, and wherein the color shifting film substantially blocks transmission of light in the excitation band at a first angle and substantially transmits light in the excitation band at a second angle.
16. The article of claim 1, further comprising additional indicia formed by at least one element selected from the group consisting of an embossed region of the color shifting film, a holographic element, and printed information.
PCT/US2001/021288 2001-02-16 2001-07-02 Color shifting film with patterned fluorescent and non-fluorescent colorants WO2002066266A1 (en)

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DE60108531T DE60108531T2 (en) 2001-02-16 2001-07-02 COLOR SHIFF WITH FLUORESCENT AND NON-FLUORESCENT COLORS IN PATTERN
JP2002565805A JP4643123B2 (en) 2001-02-16 2001-07-02 Color shift film with patterned fluorescent and non-fluorescent colorants
AT01954621T ATE287336T1 (en) 2001-02-16 2001-07-02 COLOR SHIFTING FILM WITH FLUORESCENT AND NON-FLUORESCENT COLORS IN SAMPLE FORM
CA002438059A CA2438059A1 (en) 2001-02-16 2001-07-02 Color shifting film with patterned fluorescent and non-fluorescent colorants
EP01954621A EP1361962B1 (en) 2001-02-16 2001-07-02 Color shifting film with patterned fluorescent and non-fluorescent colorants
BR0116877-0A BR0116877A (en) 2001-02-16 2001-07-02 Article comprising a chromatic distortion film and markings arranged behind the film

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Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6531230B1 (en) * 1998-01-13 2003-03-11 3M Innovative Properties Company Color shifting film
US6916047B2 (en) * 2001-08-31 2005-07-12 Bertek Systems, Inc. Secure card
FR2832687B1 (en) * 2001-11-29 2004-03-05 Plastic Omnium Cie MOTOR VEHICLE BODY PIECE HAVING A DEPTH APPEARANCE MARKED
US20030142401A1 (en) * 2002-01-25 2003-07-31 Tominari Araki Optical member
JP2004078697A (en) * 2002-08-20 2004-03-11 Fuji Xerox Co Ltd Method for processing image, method for forming image, image processor, and image forming device
US7118438B2 (en) * 2003-01-27 2006-10-10 3M Innovative Properties Company Methods of making phosphor based light sources having an interference reflector
US20040159900A1 (en) * 2003-01-27 2004-08-19 3M Innovative Properties Company Phosphor based light sources having front illumination
KR20050103200A (en) * 2003-01-27 2005-10-27 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Phosphor based light source component and method of making
US7312560B2 (en) * 2003-01-27 2007-12-25 3M Innovative Properties Phosphor based light sources having a non-planar long pass reflector and method of making
US7245072B2 (en) * 2003-01-27 2007-07-17 3M Innovative Properties Company Phosphor based light sources having a polymeric long pass reflector
US7210977B2 (en) 2003-01-27 2007-05-01 3M Innovative Properties Comapny Phosphor based light source component and method of making
US7091653B2 (en) 2003-01-27 2006-08-15 3M Innovative Properties Company Phosphor based light sources having a non-planar long pass reflector
US20040145312A1 (en) * 2003-01-27 2004-07-29 3M Innovative Properties Company Phosphor based light source having a flexible short pass reflector
US7091661B2 (en) * 2003-01-27 2006-08-15 3M Innovative Properties Company Phosphor based light sources having a reflective polarizer
US6808394B1 (en) * 2003-06-23 2004-10-26 American Polarizers, Inc. System for demonstrating effects of polarized lens
JP2005257938A (en) * 2004-03-10 2005-09-22 Calsonic Kansei Corp Variable display structure
US7361399B2 (en) * 2004-05-24 2008-04-22 International Paper Company Gloss coated multifunctional printing paper
US20060234014A1 (en) * 2005-04-14 2006-10-19 Liu Yaoqi J Patterned adhesives for tamper evident feature
US20060234040A1 (en) * 2005-04-14 2006-10-19 Liu Yaoqi J Patterned adhesives for color shifting effect
AU2006257720B2 (en) * 2005-06-17 2010-12-02 Securency International Pty Ltd Security documents incorporating colour shifting inks
GB2441261B (en) * 2005-06-17 2009-05-27 Securency Pty Ltd Security documents incorporating colour shifting inks
US7636193B2 (en) * 2006-05-02 2009-12-22 3M Innovative Properties Company Visible light-transmissive IR filter with distorted portions
US7547105B2 (en) * 2007-07-16 2009-06-16 3M Innovative Properties Company Prismatic retroreflective article with cross-linked image layer and method of making same
JP5371319B2 (en) * 2008-08-19 2013-12-18 キヤノン株式会社 Printer and print paper
WO2010036521A1 (en) * 2008-09-26 2010-04-01 International Paper Company Composition suitable for multifunctional printing and recording sheet containing same
JP2012511177A (en) * 2008-12-08 2012-05-17 スリーエム イノベイティブ プロパティズ カンパニー Prism-like retroreflective article having figure and method for producing the same
KR20110098781A (en) * 2008-12-08 2011-09-01 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Protective overlay bearing a graphic and retroreflective articles comprising the overlay
US8388024B2 (en) * 2009-01-27 2013-03-05 The Standard Register Company Double mailer intermediate
CN102307724B (en) * 2009-02-06 2015-05-13 3M创新有限公司 Light control film and multi-layer optical film stack
CA2656506A1 (en) * 2009-02-27 2010-08-27 Bank Of Canada Security device
US20110240723A1 (en) * 2010-03-31 2011-10-06 David Yost Double Postcard and Intermediate Form For Same
MX2012013699A (en) 2010-06-10 2012-12-17 3M Innovative Properties Co Display device and method of lc panel protection.
GB2488795A (en) * 2011-03-08 2012-09-12 Ian Michael Eastwood Security element for documents
US9880332B2 (en) * 2013-10-04 2018-01-30 3M Innovative Properties Company Decorative microsphere articles with information layer
US10036125B2 (en) * 2015-05-11 2018-07-31 Nanotech Security Corp. Security device
TW201819964A (en) 2016-10-18 2018-06-01 美商3M新設資產公司 Optical filters complementary angular blocking regions
WO2019069214A2 (en) * 2017-10-02 2019-04-11 3M Innovative Properties Company Partial reflector for correcting color shift

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4652464A (en) * 1982-08-23 1987-03-24 Ludlum John P Printing fine art with fluorescent and non-fluorescent colorants
EP0657297A1 (en) * 1993-12-10 1995-06-14 Agfa-Gevaert N.V. Security document having a transparent or translucent support and containing interference pigments.
WO2000024580A1 (en) * 1998-10-23 2000-05-04 General Electric Company Thermoplastic article which exhibits angular metamerism

Family Cites Families (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124639A (en) 1964-03-10 figure
US540768A (en) 1895-06-11 Richard walsingham western
US3801429A (en) 1969-06-06 1974-04-02 Dow Chemical Co Multilayer plastic articles
US3610729A (en) 1969-06-18 1971-10-05 Polaroid Corp Multilayered light polarizer
US3860036A (en) 1970-11-02 1975-01-14 Dow Chemical Co Variable geometry feed block for multilayer extrusion
US3711176A (en) 1971-01-14 1973-01-16 Dow Chemical Co Highly reflective thermoplastic bodies for infrared, visible or ultraviolet light
US4015131A (en) * 1974-01-16 1977-03-29 Pitney-Bowes, Inc. Multi-detectable ink compositions and method of use
GB1536403A (en) * 1975-12-12 1978-12-20 Pitney Bowes Inc Fluorescent machine readable ink compositions
US4162343A (en) 1977-12-23 1979-07-24 The Mearl Corporation Multilayer light-reflecting film
US4455039A (en) * 1979-10-16 1984-06-19 Coulter Systems Corporation Encoded security document
US4310584A (en) 1979-12-26 1982-01-12 The Mearl Corporation Multilayer light-reflecting film
US5766738A (en) * 1979-12-28 1998-06-16 Flex Products, Inc. Paired optically variable article with paired optically variable structures and ink, paint and foil incorporating the same and method
US4520189A (en) 1981-03-02 1985-05-28 Polaroid Corporation Optical device including birefringent aromatic amino carboxylic acid polymer
US4525413A (en) 1981-03-02 1985-06-25 Polaroid Corporation Optical device including birefringent polymer
US4521588A (en) 1981-03-02 1985-06-04 Polaroid Corporation Optical device including birefringent polyhydrazide polymer
US4446305A (en) 1981-03-02 1984-05-01 Polaroid Corporation Optical device including birefringent polymer
US4720426A (en) 1986-06-30 1988-01-19 General Electric Company Reflective coating for solid-state scintillator bar
US5211878A (en) 1988-03-10 1993-05-18 Merck Patent Gesellschaft Mit Beschrankter Haftung Difluorobenzonitrile derivatives
US5486949A (en) 1989-06-20 1996-01-23 The Dow Chemical Company Birefringent interference polarizer
US5235443A (en) 1989-07-10 1993-08-10 Hoffmann-La Roche Inc. Polarizer device
SG50560A1 (en) 1989-11-01 2000-10-24 Rolic Ag Light control systems with liquid crystals
NL9000808A (en) 1990-04-06 1991-11-01 Koninkl Philips Electronics Nv LIQUID CRYSTALLINE MATERIAL AND IMAGE DISPLAY CELL CONTAINING THIS MATERIAL.
US5103337A (en) 1990-07-24 1992-04-07 The Dow Chemical Company Infrared reflective optical interference film
US5217794A (en) 1991-01-22 1993-06-08 The Dow Chemical Company Lamellar polymeric body
US5294657A (en) 1992-05-15 1994-03-15 Melendy Peter S Adhesive composition with decorative glitter
DE4326521B4 (en) 1992-08-10 2005-12-22 Bridgestone Corp. Light scattering material and method for its production
US5269995A (en) 1992-10-02 1993-12-14 The Dow Chemical Company Coextrusion of multilayer articles using protective boundary layers and apparatus therefor
EP0666993B1 (en) 1992-10-29 1999-06-09 Minnesota Mining And Manufacturing Company Formable reflective multilayer body
TW289095B (en) 1993-01-11 1996-10-21
DE69409977T2 (en) 1993-01-11 1998-10-22 Koninkl Philips Electronics Nv Lighting system and such a comprehensive display device
US5360659A (en) 1993-05-24 1994-11-01 The Dow Chemical Company Two component infrared reflecting film
US5389324A (en) 1993-06-07 1995-02-14 The Dow Chemical Company Layer thickness gradient control in multilayer polymeric bodies
US5486935A (en) 1993-06-29 1996-01-23 Kaiser Aerospace And Electronics Corporation High efficiency chiral nematic liquid crystal rear polarizer for liquid crystal displays having a notch polarization bandwidth of 100 nm to 250 nm
US5440446A (en) 1993-10-04 1995-08-08 Catalina Coatings, Inc. Acrylate coating material
AU1434795A (en) 1993-12-21 1995-07-10 Minnesota Mining And Manufacturing Company Reflective polarizer display
IL112072A0 (en) 1993-12-21 1995-03-15 Minnesota Mining & Mfg Optical polarizer
US5882774A (en) 1993-12-21 1999-03-16 Minnesota Mining And Manufacturing Company Optical film
MY121195A (en) 1993-12-21 2006-01-28 Minnesota Mining & Mfg Reflective polarizer with brightness enhancement
EP0962807B1 (en) 1993-12-21 2008-12-03 Minnesota Mining And Manufacturing Company Multilayered optical film
US5629055A (en) 1994-02-14 1997-05-13 Pulp And Paper Research Institute Of Canada Solidified liquid crystals of cellulose with optically variable properties
JP3803370B2 (en) 1994-04-06 2006-08-02 スリーエム カンパニー Polarization source
JP4034365B2 (en) 1995-03-09 2008-01-16 大日本印刷株式会社 Ultrafine particle-containing antireflection film, polarizing plate and liquid crystal display device
US5877895A (en) 1995-03-20 1999-03-02 Catalina Coatings, Inc. Multicolor interference coating
US5700077A (en) 1995-03-23 1997-12-23 Minnesota Mining And Manufacturing Company Line light source including fluorescent colorant
US5751388A (en) 1995-04-07 1998-05-12 Honeywell Inc. High efficiency polarized display
US5686979A (en) 1995-06-26 1997-11-11 Minnesota Mining And Manufacturing Company Optical panel capable of switching between reflective and transmissive states
US6080467A (en) 1995-06-26 2000-06-27 3M Innovative Properties Company High efficiency optical devices
WO1997001781A2 (en) 1995-06-26 1997-01-16 Minnesota Mining And Manufacturing Company Diffusely reflecting multilayer polarizers and mirrors
WO1997001440A1 (en) 1995-06-26 1997-01-16 Minnesota Mining And Manufacturing Company Multilayer polymer film with additional coatings or layers
US5699188A (en) 1995-06-26 1997-12-16 Minnesota Mining And Manufacturing Co. Metal-coated multilayer mirror
US5767935A (en) 1995-08-31 1998-06-16 Sumitomo Chemical Company, Limited Light control sheet and liquid crystal display device comprising the same
US5656360A (en) 1996-02-16 1997-08-12 Minnesota Mining And Manufacturing Company Article with holographic and retroreflective features
US5825543A (en) 1996-02-29 1998-10-20 Minnesota Mining And Manufacturing Company Diffusely reflecting polarizing element including a first birefringent phase and a second phase
US5783120A (en) 1996-02-29 1998-07-21 Minnesota Mining And Manufacturing Company Method for making an optical film
WO1997037252A1 (en) * 1996-04-01 1997-10-09 Reflexite Corporation A color-fast retroreflective structure
US5808794A (en) 1996-07-31 1998-09-15 Weber; Michael F. Reflective polarizers having extended red band edge for controlled off axis color
JPH10100573A (en) * 1996-09-30 1998-04-21 Toppan Printing Co Ltd Paper and printed matter for preventing forgery
US5881196A (en) * 1996-10-24 1999-03-09 Phillips; Stephen Waveguide security device
US5940149A (en) 1997-12-11 1999-08-17 Minnesota Mining And Manufacturing Company Planar polarizer for LCD projectors
US6531230B1 (en) * 1998-01-13 2003-03-11 3M Innovative Properties Company Color shifting film
KR100554582B1 (en) 1998-01-13 2006-03-03 미네소타 마이닝 앤드 매뉴팩춰링 캄파니 Modified Copolyesters and Improved Multilayer Reflective Films
US6024455A (en) 1998-01-13 2000-02-15 3M Innovative Properties Company Reflective article with concealed retroreflective pattern
US6045894A (en) 1998-01-13 2000-04-04 3M Innovative Properties Company Clear to colored security film
CA2316974A1 (en) 1998-01-13 1999-07-22 Minnesota Mining And Manufacturing Company Process for making multilayer optical films

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4652464A (en) * 1982-08-23 1987-03-24 Ludlum John P Printing fine art with fluorescent and non-fluorescent colorants
EP0657297A1 (en) * 1993-12-10 1995-06-14 Agfa-Gevaert N.V. Security document having a transparent or translucent support and containing interference pigments.
WO2000024580A1 (en) * 1998-10-23 2000-05-04 General Electric Company Thermoplastic article which exhibits angular metamerism

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JP4643123B2 (en) 2011-03-02
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TW588000B (en) 2004-05-21
US6534158B2 (en) 2003-03-18
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EP1361962A1 (en) 2003-11-19
JP2004524562A (en) 2004-08-12

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