WO2010075363A1 - Internally patterned multilayer optical films with multiple birefringent layers - Google Patents

Internally patterned multilayer optical films with multiple birefringent layers Download PDF

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Publication number
WO2010075363A1
WO2010075363A1 PCT/US2009/069160 US2009069160W WO2010075363A1 WO 2010075363 A1 WO2010075363 A1 WO 2010075363A1 US 2009069160 W US2009069160 W US 2009069160W WO 2010075363 A1 WO2010075363 A1 WO 2010075363A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
microlayers
zone
layers
birefringence
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2009/069160
Other languages
English (en)
French (fr)
Inventor
William Ward Merrill
Douglas S. Dunn
Stephen A. Johnson
David T. Yust
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
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 Co filed Critical 3M Innovative Properties Co
Priority to US13/139,856 priority Critical patent/US8792165B2/en
Priority to JP2011542565A priority patent/JP5746045B2/ja
Priority to KR1020117017057A priority patent/KR101689045B1/ko
Priority to EP09835747.8A priority patent/EP2374032B1/en
Priority to CN200980157324.3A priority patent/CN102334050B/zh
Publication of WO2010075363A1 publication Critical patent/WO2010075363A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • 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
    • B42D25/23Identity cards
    • 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
    • B42D25/24Passports
    • 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
    • B42D25/30Identification or security features, e.g. for preventing forgery
    • B42D25/36Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378Special inks
    • B42D25/391Special inks absorbing or reflecting polarised light
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/28Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/08Mirrors
    • G02B5/0816Multilayer mirrors, i.e. having two or more reflecting layers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/08Mirrors
    • G02B5/0816Multilayer mirrors, i.e. having two or more reflecting layers
    • G02B5/0825Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only
    • G02B5/0841Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only comprising organic materials, e.g. polymers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/28Interference filters
    • G02B5/285Interference filters comprising deposited thin solid films
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/28Interference filters
    • G02B5/285Interference filters comprising deposited thin solid films
    • G02B5/287Interference filters comprising deposited thin solid films comprising at least one layer of organic material
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3083Birefringent or phase retarding elements
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528Polarisers
    • G02F1/133536Reflective polarizers
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363Birefringent elements, e.g. for optical compensation
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509Filters, e.g. light shielding masks
    • G02F1/133514Colour filters
    • G02F1/133521Interference filters
    • 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

  • FIG. 6 is a schematic diagram that summarizes various transformations that can be achieved using the techniques discussed herein for multilayer optical films
  • the differences discussed above between the first and second reflective characteristics relate to reflection bands that cover a portion of the visible spectrum, the differences may be perceived as differences in color between the first and second zones of the film.
  • Multilayer optical films include individual layers having different refractive indices so that some light is reflected at interfaces between adjacent layers. These layers, sometimes referred to as “microlayers", are sufficiently thin so that light reflected at a plurality of the interfaces undergoes constructive or destructive interference to give the multilayer optical film the desired reflective or transmissive properties.
  • each microlayer For multilayer optical films designed to reflect light at ultraviolet, visible, or near-infrared wavelengths, each microlayer generally has an optical thickness (a physical thickness multiplied by refractive index) of less than about 1 ⁇ m.
  • the polymers of the various layers are preferably chosen to have similar rheological properties, e.g., melt viscosities, so that they can be co-extruded without significant flow disturbances.
  • Extrusion conditions are chosen to adequately feed, melt, mix, and pump the respective polymers as feed streams or melt streams in a continuous and stable manner.
  • Temperatures used to form and maintain each of the melt streams may be chosen to be within a range that avoids freezing, crystallization, or unduly high pressure drops at the low end of the temperature range, and that avoids material degradation at the high end of the range.
  • the second zone is therefore characterized by a relatively large refractive index difference ( ⁇ nx) in one in-plane direction, a zero or near- zero refractive index difference ( ⁇ ny) in the other in-plane direction, and a relatively large out-of-plane refractive index difference ( ⁇ nz) of opposite polarity or sign compared to ⁇ nx.
  • ⁇ nx refractive index difference
  • ⁇ ny zero or near- zero refractive index difference
  • ⁇ nz relatively large out-of-plane refractive index difference
  • the third embodiment utilizes a non-uniform absorption profile that may be achieved, for example, by incorporating an absorbing agent into selected interior layers of the film.
  • the level of absorptivity (controlled by the local absorption coefficient) is desirably set to an intermediate level so that an adequate portion of the directed light beam is absorbed in the tailored absorbing region 915b of the film, but the absorptivity is not so high that an excessive amount of heat is delivered to the incident end of the region 915b relative to the opposite end.
  • the absorptivity in absorbing region 915b is still reasonably weak, e.g.
  • particle size and shape distributions may be important. For example, excessively large absorbing particles can over-heat relative to their surrounding film matrix, causing film defects such as degradation, wrinkling, blistering, layer delamination, or other damage. Film cleanliness may also be important, since surface and embedded dust and similar particulate matter may also cause random or unanticipated defects.
  • Other considerations include the beam shape and frequency (if a pulsed source is used) of the laser source, the scanning pattern, the mounting of the film (e.g. onto a card or other substrate by lamination such as with an adhesive or by other means), and the heat transfer, e.g. as controlled by the various thermal conductivities within and heat transfer coefficients from the film.
  • PEN:PMMA or PEN:isotropic coPEN mirror construction comprising optical packets separated by a lower melting and oriented coPEN protective boundary layer (PBL) such as a so-called low-melt PEN (LmPEN) which e.g. may comprise 90%/10% naphthalate/terephthalate carboxalate subunits.
  • PBL lower melting and oriented coPEN protective boundary layer
  • LmPEN low-melt PEN
  • the directed radiant treatment may be achieved directly after or even during film manufacture, separately but still in roll form, after sheeting, or after mounting to another substrate such as a glass plate, or plastic or paper cardstock.
  • the level of precision should be balanced against the process variations. For example, web flutter should be sufficiently handled for a roll process.
  • the directed radiant treatment could be achieved as the film moves over a roller while the film is under tension, perhaps between nips.
  • a protective film can be placed between the film and the rollers to continuously clean the rollers and otherwise prevent cosmetic defects such as scratches.
  • the film can be mounted on a fixed substrate after sheeting, or mounted or fixed over a temporary backing in a semibatch manner. For example, portions of the film roll can successively contact a protective film and slide over a plate.
  • the multilayer cast webs were then drawn or stretched so as to form doubly birefringent multilayer optical films.
  • a laboratory stretcher such as the KARO IV (available from Bruekner) was used for the present examples.
  • the cast webs were generally pre -heated (with a pre-heat time and temperature) and then stretched at a uniform separation speed of the grippers corresponding to an initial strain rate (given by a % strain rate) to nominal draw ratios (the ratio of initial to final gripper separation) in two orthogonal in-plane directions referred to as x- and y- directions.
  • strong reflection band strong color
  • This disclosure encompasses multilayer optical films that contain at least one doubly birefringent microlayer stack suitable for processing, or that has been processed, in one or more processed zones in any desired pattern or design, the processed zones being characterized by a reduced birefringence of at least some of the microlayers that make up the stack, and a changed reflective characteristic associated with the reduced birefringence.
  • the degree of processing, and/or the degree of birefringence reduction may be the same in all processed areas, or it may be different.
  • the stack may have one or more first areas or zones with no processing, and with a first reflective characteristic associated with a first degree of birefringence.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Credit Cards Or The Like (AREA)
  • Optical Filters (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Liquid Crystal (AREA)
PCT/US2009/069160 2008-12-22 2009-12-22 Internally patterned multilayer optical films with multiple birefringent layers Ceased WO2010075363A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US13/139,856 US8792165B2 (en) 2008-12-22 2009-12-22 Internally patterned multilayer optical films with multiple birefringent layers
JP2011542565A JP5746045B2 (ja) 2008-12-22 2009-12-22 複数の複屈折層を有する内部パターン形成多層光学フィルム
KR1020117017057A KR101689045B1 (ko) 2008-12-22 2009-12-22 복수의 복굴절성 층을 구비한 내부 패턴화된 다층 광학 필름
EP09835747.8A EP2374032B1 (en) 2008-12-22 2009-12-22 Internally patterned multilayer optical films with multiple birefringent layers
CN200980157324.3A CN102334050B (zh) 2008-12-22 2009-12-22 具有多个双折射层的内部图案化的多层光学膜

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US13973608P 2008-12-22 2008-12-22
US61/139,736 2008-12-22
US15800609P 2009-03-06 2009-03-06
US15799609P 2009-03-06 2009-03-06
US61/157,996 2009-03-06
US61/158,006 2009-03-06

Publications (1)

Publication Number Publication Date
WO2010075363A1 true WO2010075363A1 (en) 2010-07-01

Family

ID=42288117

Family Applications (5)

Application Number Title Priority Date Filing Date
PCT/US2009/069160 Ceased WO2010075363A1 (en) 2008-12-22 2009-12-22 Internally patterned multilayer optical films with multiple birefringent layers
PCT/US2009/069192 Ceased WO2010075383A1 (en) 2008-12-22 2009-12-22 Multilayer optical films having side-by-side polarizer/polarizer zones
PCT/US2009/069173 Ceased WO2010075373A1 (en) 2008-12-22 2009-12-22 Multilayer optical films suitable for bi-level internal patterning
PCT/US2009/069120 Ceased WO2010075340A1 (en) 2008-12-22 2009-12-22 Multilayer optical films having side-by-side mirror/polarizer zones
PCT/US2009/069153 Ceased WO2010075357A1 (en) 2008-12-22 2009-12-22 Internally patterned multilayer optical films using spatially selective birefringence reduction

Family Applications After (4)

Application Number Title Priority Date Filing Date
PCT/US2009/069192 Ceased WO2010075383A1 (en) 2008-12-22 2009-12-22 Multilayer optical films having side-by-side polarizer/polarizer zones
PCT/US2009/069173 Ceased WO2010075373A1 (en) 2008-12-22 2009-12-22 Multilayer optical films suitable for bi-level internal patterning
PCT/US2009/069120 Ceased WO2010075340A1 (en) 2008-12-22 2009-12-22 Multilayer optical films having side-by-side mirror/polarizer zones
PCT/US2009/069153 Ceased WO2010075357A1 (en) 2008-12-22 2009-12-22 Internally patterned multilayer optical films using spatially selective birefringence reduction

Country Status (6)

Country Link
US (9) US9291757B2 (enExample)
EP (5) EP2376956A4 (enExample)
JP (8) JP2012513608A (enExample)
KR (5) KR101762452B1 (enExample)
CN (5) CN102325830B (enExample)
WO (5) WO2010075363A1 (enExample)

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WO2012003213A1 (en) 2010-06-30 2012-01-05 3M Innovative Properties Company Diffuse reflective optical films with spatially selective birefringence reduction
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WO2012003247A2 (en) 2010-06-30 2012-01-05 3M Innovative Properties Company Multi-layer articles capable of forming color images and methods of forming color images
WO2012012177A1 (en) 2010-06-30 2012-01-26 3M Innovative Properties Company Mask processing using films with spatially selective birefringence reduction
US8879151B2 (en) 2008-12-22 2014-11-04 3M Innovative Properties Company Internally patterned multilayer optical films using spatially selective birefringence reduction
US8975011B2 (en) 2010-06-30 2015-03-10 3M Innovative Properties Company Multi-layer articles capable of forming color images and method of forming color images
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US9081147B2 (en) 2012-01-03 2015-07-14 3M Innovative Properties Company Effective media retarder films with spatially selective birefringence reduction
USD746974S1 (en) 2013-07-15 2016-01-05 3M Innovative Properties Company Exhalation valve flap
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US10783601B1 (en) 2015-03-20 2020-09-22 Digimarc Corporation Digital watermarking and signal encoding with activable compositions
US10872392B2 (en) 2017-11-07 2020-12-22 Digimarc Corporation Generating artistic designs encoded with robust, machine-readable data
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US10928571B2 (en) 2013-12-06 2021-02-23 3M Innovative Properties Company Multilayer reflective polarizer with embedded absorbing elements
US11062108B2 (en) 2017-11-07 2021-07-13 Digimarc Corporation Generating and reading optical codes with variable density to adapt for visual quality and reliability
US11386281B2 (en) 2009-07-16 2022-07-12 Digimarc Corporation Coordinated illumination and image signal capture for enhanced signal detection
US11813581B2 (en) 2017-07-14 2023-11-14 3M Innovative Properties Company Method and adapter for conveying plural liquid streams
US11877604B2 (en) 2007-05-03 2024-01-23 3M Innovative Properties Company Maintenance-free respirator that has concave portions on opposing sides of mask top section
US11904191B2 (en) 2007-05-03 2024-02-20 3M Innovative Properties Company Anti-fog respirator

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